JPS5955440A - X-ray electrophotographic receptor - Google Patents

Abstract

PURPOSE:To obtain an X-ray electrophotographic receptor of high sensitivity and high resolving power adaptable to diagnosis, etc., by providing an X-ray sensitive layer produced by dispersing n type semiconductor particles and a bismuth oxide composite oxide in a polymer on the conductive surface of a substrate and further providing a polymer layer thereon. CONSTITUTION:The gamma type crystal particles of the composite oxide expressed by the formula (M is >=1 kinds among Ge Si, Ti, Ga and Al, x is the number satisfying the condition 10<=x<=14, n is the number of O determined stoichiometrically by M and x) and n type semiconductor particles of >=1 kinds among ZnO, CdS, WO3 and TiO2 are dispersed uniformly in an org. binder such as a polyester resin or the like to form an X-ray sensitive layer of 10-2,000mu thickness. Such layer is formed on the conductive surface of a substrate. A polymer layer of 0.01-2,000mu thickness consisting of a polymer having film forming power such as polycarbonate, polymethyl methacrylate or the like or said polymer incorporated with a material having charge carrier transport power is formed on said layer. The X-ray electrophotographic photosensitive layer having high sensitivity, high resolution and high durability is thus obtd.

Description

[Detailed description of the invention]

The present invention has one blade on an X-ray electrophotographic photoreceptor. As the most lIIi sparrow i, r% 11C4A mouth, its composition formula is 1, (+ XN10.
Titanium, potassium and aluminum: - Uno, at least I, 1, \ is 10 <, x≦14, f+6- full, 42'F number, and nVI l-1
fL hate 11. Bismuth oxide system IM 7j Vine: Monster's body 7
The C-cubic thread (r-type) crystal became 11:1-18J. This r-type crystalline composite 111?2 compound's proboscis (l
When exposed to IX rays, it becomes conductive and f+'-
The light of a photoreceptor used in X-ray electrophotography, in which an electrostatic latent image is formed by irradiation with radiation, can be used as a photoreceptor (see No. 43531, 1971). ). X-ray quasi-photosensitivity (A-etc. is highly sensitive) provided on a gold conductive substrate with an X-ray sensitive layer comprising gamma quasicrystal particles of the above composite oxide dispersed in a binder. For example, a photoreceptor is conventionally known which is composed of a conductive substrate and an amorphous seleno layer provided by vapor deposition on the conductive substrate. Although it is practically used in manomography, etc., the above composite oxide
-')'/r- is dispersed in an organic binder to form an X-ray sensitive layer 1Δ. The sensitivity to X-rays is about 5 to 10 times higher than that of the photoreceptor used in the Juto region. By the way, the X-ray electrophotographic photoreceptor was used in X-ray electrophotography for the purpose of medical concessions to samurai.''The gift was that the photoreceptor must be as sensitive as possible in order to reduce radiation exposure to the patient. Desirable. From this point of view, it is desirable to further improve the sensitivity of a photoreceptor having an X-ray sensitive layer by dispersing the composite oxide/) r-type crystal particles in an organic binder. It is. When forming an X-ray sensitive layer, add 1 type semiconductor particles together with γ type crystal grains of the above-mentioned atomized compound into an organic binder. 51 The applicant has this 1.-: The above complex oxidation (r of the proboscis is a crystal ladle)
11 eight pieces with r-, 1 l body particle warehouse combined with 1 unit I)
1-L, X-ray electrophotographic photoreceptor gold tip with special 1 yen [out 1 head 7 (!Special application Sho 56-156695
issue). - The X-ray sensitive layer of the L photographic photoreceptor of Japanese Patent Application No. 56-156695 is as described above. The surface of the metal, which contains carbon dioxide particles in a dispersed state, is relatively homogeneous, !1'f
tl with large particle size! The coating surface of the X-ray sensitive layer using oxide-containing r-type, amorphous crystal grains, and 11-type semiconductor grains is quite large
When the No. 5 photoreceptor is used by the Carl Sono method, which involves 1. 19', transfer, and cleaning,
As described above, if the surface of the photosensitive XJJ layer is I'1, it has a negative effect on the image quality of the obtained image and the cleaning operation of the photoreceptor after image formation. In other words, the patent application was filed in 1983.
The photoreceptor of No. 6695 tends to cause fogging during I/color development, and therefore, images produced by I/I generally have a high fog density and a low I/C degree. 7F
/r='1. llll! +! 11 Showa 5 ()-1566
The photoreceptor No. 95 is generally used in photoreceptors with an amorphous selenium X-ray sensitive layer that are used in Toyoto.The remaining toner is removed by the normal cleaning/greasing method, which has an adverse effect on the next image formation. It is difficult to remove it to the extent that it does not cause any damage. The X#il electrophotographic photoreceptor of the present invention is I: Me 4&I
s: [j No. 56-156695) X aft photo E
te+ A layer of a polymer having a film-forming ability as an overcoat layer on the electro-sensitive X-ray layer, or an electro-fdf body transport material made by adding and mixing an organic charge J'lJ body transport substance to a polymer having a film-forming ability. A layer of a composition having the ability to improve the surface roughness of the photoreceptor, thereby improving the overall image quality of images obtained by the photoreceptor, as well as cleaning the photoreceptor after imaging. It is designed so that it can be done easily. That is, the first X-ray FL photographic photoreceptor d of the present invention includes: 1) a substrate at least one of which is electrically conductive; ii) a substrate for improving conductivity of the substrate; , an organic binder, and
dispersed in this organic binder. ) a layer consisting of the above-mentioned f quasicrystalline particles of the hibismuth-based composite oxide and 1)) n-type semiconductor particles, and iii)
There are 71 features consisting of a polymer layer having film-forming ability provided on the irradiation X-ray layer. Further, the second X-ray electrophotographic photoreceptor of the present invention comprises: - the first X-ray electrophotographic photoreceptor of the present invention;
In the
Ability to rupture membranes instead of a layer of polymers with - 6: Organic charge carrier transporter 'J! [5. Electron b'fJ-IJ, which is formed by addition and mixing, is provided with a layer of a composition having a body+14ii delivery ability. Detailed description of the present invention 1. The photographic sensitizer itself of the present invention is manufactured by the method described below. The feeling that is finally formed without doing
One or more types of organic substances (or two) that serve as organic binders for the ffM layer, such as specific sphere resins and their crosslinking agents, react with the binder during heat drying to form the final product. The feeling X formed in
γ of the bismuth oxide-based composite oxide described in -1- is added to a solution prepared by dissolving two or more organic substances serving as organic binders for the linear layer, or 2) J) and 2) in an appropriate solvent. 5) A dispersion liquid in which quasicrystal particles and n-type semiconductor particles are completely dispersed is prepared (hereinafter 1-1).
Notes 1), 2) and I) are referred to as 1-organic binder raw material), and the organic binder raw material is a complex acid, 1-arsenic R-type crystal particles, and n-type semiconductor particles. The counterfeit gold-forming material in which these particles are dispersed and has at least sufficient mechanical strength to withstand handling by ordinary X-ray electrophotographic processing methods shall not be made of any organic material. Good too. One or two types of organic binders that are generally known to be able to be used as raw materials for the organic binder constituting the photosensitive layer of the conventional electrophotographic photosensitive layer.
More than one type of organic substance can also be used as the base phase of the binder binder in the present invention. In addition, the molten material for dissolving the binder material in the note-taking machine to form a solution is appropriately selected depending on the organic binder raw material to be used. Particularly preferable organic binders constituting the X-ray sensitive layer of the X-ray electrophotographic photoreceptor of the present invention are polyester resins, polyester resins, and alkyd resins, for example, 1:1. , I: Mixtures with other resins, polynisder resins crosslinked with crosslinking agents such as diisocyanates, and mixtures of polyester resins crosslinked with said crosslinking agents and other resins such as alkyd resins. Do-+ Pu; C, Tokukaisho -55
In No. 49, r quasicrystal particles of the above-mentioned hismuth oxide-based composite oxide were electrolytically 1al J'1. An X-ray electrophotographic photoreceptor having an X-ray sensitive layer dispersed in a J-heavy binder having an ability to transport J-isomers has been disclosed. The organic binder may be one having a charge carrier transport ability as used in the photoreceptor disclosed in the above-mentioned publication. For specific examples of organic binders having charge carrier transport ability, please refer to, for example, ``2 Publication No. 2''. The r-quasicrystalline particles of bismuth oxide-based composite oxides are produced by crushing γ-type crystals (single crystals or polycrystals) of the composite oxide produced by conventionally known methods such as the Czochralski method. The composite oxide γ-type crystal particles generally have a particle size of 1000 μm or less, preferably 200 μm or less, more preferably], O08m.
The following are used: Among the bismuth oxide-based composite oxides used in the present invention, from the viewpoint of the sensitivity of the resulting photoreceptor, composites in which M in the above compositional formula is germanium, 1t, or one or both of germanium and silicon are preferred. oxide, that is, its compositional formula is 13tx((ic+-y, Sly) On (where X and I) have the same definition as above, and y is O≦y-=, 1
The complex oxide represented by the following formula is particularly useful. Among these specific composite oxides, a composite oxide having the above compositional formula 0 (B i 12Ge020
) and a composite oxide in which X is 12, y is 1, and 1] is 20 (ie Ui + zSiO2o) is particularly preferred. As a specific example of the n-type semiconductor particles used in the present invention, C
(diamond), Mg zAl 204, β-3iC
, Ti(J2, V2O5, V2O4, MIT02,
Fc203, FeS2. ZnO, Cu2S, Cu
1nSez, ZnS 1Zone. ZnTe 5GeSe 1SrO, NbzOs, N1
)20.1, N+1203, MOO3, MoS,
MO82, β-AgzS, β-Δgzsc, β-Ag
2Tc, (,:dS, Inse, Sou
, 5ll(12,5ure,5bzO4,'L'a
2Q3, Ta205, WO3, 11g5c, l(i
2S:l, 13i zsea, CeO2, NdzO
Examples include particles such as 3, PbCrO4, and IIgS. Among these n-type semiconductor particles, ZnO1CdSSWO3 and 'J'i
Particularly preferred are particles of . In general, the type 11 semiconductor particles used have a particle size equivalent to, but smaller than, the composite oxide γ type crystalline particles used in combination. Composite oxide γ quasicrystal particles and type I semiconductor particles are generally 1
The amount of type 1 semiconductor particles is used in a ratio such that the total amount of both particles is 0.1 to 50% by volume, preferably 1 to 30% by volume.
They should be used in proportions such that there are 3 to 10 volume fractions, more preferably 3 to 10 volume fractions. In addition, composite oxide γ quasicrystal particles, n
Generally, the amount of the organic binder material is 1 to 90% of the total amount of the semiconductor particles and the organic binder material.
It is preferably used in a proportion of 10 to 70 volumes, more preferably 20 to 50 volumes. Preparation of dispersion liquid &j, complex oxide γ quasicrystal particles and n 711! J
This is carried out by adding semiconductor particles and thoroughly stirring and mixing using an appropriate means. In this case, the J and 11 type semiconductor particles on the composite oxide γ type crystal particles are as primary particles as possible in the organic binder.
-1 It is preferable that it is dispersed in the solution. The dispersion prepared as described above is then applied uniformly onto the electrically conductive surface of a substrate, at least one of which is electrically conductive. The substrate used is the surface to which the dispersion is applied,
That is, any material may be used as long as the surface on which the X-ray sensitive layer is formed is conductive, but generally a metal plate is used as the substrate. Among metal plates, aluminum plates, stainless steel plates, and zinc plates are preferably used from the viewpoint of economy and handling.
stomach. The dispersion can be applied using a wire bar, doctor grade,
Row 1 is coated by a conventional coating method using a roll coater, knife coater, or the like. Generally, the dispersion is applied so that the thickness after heating and drying as described below (that is, the thickness of the X-ray sensitive layer) is 10 to 2000 μm, preferably 30 to 800 μm, more preferably 100 to 40 μm.
It is applied so that the thickness is 0 μm. After coating the dispersion, the dispersion coating is dried by agitation at a temperature of 1.1 degrees higher than the boiling point of the solvent contained in the dispersion. This heating drying is carried out to remove the solvent contained in the dispersion liquid at ℃°C to form an X-ray sensitive layer on the substrate, and the organic binder raw material is 2) or 3) above. In some cases, this heat drying also serves to react the reactive components constituting the raw material to form an organic binder or a part of the organic binder. The X-ray sensitive layer formed by this heat drying is composed of an organic binder, and complex oxide γ quasicrystal particles and 11 type semiconductor particles dispersed in the organic binder. In addition, when the X-ray sensitive layer formed on the substrate as described above is further heat-treated at a temperature higher than the softening point of the organic binder constituting the X-ray sensitive layer but lower than its decomposition start temperature. In this case, the sensitivity of the X and i1 layers is further improved. This heat treatment has a sufficient sensitivity improvement effect (1 ton, 5
The temperature and time must be strictly controlled (i.e., when heat treatment is carried out at or near the softening point of the organic binder, in order to obtain a sufficient sensitivity improvement effect, 4149',' requires a relatively long heat treatment, and conversely, when heat radiation 1JP is carried out at a temperature close to 1!iA degrees at which the organic binder starts to decompose, a relatively short time is required. A sufficient sensitivity improvement effect can be obtained by heat treatment 1. In particular, if the heat treatment causes the organic i-antagonist to decompose at 61.311 degrees, the sensitivity will increase. The heat treatment time needs to be controlled more strictly to prevent burning or scorching of the X-ray layer.Generally, the sensitivity of the X-ray sensitive layer subjected to the above heat treatment is the same as that of the X-ray sensitive layer before heat treatment. The sensitivity of the X-ray sensitive layer is improved by the heat radiation 14j, which is about 2 to 3 times the sensitivity. This is thought to be due to improved contact with the substrate. The X-ray sensitive layer consists of an organic binder, a) gamma quasicrystal particles of the bismuth oxide-based composite oxide, and l) type II semiconductor particles dispersed in the organic binder. An electrophotographic photoreceptor (i.e., the X-ray electrophotographic photoreceptor of the above-mentioned Japanese Patent Application No. 156,695/1983) is obtained, but the surface of the X-ray sensitive layer of this photoreceptor is generally rough, and in particular, the surface of an Crystal particle O type 6 and 11”
l′□! The surface of the X-ray sensitive layer where the 'h-body particles are used is quite rough. In order to improve the surface smoothness of the X-ray sensitive layer of this X-ray electrophotographic photoreceptor, next, a layer of a polymer having film-forming ability or a polymer having film-forming ability is charged with an organic charge on the Xa layer of this photoreceptor. A layer of a composition having a charge carrier transport ability, which is obtained by adding and mixing a carrier transport substance, is formed as an overcoat layer. Examples of polymers having θυ film-forming ability constituting the overcoat layer of the X-ray electrophotographic photoreceptor of the present invention, either alone or mixed with an organic tL carrier transport substance, include (lower polycarbonate-I). , poly”crystallized vinyl, j
δ Vinyl 11ide-vinyl acetate copolymer, vinylidene chloride vinyl chloride copolymer, vinylidene chloride acrylonitrile copolymer, poly; 1-burene, poly-α
Methyl styrene, poly, nopur methacrylate, polymethyl acrylate, polybutyl acrylate, polyvinyl butyral, polyvinyl formal, polyvinyl pyrrolidone, polyvinyl alcohol, polyacrylamide, polyacrylonitrile, diacetylcellulose, triacetylcellulose, Cellulose nitrate, 11-11-sulfitate, ethylcellulose, cyanoethylcellulose, poly-N
Vinylcarbazole, polyvinylpyrene, polyester, PoIJ7mide, styrene-butadiene copolymer, styrene-methyl methacrylate copolymer, styrene acrylonitrile copolymer, vinylidene chloride-vinyl acetate copolymer, chlorinated polyethylene, chlorine [hypolypropylene, phenol-forno- Aldehyde resin etc. can be used alone. Here, the monomer content ratio of the copolymer is not particularly limited. Among the above polymers, organic polymers with high mechanical strength 11-! Particularly preferable materials for the overcoat layer of the present invention include polycarbonate, polymethyl methacrylate, polyvinyl butyral, etc., since they have a high charge 111 body transport efficiency. Of course, the two polymers having film-forming ability as described in item 1 may be mixed together and used as the overcoat layer 4A. Na,t
δ, -, Il j does not self-support and does not form a model (J-J among the polymers, polyN vinylcarbazole and polyvinylpyrene have the ability to transport 4 μm charge bodies. The organic charge carrier transporting material constituting the overcoat layer of the photoreceptor of the present invention may be an electron-accepting material or an electron-donating material. Examples of receptive organic charge carrier transport substances include compounds having an electron-accepting N-nuclear structure such as carboxylic acid anhydrides, ortho- or para-quinoid structures, electron-accepting compounds such as nitro groups, nitroso groups, and cyano groups. Examples include aliphatic compounds, aliphatic cyclic compounds, compounds, heterocyclic compounds, etc. having a substituent of The organic charge carrier transport substances are 4-nitrogyzanthone, 9.10-dinitroanthracene, ]-nitroanthracene, 2-nitrophenanthrenequinone, 2.5-dinitrofluorenone, 2
, 6-dinitrofluorenone, 3゜6-dinitrofluorenone, 2,7-dinitrofluorenone' 2+4+
7-i21・Loa /L/Olenone, 2,4,5.7
-tetranitrofluorenone, 3,6-sinitrofluorenone mantenonitrile, 3-nitrofluorenone mandenonitrile) IJru, etc. Examples of electron-donating organic charge carrier transport substances include triarylmethanes (US 3,542,547), triarylalkanes and tetraarylmethanes (US 3,542).
, 544), diarylalkanes (US 3,615)
, 402), N,N-dibenzylaniline derivatives (US
3,767°393), aniline derivatives (13 "mouth 1,
316°994), distyryl-containing aromatic compounds (US
3.873.311), polyaryl hydrocarbons (US4
．． 045,220),) Litriamine (tJs3゜732.554), Arylamines (
US3°240,597, US3,180,730, US3,567+450, US3,658,520. Same 3,6
15,414), tetraphenyldiaminobiphenyl M
(Us, t. 047.948, 4,047,949), 4-diarylamino substituted chalcones (US3.fi15°414)
), pyrazolines (TL83, 837, 851, TL 3,180,729), oxadiazoles (US 3.
18! l, 4117L thiadiazole j'JI (ll
r i tl, 004,929), 5-aminothiazoles (tl83,161.5(15),) Rifso 7+4ji (US3.112.J97, US3.112.
2,435.1.3rit951, J'O(i, same95
2,906), (Migzo r17 class (US 3,097,
095), Oxyryzole j, 1] (lJrit 87
/I, 634), thiazole JJ'l (Ilr
i tl, 008,631), imidazole j, self (
Ilri1938.434), bisimidazo! J
'1, l'i (US3.127,266)
1), J, 2,4-triazine'Igl (tJs3゜1
30.046), arylidene oxyresolones (U.S.
3,072,479), benzothiazoles, benzimidazoles, benz, tA-zazoles (130L895
, 001, same], 008. (i32), quinazolines (
US 3,139,339), benzofurans (US
3,140,946), acridine and phenazines (
US 3,244,5] (i), carbazoles (US
3,206,306), ethylene derivatives (US 3
, 24.6, 983)-, benzylideneanilines (13rit 836.151), polyenes (13
rit 964, 874), aminostilbenes (U
S 3,158,475), aryl ketones (Br 1,008,633), and the like. Here, the US has a US patent under 130

[ represents a British patent, and specific examples of the above-mentioned compounds are shown in the specifications of these patents. Matter/quality is 1, 3, 5
− ) ') Phenylhylasoline, ]-phenyl-3-
(p-dimethylaminostyryl)-5-(1)-trimethylaminophenyl)-pyrazoline, 1-phenyl-3
-(P-methoxystyryl)-5-(+)-methoxyphenyl)-pyrazolino, 1-phenyl-3-styryl-
Pyrazolines such as 5-phenylhylasoline, ]-]phenyl-3-phenyl-5-p~dimethylaminophenyl)-pyrazoline; Triaryl or diarylmethane M such as leucomalachite green, leuco crystal violet, and tetrabase; 4,4 '-Benzyritine bis(N. N-diethyl-111-toluidine), 2',2"-dimethyl-4,4',4"-)lis(dimethylamino)
Triphenylmethane, 1!7) 1', country 9'! Triarylmethane compounds described in J° Pat. )/U.S. patents 3, 6 for clohexane, etc.
Diarylalkane compounds described in 15,402M; U.S. Pat. 4-N,N-dimethylaminophenyl-4'-N,
N-dimethylaminostyryl ketone, 1-(p-N,
N-dimethylaminobenzoyl)-4-(p-N, N-
dimethylaminophenyl)-butadiene-1゜3, di(
p-N, N-dimethylaminostyryl) ketone, di(p
Chalcone and diaryl ketones such as -N, N-diethylaminophenyl coketone; p-N, N-dimethylaminostilbene, p -p/ -N, N,
Aminated hydrocarbons such as N', N'-tetramethyldiaminostilbene, etc., and particularly preferred among these are], , 3, 5-) liphenylvirazoline,
1-phenyl-3-(p-dimethylaminostyryl)-
5-(p-dimethylaminophenyl)pyrazoline, 1-
Phenyl-3-(1)-methoxystyryl)-5-(p
-methoxyphenyl) -pyrazoline, 1-phenyl-
Pyrazoline compounds such as 3-,1-IJ-5-phenylvirasoline, 1-phenyl-3-phenyl-5-(1)-cyaminophenyl)pyrazoline, 4,4
'-Benzylidene-bis(N. N-dimethyl-lo]-toluidine), 1,1-bis(4
-N, N-dimethylaminophenyl)-4-methylchlorohexane, tos(t+-tolyl)amine, and the like. The Onibarcode layer is made by dissolving a polymer capable of forming a film in a solvent that can dissolve the polymer. Prepare,
The resulting solution is applied onto the X-ray sensitive layer by a general coating method using a wire bar, doctor blade, roll coater, knife coater, etc., and then the coating film is heated and dried. . The ratio of polymer to solvent is preferably about 50 to 0.5 mw. Alternatively, the overcoat layer can be formed by dissolving a polymer having film-forming ability in a solvent capable of dissolving the polymer, and dissolving or dispersing the organic heavy carrier carrier Y'[A') or its solution in the resulting solution. 4: Adjust and apply this coating solution to the 2nd X-ray layer by a general coating method using a wire bar, doctor blade, roll coater, knife, etc. It is formed by coating and then heating and drying the coating film. The ratio of polymer to solvent is preferably about 50 to 0.5 parts by weight, and the content of organic charge carrier transport material is generally 0.3 x 10-'' to 3 x ] O-3 mol, based on polymer 19.
Particularly bright is 0.8X10' to 2X10-"mal. Charge 11-body transport ability formed by adding and mixing an organic charge carrier transport substance to a layer of a polymer having a film-forming ability or a polymer having a film-forming ability. The solvent used when forming the layer of the composition is preferably one that can dissolve the polymer having film-forming ability and that is suitable for dissolving the organic binder constituting the X-ray sensitive layer. Oats: - The thickness of the coating layer is appropriately selected depending on the degree of roughness of the surface of the X-ray sensitive layer, but is generally 0.01 to 2000 μm, preferably 0.1 to 200 μm. The X-ray electrophotographic photoreceptor of the present invention obtained by the manufacturing method described includes: 1) a substrate having a small amount (both sides of which are conductive); agent and dispersed in this organic binder; 1)
γ-type crystal 1 of the above bismuth oxide-based composite oxide: Q/, crystal and I)) 11-type semiconductor particles x +fj
J layer, and a layer of a polymer having a membrane rupture forming ability provided on the X-ray sensitive layer 11D, or an organic charge 41. ! It consists of a layer (overcoat layer) of a composition having a charge carrier transport ability, which is made by adding and mixing a body transport substance. On the surface of the photoreceptor of the present invention, that is, on the polymer having a film-forming ability or the polymer having a film-forming ability, an organic charge carrier transport substance t'f'<+-
The surface of the overcoat layer of the charge carrier transport ability Br composition obtained by adding and mixing 4 is significantly smoother than the surface of the photoreceptor before the overcoat layer is provided, that is, the surface of the X-ray sensitive layer. . Therefore, when used according to the Carlson method, the photoreceptor of the present invention is provided with the above-mentioned overcoat layer.
Comparison 1. Tei・
An organic charge carrier transporting substance is added to a polymer that does not easily cause fogging during color development and has the ability to form image apertures and edges 111 obtained by the uninvented photoreceptor in II'1-J, or to a polymer that has the ability to form a film. The fog density is lower and the resolution is higher than that of an image obtained by depositing on a photoreceptor without an overcoat layer of a composition having a charge carrier transport ability, which is formed by adding and mixing the composition. In addition, a photoreceptor (・It is difficult to remove residual toner to a degree that does not adversely affect the next image formation using the normal cleaning method that is generally applied to photoreceptors having a conventional amorphous selenium-sensitive X-ray sensitive layer. However, since the photoreceptor of the present invention has an improved surface smoothness, it is possible to almost completely remove residual toner by the above-mentioned normal cleaning method, and the photoreceptor of the present invention can be cleaned. The photoreceptor can be used as it is for the next image formation.In this way, the uninvented photoreceptor has the ability to form a film.
Organic type nrj tl-t body width'l for polymers with - or film-forming ability! l1l) 7j
All added and mixed Ci, + Ichang lU: 1 with carrier transport ability
The overcoat of the lll composition is much easier to clean than the photoreceptor without the -1 layer, and therefore, using the photoreceptor of the present invention By making cleaning easier, it is possible to simplify the image forming process, and in turn,
It is possible to downsize the line electrophotographic device. The organic charge phase transport material used in the overcoat layer of the X-ray electrophotographic photoreceptor of the present invention has excellent charge carrier transport ability. Therefore, P/! is provided on the X-ray sensitive layer to improve the smoothness of the photoreceptor surface. 8 The charge carrier transport ability obtained by adding and mixing an organic material to a polymer having film-forming ability is °J':i'-',
) The overcoat layer of the composition generally has a good Ir/, 1'
, electron: ・Has f carrier transport ability.This 5 V
It is preferable from the viewpoint of the IW sensitivity of the photoreceptor that the t2,4-barcode layer has a charge carrier transport ability. In addition, when an electron-receptive material is used as the organic charge carrier transport material, it is advantageous when positively charging the photoreceptor, and when an electron-receptive material is used, it is advantageous when negatively charged. . As explained above, the present invention was filed at the time of
A charge carrier formed by adding and mixing a polymer having a film-forming ability or an organic charge transporter to a polymer having a film-forming ability as an overcoat layer on the X-ray sensitive layer of the X-ray electrophotographic photoreceptor of No. 6695. A layer of a composition having transport properties is provided to increase the smoothness of the surface of the photoreceptor, thereby improving the quality of images obtained by the photoreceptor, and to improve the smoothness of the surface of the photoreceptor after imaging the photoreceptor. It is designed to make it easy to clean the area, and its industrial applications are large. Next, the non-invention will be explained with examples. Example J Methyl ethyl ketone and toluene
, mixed solvent 71 (polyester resin (Toyobo Byron 20 F+) 15〃, alkyd (IYJ moon 10 width I 11% ginkgo solution)
Large "1 ink chemical lower bag beno! Light f\・l-
6202-40) 1. 2 5, γ dimension;
An organic binder raw material solution was prepared by adding 0.2.9 (dipping and melting) to the organic binder raw material solution.Next, to this organic binder raw material solution was added I
-1i 12 ('ic 020 r quasicrystal particle 4 (1
, 9 and 11 type semiconductor particles as ZnO particles (capture 1
Add 2 g of Higaku Sazetsu/1000) and mix at 10000 rllllll for 3 minutes using a homogenizer.
″l″j, ,l′1′? j'I, together with IJ i,
2QcO,,6 particles and ZnOJ matrix:
' (j4 Dispersed in liquid.Hi used for one time,
The r-type crystal particles of 2(i(・()2+1) were obtained by crushing and classifying the γ-type nest crystals of Bi,..., Gc02o produced by the Czochralski method.The resulting dispersion liquid Using a large doctor blade, dry the aluminum plate-1 to a thickness of approximately 400 μm.
3 kt - evenly coated. After coating, the coating was dried by heating in the air (i 0 ''G) for 1 hour, and then heated in the same atmosphere at 120'C for 10 hours to form an X-ray sensitive layer on the aluminum plate. In this way, an approximately 400 μm thick X-ray sensitive layer in which the above 13 i , GcO 2 o γ quasicrystal particles O 6 and the above ZnO particles were dispersed in the mixture of the above polyester resin and the above alkyd resin was formed on an aluminum plate. In order to improve the sensitivity of the body, the photoreceptor was further placed in the atmosphere at a temperature of 240'C (higher than the softening point of the mixed resin described above, but its decomposition). Irradiation was carried out for 2 hours at a temperature (lower than the starting temperature) for 2 hours. After the heat treatment, a layer of a polymer capable of forming a film with a thickness of 10 μm was formed on the X-ray sensitive layer of the photoreceptor. This polymer layer was First, poly N-vinyl gabazole (Tubicol-210 manufactured by Takasago International Corporation), which is a polymer with film-forming ability, and polynisder resin (Vylon-20, manufactured by Toyobo Co., Ltd.), which is a polymer that also has film-forming ability.
0) Prepare a coating solution by dissolving 0.02゜' / 0.02゜' in the organic solvent tetrahydrofuran 90〃.
) to a thickness of 10 μnL after drying.
'C' Heat dried for 1 hour and is also popular - (
'J2 (+') was dried for 10 hours to form -(-). In this way, the line electrophotographic photoreceptor fj
)is. This photoreceptor was designated as photoreceptor 461. A photographic photoreceptor with the above-mentioned composition was prepared in the same manner as described above except that the layer with the above-mentioned composition was not provided. This photoconductor is called photoconductor/162. The surface of the overcoat layer of photoconductor T61 provided with the overcoat layer had significantly higher smoothness than the surface of the X-ray sensitive layer before the overcoat layer was formed, that is, the surface of photoconductor 462. The X-ray sensitivities of the photoreceptor of the present invention, =rc 1, and the comparative example photoreceptor 7462 obtained as described above were measured as follows. The photoreceptor Al of the present invention and the photoreceptor Galo 2 with a ratio of 1 bite were charged with a corona band at a corona voltage of -5 kV in a dark place, and then the surface potential side (for 1-1 Denki Tai 5SV-11, -50
) while defining the surface potential!・The photobody was irradiated with X-rays. X-ray irradiation a': fl is as follows. It was 11n. X-ray generation control device Toshiba kXo 15XIvII
J tube Toshiba q (l January LX-]! IO
A tube voltage 80 kV. Tube current] + lIA focal point - distance between photoreceptor] 7r + irradiation mode
− Continuous mode photoconductor surface irradiation rate 4
．． 7 ml, /sec (measured value based on Model 500 ray measuring device ν manufactured by Bili-Lean) As a measure of X-ray sensitivity, the surface 1a position in front of the X-ray illumination surface (initial pressure of about 1υ1′I) is used as a measure of X-ray sensitivity. Reduced to half 1 (necessary irradiation, &! amount (half-attenuated irradiation 111'L') i1." i
T! 11. So-no-'A? <'r:', bottom 812', n I
Table K Show-'I-n lower 11 first go 1\/door clear/work, l, 5-1, 1, 1]9] over:
The photoreceptor of the present invention was manufactured in the same manner as the photoreceptor ri1 of the present invention, except that the 111 overcoat layer was not provided. It exhibited almost the same sensitivity as the photoconductor 162 of the comparative example, which was contaminated. Table 1 Next, the resolution of the photoreceptors 461 and GALO 2 was measured as follows. Photoreceptor 7461 of the present invention and ratio ψ (example photoreceptor/46
2 in the dark at a corona voltage of -5 kV, Tt
No way, IJ4IL FUNK o) TJK
X-ray image exposure is performed using an X-ray test chart manufactured by J-'OTO, and further development is performed using powder toner positively charged by magnetic blanking to create a toner image (
It's J. Toner image as a measure of ivr image 1 h] mrn
The number of lines identified per line was measured. The results are shown below in Table 2. Note that the X-ray irradiation strip 1'1 had the same sensitivity as the sensitivity d11j described above. As is clear from Table 2 below, the photoreceptor/16 J provided with the overcoat layer of the present invention is a photoreceptor manufactured in the same manner as □f61 except that no overcoat layer is provided. It showed significantly higher 19-dimensional image resolution than that of 462. Table 2 Furthermore, the toner image obtained by the above toner development was transferred to paper by a conventional method to form a transferred image. In the case of toner images, two transfer images were obtained using the photoreceptor-tb I of the present invention, and the transferred images were obtained using the photoreceptor 162 of the comparative example.
l,, il - The resolution is significantly higher than that of the transferred image,
Moreover, the image was clear and had little fogging. Also,
The photoreceptor of the present invention, which is smaller than the Seikou body '16 J,
When 462 was cleaned using a normal cleaning method, it was found that 462 was a photoreceptor without an overcoat layer.
In contrast, it was difficult to remove residual toner to the extent that it did not adversely affect the next image formation, whereas in the photoreceptor having an overcoat layer, which was undiscovered,
1: The remaining toner was easily removed, and the toner was ready to be used for the next image formation.Example Methyl ethyl ketone and toluene were mixed A 40 wt-fi% xylene solution of polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.) and alkyd resin (Pesokolyte M manufactured by Inu Nippon Ink Chemical Industry Co., Ltd.) was added to 7.8 g of a mixed solvent prepared by mixing at a weight ratio of 1:A. -6202-40) 1., 25
g was added and dissolved with stirring to prepare an organic binder raw material solution. Next, 40 g of B i , . The mixture was stirred and mixed at 110,000 rl1 for 3 minutes to disperse the B i ,..., Gem2o particles and ZnO particles in the solution. Furthermore, the f3 + +2 CI used
C'20 r-type crystal particles were obtained by crushing and classifying γ-type nest crystals of Bi, 2Qe02o produced by the Czochralski method. The obtained dispersion was uniformly applied onto an aluminum plate using a doctor blade so that the j9 after drying was about 1100 μm. After coating, the coating film was heated and dried in the air at 60°C for 1 hour, and then dried at 20°C (in the air) for 10 hours.
An X-ray sensitive layer was formed on the aluminum plate by heating and drying for a period of time. In this way, the above-mentioned Bi is added to the mixture of the above-mentioned polyester resin and the 2nd grade alkyd resin (3c02
About 4 in which o1 type crystal particles and the above ZnO particles are dispersed
An X-ray>C photographic photoreceptor having a 00 μm thick X-ray sensitive layer on an aluminum plate was obtained, but in order to improve the sensitivity of this photoreceptor, the photoreceptor was further exposed to a temperature of 240°C (
The mixture was heat-treated for 2 hours at a temperature higher than the softening point of the mixture 1 fat but lower than its degree of decomposition initiation. After the above heat treatment, the sensitivity of the photoreceptor was X#3+! Adding an organic charge carrier transport substance to a polymer capable of forming a film with a thickness of 10μ7n in layer-1 2r+'; A layer of a composition with charge carrier transport ability was formed (-).The layer of this composition was first formed with an organic solution r5), a substance 1-phenyl-3-(τ-methoxy7-styryl), and a substance 1-phenyl-3-( )-5-(1)-Methoxyphene:2-l)-pyrazoline (06 g) and polycarbonate (04), which is a polymer having film-forming ability. A coating solution was prepared by dissolving 7 and 0.9 in the organic solvent trichloromethane], and then this coating solution was applied onto the X-ray sensitive layer using a #2° wire bar to the thickness after drying. is 10
After application, the coating film was heated and dried in the air at 60°C for 12 hours, and then in the air for 12 hours.
It was formed by heating and drying at 0° C. for 10 hours. In this way, the X-ray electrophotography of the present invention has a layer of a composition having a charge carrier transporting ability formed by adding and mixing an organic charge carrier transporting substance to a polymer having a film-forming ability on the X-ray sensitive layer. A photoreceptor was obtained. This photoreceptor was designated as photoreceptor/T63. Further, an X-ray electrophotographic photoreceptor for comparison was manufactured in the same manner as described above except that the layer of the above composition was not provided. This photoreceptor was designated as photoreceptor/764. The surface of the photoreceptor 4630 overcoat layer provided with the overcoat layer had significantly higher smoothness than the surface of the X-ray sensitive layer before the overcoat layer was formed, that is, the surface of photoreceptor /r64. The X it+1 sensitivities of the photoreceptor 11b3 of the present invention obtained as described above and the photoreceptor I64 of the comparative example were measured in the same manner as in Example 1. The results are shown in Table 3. As is clear from Table 3 below, the overcoat of the present invention
The photoreceptor /163 provided with the photoreceptor 1/1 layer showed almost the same sensitivity as the photoreceptor y164 of the comparative example, which was manufactured in the same manner as the photoreceptor of the present invention except that no overcoat layer was provided. Next, the resolution of photoreceptors 3 and 164 was measured in the same manner as in Example 1, resulting in 7j. The results are shown in the 4th section below.
Shown in the table. As is clear from Table 4 below, the overcoat 1 of the present invention is provided.
Since no overcoat layer was provided, the photoreceptor I64 had a significantly higher resolution than the photoreceptor I64, which was produced in the same manner as the photoreceptor of the present invention described above [7! showed degree. Table 4 Furthermore, a transferred image was formed in the same manner as in Example 1. As in the case of toner images, the transferred image obtained with the photoreceptor /I63 of the present invention has a significantly higher resolution than the transferred image obtained with the comparative example photoreceptor /164, and the image is clearer. There was little overlap. Further, when the photoreceptor/163 of the present invention and the photoreceptor 464 of the comparative example were cleaned by a normal cleaning method, the photoreceptor did not have an overcoat layer, -t. In 4, it was 1,14 yellow It to remove the residual toner to the extent that it did not adversely affect the next image formation, whereas in photoconductor/163 having an oat-coat layer of the present invention, it was 1,14 yellow It. The remaining toner was easily removed and the product was ready for use in the next image formation. Example 3 In the same manner as in Example J, aluminum-1 Uno and board hit XI￥
=lII layer is formed on this X-ray sensitive layer with a thickness of 10/l.
A layer of a composition having a charge carrier transporting ability was formed by mixing an organic charge carrier transport material '77↓ with an additive of 1] to a polymer having a charge carrier transporting ability of nI. The layer of this composition is ``[
4, , ll'- which is an organic charge 4' one-body transport substance
A coating solution was prepared by dissolving benzylidene-bis(N,N-diethyl-m-l-luidine) 0.6.9 and polycarbonate 0, Jj9, which is a polymer with film-forming ability, in 72710 g of trichlor, an organic solvent. Then, this coating solution was coated on the X-ray sensitive layer using a +20 wire bar so that the thickness after drying was I Ottm. After application, the coating film was dried by heating at 60° C. for 1 hour in a rotating atmosphere, and then heated at 120° C. for 10 hours in a rotating atmosphere. In this way, the feeling
Polymer with film-forming ability in the linear layer
Electron (trj 4) made by adding and mixing a charge JU body transport substance
An X-ray electrophotographic photoreceptor of the present invention having a layer of a composition having g-body transport ability was obtained. This photoreceptor was designated as photoreceptor 7.lo5. In addition, an X-Kendama P photographic photoreceptor was manufactured for comparison in the same manner as described above except that the layer of the above composition was not provided. That is, photoreceptor Galo 2 in Example] was manufactured. The surface of the overcoat layer of the photoconductor 4o5 provided with the overcoat layer was significantly higher in smoothness than the surface of the X-ray sensitive layer before the overcoat layer was formed, that is, the surface of the photoconductor 4δ2. The X-ray sensitivities of the photoreceptor/I65 of the present invention and the photoreceptor/162 of the comparative example obtained as described above were measured in the same manner as in Example 1. The results are shown in Table 5. As is clear from Table 5 below, the photoreceptor/I65 provided with the overcoat layer of the present invention is a photoreceptor of a comparative example manufactured in the same manner as the photoreceptor of the present invention except that the overcoat layer is not provided. It showed almost the same sensitivity as Body/I62. Table 5 Next, the resolution was measured in the same manner as in Example 1 using photoreceptors /165 and /162. It became j. The results are shown in Table 6 below. As is clear from the sixth coating below, the photoreceptor/f65 provided with the overcoat layer of the present invention is not provided with the overcoat layer! In the same manner as the photoreceptor of the present invention, the photoreceptor outside μ exhibited a significantly higher jQ'i' PU degree than the iC-processed photoreceptor, 162. Furthermore, when a transfer image was formed in the same manner as in Example 1, the transferred image obtained by the photoconductor 462 of the present invention was the same as that obtained by the photoconductor 462 of the comparative example. In addition, the cleaning characteristics of the photoconductor/165 of the present invention were significantly better than those of the comparative example photoconductor/165.
It was significantly better than 162. -J King Tsukin City Masashi fl (7J, l-I March 24, 1939 Special 8' Name of X-ray electrophotographic photoreceptor 3, Person making the correction A'1 Relationship 9, ° C'1 Applicant's residence
Location Kanayo Prefecture) +, 1llL l'+'i City Hanging: f'
(21 [1i1'? Place name ・, ', + 20) Hata", i: tノ: '('+ soil, ・, fL-, L
Meeting? 14.
Date of amendment order 1) No. 39.40.45.46J3J, Hi-49 in the specification
Attached is a page (values measured using a Model 500 dosimeter manufactured by CTLEAN).The X-ray sensitivity scale is taken, and the surface potential (initial voltage) immediately before X-ray irradiation is prematurely reduced, resulting in the necessary irradiation. II ft
'i (half-attenuated illumination) measurement 1. Ta. The results are shown in Table 1 below. As is clear from Table 1 below, the photoreceptor/I41 provided with the overcoat layer of the present invention was the same as the photoreceptor AI of the present invention except that no overcoat layer was provided. The sensitivity was almost the same as that of Comparative Example Photoconductor Taki 2, which was manufactured in the same manner. Next, the resolution of the photoreceptors A61 and /162 was measured as follows. Photoconductor 161 of the present invention and photoconductor waste 2 of Comparative Example were subjected to corona banding at a corona voltage of -5 kV in a dark place, and subjected to EMI L FUNK OPT 1. KJ! “0”
! '0' company XIvj! X 1li1 double image exposure was carried out using a test chart, and further development was carried out using powder toner positively charged by magnetic brush development.
” and got a toner image. As a measure of resolution, we measured how many lines the toner image could identify per 1 mW. the result! It is shown in Section 2 below. Note that the X-ray irradiation conditions were the same as in the case of the sensitivity measurement described above. It is clear from Table 2 below that J, Uni, and L-? 1 block C5 body 161 was made in the same manner as the light body 161 except that no overcoat layer was provided. Measurements were made in the same manner as in column 1 of Table 2. The results are shown in Table 3. As is clear from Table 3 below, the photoreceptor provided with the overcoat layer of the present invention y16.3 &M The sensitivity was almost the same as that of comparative example photoreceptor /164, which was manufactured in the same manner as the photoreceptor of the present invention except that no overcoat layer was provided.Next, photoreceptors //63 and The resolution of No. 164 was measured in the same group as in Example 1.The results are shown in Section 4 below.
Shown on clothing. As is clear from the following No. 4, the photoreceptor/163 provided with the uninvented overcoat layer was manufactured in the same manner as the above-mentioned photoreceptor of the present invention except for the overcoat layer. Significantly higher i!5 compared to the A photoconductor i64
It showed a good image quality. Table 4 Furthermore, a transferred image was formed in the same manner as in Example #1f41J1. As with the toner image, the photoreceptor 16. of the present invention.
The transferred image obtained by No. 3 has a significantly higher image density (compared to the transferred image obtained using the photoreceptor 164 of the comparative example)'1〒.
Moreover, the image was P1r bright and had little fog. In addition, when the photoconductor A4 of the comparative example such as the photoconductor C4 of the present invention was cleaned by a normal cleaning method, it was found that the photoconductor with the overcoat layer had a good quality of 1/164.
In some cases, residual toner may adversely affect the next image formation.
In contrast, in the photoconductor A3 having the overcoat layer of the present invention, the residual toner can be easily removed and the remaining toner can be used for the next image formation. It became pj; Table 5 Next, the resolution of photoreceptors I65 and A2 was measured in the same manner as in Example 1. The results are shown in Table 6 below. As is clear from Table 6 below, the υ photoreceptor 165 provided with the overcoat layer of the present invention is a photoreceptor manufactured in the same manner as the photoreceptor of the present invention described above except that the overcoat layer is not provided. It showed significantly higher resolution than 162. Furthermore, when a transfer image was formed in the same manner as in Example 1, 293

Claims (1)

[Scope of Claims] (J) i) At least seven of its −F faces have one conductive Td:
11) - is provided on the conductive surface of the substrate, and includes an organic binder and a) whose composition formula is 13 i XMO8 (where M is is at least one of germanium, silicon, titanium, potassium, and aluminum;
represents the number of oxygen atoms determined stoichiometrically depending on the above M and An X-ray electrophotographic photoreceptor, characterized in that it consists of an X-ray sensitive layer consisting of 7 particles, and a layer of a polymer having a film-forming ability provided in 111, 2ε12 X-ray sensitive horns, and 4. (3) The above-mentioned 3. The X-ray electrophotographic photoreceptor according to claim 2, wherein the thickness of the polymer layer having film-forming ability is 0.1 to 200 μm. (4) The X-ray electrophotographic photoreceptor according to any one of claims 1 to 3, wherein the polymer having film-forming ability is polycarbonate. (5) The polymer having film-forming ability is polymethyl methanolylate - t % The X-ray electrophotographic photoreceptor according to any one of claims 1 to 3, . (6) Claim 1, wherein the polymer having film-forming ability is polyvinyl butyral.
X-ray electrophotography according to any one of Items J] to 3) 1C body. (7) Lx I] type semiconductor particles are ZnO1 (,',
dS, ~M) 3 and i'' io 2 at least a) l N'j particles!J
'ri'1. Kiyoshi]〈rt flood 1Δj 1st to 6th terms
X-ray electrophotographic photoreceptor with +4 pins according to any of the above items. (8) Claims characterized in that 4 in the above compositional formula is one or both of germanium and silicon, Line electrophotographic photoreceptor. (9) In the above compositional formula, 4 is ° germanium, and
is 12, and n is 20, which is 1 to 5. IlO The above compositional formula 〇M is silicon, X is 12,
A patent characterized in that n is 20, claim 8
The X-ray electrophotographic photoreceptor described in . (+) 1) a substrate on which at least one surface thereof is conductive; 11) an organic binder disposed on the conductive surface of the substrate; a) Its compositional formula is iXMOn (where M is at least one of germanium, silicon, titanium, gallium, and aluminum, X is a number that satisfies the condition JO≦X≦14, and n is the above M and (indicating the number of oxygen atoms determined stoichiometrically depending on An X-ray electron layer comprising a composition having a charge carrier transporting ability, which is formed by adding and mixing an organic charge carrier transporting substance to a polymer having a film-forming ability provided on the X-ray sensing layer. Photographic photoreceptor. σa Thickness of the layer of the composition having the above charge carrier transport ability 0
()1 to 2000 /1111 -i? The range of ii'l'nfr, , J<, which has all the characteristics, is
11'', a photographic photoreceptor described on page 11, (1:3, I:Mα charge J1-i body 'f11'+n
The thickness of the layer of the composition with full delivery capacity is 200 ltm
The twelfth part of the claim takes this as an opportunity.
Note I: 1 That X-ray electrophotographic photoreceptor. O・p'' s-type film-forming ability) -r'
7t, l is a cow that is lucky to be Boritsuno-Hone-1! , 1 pm t1j search range, 1; + 1st term to + 3rd term. g'
The X-ray electrophotographic photoreceptor according to any one of claims 11 to 13, wherein the polymer is polymethyl methacrylate-1. No. 0 - The polymer having film forming ability 6 above is polyhinyl butyral k l+? X as described in any one of claims 11 to 1;
Line electrophotographic photoreceptor. (17) 1-11 type semiconductor particles or ZnO1C (Is,
An X-ray electrophotographic photoreceptor according to any one of claims 11 to 16, characterized in that it is particles of at least one of WO3 and 'J' i 02. 0υ The X-ray electrophotographic photoreceptor according to any one of claims 11 to 17, wherein M in the above compositional formula is one or both of germanium and silicon. . (9) M in the above composition formula is germanium, and
The X-ray electrophotographic photoreceptor according to claim 18JJ'↓, wherein is 12 and 11 is 20. eO In the above compositional formula, M is silicon, X or 12 teeth, n
Scope of Patent 1 Requisition No. 18 characterized in that is 20
The X-ray electrophotographic photoreceptor described in .