JP2560481B2 - Method for manufacturing electrophotographic photoreceptor - Google Patents
Method for manufacturing electrophotographic photoreceptorInfo
- Publication number
- JP2560481B2 JP2560481B2 JP1189858A JP18985889A JP2560481B2 JP 2560481 B2 JP2560481 B2 JP 2560481B2 JP 1189858 A JP1189858 A JP 1189858A JP 18985889 A JP18985889 A JP 18985889A JP 2560481 B2 JP2560481 B2 JP 2560481B2
- Authority
- JP
- Japan
- Prior art keywords
- free phthalocyanine
- type metal
- metal
- charge
- photoconductor
- 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 - Lifetime
Links
Landscapes
- Photoreceptors In Electrophotography (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、無金属フタロシアニン顔料を電荷発生物
質として用いる電子写真用感光体に関する。TECHNICAL FIELD The present invention relates to an electrophotographic photoreceptor using a metal-free phthalocyanine pigment as a charge generating substance.
有機系光導電性物質である無金属フタロシアニン顔料
を電荷発生物質として用いる電子写真用感光体（以下、
単に感光体とも称する）は700nm以上の長波長光領域に
高感度を有し、例えば半導体レーザビームプリンタ（波
長780nm程度）などに好適に用いられる可能性が大き
く、近年、盛んに開発が進められ、数多くの提案がなさ
れている。An electrophotographic photoreceptor using a metal-free phthalocyanine pigment, which is an organic photoconductive substance, as a charge generating substance (hereinafter,
(Also simply referred to as a photoconductor) has high sensitivity in a long-wavelength light region of 700 nm or more and has a high possibility of being suitably used in, for example, a semiconductor laser beam printer (wavelength of about 780 nm), and has been actively developed in recent years. , Many proposals have been made.
電子写真プロセスにおいては、感光体の光感度が大き
いことが重要であるが、暗中で表面電荷を保持する特性
（電荷保持率）も大切であり、これらの電子写真特性を
高めるために、通常、感光体の電荷発生物質に用いられ
る顔料は活性化処理の施されたものが用いられる。無金
属フタロシアニン顔料に関しても、アシッドペースト法
によるα型結晶形への変換，さらにはミリング処理によ
るＸ型，γ型への結晶形変換などにより特性改善が行わ
れている。In the electrophotographic process, it is important that the photosensitivity of the photoconductor is large, but the property of retaining the surface charge in the dark (charge retention rate) is also important. The pigment used for the charge generating substance of the photoconductor is one which has been activated. The characteristics of the metal-free phthalocyanine pigment have also been improved by conversion to the α-type crystal form by the acid paste method and further conversion to the X-type and γ-type crystal forms by milling treatment.
ところが、無金属フタロシアニン顔料を電荷発生物質
として用いる感光体に上述のような処理を施された顔料
を用いることにより光感度は改善できるが、電荷保持率
に関しては値がばらつくことが多く、その結果、得られ
る画像に地かぶりなどの画像不良がしばしば発生してい
た。鮮明な画像を得るためには電荷保持率が高くてばら
つきが少ないことが不可欠である。However, although photosensitivity can be improved by using a pigment that has been subjected to the above-described treatment on a photoreceptor that uses a metal-free phthalocyanine pigment as a charge generating substance, the charge retention rate often varies, resulting in The image obtained often had image defects such as background fog. In order to obtain a clear image, it is essential that the charge retention rate is high and the variation is small.
この発明が解決しようとする課題は、上述の問題点を
解消して、無金属フタロシアニン顔料を電荷発生物質と
して用い、高感度で、かつ、電荷保持率が高くてばらつ
きが少ない感光体を提供することにある。The problem to be solved by the present invention is to solve the above-mentioned problems and to provide a photoconductor using a metal-free phthalocyanine pigment as a charge generating substance, which is highly sensitive and has a high charge retention rate and less variation. Especially.
上記の課題は、この発明によれば、無金属フタロシア
ニンをアシッドペースティング法によりα型無金属フタ
ロシアニンとし、α型無金属フタロシアニンをミリング
処理してＸ型無金属フタロシアニン顔料の微粉末を得、
該Ｘ型無金属フタロシアニンを樹脂中に分散して電子写
真感光体の電荷発生層とする電子写真感光体の製造方法
において、 前記アシッドペースティング後，α型無金属フタロシ
アニンを得る前の段階において，洗浄・濾過することに
より、前記Ｘ型無金属フタロシアニン顔料に含有されて
いるSO4 2-を500重量ppm以下とすることによって解決さ
れる。According to the present invention, the metal-free phthalocyanine is converted into an α-type metal-free phthalocyanine by an acid pasting method, and the α-type metal-free phthalocyanine is milled to obtain a fine powder of an X-type metal-free phthalocyanine pigment.
In the method for producing an electrophotographic photosensitive member, wherein the X-type metal-free phthalocyanine is dispersed in a resin to form a charge generation layer of an electrophotographic photosensitive member, in the stage after the acid pasting and before obtaining the α-type metal-free phthalocyanine, This can be solved by washing and filtering the SO 4 2- contained in the X-type metal-free phthalocyanine pigment to 500 ppm by weight or less.
無金属フタロシアニン顔料のロットにより感光体の電
荷保持率に差が見られることから、分析手法により鋭意
調査した結果、無金属フタロシアニン顔料を活性化処理
する過程で、SO4 2-イオンの混入はある程度避けられ
ず、混入してくるSO4 2-の含有量が多くなると電荷発生
層の暗電流が増加し、感光体の電荷保持率が下がること
を見いだした。そうして、顔料中に含まれる残存SO4 2-
を500重量ppm以下に抑えることにより、再現性良く高い
電荷保持率が現実でき、高感度で、かつ、電荷保持率が
高くてばらつきが少ない感光体を、顔料のロットに左右
されることなく、安定して得ることが可能となった。Since there is a difference in the charge retention rate of the photoconductor depending on the lot of metal-free phthalocyanine pigment, as a result of diligent research using an analytical method, it was found that SO 4 2- ions were mixed to some extent in the process of activation treatment of metal-free phthalocyanine pigment. It has been unavoidable that the dark current of the charge generation layer increases and the charge retention rate of the photoconductor decreases when the content of SO 4 2− mixed in increases. Then, the residual SO 4 2- contained in the pigment is
By suppressing the amount to be 500 ppm by weight or less, it is possible to realize a high charge retention rate with good reproducibility, high sensitivity, and a photoreceptor with a high charge retention rate and little variation, without being influenced by the pigment lot, It became possible to obtain it stably.
無金属フタロシアニン（東京化成工業（株）製）25g
を濃硫酸250gに溶かしたのち、5kgの氷水中に注入し、
析出した結晶を濾別する。この，濃硫酸に溶かしたのち
氷水中に注入して析出した結晶を濾別する操作は，一般
にアシッドペースティング法と呼ばれるものである。得
られた結晶粉末を洗浄・濾過したのち乾燥して23gのα
型無金属フタロシアニンを得る。このα型無金属フタロ
シアニン粉末をボールミルで72時間ミリング処理して結
晶形を変換させてＸ型無金属フタロシアニンとする。こ
のような一連の活性化処理において、洗浄液として水と
メタノールを1:1で混合した溶剤および水を用い、洗浄
・濾過の回数を１回ないし５回と変えて、No.1ないしN
o.10のＸ型無金属フタロシアニンを得た。25 g of metal-free phthalocyanine (manufactured by Tokyo Chemical Industry Co., Ltd.)
After dissolving in 250 g of concentrated sulfuric acid, pour into 5 kg of ice water,
The precipitated crystals are filtered off. This operation of injecting into ice water after dissolving in concentrated sulfuric acid and filtering out the precipitated crystals is generally called an acid pasting method. The obtained crystal powder was washed, filtered, and dried to give 23 g of α.
A type metal-free phthalocyanine is obtained. The α-type metal-free phthalocyanine powder is milled in a ball mill for 72 hours to convert the crystal form into X-type metal-free phthalocyanine. In such a series of activation treatments, using a solvent and water in which water and methanol were mixed at a ratio of 1: 1 as the washing liquid, the number of washing and filtration was changed from 1 to 5 times, and No. 1 to N
O-type X-free metallophthalocyanine was obtained.
このようにして得られたＸ線無金属フタロシアニンに
ついて、それぞれSO4 2-の含有量を調べた。その結果を
第１表に示す。Regarding the X-ray metal-free phthalocyanine thus obtained, the content of SO 4 2− was examined. The results are shown in Table 1.
第１表より、洗浄液は単なる水よりも水とメタノール
との1:1の混合溶剤の方がSO4 2-の除去効果が大きく、ま
た、洗浄・濾過を繰り返すほどSO4 2-の含有量が少なく
なることが判る。 From Table 1, it can be seen that a 1: 1 mixed solvent of water and methanol has a greater effect of removing SO 4 2− as the cleaning liquid than simple water, and the content of SO 4 2− increases as the cleaning / filtration is repeated. It turns out that
次に、これらのＸ型無金属フタロシアニン10重量部と
ポリエステル樹脂（商品名バイロン200:東洋紡績（株）
製）10重量部とをジクロロメタン1000重量部に分散，溶
解させて、電荷発生層用塗液を10種類調製した。Next, 10 parts by weight of these X-type metal-free phthalocyanines and polyester resin (trade name: Byron 200: Toyobo Co., Ltd.)
10 parts by weight) were dispersed and dissolved in 1000 parts by weight of dichloromethane to prepare 10 kinds of coating liquids for the charge generation layer.
ジエチルアミノフェニルヒドラゾン100重量部とポリ
カーボネート（商品名パンライトＬ−1225:帝人（株）
製）100重量部とをジクロロメタンに溶解させて調製し
た電荷輸送層用塗液を、アルミニウム合金円筒基体の外
表面に浸漬塗布して、電荷輸送層を形成し、その上に上
述の10種類の電荷発生層用塗液をそれぞれ塗布して、10
種類の感光体No.1ないしNo.10を作製した。100 parts by weight of diethylaminophenylhydrazone and polycarbonate (trade name Panlite L-1225: Teijin Limited)
100 parts by weight of the charge transport layer coating solution prepared by dissolving 100 parts by weight in dichloromethane is applied to the outer surface of the aluminum alloy cylindrical substrate by dip coating to form a charge transport layer, on which the above 10 types of Apply each of the charge generation layer coating solutions and
A variety of photoreceptors No. 1 to No. 10 were produced.
これらの感光体について電子写真特性を測定した。そ
の結果を、各感光体に用いたＸ型無金属フタロシアニン
のSO4 2-含有量と対比させて第２表に示す。ここに、V0
は暗中でコロナ放電により感光体表面を帯電させたとき
の初期の帯電位、VK5は放電中止後５秒後の感光体表面
の電荷保持率、VLは帯電した感光体表面を波長780nmの
光で1.2μJ/cm2照射したときの感光体の表面電位（明部
電位）、Ｅ1/2は帯電した感光体表面を波長780nmの光で
照射したとき帯電位を1/2に減衰させるに必要な半減衰
露光量である。The electrophotographic characteristics of these photoreceptors were measured. The results are shown in Table 2 in comparison with the SO 4 2− content of the X-type metal - free phthalocyanine used for each photoreceptor. Where V 0
Is the initial charge position when the surface of the photoconductor is charged by corona discharge in the dark, V K5 is the charge retention rate of the photoconductor surface 5 seconds after the discharge is stopped, and V L is the charged photoconductor surface with a wavelength of 780 nm. The surface potential (bright part potential) of the photoconductor when irradiated with light at 1.2 μJ / cm 2 , E 1/2 is the charge potential attenuated to 1/2 when the charged photoconductor surface is irradiated with light having a wavelength of 780 nm. This is the half-attenuation exposure amount required for.
電荷保持率VK5は95％以上であることが要望されてい
るが、第２表より感光体に用いる電荷発生物質としての
Ｘ型無金属フタロシアニンに含有されるSO4 2-が500重量
ppm以下であれば、この要望を充たすことが可能である
ことが判る。さらに、第２表より、このSO4 2-の含有量
が少なくなるほどV0,VL,E1/2も向上する傾向があり、感
光体として好ましいことも判る。 The charge retention rate V K5 is required to be 95% or more, but from Table 2 , 500 wt% of SO 4 2- contained in the X-type metal-free phthalocyanine as a charge generating substance used in the photoconductor is used.
It can be seen that this requirement can be satisfied if it is below ppm. Further, it can be seen from Table 2 that as the content of SO 4 2− decreases, V 0 , V L , and E 1/2 also tend to improve, which is preferable as a photoreceptor.
実施例においては、無金属フタロシアニンの活性化処
理に際して、洗浄・濾過を水とメタノールを1:1で混合
した溶剤を用いて３回以上繰り返すことによりSO4 2-の
含有量を500重量ppm以下に少なくしているが、この方法
に限られるものではない。また、感光体の感光層の構成
も実施例の構成に限られず、電荷発生層上に電荷輸送層
が積層された構成においても、この発明は同様に有効で
ある。In the examples, in the activation treatment of the metal-free phthalocyanine, washing and filtration were repeated three times or more using a solvent in which water and methanol were mixed at a ratio of 1: 1, so that the content of SO 4 2- was 500 ppm by weight or less. However, it is not limited to this method. Further, the constitution of the photosensitive layer of the photoreceptor is not limited to the constitution of the embodiment, and the present invention is similarly effective in the constitution in which the charge transport layer is laminated on the charge generation layer.
この発明によれば、電荷発生物質として用いるＸ型無
金属フタロシアニン顔料に含有されているSO4 2-の量
を，α型無金属フタロシアニンを得る前の段階で洗浄・
濾過することにより500重量ppm以下とすることにより、
高感度で、かつ、電荷保持率が高くてばらつきが少ない
感光体を顔料のロットにより左右されることはなく安定
して得ることができる。この発明による感光体を用いる
ことにより、地かぶりなどのない鮮明な良質の画像を安
定して得ることが可能となる。According to the present invention, the amount of SO 4 2- contained in the X-type metal-free phthalocyanine pigment used as the charge generating substance is washed before the α-type metal - free phthalocyanine is obtained.
By making it 500 ppm or less by filtration,
It is possible to stably obtain a photoconductor having high sensitivity, high charge retention rate and little variation, without being influenced by the lot of pigment. By using the photoconductor according to the present invention, it is possible to stably obtain a clear and high-quality image without background fog.
Claims (1)
ィング法によりα型無金属フタロシアニンとし、 α型無金属フタロシアニンをミリング処理してＸ型無金
属フタロシアニン顔料の微粉末を得、 該Ｘ型無金属フタロシアニンを樹脂中に分散して電子写
真感光体の電荷発生層とする電子写真感光体の製造方法
において、 前記アシッドペースティング後，α型無金属フタロシア
ニンを得る前の段階において，洗浄・濾過することによ
り、前記Ｘ型無金属フタロシアニン顔料に含有されてい
るSO4 2-を500重量ppm以下とすることを特徴とする電子
写真感光体の製造方法。1. A metal-free phthalocyanine is converted to an α-type metal-free phthalocyanine by an acid pasting method, and the α-type metal-free phthalocyanine is milled to obtain a fine powder of an X-type metal-free phthalocyanine pigment. In the method for producing an electrophotographic photosensitive member which is dispersed in a resin to form a charge generating layer of the electrophotographic photosensitive member, by washing and filtering after the acid pasting and before obtaining α-type metal-free phthalocyanine, A method for producing an electrophotographic photosensitive member, characterized in that SO 4 2- contained in the X-type metal-free phthalocyanine pigment is 500 ppm by weight or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1189858A JP2560481B2 (en) | 1989-07-21 | 1989-07-21 | Method for manufacturing electrophotographic photoreceptor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1189858A JP2560481B2 (en) | 1989-07-21 | 1989-07-21 | Method for manufacturing electrophotographic photoreceptor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0354572A JPH0354572A (en) | 1991-03-08 |
| JP2560481B2 true JP2560481B2 (en) | 1996-12-04 |
Family
ID=16248360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1189858A Expired - Lifetime JP2560481B2 (en) | 1989-07-21 | 1989-07-21 | Method for manufacturing electrophotographic photoreceptor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2560481B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10293407A (en) * | 1997-04-21 | 1998-11-04 | Fuji Electric Co Ltd | Electrophotographic photoreceptor and its manufacture |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3357989A (en) * | 1965-10-29 | 1967-12-12 | Xerox Corp | Metal free phthalocyanine in the new x-form |
| JPS63180962A (en) * | 1987-01-21 | 1988-07-26 | Alps Electric Co Ltd | Production of x type metal free phthalocyanine |
| JP2636254B2 (en) * | 1987-08-27 | 1997-07-30 | 富士ゼロックス株式会社 | Electrophotographic photoreceptor |
-
1989
- 1989-07-21 JP JP1189858A patent/JP2560481B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0354572A (en) | 1991-03-08 |
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