Highly heat-resistant, negative-type photosensitive resin composition
Disclosed is a negative type photosensitive resin composition comprising (A) a polyamide having a photopolymerizable unsaturated double bond, (B) a monomer having a photopolymerizable unsaturated double bond, (C) a photopolymerization initiator and (D) a melamine resin.
1. A negative type photosensitive resin composition which comprises:
(A) 100 parts of a polyamide having a structural unit represented by the following formula (1) and having a photopolymerizable unsaturated double bond,
(B) 1-50 parts of a monomer having a photopolymerizable unsaturated double bond,
(C) 1-20 parts of a photopolymerization initiator, and
(D) 5-30 parts of a melamine resin,
(where X is a 2-4 valent aromatic group and Y is a 2-4 valent aromatic group, i and j are integers of 0-2 and satisfy i+j=2, k is an integer of 2-150, R A is independently a monovalent organic group having a photopolymerizable unsaturated double bond and represented by the following formula (2) or a saturated aliphatic group of 1-4 carbon atoms, and R B is independently a hydrogen atom or a monovalent organic group having a photopolymerizable unsaturated double bond and represented by the following formula (3), with the proviso that when the total mol number of R B is assumed to be 100 mol %, not less than 10 mol % and not more than 50 mol % thereof is the monovalent organic group having a photopolymerizable unsaturated double bond and represented by the following formula (3),
where R 8 is a hydrogen atom or an organic group of 1-3 carbon atoms, R 9 and R 10 are independently a hydrogen atom or an organic group of 1-3 carbon atoms, and q is an integer of 2-10,
where R 3 is a hydrogen atom or an organic group of 1-3 carbon atoms, R 4 and R 5 are independently a hydrogen atom or an organic group of 1-3 carbon atoms, and m is an integer of 2-10).
2. A negative type photosensitive resin composition according to claim 1 , wherein the polyamide (A) having a photopolymerizable unsaturated double bond is a polybenzoxazole precursor having a structural unit represented by the following formula (4):
(where X 1 is a divalent aromatic group, Y 1 is a tetravalent aromatic group, n is an integer of 2-150, and R 1 and R 2 are independently a hydrogen atom or a monovalent organic group having a photopolymerizable unsaturated double bond and represented by the following formula (3), with the proviso that when the total mol of R 1 and R 2 is assumed to be 100 mol %, not less than 10 mol % and not more than 50 mol% of R 1 and R 2 are the monovalent organic groups having a photopolymerizable unsaturated double bond and represented by the following formula (3):
where R 3 is a hydrogen atom or an organic group of 1-3 carbon atoms, R 4 and R 5 are independently a hydrogen atom or an organic group of 1-3 carbon atoms, and m is an integer of 2-10).
3. A negative type photosensitive resin composition according to claim 1 , wherein the polyamide (A) having a photopolymerizable unsaturated double bond is a polyimide precursor having a structural unit represented by the following formula (5):
(where X 2 is a tetravalent aromatic group, and the —COOR 6 group and the —COOR 7 group, and the —CONH— group adjacent thereto are in the ortho position to each other, Y 2 is a divalent aromatic group, p is an integer of 2-150, and R 6 and R 7 are independently a monovalent organic group having a photopolymerizable unsaturated double bond and represented by the following formula (2) or a saturated aliphatic group of 1-4 carbon atoms:
where R 8 is a hydrogen atom or an organic group of 1-3 carbon atoms, R 9 and R 10 are independently a hydrogen atom or an organic group of 1-3 carbon atoms, and q is an integer of 2-10).
4. A negative type photosensitive resin composition according to any one of claims 1 - 3 , wherein the melamine resin (D) has a polymerization degree of not less than 1.0 and not more than 2.2.
5. A negative type photosensitive resin composition according to any one of claims 1 - 3 , wherein the melamine resin (D) is a hexamethoxymethylated melamine.
6. A method for forming a heat resistant and chemical resistant relief pattern which comprises:
(1) coating the negative type photosensitive resin composition according to any one of claims 1 - 3 on a substrate,
(2) subjecting the coating to exposure by irradiating with active rays through a patterning mask,
(3) dissolving and removing the unexposed portions of the coating using a developer to form a relief pattern, and
(4) heating the coating at a temperature of not lower than 200° C. to cure the coating.
7. A method for producing a semiconductor device which includes forming a relief pattern by the relief pattern forming method according to claim 6 .
8. A method for forming a heat resistant and chemical resistant relief pattern which comprises:
(1) coating the negative type photosensitive resin composition according to claim 4 on a substrate,
(2) subjecting the coating to exposure by irradiating with active rays through a patterning mask,
(3) dissolving and removing the unexposed portions of the coating using a developer to form a relief pattern, and
(4) heating the coating at a temperature of not lower than 200° C. to cure the coating.
9. A method for producing a semiconductor device which includes forming a relief pattern by the relief pattern forming method according to claim 8 .
10. A method for forming a heat resistant and chemical resistant relief pattern which comprises:
(1) coating the negative type photosensitive resin composition according to claim 5 on a substrate,
(2) subjecting the coating to exposure by irradiating with active rays through a patterning mask,
(3) dissolving and removing the unexposed portions of the coating using a developer to form a relief pattern, and
(4) heating the coating at a temperature of not lower than 200° C. to cure the coating.
11. A method for producing a semiconductor device which includes forming a relief pattern by the relief pattern forming method according to claim 10 .