Synthesis of photosensitive and thermosetting poly(phenylene ether) based on poly[2,6‐di(3‐methyl‐2‐butenyl)phenol‐co‐2,6‐dimethyl‐phenol] and a photoacid generator
Synthesis of photosensitive and thermosetting poly(phenylene ether) based on poly[2,6‐di(3‐methyl‐2‐butenyl)phenol‐co‐2,6‐dimethyl‐phenol] and a photoacid generator
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基于聚[2,6-二(3-甲基-2-丁烯基)苯酚-共聚-2,6-二甲基苯酚]和光产酸剂的光敏热固性聚苯醚的合成
DOI：
10.1002/pola.20490
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发表时间：
2005
期刊：
影响因子：
--
通讯作者：
M. Ueda
中科院分区：
文献类型：
--
作者：
Kazuya Matsumoto;Y. Shibasaki;S. Ando;M. Ueda
以聚[2,6-二（3-甲基-2-丁烯基）苯酚（15摩尔%）-co-2,6-二甲基苯酚（85摩尔%）]（3c）和光酸生成剂[（5-丙基磺酰基氧亚胺- 5h -噻吩-2-乙基）-（2-甲基苯基）乙腈]为原料，制备了化学放大的光敏热固性聚合物。以2,6-二（3-甲基-2-丁烯基）苯酚和2,6-二甲基苯酚为原料，在氯化铜(I)和吡啶的催化下，在氧流下氧化偶联共聚制得高分子量（数平均分子量~ 24000）的聚[2,6-双（3-甲基-2-丁烯基）苯酚]-co-2,6-二甲基苯酚](3)。用IR、1h NMR和13c NMR对其中3个化合物的结构进行了表征。3在300℃下，在n2条件下进行热处理，交联1h。固化共聚物的5%失重温度和玻璃化转变温度分别达到420°C和300°C左右。固化共聚物（3c）膜的平均折射率为1.5452，由此估计1 MHz时的介电常数为2.6。在436 nm光下，曝光后145℃烘烤5 min， 25℃用甲苯显影，光敏度为35 mJ cm -2，对比度为1.6。在接触印刷模式下，在436 nm光下暴露于100 mJ cm -2的薄膜上获得了具有8 μm线间距图案的精细负像。
A chemically amplified photosensitive and thermosetting polymer based on poly[2,6-di(3-methyl-2-butenyl)phenol (15 mol %)-co-2,6-dimethylphenol (85 mol %)] (3c) and a photoacid generator [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile] was developed. Poly[2,6-bis(3-methyl-2-butenyl)phenol]-co-2,6-dimethylphenol)] (3) with high molecular weights (number-average molecular weight ∼ 24,000) was prepared by the oxidative coupling copolymerization of 2,6-di(3-methyl-2-butenyl)phenol with 2,6-dimethylphenol in the presence of copper(I) chloride and pyridine as the catalyst under a stream of oxygen. The structures of 3 were characterized with IR, 1 H NMR, and 13 C NMR spectroscopy. 3 was crosslinked by a thermal treatment at 300 °C for 1 h under N 2 . The 5% weight loss temperatures and glass-transition temperatures of the cured copolymers reached around 420 °C in nitrogen and 300 °C, respectively. The average refractive index of the cured copolymer (3c) film was 1.5452, from which the dielectric constant at 1 MHz was estimated to be 2.6. The resist showed a sensitivity of 35 mJ cm -2 and a contrast of 1.6 when it was exposed to 436-nm light, postexposure-baked at 145 °C for 5 min, and developed with toluene at 25 °C. A fine negative image featuring 8-μm line-and-space patterns was obtained on a film exposed to 100 mJ cm -2 with 436-nm light in the contact-printed mode.