Synthesis of a highly transparent poly(o‐hydroxyamide) in the i‐line region and its application to photosensitive polymers

Abstract

A novel poly(o-hydroxyamide) (PHA) based photosensitive polymer that exhibits high transparency at 365 nm wavelength (i-line) has been developed. Timedependent density functional theory (TD-DFT) calculations using the B3LYP hybrid functional were performed to predict the transparencies of various hydroxyamides in the i-line region. Based on the calculations, 4,4 0 -sulfonylbis(o-aminophenol) (SAP) was prepared and polymerized with 4,4 0 -oxybis(benzoyl chloride) (OBBC), and the resulting PHA, which is abbreviated as PHA-S, showed a high transparency comparable to that of PHA derived from 4,4 0 -(hexafluoroisopropylidene)bis(o-aminophenol). Positive-type photosensitive PHA was then formulated based on PHA-S with a crosslinker 1,3,5-tris[(2-vinyloxy)ethoxy]benzene (TVEB) and a photoacid generator (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-2-(methylphenyl)acetonitrile (PTMA) (17:3:1 in weight ratio), and demonstrated photosensitivity and contrast of 14 mJ/cm 2 and 2.7, respectively, when the resist film was prebaked at 120 8C for 5 min, irradiated by i-line, post exposure baked at 120 8C for 5 min, developed with an 2.38 wt% TMAH solution for 5 s. A clear positive image featuring 10-mm line-and-space was also printed in a film which was exposed to 50 mJ/cm 2 of i-line by contact-printing.

Highly Transparent Photosensitive Polybenzoxazole: Poly(o-hydroxy amide) Derived from 4,4′-(Hexafluoroisopropylidene)bis(o-aminophenol) and o-Substituted Dicarboxylic Acid Chlorides

“…Bis(o-hydroxyamide)s 12 and 13 were prepared according to the literature. 18 Compounds 8a and 10a were purchased from TCI Organic Chemicals and used as received. PHAs were prepared by polycondensation of diacid chlorides and bis(oaminophenol)s in the presence of LiCl as an additive.…”

“…Therefore, we designed and prepared a novel transparent PSPBO based on 4,4 0 -sulfonylbis(o-aminophenol) (13) and 4,4 0 -oxybis(benzoyl chloride) (8b) for i-line lithography. 18 Introduction of a sulfone group as a substitute for hexafluoroisopropylidene group is effective to lower the HOMO levels, and thus increases y To whom correspondence should be addressed (E-mail: mueda@polymer.titech.ac.jp).…”

Recent Development of Photosensitive Polybenzoxazoles

“…Time-dependent density functional theory (TD-DFT) calculations using B3LYP hybrid functionals with the 6-311++G(d,p) basis set are a very useful tool for predicting the absorption spectra of hydroxyamide compounds derived from various aminophenol moieties. 38 The TD-DFT calculation is based on the transition between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). This transition is responsible for the absorption at the longest wavelength.…”

Synthesis and characterization of photosensitive methacrylates to give heat-resistant polymers

“…Some of these epoxy-compounds have a heat-resistant framework structure [17] such as naphthalene or biphenyl derivatives having multiple glycidyl groups. Our new epoxyacrylates were started from these naphthalene and biphenyl derivatives, that is, diglycidyl ether of naphthalene (1), the triglycidyl and, tetraglycidyl ethers of naphthalene derivatives ((2) and (3), respectively), diglycidyl ether of biphenyl (4), and diglycidyl ether of bisphenol-A (5). New photosensitive monomers having methacryloyloxy groups were synthesized via the reaction using epoxy-compounds mentioned with methacrylic acid.…”

“…They included bichromates, cinnamyl compounds, diazo compounds, azides, and acrylates, and have been referred to as five common photosensitive compounds. Among them, the polymers having acryloyloxy group (acrylate-type photopolymer [1][2][3][4][5][6][7][8]) surpassed the others in terms of the extent of utilizing fields and consumption, because of their advantages to form transparent, flexible, strong, and thick films. One of their uses is solder resist [9][10][11][12] in which the key structure is epoxyacrylate [13][14][15][16].…”