Polymer-supported sulfonium salt (PS) was synthesized by the reaction of sulfur-containing compounds, present in light oil, with iodomethylpolystyrene (IMP) and AgBF₄. Dibenzothiophenes (DBTs) and benzothiophenes (BTs) in the oil were successfully anchored on the IMP as the corresponding sulfonium salts, via nucleophilic displacement of the iodide atom on IMP with the sulfur atom on DBTs and BTs. By this means, the sulfur content of the light oil was decreased successfully to the required deep desulfurization level (0.05 wt%). The PS, obtained from light oil, showed significantly high activity as phase transfer catalyst for the anion exchange reaction of 1-bromooctane with potassium thiocyanate in the organic/water two-phase system. This high activity for the PS results since the highly lipophilic alkyl-substituted DBTs and BTs are anchored on the PS as the sulfonium salts.

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筆者らは，ポリイミドをはじめとするエンジニアリングプラスチック(エンプラ)に感光性を付与する新しい手法である「反応現像画像形成(RDP)」を開発した．従来の感光性ポリイミドはアルカリ水溶液への溶解や架橋を行うための官能基を必要とするのに対し，RDP ではポリイミド中のイミド基と現像液中の求核剤との反応をパターン形成に利用するため，特別な官能基を高分子鎖に導入する必要がない．また，イミド基以外のカルボン酸類縁基を有するポリカーボネートやポリアリレートにも感光性を付与し微細パターンを形成することができる．アミンを求核剤とするポジ型 RDP では，市販のポリエーテルイミドやポリアリレートなど種々のエンプラへの感光性付与が可能となった．求核剤としてアルコキシドを利用することにより，ビニルポリマー側鎖のイミド基を用いたポジ型パターン形成にも成功した．一方，(CH₃)₄N⁺OH^- を求核剤として用いるネガ型 RDP では，ポジ型 RDP よりも少ない感光剤量で大幅な高感度化が可能であり，化学増幅機構の適用によりさらなる高感度化も可能であった．また，ポリイミド主鎖構造を適切に設計することにより，アルカリ水溶液のみを現像液としたパターン形成も可能となることが示された．

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In this study, we successfully fabricated positive photosensitive epoxy resins based on the Reaction Development Patterning (RDP) by using B-staged polymers prepared by polyaddition between an epoxy base resin and an acid anhydride curing agent during mixing and prebaking processes. Application of RDP to the B-staged polymers afforded positive fine patterns by the use of 15-mol% sodium 2-aminoethoxide in ethanolamine / NMP mixtures. Furthermore, the fine epoxy patterns were not deformed after heat treatment for complete curing, indicating that the cress-linked epoxy patterns have high tolerability to thermal stresses. These results suggest the possibility of practical application of RDP-based positive photosensitive epoxy resins.

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接触式基板検査装置であるフライングプローブ検査機のプローブ接触痕を測定したので報告します。接触式電気検査ではさけて通れないプローブ接触痕は、プロービング速度との関係が深いため、その点を重点に考察しました。測定については、基板検査装置使用者の関心が高い、接触痕の深さと面積について調査しましたので報告します。

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スチレン-N-フェニルマレイミド交互共重合体(PMS)にグラフト鎖としてポリエチレンオキシド(PEO)を導入したコポリマー(gPMSE)をエポキシ樹脂系中にて in situ 生成させ，エポキシ樹脂の熱的，機械的特性を損なうことなくじん性を向上させることを試みた．その結果，改質剤添加量が 16 wt%の系で，未改質系に比べて K_IC の値が約 2.5 倍に向上した．この時，曲げ強度の低下は約 10%に抑制され，曲げ弾性率，ガラス転移温度(T_g)は未改質系の値が維持された．改質硬化物断面の透過型電子顕微鏡(TEM)より，数十 nm 程度の改質剤相がエポキシマトリックス中に分散していることが観察された．PMS にグラフト鎖として PEO ユニットを導入する方法が，改質剤とエポキシマトリックスの相容性向上に有効であり，エポキシ樹脂のじん性が向上することが確認された．

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We report here a rare form of invasive ductal carcinoma composed of a mass protruding from the tip of the nipple in a 43-year-old woman with hyperprolactinemia. She had been amenorrheic for 15 years following an incomplete pituitary adenomectomy for prolactinoma. She presented with a mass on the left nipple that had been growing for 6 months. Morphologically, the mass resembled adenoma of the nipple. Another mass was located in the subareolar region. She underwent mastectomy after invasive ductal carcinoma was diagnosed. Histopathologically, the tumor of the nipple was invasive ductal carcinoma, which had extended intraductally from another invasive ductal carcinoma in the subareolar region, and had infiltrated the epidermis of the nipple (Paget's disease). MR mammography successfully detected the relationship between the tumors. Postoperatively, the plasma prolactin level was abnormally high, while the plasma estradiol level was quite low, although macro-pituitary adenoma was not detected by MRI. The patient was treated with bromocriptine mesilate, in addition to adjuvant chemotherapy for breast cancer, and the plasma prolactin level has since normalized.

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Polyarylates containing diazonaphthoquinone (DNQ) structure as a photosensitive group in their chains (DNQ-introduced PArs (DPArs)) were synthesized by solution polycondensation using a DNQ having bisphenol structure (BADNQ1) as a diol monomer. Reaction development patterning (RDP) of the DPAr films afforded fine positive-tone patterns in shorter development time and higher resolution than that of the PAr film containing DNQ as an external photosensitive agent. It was also revealed that DPArs could be used as high-molecular-weight photosensitive agents and RDP-based pattern formation using the PAr/DPAr films was achieved in shorter development time and higher resolution than that using the PAr film containing low-molecular-weight DNQ. In addition, the PAr/DPAr film showed higher thermal and mechanical properties than the PAr/DNQ film. Furthermore, mechanical property of the PAr/DPAr was higher than that of the PAr itself, probably due to partial crosslinking induced by carbene species generated from DNQ during heating.

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光反応性基や酸性基のような特殊な官能基を含まない市販の耐熱性エンプラ(ポリイミド、ポリエーテルイミド、ポリアリレート、ポリカーボネートなど)に光酸発生剤を混合して作成した薄膜へ光照射後、アミン含有現像液で現像することにより、10ミクロン以上の解像度をもつ耐熱性パターンの形成が可能となった。この新規画像形成の原理について発表する。

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We investigated mechanism of the dissolution of HBPE-NO₂ films to the developer by analysis of the developer after development. A HBPE-NO₂ film containing BADNQ2 was irradiated with 500 mJ/cm² of exposure dose and developed with 25wt% TMAHaq. The developer was then neutralized by HClaq. and the solution was evaporated and dried at 90 °C in vacuo. ¹H-NMR spectrum of the resulting product after development is shown in Fig. 3. The 1H-NMR spectrum shows signals assigned to the monomers, terephthalic acid derived from TPC and THPE, and 4-nitrobenzoic acid derived from the end groups. However, no signal that can be assigned to the original HBPE-NO₂ protons was observed. This result suggests that RDP of HBPE-NO₂ is not based on solubilization of the polymer by the reaction at the end groups but on decomposition of the polymer induced by nucleophilic attack of the OH^- to the ester linkages to give low-molecular-weight products.

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ポリ (エーテルケトンケトン) によるシアナート樹脂の改質を検討した。ポリ (エーテルケトンケトン) としてポリ (フタロイルジフェニルエーテル) (PPDE), ポハリ (フタロイルジフェニルエーテル-co-イソフタロイルジフェニルエーテル) (PPIDE), ポリ (フタロイルジフェニルエーテル-co-テレフタロイルジフェニルエーテル) (PPTDE) を用いた。硬化物のミクロ構造は, 走査型電子顕微鏡や動的粘弾性測定により検討した。PPDEは, PPIDE (イソフタロイルユニット50モル%) やPPTDE (テレフタロイルユニット50モル%) より有効な改質剤であり, PPDE (MW28,300) を15重量%添加した硬化物は海島構造を有し,破壊靱性値 (K_IC) は未改質硬化物に比して30%増加した。改質硬化物の熱的性質は, 未改質硬化物と同程度であった。PPDE改質硬化物の吸水性は, 未改質硬化物に比してやや低下した。

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RDP using mixtures of TMAH / water / NMP / methanol as developers was applied to the commercially available polyimide-silicone copolymer, and when the amount of NMP in the developer was small, pattern having sufficient concavo- convex shape was not obtained. On the other hand, the use of the developer containing a large amount of NMP resulted in the formation of clear negative-tone patterns. The pattern-forming mechanism is considered to be the same as that proposed for negative-tone pattern formation of polyetherimide by RDP, that is, retardation of the reaction between imide groups in the polymer and OH^- in the developer induced by the photo-generated insoluble PMI dimer and the reaction between OH^- and the photo-generated acid from DNQ.

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