JPS604981B2 - Photoconductive materials for electrophotography - Google Patents

Description

[Detailed description of the invention] The present invention relates to photoconductive materials for electrophotography.

More specifically, the object is to provide a photoconductive material for electrophotography that has both excellent film-forming ability and excellent photosensitivity, and in which the photosensitive film itself is transparent.
Conventionally known photoconductive substances used in electrophotographic photosensitive materials include inorganic substances such as selenium zinc oxide and cadmium sulfide, or anthracene, carbazole, anthraquinone, berylene, etc., or a series of heterocyclic compounds,
and organic substances such as polyvinylcarbazole, polyvinylphenylanthracene, and the like.

Xerox, electrophoax, etc. are known as those using inorganic substances. On the other hand, even if organic substances such as anthracene, carbazole, anthraquinone, and berylene and a series of heterocyclic compounds are used, these are all low-molecular compounds and do not have the ability to form a film by themselves.
Approximately 50% of synthetic resin or natural resin is added as a binder and used in the form of a solid solution with the photosensitive material (photoconductive substance). Furthermore, photosensitive materials using polyvinylcarbazole, polyvinylphenylanthracene, etc. are extremely brittle and have a weak film-forming ability, so they still require a binder. As a result of intensive research into an electrophotographic flash conductive material (photosensitive material) that has both sufficient film-forming ability and photosensitivity, and in which the photosensitive film itself is transparent, the present inventor discovered that naphthalenedicarpone It was discovered that a polyester containing an acid as the main dicarboxylic component and a strong electron acceptor blended with it has such characteristics, and the present invention was arrived at.

That is, the present invention provides an electrophotographic material for electrophotography whose main component is a mixture of a naphthalene-containing polyester containing naphthalenedicarboxylic acid as the main carboxyl component and an alkylene glycol having 2 to 6 carbon atoms as the main glycol component, and a strong electron acceptor. It is a photoconductive material. The polyester used in the present invention is
The dicarboxylic brewing component is mainly composed of naphthalene dicarboxylic acid.

Of the dicarpon brewing ingredients, naphthalene dicarboxylic acid accounts for 8
It is preferable that it accounts for 5 mol% or more. Any one of its ten isomers can be used as the naphthalene dicarboxylic acid, but naphthalene-2,6-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, etc. are preferably used. Naphthalene dicarboxylic acids may be used alone or in combination of two or more. The diol component of the polyester is preferably an alkylene glycol having 2 to 6 carbon atoms, particularly preferably a linear alkylene glycol having 2 to 6 carbon atoms (e.g., ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, etc.). Any method can be used to produce the polyester used. For example, a dicarboxylic acid and a diol may be directly polymerized, a gester of a dicarboxylic acid and a diol may be transesterified and then polymerized, or a di(hydroxyalkyl) ester of a dicarboxylic acid may be subjected to a deglycol reaction. Polymerization may be carried out by In the present invention, a strong electron acceptor is blended with the polyester. Any strong electron acceptor can be used, but representative ones include '11 Nitrofluorenolenes 2,4,7-trinitrofluorenone, 2,4,5,7
-Tetranitrofluorenone, '2) Quinones quinone, chloranil, 2,6-dichlorobenzquinone,
Naphthoquinone (1,4) [3' organic acids mono-, di-, or trichloroacetic acid, mono-, di-, or trifluoroacetic acid, phenylacetic acid, 6-methylcoumarinyl acetic acid, p-triolsulfonic acid, benzolsulfonic acid ,
4-chloro-3-nitrobenzole phosphoric acid, 4-nitrophenol, picric acid, {4' acid anhydride acetic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, maleic anhydride, tetrachlorophthalic anhydride, anhydride Chrysene-2,3,8,9-tetracarboxylic acid '5}
Polycyano compounds tetracyanoethylene, terephthalaldimalonitrile, tetracyanquinodimethane, pyromellitonitrile,
etc. are exemplified.

The blending ratio of the strong electron acceptor is preferably 0.1 to 10% by weight, particularly 1 to 3% by weight, based on the polyester.

Any method can be used to blend the strong electron acceptor into the polyester. Therefore, both may be melt-mixed (for example, using a melt extruder), or both may be mixed as a solution, or one may be dissolved and mixed with the other (by applying a coating solution to the support). The strong electron acceptor may be impregnated from the surface of the polyester film after it has been formed. The polyester blended with a strong electron acceptor has both film formation and photoconductivity (photosensitivity), and can be used as a photoconductive material for electrophotography as it is or with a sensitizer etc. as necessary. In addition, it is used by making a solution and coating it on a support and drying it.

Alternatively, the polyester may be used as it is or a sensitizer may be added thereto if necessary, and the solution may be applied and dried on a support to form a film, and then a strong electron acceptor may be removed from the surface of the film. You can also let it soak in. When a sensitizer is used, it is preferably used in a proportion of 0.001 to 5% by weight based on the photoconductive material (total of the polyester and strong electron acceptor). Examples of sensitizers include the following: (1) Pigments Triphenylmetho dyes: Brilliant Green, Victoria Purieux B, Methyl Violet, Crystal Violet, Acid Violet 8B Rhodamines:.

-Rhodamine B, Rhodamine 63, Rhodamine G Extra, Sulforhodamine B, Fast Acid Eosin G・Iolo-, acridine・
Orange, trypaflapine, quinone dye: alizarin,
Alizarin Red S, quinizarin, quinoline dye: pinacyanol, cributocyaninin allylmethane dye:
Chlorophyll violet fuchsin, erythrosin 2
Na, Rhodamine B500, Huanal Pink B, Rhodamine 80DN, Auramine, Polymethine dye: 3,3-jethyl thiacarbocyanine iodide, Azo dye: Eriochrome Flu Black R, Azomethine dye: Bis(p-dimethylaminobenzal) ) Azine carbonyl dye: Solway Ultra Blue B, Alizarin Cyanine Green GWA, Phthalocyanine dye: Segnal, Night, Turquoise NB, Multi-stranded ring compound: N・N-pentamethylenebis(benzthiazole) perchlorate, the photoconductive material Any known method may be used to apply the containing solution to the support.

For example, methods such as casting the solution, spin coating, spraying, and brush coating may be used. The thickness of the coating is usually 2-3
0 mm is preferred. The support may be any material that can be used as a support for the photosensitive layer for electrophotography, such as metal plates such as aluminum, zinc, and steel, and surfaces treated with synthetic resin to prevent solvent from penetrating inside. Materials with a surface resistivity lower than that of the photoconductive layer, such as synthetic resin films mixed with or coated with antistatic agents or surfactants to lower the electrical resistivity, that is, usually Anything less than 1 pi○, preferably 1 and Q, skin may be used. The photoconductive material of the present invention is not coated on another support, but is used as a film (or sheet) with a conductor on one side (if a transparent material is used, a transparent photosensitive film can be obtained as a whole). can be applied and used for electrophotography.

Such films (or sheets) can be produced by melt extruding the photoconductive material or by casting the photoconductive material in solution.
In addition, the polyester (which may or may not contain sensitizers and other additives) is formed into a film (or sheet) by melt extrusion or solution casting, and a strong An electron acceptor (a sensitizer and other additives may be used in combination) may be impregnated. Any conventionally known method may be used as the operating method for obtaining an electrophotographic image, and the charging potential may be either positive or negative.
The electrophotographic light-sensitive material of the present invention has excellent sensitivity and excellent film formation properties.

Therefore, a photosensitive sheet made by coating this on a transparent film is
It can be used as a master or duplicate for slides, micro-photographs, overhead projectors, etc. Also, when coated on a metal cylinder, it can be used as a transfer tube for xerography. Furthermore, compared to conventional zinc oxide coated paper, the material coated on paper is more similar to plain vapor copies, and it is possible to obtain copies that are similar to plain vapor copies without using a transfer process. Hereinafter, the present invention will be explained in detail with reference to Examples.

In the examples, "parts" means "parts by weight." Example 1 Poly(ethylene-2.6 naphthalene dicarboxylate) homopolymer ([ri]=0.894) 1 part and 2
0.2 parts of 4.7-trinitrofluorenone was added to 1 volume of 0-chlorophenol, mixed and melted, and applied onto a film with a transparent telephone pole attached to form a film with a thickness of 10 mm.

The coating was negatively charged by corona discharge. The original was placed in close contact with this and exposed for 1 second using a 300 W lamp placed at a distance of 3 melons. When the electrostatic latent image was developed using resin powder colored with carbon black, an image faithful to the original image was obtained and could be fixed by gentle heating. Example 2 For 1 part of the same polyester used in Example 1, 2.
0.1 part of 4,5,7-tetranitrofluorenone and 0.0005 part of crystal violet were mixed and dissolved in 1 part of 0-chlorophenol, and the mixture was cast and coated on a film with transparent electrodes. A photosensitive layer with a thickness of .

This layer was negatively charged by corona discharge, a document was brought into close contact with the layer, and a 0.9 pitch exposure was performed using a 300 W lamp placed at a distance of 30 nodes. When the static lightning latent image was developed using resin powder colored with carbon black, an image faithful to the original was obtained and could be fixed by gentle heating. Example 3 Poly(ethylene naphthalene-1,5-dicarboxylate)
g) Homobolimer ([sword] = 0.762) parts 1 and 2
- 0.2 parts of 417-trinitrofluorenone was mixed and dissolved in 10 parts of 0-chlorophenol, and the mixture was coated on a film provided with a transparent electrode, and a photosensitive layer having a thickness of 12 mm was fixed.

The photosensitive layer was negatively charged by corona discharge. The manuscript was placed in close contact with this and exposed for 1 second using a 300W lamp placed at a distance of 30 arcs.When the static latent image was developed using resin powder colored with carbon black, an image faithful to the original was obtained. was obtained and could be fixed by mild heating.Example 4 1 part of poly(hexamethylenenaphthaliso-2,6-dicarboxylate) homopolymer ([ri]=0.815),
Add 0.15 parts of 2,4,7-trinitrofluorenone to -
Chlorphenol was mixed and dissolved in 1 cup of water, and the solution was applied onto an aluminum plate to form a photosensitive layer with a thickness of 10 cm.

Claims (1)

[Claims] 1. A photoconductive material for electrophotography, the main component of which is a mixture of a naphthalene-containing polyester containing naphthalene dicarboxylic acid as the main dicarboxylic component and a glycol having 2 to 6 carbon atoms as the main glycol component, and a strong electron acceptor.