New Negative-Type Photosensitive Poly(phenylene ether):2 Poly(2-hydroxy-6-methylphenol-co-2,6-dimethylphenol), a Cross-Linker, and a Photoacid Generator.

Abstract

A negative working thermally stable and photosensitive polymer 3 based on poly(2-hydroxy-6-methylphenol-co-2,6-dimethylphenol), 2,6-bis(hydroxymethyl)-4-methylphenol (BHMP) as a cross-linker, and a photoacid generator diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate (DIAS) has been developed. Polymer 3 was prepared by oxidative coupling polymerization of 2-(tetrahydropyran-2-yl)oxy-6-methylphenol 1 with 2,6-dimethylphenol 2 in the molar ratio of 0.85 : 0.15, followed by acid-hydrolysis. Polymer 3 showed excellent transparency above 300 nm in the UV-visible spectrum. The photosensitive polymer containing polymer 3 (72 wt%), MBHP (18 wt%), and DIAS (10 wt%) showed a sensitivity (D"5) of 7.9 mJlcm2 and a contrast (r15) of 9.3 when it was exposed 365 nm light and postbaked at 125 °C for 3 min, followed by developing a 2.38 wt% aqueous tetramethylammonium hydroxide TMAH solution at 25°C.

The Photopolymer Science and Technology Award

“…He also reported many thermally stable and photosensitive polymers based on various engineering plastics such as poly(phenylene ether) (37)(38)(39)(40)(41)(42), poly(naphthalene) (43), poly(ether ketone) (44), etc.…”

A Negative Type Photosensitive Polymer Based on Poly(naphthylene ether), a Cross-Linker, and a Photoacid Generator with Low Dielectric Constant

“…On the other hand, a higher loading of CYMEL achieves the larger dissolution contrast, which saturates at a 10 wt % loading. However, some extent of decrease in film thickness was observed at even a 15 wt % CYMEL loading probably because the cross-linker with an aromatic ring (CYMEL) is less reactive than that with a hydroxyl group (e.g., 4,4 0 -methylenebis[2,6-di(hydroxymethyl)]phenol 11,12 ). Therefore, the effect of PTMA loading was studied at a 10 wt % CYMEL loading as shown in Figure 3.…”

“…As substitutes of PIs, there are several matrix polymers such as poly(benzoxazole)s (PBOs) [8][9][10] and poly-(phenylene ether)s (PPEs), 11 which are successfully applied to the photosensitive polymers. Poly(2,6-dihydroxy-1,5-naphthylene) (PDHN) exhibits low " of 2.8, and have been applied to both negative- 12 and positive-type 13 photosensitive polymers because of moderate dissolution behavior in an alkaline developer.…”

Recent Development of Photosensitive Polybenzoxazoles

“…24 A three-component positive-type PSPBO system consisting of PHA, PAG, and an acid-labile dissolution reverser has been developed (Figure 8), where the dissolution reverser acted as a dissolution inhibitor to 2.38 wt % TMAHaq before photo-irradiation, and a dissolution promoter after photo-irradiation. 25 A negative-type chemically amplified PSPBO has also been reported, 26 which was based on PHA capped with norbornene imide (PHA-NI), 4,4 0 -methylenebis-[2,6-di(hydroxymethyl)]phenol (MBHP) as a crosslinker, [27][28][29] and (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile (PTMA) as a PAG 30 (Scheme 6). PHA-NI was easily prepared as described above except using 5-norbornene-endo-2,3-dicarboxylic anhydride as an end-capping agent.…”