JPS6030936B2 - organic photoconductive materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in organic photoconductive materials containing polycyclic aromatic vinyl polymers, particularly 9-(P-vinylphenyl)anthracene polymers, as a main component.

In organic photoconductive materials containing polycyclic aromatic vinyl polymers, especially 9-(P-vinylphenyl)anthracene polymers as a main component, it is used as a plasticizer to improve the flexibility of the polymer. , terphenyl, chlorinated polyphenyl,
Polyester resin, polycarbonate, etc. were used. However, although these above-mentioned plasticizers all showed good results in terms of transparency and coatability, the flexibility and peel strength of the resulting coating films were still insufficient. An object of the present invention is to overcome the drawbacks of the prior art and to provide an organic photoconductive material having excellent flexibility and coating properties.

According to the invention, it has been found that said object is achieved by using phosphate ester compounds as plasticizers.

That is, the present invention provides 9-(P-vinylphenyl)anthracene polymers, polymers of 9-(P-vinylphenyl)anthracene and other polymerizable monomers, and 9-(P-vinylphenyl)anthracene polymers. The present invention relates to an organic photoconductive material comprising at least one polycyclic aromatic pinyl polymer selected from brominated compounds and at least one phosphate ester compound. To summarize the present invention, a polycyclic aromatic vinyl polymer is a polymer having repeating units represented by the general formula, and has a molecular weight of 2000 to 1500.
0 9-(P-vinylphenyl)anthracene polymer,
9-(P-vinylphenyl)anthracene and other copolymerizable monomers such as styrene, acrylonitrile, N-pinylcarbazole, vinyl acetate or methacrylic acid,
These are acrylic acid or a copolymer with these esters, or a brominated polymer of the 9-(P-vinylphenyl)anthracene polymer.

In the organic photoconductive material of the present invention, an additive for a burnt sensation may be used in combination with the polymer.

These additives include 2nitrofluorenone, 2
, 4-dinitrofluorenone, 2,5-dinitrofluorenone, 2,7-dinitrofluorenone, 2,4,5-
Nitrated fluorenone such as trinitrofluorenone, 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, brilliant green,
Triarylmethane dyes such as methyl violet, crystal violet, and acid violet, xanthene dyes such as rhodamine B, and sulforhodamine B, acridine dyes such as acridine orange and trivalaflavin, fluorosin, eosin S, essulosin,
Examples include phthalein dyes such as phloxine and rose bengal.

These may be added in an amount of 0.01 to 150 parts by weight, depending on the type, based on 100 parts by weight of the polycyclic aromatic vinyl polymer. In the present invention, aromatic and aliphatic phosphate esters are used as the phosphate esters blended into the polymer or the polymer to which additives have been added, examples of which include triphenyl phosphate and tricresyl phosphate. , cresyl diphenyl phosphate, octyl diphenyl phosphate, trimethyl phosphate, tri-n-butyl phosphate, dibutyl phosphate, tri-phosphate
n-amyl, triallyl phosphate, trioctyl phosphate,
Trichloroethyl phosphate, tridichloropropyl phosphate, tridipromopropyl phosphate, triethyl phosphate, tributoxethyl phosphate, tricylenyl phosphate, mono(dichloropropyl)pis(dibromopropyl) phosphate, etc. There is.

These phosphate esters do not affect their photoconductivity, and they form clear images not only in their malleability but also in the coating surface, which is better than when conventional plasticizers are used.

It is desirable that these phosphate esters be added in an amount of 1 to 5 parts by weight per 100 parts by weight of the polymer.

In the present invention, other plasticizers such as m-terphenyl, p-terphenyl,
Polycarbonates, polyester resins, chlorinated polyphenyls can also be used. These are the polymer 1
It can be added in an amount of 0.1 to 6 parts by weight per 0 parts by weight. The photoconductive material of the present invention is produced by dissolving the polymer, additives, and plasticizer in a solvent and mixing them.

Further, in consideration of the difference in solubility, for example, the additive may be added after being dissolved in a separate solvent. As these solvents, aromatic solvents such as benzene, toluene, xylene, and chlorobenzene, or dichloromethane, dichloroethane, and tetrahydrofuran are used. The organic photoconductive material of the present invention is used as an electrophotographic photosensitive material by coating it on a conductive-treated support.

Next, the present invention will be described with reference to Examples, but the present invention is not limited thereto in any way.

Example 1 Poly-9-(P-vinylphenyl)anthracene 10 times, m-terphenyl 5 times, brilliant green 0.1
Toluene was dissolved in 80% toluene, and tricresyl phosphate was added to this in various amounts to form conductive-treated polyester films (manufactured by Toray Industries, Ltd.).
An electrophotographic photosensitive film was prepared by casting on a beam (TL-100).

A mandrel bending test (using a mandrel testing machine manufactured by Toyo Seiki Co., Ltd.) was conducted using these pieces as cut pieces with 10 pieces in each cut. A load of 200 kg was applied to both ends of the cut piece, and the cut piece was placed on a test bar for 2 minutes, and the occurrence of peeling and cracking was observed. Figure 1 shows the results. The horizontal axis in Figure 1 is the polymer 1
The amount of tricresyl phosphate added per 00 parts by weight, the vertical axis is the minimum round heel diameter (unit side diameter, hereinafter referred to as mirror crack initiation diameter) when a crack occurs in the mandrel bending test. Straight line A shows the crack diameter when tricresyl phosphate is not added, and broken line B shows the relationship between the amount added and the crack diameter when tricresyl phosphate is added. It is clear that this has a significant positive effect on flexibility. Conventionally, it has been considered that a crack initiation diameter of 1 mm or less is practical, but from FIG. 1 it can be seen that it is already practical with an addition amount of 1 part by weight. Example
2 xylene solution 1 containing 5 parts by weight of di-tert-butyl peroxide in 10 parts by weight of a composition prepared by mixing 9-(P-vinylphenyl)anthracene and 9-vinylcarbazole in a molar ratio of 3:2. was sealed in a polymerization tube and heated at 130 pm.
, 10 parts of the copolymer obtained by heating for 1 hour, 2 parts of polycarbonate, and 5 parts of 2,4,7-trinitrofluorenone were dissolved in 150 parts of toluene, and octyl diphenyl phosphate was dissolved in this. Each of the compositions added in various amounts was cast onto an aluminum plate to produce an electrophotographic light-sensitive film.

This film was charged by Ichiro V's negative corona discharge, and the potential attenuation at certain points and the potential attenuation when irradiated with 10 lux light were measured. The results are shown in FIG.
The axis of FIG. 2 is the time of leaving (unit: seconds), and the vertical axis is the potential decay rate (unit: %). Curve C is when octyldiphenyl phosphate is not added, curve D is when 1 part by weight of the phosphate ester is added to 100 parts by weight of the polymer, and curves E, F, and G are 10, 50, The case where 10 parts by weight of the compound was added is shown. The addition of phosphate esters increases the potential attenuation at the floor. In the case of addition of 10 parts by weight as shown in curve G, the potential attenuation rate is 50% or more, and although some measures are required for practical use, it can be seen that addition of 6 parts by weight is well within the practical range. On the other hand, no major change was observed regarding photosensitivity. Example 3 Brominated product of 9-(P-vinylphenyl)anthracene polymer (bromination rate 10 as a mono-substituted product of anthracene nucleus)
Polyester obtained by dissolving 10 parts of tridichlorofuropyl phosphate, 0.02 parts of Nile Blue, and 0.025 parts of 2,4,7-trinitrofluorenone in 50 parts of tetrahydrofuran and conducting conductive treatment. An electrophotographic photosensitive film was prepared by casting on a film (TM film manufactured by Tijin Co., Ltd.).

After this film is negatively charged by general V corona discharge, it is exposed to 20 lux white light at 0.9 sand under the original image. Next, when liquid development (Match-1 type liquid developer manufactured by Ricoh Co., Ltd.) is performed, an image faithful to the original image is obtained. This film passed the mandrel test in one pass according to the method shown in Example 1, and could be put to practical use as a slide. Example
4 0.52 parts of acrylic acid butyl ester, 5.6 parts of (P-pynylphenyl) anthracene, and 1.56 parts of di-tert-butyl peroxide were dissolved in 8 parts of xylene, and the mixture was heated at 130°C in a nitrogen gas stream. , and reacted for 8 hours.

The produced polymer has 1 acrylic acid butylester moiety.
Contains 7.4 mol%. This polymer 1.5 minutes, 2, 4, 5,
0.04 ml of 7-tetranitrofluorenone was dissolved in 5 ml of xylene, and then various phosphate esters were added in varying amounts to form a solution. Cast coating onto TL-100). The resulting coating film thickness is 3 to 5 mm. These films were subjected to a mandrel bending test to compare their performance with phosphate esters. The results are shown in Table 1.
In Table 1, the mark 0 indicates the 10-rib mandrel bending test by the method described in Example 1. It indicates that the sample has passed the test and can be put to practical use without problems in terms of transparency and electrophotographic properties.

In either case, good results are obtained when the phosphoric acid ester is used in an amount of 1 to 5 parts by weight based on 100 parts by weight of the polymer. Trixylenyl acids and the like can be added in large amounts and tend to provide more flexibility. On the other hand, aliphatic trimethyl phosphate, tri-n-butyl phosphate, and trioctyl phosphate are not preferable because if they are added in large amounts, the coating film becomes cloudy and the components separate.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the relationship between the mandrel bending test results of an electrophotographic photosensitive film using an organic photoconductive material, which is a specific example of the present invention, and the amount of phosphate ester added. FIG. 2 is a curve diagram showing the relationship between the electrophotographic properties of a photosensitive film and the amount of phosphate ester added. 1 spear, 2 spears

Claims (1)

[Scope of Claims] 1 9-(P-vinylphenyl)anthracene polymer,
Copolymer of 9-(P-vinylphenyl)anthracene and other copolymerizable monomer and 9-(P-vinylphenyl)
At least one selected from anthracene polymer bromide
An organic photoconductive material comprising a polycyclic aromatic vinyl polymer and at least one phosphoric acid ester compound. 2. The organic photoconductive material according to claim 1, wherein the amount of the phosphoric acid ester compound is 1 to 50 parts by weight based on 100 parts by weight of the polycyclic aromatic vinyl polymer.