Positive photosensitive resin composition and method of forming cured film from the same
According to one embodiment, a positive photosensitive resin composition includes a resin containing a specified acrylic acid besed-structural unit which generates a carboxyl group when its dissociative group is dissociated, which resin is insoluble in alkali or sparingly soluble in alkali but when its acid-dissociative group is dissociated, becomes soluble in alkali, a resin containing a structural unit derived from a radical-polymerizable monomer containing an epoxy group, a compound containing two or more epoxy groups in its molecule, provided that the resin containing the structural unit derived from a radical-polymerizable monomer containing an epoxy group is not included in this compound, and a compound that when exposed to actinic rays of 300 nm or longer wavelength, generates an acid.
1. A positive photosensitive resin composition comprising (A1) a resin containing any of structural units of general formula (1) below, which resin is insoluble in alkali or sparingly soluble in alkali but when its acid-dissociative group is dissociated, becomes soluble in alkali; (A2) a polymer or copolymer containing a structural unit derived from a radical-polymerizable monomer containing an epoxy group; (B) a compound containing two or more epoxy groups in its molecule, provided that the polymer or copolymer (A2) is not included in this compound; and (C) a compound that when exposed to actinic rays of 300 nm or longer wavelength, generates an acid,
in which
R 1 represents a hydrogen atom, a methyl group, a halogen atom or a cyano group,
each of R 2 and R 3 independently represents a hydrogen atom, or a linear alkyl group, provided that R 2 and R 3 are not simultaneously hydrogen atoms, and
R 4 represents a linear, branched or cyclic alkyl group or an aralkyl group, wherein the alkyl group is optionally subtituted with an alkoxy group having 1 to 5 carbon atoms or a halogen atom,
provided that R 2 and R 4 may be linked to each other to thereby form a cyclic ether.
2. The positive photosensitive resin composition according to claim 1 , wherein the component (A2) contains the structural unit derived from a radical-polymerizable monomer containing an epoxy group and any of structural units of general formula (1).
3. The positive photosensitive resin composition according to claim 1 , wherein the radical-polymerizable monomer containing an epoxy group is 3,4-epoxycyclohexylmethyl acrylate or 3,4-epoxycyclohexylmethyl methacrylate.
4. The positive photosensitive resin composition according to claim 1 , wherein the component (C) contains a compound containing any of oxime sulfonate groups of general formula (2) below,
in which
R 5 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group.
5. The positive photosensitive resin composition according to claim 1 , wherein the component (C) contains any of compounds of general formula (3) below,
in which
R 5 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group,
X represents an alkyl group, an alkoxy group or a halogen atom, and
m is an integer of 0 to 3, provided that when m is 2 or 3, a plurality of X's may be identical to or different from each other.
6. The positive photosensitive resin composition according to claim 1 , further comprising an adhesion aid (D).
7. A method of forming a cured film, comprising the steps of applying the positive photosensitive resin composition according to claim 1 to a substrate and drying the applied composition to thereby form a film; exposing the film through a mask to actinic rays of 300 nm or longer wavelength; developing the exposed film with an alkali developer to thereby form a pattern; and baking the formed pattern.
8. The method of forming a cured film according to claim 7 , further comprising exposing the pattern on its entire surface after the development with an alkali developer to thereby form a pattern but before the baking of the formed pattern.
9. A cured film obtained by the method of claim 7 .
10. The positive photosensitive resin composition according to claim 1 , wherein the mass ratio of component (A1) to component (A2) is 30:70 to 70:30.
11. The positive photosensitive resin composition according to claim 1 , wherein the number of carbon atoms of an alkyl group in R 2 and R 3 of general formula (1) is 1-6.
12. A positive photosensitive resin composition comprising (A′) a resin containing not only any of structural units of general formula (1) below but also a structural unit containing a functional group capable of reacting with a carboxyl group to thereby form a covalent bond, which resin is insoluble in alkali or sparingly soluble in alkali but when its acid-dissociative group is dissociated, becomes soluble in alkali; (B) a compound containing two or more epoxy groups in its molecule, provided that the resin (A′) is not included in this compound; and (C) a compound that when exposed to actinic rays of 300 nm or longer wavelength, generates an acid,
in which
R 1 represents a hydrogen atom, a methyl group, a halogen atom or a cyano group,
each of R 2 and R 3 independently represents a hydrogen atom, or a linear alkyl group, provided that R 2 and R 3 are not simultaneously hydrogen atoms, and
R 4 represents a linear, branched or cyclic alkyl group or an aralkyl group, wherein the alkyl group is optionally subtituted with an alkoxy group or a halogen atom,
provided that R 2 and R 4 may be linked to each other to thereby form a cyclic ether.
13. The positive photosensitive resin composition according to claim 12 , wherein the functional group capable of reacting with a carboxyl group to thereby form a covalent bond, contained in the component (A′) is an epoxy group.
14. The positive photosensitive resin composition according to claim 12 , wherein the structural unit containing a functional group capable of reacting with a carboxyl group to thereby from a covalent bond is the structural unit derived from 3,4-epoxycyclohexylmethyl acrylate or 3,4-epoxycyclohexylmethyl methacrylate.
15. The positive photosensitive resin composition according to claim 12 , wherein the functional group capable of reacting with a carboxyl group to thereby form a covalent bond, contained in the component (A′) is an oxetane group.
16. The positive photosensitive resin composition according to claim 12 , wherein the component (C) contains a compound containing any of oxime sulfonate groups of general formula (2) below,
in which
R 5 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group.
17. The positive photosensitive resin composition according to claim 12 , wherein the component (C) contains any of compounds of general formula (3) below,
in which
R 5 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group,
X represents an alkyl group, an alkoxy group or a halogen atom, and
m is an integer of 0 to 3, provided that when m is 2 or 3, a plurality of X's may be identical to or different from each other.
18. The positive photosensitive resin composition according to claim 12 , further comprising an adhesion aid (D).
19. A method of forming a cured film, comprising the steps of applying the positive photosensitive resin composition according to claim 12 to a substrate and drying the applied composition to thereby form a film; exposing the film through a mask to actinic rays of 300 nm or longer wavelength; developing the exposed film with an alkali developer to thereby form a pattern; and baking the formed pattern.
20. The method of forming a cured film according to claim 19 , further comprising exposing the pattern on its entire surface after the development with an alkali developer to thereby form a pattern but before the baking of the formed pattern.
21. A cured film obtained by the method of claim 19 .
22. The positive photosensitive resin composition according to claim 1 , wherein at least one of component (A1) and component (A2) further contains a structural unit derived from acrylic acid or methacrylic acid.