JPS58185411A - Preparation of cadmium selenide sulfide particle - Google Patents

Abstract

PURPOSE:To prepare cadmium selenide sulfide particle having stable characteristics for electrostatic photography, by introducing H2S into an aqueous solution of Cd ion dispersed with cadmium selenide, and calcining the produced mixture of cadmium selenide and cadmium sulfide. CONSTITUTION:Cadmium selenide is dispersed in an aqueous solution containing Cd ion such as cadmium sulfate, etc. and preferably acidified with sulfuric acid. The concentration of sulfuric acid is preferably 1.5-3.0 N. The amount of the cadmium selenide added to the solution is preferably 5-30mol% based on the resultant mixed crystal. H2S is introduced into the aqueous solution, and the produced precipitate is filtered and dried. The dried mixture is mixed thoroughly with a flux (e.g. NaCl-CdCl2 flux mixture), and calcined preferably at <=600 deg.C to obtain the objective cadmium selenide sulfide particle.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing cadmium selenide sulfide particles O for use in electrophotography.Cadmium sulfide selenide particles are characterized in that 411 is coprecipitated with cadmium sulfide using cadmium selenide as a core. The manufacturing method is described below.

In general, cadmium sulfide cadmium mixed crystals (photoconductors made of cadmium sulfide alone) also produce high-sensitivity ftk.
Therefore, if a highly sensitive photoconductor is required, a sulfuric selenide wire can be used.

It is advantageous to choose Mium.

Cadmium selenide sulfide is created by mixing cadmium sulfide particles and selenium particles or cadmium selenide particles and firing the mixture at a high temperature. However, the 9lI produced by such conventional methods had the following drawbacks: Cadmium Renide Co., Ltd. That is.

1. Slight fluctuations in cadmium selenide in the raw materials 411 used have a large effect on the photoconductor, that is, the quality of the cadmium selenide supplied does not maintain a constant quality level. In the case, the properties of the cadmium sulfur selenide produced are given life.

2. Caddonium sulfide, caddonium sulfide, sulfur, sulfide, caddonium O mixed with a large amount are required, and.

Mixing is not always uniform.

Therefore, the main object of the present invention is to provide a manufacturing method that solves these drawbacks.

The method for producing cadmium selenide sulfate particles according to the present invention includes:
This method is characterized by dispersing cadmium selenide and introducing aqueous sulfide into an aqueous solution of nine cadmium ions to produce a warm mixture of cadmium selenide and cadmium sulfide, and then firing the mixture.

That is, the present invention overcomes the above drawbacks by forming a precipitate of cadmium sulfide using cadmium selenide as a core.

The advantage of this method is that a mixture of cadmium sulfide and cadmium selenide is created when making cadmium sulfide, and the mixing is easy! It can be carried out uniformly, furthermore, the mixing knee can be eliminated, and incidentally, if a mixture prepared by the wrinkle method is used, donor impurities can be further reduced. It has advantages such as long wavelength sensitivity. This rounding optical memory can be further reduced, and the stability of characteristics is further increased.

Note that as the optical memory increases, the photoresponse blockage becomes slower and ζ
If a photoreceptor made using o**cas is applied to a high-speed 01 photocopier, the electrostatic contrast between bright and dark areas in initial copying will be insufficient.

In particular, as the demand for copying using a laser light source began to increase, photoreceptor particles with long wavelengths, 411 and those with sensitivity over 750 to 800 nu due to laser light, became necessary. come. This round K is made by adding micronized Kowloon cadmium phosphide to a sulfuric acid acidified cadmium ion solution containing Group 1 and JIII elements, and then blowing hydrogen sulfide to precipitate the cadmium sulfide. It is preferable to create

Group Ⅰ and group phoenix elements are respectively Aku-shichibuta.

(acts as a donor impurity), per mole of the resulting mixed crystal (i & cadmium selenide)! 1
It is preferable to add Group 11 in an amount of 5X10-' to 15x1O-' and add Group 11 in an amount of 5X10"-' to 21)X10'.

The cadmium ion aqueous solution is preferably acidic with sulfuric acid, and the sulfuric acid concentration must be determined depending on the particle size of the resulting particles, the amount of cadmium selenide added as nuclei, etc. 1.5M~6. A value within the range of OM is suitable for the properties of the cadmium selenide sulfide that is finally produced.

The amount of cadmium selenide added as a nucleus is preferably added so that the composition becomes 5 mmox·% to 5QmO1e% with respect to the finished mixed crystal. If it is less than 5%,
It is difficult to see the effect of adding selenium, and when it exceeds 50%, it becomes 9
The movement of carriers that occurs becomes apparent. ii The shape of the selenizing power domicum was made up of secondary particles, which are strong aggregates formed by particles gathering together, and these secondary particles are three-dimensional! When JA is combined into a block-like shape, or when it is two-dimensionally aggregated and has a flat plate-like shape,
A photoconductor produced using a photoreceptor made of a sulfurized selenide frame containing a large number of such coarse particles has a sluggish feel and has insufficient resolving power. Therefore, it is desired to produce cadmium selenide sulfate that does not contain coarse particles, and one method for this purpose is to devise firing conditions. That is, a mixture of cadmium sulfide and cadmium selenide together with 20% by weight or more of a fluxing agent,
Fire with an electric key that is 50°C or more higher than the melting point of the flux.

The flux used is C60t, which is commonly used when diffusing active agents into CaS.

Zn012. KCl, MaOt, M1140t
, CdSO4, etc., in an appropriate ratio.

A preferred example of a mixture used in combination is a mixture of aaoz and an alkali metal chloride. Typical alkali metal chlorides include MaOt and XCZ. The content of the alkali metal chloride in the entire flux is preferably 90 mol or less and 10 mol % or more.

In the present invention, the amount of the flux is preferably 20% or more, 1%, preferably 50-50%.

If it is less than 20%, the ram particles will sinter into the produced sulfur selenide edges and become coarse particles), and the surface shape will be uneven.
It becomes a CaS that does not have sufficient potential retention properties and lacks sexual behavior.

(9) If the calcination is carried out at a temperature lower than 11°C which is 50°C higher than the melting point of the flux, the produced cadmium selenide sulfate particles will have a large particle size and will have poor decomposition and poor coatability.

9 In the O manufacturing method of the present invention, the firing temperature is 6O
The temperature is preferably 0°C or lower. From the viewpoint of yield, the amount of flux added to the mixture is preferably 65% or less.

The thus-fired film with large sulfide edges is then re-fired, and this re-firing process further stabilizes the electrostatic contrast of the image formed when it is used as a photoreceptor. It is preferable that the re-firing is carried out at a temperature of 500 DEG C. or lower, and 411, 400 to 450 DEG C.; 411, K11lf charges in the photoreceptor are likely to increase (WA) at a firing temperature of 500 DEG C. or higher.

This will be explained below using an example.

Example 1 Indium sulfate and copper sulfate were each mixed at 10×10. 8X
2.5 M containing 4 moles of cadmium sulfate containing 10-' moles
After adding 1 mol of sulfuric acid solution @ 10 tK cadmium selenide mold powder, hydrogen sulfide was blown into the mixture at a flow rate of 21/- for 50 minutes at 65° C. for 1 reaction. The resulting precipitate was thoroughly washed with pure water, passed through one mouth, and then dried at 200° C. overnight.

Sodium chloride-cadmium chloride mixed flux (Wool 60% by weight, cac
z240'31% by weight) was added, thoroughly mixed, and then filled into a quartz crucible and fired at 550°C for 50 minutes.The fired product was thoroughly washed and then dried at 70°C overnight. Next, the thus obtained nine-sulfur selenide cadmium was filled into the crucible again and fired again at 450°C for 1 hour. After removing and drying, this cadmium selenide sulfate was dispersed in a vinyl chloride/vinyl acetate copolymer and coated on an aOS rhinoceros on a post-mortem 50μ aluminum substrate, resulting in a 25μ thick photosensitive plate. A photoreceptor having a three-layer structure was obtained by quickly applying the polyester film, and the surface was extremely smooth.

Examples 2 to 4 Cadmium selenide sulfate was prepared in the same manner as in Example 1 under the reaction conditions shown in the table below, and then made into a photoreceptor in the same manner as in Example 1.

/ Regarding the photoreceptors of each of the above examples, the following constants were performed and the effects were compared.

Measurements were made using the measuring device shown in Figure 1.

That is, a glass plate 5 having a transparent electrode 4 is pressed against the insulating layer surface of the photoreceptor 9, and the transparent electrode 4 is connected to a high voltage DC power source 6 via a relay switch 5. In the measurement, white light from halogen lamp 1 is used as front light by shutter 2, j*o, 2.
After irradiating with s・C and leaving it for 0.2 seconds, close the relay switch 5 for 0.2 seconds to apply a high voltage (Vm) to the photoconductor, and after leaving it for 0.2 seconds, apply sufficiently strong light for 0.2 seconds. After the second irradiation, the voltage level K on the surface of the photoreceptor (that is, the insulating layer surface 1i) was kept constant using the metal plate 7 and the surface potentiometer 8, which were at the same voltage as the photoreceptor. Applied voltage to the photoconductive layer when applying high voltage (
1/d can be calculated by Va-Va', so if vp is 6
Va (hereinafter referred to as V, -to) at which the voltage becomes 00V was determined, and the sensitivity was kept constant using the following method. That is.

V on the photoreceptor! Apply L-400 and irradiate measurement light in a friendly state. After irradiating the light, leave it for 0.2 seconds, as above,
is irradiated with strong light for 0.2 seconds, and the voltage U) on the surface of the photoreceptor is kept constant in the same manner as above.

The applied voltage (Ml) to the photoconductive layer when applying Va-40 and simultaneous constant light irradiation is Va-aoa-Va')
Since it can be calculated, Vp' Kas o o v Ktkh
6N1km constant light exposure (1m) is halved (1%)
In this way, the sensitivity of the photoreceptor can be displayed.

If you shoot 800nlllO party with K0j)K,
When the half-decrease exposure amount was calculated, the following results were obtained.

2 -850 1.4 5 -920 1.6 4 -840 1.2 In addition, Va is set to -20007 and the value of Marubasha's map p is constant. From this result, it can be seen that the photoreceptor according to the present invention has a sensitivity of one inch on the long wavelength side and also has a sufficient charge retention ability.

[Brief explanation of drawings]

4...Transparent electrode 5...Relay switch 4...High voltage DC power supply 7...Metal plate 8...Surface potential needle 9...Photosensitive plate Applicant: Canon Co., Ltd. Yoshihito Marushima Gi - “゛ 1).

Claims (1)

[Claims] t Selenium sulfate characterized by dispersing cadmium selenide and introducing hydrogen sulfide into an aqueous solution of nine cadmium ions to generate a mixture of cadmium selenide and cadmium sulfide, and then firing the axillary compound. A method for producing cadmium chloride particles.