JPS607782B2 - Electrophotographic materials - Google Patents
Electrophotographic materialsInfo
- Publication number
- JPS607782B2 JPS607782B2 JP10998578A JP10998578A JPS607782B2 JP S607782 B2 JPS607782 B2 JP S607782B2 JP 10998578 A JP10998578 A JP 10998578A JP 10998578 A JP10998578 A JP 10998578A JP S607782 B2 JPS607782 B2 JP S607782B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- rutile
- titanium
- electrophotographic
- photosensitive
- 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.)
- Expired
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- Photoreceptors In Electrophotography (AREA)
Description
【発明の詳細な説明】
本発明は感光性顔料として酸化チタンを用いた電子写真
感光材料に係り、特に酸化チタンとして少量のアナター
ゼ結晶を含むルチル結晶のものを使用する電子写真感光
材料に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrophotographic material using titanium oxide as a photosensitive pigment, and particularly to an electrophotographic material using a rutile crystal containing a small amount of anatase crystal as titanium oxide.
電子写真は、感光材料の表面をコロナ放電によって均一
に帯電させた後、画像露光して露光部の電荷を減衰させ
て静電荷潜像を形成させ、次いで検電性着色トナーを静
電荷潜像上に付着させて可視像を感光材料上に形成させ
るものである。In electrophotography, the surface of a photosensitive material is uniformly charged by corona discharge, then imagewise exposed to attenuate the charge in the exposed area to form an electrostatic latent image, and then an electroscopic colored toner is applied to the electrostatic latent image. A visible image is formed on a photosensitive material by depositing it on the photosensitive material.
こ)に使用する感光材料は必要な電子写真特性を備えて
いなければならないことはもちろんであるが、特に、帯
電操作開始後その表面電位が短時間に高い値に達するこ
とができるような帯電性、帯電停止後膳所でその表面電
位が低下することなく操作に必要な時間保たれるような
階保持性、および露光開始後その表面電位が露光量に応
じて速やかに減衰するような光減衰性(光感度)は基本
的に必須のものである。電子写真感光材料として現在実
用されているのは、セレン、ポリビニルカルバゾールな
どのほか、酸化亜塩、硫化カドミウムなどの感光性顔料
を樹脂バインダー中に分散させたものである。It goes without saying that the photosensitive material used in this method must have the necessary electrophotographic properties, but in particular it must have charging properties that allow its surface potential to reach a high value in a short time after the charging operation starts. , light retention properties such that the surface potential is maintained for the time required for operation without decreasing after the charging stops, and light attenuation properties such that the surface potential quickly attenuates in accordance with the exposure amount after the start of exposure. (Photosensitivity) is basically essential. Electrophotographic materials currently in practical use include photosensitive pigments such as selenium, polyvinylcarbazole, subsalt oxide, and cadmium sulfide dispersed in a resin binder.
酸化チタンは、特にルチル型結晶構造をもった高純度品
が感光性顔料としての特性を有していることが知られて
おり、電子写真への応用について検討されてきたが、例
えば酸化亜鉛に〈らべて光感度、階保持性に劣り、未だ
実用化されるに至っていない。本発明者等は、酸化チタ
ン、特に現在工業化されている技術の中で最も高純度の
ルチル型結晶構造のものが得られる四塩化チタンの気相
酸化法、所謂塩素法により製造される酸化チタンの感光
性顔料としての使用について研究をおこなっていたとこ
ろ、意外にも特殊な反応条件で少量のアナターゼ型結晶
が混在するように製造した場合にすぐれた電子写真特性
がもたらされることを見いだし、更に硫酸チタン溶液の
加熱加水分解と生成する水和酸化チタンの焼成とを経る
所謂硫酸法により製造される酸化チタンにおいても同様
の傾向を確認した。Titanium oxide, especially high-purity products with a rutile crystal structure, is known to have properties as a photosensitive pigment, and its application to electrophotography has been considered. (Comparatively, it has poor photosensitivity and color retention, so it has not yet been put into practical use.) The present inventors have developed titanium oxide, especially titanium oxide produced by the gas phase oxidation method of titanium tetrachloride, which yields the rutile crystal structure with the highest purity among the currently industrialized technologies, the so-called chlorine method. While conducting research on its use as a photosensitive pigment, it was surprisingly discovered that when produced under special reaction conditions in which a small amount of anatase type crystals were mixed, excellent electrophotographic properties were brought about. A similar tendency was confirmed in titanium oxide produced by the so-called sulfuric acid method, which involves heating and hydrolyzing a titanium sulfate solution and calcination of the resulting hydrated titanium oxide.
本発明の目的は電子写真特性、特に帯電性、階保持性及
び光感度が改良された酸化チタンを使用する電子写真感
光材料を提供することにある。An object of the present invention is to provide an electrophotographic light-sensitive material using titanium oxide that has improved electrophotographic properties, particularly chargeability, color retention, and photosensitivity.
本発明の他の目的は電子写真特性が全般的に実用可能程
度に高められ、しかも高い白色度を有する電子写真感光
材料を提供することにある。本発明は、樹脂バインダー
中に感光性顔料としての酸化チタンを分散させた感光層
を導電性基材上に積層してなる電子写真感光材料であっ
て、該酸化チタンは、0}ハロゲン化チタンを気相酸化
分解するか、‘2}ハロゲン化チタンを加水分解し次い
で得られた水和酸化チタンを焼成するか、または‘3}
チタン塩を加水分解し次いで得られた水和酸化チタンを
焼成するかして、ルチルノアナターゼ結晶混合物として
生成させたもので、全Ti02を3 Z〜40%がアナ
ターゼ型結晶であることを特徴とする、電子写真感光材
料である。本発明に使用する酸化チタンは、ルチルノア
ナターゼ結晶混合物として生成させたものであり、例え
ば次記のようにして製造する。Another object of the present invention is to provide an electrophotographic light-sensitive material whose electrophotographic properties are generally improved to a practically practicable degree and which also has a high degree of whiteness. The present invention is an electrophotographic photosensitive material in which a photosensitive layer in which titanium oxide as a photosensitive pigment is dispersed in a resin binder is laminated on a conductive substrate, the titanium oxide being 0} titanium halide. '2} Hydrolyze the titanium halide and then sinter the obtained hydrated titanium oxide, or '3}
It is produced as a rutile noanatase crystal mixture by hydrolyzing titanium salt and then calcining the obtained hydrated titanium oxide, and is characterized by that 3Z to 40% of the total Ti02 is anatase type crystals. This is an electrophotographic light-sensitive material. The titanium oxide used in the present invention is produced as a rutile noanatase crystal mixture, and is produced, for example, as follows.
塩素法におし、Zては、四塩化チタンの蒸気を高温で酸
素と反応させ酸化チタンを得るが、工業的に実施されて
いる顔料級酸化チタンの製造においては普通100%ル
チル型の結晶構造をもつものが生成する。従ってルチル
ノアナターゼ結晶混合物を得るには、例えば‘ィ’一般
に添加剤として用いられている三塩化アルミ、水などの
全部もしくは大部分を反応系から排除する、‘oーアナ
ターゼ化の作用が認められているホウ素化合物の少量を
反応系に添加する、し一四塩化チタン、酸素の2ガスの
高温反応城での接触、混合速さを調節する、などの手段
を採用し、更に反応温度、反応時間などの諸条件を調整
して、所望のルチル/アナターゼ混合割合のものを得る
。また、硫酸法においては、硫酸チタン水溶液の加熱加
水分解時にルチル種を添加し、生成する水和酸化チタン
を焼成してアナターゼからルチルへの結晶転位をおこさ
せるので、例えば{ィーカロ水分解時のルチル種の添加
量を100%ルチルを期待する場合にくらべて減少させ
る、‘oー焼成添加剤の種類、量、焼成温度、焼成時間
を調節する、などの手段で所望のルチル/アナターゼ混
合割合の酸化チタンを製造することができる。このよう
にして得られた全Ti02の3〜40%がアナターゼ結
晶構造をもち、残余の60〜97%がルチル結晶構造を
もつルチル/アナターゼ結晶混合物が本発明の感光材料
の感光性顔料として用いられる。In the chlorine method, titanium oxide is obtained by reacting titanium tetrachloride vapor with oxygen at high temperatures, but in the industrial production of pigment-grade titanium oxide, 100% rutile crystals are usually used. Something with structure is generated. Therefore, in order to obtain a rutile noanatase crystal mixture, for example, it is necessary to remove all or most of aluminum trichloride, water, etc., which are generally used as additives, from the reaction system, and to form anatase. By adding a small amount of boron compound to the reaction system, bringing titanium tetrachloride and oxygen into contact in a high-temperature reaction chamber, and adjusting the mixing speed, we further controlled the reaction temperature and reaction. Conditions such as time are adjusted to obtain the desired rutile/anatase mixing ratio. In addition, in the sulfuric acid method, rutile seeds are added during heating and hydrolysis of an aqueous titanium sulfate solution, and the resulting hydrated titanium oxide is calcined to cause crystal rearrangement from anatase to rutile. The desired rutile/anatase mixing ratio can be achieved by reducing the amount of rutile added compared to when 100% rutile is expected, adjusting the type and amount of firing additives, firing temperature, and firing time, etc. of titanium oxide can be produced. The thus obtained rutile/anatase crystal mixture in which 3 to 40% of the total Ti02 has an anatase crystal structure and the remaining 60 to 97% has a rutile crystal structure is used as a photosensitive pigment in the photosensitive material of the present invention. It will be done.
アナターゼの含有割合が前記範囲より多いと、帯電性、
暗保持性に劣り、少し、と光感度に劣る結果となる。ま
た、硫酸法により製造する場合のように焼成工程を経る
ときは、例えば焼成が500qoで2時間といった不十
分な焼成のものは例えアナターゼ含有割合が前記範囲内
にあっても帯電性、暗保持性が低下し、逆に1000午
0で2時間の如く過焼成のものは光感度が低下するので
留意しなければならない。前記酸化チタンは、また、通
常粒度分布のメジアン値が約0.2〜0.4〃のもので
ある顔料級酸化チタンに比較して若干粒径の大きいもの
が望ましいことがわかった。When the content of anatase is higher than the above range, charging property,
The result is poor dark retention and slightly poor light sensitivity. In addition, when going through a firing process such as in the case of manufacturing by the sulfuric acid method, if the firing is insufficient, for example, at 500 qo for 2 hours, even if the anatase content is within the above range, the chargeability and dark retention will deteriorate. On the other hand, if the film is overfired at 1000 o'clock for 2 hours, the photosensitivity will be reduced, so care must be taken. It has also been found that it is desirable that the titanium oxide has a slightly larger particle size than pigment grade titanium oxide, which usually has a median particle size distribution of about 0.2 to 0.4.
すなわち、ルチル/アナターゼ結晶混合物である酸化チ
タンは、粒度分布のメジアン値が0.4一以上、望まし
くは0.6仏〜5仏の範囲にあるものがよい。粒径が小
さ過ぎると光感度が低下する。逆に大き過ぎて例えば1
0仏以上の粗大粒子を相当量含むものは画像が粗くなっ
て好ましくないo従来からの認識に従って「本発明で使
用する酸化チタンは、有色不純物或は原料、添加物に由
来する不純物は極力小さくすることが望まれ、Fe,M
n,Ni,Co,V,Cr,P,AI,Siなどは酸化
物換算の合量で0.1%以下に抑える必要がある。That is, the titanium oxide which is a rutile/anatase crystal mixture preferably has a median particle size distribution of 0.41 or more, preferably in the range of 0.6 to 5 degrees. If the particle size is too small, photosensitivity will decrease. On the other hand, if it is too large, for example 1
If the titanium oxide contains a considerable amount of coarse particles of 0 or more, the image will become rough, which is undesirable.According to the conventional wisdom, the titanium oxide used in the present invention should contain as few colored impurities or impurities derived from raw materials or additives as possible. It is desired that Fe, M
It is necessary to suppress the total amount of n, Ni, Co, V, Cr, P, AI, Si, etc. to 0.1% or less in terms of oxides.
しかしZn,Ca,Mg,Li,Ba及びSrは、0.
01〜5モル%を酸化チタンの結晶構造中に存在させて
、電子写真特性を向上させることがわかっており、例え
ば硫酸法によって本発明の酸化チタンを製造する際に焼
成工程において添加して望ましい結果をもたらす。前記
の酸化チタンを感光性顔料として使用するほかは、本発
明の電子写真感光材料は、従来の方法に従って調製する
ことができる。However, Zn, Ca, Mg, Li, Ba and Sr are 0.
It is known that the presence of 01 to 5 mol% in the crystal structure of titanium oxide improves the electrophotographic properties, and it is desirable to add it in the firing process when producing the titanium oxide of the present invention, for example, by the sulfuric acid method. bring results. The electrophotographic material of the present invention can be prepared according to conventional methods except for using the titanium oxide described above as a photosensitive pigment.
すなわち、この感光性顔料を樹脂バインダー中に35〜
6既容量%の割合で分散させ、これを導電性基材上に普
通10仏〜30仏の厚さで塗布し、乾燥して感光材料と
する。通常酸化チタンと樹脂バインダーとの混練の際に
は電子写真特性の各種改良処理剤が1種又は2種以上組
合せて使用される。例えば分光感度特性改良剤としては
アントラキノン系、フタレィン系、キサンテン系、シア
ニン系、トリフェニルメタン系、アゾ系、アジン系、オ
キサジン系などの色素類が、階保持特性改良剤としては
アミン類、有機酸類、シランカップリング剤類、樹脂類
、金属石けん類、炭素数6以上のアルコール類が、前露
光疲労抑制剤としては前記色素類、フェノール類、アミ
ン類が、また帯電特性改良剤としては金属石けん類、有
機酸類、フェノール類、アミン類、シランカップリング
剤類、樹脂類、炭素数6以上のアルコール類などが使用
できる。かかる処理剤は酸化チタンと樹脂バインダーと
を混練するときに単に添加、混練してもよいが、電子写
真特性上処理剤を一旦顔料粒子表面に強く吸着させてか
ら樹脂バインダーと混練する方法が望まれる。即ち処理
剤と酸化チタンとの混練前〜混練後の間に、普通90午
0以上望ましくは120〜25000、1〜4時間望ま
しくは2〜3時間加熱し、その後樹脂バインダーと混練
し塗布して前記加熱温度より低い温度で乾燥すれば処理
剤は顔料粒子表面に緊密に吸着保持されるので元来処理
剤の持っている以上の改良効果がもたらされると共にそ
の他の写真特性の改良効果も向上することがある。樹脂
バインダーは成膜性を有する電気絶縁性の大きい樹脂を
適宜選択して使用できる。例えばアクリル樹脂、アルキ
ッド樹脂、ポリエステル樹脂、ビニル系樹脂、ポリウレ
タン系樹脂、各種の天然樹脂、合成ゴム、アミノ樹脂、
ポリオレフイン樹脂などが使用できる。導電性基村は、
光導電層よりも電導度の大きいものであればよく、通常
電子写真に用いられている導電性物質を塗布した紙や布
、或は金属シート、金属を蒸着したプラスチックシート
、金属箔を薄層した紙などを使用する。本発明の感光材
料は、酸化チタンのすぐれた顔料性によって白色度が高
く、生目の細い良好な画像が得られる。That is, this photosensitive pigment is mixed into a resin binder at a concentration of 35 to
It is dispersed at a ratio of 6% by volume and coated on a conductive substrate to a thickness of usually 10 to 30 mm, and dried to form a photosensitive material. Usually, when kneading titanium oxide and a resin binder, one type or a combination of two or more types of various processing agents for improving electrophotographic properties are used. For example, dyes such as anthraquinones, phthalenes, xanthenes, cyanines, triphenylmethanes, azos, azines, and oxazines are used as spectral sensitivity property improvers, while amines and organic dyes are used as spectral sensitivity property improvers. Acids, silane coupling agents, resins, metal soaps, and alcohols having 6 or more carbon atoms are used as pre-exposure fatigue inhibitors, the above-mentioned dyes, phenols, and amines are used as pre-exposure fatigue inhibitors, and metals are used as charging property improvers. Soaps, organic acids, phenols, amines, silane coupling agents, resins, alcohols having 6 or more carbon atoms, and the like can be used. Such a processing agent may be simply added and kneaded when titanium oxide and the resin binder are kneaded, but due to the characteristics of electrophotography, it is preferable to first strongly adsorb the processing agent on the surface of the pigment particles and then knead with the resin binder. It will be done. That is, between before and after the kneading of the treatment agent and titanium oxide, heating is usually carried out for more than 90 minutes, preferably for 120 to 25,000 hours, preferably for 1 to 4 hours, preferably for 2 to 3 hours, and then kneaded with a resin binder and coated. If the processing agent is dried at a temperature lower than the heating temperature mentioned above, the processing agent is closely adsorbed and retained on the surface of the pigment particles, so that an improvement effect beyond that originally possessed by the processing agent is brought about, and the effect of improving other photographic properties is also improved. Sometimes. As the resin binder, a resin having film-forming properties and high electrical insulation properties can be appropriately selected and used. For example, acrylic resin, alkyd resin, polyester resin, vinyl resin, polyurethane resin, various natural resins, synthetic rubber, amino resin,
Polyolefin resin etc. can be used. Conductive Motomura is
Any material with higher conductivity than the photoconductive layer may be used, such as paper or cloth coated with a conductive substance commonly used in electrophotography, a metal sheet, a plastic sheet coated with metal, or a thin layer of metal foil. Use paper, etc. The light-sensitive material of the present invention has a high degree of whiteness due to the excellent pigment properties of titanium oxide, and can produce good images with fine grains.
また酸化チタンは誘導率が大きく電荷保持量が大きいの
で、感光層を薄くすることができ全体として軽量である
。更に連続階調再現性が極めてすぐれており、銀塩写真
に匹敵する画像が得られ、カラープリントに適用できる
大きな利点を有している。次に本発明に係る実施例を記
載する。Furthermore, since titanium oxide has a high dielectric constant and a large charge retention capacity, the photosensitive layer can be made thinner and the whole material is lighter. Furthermore, continuous tone reproducibility is extremely excellent, and images comparable to silver halide photography can be obtained, which has the great advantage of being applicable to color printing. Next, examples according to the present invention will be described.
例1
四塩化チタンを気相酸化分解して得た所定の酸化チタン
27.5夕、アロセツト斑04XC(アクリル樹脂、日
触アロー化学株式会社製)13.0夕、キシレン12の
‘、混合色素MD−19(NK−1410、クレジルバ
イオレツト、ウラニン、エリオクロムブラックT及びア
ズールロ;色素−1)のメタノール溶液3.44の【、
アゼラィン酸ジオクチル0.72夕及びガラスビーズ1
03夕を240M客のガラス容器に入れ、クイックミル
でよく振とうした後、ガラスビーズを分離して塗液を得
た。Example 1 Specified titanium oxide obtained by vapor phase oxidative decomposition of titanium tetrachloride 27.5 mm, Alloset spots 04XC (acrylic resin, manufactured by Nippon Arrow Chemical Co., Ltd.) 13.0 mm, xylene 12 mm, mixed pigment Methanol solution of MD-19 (NK-1410, Cresyl Violet, Uranine, Eriochrome Black T and Azururo; Dye-1) at 3.44 [,
Dioctyl azelate 0.72 mm and glass beads 1
03 was placed in a 240M glass container, shaken well with a quick mill, and the glass beads were separated to obtain a coating liquid.
この塗液をアルミラミネート紙上に50ムドクターブレ
ードで塗布し、looこ0で1雌ご間乾燥して感光紙と
し、これを階所に2昼夜放置して電子写真特性測定用の
試料とした。電子写真特性のうち帯電性及び階保持性に
ついては川口電機製SP−42母型ペーパーアナライザ
ーを使用してターンテーブル法(ダイナミック法)によ
って帯電曲線及び階減衰曲線を描かせ、2鼠砂間の帯電
で達する電位Voと、帯電後膳所で20秒間放置した後
の電位V2。This coating solution was applied onto aluminum laminated paper using a 50-m doctor blade, dried for one coat on a loo dryer to make photosensitive paper, and this was left in a room for two days and nights to be used as a sample for measuring electrophotographic properties. . Among the electrophotographic properties, chargeability and scale retention were determined by drawing charging curves and scale attenuation curves by the turntable method (dynamic method) using Kawaguchi Denki's SP-42 matrix paper analyzer. The potential Vo reached by charging and the potential V2 after being left for 20 seconds in the tray after charging.
とを読み取り、Voを以つて帯電性を、V2o/Vo×
100の値を以つて階保持性を示した。光減衰性はスコ
ロトロン帯電器によって300V‘こ帯電した後、表面
電位計(JII口電機製SSVロー30)で電位を測定
しながら光照射を行ない、電位が露光直前の電位(30
0V)から10分の1(30V)に減衰するのに要する
時間tl/10秒を測定し、これを以つて示した。露光
は150Wタングステン電球を使用しダィクロィックフ
ィルターによって青、緑及び赤に分光した光を、試料面
で各照度が青:43い緑:1350及び赤:720ルッ
クスになるように調整して照射した。酸化チタンのルチ
ル/アナターゼ比は粉砕した酸化チタンをX線回折法に
よりルチル及びアナターゼの100面の回折強度をそれ
ぞれ測定し、その強度比とルチル/アナターゼ比との関
係を予め測定して得た相関曲線上で読み取る方法で求め
た。is read, and the chargeability is determined by Vo, and V2o/Vox
A value of 100 indicates floor retention. The light attenuation property was determined by charging to 300 V' with a scorotron charger, then irradiating with light while measuring the potential with a surface potentiometer (JII Kuchi Denki SSV Rho 30), and the potential was the same as the potential just before exposure (30
The time tl/10 seconds required for the voltage to decay from 0V to one-tenth (30V) was measured and is shown here. For exposure, a 150W tungsten bulb was used, and the light was separated into blue, green, and red by a dichroic filter, and the illuminance was adjusted so that each illuminance was 43 lux for blue, 1350 lux for green, and 720 lux for red on the sample surface. Irradiated. The rutile/anatase ratio of titanium oxide was obtained by measuring the diffraction intensities of 100 planes of rutile and anatase on crushed titanium oxide using an X-ray diffraction method, and measuring the relationship between the intensity ratio and the rutile/anatase ratio in advance. It was determined by reading it on a correlation curve.
酸化チタンのメジアン径は遠心沈降法によるジョィス・
レベル社のディスク型測定器を用いて累積粒度分布曲線
を描き、その中央値を求めた。試験結果を表1に示す。
表1
例2
前記例1において酸化チタンをアィソパー日中に分散さ
せ、ナフテン酸亜鉛をZnとして0.2重量%(Ti0
2基準)加えた後沸点(約188午0)で30分間加熱
燈拝し、炉過乾燥して表面処理を行なうこ**と、また
色素としてェリオクロムブラックT(色素−ロ)を添加
する場合は酸化チタン基準で0.02重量%処理するこ
とを除いては前記例1の場合と同様にして感光材料を作
成し、電子写真特性を測定して表2の結果を得た。The median diameter of titanium oxide was determined by Joyce's centrifugal sedimentation method.
A cumulative particle size distribution curve was drawn using a disc-type measuring device manufactured by Revell Inc., and its median value was determined. The test results are shown in Table 1.
Table 1 Example 2 In Example 1 above, titanium oxide was dispersed in Isopar daylight, and zinc naphthenate was used as Zn in an amount of 0.2% by weight (Ti0
2 standards), heat for 30 minutes at the boiling point (approx. When using titanium oxide, a photosensitive material was prepared in the same manner as in Example 1 except that the treatment was carried out in an amount of 0.02% by weight based on titanium oxide, and the electrophotographic properties were measured to obtain the results shown in Table 2.
表2
例3
少量のルチル種の存在下に硫酸チタンの水溶液を加熱加
水分解して比較的粒径の大きな水和酸化チタンを得た。Table 2 Example 3 An aqueous solution of titanium sulfate was heated and hydrolyzed in the presence of a small amount of rutile species to obtain hydrated titanium oxide having a relatively large particle size.
この水和酸化チタンに酸化亜鉛を1モル%(Ti02基
準)添加し、800ooに調整されている電気炉に入れ
て焼成した。焼成時間を適宜変えることによりルチルと
アナターゼとの比率が異なる酸化チタンを製造し、焼成
後粉砕して感光性顔料とし、前記例2と同機に混合色素
MD−19(色素−1)及び表面処理を行なって感光材
料を作成し、電子写真特性を測定して表3の結果を得た
。なお、この酸化チタンのメジアン径は前記例1と同様
にして測定したところ、いずれも0.6〜0.8仏であ
った。1 mol % of zinc oxide (based on Ti02) was added to this hydrated titanium oxide, and the mixture was fired in an electric furnace adjusted to 800 oo. By appropriately changing the firing time, titanium oxide with different ratios of rutile and anatase was produced, and after firing, it was crushed to make a photosensitive pigment, and mixed dye MD-19 (dye-1) and surface treatment were added to the same machine as in Example 2. A photosensitive material was prepared by performing the above steps, and the electrophotographic properties were measured to obtain the results shown in Table 3. The median diameter of this titanium oxide was measured in the same manner as in Example 1, and was found to be 0.6 to 0.8 mm.
表3Table 3
Claims (1)
を分散させた感光層を導電性基材上に積層してなる電子
写真用感光材料であって該酸化チタンは、(1)ハロゲ
ン化チタンを気相酸化分解するか、(2)ハロゲン化チ
タンを加水分解し次いで得られた水和酸化チタンを焼成
するか、または(3)チタン塩を加水分解し次いで得ら
れた水和酸化チタンを焼成するかしてルチル/アナダー
ゼ結晶混合物として生成させたもので、全TiO_2の
3〜40%がアナターゼ型結晶であることを特徴とする
電子写真感光材料。1 An electrophotographic photosensitive material comprising a photosensitive layer in which titanium oxide as a photosensitive pigment is dispersed in a resin binder is laminated on a conductive substrate, and the titanium oxide is prepared by (1) dispersing titanium halide (2) hydrolyzing a titanium halide and then calcining the resulting hydrated titanium oxide; or (3) hydrolyzing a titanium salt and then calcining the resulting hydrated titanium oxide. An electrophotographic light-sensitive material characterized in that 3 to 40% of the total TiO_2 is anatase-type crystals, which are produced as a rutile/anadase crystal mixture.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10998578A JPS607782B2 (en) | 1978-09-07 | 1978-09-07 | Electrophotographic materials |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10998578A JPS607782B2 (en) | 1978-09-07 | 1978-09-07 | Electrophotographic materials |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5536853A JPS5536853A (en) | 1980-03-14 |
JPS607782B2 true JPS607782B2 (en) | 1985-02-27 |
Family
ID=14524149
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10998578A Expired JPS607782B2 (en) | 1978-09-07 | 1978-09-07 | Electrophotographic materials |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS607782B2 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59187133A (en) * | 1983-03-04 | 1984-10-24 | Mazda Motor Corp | Balancer device for three-cylinder engine |
JPS6013930A (en) * | 1983-07-04 | 1985-01-24 | Nissan Motor Co Ltd | Vibration damping apparatus for multi-cylinder internal-combustion engine |
EP0287218B1 (en) * | 1987-03-17 | 1992-12-02 | Mitsubishi Denki Kabushiki Kaisha | Method of making photoconductive particles |
-
1978
- 1978-09-07 JP JP10998578A patent/JPS607782B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS5536853A (en) | 1980-03-14 |
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