Positive-type Alkaline Developable Photosensitive Branched Polyamides with Low Degree of Branching and Diazonaphthoquinone as a Photosensitive Compound

Abstract

ABSTRACT:A positive-type photosensitive polyamide based on the branched polyamides with low degree of branching and 1-{1,1-bis[4-(2-diazo-1-(2H)naphthalenone-5-sulfonyloxy)phenyl]ethyl}-4-{1-[4-(2-diazo-1-(2H)naphthalenone-5-sulfonyloxy)phenyl]methylethyl}benzene (S-DNQ) as a photosensitive compound has been developed. The branched polyamides with low degree of branching having amino end groups (2a and 2b) were prepared from a ABB 0 type monomer, 4-(2,4-diaminophenoxy) benzoic acid 1 in the presence of diphenyl(2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate (DBOP) and triphenylphosphite/pyridine (TPP/Py) as a condensing agent, of which the degrees of branching (DB) were 0.10 and 0.36, respectively. Followed by end-capping with 4-hydroxy benzoic acid, endmodified polymers with phenolic hydroxy groups (4a and 4b) were successfully prepared. The polymer properties were characterized by 1 H and 13 C NMR, GPC, TG/DTA and DSC, respectively. The photosensitive polymer based on polymer 4a and 30 wt % S-DNQ showed a sensitivity of 140 mJ cm À2 and a contrast of 2.1 when it was pre-baked at 80 C for 5 min, subsequently exposed to a 436 nm light (g-line) and developed with a developer of 5 wt % aqueous tetrametylammonium hydroxide (TMAH) solution: 2-propanol (4:1 by weight ratio) at 25 C. A fine positive image of 6 mm line-and-space pattern was obtained when the film was exposed to 300 mJ cm À2 by contact-printing mode. Aromatic polyamide is well known as an important class of high-performance polymeric materials due to their high thermal stability and excellent mechanical property. The applications, however, are restricted by their poor processability due to their insolubility and high softening temperature. The key reasons for insolubility and non-melting character in aromatic polyamides are the lack of chain flexibility and strong intermolecular interactions due to high symmetry, highly polar groups and extensive hydrogen bonding. To remedy this, a great deal of efforts have been expended by introducing bulky pendant groups or flexible segment along the polymer backbone, incorporating a crank and twisted non-coplanar into the polymer backbone, and replacing symmetrical aromatic rings by unsymmetrical ones and so on.1-5 On the other hand, a strategy to utilize the abilities in dendritic macromolecules to avoid the strong chain entanglement and to introduce a variety of functional end groups is particular recent interests. Dendritic aromatic polyamides consists of dendrimer, dendron, or hyperbranched type structures possess a variety of unique properties such as good solubility, low viscosity, multivalence, and encapsulation effects, which mainly are caused by the branching and spherical architecture. In particular, hyperbranched polyamides are of great interest from a synthetic point of view because of relatively easier for rapid and large-scale synthesis compared with the dendrimers. However, producing the film with good physical properties still remains a challenge for conventional hyperbranched polymers due to the la...

Synthesis of soluble and autophotosensitive hyperbranched polyimides with good optical properties and thermal properties

“…In addition, the high functionality of the peripheral photosensitive groups is expected to produce high sensitivity toward exposure. Kakimoto et al 19 reported a positive-type photosensitive polyamide based on the branched polyamides with low degree of branching and S-DNQ as a photosensitive compound; it showed a sensitivity of 140 mJ cm À2 under 436 nm (g-line) light exposure. Tang et al 20 described a new route to hyperbranched polyarylenes (hb-PAs) that was functionality tolerant and regioselective.…”