JPH04264133A - Alkyl-substituted diphenylpolysilane and its production - Google Patents
Alkyl-substituted diphenylpolysilane and its productionInfo
- Publication number
- JPH04264133A JPH04264133A JP4548091A JP4548091A JPH04264133A JP H04264133 A JPH04264133 A JP H04264133A JP 4548091 A JP4548091 A JP 4548091A JP 4548091 A JP4548091 A JP 4548091A JP H04264133 A JPH04264133 A JP H04264133A
- Authority
- JP
- Japan
- Prior art keywords
- substituted
- alkyl
- diphenylpolysilane
- absorption
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- FTHMSTGYKFHWEF-UHFFFAOYSA-N dichloro-bis(2-ethylphenyl)silane Chemical compound CCC1=CC=CC=C1[Si](Cl)(Cl)C1=CC=CC=C1CC FTHMSTGYKFHWEF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 19
- 229920000548 poly(silane) polymer Polymers 0.000 abstract description 12
- 229910008045 Si-Si Inorganic materials 0.000 abstract description 9
- 229910006411 Si—Si Inorganic materials 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 7
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 5
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- 239000011734 sodium Substances 0.000 abstract description 5
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 abstract 1
- 238000000862 absorption spectrum Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 239000010409 thin film Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 108091008695 photoreceptors Proteins 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000005384 cross polarization magic-angle spinning Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000000807 solvent casting Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 methylphenylcyclohexasilane Chemical compound 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- PLUQSKKKNPNZCQ-UHFFFAOYSA-N tetrasiletane Chemical compound [SiH2]1[SiH2][SiH2][SiH2]1 PLUQSKKKNPNZCQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、フォトレジスト、光導
波路材料、シリコンカーバイドの前駆体、半導体、電子
写真感光体、非線型光学材料として、炭素を骨格とする
従来の高分子材料にはないユニークな特徴を持つ新しい
タイプの機能材料である、シリコンを骨格とする可溶性
アルキル置換ジフェニルポリシラン高分子に関する。[Industrial Application Field] The present invention is applicable to photoresists, optical waveguide materials, silicon carbide precursors, semiconductors, electrophotographic photoreceptors, and nonlinear optical materials, which are not available in conventional polymeric materials with carbon skeletons. This research concerns a soluble alkyl-substituted diphenylpolysilane polymer with a silicon backbone, which is a new type of functional material with unique characteristics.
【０００２】0002
【従来の技術】近年シリコンを骨格とする高分子である
可溶性有機ポリシランは、フォトレジスト、シリコンカ
ーバイドの前駆体、半導体、電子写真感光体、非線型光
学材料、光導波路として、炭素を骨格とする従来の高分
子材料にはないユニークな特徴を持つ新しいタイプの機
能性材料として多くの注目を集めている。有機ポリシラ
ンが興味を引いた原因の一つは有機溶剤に溶解し、繊維
や薄膜に容易に加工できるためである。しかしながらこ
れまで知られている有機ポリシランのほとんどは、Ｓｉ
に有機置換基が２個導入された（ＳｉＲ１ Ｒ２ ）（
Ｒ１ 、Ｒ２ は有機置換基）を繰返し単位とする化学
構造である。そのため、例えば、光化学的な開裂反応や
架橋反応を利用したフォトレジストや光導波路のような
数ミクロン程度の厚みの薄膜加工に対して、３００から
４００ｎｍ付近に現われるＳｉ−Ｓｉ結合に由来する強
い紫外吸収帯による自己吸収のため膜厚を厚くできない
、感度が十分でないなどの理由から、従来の炭素系高分
子材料に比べ特性的に満足のいくものではなかった。膜
厚の厚い有機ポリシランを用いた微細加工を行う上で、
紫外線照射に対して活性なＳｉ−Ｓｉ結合連鎖構造を有
しながら、かつ３００から４００ｎｍ付近に現われる有
機ポリシランに特有の強い紫外吸収帯を弱めることが必
要である。しかしながら、これまで知られている有機ポ
リシラン化学の常識では、有機ポリシランは３００から
４００ｎｍ付近にはＳｉ−Ｓｉ連鎖に特有の強い紫外吸
収帯が現われるとされてきた。[Prior Art] In recent years, soluble organic polysilanes, which are polymers with a silicon skeleton, have been used as photoresists, silicon carbide precursors, semiconductors, electrophotographic photoreceptors, nonlinear optical materials, and optical waveguides. It is attracting a lot of attention as a new type of functional material with unique characteristics not found in conventional polymer materials. One of the reasons why organic polysilanes have attracted interest is that they dissolve in organic solvents and can be easily processed into fibers and thin films. However, most of the organic polysilanes known so far are Si
Two organic substituents were introduced into (SiR1 R2) (
It is a chemical structure in which R1 and R2 are organic substituents) as repeating units. Therefore, for example, when processing thin films of several microns in thickness such as photoresists and optical waveguides using photochemical cleavage reactions and crosslinking reactions, strong ultraviolet Due to self-absorption in the absorption band, it is not possible to increase the film thickness, and the sensitivity is not sufficient, so the characteristics are not satisfactory compared to conventional carbon-based polymer materials. When performing microfabrication using thick organic polysilane,
It is necessary to have a Si-Si bond chain structure that is active against ultraviolet irradiation, and at the same time to weaken the strong ultraviolet absorption band characteristic of organic polysilanes that appears in the vicinity of 300 to 400 nm. However, conventional wisdom regarding organic polysilane chemistry has been that organic polysilanes exhibit a strong ultraviolet absorption band characteristic of Si--Si chains in the vicinity of 300 to 400 nm.
【０００３】0003
【発明が解決しようとする課題】本発明の目的は、高感
度なフォトレジスト、導波損失の少ない光導波路材料、
ｐ／ｎ型ドーピング可能な半導体、変換効率の高いシリ
コンカーバイドの前駆体、高感度な電子写真感光体、高
効率な非線型光学材料として期待される、有機溶媒に可
溶でかつ３００から４００ｎｍ付近にはＳｉ−Ｓｉ連鎖
に特有の強い紫外吸収帯を持たないアルキル置換ジフェ
ニルポリシランを提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a highly sensitive photoresist, an optical waveguide material with low waveguide loss,
A semiconductor capable of p/n doping, a silicon carbide precursor with high conversion efficiency, a highly sensitive electrophotographic photoreceptor, and a highly efficient nonlinear optical material that is soluble in organic solvents and has a wavelength of around 300 to 400 nm. The object of the present invention is to provide an alkyl-substituted diphenylpolysilane that does not have the strong ultraviolet absorption band characteristic of Si--Si chains.
【０００４】0004
【課題を解決するための手段】本発明を概説すれば、本
発明の第１の発明は、アルキル置換ジフェニルポリシラ
ンに関する発明であって、下記構造式（化１）：[Means for Solving the Problems] To summarize the present invention, the first invention of the present invention relates to an alkyl-substituted diphenylpolysilane, which has the following structural formula (Formula 1):
【化１
】
（ｎは重量平均重合度を示す）で表されることを特徴と
する。本発明の第２の発明は、上記構造式（化１）で表
されるアルキル置換ジフェニルポリシランの製造方法に
関する発明であって、ビス（ｏ−エチルフェニル）ジク
ロロシランを金属ナトリウムで縮合させることを特徴と
する。[Chemical 1
] (n represents the weight average degree of polymerization). A second invention of the present invention relates to a method for producing an alkyl-substituted diphenylpolysilane represented by the above structural formula (Chemical formula 1), which comprises condensing bis(o-ethylphenyl)dichlorosilane with metallic sodium. Features.
【０００５】本発明の目的化合物の例としては、単分散
ポリスチレンを基準にしたゲルパーミエーションクロマ
トグラフ法により求めた方法で、ｎの値が１０以上であ
ることを特徴とするアルキル置換ジフェニルポリシラン
、及び単分散ポリスチレンを基準にしたゲルパーミエー
ションクロマトグラフ法により求めた方法でｎの値が１
０以上で、かつ２９Ｓｉ−ＦＴＮＭＲ（ＣＲ−ＭＡＳ法
）で約１０から−４０ｐｐｍにわたって幅広いピークを
持つことを特徴とするアルキル置換ジフェニルポリシラ
ンが挙げられる。Examples of the target compounds of the present invention include alkyl-substituted diphenylpolysilanes characterized in that the value of n is 10 or more as determined by gel permeation chromatography using monodisperse polystyrene; and the value of n is 1 as determined by gel permeation chromatography based on monodisperse polystyrene.
Examples include alkyl-substituted diphenylpolysilanes which are characterized by having a range of 0 or more and having a broad peak ranging from about 10 to -40 ppm in 29Si-FTNMR (CR-MAS method).
【０００６】本発明方法の原料単量体であるビス（ｏ−
エチルフェニル）ジクロロシランは、下記の反応方程式
（化２）に基づいて合成した。なお、反応操作及び精製
操作は、すべてアルゴンガス雰囲気下、及び室内光をカ
ットして行い目的原料化合物（３）を合成した。Bis(o-
Ethylphenyl) dichlorosilane was synthesized based on the following reaction equation (Chemical formula 2). Note that the reaction operations and purification operations were all performed under an argon gas atmosphere and with room light cut off to synthesize the target raw material compound (3).
【０００７】[0007]
【化２】[Case 2]
【０００８】（３）は、以下の方法で調製した。テトラ
ヒドロフラン２００ｍｌにマグネシウム１５ｇを入れ、
かくはんしながらこれに油浴温度５０℃にて、（１）１
０２ｇを添加した。この反応溶液（２）を、ＳｉＣｌ４
の４６ｇとテトラヒドロフラン１００ｍｌの混合溶液
に室温で添加し、そのまま一昼夜反応させた。（３）は
、反応溶液にヘキサンを加え、ヘキサン可溶成分を分別
蒸留することによって、精製した。沸点１１８．５〜１
２１．５℃／０．２ｍｍＨｇ、収量２７．５ｇ。(3) was prepared by the following method. Add 15g of magnesium to 200ml of tetrahydrofuran,
While stirring, add (1) 1 to this at an oil bath temperature of 50°C.
02g was added. This reaction solution (2) was mixed with SiCl4
The mixture was added to a mixed solution of 46 g of and 100 ml of tetrahydrofuran at room temperature, and the mixture was allowed to react overnight. (3) was purified by adding hexane to the reaction solution and fractionally distilling the hexane-soluble components. Boiling point 118.5-1
21.5°C/0.2mmHg, yield 27.5g.
【０００９】[0009]
【実施例】以下、本発明を実施例及び応用例により更に
具体的に説明するが、本発明はこれらに限定されない。[Examples] The present invention will be explained in more detail below with reference to Examples and Application Examples, but the present invention is not limited thereto.
【００１０】実施例１
反応容器内を十分に脱水脱気し、アルゴンガス置換した
後、ビス（ｏ−エチルフェニル）ジクロロシラン（３）
６．０ｇとトルエン３５ｍｌをフラスコに入れた。油浴
温度１１０℃において金属ナトリウム分散液（トルエン
３０％）５．０ｇを一度に添加し、添加後更に約３時間
反応させた。反応混合溶液を加圧ろ過し、メチルアルコ
ールにろ液を加えた。生じた油状生成物を更にエチルア
ルコール／メチルアルコール／水の混合溶媒から分別沈
殿で精製した。沈殿を遠心分離機で回収し、６０℃で真
空乾燥した。収量は０．１５ｇでジクロロジフェニルシ
ラン単量体を基準にした収率で３．２％であった。単分
散ポリスチレンを基準にしたゲルパーミエーションクロ
マトグラフ法により求めた重量平均重合度が１６．８、
分散度（＝重量平均重合度／数平均重合度）が２．５の
単峰性の高分子が得られ、重合度は１０５から５の範囲
にわたっていた。得られたアルキル置換ジフェニルポリ
シランはスピンコート法や溶媒キャスト法で容易に薄膜
を形成することができた。Example 1 After thoroughly dehydrating and deaerating the inside of the reaction vessel and purging with argon gas, bis(o-ethylphenyl)dichlorosilane (3) was added.
6.0 g and 35 ml of toluene were placed in a flask. At an oil bath temperature of 110° C., 5.0 g of a metal sodium dispersion (toluene 30%) was added at once, and the reaction was continued for about 3 hours after the addition. The reaction mixture solution was filtered under pressure, and the filtrate was added to methyl alcohol. The resulting oily product was further purified by fractional precipitation from a mixed solvent of ethyl alcohol/methyl alcohol/water. The precipitate was collected using a centrifuge and vacuum dried at 60°C. The yield was 0.15 g, which was a yield of 3.2% based on dichlorodiphenylsilane monomer. The weight average degree of polymerization determined by gel permeation chromatography based on monodisperse polystyrene is 16.8,
A monomodal polymer with a degree of dispersion (=weight average degree of polymerization/number average degree of polymerization) of 2.5 was obtained, and the degree of polymerization ranged from 105 to 5. The obtained alkyl-substituted diphenylpolysilane could be easily formed into a thin film by spin coating or solvent casting.
【００１１】溶媒キャスト法で作製した、実施例１で得
られたアルキル置換ジフェニルポリシラン薄膜のＦＴ−
ＩＲ吸収スペクトルを図１に示す。帰属は以下の通りで
ある。芳香族Ｃ−Ｈ伸縮振動３０５２ｃｍ−１、脂肪族
Ｃ−Ｈ伸縮振動２９６６、２９３２、２８７２ｃｍ−１
、Ｓｉ−Ｈ伸縮振動２１２２ｃｍ−１、芳香族Ｃ＝Ｃ伸
縮振動１５８８、１５６２ｃｍ−１、脂肪族Ｃ−Ｈ変角
振動１４６２ｃｍ−１、Ｓｉ−フェニル振動１１２８、
１０７２、７５６ｃｍ−１、Ｓｉ−Ｓｉ伸縮振動４３４
ｃｍ−１。またＳｉ−０−Ｓｉに特徴的な１０００〜１
１００ｃｍ−１付近の幅広い強い吸収は認められない。
なお、図１において横軸は波数（ｃｍ−１）、縦軸は吸
光度を示し、基板はＫＢｒである。FT-FT of the alkyl-substituted diphenylpolysilane thin film obtained in Example 1 prepared by solvent casting method.
The IR absorption spectrum is shown in FIG. The attribution is as follows. Aromatic C-H stretching vibration 3052 cm-1, aliphatic C-H stretching vibration 2966, 2932, 2872 cm-1
, Si-H stretching vibration 2122cm-1, aromatic C=C stretching vibration 1588, 1562cm-1, aliphatic C-H bending vibration 1462cm-1, Si-phenyl vibration 1128,
1072, 756 cm-1, Si-Si stretching vibration 434
cm-1. In addition, 1000 to 1, which is characteristic of Si-0-Si,
No broad strong absorption near 100 cm-1 is observed. In FIG. 1, the horizontal axis represents wave number (cm-1), the vertical axis represents absorbance, and the substrate is KBr.
【００１２】実施例１で得られたアルキル置換ジフェニ
ルポリシラン固体の１３Ｃ−ＦＴＮＭＲ（ＣＰ−ＭＡＳ
法）を図２と１３Ｃ−ＦＴＮＭＲ（プロトンノイズデカ
ップル法、溶媒ＣＤＣｌ３ ）を図３にそれぞれ示す。
主なピークとして、約１２５から１５０ｐｐｍにかけて
芳香環炭素に基づく６本のピーク（１５０．４、１３７
．４、１３５．７、１２９．３、１２７．８、１２４．
９ｐｐｍ）（固体は４本）並びに１５から３０ｐｐｍに
かけて脂肪族炭素に基づく２本のピーク（２９．１、１
４．６から１４．９ｐｐｍ）が観測される。これから脂
肪族炭素とシリコンが結合した構造は認められない。な
お、図２及び図３において横軸の単位はｐｐｍである。
また図２中、ｓｓｂはスピニングサイドバンドを指し、
ノイズである。13C-FTNMR (CP-MAS) of the alkyl-substituted diphenylpolysilane solid obtained in Example 1
2 and 13C-FTNMR (proton noise decoupling method, solvent CDCl3) are shown in FIG. 2 and 3, respectively. The main peaks include six peaks based on aromatic ring carbon (150.4, 137 ppm) from about 125 to 150 ppm.
．． 4, 135.7, 129.3, 127.8, 124.
9 ppm) (4 solids) and two peaks based on aliphatic carbon from 15 to 30 ppm (29.1, 1
4.6 to 14.9 ppm) is observed. From this, no structure in which aliphatic carbon and silicon are bonded is recognized. In addition, in FIG. 2 and FIG. 3, the unit of the horizontal axis is ppm. In addition, in FIG. 2, ssb refers to the spinning sideband,
It's noise.
【００１３】実施例１で得られたアルキル置換ジフェニ
ルポリシラン固体の２９Ｓｉ−ＦＴＮＭＲ（ＣＰ−ＭＡ
Ｓ法）を図４に示す。幅広いピークが約１０から−４０
ｐｐｍにかけて存在し、更に約３．８、１０．３、１６
．５ｐｐｍ付近に３本のピークを有する。幅広いピーク
が１０から−４０ｐｐｍにかけて存在することは、本発
明で得られたアルキル置換ジフェニルポリシランのＳｉ
主鎖構造が、フェニルのオルト位に導入されたエチル基
の立体障害のため、かなり乱れていることを示す。また
、３．８、１０．３、１６．５ｐｐｍ付近に現われる大
きなピークは、オールトランス構造を取るとされている
可溶性のビス（ｐ−ブチルフェニル）ポリシランの−２
８ｐｐｍという値に比べ、約３２〜１１ｐｐｍだけ低磁
場シフトしている。この原因として、Ｓｉ−Ｓｉ結合角
が標準的な１０９．５４°からかなり小さくなることに
よる角度歪みか、もしくは、ゴーシュ構造をとることに
よる立体効果が低磁場方向に働いたものとした解釈が可
能である。事実、一連のパーメチルシクロシラン系〔Ｓ
ｉ（ＣＨ３ ）〕ｎ（ｎ＝４、５、６）において、ｎが
６、５、４と小さくなるにつれ、−４１．８、−４２．
１２、−２７．６ｐｐｍと変化し、特に角度歪みが大き
な〔Ｓｉ（ＣＨ３ ）〕４ は、他のシクロシランより
も約１５ｐｐｍだけ低磁場シフトすることが知られてい
る〔参考：１９８１年スプリンガー（ｓｐｒｉｎｇｅｒ
） 社発行、Ｐ．ディール、Ｅ．フラック、Ｒ．コスフ
ェルト（Ｐ．Ｄｉｅｈｌ 、Ｅ．Ｆｌｕｃｋ 、Ｒ．Ｋ
ｏｓｆｅｌｄ ）編、ＮＭＲ１７、第９０〜９１頁〕。
また、メチルフェニルポリシランやメチルフェニルシク
ロヘキサシランにおいては、アイソタクチック構造（メ
ソ−メソ）はシンジオクタチック構造（ラセミ−ラセミ
）に比べて、約２から５ｐｐｍだけ低磁場シフトするこ
とが最近明らかになっている。アイソタクチック構造は
一種のゴーシュ構造に対応し、シンジオタクチック構造
は一種のトランス構造に対応する。一般に、ゴーシュ配
置にあるシリコンは、トランス配置にあるシリコンに比
べ、低磁場シフトを引起こすことは以前から知られてい
るが、その原因については明らかでない（参考：上記引
用文献）。本発明のポリシランが平均重合度が少なくと
も１０はあるような系で、Ｓｉ−Ｓｉ連鎖の結合角が、
シクロテトラシランのように結合角が約９０°近く歪ん
でいるとは考えられない。したがって、３．８、１０．
３、１６．５ｐｐｍ付近に現われるシリコンピークシフ
トの原因は、本発明で得られたアルキル置換ジフェニル
ポリシランのＳｉ主鎖構造が、結合角歪みよりは、フェ
ニルのオルト位のエチル基の立体障害の影響でトランス
型主鎖構造をとることができず、ゴーシュ型配置構造を
とっているためと推測される。29Si-FTNMR (CP-MA) of the alkyl-substituted diphenylpolysilane solid obtained in Example 1
S method) is shown in FIG. Broad peak from about 10 to -40
ppm, and about 3.8, 10.3, 16
．． It has three peaks around 5 ppm. The presence of a broad peak from 10 to -40 ppm indicates that the Si of the alkyl-substituted diphenylpolysilane obtained in the present invention is
The main chain structure is shown to be highly disordered due to steric hindrance of the ethyl group introduced at the ortho position of the phenyl. In addition, the large peaks appearing around 3.8, 10.3, and 16.5 ppm are the -2
Compared to the value of 8 ppm, there is a downfield shift of about 32-11 ppm. The cause of this can be interpreted as angular distortion due to the Si-Si bond angle becoming considerably smaller than the standard 109.54°, or steric effect due to the gauche structure acting in the direction of the lower magnetic field. It is. In fact, a series of permethylcyclosilanes [S
i(CH3)]n (n=4, 5, 6), as n becomes smaller as 6, 5, 4, -41.8, -42.
It is known that [Si(CH3)]4, which has a particularly large angular distortion, shifts down the magnetic field by about 15 ppm compared to other cyclosilanes [Reference: 1981 Springer
) Published by P. Diehl, E. Flack, R. Kosfeld (P.Diehl, E.Fluck, R.K.
Osfeld), NMR 17, pp. 90-91]. Furthermore, in methylphenylpolysilane and methylphenylcyclohexasilane, it has recently been revealed that the isotactic structure (meso-meso) is shifted down the magnetic field by about 2 to 5 ppm compared to the syndiotactic structure (racemic-racemic). It has become. The isotactic structure corresponds to a type of gauche structure, and the syndiotactic structure corresponds to a type of trans structure. In general, it has been known for some time that silicon in the gauche configuration causes a lower magnetic field shift compared to silicon in the transformer configuration, but the cause is not clear (reference: cited document above). The polysilane of the present invention is a system in which the average degree of polymerization is at least 10, and the bond angle of the Si-Si chain is
It is unlikely that the bond angle is distorted by nearly 90° as in cyclotetrasilane. Therefore, 3.8, 10.
3. The cause of the silicon peak shift that appears around 16.5 ppm is that the Si main chain structure of the alkyl-substituted diphenylpolysilane obtained in the present invention is affected by steric hindrance of the ethyl group at the ortho position of phenyl, rather than bond angle distortion. This is presumed to be due to the fact that it cannot adopt a trans-type main chain structure and adopts a gauche-type configuration.
【００１４】実施例１で得られたアルキル置換ジフェニ
ルポリシランのＵＶ吸収スペクトルを図５に示す（溶媒
：テトラヒドロフラン、室温）。通常の有機ポリシラン
に見られるような３００から４００ｎｍ帯での強い特性
吸収は認められず、約２７０ｎｍ付近の肩に幅広く、吸
収係数約４０００（単位Ｓｉモノマー）−１（１）−１
のＳｉ−Ｓｉ連鎖に由来する吸収が弱く認められる。こ
れは、本発明で得られたアルキル置換ジフェニルポリシ
ランのＳｉ主鎖構造が、オルト位のエチル基の影響でゴ
ーシュ型配置構造をとっているため、通常の有機ポリシ
ランに見られるような３００から４００ｎｍ帯の強いエ
キシトン吸収が消失したことによるものと推測される。FIG. 5 shows the UV absorption spectrum of the alkyl-substituted diphenylpolysilane obtained in Example 1 (solvent: tetrahydrofuran, room temperature). There is no strong characteristic absorption in the 300 to 400 nm band as seen in ordinary organic polysilanes, and there is a broad shoulder around about 270 nm, with an absorption coefficient of about 4000 (unit: Si monomer) -1 (1) -1
A weak absorption originating from the Si-Si chain is observed. This is because the Si main chain structure of the alkyl-substituted diphenylpolysilane obtained in the present invention has a gauche type arrangement structure due to the influence of the ethyl group at the ortho position. This is presumed to be due to the disappearance of the strong exciton absorption in the band.
【００１５】応用例１
得られたアルキル置換ジフェニルポリシランが、２５０
〜３５０ｎｍにわたって、図５に示すように幅広い吸収
を有することから、キセノン、重水素、水銀などを封入
した紫外光源あるいは窒素レーザーやエキシマレーザー
などの強力光源による微細加工が容易になることが期待
される。事実、得られたアルキル置換ジフェニルポリシ
ラン薄膜（厚み約０．３ミクロン）に波長２５４ｎｍの
水銀ランプ（出力６Ｗ）を照射すると約１０分位でヘプ
タンなどの非極性溶媒に対して不溶化を起こし、いわゆ
るネガ型パターン特性を示す。また、アルキル置換ジフ
ェニルポリシラン厚膜（厚み約１０ミクロン）に波長３
６５ｎｍの水銀ランプ（出力６Ｗ）を照射すると同様に
約６０分で不溶化を起こした。Application Example 1 The obtained alkyl-substituted diphenylpolysilane was
Since it has a wide absorption range of ~350 nm as shown in Figure 5, it is expected that microfabrication will become easier using an ultraviolet light source filled with xenon, deuterium, mercury, etc., or a powerful light source such as a nitrogen laser or excimer laser. Ru. In fact, when the obtained alkyl-substituted diphenylpolysilane thin film (about 0.3 microns thick) is irradiated with a mercury lamp with a wavelength of 254 nm (output 6 W), it becomes insolubilized in nonpolar solvents such as heptane in about 10 minutes, and the so-called Shows negative pattern characteristics. In addition, wavelength 3
When irradiated with a 65 nm mercury lamp (output 6 W), insolubilization similarly occurred in about 60 minutes.
【００１６】アルキル置換ジフェニルポリシラン薄膜の
光反応を空気中室温で、紫外吸収スペクトルとＦＴ−Ｉ
Ｒを用いて追跡した。実施例１で合成されたアルキル置
換ジフェニルポリシラン薄膜の紫外線照射に伴うＵＶ吸
収スペクトルの経時変化を図６に、ＦＴ−ＩＲ吸収スペ
クトルの経時変化を図７に表す（波長：２５４ｎｍ、出
力６Ｗ、空気中、室温）。図８は、実施例１で合成され
たアルキル置換ジフェニルポリシラン薄膜の紫外線照射
前後におけるＦＴ−ＩＲ吸収スペクトルの差スペクトル
を表す（波長：２５４ｎｍ、出力６Ｗ、空気中、室温、
時間６０分）。図６からは、紫外吸収スペクトルからは
、光照射時間と共に、２３５〜３５０ｎｍにわたるＳｉ
−Ｓｉ連鎖に由来する幅広い吸収帯が少し消失し、フェ
ニル基の存在に由来する２５０〜３００ｎｍ付近の微細
構造を持つ吸収帯のみとなった。図７及び図８からは、
アルキル置換ジフェニルポリシランに由来する２１２２
ｃｍ−１のＳｉ−Ｈ伸縮振動並びに４７２ｃｍ−１付近
のＳｉ−Ｓｉ結合に由来する伸縮振動が弱くなった。そ
れに対して、ポリシロキサン構造が生成することによっ
てＳｉ主鎖上の電子が局在することに由来する２１５５
ｃｍ−１付近のＳｉ−Ｈ伸縮振動、１０００〜１１００
ｃｍ−１付近のＳｉ−Ｏ−Ｓｉ結合に由来するブロード
伸縮振動、ケトン構造に由来する１７２０ｃｍ−１付近
のブロードな吸収、そして、Ｓｉ−ＯＨ結合会合体に由
来する３４００、８６０ｃｍ−１付近の幅広い吸収が出
現した。更に、１１００〜１０００ｃｍ−１に同定のつ
かない一連の強いシャープな吸収帯が現われ、Ｓｉ−Ｃ
Ｈ２ −Ｓｉ、Ｓｉ−（ＣＨ２ ）２ −Ｓｉ構造、あ
るいはＳｉ−フェニル−Ｓｉなどの構造が生成している
可能性がある。これらのことから、アルキル置換ジフェ
ニルポリシラン膜は、光照射により速やかに、主鎖のＳ
ｉ−Ｓｉ結合が主としてＳｉ−ＯＨやＳｉ−Ｏ−Ｓｉ結
合に変化し、一部のＳｉ−Ｓｉ結合はＳｉ−ＣＨ２ −
Ｓｉ、Ｓｉ−（ＣＨ２ ）２ −Ｓｉ構造、あるいはＳ
ｉ−フェニル−Ｓｉといった構造に光異性化を起こして
いる可能性がある。これまで知られている有機ポリシラ
ンは光照射で主鎖のＳｉ−Ｓｉ結合がＳｉ−Ｏ−Ｓｉ結
合に変化し溶媒に対する溶解度が向上するため、いわゆ
るポジ型のパターン化特性を示す。本発明で示された高
分子量アルキル置換ジフェニルポリシランは逆にネガ型
パターン化特性を示す。The photoreaction of alkyl-substituted diphenylpolysilane thin films was measured in air at room temperature using ultraviolet absorption spectra and FT-I.
It was tracked using R. Figure 6 shows the change over time in the UV absorption spectrum of the alkyl-substituted diphenylpolysilane thin film synthesized in Example 1 due to ultraviolet irradiation, and Figure 7 shows the change over time in the FT-IR absorption spectrum (wavelength: 254 nm, output 6 W, air medium, room temperature). FIG. 8 shows the difference spectrum of the FT-IR absorption spectrum before and after UV irradiation of the alkyl-substituted diphenylpolysilane thin film synthesized in Example 1 (wavelength: 254 nm, output 6 W, in air, room temperature,
time 60 minutes). From FIG. 6, the ultraviolet absorption spectrum shows that Si
The broad absorption band derived from the -Si chain disappeared a little, and only an absorption band with a fine structure around 250 to 300 nm derived from the presence of the phenyl group remained. From FIGS. 7 and 8,
2122 derived from alkyl-substituted diphenylpolysilane
The Si-H stretching vibration at cm-1 and the stretching vibration originating from the Si-Si bond near 472 cm-1 became weaker. On the other hand, the 2155
Si-H stretching vibration near cm-1, 1000-1100
Broad stretching vibrations originating from the Si-O-Si bond near cm-1, broad absorption near 1720 cm-1 originating from the ketone structure, and near 3400 and 860 cm-1 originating from the Si-OH bond association. A wide range of absorption emerged. Furthermore, a series of strong and sharp absorption bands that cannot be identified appear between 1100 and 1000 cm-1, and Si-C
There is a possibility that a structure such as H2-Si, Si-(CH2)2-Si structure, or Si-phenyl-Si is generated. From these facts, the alkyl-substituted diphenylpolysilane film can be rapidly converted to S in the main chain by light irradiation.
i-Si bonds mainly change to Si-OH and Si-O-Si bonds, and some Si-Si bonds change to Si-CH2 -
Si, Si-(CH2)2-Si structure, or S
There is a possibility that photoisomerization occurs in a structure such as i-phenyl-Si. Conventionally known organic polysilanes exhibit so-called positive patterning characteristics because the Si--Si bonds in the main chain change to Si--O--Si bonds upon irradiation with light, improving their solubility in solvents. The high molecular weight alkyl-substituted diphenylpolysilanes shown in this invention, on the contrary, exhibit negative patterning properties.
【００１７】[0017]
【発明の効果】以上説明したように、ビス（ｏ−エチル
フェニル）ジクロロシランを金属ナトリウムで脱塩素縮
重合することによって、少なくとも重量平均重合度１０
以上の薄膜形成能に優れたアルキル置換ジフェニルポリ
シランを提供することができる。本発明で得られたアル
キル置換ジフェニルポリシランは、フェニルのオルト位
にエチル基を導入することでその立体障害の影響で、通
常の有機ポリシランに見られるような３００から４００
ｎｍ帯の強い吸収帯が消失した紫外吸収スペクトルを与
えることができる。本発明で得られた高分子量アルキル
置換ジフェニルポリシランは、高感度なフォトレジスト
、導波損失の少ない光導波路材料、ｐ／ｎ型制御可能な
半導体、変換効率の高いシリコンカーバイドの前駆体、
高感度な電子写真感光体、高効率な非線型光学材料とし
て、幅広い分野の応用が期待される。特に波長３００〜
４００ｎｍにＳｉ−Ｓｉ連鎖に基づく弱い吸収帯が存在
するため、微細加工用レジスト材料として増感材のいら
ない高分子厚膜のパターン化に適している。Effects of the Invention As explained above, by dechlorinating and polycondensing bis(o-ethylphenyl)dichlorosilane with metallic sodium, the weight average degree of polymerization is at least 10.
It is possible to provide an alkyl-substituted diphenylpolysilane having excellent thin film-forming ability as described above. The alkyl-substituted diphenylpolysilane obtained in the present invention has a 300 to 400
It is possible to provide an ultraviolet absorption spectrum in which the strong absorption band in the nm band has disappeared. The high molecular weight alkyl-substituted diphenylpolysilane obtained in the present invention can be used as a highly sensitive photoresist, an optical waveguide material with low waveguide loss, a semiconductor capable of controlling p/n type, a silicon carbide precursor with high conversion efficiency,
It is expected to be applied in a wide range of fields as a highly sensitive electrophotographic photoreceptor and a highly efficient nonlinear optical material. Especially wavelength 300 ~
Since a weak absorption band based on Si-Si chains exists at 400 nm, it is suitable as a resist material for microfabrication for patterning thick polymer films that do not require a sensitizer.
【図１】本発明の実施例１で合成されたアルキル置換ジ
フェニルポリシランのＦＴ−ＩＲ吸収スペクトルを表す
図である（基板：ＫＢｒ）。FIG. 1 is a diagram showing the FT-IR absorption spectrum of alkyl-substituted diphenylpolysilane synthesized in Example 1 of the present invention (substrate: KBr).
【図２】本発明の実施例１で合成されたアルキル置換ジ
フェニルポリシランの１３Ｃ−ＦＴＮＭＲスペクトルを
表す図である（ＣＰ−ＭＡＳ法）。FIG. 2 is a diagram showing a 13C-FTNMR spectrum of the alkyl-substituted diphenylpolysilane synthesized in Example 1 of the present invention (CP-MAS method).
【図３】本発明の実施例１で合成されたアルキル置換ジ
フェニルポリシランの１３Ｃ−ＦＴＮＭＲスペクトルを
表す図である（プロトンノイズデカップル法、溶媒ＣＤ
Ｃｌ３ ）。FIG. 3 is a diagram showing the 13C-FTNMR spectrum of the alkyl-substituted diphenylpolysilane synthesized in Example 1 of the present invention (proton noise decoupling method, solvent CD
Cl3).
【図４】本発明の実施例１で合成されたアルキル置換ジ
フェニルポリシランの２９Ｓｉ−ＦＴＮＭＲスペクトル
を表す図である（ＣＰ−ＭＡＳ法）。FIG. 4 is a diagram showing a 29Si-FTNMR spectrum of the alkyl-substituted diphenylpolysilane synthesized in Example 1 of the present invention (CP-MAS method).
【図５】本発明の実施例１で合成されたアルキル置換ジ
フェニルポリシランのＵＶ吸収スペクトルを表す図であ
る（溶媒：テトラヒドロフラン、室温）。FIG. 5 is a diagram showing the UV absorption spectrum of the alkyl-substituted diphenylpolysilane synthesized in Example 1 of the present invention (solvent: tetrahydrofuran, room temperature).
【図６】本発明の実施例１で合成されたアルキル置換ジ
フェニルポリシラン薄膜の紫外線照射に伴うＵＶ吸収ス
ペクトルの経時変化を表す図である（波長：２５４ｎｍ
、出力６Ｗ、空気中、室温）。FIG. 6 is a diagram showing the change over time in the UV absorption spectrum of the alkyl-substituted diphenylpolysilane thin film synthesized in Example 1 of the present invention upon irradiation with ultraviolet light (wavelength: 254 nm).
, output 6W, in air, room temperature).
【図７】本発明の実施例１で合成されたアルキル置換ジ
フェニルポリシラン薄膜の紫外線照射に伴うＦＴ−ＩＲ
吸収スペクトルの経時変化を表す図である（波長：２５
４ｎｍ、出力６Ｗ、空気中、室温）。FIG. 7: FT-IR of the alkyl-substituted diphenylpolysilane thin film synthesized in Example 1 of the present invention upon UV irradiation.
It is a diagram showing the change in absorption spectrum over time (wavelength: 25
4nm, output 6W, in air, room temperature).
【図８】本発明の実施例１で合成されたアルキル置換ジ
フェニルポリシラン薄膜の紫外線照射後におけるＦＴ−
ＩＲ吸収スペクトルの差スペクトルを表す図である（波
長：２５４ｎｍ、出力６Ｗ、空気中、室温、時間６０分
）。FIG. 8: FT- after UV irradiation of the alkyl-substituted diphenylpolysilane thin film synthesized in Example 1 of the present invention.
It is a diagram showing a difference spectrum of IR absorption spectra (wavelength: 254 nm, output 6 W, in air, room temperature, time 60 minutes).
Claims (2)
するアルキル置換ジフェニルポリシラン。1. An alkyl-substituted diphenylpolysilane represented by the following structural formula (Chemical formula 1): [Chemical formula 1] (n represents a weight average degree of polymerization).
シランを、金属ナトリウムで縮合させることを特徴とす
る請求項１に記載の構造式（化１）で表されるアルキル
置換ジフェニルポリシランの製造方法。2. The method for producing an alkyl-substituted diphenylpolysilane represented by the structural formula (Chemical formula 1) according to claim 1, characterized in that bis(o-ethylphenyl)dichlorosilane is condensed with sodium metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4548091A JPH04264133A (en) | 1991-02-19 | 1991-02-19 | Alkyl-substituted diphenylpolysilane and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4548091A JPH04264133A (en) | 1991-02-19 | 1991-02-19 | Alkyl-substituted diphenylpolysilane and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04264133A true JPH04264133A (en) | 1992-09-18 |
Family
ID=12720566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4548091A Pending JPH04264133A (en) | 1991-02-19 | 1991-02-19 | Alkyl-substituted diphenylpolysilane and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04264133A (en) |
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| US7181156B2 (en) | 2003-07-25 | 2007-02-20 | Ricoh Company, Ltd. | Image forming apparatus using a cleaning member for preventing noises and process cartridge therefor |
| EP2146251A1 (en) | 2008-07-15 | 2010-01-20 | Ricoh Company, Ltd. | Electrophotographic photoconductor, image forming apparatus using the same, and process cartridge |
| EP2278407A1 (en) | 2009-07-23 | 2011-01-26 | Ricoh Company, Ltd. | Image forming apparatus |
| US7897313B2 (en) | 2006-04-27 | 2011-03-01 | Ricoh Company Limited | Electrostatic latent image bearing member, and image forming apparatus and process cartridge using the electrostatic latent image bearing member |
| US7995950B2 (en) | 2005-07-15 | 2011-08-09 | Ricoh Co., Ltd. | Image forming apparatus, image forming method and process cartridge involving the use of a cleaning blade that removes toner remaining on a surface of an image bearing member |
| WO2012099182A1 (en) | 2011-01-21 | 2012-07-26 | Ricoh Company, Ltd. | Electrophotographic photoconductor, and image forming method, image forming apparatus, and process cartridge using the electrophotographic photoconductor |
-
1991
- 1991-02-19 JP JP4548091A patent/JPH04264133A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7181156B2 (en) | 2003-07-25 | 2007-02-20 | Ricoh Company, Ltd. | Image forming apparatus using a cleaning member for preventing noises and process cartridge therefor |
| US7295802B2 (en) | 2003-07-25 | 2007-11-13 | Ricoh Company, Ltd | Image forming apparatus using a cleaning unit for preventing noises |
| US7995950B2 (en) | 2005-07-15 | 2011-08-09 | Ricoh Co., Ltd. | Image forming apparatus, image forming method and process cartridge involving the use of a cleaning blade that removes toner remaining on a surface of an image bearing member |
| US7897313B2 (en) | 2006-04-27 | 2011-03-01 | Ricoh Company Limited | Electrostatic latent image bearing member, and image forming apparatus and process cartridge using the electrostatic latent image bearing member |
| EP2146251A1 (en) | 2008-07-15 | 2010-01-20 | Ricoh Company, Ltd. | Electrophotographic photoconductor, image forming apparatus using the same, and process cartridge |
| EP2278407A1 (en) | 2009-07-23 | 2011-01-26 | Ricoh Company, Ltd. | Image forming apparatus |
| WO2012099182A1 (en) | 2011-01-21 | 2012-07-26 | Ricoh Company, Ltd. | Electrophotographic photoconductor, and image forming method, image forming apparatus, and process cartridge using the electrophotographic photoconductor |
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