JPS58145958A - Electrophotographic receptor and its manufacture - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic receptor having high sensitivity even to X rays, by mechanically combining a photoconductive thin plate obtd. by dispersing gamma type crystalline particles of a composite oxide composed of bismuth oxide into an amorphous chalcogen substance with the surface of a conductive substrate. CONSTITUTION:Particles <=2mm. particle diameter of gamma type crystals of oxides represented by the formula (M is at least one of Ge, Si, Ti, Ga, and Al; 10>=x >=14; and n is number of O stoichiometrically depending on M and x) is added by 10mg-10g per cm<3> of photoconductor, and said gamma type crystal particles are mixed with a chalcogen substance, such as Se, As2Se3, in (1:50)-(200:1) ratio by weight to prepare a mixture 15. The mixture 15 is placed on a conductive substrate 14 made of stainless steel, laid on the receiver 11 of a pressure molding machine, and pressure molded with a pressing piston 13. At the same time, the mixture 15 molded is heated to a temp. at which the chalcogen substance is melted, but the crystal particles are not melted, and then, it is cooled so as not to crystallize the chalcogen substance, thus obtaining a photoreceptor having high sensitivity also to X rays, and high mechanical strength.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrophotographic photoreceptor using a bismuth oxide-based composite oxide photoconductive phase material and a method for manufacturing the same.
xMO.

(However, M is at least one of germanium, silicon, f-tano, gallium, and aluminum, X is a number that satisfies the following conditions: 10':, The crystalline bismuth oxide-based composite oxide that is passed through (indicates the number of oxygen atoms determined stoichiometrically) becomes conductive when irradiated with X-rays or γ-rays. It is disclosed that it can be used as a photoconductive material for photoreceptors used in electrophotography in which an electrostatic latent image is formed by irradiation.
wthJ Vol. 1 No. 37 ~. 10 pages (1967)
K }3i, □Gem2.

As described in the electrophotographic method, the crystalline composite oxide becomes conductive even when exposed to visible light, and thus an electrostatic latent image is formed upon exposure to visible light: It is also useful as a photoconductive material for photoreceptors that are exposed to ζI{].

In addition, there are two crystal systems in the above-mentioned composite oxide: a body-cubic system (γ-type) and a plane-cubic system (δ-type).
It is the former that shows the above-mentioned photoconductivity in the title of the book.

JP-A-53-43531 mentioned above describes an electrophotographic photoreceptor using the above-mentioned crystalline composite oxide as a photoconductive material. It is not stated whether it is j, or δ type (
), this electrophotographic photoreceptor is described below. ) 2 1
Manufactured using M method. In the first method C, a layer of polycrystalline particles of the composite oxide is first formed on one surface of a conductive substrate. It has been stated that this polycrystalline particle coating is formed by a vacuum vaporization method, a spraying method, etc. The polycrystalline particle coating is sintered to form a thin plate-like polycrystalline body. For example, 1
3 + 12 'ie 020 VC in air or other oxidizing atmosphere from 8oo to 930'
It is stated that this is carried out at a hood degree of C. Sintered, i
/, in the Q culm, the polycrystalline grains have comrades #, V
At the same time as it is mechanically bonded to form a thin plate-like polycrystal, a part of it is also mechanically bonded to the conductive substrate. That is, what is manufactured by the first method (sintering method) is a conductive substrate and a thin plate-like polycrystal of the composite oxide mechanically bonded to one surface of the conductive substrate. The present invention is an electrophotographic photoreceptor in which the thin plate-like polycrystalline body (photoconductive layer) is a sintered body of polycrystalline particles of the composite oxide described in 1- above. In addition, as an alternative method to the above sintering method, first sintering the polycrystalline particles of the above composite oxide to form a thin plate-like polycrystalline body,
Thereafter, a method is described in which the -.no.1 surface of a conductive substrate is coated with this thin plate-like polycrystalline material.

In the second method G, the thin plate-like polycrystalline composite oxide is adhered onto one surface of a conductive substrate using a conductive adhesive. In other words, the electrophotographic photoreceptor manufactured by this second method (adhesion method) K consists of a conductive substrate, a conductive adhesive layer, and a thin plate-like polycrystalline body (photoconductive layer) of the above composite oxide. ) are stacked in this order. The thin polycrystalline material adhered to the conductive substrate by a conductive adhesive is likely to be cut from a large polycrystalline mass (polycrystal mass).

JP-A-56-5549 discloses that bismuth sirenite crystals represented by the composition formula 8% (where R is germanium, silicon, or titanium) included in the bismuth oxide-based composite oxide are photoconductive. An electrophotographic photoreceptor of a different type from the electrophotographic photoreceptor obtained by the above-mentioned sintering method or adhesion method, which is used as a material, is disclosed. That is, JP-A-56-55.
No. 19&C Opening and Engineering <Sit(・Runo) is a binder-dispersed electrophotographic photoreceptor. It is characterized by having a photoconductive layer of bismuth sirenite crystal particles or "-" (also used here, the crystal system of bismuth sirenite is γ-type or δ-type (・ is δ-type). All (d)4 are not listed (・). In the above-mentioned publication, several organic materials are described as specific examples of binders having charge carrier transport ability.

However, in the above-mentioned publication, all inorganic binders having charge carrier transport ability are not described.

(a) The invention is broadly (1) r of the above-mentioned bismuth oxide-based composite oxide.
The purpose of the present invention is to provide a novel electrophotographic photoreceptor with high sensitivity to X-rays, etc., using a type crystal as a photoconductive material, and a method for manufacturing the same.

I'lRIn the body, the present invention uses an inorganic binder, this υ)
A novel binder dispersion with high sensitivity to An object of the present invention is to provide an electrophotographic photoreceptor and a method for manufacturing the same.

The present inventors have so far conducted extensive research on forming a photoconductive layer of an electrophotographic photoreceptor by dispersing γ-type crystal particles of the above-mentioned bismuth oxide-based composite oxide in an inorganic (-4F-+) medium. As a result, the γ-type crystal particles of the bismuth oxide-based composite oxide and elemental selenium (S
e) A chalcogen substance such as arsenic selenide (As2Se3) is mixed in an appropriate ratio, and the resulting mixture is pressure-molded on a conductive substrate to form a thin plate-like molded product of the mixture on the substrate. After this pressure molding, or simultaneously with this υ0 pressure forming, the molded product is heated to an appropriate temperature with a conductive substrate.
The chalcogen substance in the molded product is heated to melt the chalcogen substance in the molded product, and then the heated molded product is cooled together with the conductive substrate at an appropriate rate to solidify the molten chalcogen substance as a J1 quality product. and thereby forming a thin plate-like photoconductive layer on a conductive substrate, comprising an amorphous body of a chalcogen substance and γ-type crystal particles of the bismuth oxide-based composite oxide dispersed in this amorphous body. It was discovered that the resulting photoreceptor has high sensitivity to X-rays, etc., and the present invention was completed.

The electrophotographic photoreceptor of the present invention comprises a conductive substrate and a thin plate-like photoconductive layer mechanically bonded to one surface of the conductive substrate, and the photoconductive layer is made of an amorphous material of a chalcogen substance. , dispersed in this amorphous body. It is characterized in that it consists of γ-type crystal particles of the bismuth oxide-based composite oxide. In general, the amorphous form of chalcogen substances has good electron and hole properties (
It has the ability to transport charge carriers) and at the same time has the ability to generate charge carriers.For this reason, the electrophotographic photoreceptor of the present invention generally has the ability to transport charge carriers (charge carriers). An electrophotographic method having a photoconductive layer in which body particles are dispersed in an organic material having a charge carrier transporting ability (not having a charge carrier generating ability) as described in JP-A No. 56-5549. It has higher sensitivity to X-rays and the like than a photoreceptor.

Further, the method for manufacturing an electrophotographic photoreceptor of the present invention includes: 1) mixing a chalcogen substance and γ-type crystal particles of the bismuth oxide-based composite oxide; 11) applying trn to the resulting mixture on a conductive substrate. Forming a thin plate-like molded product of the mixture on the conductive substrate, 110 Pressing the molded product together with the conductive substrate to form γ-type crystals of the bismuth oxide-based composite oxide at a temperature higher than the melting point of the chalcogen substance. IV) The chalcogen substance in the molded article is heated to a temperature lower than the melting point of the body to melt it, and then IV) the chalcogen substance in the molten state becomes amorphous.
- Cooling the heated molded product together with the conductive substrate at a rate sufficient to solidify in a solid state, thereby forming an amorphous body of the chalcogen substance and a γ-form dispersed in the amorphous body. The present invention is characterized in that a thin plate-like photoconductive layer is formed of crystalline particles and is mechanically bonded to the conductive substrate.

Furthermore, another method of producing an electrophotographic photoreceptor according to the present invention is to: 1) mix a chalcogen substance and the γ-type crystal particles of the bismuth oxide-based composite oxide, and 11) produce a conductive substrate that is the resulting mixture. At the same time, the mixture is formed at a temperature higher than the melting point of the chalcogen substance, but lower than the melting point of the γ-type crystal of the bismuth oxide-based composite oxide. 111) Heat the hot molded article to a low temperature to melt the chalcogen substance, and then heat the hot molded product with the conductive substrate at a rate sufficient to solidify the molten chalcogen substance in an amorphous state. (A thin plate-shaped light beam consisting of an amorphous body of the chalcogen substance and L-type γ-type crystal particles dispersed in the amorphous body, and mechanically bonded to the conductive substrate) Form a conductive layer.

It is characterized by

In the former method, a mixture of a chalcogen substance and γ-type crystal particles of a bismuth oxide-based composite oxide is first pressure-molded into a thin plate-like molded product, and then heated to release the chalcogen substance in the mixture. In contrast, in the latter method, the mixture is pressure-molded into a sheet-like molded product and at the same time heated v1 to melt the chalcogen substance in the mixture. In this way, in the latter method, the mixture is heated under pressure to melt the chalcogen substance, so that the photoconductive layer of the photoreceptor manufactured by the latter method is similar to that of the photoreceptor manufactured by the former method. The filling factor is higher than that of the photoconductive layer, and for this reason, photoreceptors made by the latter method generally have higher sensitivity than photoreceptors made by the former method. The photoreceptor manufactured by the former method has a smoother surface in terms of light guide than the photoreceptor manufactured by the former method.

The present invention will be explained in detail below.

The chalcogen compound, an amorphous substance of which is used as a binder in the electrophotographic photoreceptor of the present invention, is a sulfur group element,
Namely, sulfur (S), selenium (Sc) and tellurium (
A simple substance of Te), a compound of a sulfur group element, and a composition containing a sulfur group element are audibly exhaled. Here, the compound of sulfur group elements refers to compounds of sulfur group elements and As, Sb, Bi, Ge.
.

5117 yen), In, Ga, Cd, Cu, Zn, Ag,
Ti, Fe, Cr, Tl.

It is a compound consisting of elements such as lJg, Si, etc., and its representative examples include arsenic sulfide (As2S3), selenium (As25e3), and germanium sulfide (G).
e S2 ), germanium selenide (GeSe2),
Arsenic telluride (hes2'l"e3)1, bismuth sulfide (
B12S3), etc. In addition, compositions containing sulfur group elements refer to M-sulfur group elements, sulfur group elements-\, M
-Sulfur group element-X, sulfur group element-X-Y, M-sulfur group element-1-Y, etc., where M is As
, Sb, Bi, (ie, Sn, Pb, In
.

Ga, Cd, Cu, Zn, Ag, T+, Fe, Cr
, T l, f(g, S+3 elements, and X and Y
are Al and Sr, respectively).

Si, Mg, Ti, V, Mn, Cohigh, Ta
,Mo,W,Sn,'/,n,Pb.

Bi, Ag, Pd, In, (ia, S, Se, Te,
0. P., F., C.J., and Hr.

Indicates an element of 1st class. A typical composition containing a sulfur group element is Se doped with 1000 ppm of As.
+ segg As, l seg5T e5 +
5e9oAs5 Te5 +Ge2oBIxSe8o-
x (provided that X is 0≦x 730 ), etc. (the numbers at the bottom of each of the above compositional formulas indicate atomic percentages).

Among the simple substances of the sulfur group elements, the simple substance Se is particularly preferable, and among the compounds of the sulfur group elements, As25e3 is particularly preferable, and among the compositions containing the sulfur group elements in F, particularly preferable are Ge
Examples include HixSe8o.

The γ-type crystal of the bismuth oxide-based fused oxide, which is dispersed as particles in the amorphous body of the chalcogen substance described above and constitutes the photoconductive layer of the electrophotographic photoreceptor of the present invention, is The Ralski method, a single crystal pulling method using seed crystals [for example, the above-mentioned [Journal of (
,'ryslal (irowthJ Vol. 1 No. 37-4
0 (1967)], solid phase reaction method [e.g.
es, to atl, t3ur, Std, 68A (2) 1st
97-206 (1964)], a method of cooling and solidifying the molten liquid of the above-mentioned complex oxide while subjecting it to mechanical impact [for example, Kyoto University Chemical Research Institute [Hul.
Letin of the 1st-i tulc
For Chemical) tsearch J Vol. 55 No. 5 No. 447-456 (1977)]
, L composite oxide melt using a double crucible 3) Temperature gradient slow cooling method (41st Spring of the Chemical Society of Japan) F, Proceedings of the meeting [γ-6131゜03.
It may be manufactured by any of the conventionally known methods for manufacturing the r-type crystal, such as 9 in ``Production of 5in2 Crystal Plate'' (Of course, the γ-type crystal of the above composite oxide body: is a polycrystalline body (・ is a single crystalline body (・even if it is a deviation)
- is preferably a single crystal produced by the Czochralski method or the like from the viewpoint of photoconductivity. Generally, the γ-type crystals of the above-mentioned composite oxides obtained by conventionally known production methods are in the form of lumps, and therefore, after production, they are pulverized into particles having a particle size of about 9 (diameter) for use in the present invention.

From the viewpoint of photoconductivity, among the bismuth acid acetate complex oxides used as γ-type crystal particles in the electrophotographic photoreceptor of the present invention, M in the above compositional formula is one of germanium and silicon. A composite oxide that is either one or both, that is, its compositional formula is B + x (Ge 1y + Sry) On (
However, X and n have the same definitions as above, and y is a number satisfying the condition 0≦y≦1.) Complex oxides having the following formula are particularly preferred. 0) Among the specific composite oxides, the composite oxide with the above compositional formula 0 (i.e. 1311□Ge02o)
A composite oxide in which X is 12, y is 1, and n is 20 (i.e., B + +28r 028) is particularly preferable. Ru.

First, a γ-type aggregate of toric acid bismuth acetate-based composite oxide and an L chalcogen substance are mixed to prepare a raw material for an electrically conductive layer. Generally, composite oxide r-type crystal particles have a particle size of 2
min or less is used, preferably 200 μm
The following are used: 1. The weight ratio of composite oxide γ-type crystal particles and chalcogen substance is generally 1:50 to 2.
00:1, preferably 1:15 to 6:1. Mixing of the two is carried out using a mortar, ball mill, mixer mill, etc.

Next, the obtained mixture (light-guiding layer raw material) is placed on a conductive substrate, and molded on the substrate. By this pressure molding, a thin plate-shaped molded product of the above mixture with good surface flatness on the conductive substrate and improved filling and filling properties is formed. As long as the crystal particles are not distorted or destroyed, it is preferable that the pressure is as high as possible, and that the surface flatness and filling rate of the obtained thin plate-like molded product are increased as much as possible. The above mixture finally forms IJ
y, an amount such that the content of R-type composite oxide crystal particles in the photoconductive layer is from IC11 to 10 g per 1 d, preferably from 30 m9 to 19 g Conductive substrate-F
It will be posted on.

For example, the above-mentioned mixture may be pressure-molded using an apparatus such as the one shown in FIG. 1, which is a schematic cross-sectional view of its use.

This pressure molding device consists of a pedestal 11 having a convex portion in the center, a cylinder 12 attached to the pedestal 11 with one opening fitted into the convex portion of the pedestal 11, and a cylinder 12 attached to the pedestal 11. It consists of a JU piston 13 inserted from an opening. When adding the above mixture, the conductive substrate 14 is first inserted from the top of the cylinder 12 and placed on the convex part of the pedestal 11, and then the composite oxide γ-type crystal particles and the chalcogen substance are combined. A mixture 15 of
The liquid is introduced from above and placed on the conductive plate 14.

After that, the pressurizing piston 13 is inserted into the cylinder 12, pressure is applied to the upper part of the piston 13 by an oil EF press machine, etc., so that the piston 13 is not pushed down, and the mixture 15 is press-molded. After pressure forming, the piston 13 is removed from within the cylinder 12, the cylinder 12 is removed from the pedestal 11, and the conductive substrate 14 is removed.
The composite body consisting of the conductive substrate 14 and the thin plate-shaped molded mixture 15 formed on the conductive substrate 14 is removed from the convex portion of the pedestal 11. .

In addition, the conductive substrate used maintains the intensity of light at the temperature used to intimidate chalcogen substances in the molded product as described below, and・It is a conductive plate that does not react with air, and it can be made of any material (for example, aluminum, iron, copper,
A plate of car body metal such as nickel, molybdenum, tantalum, etc. and a plate of alloy such as stainless steel or chromel are used as the conductive plate.

Next, the thin plate-shaped object formed on the conductive substrate is heated together with the conductive substrate, and the chalcogen substance in the formed object is melted. For example, this heating is carried out by placing a composite body consisting of a conductive substrate and a thin plate-like molded product formed with the conductive base i J: :v on a panel-like heater such as a direct heating type heating plate. In addition, since this heating is intended to melt only the chalcogen substance in the molded article, the temperature is higher than the melting point of the chalcogen substance, but the bismuth oxide-based composite oxide that constitutes the molded article together with the chalcogen/substance is The first step is carried out at a temperature lower than the melting point of the γ-type crystal.
．． From the point of view of economy, etc., it is preferably carried out at a temperature slightly higher than the melting point of the chalcogen substance. In general, chalcogen substances have a much lower melting point than the γ-type crystals of bismuth oxide-based composite oxides. For example, the melting point of the γ-type crystal of B11°GeO2° is about 923°C, while
The melting points of Se and As2Se2 are approximately 22
0°C and about 180°C.

-F After the second heat treatment, the heated composite is cooled, and the molten chalcogen substance in the heated molded product is solidified as an amorphous body. In order for the chalcogen material in the molten state to assimilate into the amorphous material, the hot molded article must be cooled at a fairly rapid rate, and therefore generally υ1
Cooling of the thermal complex is forcibly performed using a cooler such as water. For example, the heating complex is cooled by placing the heating complex on a panel-shaped cooler such as a water-cooled cooling plate. By this cooling, the molten chalcogen substance in the heated molded product solidifies into an amorphous substance with γ-type crystal particles of the r-liquefied bismuth-based plate base oxide dispersed therein.
At the same time, part 0) The part in contact with the conductive substrate is the conductive substrate and mfTl! In this way, it consists of an amorphous body of a chalcogen substance and γ-type crystal particles of a bismuth oxide-based composite oxide dispersed in this amorphous body,
A lamellar photoconductive layer mechanically bonded to the conductive substrate is formed on the conductive substrate-L.

It should be noted that chalcogen substances in a molten state have extremely high reactivity, and therefore both the upper Mejrn heat treatment and the cooling treatment must be carried out in an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in a vacuum. However, when these treatments are carried out in vacuum, measures must be taken to prevent evaporation of the chalcogen substances, so it is particularly preferred that these treatments are carried out in an inert atmosphere. Further, it is preferable that the heat treatment and the cooling treatment are performed continuously in the same system (in the same atmosphere). For example, in heat treatment and cooling treatment, a panel-shaped heater such as an electric heating plate and a panel-shaped cooler such as a water-cooled cooling plate are installed inside the oven. It is carried out continuously in a glove box which is purged with active gas.

In the production method of the present invention described above (hereinafter, this production method will be referred to as the "first production method"), a chalcogen substance and γ-type crystal particles of a bismuth oxide-based composite oxide are mixed. The mixture is first pressure-formed into a thin plate-like molded product, and then heated to melt the chalcogen substance in the mixture, but the mixture is heated at the same time as it is pressure-formed into a thin-plate-like molded product. In another production method of the present invention (hereinafter referred to as "second production method 1"), the chalcogen substance in the mixture is melted. The above mixture is pressure-molded into a thin plate-like molded product and simultaneously heated to melt the chalcogen substance in the mixture.

In the second production method of the present invention, a mixture of a chalcogen substance and γ-type crystal particles of a bismuth oxide-based composite oxide prepared in the same manner as in the first production method (photon) is used. The conductive layer raw material) is attached to the conductive substrate on the substrate.
At the same time as the one-pressure molding, the substrate is heated together with the substrate, and the chalcogen substance contained therein is melted. As in the case of the first manufacturing method above, it is recommended that the pressure molding be carried out at a pressure that is as high as possible so that the composite oxide γ-type crystal particles are not distorted or broken. Preferably, heating is carried out at the same time as this pressure molding, and heating is also carried out at a temperature that is above the melting point of the chalcogen substance but lower than the melting point of the complex oxide γgSri tetracrystal, as in the case of the first production method. is carried out at a temperature slightly above the melting point of the chalcogen substance. Note that the pressure molding may be performed at a constant pressure, or may be performed by adjusting the pressure as appropriate depending on the degree of melting of the chalcogen substance. The latter α) Lifting platform It is generally preferred that the pressure be increased as the chalcogen substance melts. By this coloring and simultaneous heating, a thin plate-like heated molded product of the clay mixture containing the chalcogen substance in a molten state is formed on the conductive plate. As in the case of the first manufacturing method, the amount of the mixture is generally such that the content of R-type oxide crystal particles in the finally formed photoconductive layer is 10 m9 to 10 g per 1. , preferred (2 or 3
It is placed on a plate with a constant conductivity of 0 my to 1 g.

For example, pressure molding of the above mixture and simultaneous υ11
The heating is provided by a device such as that shown in schematic cross-section in its use in FIGS. 2 and 3, respectively. The υII JIE forming and h1 heating apparatus shown in FIG. 2 is an arrangement in which the pressure forming apparatus shown in FIG.
(, transmitted. Inside the heating plate 21, a cavity is provided from one end to the center, and the temperature adjustment thermocouple 23 is inserted into the cavity. Similarly, the mixture 15 placed on the conductive substrate 14 is pressure-molded by the pressure-forming device, and at the same time, the conductive base 1
4 and the mixture 15 is heated at an appropriate temperature by an electric heating plate, thereby producing a thin plate-shaped heated molded product of the mixture 15 in which the chalcogen substance is molten on the conductive substrate 14. is formed. Also the third
The pressure molding and heating device shown in the figure is the pressure molding device of FIG. 1 placed in a pressure jig and placed on an electric heating plate as in FIG. 2. The pressurizing jig includes a pressurizing frame 31 in which the pressurizing device shown in FIG. 1 is placed;
A pressure screw 32 is attached to the frame 31 so as to be located above the pressure piston 13 of the pressure molding device placed in the frame 31, and the tightening torque of this screw 32 is applied to the pressure molding device. A ball bearing 33 and a bearing receiver 34 for transmitting data to the piston 13 of
It is composed of L. A bearing receiver 34 and a ball bearing 33 are placed on the L portion of the piston 13 of the pressure molding device in which the conductive substrate 14 and the mixture 15 are loaded and the piston 13 is inserted, and tightened by turning the screw 32. It will be done. Tightening screw 32-)
The torque is transmitted to the former part of the piston 13 via the ball bearing 33 and the bearing receiver 34, and the piston 13 is thereby pushed down and the mixture 15 is pressure-molded. Set by. Meanwhile, at the same time as the pressure forming, the entire pressure forming apparatus and the pressure jig are heated to an appropriate temperature by an electric heating plate, whereby a thin plate of the mixture 15 in which the chalcogen substance is in a molten state is placed on the conductive substrate 14. A shaped heated molded article is formed. In addition, according to the pressure molding and heating apparatus shown in FIG. 3, the pressure of the horn 11 pressure molding can be changed during heating. As mentioned above, in general, as the chalcogen substance in the mixture 15 melts (it is preferable that the tightening torque of the screw 32 is increased to increase the pressure of press forming).

Next, in the thin plate-shaped heat-molded product formed on the conductive substrate as described above, the molten chalcogen substance in the heat-molded product solidifies as an amorphous body in the same manner as in the first manufacturing method described above. To: cool down the conductive substrate at a sufficient rate,
As a result, a thin plate-like light beam consisting of an amorphous body of a chalcogen substance and γ-type crystal particles of a bismuth oxide-based composite oxide dispersed in the second amorphous body is mechanically bonded to a conductive substrate. A conductive layer is formed on the conductive substrate.

In addition, in the second manufacturing method of the present invention, in order to prevent the reaction of the chalcogen substance in the molten state, the above-mentioned pressure molding, zero-mouth heat treatment, and cooling treatment are performed in a nitrogen atmosphere, an argon atmosphere, etc. These treatments must be carried out in an active atmosphere or in a vacuum.In particular, these treatments are preferably carried out in an inert atmosphere, and preferably carried out consecutively in the same system (in the same atmosphere). For example, in pressure molding, heating treatment, and cooling treatment, a pressure molding and heating device and a panel-shaped cooler such as a water-cooled cooling plate are installed inside as shown in Fig. 2 or 3. The test is carried out continuously in a glove box whose interior is replaced with an inert gas such as nitrogen gas or argon gas.

The second manufacturing method of the present invention described above is different from the first method of the present invention in that the mixture of chalcogen substance and bismuth oxide composite oxide γ-type crystal particles is pressure-molded and heated at the same time. The manufacturing method is different. Thus, in the second production method of the present invention, the above mixture is 1111 H
: , the chalcogen substance contained therein is melted, so that the photoconductive layer of the photoreceptor obtained by the second production method of the present invention is as good as the photoconductive layer obtained by the first production method of the present invention. The charge is higher than the photovoltaic layer of the body by 1.
(2) In general, the photoconductor produced by the second manufacturing method of the present invention has a higher resistance to X-rays, etc. than the photoconductor obtained by the first production method of the present invention. High sensitivity.Also L
As mentioned above, in the second manufacturing method of the present invention, the mixture is heated under pressure to melt the chalcogen substance contained therein, so that the actual shape of the carving does not occur in 17 when the chalcogen substance is melted. For this purpose, the photoconductive layer of the photoreceptor obtained by the second manufacturing method of the present invention is
The surface of the photoconductive layer is smoother than that of the photoconductive layer of the photoreceptor obtained by the manufacturing method described above. From these points, it can be said that the second manufacturing method of the present invention is a superior Ve method to the first manufacturing method of the present invention.

The electrophotographic photoreceptor of the present invention obtained by the manufacturing method described above (the first and second manufacturing methods) includes a conductive substrate and a thin plate-like photoconductor mechanically bonded to one surface of the conductive substrate. The photoconductive layer is characterized by comprising an amorphous body of a chalcogen substance and γ-type crystal particles of the bismuth oxide-based composite oxide dispersed in the amorphous body. It is.

In order for an electrophotographic photoreceptor using a bonding dispersion system to have high sensitivity, the binder, which is a dispersion medium for photoconductive material particles, has the ability to transport electrons and holes (charge carriers), and the photoconductive material It is necessary that the Ek carriers generated within the particles be transported within the photoconductive layer with a sufficient lifetime. In the electrophotographic photoreceptor of the present invention, the amorphous chalcogen substance constituting the photoconductive layer acts as a binder for the γ-type crystal particles of the bismuth oxide complex oxide. Crystalloids generally have good charge carrier transport ability. Therefore, in the electrophotographic photoreceptor of the present invention, the charge carriers generated within the γ-type crystal particles of the bismuth oxide complex oxide are chalcogen-based. The amorphous substance can be transported within the photoconductive layer with sufficient life using the amorphous substance as a medium.In this way, the amorphous substance of the chalcogen substance, which is the binder of the photoconductive layer of the electrophotographic photoreceptor of the present invention, can be transported within the photoconductive layer with sufficient life. Generally (2) It has good charge carrier transport ability, but at the same time it also has charge carrier generation ability,
Therefore, the electrophotographic photoreceptor of the present invention generally contains r-type crystal particles of a bismuth oxide-based composite oxide as described in JP-A No. 56-5549. It has higher sensitivity to X-rays and the like than an electrophotographic photoreceptor having a photoconductive layer dispersed in an organic material having a charge carrier transporting ability (generally not having a charge carrier generating ability) such as (.).

As is clear from the above description of the manufacturing method, the quantitative ratio of the γ-type crystal particles of the bismuth oxide-based composite oxide and the amorphous substance of the chalcogen substance constituting the photoconductive layer of the electrophotographic photoreceptor of the present invention is as follows. The weight ratio is generally 1:50 to 200:1, preferably 1:15 to 6:1. In addition, the amount of composite oxide γ type crystal particles contained in the photoconductive layer is generally 1 cr.
10 m9 to 10 g per I, preferably 30 m9
The amount is between 1g and 1g.

Furthermore, as explained earlier, among the nine electrophotographic sensors of the present invention, the photoreceptor obtained by the second manufacturing method has a higher photoconductivity than the photoreceptor obtained by the first manufacturing method. The filling factor of the layer is high (for this reason, the former generally has higher sensitivity than the latter. Also, the former has a smoother photoconductive layer surface than the latter.

The manufacturing method of the present invention is similar to the sintering method described in JP-A-53-43531 mentioned above in that heat treatment is performed during the process.

However, the manufacturing method of the present invention has the following advantages over the sintering method.

1 In the sintering method, the photoconductive layer is formed only from γ-type crystal particles of bismuth oxide-based composite oxide, so a photoconductive layer with high mechanical strength and charge carrier transport ability is formed. The contact area between the composite oxide γ-type crystal particles must be large (therefore, the grain boundary growth between the shallow composite oxide γ-type crystal particles must occur sufficiently).
・. 2) In the sintering method, the heat treatment needs to be carried out at high temperature for a long time (for example, Bi
, 20<em>O , the sintering should be carried out at a temperature of 800 to 930° C., as described in the above-mentioned Japanese Patent Application Laid-Open No. 53-43531).

Therefore, the sintering method requires large-scale equipment, which results in high equipment costs and high power consumption.On the other hand, in the manufacturing method of the present invention, the above-mentioned A mixture of composite oxide r-type crystal particles and a chalcogen substance is heat-treated, but this heat treatment generally melts only the chalcogen substance, which has a considerably lower melting point than the composite oxide γ-type crystal particles. Since it is aimed at the following, it does not require relatively low temperatures, and therefore the equipment cost is lower and power consumption is lower than that of the sintering method.

In addition, in the manufacturing method of the fourth invention, the photoconductive layer formed has sufficient mechanical strength because the composite oxide r-type crystal particles are dispersed in the amorphous body (binder) of the chalcogen substance. In addition, the amorphous form of chalcogen substances has the ability to transport charge carriers as well as the ability to generate charge carriers, so
High sensitivity to lines, etc.

2 As mentioned above, in the sintering method, heat treatment needs to be carried out at high temperature for a long time, but such heat treatment at high temperature and for a long time can damage the crystal system of bismuth oxide-based composite oxide γ-type crystal particles. J+ may partially change or increase lattice defects in the crystal grains, and the photoconductivity of the crystal grains may be degraded by J+. On the other hand, in the production method of the present invention, the heat treatment is performed at a low temperature such as
Therefore, the photoconductivity of the composite oxide γ-type crystal particles can be achieved at a temperature of t.
,(・can be reflected as is.

3 As mentioned above, in the sintering method, the heat treatment for sintering θ) needs to be performed at a high temperature, but this may cause the conductive substrate and the bismuth oxide-based composite oxide γ-type crystal particles to react. There is. Such a reaction reduces the resistivity of the photoconductive layer formed, making it impossible for the photoconductive layer to be corona charged, or otherwise deteriorating the photoconductivity of the photoconductive layer formed. Therefore, in the sintering method, the conductive substrate must be made of a material that does not easily react with the composite oxide γ-type crystal particles at the sintering temperature (for example, 800 to 930°C), and the selection of the conductive substrate The degree of freedom is quite low. In fact, JP-A-53-43531 mentioned above mentions a metal substrate coated with platinum as a conductive substrate suitable for the sintering method, but such a substrate is quite expensive. On the other hand, in the manufacturing method of the present invention, the heat treatment is performed at a relatively low temperature, so the degree of freedom in selecting the dedicated substrate in the manufacturing method of the present invention is high (for example, aluminum, iron, Single metal plates such as copper, nickel, molybdenum, tantalum, etc., and alloy plates such as stainless steel, chromel, etc. can be used as the conductive substrate.

As explained below, the present invention uses γ-type crystal particles of a bismuth oxide-based composite oxide as a photoconductive material, and incorporates the γ-type crystal particles of a bismuth oxide into an amorphous body of a chalcogen substance. X dispersed to form a photoconductive layer on a conductive substrate.
The present invention provides a binder-dispersed electrophotographic photoreceptor with high sensitivity to radiation, etc., and a method for manufacturing the same, and its industrial utility value is extremely large.

Next, the present invention will be explained by examples.

Example 1 B11□(”+c
()2o massive γ-type nested crystals were crushed using a pin mill, and the resulting powder was classified using a sonic cylinder to obtain a particle size of 2.
Particles ranging from 0 to 37 μm were obtained. This Bi, □Ge O2
γ-type crystal particles of o, 1.314 particles, and simple Se particles (
(purity 99.999%) and 0672.9 were thoroughly mixed using an agate mortar.

Next, the obtained mixture was poured into a stainless steel disk with a diameter of 40 mm (
conductive substrate) and pressure-molded on a stainless steel plate at a pressure of 2 kip/ffl using a pressure-forming device as shown in No. 14 to form a thin plate-like molded product of the mixture on the stainless steel plate. did.

Next, a composite body consisting of a stainless steel plate and a thin plate-shaped molded product of the above mixture formed on the stainless steel plate was placed on an electric heating plate and heated to a temperature of 230°C to remove the SL in the thin plate-shaped molded product.・The particles were melted. Immediately thereafter, it was transferred onto a water-cooled cooling plate, which is a heating complex, and rapidly cooled to room temperature at a cooling rate of 6.7° C./min, thereby solidifying cr)% molten Se in the heated molded product. The above-mentioned boosting treatment and cooling treatment were carried out continuously in a glove box in which an electric heating plate and a water-core TIR plate were installed, and the inside of which was replaced with nitrogen gas at 1 atm. I did it.

As described above, it consists of the above stainless steel plate and a 450 μm JI no. S + + 2 ('3 c02
An electrophotographic photoreceptor containing 0 gamma type crystal particles was obtained.

Next, I! measuring the X-ray sensitivity of the electrophotographic photoreceptor,
Ta. The corona charging conditions and X-ray irradiation conditions used in this X-ray sensitivity measurement and the measurement results were as follows.

1) Corona charging conditions Corona voltage; ±3 to 5 kV (Vmax ±200 to 15
00V) Diameter and number of corona wires; 30 μm,
2 2) X-ray irradiation conditions Photoreceptor surface irradiation dose rate; 4.65 mH/cedar (611 by Victorine 1 model 500 radiosensitivity meter) 3) Example of measurement results 2 Heating a pressure molded plate as shown in Figure 2 An electrophotographic photoreceptor was manufactured in the same manner as in Example 1, except that the pressure molding treatment of the mixture and the υ1 heat treatment were performed simultaneously using the apparatus (the ρ was used). The same procedure as in Example 1 was carried out at a pressure of 2 kg/~ and a temperature of 230'C.

In addition, for pressure forming, heating treatment, and cooling treatment, the pressure forming and heating device shown in Figure 2 and a water-cooled cooling plate are installed inside, and the inside is purged with nitrogen gas at 1 atm. The test was carried out continuously in a glove box.

The photoconductive layer of the obtained electrophotographic photoreceptor was made of the same components as the photoconductive layer of the electrophotographic photoreceptor of Example 1, but its thickness was 400 μm. The filling rate was higher than that of the photoconductive layer of the electrophotographic photoreceptor of Example 1. Moreover, the surface of this photoconductive layer is the electron "J'" of Example 1.
The surface of the photoconductive layer was smoother than that of the jE photoreceptor. When the X-ray sensitivity was measured in the same manner as in Example 1, this electrophotographic photoreceptor had a slightly higher sensitivity than the electrophotographic photoreceptor of Example 1.

Example 3 Using 083 g of AS2Se3 particles instead of Se particles,
An electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the temperature of the heat treatment was 200°C. The obtained electrophotographic photoreceptor consists of the stainless steel plate and a 450 μm thick thin photoconductive layer mechanically bonded to the stainless steel plate, and the photoconductive layer is made of amorphous A S 2 Sc and this The above 1'3 + dispersed in amorphous As2Se3
+ 2 (i +: 02°).

The As2Se2 particles used were obtained by first mixing S and Sc in a molar ratio of 2:3 (the mixture was sealed in a quartz tube under vacuum, then heated to melt it, and the molten material was cube-cooled. As a result, a lump of As2Se2 was obtained, and then this lump of AS2Se3 was crushed and classified.

When the X-ray sensitivity was measured in the same manner as in Example 1, the X-ray sensitivity of this electrophotographic photoreceptor was almost the same as that of the electrophotographic photoreceptor of Example 1.

Example 4゜AS2Se3 particles of Example 3 and Hi,□Gc02(,
Using a mixture with γ-type crystal particles, a mixture of
℃)) An electrophotographic photoreceptor was manufactured.

The photoconductive layer of the obtained electrophotographic photoreceptor was composed of the same components as the photoconductive layer of the electrophotographic photoreceptor of Example 3.
Its thickness was 400 μm, and therefore, this photoconductive layer had a higher filling rate than the photoconductive layer of the electrophotographic photoreceptor of Example 3. Further, the surface of this photoconductive layer was smoother than the surface of the photoconductive layer of the electrophotographic photoreceptor of Example 3. When the X-ray sensitivity was measured in the same manner as in Example 1, the sensitivity of this electrophotographic photoreceptor was somewhat higher than that of Examples 3υ and 7W photoreceptors.

Friend Example 5 8 (・Chalcogenide glass t...j' instead of particles
(Using 1,83y), heat treatment temperature to 250 (2). .In addition, the above-mentioned power Lucogenai 1-Gafs (O1i54 completed white- fraction is 20% (3
e, a composition consisting of 5% Bi and 75% Se.

The obtained electrophotographic photoreceptor consists of the stainless steel plate, a 500 μm thick thin photoconductive layer mechanically bonded to the stainless steel plate, the chalcogenide glass in which the photoconductive layer is amorphous, γ-type crystals of the above B11□Ge02o dispersed in this amorphous chalcogenide glass.
It consisted of a child. When the X-ray sensitivity was measured in the same manner as in Example 1, the X-ray sensitivity of this electrophotographic photoreceptor was almost the same as that of the electrophotographic photoreceptor of Example 1.

Example 6 Chalcogenide glass particles of Example 5 and B1.2GeO
An electrophotographic photoreceptor was produced in the same manner as in Example 2 (however, the heating temperature was 250° C. as in Example 5) using a mixture of 2o and γ-type crystal particles.

The photoconductive layer of the obtained electrophotographic photoreceptor has the same components as the photoconductor layer of the electrophotographic photoreceptor of Example 5, but its thickness is 450 μm. The filling factor was higher than that of the light guide layer of the electron 'lJ' electron receptor in Example 5. Further, the surface of this photoconductive layer was smoother than that of the photoconductive layer of the electron lJ receptor of Example 5. The X-ray sensitivity was measured in the same manner as in Example 1, and the sensitivity of this electrophotographic photoreceptor was somewhat higher than that of the iM electrophotographic photoreceptor of Example 5.

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view of a molding apparatus used in the first manufacturing method of the present invention. FIG. 2 shows the method used in the second manufacturing method of the present invention.
FIG. 2 is a schematic cross-sectional view of the non-generation type and the heating device in use. FIG. 3 is a schematic cross-sectional view of the pressure forming and heating device used in the second manufacturing method of the present invention.・
・Pressurizing piston 14...4 electrically conductive board 15...
・γ7 of bismuth oxide-based composite oxide (・Mixture of I crystal particles and chalcogen substance 21...Heating Temporary 22...H -
-23...Thermocouple 31...+1]-
: River frame 32... Pressure screw 33... Ball pair 34... Bearing receiver Th' 1 Figure tP, 2 Figure 3 Figure 3

Claims (1)

[Claims] (Comprised of an 11-conductive substrate and a thin plate-like photoconductive layer mechanically bonded to one surface of the conductive substrate, the photoconductive layer being a chalcogen substance) Amorphous The compositional formula of the amorphous body and its composition dispersed in this amorphous body is i MO (where M is at least one of germanium, silicon, titanium, gallium, and aluminum, and X is 10≦X: , 14 and n indicates the number of oxygen atoms determined stoichiometrically depending on M and X above. 7.) Electrophotographic photoreceptor. (2) The weight ratio of the γ-type crystal particles of the bismuth oxide-based composite oxide listed in L and the amorphous body of the chalcogen/substance labeled F is 1 by weight.
The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor has a ratio of :50 to 200:1. (3) 1 to γ of the above bismuth oxide-based composite oxide! The electrophotographic photoreceptor according to claim 2, wherein the ratio of the crystalline particles to the amorphous material of the chalcogen substance is from 1:15 to 6:l by weight. . (4) Is the photoconductive layer lcr/? Per-F acid bismuth oxide-based composite oxide r-type crystal particles YIO ~ ~ lo
An electrophotographic photoreceptor according to any one of claims 1 to 3, characterized in that the content of g is 7. (5) The electrophotograph according to claim 4, wherein the photoconductive layer contains 30 to 1 g of r-type crystal particles of the bismuth oxide-based composite oxide per 1 cm. Photoreceptor. (6) Claims 1 to 5), characterized in that the γ-type crystal particles of the bismuth oxide-based composite oxide have a particle size of 2 mm or more. An electrophotographic photoreceptor according to Item 1 of ΔP. (7) Claim 6, characterized in that the γ-type crystal particles of the bismuth oxide-based composite oxide have a particle size of 200 μm or less. fil J: The chalcogen substance is elemental selenium (Se
)-Q' The electrophotographic photoreceptor according to any one of claims 1 to 7. (9+ L chalcokene substance is arsenic selenide (As,
. Scρ as described in any one of claims 1 to 7]) An electrophotographic photoreceptor. (10) , ): The chalcogen substance has an atomic percentage of 2
0% germanium, O to 30% bismuth and 8
An electrophotographic photoreceptor according to any one of claims 1 to 7, characterized in that the composition is composed of 0 to 50 selenium. The electrophotographic image according to any one of claims 1, 7', and 10, wherein M is germanium and silicon, 0), 5), 0), 5), or both. Photoreceptor. (12) Group of the above bismuth oxide-based composite oxide) Irio M
12. The electrophotographic photoreceptor according to claim 11, wherein is germanium, X is 12, and n is 20. (13) Electrophotographic photoreceptor 5 according to claim 11, characterized in that in the compositional formula of the bismuth oxide-based composite oxide, M is silicon, X is 12, and n is 20. , (14)1) A chalcogen substance and its compositional formula i
MO (however, N1 is at least one of germanium, silicon, titanium, gallium, and aluminum, and X is a number that satisfies the condition 1011X≦14), and n is a chemical depending on M and 11) Mix the resulting mixture with γ-type crystal particles of a bismuth oxide-based composite oxide represented by 111) forming a thin plate-like molded product of the abrasive mixture on the conductive substrate); Heating to a temperature lower than the body's melting point1
- melt the chalcogen substance in the molded article, and then 1) melt the chalcogen substance in the thermoformed article at a rate sufficient to solidify the chalcogen substance in the molten state in a crystallized state; Cooled together with the conductive substrate 1, thereby forming the amorphous body of the chalcogen substance and the γ-type crystal particles of the bismuth acetate-based composite oxide dispersed in the amorphous body. A method for producing an electrophotographic photoreceptor, comprising forming a thin plate-like photoconductive layer that is mechanically bonded to a conductive substrate. (15) The 7'-type crystal particles of the bismuth oxide-based composite oxide and the chalcogen substance are mixed at a ratio of 1:50 to 200:1. The manufacturing method described in Section 1.1. (16) The gamma-type crystal particles of the bismuth oxide-based composite oxide and the chalcogen substance are mixed in a ratio of 1-15 to 6:1 in terms of a -Yamabake ratio. As stated in Section 15! 8! Construction method. (17) Claims 14 to 1, characterized in that the photoconductive layer contains 10 m9 to 10 p of γ-type crystal particles of the arsenth oxide-based composite oxide per 1 d.
The manufacturing method described in any of Item 6. , (18) The photoconductive layer contains γ-type crystal particles of the bismuth oxide-based composite oxide per 1 d of 30 m9 to 'r':19
18. The manufacturing method according to claim 17, which comprises: (19) Claims 14 to 18, characterized in that the γ-type aggregate particles of the bismuth oxide-based composite oxide have a particle size of 2 mm or less. (:1)) according to claim 19, characterized in that the γ-type crystal particles of the t-acid bismuth acetate-based composite oxide have a particle size of 200 μm or less! E! , 1 Your method. (21) +-Recording force is elemental selenium (Se
) 1-saving method according to any one of claims 14 to 20, characterized in that: (η) F-, the chalcogen/substance is arsenic senodide (A, s
2S c, 3) A manufacturing method according to any one of claims 11 to 20, characterized by a dot 8. (Z3) I]ti self-chalcogen substance is a atomic percent composition of 20% germanium, 0 to 30% bismuth and 80 to 50% selenium. The manufacturing method according to item 11, in which M in the composition formula of the bismuth oxide-based composite oxide is 5 of germanium and silicon. Claim 1 characterized in that it is either one or both.
The manufacturing method described in Items 1 to 1-, and Shi/Zuneka in Item 23. (25) The manufacturing method according to claim 24, wherein M in the compositional formula of the bismuth oxide-based composite oxide is germanium, x is 12, and n is 20. (26) M of the above-mentioned bismuth oxide-based composite oxide
25. The manufacturing method according to claim 24, wherein is silicon, X is 12, and n is 20. (27)1) A chalcogen substance and its compositional formula i
MO (where M is at least one of germanium, silicon, tita,..., gallium, and aluminum, X is a number that satisfies the condition 10≦X≦14, and n is a chemical depending on the above M and (indicating the number of oxygen atoms determined stoichiometrically) and γ-type crystal particles of a bismuth oxide-based composite oxide represented by At the same time as forming a thin plate-like molded product on the conductive substrate, the mixture is heated to a temperature higher than the melting point of the chalcogen substance but lower than the melting point of the γ-type crystal of the bismuth oxide-based composite oxide. melting the chalcogen material, and then 111) cooling the molten chalcogen material together with the thermoformed conductive substrate at a rate sufficient to cause the chalcogen material to solidify in an amorphous form, thereby melting the chalcogen material; It consists of an 11-particle substance and γ-type crystal particles of a 1-bismuth acetate composite oxide dispersed in this amorphous substance, and is Thin plate photoconductive 1!
', -: A method for producing an electrophotographic photoreceptor characterized by forming tF. (28) Claims characterized in that the bismuth oxide-based composite oxide J) gamma crystal particles and the chalcogen substance are mixed at a ratio of 1:50 to 200:1 in terms of middle eyelid ratio. The manufacturing method according to item 27. (29) The Φ1 ratio of the γ-type crystal particles of the bismuth oxide-based composite oxide and the chalcogen substance is 1:15 to 6.
29. The manufacturing method according to claim 28, wherein the mixing is performed at a ratio of 1:1. (I)) Claims 27 to 29, characterized in that the photoconductive layer contains 10 m9 to 10 g of γ-type crystal particles of the bismuth oxide-based composite oxide per 1 d.
The manufacturing method described in any of the paragraphs. (31) The manufacturing method according to claim 30, wherein the photoconductive layer contains 30 m9 to 1 g of γ-type crystal particles of the bismuth oxide-based composite oxide per 1 d. (:C) k: Any one of claims 27 to 31, characterized in that the particle size of the γ-type crystal particles of the bismuth acid acetate-based composite oxide is 2 mm or less. Manufacturing method described. (Claim 32) A manufacturing method, characterized in that the particle size of the γ-type aggregate particles of the bismuth oxide-based composite oxide is 200 μm or less. (31) The chalcogen substance h is elemental selenium (Se)
The manufacturing method according to any one of claims 27 to 33, characterized in that: C5) The chalcogen substance in F is arsenic selenide (A S
28e3) The manufacturing method according to any one of claims 27 to 33. C11i) j The bilayer chalcogen substance has an atomic percentage of 2
0 T germanium, 0 to 30 T bismuth and 8
Claims 27 to 33, characterized in that the composition is composed of 0 to 50% selenium.
The manufacturing method described in item 7L. (37) Claims 27 to 36, characterized in that M in the compositional formula of the bismuth oxide-based composite oxide is 5t, σ, or both of germanium and silicon. (38) A patent claim characterized in that in the compositional formula of the bismuth oxide-based composite oxide, 4 is germanium, X is 12, and n is 20. The manufacturing method according to item 37. (39) 1 of the compositional formula of the bismuth oxide-based composite oxide.
38. The manufacturing method according to claim 37, wherein is silicon, X is 12, and n is 20. (4o) The manufacturing method according to any one of claims 27 to 39, characterized in that the pressure molding is performed at a constant pressure. (41) During the heating, the Claims 27 to 3 are characterized in that the pressure of pressure molding is changed.
The manufacturing method described in any of Item 9.