JPS63187248A - Electrophotographic sensitive body - Google Patents

Electrophotographic sensitive body

Info

Publication number
JPS63187248A
JPS63187248A JP1819787A JP1819787A JPS63187248A JP S63187248 A JPS63187248 A JP S63187248A JP 1819787 A JP1819787 A JP 1819787A JP 1819787 A JP1819787 A JP 1819787A JP S63187248 A JPS63187248 A JP S63187248A
Authority
JP
Japan
Prior art keywords
phthalocyanine
parts
photoreceptor
binder
coating
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.)
Granted
Application number
JP1819787A
Other languages
Japanese (ja)
Other versions
JPH0560866B2 (en
Inventor
Ichiro Yoshida
一郎 吉田
Shinichi Tamura
信一 田村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KINOSHITA KENKYUSHO KK
Toyo Ink SC Holdings Co Ltd
Original Assignee
KINOSHITA KENKYUSHO KK
Toyo Ink Mfg Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by KINOSHITA KENKYUSHO KK, Toyo Ink Mfg Co Ltd filed Critical KINOSHITA KENKYUSHO KK
Priority to JP1819787A priority Critical patent/JPS63187248A/en
Publication of JPS63187248A publication Critical patent/JPS63187248A/en
Publication of JPH0560866B2 publication Critical patent/JPH0560866B2/ja
Granted legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0696—Phthalocyanines
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/056—Polyesters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0575—Other polycondensates comprising nitrogen atoms with or without oxygen atoms in the main chain

Abstract

PURPOSE:To improve the dispersion stability of a coating compd. for a photosensitive body at the time of production thereof by dispersing phthalocyanine photoconductive powder into a binder consisting of polyester having a specific mol.wt. and acid value and melamine resin. CONSTITUTION:A mixture composed of the polyester having 500-5,000mol.wt. and 2-30 acid value and the melamine resin is used as the binder of the phthalocyanine photoconductive powder (e.g.: copper phthalocyanine powder). The photosensitive layer is formed by dispersing the above-mentioned components together with a solvent by a kneading and dispersing machine, then coating the mixture on a conductive based and crosslinking the coating by heating. The above-mentioned polyester can be synthesized by bringing arom. satd. acid such as phthalic anhydride, unsatd. acid such as maleic anhydride and diol such as diethylene glycol into condensation reaction. The dispersibility of the coating soln. is improved according to this constitution and, therefore, the photosensitive body having the excellent sensitivity, electric chargeability and durability is obtd.

Description

【発明の詳細な説明】 本発明は電子写真用感光体、特に複写機またはレーザー
プリンターに利用し得るフタロシアニン誘導体を絶縁性
高分子材料からなる結着材に分散させてなる単層型感光
体に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrophotographic photoreceptor, particularly a single-layer type photoreceptor that can be used in copying machines or laser printers and is made by dispersing a phthalocyanine derivative in a binder made of an insulating polymer material. .

（従来技術） 電子写真法は、既に、カールソンが米国特許第２．２９
７．６９１号に明らかにしたように、この写真法は光導
電性と静電現象とを巧妙に組み合わせたものであり、光
導電性感光体を暗所にて、コロナ放電等により表面を一
様に帯電させたのち、光導電性を利用して光像を静電潜
像に変え、これに着色した電荷粉体（トナー）を付着さ
せて可視像に変える画像形成法の一種である。(Prior art) The electrophotographic method has already been published by Carlson in U.S. Patent No. 2.29.
As disclosed in No. 7.691, this photographic method is a clever combination of photoconductivity and electrostatic phenomena, in which the surface of a photoconductive photoreceptor is uniformly exposed by corona discharge etc. in a dark place. This is a type of image forming method that uses photoconductivity to convert the optical image into an electrostatic latent image, which is then converted into a visible image by attaching colored charged powder (toner) to it. .

電子写真法における感光体に要求される基本的な電気的
特性として、暗所に於て適当な電位に帯電できること、
更に、光照射により速やかに電荷が逸散することが出来
ることなどが上げられろ。このような電子写真感光体の
光導電体素子として、従来より、アモルフフ　　マ　　
？ノ　　ＩＩ　　　−Ｔ　　’／　　　　　　マ　エ　
　ＩＬ　　−フ　　フ　　７　　→ツ　　１ノ　　ゝノ
ー　　　　薯　イｌｌｔドミウム、酸化亜鉛などの無機
材質が広く使用されてきた。これらの無機光導電性物質
は光導電特性は備えているものの、欠点も同時にある０
例えば硫化カドミウム、アモルファスセレンは公害物質
として人体に有害である。The basic electrical properties required of a photoreceptor in electrophotography are that it can be charged to an appropriate potential in a dark place;
Furthermore, the charge can be quickly dissipated by light irradiation. Conventionally, amorphous polymers have been used as photoconductor elements for such electrophotographic photoreceptors.
?ノ II -T' / Mae
Inorganic materials such as dome and zinc oxide have been widely used. Although these inorganic photoconductive materials have photoconductive properties, they also have drawbacks.
For example, cadmium sulfide and amorphous selenium are harmful to the human body as pollutants.

またアモルファスシリコンは製法が蒸着法によらなくて
はならず、製造コストが高価となる。近年これらの無機
系光導電性物質の欠点を排除するために、有機系感光体
の研究が進み、無公害性、可　性、製造の容易性、分光
感度の多様性等の多くの長所を生かして種々の有機系感
光体が考案され、実用に供されている。Furthermore, amorphous silicon must be manufactured by vapor deposition, resulting in high manufacturing costs. In recent years, in order to eliminate the drawbacks of these inorganic photoconductive materials, research into organic photoreceptors has progressed, making use of their many advantages such as non-pollution, flexibility, ease of manufacture, and diversity in spectral sensitivity. Various organic photoreceptors have been devised and put into practical use.

有機系感光体の光導電性素子として種々のものが上げら
れているが、中でもフタロシアニンは長波長光に感度を
有するためにレーザープリンターなどの感光体に用いら
れるようになってきた。しかしこれらのフタロシアニン
有機系感光体については実用的には電荷発生層と電荷輸
送層とを分離した積層型感光体として用いられている。Various types of photoconductive elements have been proposed for organic photoreceptors, and among them, phthalocyanine has come to be used in photoreceptors such as laser printers because it is sensitive to long wavelength light. However, these phthalocyanine organic photoreceptors are practically used as laminated photoreceptors in which a charge generation layer and a charge transport layer are separated.

これら積層型感光体はコロナ放電器により負帯電にて用
いられているために、負のコロナ放電器により発生する
オゾン量は正のコロナ放電器に比べ約１０倍もの量に達
する。この為、連続使用に際しては、室内のオゾン濃度
が高くなり、労働衛生法上支障を来すことが知られてい
る。さらに、感光体においても発生するオゾンのため電
解質が副次的に発生し、表面汚染を起こし易く、感光体
寿命が短くなる欠点が指摘されている。Since these laminated photoreceptors are used while being negatively charged by a corona discharger, the amount of ozone generated by a negative corona discharger reaches about 10 times that of a positive corona discharger. For this reason, it is known that when used continuously, the indoor ozone concentration increases, causing problems under the Industrial Health Act. Furthermore, it has been pointed out that electrolyte is generated as a secondary product due to ozone generated in the photoreceptor, which tends to cause surface contamination and shortens the life of the photoreceptor.

ところで、フタロシアニンはＰ型半導体であるために、
これを分散型感光体として用いれば、正帯電での使用が
可能である。、そこで、フタロシアニンを分散型感光体
として用いるための試みは従来から多く検討されている
。By the way, since phthalocyanine is a P-type semiconductor,
If this is used as a dispersion type photoreceptor, it can be used with positive charging. Therefore, many attempts have been made to use phthalocyanine as a dispersed photoreceptor.

たとえば、特開昭５９−１０５５５０号公報では特定の
フェノール樹脂を用いてフタロシアニン系顔料を均一に
分散させ、感度を向上させる方法、特開昭５７−１８５
０４４号公報ではポリ−Ｎ−ビニルカルバゾールおよび
分子量５０００−４００，０００のポリエステル樹脂の
混合物からなる結着材を用いて感度の向上をはかってい
る。特開昭５９−１５２５０号及び特開昭５９−２１９
７５２号公報では分子量２０００−４００００のアクリ
ル樹脂とメラミン樹脂等を混合して結着材に用い、繰り
返し使用時の耐剛性等を改善している。また特開昭６０
−２０７１４５号公報では結着材としてポリエステル、
ポリカーボネート、及びアクリル樹脂の混合物を用いる
ことで耐湿性を向上させている。For example, JP-A-59-105550 discloses a method for improving sensitivity by uniformly dispersing phthalocyanine pigments using a specific phenol resin, JP-A-57-185.
No. 044 attempts to improve sensitivity by using a binder made of a mixture of poly-N-vinylcarbazole and a polyester resin having a molecular weight of 5,000 to 400,000. JP-A-59-15250 and JP-A-59-219
No. 752 uses a mixture of acrylic resin with a molecular weight of 2,000 to 40,000, melamine resin, etc. as a binder to improve stiffness during repeated use. Also, JP-A-60
-207145 publication uses polyester as a binder,
Moisture resistance is improved by using a mixture of polycarbonate and acrylic resin.

これらの技術では個々の目的とする効果は得られるもの
の、総合的に電子写真特性の優れた分散単層型感光体と
して実用的に供するには未だ十分とは言えない０例えば
、従来結着材成分として用いられてきたアクリル樹脂は
分子量が２０００−４００００の例があるが、分子量２
００００程度では液状を呈し、また分子量２００００以
上では有機溶剤への溶解が困難であるため結着材として
は実用的に使用可能な範囲は分子ｉｌｌ　００００−２
００００であるが、この分子量範囲のものでもフタロシ
アニン粒子の被覆状態が不完全であるために暗減衰率が
大きく実用的には支障を来す。Although each of these techniques can achieve the desired effect, it is still not sufficient to provide a practical dispersed single-layer photoreceptor with comprehensive electrophotographic properties. There are examples of acrylic resins used as components having a molecular weight of 2,000 to 40,000;
If the molecular weight is about 0000, it becomes liquid, and if the molecular weight is more than 20,000, it is difficult to dissolve in organic solvents, so the range that can be practically used as a binder is the molecular ill 0000-2.
0,000, but even in this molecular weight range, the dark decay rate is large and poses a problem in practical use because the phthalocyanine particles are incompletely coated.

し使用時に帯電電位が低下してしまうことである。電子
写真感光体として帯電できない状態は致命的な欠点とい
わなければならない。However, the charging potential decreases during use. The inability to charge an electrophotographic photoreceptor is a fatal drawback.

フタロシアニンを実用感度を持たせた上で分散型感光体
として実用化するための問題点としては、　（１）帯電
、露光の繰り返しによって帯電電位が低下すること、　
（２）光照射直後の表面電位の減衰に遅れを生じる、い
わゆるインダクションと称する誘導期間を有するため、
あたかも感度が低下したかのような現象を有する。　（
３）感光体を製造する塗工工程においてフタロシアニン
の分散が困難であるため分散塗液を製造することが難し
いこと、　（４）湿度や酸性雰意気ガス下に於て感度や
帯電性の劣化が起こることなどが上げられる。　（１）
、　（２）、　（４）に間しては光導電体として用いる
場合の基本的な問題であるが、この原因としては、フタ
ロシアニンより発生したキャリアーがフタロシアニンと
結着材との界面や結着材中にトラップされること、ある
いは、帯電、露光による繰り返し時ンやＮＯＸによる感
光体表面の劣化等が主な原因として考えられている。と
ころで、分散型感光体では電荷保持を行う層は感光体表
面の極薄い部分にあり、そこにおけるフタロシアニンの
状態が帯電性や感度に大きく影響する。ところでフタロ
シアニンは、ＮＯＸの吸着センサーとして用いられるこ
とが知られているように、ＮＯＸ等のアクセプター物質
を吸着する。この様な性質のため、フタロシアニンの含
有量を多くすると電子写真プロセスの中で発生するオゾ
ン、ＮＯＸの吸着により耐久性が著しく下がる。しかし
実際の感光体を使用する環境下においては更に種々の有
害物質が存在し、これらを吸着することにより、複合的
な汚染効果も起こし耐久性が下がる。The problems with practical use of phthalocyanine as a dispersion type photoreceptor with practical sensitivity are: (1) the charging potential decreases due to repeated charging and exposure;
(2) It has an induction period called induction, which causes a delay in the decay of the surface potential immediately after light irradiation.
The phenomenon appears as if the sensitivity has decreased. (
3) It is difficult to disperse phthalocyanine in the coating process for producing photoreceptors, making it difficult to produce a dispersion coating solution; (4) Sensitivity and chargeability deteriorate under humidity and acidic atmospheric gases. Things that happen are mentioned. (1)
, (2), and (4) are fundamental problems when used as a photoconductor, and the reason for this is that the carriers generated from the phthalocyanine may cause damage to the interface between the phthalocyanine and the binding material, or to the binding material. The main causes are thought to be trapping in the material, deterioration of the surface of the photoreceptor due to repeated charging and exposure, and NOx. Incidentally, in a dispersion type photoreceptor, the layer for charge retention is located in an extremely thin portion of the surface of the photoreceptor, and the state of phthalocyanine there greatly affects charging properties and sensitivity. By the way, phthalocyanine adsorbs acceptor substances such as NOX, as is known to be used as a NOX adsorption sensor. Due to these properties, when the content of phthalocyanine is increased, the durability is significantly reduced due to the adsorption of ozone and NOX generated during the electrophotographic process. However, in the actual environment in which the photoreceptor is used, there are various other harmful substances, and adsorption of these substances causes a complex contamination effect and reduces durability.

これらの吸着を防ぐには感光体の表面に保護層を設ける
とか、酸化防止材などの添加剤を添加させ防止するなど
の方法もあるが機械的耐久性や静電特性が損なわれるこ
とより本質的なものではない。本質的には結着材中のフ
タロシアニンを十分にバリアー性をもたすように被覆す
るか、使用するフタロシアニンの結着材中の量を低くし
なければならない。There are methods to prevent these adsorptions, such as providing a protective layer on the surface of the photoreceptor or adding additives such as antioxidants, but this is essential as it impairs mechanical durability and electrostatic properties. It's not a typical thing. Essentially, the phthalocyanine in the binder must be coated to provide sufficient barrier properties, or the amount of phthalocyanine used in the binder must be reduced.

しかし、今まで知られている結着材組成物に於てフタロ
シアニンを被覆したり、フタロシアニンの量を減らした
場合、キャリアーの減少やキャリアートラップの点から
感度の低下や静電特性の変化などの副作用が起こる。ま
た（２）に間してはフタロシアニンと結着材を混合さ゛
せる際に電子吸引物質、例えばジクロルベンゾキノン等
を添加する方法が知られているが暗減衰が増加する等の
欠陥が現われる。また（３）における製造上の問題点と
しては感光層表面における平滑性の不足、あるいは感光
層内部でのフタロシアニンの凝集物にもとずく画質上の
ノイズや、画像品質の安定性にもかかわる問題である。However, when coating with phthalocyanine or reducing the amount of phthalocyanine in the binder compositions known so far, there are problems such as a decrease in sensitivity and changes in electrostatic properties due to a decrease in carriers and carrier traps. Side effects occur. Regarding (2), a method is known in which an electron-withdrawing substance such as dichlorobenzoquinone is added when mixing the phthalocyanine and the binder, but this method suffers from defects such as increased dark decay. In addition, manufacturing problems related to (3) include insufficient smoothness on the surface of the photosensitive layer, noise in image quality due to aggregates of phthalocyanine inside the photosensitive layer, and problems related to stability of image quality. It is.

フタロシアニンは顔料として、インク、ペイントにも多
く用いられているが、これらの用途では界面活性剤を用
いて分散を補助することが行なわれている。しかし、電
子写真感光体では電気抵抗の関係から、これら低抵抗物
質である界面活性剤の使用は帯電性の低下をもたらすた
めに使用することがａ来ない。Phthalocyanine is often used as a pigment in inks and paints, and in these applications, surfactants are used to assist in dispersion. However, in electrophotographic photoreceptors, due to electrical resistance, the use of surfactants, which are low-resistance substances, leads to a decrease in charging properties, so they cannot be used.

（発明の目的） 本発明者らはフタロシアニンを用いた分散単層型感光体
において、電子写真特性に有害な添加剤などを使用する
ことなく、感光体塗液製造時での分散安定性を向上させ
、更に電子写真特性における上述の欠点を改良、向上さ
せることにある。(Purpose of the Invention) The present inventors have improved the dispersion stability during the production of a photoreceptor coating liquid in a dispersed single-layer photoreceptor using phthalocyanine without using additives harmful to electrophotographic properties. The object of the present invention is to further improve and improve the above-mentioned defects in electrophotographic properties.

（発明の構成） 本発明者らは上述の目的を達成することを試み、莫大な
種類の結着材の組成物とフタロシアニンとの組合せによ
り鋭意研究を行った結果、ニトロ基等の電子吸引基を含
有する金属フタロシアニンを感光成分とする電子写真感
光体において、結着材として特定の低分子ポリエステル
樹脂および低分子メラミン樹脂を併用して用いることに
より、分散性を同上させ、更に、感光体の感度の保障、
繰り返し帯電特性の安定性を向上させ、耐久性の優れた
長寿命感光体を得ることを発見し、本発明に至った。(Structure of the Invention) The present inventors attempted to achieve the above-mentioned object, and as a result of conducting intensive research using a vast variety of binder compositions in combination with phthalocyanine, we found that electron-withdrawing groups such as nitro groups In an electrophotographic photoreceptor whose photosensitive component is a metal phthalocyanine containing Guaranteed sensitivity,
It was discovered that the stability of repeated charging characteristics can be improved, and a long-life photoreceptor with excellent durability can be obtained, leading to the present invention.

本発明に係わる感光体の構成は、フタロシマー１ノ工宿
轡紳館７＋　ｆ−ＪＪ　１１〒η二１１恨陽七しびメラ
ミン樹脂の混合物からなること結着材に分散させて作ら
れた単層型感光体から成るものである。The structure of the photoreceptor according to the present invention is that it is made of a mixture of melamine resin and a melamine resin dispersed in a binder. It consists of a layered photoreceptor.

本発明に係わるフタロシアニンとしては無金属フタロシ
アニンおよび、金属フタロシアニン、あるいはこれらの
混合物である。金属フタロシアニンの金属としては銅、
銀、ベリリウ、マグネジろム、カルシウム、亜鉛、カド
ミウム、ベリリウム、マグネシウム、水銀、ガリウム、
インジウム、ランタン、ネオジウム、チタン、錫、鉛、
バナジウム、アンチモン、クロム、モリブデン、ウラン
、マンガン、鉄、コバルト、パラジウム、アルミニウム
、銀および白金などである。また、フタロシアニンの中
心核として金属原子ではなく、３価以上の原子価を有す
るハロゲン化金属であってもよい、更に、低ハロゲン化
フタロシアニンであってもよい、なお、フタロシアニン
はどのような製法によって得られたフタロシアニンであ
ってもよく、クルードと称されているフタロシアニンは
勿論、ＩＪＮ化されたフタロ９ア二′７か田いＴ鹸、）
１１−　寸へ　１七門、−ノアニンは合成法、精製法、
顔料化の条件によって種々の結晶型が得られることが知
られている。例えば、銅フタロシアニンにおいては、α
型、　β型、　τ型、　δ型、　ε型、　Ｘ型、　また
、無金属フタロシアニンにおいてもα型、β型、τ型、
δ型、ε型、Ｘ型、τ型等が知られているが本発明はこ
れ等の結晶型に限定されるものではない、しかし、好ま
しくは光導電性にすぐれたフタロシアニンを用いること
が望ましく、これらとしては特公昭４５−８１０２号、
特公昭４５−１１０２１号、特公昭４６−４２５１１号
、特公昭４８−１６３号、特公昭４９−１７５３５号、
特公昭５０−５０５９号、特公昭５０−３８５４３号公
報等に記載されている光導電性フタロシアニン系化合物
である。The phthalocyanine according to the present invention includes metal-free phthalocyanine, metal phthalocyanine, or a mixture thereof. The metal of metal phthalocyanine is copper,
Silver, beryllium, magnesium, calcium, zinc, cadmium, beryllium, magnesium, mercury, gallium,
Indium, lanthanum, neodymium, titanium, tin, lead,
These include vanadium, antimony, chromium, molybdenum, uranium, manganese, iron, cobalt, palladium, aluminum, silver and platinum. In addition, the central nucleus of the phthalocyanine may not be a metal atom, but may be a metal halide having a valence of 3 or more, and may also be a low-halogenated phthalocyanine. The obtained phthalocyanine may be used, including phthalocyanine called crude, as well as IJN-formed phthalocyanine, etc.)
11- To the 17th gate, - Noanine is a synthesis method, a purification method,
It is known that various crystal forms can be obtained depending on the pigmentation conditions. For example, in copper phthalocyanine, α
type, β type, τ type, δ type, ε type, X type, and also for metal-free phthalocyanine, α type, β type, τ type,
Although δ-type, ε-type, X-type, τ-type, etc. are known, the present invention is not limited to these crystal forms. However, it is preferable to use phthalocyanine having excellent photoconductivity. , these include Special Publication No. 45-8102,
Special Publication No. 45-11021, Special Publication No. 46-42511, Special Publication No. 163-1973, Special Publication No. 17535-1977,
It is a photoconductive phthalocyanine compound described in Japanese Patent Publication No. 50-5059, Japanese Patent Publication No. 38543-1980, etc.

即ち、フタロシアニン光導電材料としてはフタロシアニ
ン分子中のベンゼン核の水素原子がニトロ基、シアノ基
、ハロゲン基、スルホン基、及びカルボキシル基からな
る群から選ばれた少なくとも１種の電子吸引性基で置換
されたフタロシアニン誘導体と、金属フタロシアニン及
び無金属フタロシアニンの少なくとも１種とを、それら
と塩を形成しろる無機酸例えば濃硫酸と混合し、水また
は塩基性物質によって析出させることによって得られる
フタロシアニン光導電性組成物を使用することが好まし
い。That is, in the phthalocyanine photoconductive material, the hydrogen atom of the benzene nucleus in the phthalocyanine molecule is substituted with at least one electron-withdrawing group selected from the group consisting of a nitro group, a cyano group, a halogen group, a sulfone group, and a carboxyl group. A phthalocyanine photoconductive material obtained by mixing the phthalocyanine derivative obtained above and at least one of a metal phthalocyanine and a metal-free phthalocyanine with an inorganic acid, such as concentrated sulfuric acid, which forms a salt with them, and precipitating the mixture with water or a basic substance. Preferably, a sexual composition is used.

感光体に用いられる結着材は高抵抗でありかつ、キャリ
アーが結着材中にトラップされずに速やかに移動するこ
と、また、フタロシアニンより発生されるキャリアーが
速やかに結着材中に注入されなければならない。このた
めには、フタロシアニンと結着材との接触が十分かつ密
でなくてはならない。即ち、用いられる結着材とフタロ
シアニンとの親和性が大であり、かつ十分にフタロシア
ニン粒子を被覆していなくてはならない。そのためには
フタロシアニン粒子表面に配向し易く、吸着し易い結着
材分子の形状として、直鎖に近い形を有し、分子量の小
さなものが適していることを知った。更に、フタロシア
ニン粒子表面に配向しやすくまた吸着し易くなるための
要素として、フタロシアニンが塩基性物質であることに
より、フタロシアニンとの親和性を持つためには酸性物
質であることが好ましい、しかし、余り強く吸着するよ
うな酸性物質は通常電気抵抗は低い。あるいは、そうで
なくても、この様な物質でフタロシアニンを被覆した場
合、帯電時の電界によっても電荷を保持するための電気
的に良好な界面が形成され難いため、感光体として用い
る場合、電荷の保持が成されない、また、感光塗液の製
造に間しても長期の分散安定性が良くない。The binder used for the photoreceptor has high resistance, and the carrier is not trapped in the binder and moves quickly, and the carrier generated from phthalocyanine is quickly injected into the binder. There must be. For this purpose, the contact between the phthalocyanine and the binder must be sufficient and intimate. That is, the binder used must have a high affinity with the phthalocyanine, and must sufficiently cover the phthalocyanine particles. For this purpose, we have learned that the shape of binder molecules that are close to linear and have a small molecular weight is suitable because they are easily oriented and adsorbed onto the surface of phthalocyanine particles. Furthermore, since phthalocyanine is a basic substance, it is preferable to use an acidic substance in order to have an affinity with phthalocyanine, which makes it easier to align and adsorb onto the surface of phthalocyanine particles. Acidic substances that are strongly adsorbed usually have low electrical resistance. Alternatively, if phthalocyanine is coated with such a substance, it is difficult to form an electrically good interface for retaining charge even in the electric field during charging, so when used as a photoreceptor, the charge Moreover, the long-term dispersion stability during the production of photosensitive coating liquids is also poor.

従って、適当な酸性度を有してなくてはならない。酸性
度としては、カルボキシル基程度の酸性度が好ましく、
また、酸価が２−３０の間の低分子ポリエステル樹脂が
優れていることが分かった。しかし、低分子ポリエステ
ル樹脂はその分子の形状から考えて、フタロシアニン粒
子表面への吸着能に優れており、フタロシアニン粒子の
被覆性が優れている特徴がある反面、もろい固形物であ
るので単独で結着材として用いた場合には機械的に非常
に弱い感光層しか得られず、このままでは使を保持する
ことを更に考慮すれば、塩基性を有する化合物の併用が
分散安定性を向上させることに大きな効果があることを
見いだした。Therefore, it must have appropriate acidity. The acidity is preferably about the same as a carboxyl group,
Furthermore, it has been found that low molecular weight polyester resins having an acid value between 2 and 30 are excellent. However, considering the shape of its molecules, low-molecular polyester resins have excellent adsorption ability to the surface of phthalocyanine particles and are characterized by excellent coverage of phthalocyanine particles. When used as an adhesion material, only a mechanically very weak photosensitive layer is obtained, and considering that it will retain its usefulness if left as is, the combination of a basic compound will improve the dispersion stability. I found that it had a big effect.

これらの塩基性化合物はフタロシアニン粒子表面に配向
したポリエステル樹脂分子の吸着間係を乱すものであっ
てはならない、更に、ポリエステル樹脂分子の多くの官
能基はフタロシアニン粒子°表面への吸着能に優れてい
る為に、粒子の被覆性、分散性、静電特性に寄与してい
るのであり、これらの吸着平衡が損なわれてはならない
。これらの条件を満たす化合物としてメラミン化合物が
適していることを見いだした。These basic compounds must not disturb the adsorption relationship of the polyester resin molecules oriented on the surface of the phthalocyanine particles.Furthermore, many functional groups of the polyester resin molecules have excellent adsorption ability on the surface of the phthalocyanine particles. Therefore, it contributes to the coverage, dispersibility, and electrostatic properties of the particles, and the adsorption equilibrium of these must not be impaired. We have found that melamine compounds are suitable as compounds that meet these conditions.

本発明では、低分子メラミン樹脂を併用することによっ
て、ポリエステル樹脂分子の多くの官能基はフタロシア
ニン粒子に吸着しており、フタロシアニンの被覆に関与
しているが、ポリエステル樹脂分子末端の一部のカルボ
キシル基または水酸基はメラミン樹脂のブチル化メチロ
ール基との間で加熱することにより縮合反応を起こし、
架橋させて強固な感Ｎ轟　ＭＬ　　づ！　ス　ｙ　し　
礒イ　プ　壽　ス　　　　寸　九　　　　７　小　ｔｋ
　尊　倉す樹脂組成物を用いた場合、フタロシアニンの
分散性の向上のみならず、使用するフタロシアニンの量
を今まで知られている結着材樹脂に比べて使用するフタ
ロシアニンの量を４０％程削減できることが分かった。In the present invention, by using a low-molecular-weight melamine resin in combination, many functional groups of the polyester resin molecules are adsorbed to the phthalocyanine particles and are involved in coating the phthalocyanine particles, but some of the carboxyl groups at the terminals of the polyester resin molecules The group or hydroxyl group causes a condensation reaction by heating with the butylated methylol group of the melamine resin,
Cross-linked to create a strong feeling N Todoroki ML! S y shi
7 small tk
When using Takakurasu's resin composition, it not only improves the dispersibility of phthalocyanine, but also reduces the amount of phthalocyanine used by approximately 40% compared to conventional binder resins. I found out that it can be done.

感光体表面の硬度は鯖筆硬度で２Ｈてあった。これは現
在実用札、寝ている積層型有機感光体の表面硬度が鉛筆
硬にでＢからＨＢ程度であるのに比べ、はるかに　゛）
ことが認められる。これによって感光体が現像時、クリ
ーニング時、転写時に受ける機械的な摩擦力に対する抵
抗力は増大する。さらに、良分散状態の効果として感光
体の表面平滑性が向上し、画質の向上、種々の環境下に
おいてもフタロシアニン粒子が樹脂に十分に被覆されて
いることに耐環境性に間して、より著しい向上が認めら
れた。The hardness of the surface of the photoreceptor was 2H in terms of mackerel brush hardness. This is much higher than the surface hardness of the laminated organic photoreceptors currently used in practical banknotes, which are pencil hard, ranging from B to HB.
It is recognized that This increases the resistance to mechanical frictional forces that the photoreceptor receives during development, cleaning, and transfer. Furthermore, as a result of the well-dispersed state, the surface smoothness of the photoreceptor improves, image quality improves, and the phthalocyanine particles are sufficiently coated with the resin even under various environments, which improves environmental resistance. A significant improvement was observed.

本発明に係わる結着材樹脂として使用されるポリエステ
ル樹脂の原料としては無水フタル酸、テレフタル酸等の
芳香族飽和酸、ヘキサドロ無水フタル酸、コハク酸、ア
ゼライン酸等の脂肪族飽和酸、無水マレイン酸等の不飽
和酸を多塩基酸成分として、少なくとも１種また、多価
アルコール成分としては、エチレングリコール、プロピ
レングリコール、ジエチレングリコール、ジプロピレン
グリコール等のジオール類のうち少なくとも１種を縮合
反応させ分子量が５００−５０００．　　酸価が２−３
０が源正である。Raw materials for the polyester resin used as the binder resin in the present invention include aromatic saturated acids such as phthalic anhydride and terephthalic acid, aliphatic saturated acids such as hexadrophthalic anhydride, succinic acid, and azelaic acid, and maleic anhydride. At least one unsaturated acid such as an acid is used as a polybasic acid component, and as a polyhydric alcohol component, at least one diol such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, etc. is subjected to a condensation reaction to obtain a molecular weight is 500-5000. Acid value is 2-3
0 is Genmasa.

低分子メラミン樹脂としてはメラミンとホルマリンとの
縮合物も用いられるが、ポリエステル樹脂との相溶性の
点からブチルアルコールによるエーテル化合物が好まし
い。ポリエステル樹脂の分子量が適正な範囲を越えて大
きくなるとメラミン樹脂との相溶性を損なうので好まし
くない。Although a condensate of melamine and formalin can be used as the low-molecular melamine resin, an ether compound made of butyl alcohol is preferred from the viewpoint of compatibility with the polyester resin. It is not preferable that the molecular weight of the polyester resin exceeds the appropriate range because it impairs its compatibility with the melamine resin.

ポリエステル樹脂とメラミン樹脂の配合比については固
形分比でポリエステル樹脂１００！量部に対してメラミ
ン樹脂１０−５０重量部である。メラミン樹脂が多くな
るに従って塗膜硬度が上昇するが硬化速度が遅くなる・
フタロシアニン光導電性粉末と結着材との配合比はフタ
ロシアニンの量が増加するに従い感度は向上するが暗減
衰が増大して電荷の保持が難しくなり、実用性が乏しく
なるので結着材固形分１００！量部に対してフタロシア
ニンの量は１２−５０重ｊ１部の範囲が選ばれるが、環
境性や分散性、機械的強度の点から１２−３０重量％が
好ましい。Regarding the blending ratio of polyester resin and melamine resin, the solid content ratio is 100% polyester resin! The amount is 10-50 parts by weight of melamine resin. As the amount of melamine resin increases, the hardness of the coating increases, but the curing speed slows down.
As the amount of phthalocyanine increases, the sensitivity improves, but the dark decay increases, making it difficult to retain charge and impractical, so the solid content of the binder increases. 100! The amount of phthalocyanine is selected in the range of 12 to 50 parts by weight, but from the viewpoint of environmental friendliness, dispersibility, and mechanical strength, it is preferably 12 to 30 parts by weight.

本発明は上述したフタロシアニン光導電性粉末とポリエ
ステル樹脂、メラミン樹脂を所定の比率でシクロヘキサ
ノン、酢酸エチル、セロソルブ等の溶剤に溶解した溶液
中に均一に分散させ、得られた塗液を導電性基体上に塗
布乾燥させることにより完成される。感光層の厚みは５
−３０ミクロンとすることが好ましい。乾燥条件として
は１００℃−１８０℃の加熱下で１０分−３０分である
ことが好ましい。乾燥が不十分の場合では暗抵抗が低下
して帯電性を損ない、過剰に高温下で乾燥した場合は感
度低下をきたす。The present invention involves uniformly dispersing the above-mentioned phthalocyanine photoconductive powder, polyester resin, and melamine resin in a solution in a solvent such as cyclohexanone, ethyl acetate, or cellosolve at a predetermined ratio, and applying the resulting coating liquid to a conductive substrate. It is completed by applying it on top and letting it dry. The thickness of the photosensitive layer is 5
-30 microns is preferred. The drying conditions are preferably 10 minutes to 30 minutes under heating at 100°C to 180°C. If the drying is insufficient, the dark resistance decreases and the chargeability is impaired, and if the drying is excessively high, the sensitivity decreases.

本発明に係わる組成物を電子写真感光体として使用する
には該組成物を結着材樹脂、溶剤等と共に、ボールミル
、アトライター等の混線分散機で均一に分散させ、導電
支持体上しては、必要ならば光導電性組成物に溶剤を加
えて粘度を調整し、エアードクターコター、ブレードコ
ーター、ロッドコーター、リバースロールコータ−、ス
プレーコーター、ホットコーター、スプレーコーター、
ディプコーター等の塗布方法で皮膜形成を行う。塗布後
、光導電性層として十分な帯電電荷を受容するようにな
るまで適当な乾燥装置を用いて乾燥を行う。In order to use the composition according to the present invention as an electrophotographic photoreceptor, the composition is uniformly dispersed together with a binder resin, a solvent, etc. using a mixed wire dispersion machine such as a ball mill or an attritor, and then placed on a conductive support. If necessary, add a solvent to the photoconductive composition to adjust the viscosity, and use an air doctor coater, blade coater, rod coater, reverse roll coater, spray coater, hot coater, spray coater,
Form a film using a coating method such as a dip coater. After coating, the photoconductive layer is dried using a suitable drying device until it accepts a sufficient electrical charge.

本発明の電子写真感光体に用いる支持体としては、導電
性が付与されていればいずれのものでも良く、従来用い
られているいずれのタイプの導電層であってもさしつか
えない。The support used in the electrophotographic photoreceptor of the present invention may be any support as long as it is endowed with conductivity, and any type of conductive layer conventionally used may be used.

具体的には、アルミニウム、銅、ステンレス、真ちゅう
等の金属、アルマイト、酸化インジウムや酸化錫などを
蒸着またはラミネートしたプラスチックあるいは導電性
粒子、例えばカーボンブラック、錫粒子、アルミニウム
粒子を分散したプラスチックなどを挙げることが出来る
。また、その形状については、シート上、その他のもの
であっても差し支えない。Specifically, metals such as aluminum, copper, stainless steel, and brass, alumite, plastics with vapor-deposited or laminated indium oxide, tin oxide, etc., or plastics with conductive particles such as carbon black, tin particles, and aluminum particles dispersed therein are used. I can list them. Moreover, the shape may be on a sheet or other shapes.

ナ１１お　＋ｂ賄戸１プ轡ヱ譬宵隨班汁を油ｍする際に
、光源は通常のハロゲンランプ等の他・感度が７５０部
ｍ以上にもあるために、ガリウムーアルミニウムーヒ素
半導体レーザー（発振波長７８０ｎｍ）の様なレーザー
光を用いることも出来る。When dipping the soup into oil, the light source is not only a normal halogen lamp but also a gallium-aluminum-arsenic semiconductor, which has a sensitivity of more than 750 parts. Laser light such as a laser (oscillation wavelength 780 nm) can also be used.

以下に実施例を持って具体的に説明する。This will be explained in detail below using examples.

実施例１ 無水フタル酸２２２部（重量部を示す、以下省略）、無
水マレイン酸４９部、ジエチレングリコール２３３部を
窒素ガス雰囲気中で加熱反応させ、酸価が１５になるま
で反応を続けた。得られたポリエステル樹脂は淡黄色の
もろｃ１固形樹脂で分子量は約３０００であった。Example 1 222 parts of phthalic anhydride (indicated by weight, omitted below), 49 parts of maleic anhydride, and 233 parts of diethylene glycol were heated and reacted in a nitrogen gas atmosphere, and the reaction was continued until the acid value reached 15. The obtained polyester resin was a pale yellow solid resin with a molecular weight of about 3,000.

別に鋼フタロシアニン４０部、テトラニトロ銅フタロシ
アニン０．　５部を９８％Ｓ硫酸５００部に十分攪　し
ながら溶解する。溶解した液を水５０００部にあけ、銅
フタロシアニン、テトラニトロ銅フタロシアニンの組成
物を析出させた後、口過、水洗し、減圧下１２０℃で乾
燥して光導電性粉体を得た。Separately, 40 parts of steel phthalocyanine, 0.0 parts of tetranitro copper phthalocyanine. Dissolve 5 parts in 500 parts of 98% S sulfuric acid with thorough stirring. The dissolved solution was poured into 5,000 parts of water to precipitate a composition of copper phthalocyanine and tetranitrocopper phthalocyanine, followed by filtration, washing with water, and drying at 120° C. under reduced pressure to obtain a photoconductive powder.

ポリエステル樹脂１２．６ｆＢ、メラミン樹脂（スパー
ベッカミン−１０９−６部５大日本インキ化学（株）製
）５．０部、先に作られた鋼フタロシアニン４部、シク
ロへキサノン７５部からなる組成物を磁性ボールミルに
て２４時間混練して光導電性塗液を得た。次に厚さ８０
ミクロンのアルミニウム箔上に乾燥膜厚が１５ミクロン
になるようにコートし、１３０℃で３０分間加熱乾燥さ
せ、電子写真感光体とした。Composition consisting of 12.6 fB of polyester resin, 5.0 parts of melamine resin (Super Beckamine-109-6 parts, manufactured by Dainippon Ink Chemical Co., Ltd.), 4 parts of the steel phthalocyanine made earlier, and 75 parts of cyclohexanone. The material was kneaded for 24 hours in a magnetic ball mill to obtain a photoconductive coating liquid. Next, the thickness is 80
It was coated on micron aluminum foil to a dry film thickness of 15 microns, and dried by heating at 130° C. for 30 minutes to obtain an electrophotographic photoreceptor.

この感光体の最大表面電位は＋１２００ボルトであり実
用的には＋６００ボルト程度で使用するため帯電能は十
分な余裕を有する。The maximum surface potential of this photoreceptor is +1200 volts, and since it is practically used at about +600 volts, the charging capacity has sufficient margin.

゛暗減衰率は５秒後で７％、半減値感度は３ルツクス、
秒、残留電位は２０ボルトであった。゛Dark decay rate is 7% after 5 seconds, half-value sensitivity is 3 lux,
seconds, the residual potential was 20 volts.

帯電、露光の繰り返し、１００００回後の帯電電位は・
はとんど変化しなかフた。また感度変化もほとんど認め
られなかった。The charging potential after 10,000 repetitions of charging and exposure is...
There was almost no change. In addition, almost no change in sensitivity was observed.

実施例２ 無水フタル酸２２２部（重量部を示す。以下省略）、無
水マレイン酸４９部、ジエチレングリコール２６９．５
部を窒素ガス雰囲気中で加熱反応させ、酸価が７になる
まで反応を続けた。得られたポリエステル樹脂は淡黄色
のもろい固形樹脂で分子量は約３２００であった。Example 2 222 parts of phthalic anhydride (indicates parts by weight, omitted below), 49 parts of maleic anhydride, 269.5 parts of diethylene glycol
The mixture was heated and reacted in a nitrogen gas atmosphere, and the reaction was continued until the acid value reached 7. The obtained polyester resin was a pale yellow brittle solid resin with a molecular weight of about 3,200.

次に、実施例１で得られた鋼フタロシアニン４部、ポリ
エステル樹Ｔｆ１１２．６部、メラミン樹脂（スパーベ
ッカミン−１０９−６５大日本インキ化学（株）製）５
．０部、先に作られた銅フタロシアニン４部、シクロへ
キサノン７５部からなる組成物を磁性ボールミルにて２
４時間混練して光導電性塗液を得た。Next, 4 parts of steel phthalocyanine obtained in Example 1, 112.6 parts of polyester tree Tf, 5 parts of melamine resin (Super Beckamine-109-65 manufactured by Dainippon Ink Chemical Co., Ltd.)
．． 0 parts, 4 parts of copper phthalocyanine, and 75 parts of cyclohexanone were mixed in a magnetic ball mill for 2 parts.
A photoconductive coating liquid was obtained by kneading for 4 hours.

次に厚さ８０ミクロンのアルミニウム箔上に乾燥膜厚が
１５ミクロンになるようにコートし、１３０℃で３０分
間加熱乾燥させ、電子写真感光体とした。Next, it was coated onto an aluminum foil having a thickness of 80 microns to a dry film thickness of 15 microns, and was dried by heating at 130° C. for 30 minutes to obtain an electrophotographic photoreceptor.

この感光体の最大表面電位は＋１１５０ボルトであり実
用的には＋６００ボルト程度で使用するため帯電能は十
分な余裕を有する。The maximum surface potential of this photoreceptor is +1150 volts, and since it is practically used at about +600 volts, the charging ability has sufficient margin.

暗減衰率は５秒後で６．５％、半減値感度は３、　１ル
ツクス、秒、残留電位は２２ボルトであった。帯電、露
光の繰り返し、ｉ　ｏｏ。The dark decay rate was 6.5% after 5 seconds, the half-value sensitivity was 3.1 lux, seconds, and the residual potential was 22 volts. Charging, repeated exposure, i oo.

０回後の帯電電位はほとんど変化しなかった。The charging potential after 0 cycles hardly changed.

実施例３ 無水フタル酸２２２部（重量部を示す。以下省略）、無
水マレイン酸９８部、ジエチレングリコール２３３部を
窒素ガス雰囲気中で加熱反応させ、酸価、が２５になる
まで反応を続けた。得られたポリエステル樹脂は淡黄色
のもろい固形樹脂で分子量は約２５００であった。Example 3 222 parts of phthalic anhydride (parts by weight are omitted below), 98 parts of maleic anhydride, and 233 parts of diethylene glycol were heated and reacted in a nitrogen gas atmosphere, and the reaction was continued until the acid value reached 25. The obtained polyester resin was a pale yellow brittle solid resin with a molecular weight of about 2,500.

次に、実施例１で得られた銅フタロシアニン４部、ポリ
エステル樹脂１２．６部、メラミン樹脂（スパーベッカ
ミン−１ｏ９ｆｓｓｓ大日本インキ化学（株）製）５．
０部、先に作られた銅フタロシアニン４部、シクロへキ
サノン７５部からなる組成物を磁性ボールミルにて２４
時間混練して光導電性塗液を得た。Next, 4 parts of copper phthalocyanine obtained in Example 1, 12.6 parts of polyester resin, melamine resin (Super Beckamine-1o9fsss manufactured by Dainippon Ink Chemical Co., Ltd.), 5.
A composition consisting of 0 parts, 4 parts of copper phthalocyanine, and 75 parts of cyclohexanone prepared above was mixed in a magnetic ball mill for 24 hours.
A photoconductive coating liquid was obtained by kneading for a period of time.

次に厚さ８０ミクロンのアルミニウム箔上に乾燥膜厚が
１５ミクロンになるようにコートし、１３０℃で３０分
間加熱乾燥させ、電子写真感光体とした。Next, it was coated onto an aluminum foil having a thickness of 80 microns to a dry film thickness of 15 microns, and was dried by heating at 130° C. for 30 minutes to obtain an electrophotographic photoreceptor.

この感光体の最大表面電位は＋１１００ボルトであり実
用的には＋６００ボルト程度で暗減衰率は５秒後で８％
、半減値感度は２・９ルツクス、秒、残留電位は１８ボ
ルトであった。帯電、露光の繰り返し、１００００回後
の帯電電位はほとんど変化しなかった。また感度変化も
ほとんど認められなかった。The maximum surface potential of this photoreceptor is +1100 volts, which is practically about +600 volts, and the dark decay rate is 8% after 5 seconds.
The half-value sensitivity was 2.9 lux, seconds, and the residual potential was 18 volts. After 10,000 repetitions of charging and exposure, the charging potential hardly changed. In addition, almost no change in sensitivity was observed.

実施例４ 実施例１で得られた鋼フタロシアニン４部、酸価が３−
７、分子量が約４０００の市販ポリエステル樹脂（アル
マテックス６４５三井東圧（株）製）２１部、メラミン
樹脂（ニーパン２０ＨＳ三井東圧（株）製）４．６部、
シクロへキサノン６５部からなる組成物を磁性ボールミ
ルにて２４時間混練して光導電性塗液を得た。次に厚さ
８０ミクロンのアルミニウム箔上に乾燥膜厚１５ミクロ
ンになるようにコートし、１５０℃で２０分間加熱乾燥
させ電子写真感光体とした。感光体の表面硬度は鉛筆硬
度で２Ｈであった。また耐摩耗性が優れていた。この感
光体の最大表面電位は＋１１００ボルトで実用的には＋
６００ボルト程度で使用するなめ帯電能は十分な余裕を
有する。暗減衰率は５秒後で９％、半減値感度は３．６
ルツクス、秒、残留電位は２０ボルトであフた。帯電、
露光の繰り返し１００００回後の帯電電位はほとんど変
化しなかった。また、感度変化もほとんど認められなか
った・ 比較例１ 実施例１で得られたフタロシアニン４部、アクリル樹脂
（アルマテックス７６２ＬＶ５５Ａ三井東圧（株）製）
２０．６部、メラミン樹脂（ニーパン２０Ｈ５三井東圧
（株）製）５．８部、シクロへキサノン６０部からなる
組成物を磁性ボールミルにて２４時間混練りして光導電
性塗液を得た。次に８０ミクロンのアルミニウム箔上に
乾燥膜厚１５ミクロンになるようにコートし、１５０℃
で３０分間加熱乾燥させ電子写真感光体とした。この感
光体の最大帯電電位は＋８００ボルトであり暗減衰率は
５秒後で２０％、半減値感度は４ルツクス、秒であった
。帯電露光の繰り返しに５００回後には帯電電位は初期
の５０％に低下した。Example 4 4 parts of steel phthalocyanine obtained in Example 1, acid value 3-
7. 21 parts of commercially available polyester resin with a molecular weight of about 4000 (Almatex 645 manufactured by Mitsui Toatsu Co., Ltd.), 4.6 parts of melamine resin (Niepan 20HS manufactured by Mitsui Toatsu Co., Ltd.),
A composition consisting of 65 parts of cyclohexanone was kneaded for 24 hours in a magnetic ball mill to obtain a photoconductive coating liquid. Next, it was coated onto an aluminum foil having a thickness of 80 microns to a dry film thickness of 15 microns, and was dried by heating at 150° C. for 20 minutes to obtain an electrophotographic photoreceptor. The surface hardness of the photoreceptor was 2H in terms of pencil hardness. It also had excellent wear resistance. The maximum surface potential of this photoreceptor is +1100 volts, which is +
The slick charging capacity used at about 600 volts has sufficient margin. Dark decay rate is 9% after 5 seconds, half-value sensitivity is 3.6
Lux, seconds, residual potential was 20 volts. electrification,
After 10,000 repetitions of exposure, the charged potential hardly changed. In addition, almost no change in sensitivity was observed. Comparative Example 1 4 parts of phthalocyanine obtained in Example 1, acrylic resin (Almatex 762LV55A manufactured by Mitsui Toatsu Co., Ltd.)
A composition consisting of 20.6 parts of melamine resin (Niepan 20H5 manufactured by Mitsui Toatsu Co., Ltd.), 5.8 parts of cyclohexanone, and 60 parts of cyclohexanone was kneaded for 24 hours in a magnetic ball mill to obtain a photoconductive coating liquid. Ta. Next, it was coated on an 80 micron aluminum foil to a dry film thickness of 15 microns, and heated to 150°C.
The electrophotographic photoreceptor was dried by heating for 30 minutes. The maximum charging potential of this photoreceptor was +800 volts, the dark decay rate was 20% after 5 seconds, and the half-value sensitivity was 4 lux, seconds. After repeating charging exposure 500 times, the charging potential decreased to 50% of the initial value.

比較例２ 無水フタル酸２２２部（重量部を示す、以下省略）、無
水マレイン酸４９部、ジエチレングリコール４６２部を
窒素ガス雰囲気中で加熱反応させ、酸価が１．　５にな
るまで反応を続けた。得られたポリエステル樹脂は淡黄
色のもろい固形樹脂で分子量は約１８００であった。Comparative Example 2 222 parts of phthalic anhydride (indicates parts by weight, omitted below), 49 parts of maleic anhydride, and 462 parts of diethylene glycol were heated and reacted in a nitrogen gas atmosphere until the acid value was 1. The reaction continued until it reached 5. The obtained polyester resin was a pale yellow brittle solid resin with a molecular weight of about 1,800.

次に、実施例１で得られた銅フタロシアニン４部、ポリ
エステル樹脂１２．６部、メラミン樹脂（スパーベッカ
ミン−１０９−６５％日本インキ化学（株）製）５．０
部、先に作られた銅フタロシアニン４部、シクロへキサ
ノン７５部からなる組成物を磁性ボールミルにて２４時
間混練して光導電性塗液を得た。Next, 4 parts of copper phthalocyanine obtained in Example 1, 12.6 parts of polyester resin, and 5.0 parts of melamine resin (Superbeckamine-109-65% manufactured by Nippon Ink Chemical Co., Ltd.)
A photoconductive coating liquid was obtained by kneading the previously prepared composition consisting of 4 parts of copper phthalocyanine and 75 parts of cyclohexanone in a magnetic ball mill for 24 hours.

次に厚さ８０ミクロンのアルミニウム箔上に乾燥膜厚が
１５ミクロンになるようにコートし、１３０℃で３０分
間加熱乾燥させ、電子写真感光体とした。Next, it was coated onto an aluminum foil having a thickness of 80 microns to a dry film thickness of 15 microns, and was dried by heating at 130° C. for 30 minutes to obtain an electrophotographic photoreceptor.

この感光体の最大表面電位は＋１０００ボルトであり実
用的には＋６００ボルト程度で使用するため帯電能は十
分な余裕を有する。The maximum surface potential of this photoreceptor is +1000 volts, and since it is practically used at about +600 volts, the charging ability has sufficient margin.

ロイ４やｉ号−一１＝中ンートＣ；寥ホイ（（−１−Ｍ
ｎ／１１イーート！プず関キｉ崗１１＾８ルックス、秒
、残留電位は１８ボルトであった。しかし、帯電、露光
の繰り返しでは、２０００回位で初期の帯電電位の半分
位となり実用的に使用するには不十分のものであった。Roy 4 and i-11 = Middle C; Hoi Hui ((-1-M
n/11 Eat! 11^8 lux, seconds, residual potential was 18 volts. However, when charging and exposure were repeated about 2,000 times, the initial charging potential was about half, which was insufficient for practical use.

比較例３ 無水フタル酸２２２部（重量部を示す。以下省略）、無
水マレイン酸１９６部、ジエチレングリコール２３３部
を窒素ガス雰囲気中で加熱反応させ、酸価が３５になる
まで反応を続けた。得られたポリエステル樹脂は淡黄色
のもろい固形樹脂で分子量は約４０００であった。Comparative Example 3 222 parts of phthalic anhydride (parts by weight are shown, omitted below), 196 parts of maleic anhydride, and 233 parts of diethylene glycol were heated and reacted in a nitrogen gas atmosphere, and the reaction was continued until the acid value reached 35. The obtained polyester resin was a pale yellow brittle solid resin with a molecular weight of about 4,000.

次に、実施例１で得られた銅フタロシアニン４部、ポリ
エステル樹脂１２．６部、メラミン樹脂（スパーベッカ
ミン−１０９−６５％日本インキ化学（株）Ｕ）５．０
部、先に作られた銅フタロシアニン４部、シクロへキサ
ノン７５部からなる組成物を磁性ボールミルにて２４時
間混練して光導電性塗液を得た。Next, 4 parts of copper phthalocyanine obtained in Example 1, 12.6 parts of polyester resin, and 5.0 parts of melamine resin (Super Beckamine-109-65% Nippon Ink Chemical Co., Ltd. U)
A photoconductive coating liquid was obtained by kneading the previously prepared composition consisting of 4 parts of copper phthalocyanine and 75 parts of cyclohexanone in a magnetic ball mill for 24 hours.

次に厚さ８０ミクロンのアルミニウム箔上に浄＃　　＾
ａ　　ｒｎｔ　　百家１　　　ζ　　）　　ｈ　−−１
啼　諷　啼　　書　　！　　隻啼　−瞥し、１３０℃で
３０分間加熱乾燥させ、電子写真感光体とした。Next, clean it onto an 80 micron thick aluminum foil.
a rnt Hyakke 1 ζ ) h −−1
啼蕼啼書! The mixture was dried by heating at 130° C. for 30 minutes to obtain an electrophotographic photoreceptor.

この感光体の最大表面電位は＋４９０ボルトであり実用
的使用するには不十分の感光体しか得られなかった。The maximum surface potential of this photoreceptor was +490 volts, which was insufficient for practical use.

（発明の効果） 本発明ではフタロシアニン光導電性粉体は分子内に電子
吸引性基を有する鳥兜に述べた光減衰の遅れによる、い
わゆるインダクション現象が生じ難く、結着材に用いら
れるポリエステル樹脂とメラミン樹脂の分散効果と補い
あフて感度が保障されるので、前述したフタロシアニン
と結着材を用いて製造された感光体は優れた感度を有し
、帯電、露光に際して繰り返し動作を多数回行なった後
も帯電電位の変動がほとんどなく、かつ表面硬度が高い
ために機械強度が大きく、耐摩耗性が優れ、また、フタ
ロシアニ２粒子が十分に結着材に被覆されているために
、耐環境性、表面が平滑性に優れた特性を有し従来の単
層型感光体の欠点を大幅に改良された電子写真感光体が
得られた。(Effects of the Invention) In the present invention, the phthalocyanine photoconductive powder has an electron-withdrawing group in its molecule and is less likely to cause the so-called induction phenomenon due to the delay in light attenuation described in Tori Kabuto, and is similar to the polyester resin used as a binder. Since sensitivity is guaranteed through the dispersion effect and supplementation of melamine resin, photoreceptors manufactured using the aforementioned phthalocyanine and binder have excellent sensitivity and require repeated operations many times during charging and exposure. There is almost no change in the charging potential even after the coating, and the high surface hardness provides high mechanical strength and excellent wear resistance.In addition, the 2 phthalocyanine particles are sufficiently coated with the binder, making them highly resistant to the environment. An electrophotographic photoreceptor was obtained which had excellent properties such as hardness and surface smoothness, and which greatly improved the drawbacks of conventional single-layer type photoreceptors.

Claims (1)

【特許請求の範囲】 １、分散型感光層を設けた電子写真感光体において、フ
タロシアニン系光導電性粉体を分散させる結着材におい
て分子量が５００−５０００、かつ酸価が２−３０であ
るポリエステル樹脂およびメラミン樹脂の混合物を加熱
架橋して用いることを特徴とするフタロシアニン電子写
真感光体。 ２、フタロシアニン系光導電性粉体がフタロシアニンお
よびフタロシアニン分子のベンゼン核がニトロ基、シア
ノ基、ハロゲン基、スルホン基およびカルボキシル基か
ら選ばれる少なくとも１種の電子吸引性基によって置換
されたフタロシアニン誘導体から選ばれる特許請求範囲
第１項記載の電子写真感光体。[Claims] 1. In an electrophotographic photoreceptor provided with a dispersed photosensitive layer, the binder for dispersing the phthalocyanine-based photoconductive powder has a molecular weight of 500-5000 and an acid value of 2-30. A phthalocyanine electrophotographic photoreceptor characterized by using a mixture of a polyester resin and a melamine resin that is heat-crosslinked. 2. The phthalocyanine-based photoconductive powder is made of phthalocyanine and a phthalocyanine derivative in which the benzene nucleus of the phthalocyanine molecule is substituted with at least one electron-withdrawing group selected from a nitro group, a cyano group, a halogen group, a sulfone group, and a carboxyl group. The selected electrophotographic photoreceptor according to claim 1.
JP1819787A 1987-01-30 1987-01-30 Electrophotographic sensitive body Granted JPS63187248A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1819787A JPS63187248A (en) 1987-01-30 1987-01-30 Electrophotographic sensitive body

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1819787A JPS63187248A (en) 1987-01-30 1987-01-30 Electrophotographic sensitive body

Publications (2)

Publication Number Publication Date
JPS63187248A true JPS63187248A (en) 1988-08-02
JPH0560866B2 JPH0560866B2 (en) 1993-09-03

Family

ID=11964905

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1819787A Granted JPS63187248A (en) 1987-01-30 1987-01-30 Electrophotographic sensitive body

Country Status (1)

Country Link
JP (1) JPS63187248A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0322536A2 (en) * 1987-12-25 1989-07-05 Koichi Kinoshita Photosensitive member for inputting digital light
EP0415446A2 (en) * 1989-09-01 1991-03-06 Canon Kabushiki Kaisha Image-bearing member and apparatus including same
JP2004029489A (en) * 2002-06-27 2004-01-29 Ricoh Co Ltd Image forming apparatus
JP2006220807A (en) * 2005-02-09 2006-08-24 Ricoh Co Ltd Electrophotographic photoreceptor, and electrophotographic method, electrophotographic apparatus and process cartridge using the same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0322536A2 (en) * 1987-12-25 1989-07-05 Koichi Kinoshita Photosensitive member for inputting digital light
EP0415446A2 (en) * 1989-09-01 1991-03-06 Canon Kabushiki Kaisha Image-bearing member and apparatus including same
JP2004029489A (en) * 2002-06-27 2004-01-29 Ricoh Co Ltd Image forming apparatus
JP2006220807A (en) * 2005-02-09 2006-08-24 Ricoh Co Ltd Electrophotographic photoreceptor, and electrophotographic method, electrophotographic apparatus and process cartridge using the same
JP4568615B2 (en) * 2005-02-09 2010-10-27 株式会社リコー Electrophotographic photosensitive member, electrophotographic method using the same, electrophotographic apparatus and process cartridge

Also Published As

Publication number Publication date
JPH0560866B2 (en) 1993-09-03

Similar Documents

Publication Publication Date Title
JP2006284843A (en) Electrophotographic photoreceptor using tetracarboxylic acid derivative and electrophotographing device
JP2005115091A (en) Electrophotographic photoreceptor and method for manufacturing the same
JPS63187248A (en) Electrophotographic sensitive body
JP3287126B2 (en) Electrophotographic photoreceptor
EP1672007A1 (en) Imaging member
JP2910615B2 (en) Electrophotographic photoreceptor and method of manufacturing the same
JPS615253A (en) Electrophotographic sensitive body
JPS5842055A (en) Electrophotographic receptor
JPS60256147A (en) Electrophotographic sensitive body
JP2002023393A (en) Electrophotographic photoreceptor
JPS6095441A (en) Photosemiconductor material
JP2000239545A (en) Pigment particle and its production and electrophotographic photoreceptor using the same and electrophotographic image forming method
JPS59129856A (en) Electrophotographic sensitive body
JPH05289378A (en) Electrophotographic sensitive body
JPH0542664B2 (en)
JPS60258556A (en) Electrophotographic sensitive body
JPS62115167A (en) Photosensitive body for positive charging
JPS6019150A (en) Electrophotographic sensitive body
JPH06214414A (en) Electrophotographic sensitive body
JPS62103653A (en) Electrophotographic sensitive body
JP2012093408A (en) Coating liquid for charge generating layer, manufacturing method of organic photoreceptor, and organic photoreceptor
JPH10307411A (en) Electrophotographic photoreceptor and its production
JPH0343616B2 (en)
JPS6019144A (en) Composite type electrophotographic sensitive body
JPH05289379A (en) Electrophotographic sensitive body