JPS59166962A - Manufacture of photoconductive cadmium sulfide - Google Patents

Manufacture of photoconductive cadmium sulfide

Info

Publication number
JPS59166962A
JPS59166962A JP4200383A JP4200383A JPS59166962A JP S59166962 A JPS59166962 A JP S59166962A JP 4200383 A JP4200383 A JP 4200383A JP 4200383 A JP4200383 A JP 4200383A JP S59166962 A JPS59166962 A JP S59166962A
Authority
JP
Japan
Prior art keywords
cds
flux
cadmium sulfide
sulfuric acid
photoreceptor
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.)
Pending
Application number
JP4200383A
Other languages
Japanese (ja)
Inventor
Takeshi Ikeda
武志 池田
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.)
Canon Inc
Original Assignee
Canon Inc
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 Canon Inc filed Critical Canon Inc
Priority to JP4200383A priority Critical patent/JPS59166962A/en
Publication of JPS59166962A publication Critical patent/JPS59166962A/en
Pending legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02Charge-receiving layers
    • G03G5/04Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)

Abstract

PURPOSE:To give good sensitivity to long wavelength light, to reduce light memory, and to raise resistance by burning a mixture of CdS contg. In and a specified amt. of flux, then, washing it to remove the flux, reburning it, and heat- treating the obtained CdS in sulfuric acid. CONSTITUTION:>=20wt% flux is mixed with CdS contg. In in an amt. of (5- 30)X10<-4>mol In per mole of Cd, and the mixture is burned at a temp. >=50 deg.C higher than the m.p. of the flux. After the flux is removed in the washing process, CdS is again burned and the obtained CdS is heat-treated with 0.1-0.3 N sulfuric acid. The CdS thus obtained is uniform in particle shapes and their diameters and the coated face of a photoconductive layer is not coarse and rough, but fine and smooth. Therefore, an image of excellent quality is obtained, and said layer is improved in sensitivity to long wavelength light and enhanced in dark resistance.

Description

【発明の詳細な説明】 本発明は、光導電性硫化カドミウムの製造方法に関する
もので、特に非常に結晶性が高く、均一、単一で、且つ
長波長に感度を有する硫化カドミウム粒子の製造方法に
関するものである。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing photoconductive cadmium sulfide, particularly a method for producing cadmium sulfide particles that are highly crystalline, uniform, single, and sensitive to long wavelengths. It is related to.

電子写真感光材料を代表例として用いられる光導電性硫
化カドミウム(cdS )の製造の最も一般的な方法は
、硫酸カドミウム、塩化カドミウム、などのカドミウム
の水溶性塩に硫化水素を作用させて硫化カドミウム粒子
の沈澱を得、次いでこの硫化カドミウム粒子に活性剤を
ドーピングするために高温焼成して得るものである。
The most common method for producing photoconductive cadmium sulfide (cdS), which is typically used in electrophotographic materials, is to react hydrogen sulfide with a water-soluble salt of cadmium, such as cadmium sulfate or cadmium chloride, to produce cadmium sulfide. The cadmium sulfide particles are precipitated and then calcined at a high temperature to dope the cadmium sulfide particles with an activator.

即ち、光導電性硫化カドミウムは、硫化カドミウム粒子
に活性剤としてCuCl2.CuSO4等また、融剤と
してCdCl2. ZnC1!2等のハロゲン化物を混
入して焼成を行なうことにより、Cu、Cl等を硫化カ
ドミウム中にドープさせ製造するのが一般である。しか
しながらこのよう々従来の方法においては、焼成工程を
経て生成されたCdSは、沈澱生成時[CdSの表面付
近に非常に多くの欠陥を有している。
That is, photoconductive cadmium sulfide is produced by adding CuCl2. to cadmium sulfide particles as an activator. CuSO4 etc. and CdCl2. as a fluxing agent. It is generally manufactured by doping Cu, Cl, etc. into cadmium sulfide by mixing a halide such as ZnC1!2 and firing. However, in such conventional methods, the CdS produced through the calcination process has a large number of defects near the surface of the CdS when the precipitate is formed.

この表面欠陥は、光キャリアーのトラップ準位となるた
め、CdSの光メモリーを増大し、即ち、光応答速度を
遅くし、この様なCdSを用いて作成される感光体を高
速の複写機に適用すると初期コピーにおける明部と暗部
の静電コントラストが不十分となる。
These surface defects become trap levels for photocarriers, increasing the optical memory of CdS, that is, slowing down the optical response speed, making photoreceptors made using such CdS suitable for high-speed copying machines. If applied, the electrostatic contrast between bright and dark areas in the initial copy will be insufficient.

また、上記の様な方法で製造されたCdSの粒子形状は
、粒子が互いに集合し合って形成された強い凝集体であ
る2次粒子から々っておシ、この2次粒子は3次元的に
集合して団塊状であったすするいは2次元的に集合して
平板状であったり様々であるがその中には大きなものは
10数ミクロンから数10ミクロンに及ぶものがある。
In addition, the particle shape of CdS produced by the method described above is derived from secondary particles, which are strong aggregates formed by aggregation of particles, and these secondary particles are three-dimensional. There are various types of soot, such as the soot that aggregates in a nodule shape, or the soot that aggregates two-dimensionally and has a tabular shape, and some of them are large, ranging from 10-odd microns to several tens of microns.

この様な粗大粒子を多数含むCdSを用いて作成される
感光体は、その表面状態が劣悪となり、その結果書られ
る画像はガサつきが激しく、解像力も不十分となる。ま
た、さらに絶縁層を設ける感光体の場合には、絶縁層の
CdS層へのしみ込み等がおこり、良好な感光体を得る
ことが困難となる。
A photoreceptor made using CdS containing a large number of such coarse particles has a poor surface condition, and as a result, the image written is extremely rough and has insufficient resolution. Furthermore, in the case of a photoreceptor further provided with an insulating layer, the insulating layer may seep into the CdS layer, making it difficult to obtain a good photoreceptor.

前記欠点については本出願人の発明に係る特開昭57−
129825号公報に記載されているような方法によっ
て、克服されている。
Regarding the above-mentioned drawbacks, Japanese Patent Application Laid-Open No. 1983-1999, which is an invention of the present applicant,
This problem has been overcome by the method described in Japanese Patent No. 129825.

しかしながら、最近インテリジェント・複写機への関心
が高ま9、特にレーザー光源を用いた複写機への要求が
現われ始めると、感光体粒子としては長波長、特にレー
ザー光の関係から750〜800 Hrn以上での感度
を有するものが必要となってくる。前記発明における粒
子は、長波長側には感度を有してなく、赤外領域の光に
対しての感度は十分でなく上記目的には使用出来ない。
However, recently, interest in intelligent copying machines has increased9, and in particular, as the demand for copying machines using laser light sources has begun to appear, photoreceptor particles with long wavelengths, especially 750 to 800 Hrn or more due to laser light There is a need for something with sensitivity at . The particles according to the invention have no sensitivity on the long wavelength side, and are insufficiently sensitive to light in the infrared region, so they cannot be used for the above purpose.

本発明者等は、電子写真用’IiR化カドミウムは、I
nの存在で長波長に感度をのばす′ことが出来ることを
既に確認している。しかし、長波長に感度をのばすに必
要なだけのInをドープさせ、なおかつ、電子写真用と
して必要な暗抵抗を持たすためKは、In量に応じたC
uをアクセプターとして添加しなければならないが、こ
れを前述の方法に適用した場合、Cu量の増加に伴い、
得られる硫化カドミウムを用いて作成される電子写真用
感光体は、基板からのキャリアーの注入性が劣化する傾
向にあり、特に光導電層の上に絶縁層を設ける3層構成
の様なタイプでは、暗部電位が下がり、感度が低下する
傾向がある。
The present inventors have discovered that 'IiR cadmium for electrophotography is
It has already been confirmed that the presence of n can extend the sensitivity to longer wavelengths. However, in order to dope the necessary amount of In to extend the sensitivity to long wavelengths and to have the necessary dark resistance for electrophotography, K should be adjusted according to the amount of In.
U must be added as an acceptor, but when this is applied to the above method, as the amount of Cu increases,
Electrophotographic photoreceptors made using the resulting cadmium sulfide tend to have poor carrier injection properties from the substrate, especially in types with a three-layer structure in which an insulating layer is provided on the photoconductive layer. , there is a tendency for the dark area potential to decrease and the sensitivity to decrease.

また、Cu量のみを減少させ、In量は減少させない場
合は、長波長へ感度はのびるが光メモリーが増加し、暗
部電位の低い非常に低抵抗なイIMt化カドミウムとな
ってしまう。
If only the amount of Cu is reduced and the amount of In is not reduced, the sensitivity extends to longer wavelengths, but the optical memory increases, resulting in a very low-resistance IMt cadmium oxide with a low dark potential.

+m Lで本発明は前記方法を改良したCdSの製造方
法を提供することを目的とするものである。
+m L It is an object of the present invention to provide a method for producing CdS that is an improvement on the above method.

即ち、長波長に十分な感度を有しながら光メモリーが小
さく暗′亀位がより十分にとれる高抵抗CdSが製造で
きる製造方法を提供することを目的とする。
That is, it is an object of the present invention to provide a manufacturing method capable of manufacturing high-resistance CdS that has sufficient sensitivity to long wavelengths, has a small optical memory, and has a more sufficient dark spot.

本発明の方法は、インジウムを含むイ雨化カドミウムに
対して20重量多以上の融剤を混ぜて、融剤の融点より
も50°C以上高い温度で焼成し、洗浄工程を経て融剤
を除去した後、再焼成して得られる硫化力t゛ミウム0
.4N〜3. ONの硫酸中で加熱処理することを特徴
とするものである。
In the method of the present invention, cadmium chloride containing indium is mixed with 20% more flux by weight, fired at a temperature 50°C or more higher than the melting point of the flux, and the flux is removed through a washing process. After removal, the sulfiding power obtained by re-firing is 0.
.. 4N~3. It is characterized by heat treatment in ON sulfuric acid.

本発明により製造される硫化カドミウムは結晶性が高く
、また、走査型電子顕微鏡による形状観察では粒子が互
いに凝集していない単粒子でありかつその表面が滑らか
になっている。
The cadmium sulfide produced by the present invention has high crystallinity, and when observed using a scanning electron microscope, it is found to be a single particle with no agglomeration of particles, and its surface is smooth.

本発明により得られた硫化カドミウム粉体は粒子形状が
均一でかつ粒径がそろっているため、作成される光導電
層の塗面は、密で平滑なため、非常に良質の画像が得ら
れると共に長波長、特に800ないし850 Hmまで
感度が伸びていることがわかった。
Since the cadmium sulfide powder obtained by the present invention has a uniform particle shape and uniform particle size, the coated surface of the photoconductive layer created is dense and smooth, resulting in very high quality images. It was also found that the sensitivity was extended to longer wavelengths, particularly 800 to 850 Hm.

本発明で焼成後、硫化カドミウムの表面処理に用いる硫
酸の濃度はO,IN〜3.ONが効果的である。0.I
N以下では、長時間処理を行ってもその効果が少なく製
造上の効率が悪い、また加熱することで3N以上の濃度
の処理は、感度が低下する傾向を示すことから不適尚で
ある。
In the present invention, the concentration of sulfuric acid used for surface treatment of cadmium sulfide after firing is O.IN~3. ON is effective. 0. I
If the concentration is less than N, even if the treatment is carried out for a long time, the effect will be small and manufacturing efficiency will be poor. Furthermore, treatment at a concentration of 3N or more is unsuitable because the sensitivity tends to decrease due to heating.

また本発明においては、加熱下で硫酸処理をすることに
よって、処理時間が短縮でき、また、同じ処理効果を得
るに低映度の硫酸で済むことができる。加熱濃度は、7
0°C以上特に80゛C以上が好適である。長波長側−
に感度を持たすだめのインジウムの最低量は生成する硫
化カドミウム1モルに対して5 X 10−’モル必要
であシ最太量は電子写真用としての暗抵抗が満足される
量30X10〜4モルである。
Furthermore, in the present invention, by performing the sulfuric acid treatment under heating, the treatment time can be shortened, and sulfuric acid with a low intensity can be used to obtain the same treatment effect. The heating concentration is 7
The temperature is preferably 0°C or higher, particularly 80°C or higher. Long wavelength side -
The minimum amount of indium required to provide sensitivity is 5 x 10-' mol per 1 mol of cadmium sulfide produced, and the maximum amount is 30 x 10-4 mol to satisfy the dark resistance for electrophotography. It is.

インジウムの添加は、反応溶液中に添加して共沈によっ
て硫化カドミウムに含ませることもできるし、焼成前に
硫化カドミウムと混合させても有効に含寸せることもで
きる。
Indium can be added to the reaction solution and included in the cadmium sulfide by coprecipitation, or it can be effectively included by mixing it with the cadmium sulfide before firing.

また、銅は予め、カドミウム塩水溶液中に添加して共沈
させて、硫化カドミウム中に含ませることも出来るし、
焼成前、硫化カドミウムと混合した後焼成を行うことに
ょシ硫化カドミウム中に含ませることも出来る。CdS
に添加する銅化合物としては、銅の塩化物、硫化物、硫
酸化物などが用いられ、特に、塩化銅、硫酸鋼が好まし
い。
In addition, copper can be added in advance to a cadmium salt aqueous solution and co-precipitated to be included in cadmium sulfide.
It can also be included in cadmium sulfide before firing, by mixing with cadmium sulfide and then firing. CdS
As the copper compound to be added, copper chlorides, sulfides, sulfates, etc. are used, and copper chloride and sulfuric acid steel are particularly preferred.

焼成前に銅化合物を添加する方法は錯化合物を固体のま
ま添加混合してもよいし、銅化合物が水溶性の場合はこ
れを一度水溶液にしCdSに添加後、水分を蒸発させる
湿式法のいずれも良好な結果が得られるが、均一性の面
では湿式方法がよい。
The copper compound can be added before firing by adding and mixing the complex compound as a solid, or if the copper compound is water-soluble, it can be made into an aqueous solution and added to CdS, and then the water can be evaporated. Although good results can also be obtained using the wet method, the wet method is better in terms of uniformity.

銅の添加量はインジウム量によって最適量が異なるが硫
化カドミウム1モルに対し一’ic、1×10−4から
15 X 10−4モル特には3 X 10−4からi
 o x i O−4モルが必要である。
The optimum amount of copper to be added differs depending on the amount of indium, but it is 1'ic per mole of cadmium sulfide, 1 x 10-4 to 15 x 10-4 mol, especially 3 x 10-4 to i
ox i O-4 moles are required.

本発明に使用する融剤は、活性剤’i CdS中に拡散
する際に一般的に用いられている融剤で、CdC7z 
、 ZnCl2. KCl、 NaC/? 、 NfL
CJ 、 Cd5Q4等の1つあるいは数種類を適当な
比率に混合したものである。混合して用いる場合の好適
例として、CdCl2とアルカリ金属の塩化物との混合
物が挙げられるアルカリ金属の塩化物としては、NaC
1とKCfが代表的なものである。アルカリ金属の塩化
物の融剤全体における含有量(d、90モルチ以下で1
0モル係以上が好適である、本発明においては、この融
剤量は、20%以上、特に好ましくは30〜50係が好
ましい。
The fluxing agent used in the present invention is a fluxing agent commonly used when diffusing into the activator'i CdS, and CdC7z
, ZnCl2. KCl, NaC/? , NfL
It is a mixture of one or several types of CJ, Cd5Q4, etc. in an appropriate ratio. A suitable example of a mixture of CdCl2 and an alkali metal chloride is a mixture of CdCl2 and an alkali metal chloride.As an alkali metal chloride, NaC
1 and KCf are representative ones. The content of alkali metal chlorides in the total flux (d, 1 at 90 mol.
In the present invention, the fluxing agent amount is preferably 0 molar ratio or more, and is preferably 20% or more, particularly preferably 30 to 50 molar ratio.

20%以下では、製造されるCdS粒子は焼結して粗大
粒子になり、壕だ表面形状も不均一で、電位保持性が十
分でなく、捷だ、解像性に欠ける悪いCdSになる。ま
た、焼成t =、剤の融点よりも50℃高い温度に及ば
ない温度で行なった場合には、製造されるCdS粒子は
粒径が太きく、解像性や塗工性が悪い。
If it is less than 20%, the produced CdS particles will be sintered and become coarse particles, the surface shape of the grooves will be uneven, the potential retention will be insufficient, and the CdS will be coarse and poor in resolution. If the firing is carried out at a temperature lower than t = 50° C. higher than the melting point of the agent, the CdS particles produced will have a large particle size and poor resolution and coating properties.

なお、本発明の製造方法において、焼成温度は、600
°C以下が好適である。また、融剤のCdSに対する添
加量は、収率の点からは65%以下が好適である。
In addition, in the manufacturing method of the present invention, the firing temperature is 600
°C or less is suitable. Further, the amount of flux added to CdS is preferably 65% or less from the viewpoint of yield.

このように焼成された硫化カドミウムは本発明による硫
酸処理の前に再焼成を行う。この再焼成処理によって、
感光体に利用されたときの形成される画像の静電コント
ラストが一層安定化する。再焼成は500″C以下特に
は400〜450°Cの温度で行われることが好ましい
The cadmium sulfide thus calcined is recalcined before being treated with sulfuric acid according to the present invention. Through this re-firing process,
When used on a photoreceptor, the electrostatic contrast of the image formed becomes more stable. Preferably, the re-firing is carried out at a temperature below 500''C, particularly between 400 and 450C.

実施例1 硫酸カドミウム1 mole 、硫酸銅8 ’X 10
−’mode硫酸インジウム20 X 10−’ mo
lleを含む、3N硫酸酸性水溶液21の温度を60″
Cに保ち、硫化水素′f:300 cc/minの流量
で95分間J3じた。
Example 1 Cadmium sulfate 1 mole, copper sulfate 8'X 10
-'mode indium sulfate 20 X 10-' mo
The temperature of the 3N sulfuric acid acidic aqueous solution 21 containing lle was set to 60''.
The temperature of the reactor was maintained at 30° C., and hydrogen sulfide was heated at a flow rate of 300 cc/min for 95 minutes.

この反応で生じた硫化カドミウムを純水を用いて水洗し
、過剰に粒子表面に存在する不純物を除去した後、口過
100 ’Oの温度で1晩乾燥した。この硫化カドミウ
ム100gに対しCrtC4を201とNaClを3O
f’添加し、よく混合した上で、石英ルツボに充填し、
530°Oで30分焼成した(なお、CdC12とNa
C1の混合融剤の融点は、状態図からcdCI!2・2
NaCI!の融点の426°Cに相当する)。この様に
して得られたCdSを水洗、イオン交換樹脂による残留
イオン除去後乾燥した。この硫化カドミウムを450 
’Cで1時間再焼成した。再焼成後これを2.5N硫酸
水溶液中に入れ攪拌しながら加熱した。液温が90°C
に達してから更に40分間加熱を続行した後、純水を用
いて洗浄し、上澄み液の電気電導度を10μS /cm
まで落した後、イオン交換樹脂を添加し、60分間攪拌
した後鷲気電導度が1.0μS /cm以下になってい
ることを確認した後、樹脂を分離、濾過し、60°Cの
温度で乾燥した。
The cadmium sulfide produced in this reaction was washed with pure water to remove excess impurities present on the particle surface, and then dried overnight at a temperature of 100'O. For 100g of this cadmium sulfide, add 201 CrtC4 and 3O NaCl.
Add f′, mix well, and fill in a quartz crucible.
Calcined at 530°O for 30 minutes (note that CdC12 and Na
The melting point of the mixed flux C1 can be determined from the phase diagram cdCI! 2・2
NaCI! (corresponds to the melting point of 426°C). The CdS thus obtained was washed with water, residual ions were removed using an ion exchange resin, and then dried. This cadmium sulfide is 450
Refired for 1 hour at 'C. After re-baking, this was placed in a 2.5N sulfuric acid aqueous solution and heated while stirring. Liquid temperature is 90°C
After heating was continued for another 40 minutes, the supernatant was washed with pure water and the electrical conductivity of the supernatant was reduced to 10 μS/cm.
After the ion exchange resin was added and stirred for 60 minutes, it was confirmed that the electrical conductivity was 1.0 μS/cm or less, and the resin was separated, filtered, and heated to a temperature of 60°C. It was dried.

このCdSを塩化ビニル/酢酸ビニル共重合体中に分散
させた後アルミニウム基板上に40μの厚さに塗布乾燥
させて得た感光体に15μ厚のポリエステルフィルムを
はりつけ三層構成の感光体を得たところ、表面が非常に
平滑であった。この感光体に一次帯電、次いで光像露光
AC除電、次いで全面露光の高速電子写真プロセスを適
用したところ、十分な静電コントラストと、十分な感度
に基〈良質の画像が得られた。
After dispersing this CdS in a vinyl chloride/vinyl acetate copolymer, it was coated on an aluminum substrate to a thickness of 40μ and dried.A 15μ thick polyester film was attached to the resulting photoreceptor to obtain a three-layered photoreceptor. The surface was very smooth. When this photoreceptor was subjected to a high-speed electrophotographic process of primary charging, photoimage exposure, AC static elimination, and then full-surface exposure, a good quality image was obtained based on sufficient electrostatic contrast and sufficient sensitivity.

lF!i、に解像力は、6本/胴以上あり、シャープな
画像が得られた。さらにこの感光体を温度35゛0、湿
度85係の高温・高湿中に、24時間放置後、再び複写
機において画像出しを行なった結果明暗部のコントラス
トの低下も認められず、良質の画像が得られた。
lF! The resolution was 6 lines/cylinder or more, and a sharp image was obtained. Furthermore, this photoconductor was left in a high temperature and high humidity environment of 35°C and humidity of 85% for 24 hours, and then the image was produced again in a copying machine.As a result, no decrease in contrast between bright and dark areas was observed, and the image was of good quality. was gotten.

実施例2 硫酸カドミウム1moleを含む3N硫酸水浴液から、
実施例1と同様な方法により硫化カドミウムを沈澱生成
1〜だ、該硫化カドミウム1007に銅、インジウムが
硫化カドミウム1モルに対してそれぞれ3 X 10’
 、 6 X 10−’mole含むように、硫酸、銅
、硫酸インジウムの形で添加し、湿式法により、均−混
合後、100’0の温度で乾燥した。CdCl2.40
 gr 、 NaC1、10grから成る混合融Mll
を混入し、充分混合後500°Cで30分焼成した。こ
の様疋作成された硫化カドミウムを0.3N硫酸水溶液
中に添加、加熱。
Example 2 From a 3N sulfuric acid water bath solution containing 1 mole of cadmium sulfate,
Cadmium sulfide was precipitated by the same method as in Example 1. The cadmium sulfide 1007 contained 3 x 10' of copper and indium, respectively, per mole of cadmium sulfide.
, 6 x 10-' moles were added in the form of sulfuric acid, copper, and indium sulfate, and after homogeneous mixing by a wet method, it was dried at a temperature of 100'0. CdCl2.40
Mixed molten Mll consisting of gr, NaCl, 10gr
After thorough mixing, the mixture was baked at 500°C for 30 minutes. The cadmium sulfide prepared in this way was added to a 0.3N sulfuric acid aqueous solution and heated.

攪拌しながら、90℃に達してから120分間加熱を続
けた。水洗、濾過、乾燥後実施例1と同様にCdSを感
光体化して評価したところ、実施例1と同様の良好の結
果を得た、 比較例1 実施例1において、硫酸処理を除いて全く同様の方法で
作成された硫化カドミウム粒子について、実施例1と同
様の方法で感光体を作成した。
While stirring, heating was continued for 120 minutes after reaching 90°C. After water washing, filtration, and drying, CdS was made into a photoreceptor and evaluated in the same manner as in Example 1, and the same good results as in Example 1 were obtained.Comparative Example 1 Exactly the same as in Example 1 except for the sulfuric acid treatment. A photoreceptor was produced in the same manner as in Example 1 using the cadmium sulfide particles produced by the method described above.

比較例2 実施例2において硫酸処理を除いて全く同様な方法で製
造した硫化カドミウム粒子を用いて実施例2と同様にし
て感光体を製造した。以上の実施例および比較例で製造
した感光体について第1図に示す測定装置を用いて感光
体の特性を測定した。
Comparative Example 2 A photoreceptor was manufactured in the same manner as in Example 2 using cadmium sulfide particles manufactured in exactly the same manner as in Example 2 except for the sulfuric acid treatment. The characteristics of the photoreceptors manufactured in the above Examples and Comparative Examples were measured using the measuring apparatus shown in FIG.

即ち、感光体9の絶縁層面に透明電極4をもつガラス板
3を押しつけた。透明電極4はリレースイッチ5を介し
て高圧直流電源6に接続さiする。測定はリレースイッ
チ5を0.2秒間とじて高電圧(Va)を印加し、0.
2秒間放置(オープン)後光を0゜2秒間照射しその時
の電圧変化(Vp)を感光体と同電圧にある金属板7と
表面電位計8で測定した。同、Vpは光導電層に印加さ
れている電圧である。
That is, the glass plate 3 having the transparent electrode 4 was pressed against the insulating layer surface of the photoreceptor 9. The transparent electrode 4 is connected to a high voltage DC power source 6 via a relay switch 5. The measurement was performed by closing the relay switch 5 for 0.2 seconds and applying a high voltage (Va).
After leaving it for 2 seconds (open), it was irradiated with light at 0.degree. for 2 seconds, and the voltage change (Vp) at that time was measured using the metal plate 7 and the surface electrometer 8, which were at the same voltage as the photoreceptor. Similarly, Vp is the voltage applied to the photoconductive layer.

更に前露光としてハロゲンランプ1の白色光をシャッタ
ー2により0.25(9)照射し、(12sec放iW
 l、た後、Va印加し、0.2 sec放置放置後光
を0.2sec照射しその時の電圧変化■p′を測定し
た。Va −2000Vとした場合のVpおよびVp’
 iたVaを+2000Vとした場合のVpO値を測定
しVa : −12000V印加時のVp−Vp’から
光メモリーの大小が判断できる。
Further, as a pre-exposure, 0.25(9) of white light from the halogen lamp 1 was irradiated by the shutter 2, and
1, then Va was applied, and after being left for 0.2 seconds, light was irradiated for 0.2 seconds and the voltage change (p') at that time was measured. Vp and Vp' when Va -2000V
The VpO value is measured when Va is set to +2000V, and the size of the optical memory can be determined from Vp-Vp' when Va: -12000V is applied.

次に同じ測定装置を用いて感光体のtr’g度を測定し
た。
Next, the tr'g degree of the photoreceptor was measured using the same measuring device.

即ち、感光体9の絶縁層面に透明電極4をもつガラス板
3を押しつけた。透明電極4はリレースイッチ5を介し
て高圧iff流電源6に接続される。測定は前露光とし
てハロゲンランプ1の白色光をシャッター2により0,
2s(支)照射し、0.2気放置した後、リレースイッ
チ5を0.2秒間とじて高電圧(Va)を1・&光体に
印加し、0.2秒間放置後十分に強い光を02秒間照射
後、感光体表面(即ち、絶縁層表面)における市:圧(
Va’)を感光体と同電圧にある金属板7と表面電位計
8で測定した。高電圧印加時における光導電層への印加
電圧(Vp)ばVa−Va’により算出できるのでVp
が600VになるVa (以下Va −600という)
を定めて以下の方法で感度を測定した。
That is, the glass plate 3 having the transparent electrode 4 was pressed against the insulating layer surface of the photoreceptor 9. The transparent electrode 4 is connected to a high voltage IF current power source 6 via a relay switch 5. In the measurement, white light from halogen lamp 1 is used as pre-exposure with shutter 2 at 0,
After irradiating for 2 seconds and leaving it for 0.2 seconds, close the relay switch 5 for 0.2 seconds and apply high voltage (Va) to the light body, and after leaving it for 0.2 seconds, apply a sufficiently strong light. After irradiating for 02 seconds, the pressure (
Va') was measured using a metal plate 7 at the same voltage as the photoreceptor and a surface potentiometer 8. The voltage (Vp) applied to the photoconductive layer when applying a high voltage can be calculated from Va - Va', so Vp
Va becomes 600V (hereinafter referred to as Va -600)
was determined and the sensitivity was measured using the following method.

即ち、感光体にVa −600を印加した状態で測定光
(800nm)’に照射する。光照射後02秒間放置後
、上記と同様に十分に強い先金02秒間照射して感光体
表面における電圧(Va″)を上記と同様にして測定す
る。Va−600印加と同時測定光照射時における光導
電層への印加電圧(Vp″)はVa−600−Va″に
より算出できるから、Vp”が300vになる必要な測
定光の露光量■)が半減露光量(Ei/2)であり、感
光体のp2 H7を表示することができる。
That is, the photoreceptor is irradiated with measurement light (800 nm)' while applying Va -600. After leaving it for 02 seconds after irradiation with light, irradiate the photoreceptor for 02 seconds with sufficient intensity as above and measure the voltage (Va'') on the surface of the photoconductor in the same manner as above. Va-600 application and simultaneous measurement When irradiated with light Since the voltage (Vp'') applied to the photoconductive layer in can be calculated as Va-600-Va'', the exposure amount (■) of the measurement light required to make Vp'' 300V is the half-reduced exposure amount (Ei/2). , p2 H7 of the photoreceptor can be displayed.

下表にそれら特性を示す。The characteristics are shown in the table below.

表から、硫酸処理を行った感光体についてはVp −V
p’の差が比較例に比べて小さい。このことは前露光に
よる影響がより少ないこと、換言すれば光減衰の速さが
実施例の感光板の方が速いことを示している。
From the table, for the photoreceptor treated with sulfuric acid, Vp -V
The difference in p' is smaller than that of the comparative example. This shows that the influence of pre-exposure is smaller, in other words, the speed of light attenuation is faster in the photosensitive plate of the example.

寸だ、Vp′が大きくなっている点から、比較例に比[
7て高抵抗型となっており、電位が取れる方向に変化し
ている。光メモリ−、感度のいづれも比較例に較べて改
良されている。
Compared to the comparative example, the Vp′ is larger.
7, it is a high resistance type and changes in the direction that the potential can be taken. Both optical memory and sensitivity are improved compared to the comparative example.

【図面の簡単な説明】[Brief explanation of drawings]

第1図は感光体の感度を測定するための装置の説明図で
ある。 4・・°透明′i匠極   5・・リレースイッチ6 
・・・ [¥、5圧1負流電(涼   7   金〕、
・具う反8°次而電位計  9・・・1□113元体出
鎗人  ヤヤノン株式会社
FIG. 1 is an explanatory diagram of an apparatus for measuring the sensitivity of a photoreceptor. 4...°transparent'i Takumi Kiwami 5...Relay switch 6
... [¥, 5 pressure 1 negative current (Ryo 7 Fri)],
・An 8° angle electrometer 9...1□113 original body developer Yayanon Co., Ltd.

Claims (1)

【特許請求の範囲】[Claims] (1)1モルあたりインジウムを5〜30 X 10−
4モル含む硫化カドミウムに対して、20重量裂以上の
融剤を混ぜ、融剤の融点よりも5゜°C以上高い温度で
焼成し、洗浄工程を経て融剤を取り除いた後さらに角焼
成して得られた硫化カドミウムをO,IN −0,3N
の硫酸中で加熱処理することを特徴とする光導電性硫化
カドミウムの製造方法。
(1) 5 to 30 x 10- of indium per mole
Cadmium sulfide containing 4 moles is mixed with a flux of 20% or more by weight, fired at a temperature of 5°C or more higher than the melting point of the flux, and after the flux is removed through a washing process, it is further fired. The cadmium sulfide obtained by
1. A method for producing photoconductive cadmium sulfide, comprising heat treatment in sulfuric acid.
JP4200383A 1983-03-14 1983-03-14 Manufacture of photoconductive cadmium sulfide Pending JPS59166962A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4200383A JPS59166962A (en) 1983-03-14 1983-03-14 Manufacture of photoconductive cadmium sulfide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4200383A JPS59166962A (en) 1983-03-14 1983-03-14 Manufacture of photoconductive cadmium sulfide

Publications (1)

Publication Number Publication Date
JPS59166962A true JPS59166962A (en) 1984-09-20

Family

ID=12624015

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4200383A Pending JPS59166962A (en) 1983-03-14 1983-03-14 Manufacture of photoconductive cadmium sulfide

Country Status (1)

Country Link
JP (1) JPS59166962A (en)

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