JPS5915252A - Photoreceptor - Google Patents

Abstract

PURPOSE:To obtain a sharp fog-free copied image superior in photosensitivity characteristics, especially in E50<500>, by incorporating a specified hydrazone deriv. as a carrier transfer substance in a photosensitive layer contg. a carrier generating substance and the carrier transfer substance, formed on a conductive substrate. CONSTITUTION:The photosensitive layer formed on the conductive substrate contains a hydrazone deriv. represented by the shown formula in which Ar1, Ar2 are each optionally substd. aryl; R1 is optionally substd. alkylor aralkyl; R2 is H or optionally substd. alkyl or aryl; and R3 is H or optionally substd. alkyl or alkoxy or the like. Said hydrazone derivs. are obtained by reacting hydrazines with carbonyl compds. in a solvent, such as alcohol, in the presence of acid catalysts.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a d1 photoreceptor, and more specifically to a novel electrophotographic Jk-photoreceptor containing a hydrazone derivative as a therapeutic ingredient in the photosensitive layer.

Conventionally, photoreceptors have been made of selenium, ke? Those having a photosensitive layer containing as a main component an inorganic light guide body such as zinc oxide or cadmium sulfide were widely used.

However, selenium photoreceptors crystallize under low-temperature conditions and deteriorate electrophotographic performance, and lead oxide photoreceptors and cadmium sulfide photoreceptors have poor temperature resistance and printing durability; Cadmium has a number of drawbacks, such as high toxicity, which makes it difficult to manufacture and handle.

On the other hand, 11
Suru ゛l+j子′! J-true photoreceptors have many advantages, such as being relatively easy to manufacture, having only one composition, and generally having superior thermal stability compared to mono-selenium photoreceptors, and have been developed in recent years. It is attracting a lot of attention.

Q-1, poly-
N-vinylcaltuxol is the most well-known, and electrophotographic photoreceptors using it have been put into practical use, but they are inferior in sensitivity and printing durability and are not fully satisfactory.

On the other hand, various low-molecular organic photoconductive compounds have been proposed.
2,5-bis(p-diethylaminophenyl)-1,3,4-oxdiazole described in the specification has poor compatibility with binders, making it difficult to obtain a homogeneous and stable photosensitive layer. and the diarylalkane derivatives described in U.S. Pat. No. 3,820,989 are:
Although it has good compatibility with the binder, it has a drawback that the sensitivity of the photoreceptor gradually decreases with repeated use because it has low stability against light.

Various electrophotographic photoreceptors containing hydrazone and barrier materials as active ingredients have been proposed. For example, JP-A No. 54-81847; 1! 1. 〒Kaisho 54-15
Publication No. 0128,! JP-A-55-46760, JP-A-55-520'63, JP-A-55-5206
Publication No. 4 and the like are known.

Some of these have already been put into practical use with I:1, but the electrophotographic performance such as h. As the product is used, its sensitivity decreases and residual iris gradually accumulates, resulting in poor stability of its properties. The reality is that we have not yet been able to find anything that fully satisfies our demands as a photographer.

An object of the present invention is to provide a photoreceptor containing a carrier transport "proboscis Ih" which has excellent compatibility with a binder and excellent carrier transport ability.

Another objective is to achieve superior charging characteristics, sensitivity characteristics, and image formation characteristics. An object of the present invention is to provide an electrophotographic photoreceptor that has discharge force characteristics particularly in a low electric field region and can stably produce clear and uniform copied images.

The purpose of the song of the present invention will become clear from the description in Specification ①-.

In order to achieve the above objective, the present inventors have conducted intensive research and found that the objective can be achieved by using a specific hydrazone derivative as a carrier transport substance, and have completed the present invention. be.

The above object is achieved by providing a photosensitive layer containing a hydrazone derivative represented by the general formula CI'l on a conductive support.

General formula [■] A・艷2 In the formula, A-1 is an aryl group that is not substituted with 161, and preferred aryl groups include a phenylene group and a naphthyl group. , an anthryl group, and preferable substituents include an alkyl group having 11.1 to 5 carbon atoms, an alkyl group having 11 to 5 carbon atoms, a halogen atom, a hydroxyl group, a substituted It is an amino group, and R represents a substituted or unsubstituted alkylarafrekyl group, -''. 8 aralkyl groups from number 1 117j, preferred aralkyl groups include benzyl group, phenethyl group, preferred aryl groups include:
Represents a phenyl group, and preferred substituents thereof include an aralkyl group having 1 to 4 carbon atoms, a carbon atom number 1
from 4 to 4 1i-II alkoxy groups, halogen atoms,
They are hydroxyl group and substituted amino group.

R2 represents a hydrogen atom, an IifIi-substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group; preferred alkyl groups include an alkyl group having 1 to 4 carbon atoms; The aryl group represents a phenyl group. Preferred substituents for the phenyl group include an alkyl group having 1 to 4 carbon atoms, an aflecoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, tq, 19
! ! It is an amino group.

R3 represents a Mizuki atom, a substituted or unsubstituted argylaflecoxy group, a hydroxyl group, a halogen atom, a substituted amine group,
Preferably, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a metogyzo group, an ethoxy group, a glopioxy group, a butoxy group, a hydroxyl group, a chlorine atom, a bromine atom, a fluorine atom, or a sialyl atom group. be.

Specific examples of the hydrazone compound useful in the present invention represented by the general formula [■] include those having the following structural formula.

Exemplary compound A-(2) A-(3) A-(4) A-(5) A (6) A-(7) Shi M B U It 3 A-(8) A-(9) A - (] (1) A-(If) A-(12) A-(13), A-(14) A-(15) A A (16) A - (+7) A-(18) A - (1,9) A-(20) A-(21) A-(22) A - (2: () A-(24) A-(25) A-(26).

A-(27) A-(28) A - (', !9) A-(30) Jti A-(31) ? )■.

A - (32) A - (33) A - (34) Ihi no! The hydrazone derivative (i1) can be easily synthesized by a known method. For example, carbonyl compounds represented by the following general formulas CII] and CIII', respectively, and CARE! L'Ecole'
The hydrazone derivative 1 represented by the general formula [■] can be obtained by the reaction in the presence of a K catalyst in a solvent such as

- C1,1) CIII']Δr1
[I] Here, with A. , %2, "I,"2 and R3 represent the same groups as in general formula [I].

Next, a typical method for synthesizing the hydrazone derivative conductor used in the present invention will be described in detail.

Synthesis example! (shi1) I'm not interested in showing A (3) ” i's
IJ'x, )1-Methyl-1-phenyl[Schiff:
/29 g (0,241 ole) and N-aniblcarhasol-3-carba I resohydro 0 g (+1.27
+'Lole) was dissolved in ethanol 80 (J7nl), acetic acid 50+md was added, and the mixture was heated under reflux for 1 hour.
The precipitate that precipitated after being left to cool? Lord helmet door! 4, methyl ethyl I reketone, ethanol J and mix 1@'! ! 'L/l-
'] It crystallized twice.

Yield 1 64.1 & 79.1% Melting point
147.5℃~149.0'cFD-Mass
Since a molecular ion peak of m/θ = 405 was confirmed in I was able to confirm that I had slept.

Hydrazone derivative +L' used in present invention 9c
i, by itself, is a film-forming ability member I! 1. I7ya,
A carrier transport layer which constitutes a photosensitive layer in combination with a binder of 4:li is formed.

Any binder can be used here, but it must be hydrophobic and have a high dielectric constant <'1°C Stun 4. As such a polymer, it is desirable to use T.
L:X, For example, the following can be mentioned,
The binder used in the present invention is not limited to these.

B-(+) Polycarbonate B-(2) Polyester B-(3) Methacrylic tree 1iiIB-(4)
Acrylic Jugetsuji B-(5) Polyvinyl chloride B-(6) Polyvinylidene chloride B-(7) Polystyrene B-(8) Polyvinyl Buty C-1-B-(9)
Polyvinyl butylene chloride-acrylonide IJ + acrylonide copolymer B- (+1) vinyl chloride-vinylacetate copolymer B
-(12) Vinyl chloride-vinyl acetate-maleic anhydride copolymer B-(13) Silicone resin B-(14) / Recon-A I requino 1, 11 effect B-(15) Phenol-pho I Remaldehyde side fat B- (16) Styrene Arginoto I! Y1. i1
Effect B-(17) Styrene-butadieno copolymer B-
(18) Poly-N-vinylcarbazole These binders can be used alone or in combination of two or more binders.

By combining the well-known carrier transport layer with any carrier-generating substance selected from among various carrier-generating substances that absorb light and generate carriers,
A laminated type or dispersion type photosensitive layer can be constructed.

Examples of gear generating substances that can be effectively used in the present invention include the following: C-(1)
Selenium and selenium, i? 0 (2) Cd[,
Inorganic photoconductor C-(3) such as 0dSe, Cd SSe s 11g5 Perylene dye C-(4) Indigoid dye C-(5) T slaginone term, pyrenequinone Polycyclic quinones such as bo, frapanothrones, rnsua/slonnocho, etc. + E-(6) Bisbenzimidazo-11/based dye C
,-(7) Quinacridone dye C! -(8) Azo thread dyes such as monoazo dyes, bisazo dyes, and trisazo dyes 0-(91 Indanthrone thread dye C (ICI) Squarelylium dye c-(+1)
m Phthalocyanine dyes such as metal phthalocyanine and metal phthalocyanine c-(+2) Poly-N-vinishka 11 Deuterium-donating substances such as fupazole and avian trophs! A charge transfer complex C-(1,3) formed from rheolenone and the like, and a eutectic complex formed from a pyrylium salt or a thiapyrylium salt and polycarbonate-1. ``Carrier-generating substance K'', ] It may be used not only in Keyaki but also in combination of two or more, or in combination with a binder that cannot form a carrier-generating substance alone, and in a dispersed mixture with a binder. In case, 71! =11'ill,
For example, any binder used in the carrier transport layer may be selected.

To explain the structure of the photographic photoreceptor of the present invention, in the present invention, as shown in FIG. 1 and FIG. A photosensitive layer 4 is provided, which is a laminate of a carrier-generating substance ++', i 2 containing a substance as a main component and a carrier transport layer 3 containing the above-mentioned hydrazone derivative as a main component of a carrier transport material. As shown in FIG. 4, this photosensitive layer 4 may be disposed via an intermediate 185 provided on the flexible support IJ.

When the photosensitive layer 4 has a two-layer structure as described above, a true photoreceptor having the best electrophotographic properties can be obtained. In addition, in the present invention, as shown in FIGS. 5 and 6 [ㅅ''], fine particulate carrier generating substances 7 are contained in the 8G containing the carrier transport substance as a main component. A photosensitive layer 4 having a dispersed therein may be provided on the conductive support 1 directly or via an intermediate layer 5.

When the photosensitive layer 4 has a two-layer structure, which of the carrier tailing layer 2 and the carrier transporting layer 3 is to be the upper layer is determined by whether the charging polarity is positive or negative. That is, in the case of negative charging, it is advantageous to use the carrier@transport layer 3 as the upper layer, because the hydrazone derivative of the present invention is a substance that has a high transport ability for holes.

The carrier generation layer 2 constituting the two-layered photosensitive layer 4 is either directly on the conductive support 1 or the carrier transport layer 3, or an intermediate layer such as an adhesive layer or a barrier layer is provided as necessary. Secondly, it can be formed by the following method.

D-(1) Vacuum evaporation method D-(2) Method of applying a solution prepared by dissolving a carrier-generating substance in a suitable solvent IJ-(3)
)'Middle 4-r mill, homogenizer'
Depending on the size of the liquid, the dispersion is made into particles with 0.1% and 1%, and 1% and 1%, respectively, depending on the skin.
Preferably, the thickness is 0.01 micron to 5 micron to 11 micron, and more preferably 0.05 micron to 3 micron.

Although the thickness of the carrier@fS layer 3 may necessarily vary from 51 to 31) microns, it is preferable that the thickness is usually 5 to 31) microns. This carrier 11ii feeding layer 3
The composition ratio U1 of the carrier transport substance and the binder is preferably 0.8 to 4 parts by weight of the binder per 1 part by weight of the carrier transport substance. A photosensitive layer 4 is formed by dispersing the generated substance. Lila @
is 1 part by weight of carrier-generating material and 10 parts by weight of binder.
It is preferable to use less than a measuring part.

When the carrier generation layer 2 is formed by dispersing and mixing with the binder Mll, the binder can be used in the range of 45 parts [t1 part] for each part of the carrier source substance [t1 part]. How many cases?

The conductive support 1 used in the construction of the photoreceptor of the present invention may be a metal plate such as an aluminum plate or a stainless steel plate, or a support such as paper or a plastic film. a? A thin layer of metal such as reminium, palladium, gold, etc. is laminated or vapor-deposited, and 417. Similarly, a layer of a chemical compound provided on a support such as paper or a plastic film by coating or vapor deposition is used.

As the intermediate layer 5 such as a binding layer or a barrier layer, aluminum oxide or the like can be used in addition to the high molecular weight polymer used as a binder for the photosensitive layer.

The electrophotographic photoreceptor of the present invention has the above-described structure, and as is clear from the examples described later, it is excellent in custom charging, sensitivity characteristics, and image formation characteristics, especially in the low 1L field region. It has excellent discharge efficiency, and has a so-called good cutting feel.
It is possible to stably obtain C by repeating the characteristics of a clear copy with no scratches.

Example A? on polyester film? Polyvinyl chloride, bean acetate, maleic anhydride symbiotic combination [Esrec MF-1, O
A 0.05 micron thick intermediate layer made of J (manufactured by Tsukisui Kagaku Co., Ltd.) was provided, and on top of that was provided
A39300)' (steamed droplets to form a carrier generation layer of 5 microns).Furthermore, on top of that, 61 parts of compound (21) double and polycarbonate 1 Panlite L-1250J (Teijin Kasei Co., Ltd. A gear rear width layer was formed by dispersing 2-dichloroethane 30 m on the wheel needle part and dissolving it in the car needle part so that the film thickness after drying was 12 microns. Then, a photoreceptor was prepared for the Tt photoreceptor of the present invention.

Regarding this electrophotographic photoreceptor, the Yama 1 true characteristics were measured using a static (8) tilting paper tester model RSP-428 (Kawa 1 Denki Seisakusho) using the da, f name method.

2. In other words, the surface of the photoreceptor photoreceptor layer Ail is charged with a charging voltage fi
, (l K, surface K when charged for 5 seconds at V
(SγVA) Next, the light from the tungsten lamp is irradiated so that the illuminance on the photoreceptor surface becomes 351 ux, and the exposure (half-reduced light amount) E2. required to attenuate the surface voltage b1 from -500V to -250V. (□I, 5
ec) and "dissolving deterioration t"'5o (□□□, 5ec) to attenuate the surface voltage from -500V to -50V.
were calculated respectively.

! ! Similar measurements were repeated 50 times. The results are shown in Table 1.

Comparison sequence 1 F instead of exemplified compound (21) as a carrier delivery substance
A hydrazone derivative represented by the following structural formula was used [91
11 and pity
)Y: Create a field +)Il similar to that in implementation column 1
I made a determination.

The results are shown in Table 1.

As is clear from the results shown in Table 1, the electrophotographic photoreceptor of the present invention has higher sensitivity than the comparative electrophotographic photoreceptor.
Excellent sensitivity of 50.

In place of the exemplified compounds (], ), H compound 4m (22), (23), (2-1), (
2, 5) Other than using O and (26) respectively, fruit,
Same as martyrdom 1.

An electrophotographic photoreceptor of the present invention was prepared. These +1.
The results in Table 2 are shown in Table 2, where measurements were carried out on one photoreceptor in the same manner as in the previous example.

Table 2 Example 7 Polyester [Pylon 200. J (manufactured by Toyobo Co., Ltd.) with a thickness of o and i microns was provided, and a single layer of bisazo dye represented by the above structural formula was formed by mixing ethylenediamine, n-butylamine, and tetrahydrofuran with a ratio of M and a ratio of 1 to 1. OOHCI dissolved in 120 parts by weight of mixed tL mixed in ratios of .2:1, 1.0:2.
Ce (11) was applied so that the adhesion layer after drying was (1.2 g/m') to form a carrier generation layer; r≧.

Furthermore, on top of this, exemplified compounds (
1.
parts and 74 parts of 1,2-dichloroethane (l t M parts)
Dry the rqγ liquid? + (DI) A carrier transport layer was formed by coating to a DI1m thickness of 15 microns, thereby producing an Ichikosha S-photoreceptor of the present invention.

This electrophotographic photoreceptor was measured at 41+lJ in the same manner as in 1, and the results in Table 3 were
Ta.

In addition, this electrophotographic photoreceptor can be electrophotographed,
BIX2000RJ (manufactured by Konishiroku Photo Industry Co., Ltd.) was loaded, and the quasi-process consisting of banding, N% light and cleaning steps was repeated, and the degree of normal fatigue deterioration (sensitivity change due to repeated use) was measured. I looked into it,
61ux-sec of light m is applied to the surface of the photosensitive layer at the time of removal.
How does the surface tV of the photoreceptor change when the above-mentioned quasi-process is repeated?111! , and the results shown in FIG. 7 were obtained. (Curve I) To 1F intersection 1
+1] 2 Giw') Same as Example 13'lJ7 and 02H except that the human toranoid/induced substance shown in the F-type was used as the transporting substance.

An electrophotographic photoreceptor for comparison was prepared in the same manner.

Measurements were carried out on this comparison photoreceptor in the same manner as in IJ 7, and the results are shown in Table 3 and Figure 7 (Curve 2).
The results are good.

Part 3 It is clear from the above results that the turtle of the present invention is a child photograph A.
The photoreceptor has a comparative electrophotographic sensitivity of R4 (K I), which has excellent red sensitivity properties, and is extremely stable with little fatigue deterioration even after repeated use. .

Exemplary compounds (2), (3), (
5) , <101 and (16) were used.
An electronic photoreceptor assembly of the present invention was prepared in the same manner as +117.

These 111. The same measurements as in moxibustion treatment 1 were carried out on the child photographic photoreceptor, and 1. in Table 4 was carried out. l'i result f4I
Ta.

, 4th embodiment Aluminum vapor deposited 2-)
, + '
A 0.1 micron thick intermediate layer consisting of 0J C (manufactured by Tsukisui Kagaku Co., Ltd.) is provided, and on top of that, a bisazo dye 2 tonne and a polycarbonate +-r kneepilon S represented by the following structural formula are provided.
-10001 (made by Mitsubishi Gas Chemical Kano)] i1i Kuibu and'
f3: 1.2- dichloroethane in 150 parts of sulfuric acid, mixed for 11 minutes, 0.5
Apply it to the entire 2nd gear generation layer so that it becomes micro/
It was completed.

history (C f/lsu7J<compound(l[)) 2ff
x Sendbu and polymethyl methacrylate F, 1 Acrybets J
(manufactured by E-Hishiyon Co., Ltd.) 3 I'TI Takarabe and l+, 2
- Dichloroethane, dissolved in 30 tubes:
A 1'n, 188 photoreceptor of the present invention was prepared by applying the coating to a thickness of 12 microns after rl and rK. ``[L child photo A feeling]'' carried out on 6 bodies [&IJ 1
In the same manner as in Table 5, the results for A8111ijlL were obtained.

Comparison row 3 Except for using the hydrazone gm compound represented by the structural formula 1. as a carrier transport substance, real 7A (r II/IJ
A comparative electrophotographic photoreceptor was prepared in the same manner as in Example 13.

02H6 This comparison electrophotograph has a photoconductor size of #A and IJ l.
Measurements were made in the same manner as in Table 5, and the results shown in Table 5 were obtained.

As is clear from the results in Table 5 and above, the electrophotographic photoreceptor of the present invention showed a 1 in 143 sensitivity change compared to the comparative electrophotographic photoreceptor, especially in J and GGO odor. Orip J]
It can be expected that a clear copy image with no distortion will be obtained.

Example II/1114 The electrophotographic photoreceptor of the present invention produced in Example 13 was installed in an electrophotographic copying machine [U-B i x 2000 RJ (manufactured by Konishiroku Photo Industry Co., Ltd.), and images were copied. A clear copy image was obtained that was faithful to the original painting, had excellent contrast and gradation, and had no fogging.

Even after repeating this process 20,000 times, it was possible to obtain an image as good as the initial image.

[Brief explanation of drawings]

FIGS. 1 to 6 are sectional views showing nine mechanical configuration examples of the electrophotographic photoreceptor of the present invention, respectively. 1... Conductive support 2... Carrier generation layer 3
... Carrier transport layer 4 ... Photosensitive layer 5 ... Intermediate layer 6 ... Layer containing carrier transport substance 7 ... Smell carrier generating substance @7 [store] + si1? , of course ``7γ-J1hi1 comparison'', 2, the thread 6゜蜀(, and -isu(te [. Agent Yoshimi Kuwahara 81) Figure 65 Figure 2 Figure 64

Claims (1)

[Scope of Claims] (]) A photoreceptor comprising a photosensitive layer containing a carrier-generating substance and a carrier-transporting substance on a 4r-type support, wherein the carrier-transporting substance has the general formula [I] A photoreceptor characterized by being a hydrazone derivative represented by: General formula C1,] In the formula, "?lI" and "ht are substituted/unsubstituted aryl groups, R4 is substituted/unsubstituted allele groups, substituted/unsubstituted Kyl group, substituted/unsubstituted aryl group,
R2 is a hydrogen atom, a substituted or unsubstituted adergyl group, a substituted or unsubstituted aryl group, and R3 is a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, or a substituted amine group. figure. (2) The photosensitive layer is constituted by a laminate of a carrier-generating layer containing a carrier-generating substance as a main component and a carrier-transporting layer containing a carrier-transporting substance as a main component. Photoreceptor as described.