JPS61156129A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic sensitive body causing absorption in the near infrared or infrared region by incorporating a phthalocyanine com pound into a carrier generating layer. CONSTITUTION:At least one kind of phthalocyanine compound having groups represented by a formula -RX and/or groups represented by a formula -X' QX-[where each of X and X' is S, Se, Te or NT (T is H, alkyl or aryl), R is a univalent group, and Q is a bivalent group] is incorporated into a carrier generating layer. When the number of groups represented by the formula -RX is expressed by (x) and the number of groups represented by the formula -X'QX- by (y), an equation x+2y=6-16 is preferably established. An electrophotographic sensitive body for the near infrared or infrared region having very high stability to light or heats obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention Technical Field The present invention relates to an electrophotographic photoreceptor in which a carrier generation layer contains a phthalocyanine compound.

Prior art and its problems Electrophotographic photoreceptors are used in copiers, laser printers, and the like. This includes a functionally separated laminated photoreceptor, in which a carrier generation layer and a carrier transport layer are laminated on an electrode. The carrier generation layer is a layer that generates carriers by absorbing light, and the carrier movement layer is a layer that moves generated carriers.

Incidentally, phthalocyanine compounds have excellent fastness against heat, light, etc., and are attracting attention as photoconductive materials, and attempts have been made to apply these phthalocyanine compounds to the -j+ rear generation layer.

However, this compound cannot be used because it does not have absorption in the near-infrared or infrared region required for laser printers, etc., and improvement in this point is desired.

II. OBJECTS OF THE INVENTION An object of the present invention is to provide an electrophotographic photoreceptor that has absorption in the near-infrared to infrared region by containing a phthalocyanine compound in the carrier generation layer.

■Disclosure of invention These objects are achieved by the invention described below.

That is, the present invention provides an electrophotographic photoreceptor having a carrier generation layer and a carrier transfer layer on an electrode, in which the carrier generation layer contains a group represented by the following formula (I) and/or a group represented by the following formula (II). This is an electrophotographic photoreceptor characterized by containing at least one phthalocyanine compound having the following properties.

Formula (i) -RX Formula (II) -X'QX- (In formulas (I) and (II) above.

X and X' are S, Se, Tel or NT (
T represents H, an alkyl group or an aryl group.

R represents a monovalent group, Q represents a divalent group y,) ■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

The electrophotographic photoreceptor of the present invention has a carrier generation layer, and this layer includes a group represented by the above formula (I) and/or a group represented by the following formula (II).
) iJ of a phthalocyanine compound having a group represented by
4 or more are contained.

Formula (I) -RX Formula (II) -X'QX- In the above formulas (I) and (II), X and X'
represent S, Se, Te or NT (T is H, an alkyl group or an aryl group), respectively.

R represents a monovalent group, and Q represents a divalent group.

In this case, the number of groups represented by formula (I) is X, and formula (II)
When the number of groups represented by is y, x+27 is preferably 6 to 16.

Among these, particularly preferred are the following formulas (m) to
One or more phthalocyanine compounds represented by (V).

Formula (m) *Lid-3,8-(RX) -PcMk In the above formula (I), M is a hydrogen atom; a metal atom, such as Cu, Pb, Ni, Fe, Zn, Co
etc.; is.

k is the reciprocal of the valence of M in %.

Pc is a phthalocyanine nucleus represented by the following formula (VI), and the 3, 6) H atoms in the above formula (m) correspond to the 3 and 6 carbon atoms in phthalic anhydride from which phthalocyanine is derived. , 1 of the following formula (■).
4,5,8,9°12.13 and 16 carbon atoms substantially.

Formula (Vl) RX can be bonded to carbon atoms 1-16 around the phthalocyanine nucleus, but RX can be bonded to 3.
E is preferably bonded to five or more of the six carbon atoms, preferably all (eight). Other peripheral carbon atoms to which RX is not bonded may have other substituents, such as halogen atoms. may be substituted, but may not be substituted.

X is S, Se, Te, or NT; in NT, T is H, an alkyl group (preferably having 1 to 4 carbon atoms), or an aryl group.

R is a -valent group, particularly a -valent aromatic ring group such as a phenyl group, a naphthyl group, etc., and preferably has an arbitrary substituent.

Such a substituent is preferably an alkyl group (
For example, methyl group, n-butyl group, t-butyl group, etc.), alkoxy group (for example, methoxy group, methoxy group, dodecyloxy group, etc.), halogen atom (for example, C1, Br, etc.)
, carboxyl group, mercapto group, alkylthio group (eg, methylthio group, ethylthio group, etc.), amine group (eg, dimethylamino group, etc.).

Formula (TV) MkPc (XR)n (Y)m Formula (V) MkPc (X”-Q-X)p (XR) q (,Y)m In the above formulas (IV) and (V), M is ,Pc,
X, J: and R have the same meanings as defined in formula (m).

n is a positive integer from 6 to 16.

Y is a halogen atom, such as C1, Br, etc.

m is a positive integer between θ and IO.

X' is S, Se, Te, O or NT (T is H, an alkyl group or an aryl group).

Q is a divalent group, preferably a divalent aromatic group 1
For example, a phenylene group, etc., which may have a substituent,
Preferable examples of the substituent include an alkyl group (eg, methyl group, etc.).

p is a positive integer from 1 to 8.

q is a positive integer of 14.

However, at least 6 of the groups represented by Q and R are bonded to the octa-3,6 carbon atom through the linking group X, and the sum of n or 2p and q is 1o-t
s, preferably 12 to 16, particularly preferably 15 or 16.

Specific examples of the tutarocyanine compounds represented by the above formulas (I) to (m) are listed below.

(I) Octa-3,6-(4-methylphenylthio)
-CuPc (2) Octa-3,6-(4-methylphenylthio)
-H2Pc (3) O-phtha-3,6-(naphth-2-ylthio)-
CuPc (4) Octa-3,b-(*-methoxyphenylthio)
-CuPc (5) Octa-3,6-(4-butoxyphenylthio)
-CuPc (6) Octa-3,6-(4-methoxyphenylthio)
-H2Pc (7) Octa-3,6-(4-t-butylphenylthio) -H2Pc (8) Octa-3,6-(4-t-butylphenylthio)-CuPc (9) Octa-3,6 -(4-methylthiophenylthio) -CuPc (lO)octa-3,6-(4-dodecyloxyphenylthio)-CuPc (ii) octa-3,6-(3-methylphenylthio)
-H2Pc (I2) Octa-3,6-(3,4-dimethylphenyl) -H2Pc (I3) Octa-3,6-(2,4-dimethoxyphenylthio)-Cube (I4) Hebuta-3,6 -(4-butylphenylthio)
-Septino3.6-chloro-H2Pc(I5)deca(4-
methylphenylthio)-pentachloro-CuPc (I8) deca(4-t-butylphenylthio)-pentachloro-CuPc (I7) deca(naphth-2-ylthio)-hexachloro-(uPc (IB) deca(4-ethyl thiophenylthio)-pentachloro-CuPc (I8) unadeca(4-methylphenylthio)-bromo-CuPc (20) unadeca(4-dimethylaminophenylthio)
-Pentachloro-CuPc (21) Dodeca(4-methylphenylthio)-CuPc (22) Dodeca(4-L-butylphenylthio)-trichloro-CuPc (23) Tildeca(4-butoxyphenylthio)-dichloro-CuPc (24 ) Pentadeca(4-chlorophenylthio)CuP
c (25) Pentadeca(4-carboxylphenylthio)-Cube (26) Pentadeca(4-t-butylphenylthio)-
Cure (27) Hentade force (naphth-2-ylthio)-Cu
Pc (2B) Pentadeca(naphth-1-ylthio)-CuP
c (2a) Pentadeca(4-methoxyphenylthio)-C
uPc (30) Pentadeca(4-dodecyloxyphenylthio)-CuPc (31) Pentadeca(4-methylthiophenylthio)-
CuPc (32) Pentadeca(phenylthio)-Cube (33
) Pentadeca(4-butoxyphenylthio)-CuPc (34) Pentadeca(4-methylphenylthio)Cub
e (35) hexadeca(4-methylphenylthio)CuP
c (36) hexadeca(4-methylphenylthio)ZnP
c (37) Hexadeca(4-methylphenylthio)PbP
c (38) Hexadeca(4-methylphenylthio)H2P
c (39) Hexadeca(4-chlorophenylthio)Cub
e (40) Hebuta(4-methylphen-1,2-ylenedithio)-di(4-methyl-2-thiolphenylthio)
-CuPc (41)hebuta(4-methylphen-1,2-ylenedithio)-di(4-methyl-2-thiolphenylthio)
-H2Pc These phthalocyanine compounds are generally prepared by heating a phthalocyanine compound having halogen atoms on carbon atoms around the phthalocyanine nucleus with at least 6 equivalents of an organic thiol (or corresponding Se, Te or NT compound) in an organic solvent. It can be obtained by substituting a halogen atom with a VB or VIB group atom.

In the case of the compound represented by the above formula (I) CX=S), an octa-halophthalocyanine (at least 6 of the halogen atoms, more preferably all of them are bonded to 3,6 carbon atoms) is prepared in an organic solvent. is prepared by heating with a minimum of 8 equivalents of an organic thiol.

Compounds represented by formulas (II) and (m) (X=
S) is a phthalocyanine having at least 6 halogen atoms (halogen atoms (7), at least 6 of which are 3
．． 6 carbon atoms) with at least 6 equivalents of an organic thiol in an organic solvent. If the organic thiol further has substituents such as a second thiol group, a hydroxy group, or a primary or secondary 7-mino group, and those substituents If S is attached to the next bonded carbon atom, the organic residue of the thiol
It becomes possible to connect to two surrounding carbon atoms.

Compounds other than x:S may be prepared using corresponding Se, Te or NT compounds instead of thiols.

The organic solvent does not necessarily have to be liquid at room temperature, and only needs to dissolve a small portion of the starting material, preferably 100%
°C to 300°C, more preferably 150°C to 250″C
It is preferable to have a boiling point of The organic solvent may exhibit a catalytic effect on the reaction, but is preferably substantially inert. A suitable example is methylcyclohexa/-
Examples include lube, octatool, ethylene glycol, etc.
Particularly preferred are benzyl alcohol and quinoline.

The reaction is carried out at 100°C to 250'O2, preferably at 15
Preferably, the reaction is carried out at temperatures above 0° C. and at reflux in the presence of an acid binder such as KOH, NaOH or Na2CO3 to neutralize the halogen acids formed; the reaction product is filtered or distilled of the organic solvent. It can be separated by Purification can be achieved by repeated recrystallization using a suitable solvent such as ethanol, chloroform or pyridine, or by using a column packed with silica using an aromatic solvent such as toluene or xylene as the eluent. Alternatively, these two methods may be used together.

The phthalocyanine compound thus prepared has a 700-1
It has absorption in the infrared region of 500 nm, especially 730 to 11001 m.

Next, a specific synthesis example of the phthalocyanine used in the present invention will be shown.

Synthesis Example 1 Synthesis of Exemplified Compound (34) 12.4 g of 4-methylphenylthiol and 5,6 KOH
A mixture of g and 20 ml of quinoline was heated at 140 g for 60 minutes.
The mixture was stirred and reacted at ℃.

Thereafter, copper tetradecyl-rollo monobromophthalocyanine was added and mixed with vigorous stirring at 160 N and 180° C. for 1 hour.

The temperature of the reaction product was lowered to 100°C and diluted with 50mM ethanol (740F).

After returning to room temperature, the solid matter was filtered off, washed with ethanol and a water-ethanol mixed solvent, and dried to obtain a crude product 7.
8g was obtained. The crude product was developed on a silica column using toluene as an eluent, and the eluted main fraction was separated by evaporation to dryness to obtain 5.77 g of the target product.

The absorption maximum wavelengths measured in the reaction products toluene, pyridine, and chloroform are as follows.

Toluene 770nm Pyridine 770nm Chloroform 777nm Synthesis Example 2 Example, Synthesis of Water Compound (2) Synthesis was carried out using 4-methylphenylthiol and octa-3,6-chloropentaphthalocyanine in the same manner as in Synthesis Example 1, and the maximum absorption wavelength was It was measured.

Toluene 805 nm Chloroform 813 nm Synthesis Example 3 Synthesis of Exemplary Compound (I5) Synthesis was performed using 4-methylphenylthiol and copper tetradecylolomonobromophthalocyanine in the same manner as in Synthesis Example 1, and the maximum absorption wavelength was measured.

Toluene 752 nm Chloroform 758 nm Synthesis Example 4 Synthesis of Exemplary Compound (41) Synthesis was performed using 4-methylphenyl-1°2-dithiol and hexadecachlorophthalocyanine in the same manner as in Synthesis Example 1, and the maximum absorption wavelength was measured.

Toluene 797 nm Chloroform 800 nm Synthesis Example 5 Synthesis of Exemplary Compound (I) Synthesis was performed using 4-methylphenylthiol and copper octa-3,6-chlorophthacyanine in the same manner as in Synthesis Example 1, and the maximum absorption wavelength was measured.

Toluene 786nm Chloroform 797nm The carrier generation layer may be composed only of the above-mentioned phthalocyanine compounds, and may also be composed of azo, indigo, cyanine, perylene dyes and pigments, or various fats,
Oligomers, various additives, etc. may be mixed and used.
When mixing, the phthalocyanine compound is 50-100w.
It is desirable to contain t%.

The thickness of the carrier generation layer is preferably 0.03 to 10 m.

The electrophotographic photoreceptor of the present invention has a carrier transport layer.
The carrier transport layer has excellent electrostatic charge acceptance and charge retention, has high carrier mobility, has either no or very low spectral sensitivity to visible and near-infrared light, and has a small ionization potential. is necessary.

Materials constituting this layer include TNF-based compounds, hydrazone-based compounds, polyvinylcarbazole (PVK)-based compounds, oxazole-based compounds, dihydroxy compounds,
Examples include dicarboxylic acid-containing polyester.

A specific example is shown below.

(a)2. ,．． 5-bis=(4-diethylaminophenyl)-xadiazole-1,3,4 (b) Poly-vinyl-cal/Sol (PVK) (c) l-phenyl-3
-[p-diethylaminos + l)-5-(p-diethylaminophenyl)pyrazoline (d) N-methyl-N-phenylhydrazono-3-methylidene-9-ethylcarbazole (e) 4.4'diethylamino -triphenylmethane (i) (j) (3-(N-methyl-N-phenylhydrazone)
Methyl-9-ethylcalhezolco(k)l-phenylene3-(p-diethylaminostyryl)-5-(p-diethylaminophenyl)2Δpyrazoline(m) (n) 2,5-bis-( 4-
ethylaminophenyl)-1,3,4-year-old xadiazole (r) (S) (u) The thickness of this carrier transport layer is preferably 4 to 35 gm.

The electrode used in the electrophotographic photoreceptor of the present invention is made of a metal material and usually has a drum shape.

Although the electrophotographic photoreceptor of the present invention has a carrier generation layer and a carrier migration layer provided on the electrode, it does not matter which layer is provided on top.

In addition to the above-mentioned layers, a protective layer, a barrier layer, etc. may be provided.

To form an image using such a photoreceptor, a conventional method may be followed.

■Specific effects of the invention According to the invention, since the carrier generation layer contains at least one phthalocyanine compound having a group represented by the formula (I) and/or (II),
An electrophotographic photoreceptor with extremely high light and heat fastness for near-infrared to infrared regions can be obtained.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown, and the effects of the present invention will be explained in further detail.

EXAMPLE A carrier generation layer having a thickness of 0.1 gm and consisting of a phthalocyanine compound shown in Table 1 was formed on an aluminum electrode. Furthermore, on top of that, a thickness of 12 pm made of Omotosu Saar material is added.
A photoreceptor was prepared by providing a carrier migration layer of .

The electrophotographic photoreceptors thus obtained are designated as samples 101-105, 201 and 202 as shown in Table 1.

The sensitivity at 830 nm is shown in Table 1.

Table 1 These samples were actually mounted on a laser printer to form images, and the image quality was evaluated.

As a result, when using the samples of the present invention, good images were obtained in all cases, but in the case of the comparative samples, carriers were not generated because they did not absorb laser light, and no images were obtained.

In addition, a sample was prepared in the same manner as above except that a carrier transport layer and a carrier generation layer were formed on the electrode in this order, and the sample was treated in the same manner, but the same results as above were obtained.

From the above, the effects of the present invention are clear.

Claims (1)

[Claims] An electrophotographic photoreceptor having a carrier generation layer and a carrier transfer layer on an electrode, wherein the carrier generation layer comprises a group represented by the following formula (I) and/or
Alternatively, an electrophotographic photoreceptor comprising at least one phthalocyanine compound having a group represented by the following formula (II). Formula (I) -RX Formula (II) -X'QX- {In the above formulas (I) and (II), X and X' are S, Se, Te or NT (
T represents H, an alkyl group or an aryl group. R represents a monovalent group, and Q represents a divalent group. }