JP2881921B2 - Method for producing oxytitanium phthalocyanine and method for producing electrophotographic photoreceptor - Google Patents
Method for producing oxytitanium phthalocyanine and method for producing electrophotographic photoreceptorInfo
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- JP2881921B2 JP2881921B2 JP5620890A JP5620890A JP2881921B2 JP 2881921 B2 JP2881921 B2 JP 2881921B2 JP 5620890 A JP5620890 A JP 5620890A JP 5620890 A JP5620890 A JP 5620890A JP 2881921 B2 JP2881921 B2 JP 2881921B2
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- Prior art keywords
- phthalocyanine
- producing
- tiopc
- water
- electrophotographic photoreceptor
- Prior art date
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明はオキシチタニウムフタロシアニンの製造方法
及び該オキシチタニウムフタロシアニンを使用する電子
写真感光体の製造方法に係わるものであり、更に詳しく
は、可視光より長波長光に対して極めて高感度を示す感
光体の製造方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for producing oxytitanium phthalocyanine and a method for producing an electrophotographic photoreceptor using the oxytitanium phthalocyanine, and more specifically, to visible light. The present invention relates to a method for manufacturing a photosensitive member having extremely high sensitivity to longer wavelength light.
［従来の技術］ 従来、電子写真感光体の材料としては、セレン、酸化
亜鉛、硫化カドミウム等の光導電性物質を主成分とする
無機系感光体やポリビニルカルバゾールとトリニトロフ
ルオレノンの電荷移動錯体、有機色素を電荷発生剤とし
て作成された有機系感光体が用いられている。[Prior art] Conventionally, as a material of an electrophotographic photoreceptor, an inorganic photoreceptor mainly containing a photoconductive substance such as selenium, zinc oxide, and cadmium sulfide, a charge transfer complex of polyvinyl carbazole and trinitrofluorenone, An organic photoreceptor prepared using an organic dye as a charge generating agent is used.
近年、半導体レーザー発振器が安価に提供されるよう
になり、電子写真感光体用光源として用いられるように
なった。しかし、短波長光を発振する半導体レーザーは
出力、寿命等の点で問題が多く、実用的なレーザーの波
長は800nm前後の長波長に限られている。従って、従来
用いられてきた短波長領域に感度をもつ材料を半導体レ
ーザー用に使用するのは不適当であり、780nm以上に感
度を有する材料の開発が望まれている。In recent years, semiconductor laser oscillators have been provided at low cost, and have been used as light sources for electrophotographic photosensitive members. However, a semiconductor laser that oscillates short-wavelength light has many problems in terms of output, life, and the like, and the practical laser wavelength is limited to a long wavelength of about 800 nm. Therefore, it is inappropriate to use a conventionally used material having a sensitivity in a short wavelength region for a semiconductor laser, and development of a material having a sensitivity of 780 nm or more is desired.
かかる要望に応えるべく、長波長領域に感度をもつ材
料としてフタロシアニン系化合物の研究が盛んに行わ
れ、一部実用化されるに到っている。In order to meet such demands, phthalocyanine-based compounds have been actively studied as materials having sensitivity in a long wavelength region, and some of them have been put to practical use.
［発明が解決しようとする課題］ しかしながら、一般的に電子写真感光体用フタロシア
ニン化合物の製造法は著しく煩雑である場合が多い。例
えばオキシチタニウムフタロシアニン（以下TiOPcと略
記する）を10-5〜10-6トールの真空下で蒸着する方法
（特開昭59−166959号公報）、ジクロロチタニウムフタ
ロシアニン（以下TiCl2Pcと略記する）を濃アンモニヤ
水と共に加熱還流して加水分解したのち、ソックスレー
抽出器を用いてアセトン洗浄してTiOPcを得る方法（特
開昭61−217050号公報）、TiOPcをポリエチレングリコ
ールと共にサンドグラインダーを用いて60〜120℃の温
度で、７〜15時間摩砕したのち希硫酸で洗浄する方法
（特開昭64−17066号公報）等いずれも製造工程が複雑
で、再現性も必ずしも良好とは言い難い。[Problems to be Solved by the Invention] However, in general, a method for producing a phthalocyanine compound for an electrophotographic photosensitive member is often extremely complicated. For example, a method of depositing oxytitanium phthalocyanine (hereinafter abbreviated as TiOPc) under a vacuum of 10 -5 to 10 -6 torr (JP-A-59-166959), dichlorotitanium phthalocyanine (hereinafter abbreviated as TiCl 2 Pc) Is heated and refluxed with concentrated ammonia water to hydrolyze, and then washed with acetone using a Soxhlet extractor to obtain TiOPc (Japanese Patent Application Laid-Open No. 61-217050). The method of grinding at a temperature of about 120 ° C. for 7 to 15 hours and then washing with dilute sulfuric acid (Japanese Patent Application Laid-Open No. 64-17066) requires complicated production steps and cannot always be said to have good reproducibility.
本発明者は前述の課題を解決すべく鋭意検討を重ねた
結果、TiCl2Pc又はジブロモチタニウムフタロシアニン
（以下TiBr2Pcと略記する）をフェノール、カテコー
ル、レゾルシン、ハイドロキノン、ピロガロール等の一
価ないし多価フェノール又はそれらの含水物で接触処理
したのち、ボールミル、ペイントシエーカー、自動乳鉢
等で摩砕し、次いで水とトルエン、キシレン、ジクロロ
ベンゼン等の混合物で処理するという極めて簡単な方法
で、特有のＸ線回折スペクトルを示すTiOPcが再現性よ
く得られ、且つこれを電子写真感光体用電荷発生剤に用
いたところ、極めて高感度で耐久性に優れた電子写真感
光体が得られることを見出し、本発明に到達した。As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that TiCl 2 Pc or dibromotitanium phthalocyanine (hereinafter abbreviated as TiBr 2 Pc) is monovalent or multivalent such as phenol, catechol, resorcin, hydroquinone, pyrogallol, and the like. After a contact treatment with polyhydric phenols or their hydrates, they are ground in a ball mill, paint shaker, automatic mortar, etc., and then treated with a mixture of water and toluene, xylene, dichlorobenzene, etc. It was found that TIOPC exhibiting the X-ray diffraction spectrum of the above was obtained with good reproducibility, and when this was used as a charge generating agent for an electrophotographic photosensitive member, an electrophotographic photosensitive member having extremely high sensitivity and excellent durability was obtained. Reached the present invention.
即ち、本発明の目的は特定のＸ線回折スペクトルを示
すTiOPcの結晶を選択的に再現性よく製造すること及び
かかる特定のＸ線回折スペクトルを示すTiOPcの結晶を
電荷発生剤として含む極めて高照度で耐久性に優れた電
子写真感光体を工業的に有利に製造することにある。That is, an object of the present invention is to selectively produce a TIPc crystal exhibiting a specific X-ray diffraction spectrum with good reproducibility, and to provide an extremely high illuminance including such a TIPc crystal exhibiting the specific X-ray diffraction spectrum as a charge generating agent. And to produce an electrophotographic photosensitive member having excellent durability in an industrially advantageous manner.
［課題を解決するための手段］ 然して、かかる本発明の目的は、TiCl2Pc又はTiBr2Pc
をフェノール類と接触させた後摩砕し、次いで水と芳香
族炭化水素の混合物で処理すること及びかくして得られ
るTiOPcを、電子写真感光体用電荷発生剤として用いる
ことにより容易に達成される。[Means for Solving the Problems] However, the object of the present invention is to provide TiCl 2 Pc or TiBr 2 Pc
Can be easily achieved by contacting with phenols and then grinding, and then treating with a mixture of water and an aromatic hydrocarbon, and using the thus obtained TiOPc as a charge generating agent for an electrophotographic photoreceptor.
［作用］ 本発明に用いられるフェノール類は、一価ないし多価
フェノールで、例えばフェノール、カテコール、レゾル
シン、ハイドロキノン、ピロガロール等が挙げられる。
これらはいずれも常温で固体であるが、融点以上の温度
に加熱溶融して使用するのが好ましい。また、必要に応
じて炭化水素、エーテル類、エステル類等の低融点不活
性溶媒を、フェノール類と溶媒との重量比で通常100:1
〜80、より好ましくは100:5〜70の範囲で共存させて操
作性を改善することもできる。更に、水を加えた含水フ
ェノールの状態で用いることもでき、この場合、フェノ
ール類と水との重量比1:0.01〜100、好ましくは1:0.05
〜50の範囲である。[Function] The phenol used in the present invention is a monohydric or polyhydric phenol, and examples thereof include phenol, catechol, resorcin, hydroquinone, pyrogallol and the like.
These are all solids at ordinary temperature, but are preferably used after being heated and melted to a temperature higher than the melting point. If necessary, hydrocarbons, ethers, low melting point inert solvents such as esters, usually 100: 1 by weight ratio of phenols and solvent.
The operability can also be improved by coexistence in the range of 8080, more preferably 100: 5〜70. Further, it can be used in the form of water-containing phenol to which water has been added.In this case, the weight ratio of phenols to water is 1: 0.01 to 100, preferably 1: 0.05.
It is in the range of ~ 50.
TiCl2Pc又はTiBr2Pcフェノール類との処理温度は、20
〜250℃、好ましくは50〜200℃の範囲である。処理温度
の高過ぎるとフタロシアニンの一部が分解する恐れがあ
り低過ぎると反応速度が低下するので実用的でない。The treatment temperature with TiCl 2 Pc or TiBr 2 Pc phenols is 20
To 250 ° C, preferably 50 to 200 ° C. If the treatment temperature is too high, a part of the phthalocyanine may be decomposed, and if the treatment temperature is too low, the reaction rate decreases, which is not practical.
TiCl2Pc又はTiBr2Pcフェノール類の使用比率には特に
制限はないが、両者の接触効率を考慮すれば1:5〜100重
量比の範囲が好適である。フェノール類の使用量が少な
過ぎると接触効率が悪く、処理時間が長くなる。処理時
間は処理温度とフェノール類の使用量によって決まる
が、130℃の場合で１〜３時間が好ましい。There is no particular limitation on the usage ratio of TiCl 2 Pc or TiBr 2 Pc phenols, but a range of 1: 5 to 100 by weight is suitable in consideration of the contact efficiency between the two. If the use amount of the phenols is too small, the contact efficiency becomes poor and the treatment time becomes long. The treatment time depends on the treatment temperature and the amount of phenols used, but is preferably 1 to 3 hours at 130 ° C.
処理方法は特に制限はないが、撹拌槽内で混合する方
法が好ましい。TiCl2Pc又はTiBr2Pcは充填したカラムに
フェノール類を流通させる方法も可能であり、要するに
両者が効率的に接触し、反応が進行する方法であればよ
い。また、処理に際して空気、窒素、アルゴン、ヘリウ
ム等のガスを通入する方法も好結果をもたらすことが多
い。The treatment method is not particularly limited, but a method of mixing in a stirring tank is preferable. For TiCl 2 Pc or TiBr 2 Pc, a method in which phenols are allowed to flow through a packed column is also possible. In short, any method can be used as long as the two can efficiently contact and the reaction proceeds. In addition, a method in which a gas such as air, nitrogen, argon, or helium is introduced during the treatment often gives good results.
TiCl2Pc又はTiBr2Pcとフェノール類で処理して得られ
るフタロシアニン系化合物の摩砕は、一般的な方法例え
ばボールミル、ペイントシェーカー、自動乳鉢、サンド
ミル等に用いて行われるが、粒径は0.01〜0.5μｍの範
囲に微細化するのが好ましい。摩砕は通常乾式で行われ
るが、湿式例えば水、有機溶媒等の共存下でもよく、食
塩、芒硝、高分子化合物等の摩砕助剤を添加することも
できる。Grinding of the phthalocyanine-based compound obtained by treating with TiCl 2 Pc or TiBr 2 Pc and a phenol is performed using a general method such as a ball mill, a paint shaker, an automatic mortar, a sand mill, etc. It is preferable to reduce the size to a range of about 0.5 μm. Grinding is usually carried out in a dry manner, but may be carried out in a wet manner, for example, in the coexistence of water, an organic solvent, or the like, and a grinding aid such as salt, sodium sulfate, or a polymer compound may be added.
摩砕時間はフタロシアニン系化合物粒子の硬さや大き
さ、摩砕方法等によって異なるが、通常３〜100時間の
範囲である。The milling time varies depending on the hardness and size of the phthalocyanine-based compound particles, the milling method, and the like, but is usually in the range of 3 to 100 hours.
摩砕後のフタロシアニン系化合物を水と芳香族炭化水
素の混合物で処理する場合の水と芳香族炭化水素の重量
比は1:0.01〜２、好ましくは1:0.05〜１の範囲である。
フタロシアニン系化合物と処理剤（水＋芳香族炭化水
素）の使用比は任意に選択できるが、通常1:5〜200、好
ましくは1:10〜100重量比である。処理温度は０〜100
℃、好ましくは20〜80℃であり、処理時間は0.1〜３時
間である。芳香族炭化水素の種類は特に制限はないが、
水との混合を容易ならしめることを考慮すれば、100℃
以下の融点のものが好適であって、ハロゲンその他の置
換基を有していてもよい。When the phthalocyanine compound after milling is treated with a mixture of water and an aromatic hydrocarbon, the weight ratio of water to the aromatic hydrocarbon is in the range of 1: 0.01 to 2, preferably 1: 0.05 to 1.
The use ratio of the phthalocyanine compound and the treating agent (water + aromatic hydrocarbon) can be arbitrarily selected, but is usually 1: 5 to 200, preferably 1:10 to 100 by weight. Processing temperature is 0-100
° C, preferably 20 to 80 ° C, and the treatment time is 0.1 to 3 hours. The type of aromatic hydrocarbon is not particularly limited,
100 ° C considering easy mixing with water
Those having the following melting points are suitable, and may have a halogen or other substituent.
電子写真用感光体の感光層には種々の形態が知られて
いるが、本発明方法は、上記方法で製造されるTiOPcを
電荷発生剤として使用してなる感光体である限り、その
感光層の形態に拘らずいかなる感光体の製造に適用して
も有効である。たとえば、下記〜の感光層を有する
感光体が例示できる。Various forms are known for the photosensitive layer of the electrophotographic photoreceptor, but the method of the present invention employs the photosensitive layer as long as the photoreceptor is prepared by using the TiOPc produced by the above method as a charge generating agent. Regardless of the form, it is effective to apply to the production of any photoconductor. For example, photoconductors having the following photosensitive layers can be exemplified.
TiOPcからなる感光層 TiOPcをバインダー中に分散させた感光層 TiOPcを周知の電荷移動媒体中に分散させた感光層 前記〜の感光層を電荷発生層とし、これに周知
の電荷移動媒体を含む電荷移動量を積層した感光層 上記方法で製造されるTiOPcは、光を吸収すると極め
て高い効率で電荷キャリヤーを発生する。発生したキャ
リヤーはTiOPcを媒体として移動することもできるが、
周知の電荷移動媒体を媒体として移動させる方が好まし
い。この点から及び、最も好ましくはの形態の感
光層がとくに好ましい。Photosensitive layer made of TiOPc Photosensitive layer in which TiOPc is dispersed in a binder Photosensitive layer in which TiOPc is dispersed in a well-known charge transfer medium The above-mentioned photosensitive layer is used as a charge generation layer, and a charge containing a well-known charge transfer medium Photosensitive Layer with Laminated Movement Amount TiOPc produced by the above method generates charge carriers with extremely high efficiency when absorbing light. The generated carrier can move using TiOPc as a medium,
It is preferable to move a known charge transfer medium as a medium. From this point, the most preferred form of the photosensitive layer is particularly preferred.
本発明方法中TiOPcを材料として電子写真感光体を製
造する工程は常法に従えばよい。例えば上記の感光層
を有する感光体の場合電荷発生剤を溶媒中に分散させた
塗料、あるいは適当な結着性樹脂と共に溶媒中に分散さ
せた塗料をアルミニウム等の金属ドラム、金属シート等
の導電性支持体上に塗布し、電荷発生層を形成させる。
この上に電荷移動物質を結着性樹脂と共に溶媒中に溶解
又は分散させた塗料を積層して電荷移動層を形成させる
ことによって製造される。電荷発生層の好ましい膜厚は
0.001〜１μｍであり、電荷移動層の膜厚は５〜30μｍ
が好ましい。In the method of the present invention, the step of producing an electrophotographic photoreceptor using TiOPc as a material may be in accordance with a conventional method. For example, in the case of a photoreceptor having the above-described photosensitive layer, a paint in which a charge generating agent is dispersed in a solvent, or a paint in which a suitable binder resin is dispersed in a solvent is coated with a conductive material such as a metal drum such as aluminum or a metal sheet. To form a charge generation layer.
It is manufactured by laminating a coating material in which a charge transfer material is dissolved or dispersed in a solvent together with a binder resin in a solvent to form a charge transfer layer. The preferred thickness of the charge generation layer is
0.001 to 1 μm, and the thickness of the charge transfer layer is 5 to 30 μm
Is preferred.
電荷発生層及び電荷移動層に用いられる結着性樹脂と
して好ましく用いられるものとしては、ポリアミド、ポ
リエステル、ポリウレタン、ポリカーボネート、ポリイ
ミド、ポリアミドイミド、ポリアセタール、ポリエチレ
ンオキシド、ポリプロピレンオキシド、ブチラール樹
脂、エポキシ樹脂などが挙げられる。また、電荷発生物
質又は電荷移動物質と結着性樹脂との好ましい重量比は
1:0.2〜２である。As preferably used as the binder resin used in the charge generation layer and the charge transfer layer, polyamide, polyester, polyurethane, polycarbonate, polyimide, polyamide imide, polyacetal, polyethylene oxide, polypropylene oxide, butyral resin, epoxy resin, and the like. No. Further, the preferred weight ratio of the charge generating material or the charge transfer material to the binder resin is
1: 0.2 to 2.
電荷移動物質は一般に電子の移動媒体とホールの移動
媒体の二種に分類されるが、本発明感光体には両者とも
使用することができ、またその混合物をも使用もでき
る。電子の移動媒体としてはニトロ基、シアノ基、エス
テル結合等の電子吸引性基を有する電子吸引性化合物、
例えば２・４・７−トリニトロフルオレノン等のニトロ
化フルオレノンあるいはテトラシアノキノジメタンが挙
げられる。また、ホールの移動媒体としては電子供与性
の有機光導電性化合物、例えばカルバゾール、インドー
ル、イミダゾール、オキサゾール、チアゾール、オキサ
ジアゾール、ピラゾール、ピラゾリン、チアジアゾール
等の複素環化合物、アニリンの誘導体、ヒドラジン誘導
体、ヒドラゾンあるいはこれらの化合物からなる基を主
鎖もしくは側鎖に有する重合体（ポリビニルカルバゾー
ル、ポリグリシジルカルバゾール）等が挙げられる。か
なでも下記一般式（Ｉ） （式中Ar1、Ar2及びAr3は置換基を有していてもよい
芳香族炭化水素基、例えばフェニル基または芳香族性複
素環基を示し、ｎはＯまたは１を示す）で表されるピラ
ゾリン化合物や下記一般式（II） （式中Ar4は置換基を有していてもよい芳香族炭化水
素基、例えばフェニル基または芳香族性複素環基、例え
ばカルバゾリル基を示し、R1及びR2はアルキル基例えば
メチル基、エチル基、アリール基例えばフェニル基、ア
ラルキル基例えばベンジル基を示し、ｌは１または２を
示す）で表されるヒドラゾン化合物が特に好適である。The charge transfer materials are generally classified into two types, an electron transfer medium and a hole transfer medium, and both can be used for the photoreceptor of the present invention, and a mixture thereof can also be used. As an electron transfer medium, an electron-withdrawing compound having an electron-withdrawing group such as a nitro group, a cyano group, and an ester bond,
For example, nitrated fluorenone such as 2.4.7-trinitrofluorenone or tetracyanoquinodimethane can be mentioned. Examples of the hole transfer medium include electron-donating organic photoconductive compounds such as carbazole, indole, imidazole, oxazole, thiazole, oxadiazole, pyrazole, pyrazoline, thiadiazole, and other heterocyclic compounds, aniline derivatives, and hydrazine derivatives. , Hydrazone or a polymer having a group consisting of these compounds in the main chain or side chain (polyvinyl carbazole, polyglycidyl carbazole) and the like. The following general formula (I) (Wherein Ar 1 , Ar 2 and Ar 3 each represent an aromatic hydrocarbon group which may have a substituent, for example, a phenyl group or an aromatic heterocyclic group, and n represents O or 1). Pyrazoline compounds represented by the following general formula (II) (In the formula, Ar 4 represents an optionally substituted aromatic hydrocarbon group, for example, a phenyl group or an aromatic heterocyclic group, for example, a carbazolyl group, and R 1 and R 2 represent an alkyl group, for example, a methyl group, A hydrazone compound represented by an ethyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and 1 represents 1 or 2) is particularly preferable.
［発明の効果］ 以上詳述した如く、本発明はTiCl2Pc又はTiBr2Pcをフ
ェノール類又は含水フェノール類で処理後摩砕し、次い
で水と芳香族炭化水素の混合物で処理するという簡単な
方法で、極めて高感度な電子写真感光体用電荷発生剤を
再現性よく提供するものである。[Effects of the Invention] As described in detail above, the present invention provides a simple method of treating TiCl 2 Pc or TiBr 2 Pc with phenols or hydrous phenols, then grinding, and then treating with water and a mixture of aromatic hydrocarbons. The present invention provides a highly sensitive charge generating agent for an electrophotographic photosensitive member with good reproducibility.
［実施例］ 以下に実施例を上げて本発明を具体的に説明するが、
本発明は、その要旨を越えない限り以下の実施例によっ
て限定されるものではない。EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples.
The present invention is not limited by the following examples unless it exceeds the gist.
TiCl2Pcの合成例 温度計、撹拌器、還流冷却器を備えた１反応フラス
コにオルトフタロジニトリル92g（0.718モル）とα−ク
ロロナフタレン600mlを仕込み、撹拌下四塩化チタン20m
l（0.182モル）を加えて200℃に昇温し、５時間反応し
た。Synthesis Example of TiCl 2 Pc In a reaction flask equipped with a thermometer, a stirrer, and a reflux condenser, 92 g (0.718 mol) of orthophthalodinitrile and 600 ml of α-chloronaphthalene were charged, and titanium tetrachloride 20m was stirred.
l (0.182 mol) was added, the temperature was raised to 200 ° C, and the reaction was carried out for 5 hours.
反応液を120℃に冷却したのち熱過し、得られたTiC
l2Pcの粗ケーキを120℃のα−クロロナフタレン500mlで
洗浄してTiCl2Pcの青色湿ケーキ109gを得た。The reaction solution was cooled to 120 ° C., and then heated.
The l 2 Pc crude cake was washed with 500 ml of α-chloronaphthalene at 120 ° C. to obtain 109 g of a blue wet cake of TiCl 2 Pc.
元素分析値（乾燥品）は次の通りであった。 Elemental analysis values (dry product) were as follows.
Ｃ Ｈ Ｎ Cl 理論値％ 60.88 2.55 17.75 11.23 実測値％ 60.74 2.41 17.64 11.14 実施例１ 温度計、撹拌器を備えた200ml反応フラスコに前記合
成例で得られたTiCl2Pcの湿ケーキ11gとフェノール110g
を仕込み、120℃に昇温して４時間撹拌したのち水11gを
加えて生成物を60℃で別し、メタノール110mlで洗浄
後乾燥して青色のフタロシアニン系化合物6.7gを得た。
粉末Ｘ線スペクトルを図−１に示す。また、元素分析値
は次の通りであった。C H N Cl Theoretical% 60.88 2.55 17.75 11.23 Actual% 60.74 2.41 17.64 11.14 Example 1 In a 200 ml reaction flask equipped with a thermometer and a stirrer, 11 g of the wet cake of TiCl 2 Pc obtained in the above Synthesis Example and 110 g of phenol were added.
After heating to 120 ° C. and stirring for 4 hours, 11 g of water was added, the product was separated at 60 ° C., washed with 110 ml of methanol and dried to obtain 6.7 g of a blue phthalocyanine compound.
The powder X-ray spectrum is shown in FIG. The elemental analysis values were as follows.
C60.15％、H3.38％、N16.39％、Cl0.46％、Ash（Ti
O2）11.68％ 得られたフタロシアニン系化合物6gを100ml試薬瓶に
仕込み、直径1mmのガラスビーズ40mlを加えてペイント
シェーカー（東洋精機製作所製No488型）で20時間振盪
して摩砕した。摩砕後の粉末Ｘ線回折スペクトルを図−
２に示す。次に摩砕したフタロシアニン系化合物5gを20
0mlフラスコに仕込み、水100mlとオルトジクロロベンゼ
ン8mlを加えて20℃で１時間撹拌後水層を除去し、メタ
ノール100mlで懸濁洗浄したのち乾燥して青色のTiOPcの
粉末4.6gを得た。得られたTiOPcは、図−３にその粉末
Ｘ線回析スペクトルを示す通り、ブラッグ角（２θ±0.
2°）27.3°に明瞭な回折ピークを有する結晶型のTiOPc
で、また、元素分析値は次の通りであった。C60.15 % , H3.38 % , N16.39 % , Cl0.46 % , Ash (Ti
O 2) of 11.68% obtained phthalocyanine compound 6g charged into 100ml reagent bottles and triturated with shaking for 20 hours in a paint shaker (manufactured by Toyo Seiki Seisakusho No488 type) with addition of glass beads 40ml of diameter 1 mm. Figure of powder X-ray diffraction spectrum after milling
It is shown in FIG. Next, 5 g of the ground phthalocyanine compound
A 0 ml flask was charged, 100 ml of water and 8 ml of orthodichlorobenzene were added, and the mixture was stirred at 20 ° C. for 1 hour, and the aqueous layer was removed. As shown in the powder X-ray diffraction spectrum of FIG. 3, the obtained TiOPc has a Bragg angle (2θ ± 0.
2 °) Crystalline TiOPc with a clear diffraction peak at 27.3 °
The elemental analysis values were as follows.
Ｃ Ｈ Ｎ 理論値％ 66.68 2.80 19.44 実測値％ 66.79 2.91 19.38 得られたTiOPc0.4gとポリビニルブチラール0.2gをｎ
−プロパノール30gと共にサンドグラインダーで６時間
分散し、この分散液をポリエステル上に蒸着したアルミ
蒸着層の上にワイヤーバーにより塗布、乾燥して電荷発
生層を形成させた。塗布着量は0.3g/m2である。この層
の薄膜Ｘ線回折スペクトルを図−４に示す。C H N Theoretical value% 66.68 2.80 19.44 Observed value% 66.79 2.91 19.38 0.4 g of the obtained TIOPC and 0.2 g of polyvinyl butyral were mixed with n.
-Dispersed for 6 hours with a sand grinder together with 30 g of propanol, and this dispersion was applied on an aluminum deposition layer deposited on polyester with a wire bar and dried to form a charge generation layer. The coating amount is 0.3 g / m 2 . The thin film X-ray diffraction spectrum of this layer is shown in FIG.
この電荷発生層の上に、Ｎ−メチル−３−カルバルデ
ヒドジフェニルヒドラゾン70部とｐ−ペンゾイルオキシ
ベンザルマロノニトリル1.5部及びポリカーボネート樹
脂100部からなる膜厚17μｍの電荷移動層を積層し、積
層型の感光層を有する電子写真感光体を得た。On this charge generation layer, a 17 μm-thick charge transfer layer comprising 70 parts of N-methyl-3-carbaldehyde diphenylhydrazone, 1.5 parts of p-benzozoyloxybenzalmalononitrile and 100 parts of a polycarbonate resin was laminated. Thus, an electrophotographic photosensitive member having a photosensitive layer was obtained.
この感光体の感度として半減露光量（E1/2）を静電複
写紙試験装置（川口電気製作所製モデルSP−428）によ
り測定した。即ち、暗所でコロナ電流が22μＡになるよ
うに設定した印加電圧によるコロナ放電により、感光体
を負帯電し、次いで1luxの照度の白色光により露光し、
表面電位が−450Vから225Vに半減するに要する露光量
（E1/2）を求めたところ、0.14lux・secであった。この
時の感光体の帯電圧（初期の表面電位）は−1080V、暗
減衰は56V/sec、露光10秒後の表面電位（残留電位）は
−20Vであった。The half-life exposure (E1 / 2) was measured as the sensitivity of the photoreceptor using an electrostatic copying paper tester (Model SP-428 manufactured by Kawaguchi Electric Works). That is, the photoreceptor is negatively charged by corona discharge with an applied voltage set so that the corona current becomes 22 μA in a dark place, and then exposed to white light having an intensity of 1 lux,
The exposure amount (E1 / 2) required to reduce the surface potential from -450 V to 225 V by half was 0.14 lux-sec. At this time, the charged voltage (initial surface potential) of the photoreceptor was -1080 V, the dark decay was 56 V / sec, and the surface potential (residual potential) after 10 seconds of exposure was -20 V.
実施例２〜６ TiCl2Pcの処理条件、中間体の摩砕条件及び芳香族炭
化水素の種類等を変化させた以外は実施例１と同様に実
験した結果を表−１に示す。Processing conditions of Example 2 to 6 TiCl 2 Pc, the results except for changing the type of grinding conditions and aromatic hydrocarbons intermediates such experimented in the same manner as in Example 1 shown in Table 1.
尚、実施例３及び４のフェノール類処理後のフタロシ
アニン系化合物（中間体）の粉末Ｘ線回折スペクトル
を、それぞれ図−５及び図−６に示す。The powder X-ray diffraction spectra of the phthalocyanine compounds (intermediates) after the treatment with phenols in Examples 3 and 4 are shown in FIGS. 5 and 6, respectively.
又、該中間体を、水と芳香族炭化水素との混合物で懸
濁洗浄して得られたTiOPc結晶は、いずれも実施例１と
同様ブラッグ角（２θ±0.2°）27.3°に明瞭な回折ピ
ークを有する結晶であった。In addition, all of the TiOPc crystals obtained by suspending and washing the intermediate with a mixture of water and an aromatic hydrocarbon showed a clear diffraction at a Bragg angle (2θ ± 0.2 °) of 27.3 ° as in Example 1. The crystals had peaks.
図−１及び図−２はそれぞれ実施例１で得られたフェノ
ール処理後及び摩砕後のフタロシアニン系化合物の粉末
Ｘ線回折スペクトルであり、図−３は実施例１で得られ
た水とオルトジクロロベンゼンの混合物処理後のTiOPc
の粉末Ｘ線回折スペクトルである。図−４は実施例１で
得られたTiOPcのサンドグラインダー分散後の薄膜Ｘ線
回折スペクトルである。 図−５及び図−６はそれぞれ実施例３及び実施例５のフ
ェノール類処理後に得られたフタロシアニン化合物の粉
末Ｘ線回折スペクトルである。FIGS. 1 and 2 are X-ray powder diffraction spectra of the phthalocyanine compound after phenol treatment and after grinding obtained in Example 1, respectively. FIG. TiOPc after treatment with a mixture of dichlorobenzene
2 is a powder X-ray diffraction spectrum of the sample. FIG. 4 is a thin-film X-ray diffraction spectrum of the TiOPc obtained in Example 1 after being dispersed by a sand grinder. FIGS. 5 and 6 are powder X-ray diffraction spectra of the phthalocyanine compounds obtained after the treatment with phenols in Examples 3 and 5, respectively.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C09B 67/12 G03G 5/06 371 ＣＡ（ＳＴＮ) ＣＡＯＬＤ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) C09B 67/12 G03G 5/06 371 CA (STN) CAOLD (STN) REGISTRY (STN)
Claims (2)
ブロモチタニウムフタロシアニンをフェノール類と接触
させた後摩砕し、次いで水と芳香族炭化水素の混合物で
処理することを特徴とするオキシチタニウムフタロシア
ニンの製造方法。1. A process for producing oxytitanium phthalocyanine, comprising contacting dichlorotitanium phthalocyanine or dibromotitanium phthalocyanine with a phenol, grinding the mixture, and then treating with a mixture of water and an aromatic hydrocarbon.
ブロモチタニウムフタロシアニンをフェノール類と接触
させた後摩砕し、次いで水と芳香族炭化水素の混合物で
処理して得られるオキシチタニウムフタロシアニンを電
荷発生剤に用いることを特徴とする電子写真感光体の製
造方法。2. An oxytitanium phthalocyanine obtained by contacting dichlorotitanium phthalocyanine or dibromotitanium phthalocyanine with a phenol and then grinding the mixture with water and an aromatic hydrocarbon to use the oxytitanium phthalocyanine as a charge generating agent. A method for producing an electrophotographic photoreceptor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5620890A JP2881921B2 (en) | 1990-03-07 | 1990-03-07 | Method for producing oxytitanium phthalocyanine and method for producing electrophotographic photoreceptor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5620890A JP2881921B2 (en) | 1990-03-07 | 1990-03-07 | Method for producing oxytitanium phthalocyanine and method for producing electrophotographic photoreceptor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03258860A JPH03258860A (en) | 1991-11-19 |
| JP2881921B2 true JP2881921B2 (en) | 1999-04-12 |
Family
ID=13020695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5620890A Expired - Fee Related JP2881921B2 (en) | 1990-03-07 | 1990-03-07 | Method for producing oxytitanium phthalocyanine and method for producing electrophotographic photoreceptor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2881921B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006131897A (en) * | 2004-10-04 | 2006-05-25 | Mitsubishi Chemicals Corp | Oxytitanium phthalocyanine composition, electrophotographic sensitizer and image formation device using the same |
| US8323861B2 (en) | 2006-05-18 | 2012-12-04 | Mitsubishi Chemical Corporation | Electrophotographic photoreceptor, image-forming apparatus, and electrophotographic cartridge |
-
1990
- 1990-03-07 JP JP5620890A patent/JP2881921B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006131897A (en) * | 2004-10-04 | 2006-05-25 | Mitsubishi Chemicals Corp | Oxytitanium phthalocyanine composition, electrophotographic sensitizer and image formation device using the same |
| US8323861B2 (en) | 2006-05-18 | 2012-12-04 | Mitsubishi Chemical Corporation | Electrophotographic photoreceptor, image-forming apparatus, and electrophotographic cartridge |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03258860A (en) | 1991-11-19 |
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