JP4630804B2 - Substituted hydroxyphenyl compounds - Google Patents
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Description
本発明は、置換ヒドロキシフェニル化合物に関する。 The present invention relates to substituted hydroxyphenyl compounds.
有機電荷輸送物質としては従来、ポリアセチレン、ポリチオフェン、ポリアニリン等の共役二重結合を有する高分子化合物やピラゾリン化合物、ヒドラゾン化合物、トリフェニルアミン化合物、あるいはアミノ基を有するスチルベン化合物等が数多く提案されており、電子写真感光体、有機薄膜電界発光素子やフォトセル等の利用が検討されている。しかし、これらの殆どがいわゆる正孔を輸送する物質（正孔輸送物質）である。 As organic charge transporting substances, many polymer compounds having a conjugated double bond such as polyacetylene, polythiophene and polyaniline, pyrazoline compounds, hydrazone compounds, triphenylamine compounds, and stilbene compounds having an amino group have been proposed. The use of electrophotographic photoreceptors, organic thin film electroluminescent devices, photocells, and the like has been studied. However, most of these are so-called hole transport materials (hole transport materials).
一方、電子を輸送する物質（電子輸送物質）の例はあまり多くない。代表的なものとして２，４，７−トリニトロフルオレノン、フルオレニデンメタン化合物（例えば、特許文献１参照）、アントキノジメタン及びアントロン化合物（例えば、特許文献２参照）、ジフェノキノン化合物（例えば、特許文献３参照）、ナフトキノン化合物（例えば、特許文献４参照）、ナフタレンジカルボン酸イミド化合物（例えば、特許文献５参照）、ナフタレンテトラカルボン酸ジイミド化合物（例えば、特許文献６〜１１参照）等が開示されている。 On the other hand, there are not many examples of materials that transport electrons (electron transport materials). Typical examples include 2,4,7-trinitrofluorenone, fluorenidenemethane compounds (see, for example, Patent Document 1), anthoquinodimethane and anthrone compounds (see, for example, Patent Document 2), diphenoquinone compounds (for example, patents). Document 3), naphthoquinone compounds (for example, see Patent Document 4), naphthalene dicarboxylic acid imide compounds (for example, see Patent Document 5), naphthalene tetracarboxylic acid diimide compounds (for example, see Patent Documents 6 to 11) and the like are disclosed. ing.
また、ヒドロキシフェニル基にヒドロキシメチル基を有する化合物は、種々の用途に用いられることが知られている。例えば、塗料への応用や、平版印刷版、フォトレジスト、接着剤、成形材料、積層材料及び結合剤等の多くの分野に使用されており、優れた製膜性を有していることが知られている。しかしながら、分子内に電子受容性部位を有するものはなく、電子に対する機能性に着目されることは今まで無かった。 Moreover, it is known that the compound which has a hydroxymethyl group in a hydroxyphenyl group is used for various uses. For example, it is used in many fields such as paint applications, lithographic printing plates, photoresists, adhesives, molding materials, laminate materials and binders, and is known to have excellent film-forming properties. It has been. However, none has an electron-accepting site in the molecule, and no attention has been paid to functionality for electrons.
優れた特性を有する電子輸送物質を電子写真感光体に使用できれば、電子写真感光体が抱える種々の問題が改善される。 If an electron transport material having excellent characteristics can be used for an electrophotographic photosensitive member, various problems of the electrophotographic photosensitive member are improved.
例えば、導電性支持体上に正孔輸送物質及び電子輸送物質を含有する感光層を設けた負帯電用電子写真感光体において、導電性支持体と感光層との間に下引き層を形成し、該下引き層に電子輸送物質を含有させることで、感光層から注入される電子が、感光層／下引き層界面や下引き層中に滞留することによる、繰り返し使用時での電位変動等の電気的特性を改善できることが知られている（例えば、特許文献１２参照）。しかしながら、電荷発生物質とのエネルギー的マッチングや、感光層を形成する際の成膜性や他の構成成分との相溶性等の特性を全て高いレベルで満足する電子輸送物質がほとんどないため、更なる電子輸送物質の改良が求められている。 For example, in an electrophotographic photosensitive member for negative charging in which a photosensitive layer containing a hole transport material and an electron transport material is provided on a conductive support, an undercoat layer is formed between the conductive support and the photosensitive layer. By adding an electron transporting substance to the undercoat layer, electrons injected from the photosensitive layer stay in the photosensitive layer / undercoat layer interface or undercoat layer, potential fluctuations during repeated use, etc. It is known that the electrical characteristics can be improved (for example, see Patent Document 12). However, since there are few electron transport materials that satisfy all characteristics such as energy matching with charge generation materials, film formability when forming a photosensitive layer, and compatibility with other components, there is no further improvement. There is a need for improved electron transport materials.
また、積層型電子写真感光体の電荷発生層は、基本的に電荷発生物質とバインダー樹脂により構成されているが、一般的に電荷発生物質は電荷輸送能に劣るため、光照射により電荷発生物質で生じた正孔及び電子のうち層界面近傍に存在する電荷のみが電荷輸送層や下引き層へ輸送され、残った正孔及び電子は再結合やフリー電荷として電荷発生層中に残留してしまう。これは電子写真感光体の特性悪化を引き起こす原因となっている。このため電荷発生層は通常０．１〜１μｍ程の極薄膜で使用されるが、それでも上記問題は十分改善されていないのが現状である。これに対して電荷発生層中の生成した電荷の抜けを良くするために電荷発生層中に正孔輸送物質や電子輸送物質を添加する方法（例えば、特許文献１３参照）が従来から提案されているが、同様の理由により十分問題点を改善するに至っておらず、先に述べた様に、更なる電子輸送物質の改良が求められている。
本発明は、上記課題を解決するためになされたものであり、従来の電子輸送物質に比べ有機溶剤に対する溶解性や成膜性に優れ、かつ、電子輸送能が優れた新規な電子輸送物質を提供することを目的とする。 The present invention has been made in order to solve the above-mentioned problems, and provides a novel electron transport material that is superior in solubility and film-formability in an organic solvent as compared with conventional electron transport materials and has an excellent electron transport capability. The purpose is to provide.
本発明に従って、下記式（３）で示される置換ヒドロキシフェニル化合物であって、酸化還元電位の還元側の値がＳＣＥ参照電極（飽和カロメル電極）に対して−０．２０Ｖ〜−０．９０Ｖである置換ヒドロキシフェニル化合物が提供される。 According to the present invention, a substituted hydroxyphenyl compound represented by the following formula ( 3 ), wherein the value on the reduction side of the redox potential is −0.20 V to −0.90 V with respect to the SCE reference electrode (saturated calomel electrode). Certain substituted hydroxyphenyl compounds are provided.
上記式（３）中、Ａ １ 及びＡ ２ は、下記式（１）’で示される１価の基である。Ｘ １ 及びＸ ２ は、メチレン基、エチレン基又はｐ−フェニレン基を示す。ｌ及びｍは、０又は１を示す。Ｚは、下記式（５）’で示される構造である。
本発明によれば、繰り返し特性や画像特性が優れた電子写真感光体を提供することのできる新規な化合物を提供することができる。 According to the present invention, it is possible to provide a novel compound that can provide an electrophotographic photoreceptor excellent in repetitive characteristics and image characteristics .
まずは、下記式（１）で示される置換ヒドロキシフェニル化合物について説明する。
本発明の置換ヒドロキシフェニル化合物とは、電子受容性部位を有する構造と、置換ヒドロキシフェニル基とを、同一分子内に有する化合物を意味する。そして酸化還元電位の還元側の値がＳＣＥ参照電極に対して−０．２０Ｖ〜−０．９０Ｖを示す。また、置換ヒドロキシフェニル基の置換基の少なくとも一つがヒドロキシメチル基である。 The substituted hydroxyphenyl compound of the present invention means a compound having a structure having an electron accepting site and a substituted hydroxyphenyl group in the same molecule. The value on the reduction side of the oxidation-reduction potential is −0.20 V to −0.90 V with respect to the SCE reference electrode. Moreover, at least one of the substituents of the substituted hydroxyphenyl group is a hydroxymethyl group.
酸化還元電位の還元側の値がＳＣＥ参照電極に対して−０．２０Ｖ〜−０．６０Ｖを示すものがより好ましい。 It is more preferable that the value on the reduction side of the oxidation-reduction potential is −0.20 V to −0.60 V with respect to the SCE reference electrode.
ヒドロキシメチル基含有ヒドロキシフェニル基の中でも、該ヒドロキシメチル基の少なくとも１つの結合位置が、該ヒドロキシメチル基含有ヒドロキシフェニル基の中のヒドロキシ基に対してオルト位、つまり前記式（１）でのＲ１、Ｒ５がヒドロキシメチル基であるヒドロキシメチル基含有ヒドロキシフェニル基が好ましい。 Among the hydroxymethyl group-containing hydroxyphenyl groups, at least one bonding position of the hydroxymethyl group is ortho to the hydroxy group in the hydroxymethyl group-containing hydroxyphenyl group, that is, R in the formula (1). 1 , R 5 is preferably a hydroxymethyl group-containing hydroxyphenyl group.
また、電子受容性部位の少なくとも１つの結合位置が、置換ヒドロキシフェニル基の中のヒドロキシ基に対してパラ位、つまり前記式（１）でのＲ３の位置であるものが好ましい。 In addition, it is preferable that at least one binding position of the electron accepting site is para position with respect to the hydroxy group in the substituted hydroxyphenyl group, that is, the position of R 3 in the formula (1).
また、一つの化合物の中に、置換ヒドロキシフェニル基は１〜３個含まれていることが好ましい。 Moreover, it is preferable that 1-3 substituted hydroxyphenyl groups are contained in one compound.
例えば、下記式（２）〜（４）のいずれかである置換ヒドロキシフェニル化合物が挙げられる。 For example, the substituted hydroxyphenyl compound which is either of following formula (2)-(4) is mentioned.
上記式（２）〜（４）中、Ａ１〜Ａ３は、前記式（１）のＲ１〜Ｒ５のいずれか１個を除いた１価の基である。Ｒ１及びＲ５ は、水素原子又はヒドロキシメチル基を示し、Ｒ２〜Ｒ４は、水素原子、ヒドロキシメチル基又は電子受容性部位を有する基を示し、Ｒ １ 及びＲ ５ の少なくとも一方は、ヒドロキシメチル基であり、Ｒ ２ 〜Ｒ ４ の少なくとも１個は、電子受容性部位を有する基である。 In the above formula (2) ~ (4), A 1 ~A 3 is a monovalent group obtained by removing any one of the R 1 to R 5 in the formula (1). R 1 and R 5 represents a hydrogen atom or a hydroxymethyl group, R 2 to R 4 is a hydrogen atom, a group having a hydroxymethyl group or an electron accepting site shows at least one of R 1 and R 5 is , A hydroxymethyl group, and at least one of R 2 to R 4 is a group having an electron accepting site .
Ｘ １〜Ｘ３は、炭素数１〜８の置換基を有していてもよく枝分かれしてもよい脂肪族炭化水素基又は置換基を有していてもよい芳香族炭化水素基を示す。 X 1 to X 3 represents a substituted aliphatic even groups well branched have a hydrocarbon group or an optionally substituted aromatic hydrocarbon group having 1 to 8 carbon atoms.
ｌ、ｍ、ｎは、０又は１を示す。Ｚは、電子受容性部位を有する基を示す。 l, m, n denotes 0 or 1. Z represents a group having an electron-accepting site.
前記式（２）〜（４）のＺは、下記式（５）で示される構造からＹ １〜Ｙ６ のいずれか１〜３個、下記式（６）で示される構造からＹ ７〜Ｙ１６ のいずれか１〜３個、下記式（７）で示される構造からＹ １７〜Ｙ２４ のいずれか１〜３個、又は、下記式（８）で示される構造からＹ ２５〜Ｙ３２ のいずれか１〜３個（前記置換ヒドロキシフェニル化合物が前記式（２）で示される場合は１個、前記置換ヒドロキシフェニル化合物が前記式（３）で示される場合は２個、前記置換ヒドロキシフェニル化合物が前記式（４）で示される場合は３個）を除いた１〜３価の基である。 Z in the formula (2) to (4), 1-3 any structure or et Y 1 to Y 6 represented by the following formula (5), structure or et Y 7 represented by the following formula (6) 1-3 either to Y 16, 1-3 any structure or et Y 17 to Y 24 represented by the following formula (7), or the structure or et Y 25 represented by the following formula (8) 1 to 3 of Y 32 (one when the substituted hydroxyphenyl compound is represented by the formula (2), two when the substituted hydroxyphenyl compound is represented by the formula (3), If substituted hydroxyphenyl compound represented by the formula (4) is a monovalent to trivalent group formed by removing three).
上記式（５）中、Ｙ１及びＹ２は、置換若しくは無置換アリール基又は置換若しくは無置換アルキル基を示し、Ｙ３〜Ｙ６は、置換若しくは無置換アリール基、置換若しくは無置換アルキル基、ニトロ基、シアノ基、ハロゲン原子又は水素原子を示す。 In the above formula (5), Y 1 and Y 2 represent a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group, and Y 3 to Y 6 represent a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group. , A nitro group, a cyano group, a halogen atom or a hydrogen atom.
上記式（６）中、Ｙ７及びＹ８は、酸素原子、Ｃ（ＣＮ）２、ＮＲ、Ｃ（ＣＮ）Ｒ又はＣＲ２（Ｒは、置換若しくは無置換アリール基又は置換若しくは無置換アルキル基を示す。）を示し、Ｙ９〜Ｙ１６は、置換若しくは無置換アリール基、置換若しくは無置換アルキル基、ニトロ基、シアノ基、ハロゲン原子又は水素原子を示す。 In the above formula (6), Y 7 and Y 8 are an oxygen atom, C (CN) 2 , NR, C (CN) R or CR 2 (R is a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group. are shown.) indicates, Y 9 to Y 16 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a nitro group, a cyano group, a halogen atom or a hydrogen atom.
上記式（７）中、Ｙ１７及びＹ１８は、酸素原子、Ｃ（ＣＮ）２、ＮＲ、Ｃ（ＣＮ）Ｒ又はＣＲ２（Ｒは、置換若しくは無置換アリール基又は置換若しくは無置換アルキル基を示す。）を示し、Ｙ１９〜Ｙ２４は、置換若しくは無置換アリール基、置換若しくは無置換アルキル基、ニトロ基、シアノ基、ハロゲン原子又は水素原子を示す。 In the above formula (7), Y 17 and Y 18 are an oxygen atom, C (CN) 2 , NR, C (CN) R or CR 2 (R is a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group. are shown.) indicates, Y 19 to Y 24 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a nitro group, a cyano group, a halogen atom or a hydrogen atom.
上記式（８）中、Ｙ２５及びＹ２６は、酸素原子、Ｃ（ＣＮ）ＣＯＲ、Ｃ（ＣＮ）ＣＯＯＲ、Ｃ（ＣＮ）Ｒ又はＣ（ＣＯＯＲ）２（Ｒは、置換若しくは無置換アリール基又は置換若しくは無置換アルキル基を示す。）を示し、Ｙ２７〜Ｙ３２は、置換若しくは無置換アリール基、置換若しくは無置換アルキル基、ニトロ基、シアノ基、ハロゲン原子又は水素原子を示す。 In the above formula (8), Y 25 and Y 26 are an oxygen atom, C (CN) COR, C (CN) COOR, C (CN) R or C (COOR) 2 (R is a substituted or unsubstituted aryl group) or indicates.) of a substituted or unsubstituted alkyl group, Y 27 to Y 32 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a nitro group, a cyano group, a halogen atom or a hydrogen atom.
以下、表１に置換ヒドロキシフェニル化合物例を示すがこれらに限定される訳ではない。 Examples of substituted hydroxyphenyl compounds are shown in Table 1 below, but are not limited thereto.
本発明の上記式（１）〜（４）によって構成される電子輸送物質は、電子受容性部位を有するフェノール体をホルマリンで処理することにより得られる。 The electron transport material constituted by the above formulas (1) to (4) of the present invention can be obtained by treating a phenol body having an electron accepting site with formalin.
酸化還元電位の測定は、以下のように３電極式のサイクリックボルターメトリーにて行った。本発明ではビー・エー・エス（株）製ボルタンメトリックアナライザーＢＡＳ１００Ｂを使用した；
電極：作用電極（グラッシーカーボン電極）
対極（白金電極）
参照電極 飽和カロメル電極（０．１ｍｏｌ／ｌ ＫＣｌ−水溶液）
測定溶液（以下を調合して測定溶液を調整した）
・電解質：過塩素酸ｔ−ブチルアンモニウム ０．１モル
・測定物質：置換ヒドロキシフェニル化合物 ０．００１モル
・溶剤：アセトニトリル １リットル
The oxidation-reduction potential was measured by a three-electrode cyclic voltammetry as follows. In the present invention, a voltammetric analyzer BAS100B manufactured by BAS Co., Ltd. was used;
Electrode: Working electrode (glassy carbon electrode)
Counter electrode (platinum electrode)
Reference electrode Saturated calomel electrode (0.1 mol / l KCl-water solution)
Measurement solution (measurement solution was prepared by preparing the following)
-Electrolyte: 0.1 mol of t-butylammonium perchlorate-Measuring substance: 0.001 mol of substituted hydroxyphenyl compound-Solvent: 1 liter of acetonitrile
次に、本発明の電子写真感光体の構成について説明する。 Next, the configuration of the electrophotographic photosensitive member of the present invention will be described.
本発明の電子写真感光体は、導電性支持体上に感光層を形成する。本発明の感光層の構成は、電荷発生物質と電荷輸送物質の両方を同一の層に含有する単層型、及び電荷発生物質を含有する電荷発生層と電荷輸送物質を含有する電荷輸送層を有する積層型に大別される。積層型の構成としては、基体上に電荷発生層及び電荷輸送層をこの順に積層したもの（順層型）と、逆に電荷輸送層及び電荷発生層の順に積層したもの（逆層型）がある。 The electrophotographic photoreceptor of the present invention forms a photosensitive layer on a conductive support. The photosensitive layer of the present invention comprises a single layer type containing both a charge generation material and a charge transport material in the same layer, and a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material. It is roughly classified into a laminated type having. As a laminated structure, there are a structure in which a charge generation layer and a charge transport layer are laminated in this order on a substrate (forward layer type), and a structure in which a charge transport layer and a charge generation layer are laminated in reverse order (reverse layer type). is there.
積層型の場合、帯電極性により輸送する電荷が異なるため、用いられる材料が異なる。負帯電で用いる順層型及び正帯電で用いる逆層型の電荷輸送層中には正孔輸送性物質を含有し、正帯電で用いる順層型及び負帯電で用いる逆層型の電荷輸送層中には電子輸送性物質を含有する。 In the case of the laminated type, the charge used varies depending on the charge polarity, and therefore the materials used are different. The forward layer type used in negative charge and the reverse layer type charge transport layer used in positive charge contain a hole transporting substance, and the forward layer type used in positive charge and the reverse layer type charge transport layer used in negative charge It contains an electron transporting substance.
有機電子写真感光体を用いる電子写真プロセスにおいては一般的に負帯電で用いられることが多く、また耐久性の点から順層型が一般的である。 In an electrophotographic process using an organic electrophotographic photosensitive member, it is generally used with a negative charge, and a normal layer type is generally used from the viewpoint of durability.
以下、負帯電で使用する積層型（順層）の感光層を有する電子写真感光体について説明する。 Hereinafter, an electrophotographic photosensitive member having a laminated (normal layer) photosensitive layer used for negative charging will be described.
本発明に用いられる導電性支持体としては、アルミニウム、ニッケル、銅、金、鉄等の金属又は合金、ポリエステル、ポリカーボネート、ポリイミド、ガラス等の絶縁性支持体上にアルミニウム、銀及び金等の金属あるいは酸化インジウムや酸化スズ等の導電材料の薄膜を形成したもの、カーボンや導電性フィラーを樹脂中に分散し導電性を付与したもの等が例示できる。これらの支持体表面は、電気的特性改善あるいは密着性改善のために、陽極酸化等の電気化学的な処理を行った支持体や、導電性支持体表面をアルカリリン酸塩あるいはリン酸やタンニン酸を主成分とする酸性水溶液に金属塩の化合物又はフッ素化合物の金属塩を溶解してなる溶液で化学処理を施したものを用いることもできる。 As a conductive support used in the present invention, a metal or alloy such as aluminum, nickel, copper, gold, or iron, a metal such as aluminum, silver, or gold on an insulating support such as polyester, polycarbonate, polyimide, or glass. Or what formed the thin film of electrically conductive materials, such as an indium oxide and a tin oxide, what disperse | distributed carbon and the conductive filler in resin, and gave the electroconductivity etc. can be illustrated. The surface of these supports is a support that has been subjected to an electrochemical treatment such as anodization to improve electrical properties or adhesion, and the surface of a conductive support is alkali phosphate, phosphoric acid or tannin. It is also possible to use a solution obtained by chemical treatment with a solution obtained by dissolving a metal salt compound or a fluorine compound metal salt in an acidic aqueous solution containing an acid as a main component.
また、単一波長のレーザー光等を用いたプリンターに本電子写真感光体を用いる場合には、干渉縞を抑制するために導電性支持体はその表面を適度に粗しておくことが必要である。具体的には上記支持体表面をホーニング、ブラスト、切削、電界研磨等の処理をした支持体もしくはアルミニウム及びアルミニウム合金上に導電性金属酸化物及びバインダー樹脂からなる導電性皮膜を有する支持体を用いることが必要である。 In addition, when the electrophotographic photosensitive member is used in a printer using a single wavelength laser beam or the like, the surface of the conductive support needs to be appropriately roughened in order to suppress interference fringes. is there. Specifically, a support in which the surface of the support is subjected to honing, blasting, cutting, electropolishing, or the like or a support having a conductive film made of a conductive metal oxide and a binder resin on aluminum and an aluminum alloy is used. It is necessary.
ホーニング処理としては、乾式及び湿式での処理方法があるがいずれを用いてもよい。湿式ホーニング処理は、水等の液体に粉末状の研磨剤を懸濁させ、高速度で支持体表面に吹き付けて粗面化する方法であり、表面粗さは吹き付け圧力、速度、研磨剤の量、種類、形状、大きさ、硬度、比重又は懸濁温度等により制御することができる。同様に、乾式ホーニング処理は、研磨剤をエアーにより、高速度で導電性支持体表面に吹き付けて粗面化する方法であり、湿式ホーニング処理と同じように表面粗さを制御することができる。これら湿式又は乾式ホーニング処理に用いる研磨剤としては、炭化ケイ素、アルミナ、鉄及びガラスビーズ等の粒子が挙げられる。 As the honing treatment, there are dry and wet treatment methods, and any of them may be used. The wet honing treatment is a method in which a powdery abrasive is suspended in a liquid such as water and sprayed onto the surface of the support at a high speed to roughen the surface. The surface roughness is the spray pressure, speed, and amount of abrasive. It can be controlled by the type, shape, size, hardness, specific gravity or suspension temperature. Similarly, the dry honing process is a method in which an abrasive is sprayed onto the surface of the conductive support with air at a high speed to roughen the surface, and the surface roughness can be controlled in the same manner as the wet honing process. Examples of the abrasive used for the wet or dry honing treatment include particles such as silicon carbide, alumina, iron, and glass beads.
導電性金属酸化物及びバインダー樹脂からなる導電性皮膜をアルミニウムやアルミニウム合金の支持体に塗布し導電性支持体とする方法では、導電性皮膜中にはフィラーとして、導電性微粒子からなる粉体を含有する。この方法では、微粒子を皮膜中に分散させることでレーザー光を乱反射させ干渉縞を防ぐと共に、塗布前の支持体の傷や突起等を隠蔽する効果もある。微粒子には酸化チタンや硫酸バリウム等が用いられ、必要によってはこの微粒子に酸化錫等で導電性被覆層を設けることにより、フィラーとして適切な比抵抗としている。導電性微粒子粉体の比抵抗は０．１〜１０００Ω・ｃｍが好ましく、更には１〜１０００Ω・ｃｍが好ましい。フィラーの含有量は、導電性皮膜層に対して１．０〜９０質量％が好ましく、更には５．０〜８０質量％が好ましい。被覆層には、必要に応じてフッ素あるいはアンチモンを含有してもよい。 In the method of applying a conductive film made of a conductive metal oxide and a binder resin to an aluminum or aluminum alloy support to make a conductive support, a powder made of conductive fine particles is used as a filler in the conductive film. contains. In this method, by dispersing fine particles in the film, the laser light is diffusely reflected to prevent interference fringes, and there is also an effect of concealing scratches and protrusions on the support before coating. Titanium oxide, barium sulfate, or the like is used for the fine particles. If necessary, a conductive coating layer is provided on the fine particles with tin oxide or the like, so that the specific resistance as a filler is obtained. The specific resistance of the conductive fine particle powder is preferably 0.1 to 1000 Ω · cm, more preferably 1 to 1000 Ω · cm. The content of the filler is preferably 1.0 to 90% by mass, and more preferably 5.0 to 80% by mass with respect to the conductive film layer. The coating layer may contain fluorine or antimony as necessary.
導電性皮膜に用いられるバインダー樹脂としては、例えば、フェノール樹脂、ポリウレタン、ポリアミド、ポリイミド、ポリアミドイミド、ポリアミド酸、ポリビニルアセタール、エポキシ樹脂、アクリル樹脂、メラミン樹脂あるいはポリエステル等が好ましい。これらの樹脂は単独でも、二種以上を組み合わせて用いてもよい。これらの樹脂は、支持体に対する接着性が良好であると共に、フィラーの分散性を向上させ、かつ成膜後の耐溶剤性が良好である。上記樹脂の中でも特にフェノール樹脂、ポリウレタン及びポリアミド酸が好ましい。 As the binder resin used for the conductive film, for example, phenol resin, polyurethane, polyamide, polyimide, polyamideimide, polyamic acid, polyvinyl acetal, epoxy resin, acrylic resin, melamine resin, or polyester is preferable. These resins may be used alone or in combination of two or more. These resins have good adhesion to the support, improve the dispersibility of the filler, and have good solvent resistance after film formation. Among the above resins, phenol resin, polyurethane and polyamic acid are particularly preferable.
導電性皮膜は、例えば浸漬あるいはマイヤーバー等による溶剤塗布で形成することができる。導電性皮膜の厚みは０．１〜３０μｍが好ましく、更には０．５〜２０μｍが好ましい。また、導電性皮膜の体積抵抗率は１０１３Ω・ｃｍ以下が好ましく、更には１０１２Ω・ｃｍ以下１０５Ω・ｃｍ以上が好ましい。導電性皮膜には、被覆層を有する硫酸バリウム微粒子からなる粉体以外に、酸化亜鉛や酸化チタン等の粉体からなるフィラーを含有してもよい。更に、表面性を高めるためにレベリング剤を添加してもよい。 The conductive film can be formed, for example, by dipping or solvent application with a Meyer bar or the like. The thickness of the conductive film is preferably from 0.1 to 30 μm, more preferably from 0.5 to 20 μm. The volume resistivity of the conductive film is preferably 10 13 Ω · cm or less, more preferably 10 12 Ω · cm or less and 10 5 Ω · cm or more. The conductive film may contain a filler made of powder such as zinc oxide or titanium oxide in addition to the powder made of barium sulfate fine particles having a coating layer. Furthermore, a leveling agent may be added to enhance the surface property.
本発明において用いられる電荷発生物質の例としては、（１）モノアゾ、ビスアゾ、トリスアゾ等のアゾ顔料、（２）金属フタロシアニン、非金属フタロシアニン等のフタロシアニン顔料、（３）インジゴ、チオインジゴ等のインジゴ顔料、（４）ペリレン酸無水物、ペリレン酸イミド等のペリレン顔料、（５）アンスラキノン、ピレンキノン等の多環キノン顔料、（６）スクワリリウム色素、（７）ピリリウム塩、チアピリリウム塩類、（８）トリフェニルメタン色素等の有機物質、（９）セレン、非晶質のシリコーン等の無機物質が挙げられる。その中でも、アゾ顔料及びフタロシアニン顔料が好ましい。これらの電荷発生物質は単独で用いてもよく、２種類以上を組み合わせて用いてもよい。 Examples of charge generating materials used in the present invention include (1) azo pigments such as monoazo, bisazo, and trisazo, (2) phthalocyanine pigments such as metal phthalocyanine and nonmetal phthalocyanine, and (3) indigo pigments such as indigo and thioindigo. (4) perylene pigments such as perylene acid anhydride and perylene imide, (5) polycyclic quinone pigments such as anthraquinone and pyrenequinone, (6) squarylium dye, (7) pyrylium salt, thiapyrylium salt, (8) tri Examples thereof include organic substances such as phenylmethane dye, and (9) inorganic substances such as selenium and amorphous silicone. Of these, azo pigments and phthalocyanine pigments are preferred. These charge generation materials may be used alone or in combination of two or more.
電荷発生層は導電性支持体の上に、電荷発生物質を適当なバインダー樹脂に分散した電荷発生層用塗布液を浸漬コーティング法、スプレーコーティング法、スピンナーコーティング法、ローラーコーティング法、マイヤーバーコーティング法及びブレードコーティング法等のコーティング法、あるいは、蒸着、スパッタ及びＣＶＤ等の乾式法を用いて形成することができる。 For the charge generation layer, a charge generation layer coating solution in which a charge generation material is dispersed in a suitable binder resin is coated on a conductive support by dip coating, spray coating, spinner coating, roller coating, Meyer bar coating. And a coating method such as a blade coating method, or a dry method such as vapor deposition, sputtering, and CVD.
電荷発生層中に含有するバインダー樹脂は好ましくは８０質量％以下、より好ましくは５０質量％以下とする。また、電荷発生層の膜厚は５μｍ以下が好ましく、特には０．０１〜２μｍの範囲の薄膜層とすることが好ましい。 The binder resin contained in the charge generation layer is preferably 80% by mass or less, more preferably 50% by mass or less. The film thickness of the charge generation layer is preferably 5 μm or less, and particularly preferably a thin film layer in the range of 0.01 to 2 μm.
また、電荷発生層には、種々の増感剤、酸化防止剤、紫外線吸収剤、可塑剤、前述した正孔輸送物質、本発明の電子輸送物質又は他の電荷発生物質を必要に応じて添加することもできる。 In addition, various sensitizers, antioxidants, ultraviolet absorbers, plasticizers, the above-described hole transport materials, the electron transport materials of the present invention, or other charge generation materials are added to the charge generation layer as necessary. You can also
導電性支持体と感光層との間に中間層を有してもよい。中間層を形成する材料としては、前記バインダー樹脂の他に、例えば、ポリビニルアルコール、エチルセルロース、カルボキシルメチルセルロース、カゼイン及びＮ−アルコキシアルキルナイロン等のバインダー樹脂を用いてもよく、更に酸化スズ、酸化インジウム又は酸化チタン等の導電性物質、及び、電子輸送物質（その場合、電子輸送物質とバインダー樹脂の比率は１００／０〜１０／９０）をバインダー樹脂に含有してもよい。中間層は上述の塗布方法を用いて、導電性支持体又は導電層上に塗布することで形成する。中間層の膜厚は、好ましくは０．３〜１５μｍ、より好ましくは０．５〜１０μｍである。 An intermediate layer may be provided between the conductive support and the photosensitive layer. As a material for forming the intermediate layer, in addition to the binder resin, for example, a binder resin such as polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, casein and N-alkoxyalkyl nylon may be used, and further tin oxide, indium oxide or The binder resin may contain a conductive material such as titanium oxide and an electron transport material (in this case, the ratio of the electron transport material and the binder resin is 100/0 to 10/90). An intermediate | middle layer is formed by apply | coating on an electroconductive support body or a conductive layer using the above-mentioned coating method. The thickness of the intermediate layer is preferably 0.3 to 15 μm, more preferably 0.5 to 10 μm.
次いで、電荷発生層上に、電荷輸送物質を適当な溶媒に単独もしくは適当なバインダー樹脂と共に溶解もしくは分散せしめた電荷輸送層用塗布液を浸漬コーティング法、スプレーコーティング法、スピンナーコーティング法、ローラーコーティング法、マイヤーバーコーティング法及びブレードコーティング法等のコーティング法を用いて形成することができる。 Next, a charge transport layer coating solution in which a charge transport material is dissolved or dispersed in a suitable solvent alone or together with a suitable binder resin on the charge generation layer is subjected to a dip coating method, a spray coating method, a spinner coating method, a roller coating method. It can be formed using a coating method such as a Meyer bar coating method and a blade coating method.
電荷輸送層の膜厚は、５〜４０μｍが好ましく、特には７〜３０μｍの範囲が好ましい。また、バインダー樹脂と電荷輸送物質との配合割合は、バインダー樹脂１００質量部当たり電荷輸送物質を１０〜５００質量部とすることが好ましく、特にバインダー樹脂１００質量部当たり電荷輸送物質を３０〜１５０質量部とすることが好ましい。 The thickness of the charge transport layer is preferably 5 to 40 μm, particularly preferably 7 to 30 μm. The blending ratio of the binder resin and the charge transport material is preferably 10 to 500 parts by weight of the charge transport material per 100 parts by weight of the binder resin, and particularly 30 to 150 parts by weight of the charge transport material per 100 parts by weight of the binder resin. Part.
また本発明において用いられる正孔輸送物質の例としては、各種ブタジエン化合物、各種トリアリールアミン化合物、各種ヒドラゾン化合物、各種スチルベン化合物、各種ピラゾリン化合物、各種オキサゾール化合物、各種チアゾール化合物、各種トリアリールメタン化合物等の低分子化合物等の他に、ポリシラン化合物や特開平９−２７２７３５号公報や特開平９−６２０１９号公報等に開示されている電荷輸送性樹脂等である。これらの正孔輸送物質は単独で用いてもよく、２種類以上を組み合わせて用いてもよい。 Examples of hole transport materials used in the present invention include various butadiene compounds, various triarylamine compounds, various hydrazone compounds, various stilbene compounds, various pyrazoline compounds, various oxazole compounds, various thiazole compounds, and various triarylmethane compounds. In addition to low molecular compounds such as polysilane compounds, charge transporting resins disclosed in JP-A-9-272735, JP-A-9-62019, and the like. These hole transport materials may be used alone or in combination of two or more.
更に、電荷輸送層中に酸化防止剤、紫外線吸収剤、可塑剤又は他の公知の電荷輸送物質を必要に応じて添加することもできる。 Furthermore, an antioxidant, a UV absorber, a plasticizer, or other known charge transport materials can be added to the charge transport layer as necessary.
上記電荷発生層及び電荷輸送層に使用されるバインダー樹脂としては、広範囲なバインダー樹脂から選択でき、例えばポリカーボネート樹脂、ポリエステル樹脂、ポリアリレート樹脂、ブチラール樹脂、ポリスチレン樹脂、ポリビニルアセタール樹脂、ジアリルフタレート樹脂、アクリル樹脂、メタクリル樹脂、酢酸ビニル樹脂、フェノール樹脂、シリコーン樹脂、ポリスルホン樹脂、スチレン−ブタジエン共重合体、アルキッド樹脂、エポキシ樹脂、尿素樹脂及び塩化ビニル−酢酸ビニル共重合体等の樹脂が挙げられるが、これらに限定されるものではない。これらの樹脂は、単独又はコポリマーとして１種又は２種以上混合して用いてもよい。 The binder resin used for the charge generation layer and the charge transport layer can be selected from a wide range of binder resins, such as polycarbonate resin, polyester resin, polyarylate resin, butyral resin, polystyrene resin, polyvinyl acetal resin, diallyl phthalate resin, Examples of the resin include acrylic resin, methacrylic resin, vinyl acetate resin, phenol resin, silicone resin, polysulfone resin, styrene-butadiene copolymer, alkyd resin, epoxy resin, urea resin, and vinyl chloride-vinyl acetate copolymer. However, it is not limited to these. You may use these resin individually or in mixture of 2 or more types as a copolymer.
また、電荷発生層及び電荷輸送層作製時に使用される各塗布液に用いられる溶媒としては、Ｎ，Ｎ−ジメチルホルムアミド、トルエン、キシレン、モノクロロベンゼン、ジクロロメタン、１，２−ジクロロエタン、１，１，１−トリクロロエタン、テトラヒドロフラン、メチルエチルケトン、シクロヘキサノン、酢酸エチル、酢酸ブチル及びジメチルメタン等を挙げることができる。 In addition, as a solvent used in each coating solution used when preparing the charge generation layer and the charge transport layer, N, N-dimethylformamide, toluene, xylene, monochlorobenzene, dichloromethane, 1,2-dichloroethane, 1,1, Examples thereof include 1-trichloroethane, tetrahydrofuran, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate and dimethylmethane.
また、感光層上には保護層を設けてもよく、保護層の材料としては、バインダー樹脂を用いることができ、更に酸化スズや酸化インジウム等の導電性物質や電荷輸送物質をバインダー樹脂に含有してもよい。この際のバインダー樹脂としては上述のバインダー樹脂や硬化性樹脂等が挙げられる。 In addition, a protective layer may be provided on the photosensitive layer. As a material for the protective layer, a binder resin can be used. Further, a conductive material such as tin oxide or indium oxide or a charge transport material is contained in the binder resin. May be. Examples of the binder resin at this time include the above-described binder resins and curable resins.
本発明の電子輸送物質は、どの構成の電子写真感光体のどの層に含有していてもよい。 The electron transport material of the present invention may be contained in any layer of an electrophotographic photoreceptor having any configuration.
図１に本発明の電子写真感光体を有するプロセスカートリッジを備えた電子写真装置の概略構成を示す。 FIG. 1 shows a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.
図１において、１はドラム状の本発明の電子写真感光体であり、軸２を中心に矢印方向に所定の周速度（プロセススピード）をもって回転駆動される。電子写真感光体１は、回転過程において、一次帯電手段３によりその周面に正又は負の所定電位の均一帯電を受け、次いで、原稿からの反射光であるスリット露光やレーザービーム走査露光等の露光手段（不図示）から出力される目的の画像情報の時系列電気デジタル画像信号に対応して強度変調された露光光４を受ける。こうして電子写真感光体１の周面に対し、目的の画像情報に対応した静電潜像が順次形成されていく。 In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 in a direction indicated by an arrow with a predetermined peripheral speed (process speed). In the rotation process, the electrophotographic photosensitive member 1 is subjected to uniform charging at a predetermined positive or negative potential on its peripheral surface by the primary charging unit 3, and then, for example, slit exposure or laser beam scanning exposure that is reflected light from the original. The exposure light 4 intensity-modulated in response to the time-series electric digital image signal of the target image information output from the exposure means (not shown) is received. In this way, electrostatic latent images corresponding to the target image information are sequentially formed on the peripheral surface of the electrophotographic photoreceptor 1.
形成された静電潜像は、次いで現像手段５内の荷電粒子（トナー）で正規現像又は反転現像により可転写粒子像（トナー像）として顕画化され、不図示の給紙部から電子写真感光体１と転写手段６との間に電子写真感光体１の回転と同期して取り出されて給送された転写材７に、電子写真感光体１の表面に形成担持されているトナー像が転写手段６により順次転写されていく。この時、転写手段にはバイアス電源（不図示）からトナーの保有電荷とは逆極性のバイアス電圧が印加される。 The formed electrostatic latent image is visualized as a transferable particle image (toner image) by regular development or reversal development with charged particles (toner) in the developing means 5 and is electrophotographic from a paper supply unit (not shown). A toner image formed and carried on the surface of the electrophotographic photosensitive member 1 is transferred to the transfer material 7 which is taken out and fed between the photosensitive member 1 and the transfer unit 6 in synchronization with the rotation of the electrophotographic photosensitive member 1. The images are sequentially transferred by the transfer means 6. At this time, a bias voltage having a polarity opposite to the charge held in the toner is applied to the transfer means from a bias power source (not shown).
トナー画像の転写を受けた転写材７（最終転写材（紙やフィルム等）の場合）は、電子写真感光体面から分離されて像定着手段８へ搬送されてトナー像の定着処理を受けることにより画像形成物（プリント、コピー）として装置外へプリントアウトされる。転写材７が一次転写材（中間転写材等）の場合は、複数次の転写工程の後に定着処理を受けてプリントアウトされる。 The transfer material 7 (in the case of a final transfer material (such as paper or film)) that has received the transfer of the toner image is separated from the electrophotographic photosensitive member surface, conveyed to the image fixing means 8, and subjected to a toner image fixing process. Printed out of the apparatus as an image formed product (print, copy). When the transfer material 7 is a primary transfer material (intermediate transfer material or the like), it is printed out after a fixing process after a plurality of transfer processes.
トナー像転写後の電子写真感光体１の表面は、クリーニング手段９によって転写残りトナー等の付着物の除去を受けて清浄面化される。近年、クリーナレスシステムも研究され、転写残りトナーを直接、現像器等で回収することもできる。更に、前露光手段（不図示）からの前露光光１０により除電処理された後、繰り返し画像形成に使用される。なお、一次帯電手段３が帯電ローラー等を用いた接触帯電手段である場合は、前露光は必ずしも必要ではない。 The surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by removing the deposits such as residual toner by the cleaning means 9. In recent years, a cleanerless system has been studied, and the transfer residual toner can be directly collected by a developing device or the like. Further, after being subjected to charge removal processing by pre-exposure light 10 from pre-exposure means (not shown), it is repeatedly used for image formation. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary.
本発明においては、上述の電子写真感光体１、一次帯電手段３、現像手段５及びクリーニング手段９等の構成要素のうち、複数のものを容器に納めてプロセスカートリッジとして一体に結合して構成し、このプロセスカートリッジを複写機やレーザービームプリンター等の電子写真装置本体に対して着脱自在に構成してもよい。例えば、一次帯電手段３、現像手段５及びクリーニング手段９の少なくとも１つを電子写真感光体１と共に一体に支持してカートリッジ化して、装置本体のレール等の案内手段１２を用いて装置本体に着脱自在なプロセスカートリッジ１１とすることができる。 In the present invention, among the above-described components such as the electrophotographic photosensitive member 1, the primary charging unit 3, the developing unit 5 and the cleaning unit 9, a plurality of components are housed in a container and integrally combined as a process cartridge. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the electrophotographic photosensitive member 1 to form a cartridge, and is attached to and detached from the apparatus main body using the guide unit 12 such as a rail of the apparatus main body. A flexible process cartridge 11 can be obtained.
また、露光光４は、電子写真装置が複写機やプリンターである場合には、原稿からの反射光や透過光、あるいは、センサーで原稿を読取り、信号化し、この信号に従って行われるレーザービームの走査、ＬＥＤアレイの駆動又は液晶シャッターアレイの駆動等により照射される光である。 Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is reflected or transmitted light from the original, or the original is read by a sensor and converted into a signal, and a laser beam scanning performed according to this signal is performed. The light emitted by driving the LED array or the liquid crystal shutter array.
本発明の電子写真感光体は、電子写真複写機に利用するのみならず、レーザービームプリンター、ＬＥＤプリンター、ＦＡＸ、液晶シャッター式プリンター等の電子写真装置一般に適応し得るが、更に、電子写真技術を応用したディスプレー、記録、軽印刷、製版及びファクシミリ等の装置にも幅広く適用し得るものである。 The electrophotographic photosensitive member of the present invention can be applied not only to electrophotographic copying machines but also to general electrophotographic apparatuses such as laser beam printers, LED printers, FAX, liquid crystal shutter printers, etc. It can be widely applied to apparatuses such as applied displays, recording, light printing, plate making and facsimile.
以下に、具体的な実施例を挙げて本発明を更に詳細に説明する。ただし、本発明の実施の形態は、これらに限定されるものではない。なお、実施例中の「部」は「質量部」を意味する。また、実施例６〜１８および２０は参考例である。
Hereinafter, the present invention will be described in more detail with reference to specific examples. However, embodiments of the present invention are not limited to these. In the examples, “part” means “part by mass”. Examples 6 to 18 and 20 are reference examples.
（置換ヒドロキシフェニル化合物の合成例）
（化合物例Ｅ３の合成）
２，７−ビス−［２−（４−ヒドロキシ−フェニル）−エチル］−ベンゾ［ｌｍｎ］［３，８］フェナントロリン−１，３，６，８−テトラオン（２，７−ｂｉｓ−［２−（４−ｈｙｄｒｏｘｙ−ｐｈｅｎｙｌ）−ｅｔｈｙｌ］−ｂｅｎｚｏ［ｌｍｎ］［３，８］ｐｈｅｎａｎｔｈｒｏｌｉｎｅ−１，３，６，８−ｔｅｔｒａｏｎｅ）を水酸化カリウム水溶液１０質量部（５質量％）とジメチルホルムアミド１５０質量部に混合し、この反応液を５０℃に加熱し、ホルマリン（３７質量％）５質量部を１時間かけて滴下した。
(Synthesis example of substituted hydroxyphenyl compound)
(Synthesis of Compound Example E3)
2,7-bis- [2- (4-hydroxy-phenyl) -ethyl] -benzo [lmn] [3,8] phenanthroline-1,3,6,8-tetraone (2,7-bis- [2- (4-hydroxy-phenyl) -ethyl] -benzo [lmn] [3,8] phenanthroline-1,3,6,8-tetrane) in 10 parts by mass (5% by mass) of aqueous potassium hydroxide and 150 parts by mass of dimethylformamide The reaction solution was heated to 50 ° C., and 5 parts by mass of formalin (37% by mass) was added dropwise over 1 hour.
滴下終了後５０℃で５０時間反応を行い、反応終了後に硫酸水溶液中に投入して中和し生成物を晶析させた。得られた沈殿を水洗後、メタノール／ジメチルホルムアミドを用いて再結晶を行い、目的物を濃褐色粉末として得た。収率は３５質量％であった。下記に反応経路を示す。 After completion of the dropwise addition, the reaction was carried out at 50 ° C. for 50 hours, and after completion of the reaction, the reaction product was poured into a sulfuric acid aqueous solution to neutralize and crystallize the product. The obtained precipitate was washed with water and recrystallized using methanol / dimethylformamide to obtain the desired product as a dark brown powder. The yield was 35% by mass. The reaction route is shown below.
粉末を、逆相ＨＰＬＣ（カラム：ＳｈｏｄｅｘＣ１８−５Ｂ、昭和電工（株）製、溶媒：メタノール／水＝８０／２０）及びＧＰＣ（ゲルパーミエーションクロマトグラフィー）（カラム：ＴＯＳＯＨＴＳＫガードカラムＨＸＬ、ＴＳＫｇｅｌＧ２０００ＨＸＬ×２、ＴＳＫｇｅｌＧ３０００ＨＸＬ×１連結（東ソー（株）製、溶媒：ＴＨＦ）によって純度を測定した。テトラヒドロキシメチル体の含有率は８６％であった。 The powder was subjected to reverse phase HPLC (column: Shodex C18-5B, Showa Denko KK, solvent: methanol / water = 80/20) and GPC (gel permeation chromatography) (column: TOSOTTSK guard column HXL, TSKgel G2000HXL × 2). The purity was measured by TSKgel G3000HXL × 1 linkage (manufactured by Tosoh Corporation, solvent: THF), and the content of tetrahydroxymethyl compound was 86%.
また、質量分析を行って（ＭＡＬＤＩ−ＴＯＦ ＭＳ：ブルカー・ダルトニクス（株）製 ｕｌｔｒａｆｌｅｘ）（加速電圧：２０ｋＶ、モード：Ｒｅｆｌｅｃｔｏｒ、分子量標準品：フラーレンＣ６０）、分子量を測定した所、ピークトップ値として６２６が得られ、上記構造と同一であることを確認した。 In addition, mass spectrometry was performed (MALDI-TOF MS: ultraflex manufactured by Bruker Daltonics Co., Ltd.) (acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C 60 ), and the molecular weight was measured. 626 was obtained, and it was confirmed that the structure was the same.
（化合物例Ｅ３２の合成）
２−［６−（４−ヒドロキシ−フェニル）−２−オキソ−２Ｈ−アセナフチレン−１−イリデン］−マロノニトリル（２−［６−（４−ｈｙｄｒｏｘｙ−ｐｈｅｎｙｌ）−２−ｏｘｏ−２Ｈ−ａｃｅｎａｐｈｔｈｙｌｅｎｅ−１−ｙｌｉｄｅｎｅ］−ｍａｌｏｎｏｎｉｔｒｉｌｅ）を水酸化カリウム水溶液（５質量％）２質量部とジメチルホルムアミド３０質量部に混合し、この反応液を５０℃に加熱し、ホルマリン１質量部（３７質量％）を０．５時間かけて滴下した。
(Synthesis of Compound Example E32)
2- [6- (4-Hydroxy-phenyl) -2-oxo-2H-acenaphthylene-1-ylidene] -malononitrile (2- [6- (4-hydroxy-phenyl) -2-oxo-2H-acenaphthylene-1 -Ylidene] -malononitrile) is mixed with 2 parts by mass of an aqueous potassium hydroxide solution (5% by mass) and 30 parts by mass of dimethylformamide, the reaction solution is heated to 50 ° C., and 1 part by mass of formalin (37% by mass) is reduced to 0. Added dropwise over 5 hours.
滴下終了後５０℃で５０時間反応を行い、反応終了後に硫酸水溶液中に投入して中和し生成物を晶析させた。得られた沈殿を水洗後、メタノール／ジメチルホルムアミドを用いて再結晶を行い目的物を褐色粉末として得た。収率は４２質量％であった。下記に反応経路を示す。 After completion of the dropwise addition, the reaction was carried out at 50 ° C. for 50 hours, and after completion of the reaction, the reaction product was poured into a sulfuric acid aqueous solution to neutralize and crystallize the product. The obtained precipitate was washed with water and recrystallized using methanol / dimethylformamide to obtain the desired product as a brown powder. The yield was 42% by mass. The reaction route is shown below.
粉末を、逆相ＨＰＬＣ（カラム：ＳｈｏｄｅｘＣ１８−５Ｂ、昭和電工（株）製、溶媒：メタノール／水＝８０／２０）及びＧＰＣ（カラム：ＴＯＳＯＨＴＳＫガードカラムＨＸＬ、ＴＳＫｇｅｌＧ２０００ＨＸＬ×２、ＴＳＫｇｅｌＧ３０００ＨＸＬ×１連結（東ソー（株）製、溶媒：ＴＨＦ）によって純度を測定した。テトラヒドロキシメチル体の含有率は７９％であった。 The powder was subjected to reverse phase HPLC (column: Shodex C18-5B, Showa Denko KK, solvent: methanol / water = 80/20) and GPC (column: TOSHOTSK guard column HXL, TSKgel G2000HXL × 2, TSKgel G3000HXL × 1 linked (Tosoh Corporation). Purity was measured by a product made by Co., Ltd., solvent: THF, and the content of tetrahydroxymethyl compound was 79%.
また、質量分析を行って（ＭＡＬＤＩ−ＴＯＦ ＭＳ：ブルカー・ダルトニクス（株）製 ｕｌｔｒａｆｌｅｘ）（加速電圧：２０ｋＶ、モード：Ｒｅｆｌｅｃｔｏｒ、分子量標準品：フラーレンＣ６０）、分子量を測定した所、ピークトップ値として３８２が得られ、上記構造と同一であることを確認した。 In addition, mass spectrometry was performed (MALDI-TOF MS: ultraflex manufactured by Bruker Daltonics Co., Ltd.) (acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C 60 ), and the molecular weight was measured. 382 was obtained, and it was confirmed that the structure was the same.
（化合物例Ｅ２６の合成）
３，８−ビス−（４−ヒドロキシ−フェニル）−［１，１０］フェナントロリン−５，６−ジオン（３，８−ｂｉｓ−（４−ｈｙｄｒｏｘｙ−ｐｈｅｎｙｌ）−［１，１０］ｐｈｅｎａｎｔｈｒｏｌｉｎｅ−５，６−ｄｉｏｎｅ）を水酸化カリウム水溶液（５質量％）２質量部とジメチルホルムアミド３０質量部に混合し、この反応液を５０℃に加熱し、ホルマリン１質量部（３７質量％）を０．５時間かけて滴下した。
(Synthesis of Compound Example E26)
3,8-bis- (4-hydroxy-phenyl)-[1,10] phenanthroline-5,6-dione (3,8-bis- (4-hydroxy-phenyl)-[1,10] phenanthroline-5 6-dione) is mixed with 2 parts by mass of an aqueous potassium hydroxide solution (5% by mass) and 30 parts by mass of dimethylformamide, the reaction solution is heated to 50 ° C., and 1 part by mass (37% by mass) of formalin is 0.5%. It was added dropwise over time.
滴下終了後５０℃で５０時間反応を行い、反応終了後に硫酸水溶液中に投入して中和し生成物を晶析させた。得られた沈殿を水洗後、トルエン／ＴＨＦを用いて再結晶を行い目的物を褐色粉末として得た。収率は４２質量％であった。下記に反応経路を示す。 After completion of the dropwise addition, the reaction was carried out at 50 ° C. for 50 hours, and after completion of the reaction, the reaction product was poured into a sulfuric acid aqueous solution to neutralize and crystallize the product. The obtained precipitate was washed with water and recrystallized using toluene / THF to obtain the desired product as a brown powder. The yield was 42% by mass. The reaction route is shown below.
粉末を、逆相ＨＰＬＣ（カラム：ＳｈｏｄｅｘＣ１８−５Ｂ、昭和電工（株）製、溶媒：メタノール／水＝８０／２０）及びＧＰＣ（カラム：ＴＯＳＯＨＴＳＫガードカラムＨＸＬ、ＴＳＫｇｅｌＧ２０００ＨＸＬ×２、ＴＳＫｇｅｌＧ３０００ＨＸＬ×１連結（東ソー（株）製、溶媒：ＴＨＦ）によって純度を測定した。テトラヒドロキシメチル体の含有率は８８％であった。 The powder was subjected to reverse phase HPLC (column: Shodex C18-5B, Showa Denko KK, solvent: methanol / water = 80/20) and GPC (column: TOSHOTSK guard column HXL, TSKgel G2000HXL × 2, TSKgel G3000HXL × 1 linked (Tosoh Corporation). Purity was measured by a product manufactured by Co., Ltd., solvent: THF, and the content of tetrahydroxymethyl compound was 88%.
また、質量分析を行って（ＭＡＬＤＩ−ＴＯＦ ＭＳ：ブルカー・ダルトニクス（株）製 ｕｌｔｒａｆｌｅｘ）（加速電圧：２０ｋＶ、モード：Ｒｅｆｌｅｃｔｏｒ、分子量標準品：フラーレンＣ６０）、分子量を測定した所、ピークトップ値として５１４が得られ、上記構造と同一であることを確認した。 In addition, mass spectrometry was performed (MALDI-TOF MS: ultraflex manufactured by Bruker Daltonics Co., Ltd.) (acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C 60 ), and the molecular weight was measured. As a result, it was confirmed that the structure was the same as the above structure.
（化合物例Ｅ１６の合成）
２−［３，６−ビス−（４−ヒドロキシ−フェニル）−１０−オキソ−１０Ｈ−フェナトレン−９−イリデン］−マロノニトリル（２−［３，６−ｂｉｓ−（４−ｈｙｄｒｏｘｙ−ｐｈｅｎｙｌ）−１０−ｏｘｏ−１０Ｈ−ｐｈｅｎａｎｔｈｒｅｎｅ−９−ｙｌｉｄｅｎｅ］−ｍａｌｏｎｏｎｉｔｒｉｌｅ）を水酸化カリウム水溶液（５質量％）２質量部とジメチルホルムアミド３０質量部に混合し、この反応液を５０℃に加熱し、ホルマリン１質量部（３７質量％）を０．５時間かけて滴下した。
(Synthesis of Compound Example E16)
2- [3,6-Bis- (4-hydroxy-phenyl) -10-oxo-10H-phenanthrene-9-ylidene] -malononitrile (2- [3,6-bis- (4-hydroxy-phenyl) -10 -Oxo-10H-phenanthrene-9-ylidene] -malononitrile) is mixed with 2 parts by mass of an aqueous potassium hydroxide solution (5% by mass) and 30 parts by mass of dimethylformamide, the reaction solution is heated to 50 ° C. and 1 mass of formalin. Part (37% by mass) was added dropwise over 0.5 hours.
滴下終了後５０℃で５０時間反応を行い、反応終了後に硫酸水溶液中に投入して中和し生成物を晶析させた。得られた沈殿を水洗後、メタノール／酢酸エチルを用いて再結晶を行い目的物を褐色粉末として得た。収率は３２質量％であった。下記に反応経路を示す。 After completion of the dropwise addition, the reaction was carried out at 50 ° C. for 50 hours, and after completion of the reaction, the reaction product was poured into a sulfuric acid aqueous solution to neutralize and crystallize the product. The obtained precipitate was washed with water and recrystallized using methanol / ethyl acetate to obtain the desired product as a brown powder. The yield was 32% by mass. The reaction route is shown below.
粉末を、逆相ＨＰＬＣ（カラム：ＳｈｏｄｅｘＣ１８−５Ｂ、昭和電工（株）製、溶媒：メタノール／水＝８０／２０）及びＧＰＣ（カラム：ＴＯＳＯＨＴＳＫガードカラムＨＸＬ、ＴＳＫｇｅｌＧ２０００ＨＸＬ×２、ＴＳＫｇｅｌＧ３０００ＨＸＬ×１連結（東ソー（株）製、溶媒：ＴＨＦ）によって純度を測定した。テトラヒドロキシメチル体の含有率は８０％であった。 The powder was subjected to reverse phase HPLC (column: Shodex C18-5B, Showa Denko KK, solvent: methanol / water = 80/20) and GPC (column: TOSHOTSK guard column HXL, TSKgel G2000HXL × 2, TSKgel G3000HXL × 1 linked (Tosoh Corporation). Purity was measured by a product manufactured by Co., Ltd., solvent: THF, and the content of tetrahydroxymethyl compound was 80%.
また、質量分析を行って（ＭＡＬＤＩ−ＴＯＦ ＭＳ：ブルカー・ダルトニクス（株）製 ｕｌｔｒａｆｌｅｘ）（加速電圧：２０ｋＶ、モード：Ｒｅｆｌｅｃｔｏｒ、分子量標準品：フラーレンＣ６０）、分子量を測定した所、ピークトップ値として５６０が得られ、上記構造と同一であることを確認した。 In addition, mass spectrometry was performed (MALDI-TOF MS: ultraflex manufactured by Bruker Daltonics Co., Ltd.) (acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C 60 ), and the molecular weight was measured. 560 was obtained, and it was confirmed that the structure was the same.
（化合物例Ｅ３８の合成）
４−［２−（２，４，７−トリニトロ−フルオレン−９−イリデンアミノ）−エチル］−フェノール（４−［２−（２，４，７−ｔｒｉｎｔｒｏ−ｆｌｕｏｒｅｎｅ−９−ｙｌｉｄｅｎｅａｍｉｎｏ）−ｅｔｈｙｌ］−ｐｈｅｎｏｌ）を水酸化カリウム水溶液（５質量％）２質量部とジメチルホルムアミド３０質量部に混合し、この反応液を５０℃に加熱し、ホルマリン１質量部（３７質量％）を０．５時間かけて滴下した。
(Synthesis of Compound Example E38)
4- [2- (2,4,7-trinitro-fluorene-9-ylideneamino) -ethyl] -phenol (4- [2- (2,4,7-tritro-fluorene-9-ylideneamino) -ethyl]- phenol) is mixed with 2 parts by mass of an aqueous potassium hydroxide solution (5% by mass) and 30 parts by mass of dimethylformamide, the reaction solution is heated to 50 ° C., and 1 part by mass (37% by mass) of formalin is added over 0.5 hours. And dripped.
滴下終了後５０℃で５０時間反応を行い、反応終了後に硫酸水溶液中に投入して中和し生成物を晶析させた。得られた沈殿を水洗後、メタノール／ジメチルホルムアミドを用いて再結晶を行い目的物を褐色粉末として得た。収率は５０質量％であった。下記に反応経路を示す。 After completion of the dropwise addition, the reaction was carried out at 50 ° C. for 50 hours, and after completion of the reaction, the reaction product was poured into a sulfuric acid aqueous solution to neutralize and crystallize the product. The obtained precipitate was washed with water and recrystallized using methanol / dimethylformamide to obtain the desired product as a brown powder. The yield was 50% by mass. The reaction route is shown below.
粉末を、逆相ＨＰＬＣ（カラム：ＳｈｏｄｅｘＣ１８−５Ｂ、昭和電工（株）製、溶媒：メタノール／水＝８０／２０）及びＧＰＣ（カラム：ＴＯＳＯＨＴＳＫガードカラムＨＸＬ、ＴＳＫｇｅｌＧ２０００ＨＸＬ×２、ＴＳＫｇｅｌＧ３０００ＨＸＬ×１連結（東ソー（株）製、溶媒：ＴＨＦ）によって純度を測定した。テトラヒドロキシメチル体の含有率は７８％であった。 The powder was subjected to reverse phase HPLC (column: Shodex C18-5B, Showa Denko KK, solvent: methanol / water = 80/20) and GPC (column: TOSHOTSK guard column HXL, TSKgel G2000HXL × 2, TSKgel G3000HXL × 1 linked (Tosoh Corporation). Purity was measured by a product manufactured by Co., Ltd., solvent: THF, and the content of tetrahydroxymethyl compound was 78%.
また、質量分析を行って（ＭＡＬＤＩ−ＴＯＦ ＭＳ：ブルカー・ダルトニクス（株）製 ｕｌｔｒａｆｌｅｘ）（加速電圧：２０ｋＶ、モード：Ｒｅｆｌｅｃｔｏｒ、分子量標準品：フラーレンＣ６０）、分子量を測定した所、ピークトップ値として４９４が得られ、上記構造と同一であることを確認した。 In addition, mass spectrometry was performed (MALDI-TOF MS: ultraflex manufactured by Bruker Daltonics Co., Ltd.) (acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C 60 ), and the molecular weight was measured. 494 was obtained, and it was confirmed that the structure was the same.
（実施例１）
〔膜性評価用膜の作製及び膜性評価〕
まず、膜性評価について説明する。例示化合物Ｅ３とフェノール樹脂（商品名：ＰＬ−４８０４、群栄化学（株）製）が固形分比３／１になるように調整した液に、固形分７質量％になるようジメチルアセトアミドを加えた。得られた液を、φ３０ｍｍ×長さ２６０ｍｍのアルミニウムシリンダー上に浸漬塗布方法で塗布し、１５０℃で３０分間乾燥し、１μｍの膜を得た。膜には析出やひび割れ等は認められず、優れた成膜性を有していることが分かった。また、メチルエチルケトン（ＭＥＫ）及びトルエンに１分間浸漬しても、何れも膜の溶解等は認められなかった。室温で３０分間の減圧乾燥で形成された膜では膜の溶解が確認できたことから、Ｅ３が硬化物として存在していることが確認出来る。
Example 1
[Production and evaluation of film properties evaluation film]
First, the film property evaluation will be described. Dimethylacetamide was added so that solid content might become 7 mass% to the liquid which adjusted exemplary compound E3 and phenol resin (brand name: PL-4804, Gunei Chemical Co., Ltd.) so that solid content ratio might be 3/1. It was. The obtained liquid was applied by dip coating on an φ30 mm × 260 mm long aluminum cylinder and dried at 150 ° C. for 30 minutes to obtain a 1 μm film. No precipitation or cracking was observed in the film, and it was found that the film had excellent film formability. Moreover, even if it immersed in methyl ethyl ketone (MEK) and toluene for 1 minute, neither melt | dissolution of the film | membrane etc. were recognized. In the film formed by drying under reduced pressure for 30 minutes at room temperature, it was confirmed that the film was dissolved, and thus it was confirmed that E3 was present as a cured product.
〔電子写真感光体の作製〕
まず導電層用の塗料を以下の手順で調製した。１０％の酸化アンチモンを含有する酸化スズで被覆した導電性酸化チタン粉体５０部（質量部、以下同様）、フェノール樹脂（商品名：プライオーフェンＪ−３２５、大日本インキ化学工業製）２５部、メチルセロソルブ２０部、メタノール５部及びシリコーン化合物（ポリジメチルシロキサンポリオキシアルキレン共重合体）０．００２部、φ１ｍｍガラスビーズを用いたサンドミル装置で２．５時間分散して調製した。この塗料を、φ３０ｍｍ×長さ２６０ｍｍのアルミニウムシリンダー上に浸漬塗布方法で塗布し、１５０℃で３０分間乾燥して、膜厚が１６μｍの導電層を形成した。
[Production of electrophotographic photoreceptor]
First, a coating material for the conductive layer was prepared by the following procedure. 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide (mass parts, the same applies hereinafter), 25 parts of phenolic resin (trade name: Pryofen J-325, manufactured by Dainippon Ink & Chemicals, Inc.) And 20 parts of methyl cellosolve, 5 parts of methanol, 0.002 part of a silicone compound (polydimethylsiloxane polyoxyalkylene copolymer), and dispersed for 2.5 hours in a sand mill using φ1 mm glass beads. This paint was applied on an aluminum cylinder of φ30 mm × length 260 mm by a dip coating method and dried at 150 ° C. for 30 minutes to form a conductive layer having a film thickness of 16 μm.
次に、フェノール樹脂（商品名：ＰＬ−４８０４、群栄化学（株）製）５部、表１に記載の例示化合物Ｅ３を１０部、ジメチルホルムアミド２００部、ベンジルアルコール１５０部に溶解し、この液を前記の導電層の上に浸漬塗布方法で塗布して１６０℃で３０分間乾燥し、膜厚が０．８５μｍの中間層を形成した。 Next, 5 parts of a phenol resin (trade name: PL-4804, manufactured by Gunei Chemical Co., Ltd.), 10 parts of the exemplified compound E3 shown in Table 1 are dissolved in 200 parts of dimethylformamide and 150 parts of benzyl alcohol. The liquid was applied onto the conductive layer by a dip coating method and dried at 160 ° C. for 30 minutes to form an intermediate layer having a thickness of 0.85 μm.
次に、ＣｕＫαのＸ線回折におけるブラッグ角（２θ±０．２°）において７．３°、２４．９°及び２８．１°に強いピークを有するヒドロキシガリウムフタロシアニン顔料５部、ポリビニルブチラール（商品名：エスレックＢＸ−１、積水化学（株）製）２．５部、テトラヒドロフラン２０部及びシクロヘキサノン１５部、φ１ｍｍガラスビーズを用いたサンドミル装置で２．５時間分散して、その後に酢酸エチル２００部とシクロヘキサノン１００部とを加えて、平均粒径０．１７μｍの電荷発生層用塗料を調製した（（株）堀場製作所製ＣＡＰＡ７００で遠心沈降法で測定）。この塗料を前記中間層上に浸漬塗布方法で塗布して９５℃で１０分間乾燥し、膜厚が０．１８μｍの電荷発生層を形成した。 Next, 5 parts of a hydroxygallium phthalocyanine pigment having strong peaks at 7.3 °, 24.9 °, and 28.1 ° at a Bragg angle (2θ ± 0.2 °) in X-ray diffraction of CuKα, polyvinyl butyral (product) Name: ESREC BX-1, Sekisui Chemical Co., Ltd.) 2.5 parts, tetrahydrofuran 20 parts and cyclohexanone 15 parts, dispersed in a sand mill using φ1 mm glass beads for 2.5 hours, and then ethyl acetate 200 parts And 100 parts of cyclohexanone were added to prepare a charge generation layer coating material having an average particle size of 0.17 μm (measured by centrifugal sedimentation with CAPA700 manufactured by Horiba, Ltd.). This paint was applied onto the intermediate layer by a dip coating method and dried at 95 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.18 μm.
次に、正孔輸送性物質として下記式（９）で示されるアリルアミン化合物５０部及び下記式（１０）で示される構成単位を有するポリアリレート樹脂６０部（平均分子量Ｍｗ＝１００，０００、東ソー（株）製ゲルパーミエーションクロマトグラフィー「ＨＬＣ−８１２０」で測定し、ポリスチレン換算で計算）をモノクロロベンゼン２５０部、テトラヒドロフラン２００部に溶解し、この液を前記電荷発生層の上に浸漬塗布方法で塗布して１２０℃で６０分間乾燥し、膜厚が２０μｍの正孔輸送層を形成し、電子写真感光体を得た。 Next, as a hole transporting substance, 50 parts of an allylamine compound represented by the following formula (9) and 60 parts of a polyarylate resin having a structural unit represented by the following formula (10) (average molecular weight Mw = 100,000, Tosoh ( Co., Ltd. manufactured by Gel Permeation Chromatography “HLC-8120” and calculated in terms of polystyrene) was dissolved in 250 parts of monochlorobenzene and 200 parts of tetrahydrofuran, and this solution was applied onto the charge generation layer by a dip coating method. And it dried at 120 degreeC for 60 minute (s), the positive hole transport layer whose film thickness is 20 micrometers was formed, and the electrophotographic photoreceptor was obtained.
［電子写真感光体の評価］
評価は、上記作製した電子写真感光体をキヤノン（株）製カラーレーザープリンターＬＢＰ ２５１０（一次帯電：ローラー接触ＤＣ帯電、帯電条件可変に改造、トレック・ジャパン（株）製高圧電源Ｍｏｄｅｌ６１０使用。帯電条件：感光体表面電位が−６００ＶになるようＤＣ印加。レーザー露光量可変に改造）のシアン用プロセスカートリッジに装着し行い、表面電位の測定は、カートリッジを改造し、現像位置に電位プローブ（ｍｏｄｅｌ６０００Ｂ−８：トレック・ジャパン（株）製）を装着し、表面電位計（ｍｏｄｅｌ３４４：トレック・ジャパン（株）製）を使用して行った。
[Evaluation of electrophotographic photoreceptor]
Evaluation was made by using the above-prepared electrophotographic photosensitive member as a color laser printer LBP 2510 manufactured by Canon Inc. (primary charging: roller contact DC charging, remodeling to a variable charging condition, using a high voltage power supply Model 610 manufactured by Trek Japan Co., Ltd. : DC is applied so that the surface potential of the photosensitive member is -600 V. The process is mounted on a cyan process cartridge with a laser exposure variable variable). The surface potential is measured by modifying the cartridge and developing a potential probe (model 6000B- 8: manufactured by Trek Japan Co., Ltd.) and using a surface potential meter (model 344: manufactured by Trek Japan Co., Ltd.).
１２℃／１０％ＲＨの環境下において、露光後電位が−１５０Ｖになるよう、光量を設定した後、画像濃度１０％画像で７０００枚耐久後、再び電位を測定し、耐久による暗部電位Ｖｄ、明部電位Ｖｌの電位変化ΔＶｄ、ΔＶｌを測定した。 In an environment of 12 ° C./10% RH, the amount of light was set so that the post-exposure potential was −150 V, and after 7000 sheets were endured with an image density of 10%, the potential was measured again. Potential changes ΔVd and ΔVl of the light portion potential Vl were measured.
（実施例２〜１５）
表２に記載の処方を用いた以外は、実施例１と同様にして膜性評価用膜及び電子写真感光体を作製し、評価を行った。結果を表２に示す。
(Examples 2 to 15)
A film property evaluation film and an electrophotographic photosensitive member were prepared and evaluated in the same manner as in Example 1 except that the formulations shown in Table 2 were used. The results are shown in Table 2.
（比較例１）
置換ヒドロキシフェニル化合物として、下記式（１１）で示される化合物を加え、表２に記載の処法を用いた以外は、実施例１と同様にして膜性評価用膜及び電子写真感光体を作製し、評価を行った。結果を表２に示す。
(Comparative Example 1)
A film for evaluating film properties and an electrophotographic photosensitive member were prepared in the same manner as in Example 1 except that the compound represented by the following formula (11) was added as the substituted hydroxyphenyl compound and the method described in Table 2 was used. And evaluated. The results are shown in Table 2.
式（１１）で示される化合物の還元電位測定を行った所、−０．９２Ｖ付近に不可逆なピークが見られた。 When the reduction potential of the compound represented by formula (11) was measured, an irreversible peak was observed in the vicinity of -0.92V.
（比較例２）
置換ヒドロキシフェニル化合物の代わりに下記式（１２）で示される化合物を加え、表２に記載の処法を用いた以外は、実施例１と同様にして膜性評価用膜及び電子写真感光体を作製し、評価を行った。結果を表２に示す。
(Comparative Example 2)
A film property evaluation film and an electrophotographic photosensitive member were prepared in the same manner as in Example 1 except that the compound represented by the following formula (12) was added instead of the substituted hydroxyphenyl compound, and the method described in Table 2 was used. Fabricated and evaluated. The results are shown in Table 2.
（実施例１６）
正孔輸送性物質として下記式（１３）で示されるアリルアミン化合物を用い、表２に記載の処法を用いた以外は、実施例１と同様にして膜性評価用膜及び電子写真感光体を作製し、評価を行った。結果を表２に示す。
(Example 16)
A film for evaluating film properties and an electrophotographic photosensitive member were prepared in the same manner as in Example 1 except that an allylamine compound represented by the following formula (13) was used as the hole transporting substance and the method described in Table 2 was used. Fabricated and evaluated. The results are shown in Table 2.
（実施例１７）
電荷発生物質をＣｕＫαのＸ線回折におけるブラッグ角（２θ±０．２°）において９．０°、１４．２°、２３．９°及び、２７．１°に強いピークを有するオキシチタニウムフタロシアニン顔料に変え、表２に記載の処法を用いた以外は、実施例１と同様にして膜性評価用膜及び電子写真感光体を作製し、同様な評価を行った。結果を表２に示す。
(Example 17)
Oxytitanium phthalocyanine pigment having strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° at Bragg angles (2θ ± 0.2 °) in CuKα X-ray diffraction Instead, the film property evaluation film and the electrophotographic photosensitive member were produced in the same manner as in Example 1 except that the processing methods shown in Table 2 were used, and the same evaluation was performed. The results are shown in Table 2.
（実施例１８）
例示化合物Ｅ１６とＥ２２とを１：１の比率で、表２に記載の処法で用いた以外は、実施例１と同様にして膜性評価用膜及び電子写真感光体を作製し、評価を行った。結果を表２に示す。
(Example 18)
Except that Exemplified Compounds E16 and E22 were used in a ratio of 1: 1 in the processing method shown in Table 2, a film property evaluation film and an electrophotographic photosensitive member were prepared in the same manner as in Example 1 and evaluated. went. The results are shown in Table 2.
（実施例１９〜２０）
表２に記載の処法を用い、中間層と電荷発生層に置換ヒドロキシフェニル化合物を用いた以外は、実施例１と同様にして膜性評価用膜及び電子写真感光体を作製し、評価を行った。結果を表２に示す。
(Examples 19 to 20)
A film property evaluation film and an electrophotographic photosensitive member were prepared and evaluated in the same manner as in Example 1 except that the substituted hydroxyphenyl compound was used for the intermediate layer and the charge generation layer using the method described in Table 2. went. The results are shown in Table 2.
（比較例３）
置換ヒドロキシフェニル化合物を加えなかった以外は、実施例１と同様にして膜性評価用膜及び電子写真感光体を作製し、評価を行った。結果を表２に示す。
(Comparative Example 3)
A film property evaluation film and an electrophotographic photosensitive member were produced and evaluated in the same manner as in Example 1 except that the substituted hydroxyphenyl compound was not added. The results are shown in Table 2.
１ 電子写真感光体
２ 軸
３ 帯電手段
４ 露光光
５ 現像手段
６ 転写手段
７ 転写材
８ 定着手段
９ クリーニング手段
１０ 前露光光
１１ プロセスカートリッジ
１２ 案内手段
DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means
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| JP2001278754A (en) * | 2000-03-28 | 2001-10-10 | Kose Corp | Acid hair dye composition |
| JP2003015290A (en) * | 2001-06-28 | 2003-01-15 | Kyocera Chemical Corp | Photosensitive resin composition and positive type pattern forming method |
| JP2003252853A (en) * | 2001-12-28 | 2003-09-10 | Takeda Chem Ind Ltd | Nitrogenous cyclic ketone derivative, method for producing the same, and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001278754A (en) * | 2000-03-28 | 2001-10-10 | Kose Corp | Acid hair dye composition |
| JP2003015290A (en) * | 2001-06-28 | 2003-01-15 | Kyocera Chemical Corp | Photosensitive resin composition and positive type pattern forming method |
| JP2003252853A (en) * | 2001-12-28 | 2003-09-10 | Takeda Chem Ind Ltd | Nitrogenous cyclic ketone derivative, method for producing the same, and use |
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