JPS61198241A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic sensitive body showing absorption in the near infrared or infrared region by forming a carrier generating layer contg. a specified phthalocyanine compound. CONSTITUTION:A carrier generating layer contg. a phthalocyanine compound represented by formula 1 or 2 is formed. In the formulae 1, 2, M is H, a metallic or metalloid atom or M1X; the preferred metallic or metalloid atom is Cu, Ni, Co, Fe, Zn, Al, Pt or V; M1 is an atom of a group IIIB metal, preferably Al, Ga or In; X is a halogen atom, preferably Cl, Br or I; Pc is a phthalocyanine skeleton represented by formula 3; Y is preferably H, Cl, Br or I; and n=8-16. The phthalocyanine compound includes octa-3,6-(4- methylphenoxy)-CuPc.

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.

By the way, phthalocyanine compounds have excellent robustness against heat, light, humidity, etc., and are attracting attention as photoconductive materials.
Attempts have been made to apply this phthalocyanine compound to a carrier 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 Such 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, wherein the carrier generation layer contains a phthalocyanine compound represented by the following formula (I) or formula (II). Electrophotographic photoreceptor.

Formula (RIMk-Pc(-ORt) (Y)16-n Formula (II
) Mk-PC-(-Xi R2X2 )a(OR3)
(Y) 1B-21-.

(In formulas (1) and (II), M represents a hydrogen atom, a metal or metalloid atom, or MIX.

Ml represents an mB metal atom, and X represents a halogen atom.

When M is a hydrogen atom or a metal atom, k represents the reciprocal of 1/2 of its valence, and when M is MIX, it is 1.

Pc represents a phthalocyanine nucleus.

R1 and R3 each represent a substituted or unsubstituted aliphatic group, alicyclic group, aromatic group or heterocyclic group.

R2 is a substituted or unsubstituted divalent aliphatic group.

Represents an alicyclic group, an aromatic group, or a heterocyclic group.

Xz and x2 are Tsuretsure, O, S.

Se, Te or NT (T represents a hydrogen atom, an alkyl group or an aryl group).

Y represents a hydrogen atom or a halogen atom.

n is 5 to 16, sentence is 1 to 8, and m is a positive integer of 0 to 14).

■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 contains a phthalocyanine compound represented by the following formula (I) or formula (II).

Formula (I) M k P c (-ORt) (Y) 1
6-n formula (II) Mk-Pc+XI -R2-X2 ) a (OR3)
(Y)te-21-* layer In the above formulas (1) and (II), 1M is a hydrogen atom,
Represents a metal or metalloid atom or MIX.

Ml represents an mB metal atom, and X represents a /10 gen atom.

Examples of metal or metalloid atoms include Zn, Pb,
Cu, Ni, Fe, Co, Sr.

Ca, Yb, Li, Ag, Ru, Sm, Tb, DY,
U, Tl, Cs, Pd, Nd, G
a.

In, Sn, Si, Pt, Mn,
Ge, Be, A11. V, Sn, Mg
, Ti, etc., among which cu, Ni, Go, F
e, Zn, AfL, Pt, V, and hydrogen are better.

Ml is mB metal atom (AJI, Ga, In.

TJI, especially A sentence and Qa.

In is preferred.

or a halogen atom, such as F, C1, BY.

1st prize; Among these, CJI, Br, and I are preferred.

When 1M is a hydrogen atom or a metal atom, k represents the reciprocal of 1/2 of its valence, and when M is MIX, it is l.

Pc is a phthalocyanine nucleus represented by the following formula (m).

In the above formula (m), -OR,, -xt R2X2-1-0R3 is also substituted with I, and <t*Y is substituted at any one of the positions 1 to 16.

R1 and R3 are monovalent, R2 is divalent, and has 1 carbon number.
~20 substituted or unsubstituted aliphatic groups, alicyclic groups 1 For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, benzyl group,
Phenethyl group, cyclohexyl group, allyl group, dodecyl group, -CH2CH2CH=CH-CH2-, cyclohexene Substituted Aromatic Group 1 For example, phenyl group, tolyl group.

Phenylene group, naphthylene group, methoxyphenyl group, naphthyl group, phenyl chloride group, xylyl group, 00C2H5.

0 CH2Cl, OCH20H, styryl group, cinnamyl group, phenethyl group, methylphenylene group, 0COOC
R3, etc.; Substituted or unsubstituted heterocyclic group 1, for example, pyridyl group,
Pyrrolyl group, quinolyl group, furyl group, furfuryl group, phenyl group, piperidyl group, pyrimidyl group, etc.

Y is a hydrogen atom: Halogen atoms, such as C, Br, E, F, etc.; Among them, H, C1, Br, and I are preferable.

xl and x2 are Tsuretsure, o, s.

Se, Te or NT (T represents a hydrogen atom, an alkyl group or an aryl group).

n represents a positive integer from 5 to 16, especially from 8 to 1.
It is preferable that it is 6.

Views are 1-8. m represents a positive integer from θ to 14.

Specific examples of the phthalocyanine compounds of the present invention are listed below.

(1) Octa-3,6-(4-methylphenoxy)-Cube (2) Octa-3,6-(methoxy)CuPc (3) Octa-3,6-(-0C2Hs)CuPc (4) Octa-3 , 6-(-0C3H7)CuPC (5) Octa-3,6-(-0C4H9)H2Pc (6) Octa-3,6-(-00) CuPc (7) Octa-3,6-(-0〇C2H5 ) cupc (8) Octa-3,6-(-00CIL)-N L P
c (9) deca-(-0-Op-OCH3)CoPc (lO) deca-(-0C5Hu) -H2P cCo
re (12) Pentadeca-(-0C2H5)82PC (13) Pentadeca-(-00COOCH3)PbPc (14) Pentadeca-(-0C3H7)ZnPc (15) Octa-3,6-(-000CB3)H2P
c (16) Pentadeca-(-00)-CuPcCure (18) Pentadeca-(-0-C2Hs)CuPc (19) Pentadeca-(-0-CH3)Cure (20) Pentadeca-(-0-CH3)82Pc (21 ) Pentadeca-(-00CH3)CuPc (22) Pentadeca-(-000CH3)H2Pc (23) Hexadeca-(-0<)) -CuPc(20
Hexadeca-(-0〇CH3) H2Pc (25) Hexadeca-(-〇-CH5) CuPc (2B) Hexadeca-(-0-C2Hs) CuPc (27) Octa-3,6- (28) Octa-3, 6- (29) Hexadeca-(-0C3H7)-FePc-CuPc (31) Octa-3,6- (-0-C2Hs) Tetra-4,5- Di4,5- (-0-Ca HI3-0- )CuP
c (33) Hexadeca-(-C) CH:s) Seven no (34) Octa-3,6-(-0CH3) -A Stand
C-cross Pc (35) -)r')))-3,6-(-0C2H5)
-InC Pc (36) Octa-3,6-(-00)-GaCjLPc (37) Octa-3,6-(-0C3H7) -nBr
Pc (38) Octa-3,6-(-0C2Hs) -Ti
CjLPc (39) Octa-3,6- (40) Deca-(-o-o-CH3) -Yami B rPc (41) Deca-(-0-C2Hs) Ai I P
CaBrPc (43) Pentadeca-1--0-Cjl)InC sentence P
c (40 pentadeca-(-0(>OCH3)AjLC look Pc (45) pentadeca-(-〇〇〇C2H3)CaCjL
Pc (4B) Pentadeca = (-0-C2Hs) nIPc (47) Pentadeca-(-□-C2Hs) ・aI
Pc I ncJIPc (49) Hexadeca-(-00)GaCIPc(50
) Hexadeca-(-〇-C2Hs)nBrPc (51) Hexadeca-(-0C3H7)A Standing CIP
c (52) Hexadeca-(-0〇CH3)CaBrPc (53) Hexadeca-(-00C statement) IBrPc (54) Undeca-(-0-C2Hs) I ncuP
c (55) Octa-3,6- (-0-C2Hs) y Tora-4,5-G (-0-
Cs Hlo -0) (57) Hexadeca-(-00CH3)mono The phthalocyanine compound of the present invention can generally be synthesized by a method according to the following scheme.

Scheme l n R10-K” +MkP c (Y) 1B□
→ Mk-Pc(-OR1)n (Y) tG-n18
0-180°C, lhr.

+ By-products Purification of the reaction product using this method is carried out as follows.

The reaction product is cooled to 100° C., diluted with ethanol, then returned to room temperature and filtered. This filtered material is washed with ethanol, further washed with an ethanol-aqueous solution,
dry. The crude product thus obtained is developed on a silica column with toluene and purified by one separation.

Scheme 2 L i 2 P c-1-OR+ ) ts + nM
Purification of the reaction product in this case is carried out analogously to Scheme 1.

Scheme 3 Li2 Pc+ORI) IG+nMI XY2
130℃ in amyl alcohol, lhrM, X-PC+OR,) n(Y)
16-n Purification of the reaction product in this case is shown in Scheme 1
Do the same as.

Next, examples of synthesis of the phthalocyanine compound of the present invention will be given.

Synthesis Example 1.7″X 3 12g of ethanol and 8g of KOH were mixed in
The reaction was carried out at 5°C for 2 hours. To this, cuPc (Cj
L) Add 7g of ts.

It was made to react at 160-180 degreeC for 2 hours.

The resulting reaction product was cooled to 100° C., diluted with ethanol (E t OH), returned to room temperature, and filtered.

i! ! The separated material was washed with EtOH, and further Et
Washed with 0H-R20' (1:1) solution and dried.

The crude product thus obtained was developed on a silica column with toluene, separated and purified. This process was repeated twice to obtain the desired product.

Yield 35% Elemental analysis CON Cu Calculated value/% 4L52 11.01 9. [135,
48 Actual value/% 47.21 11.31 9.89
5.52 Absorption maximum input max 710 nm (measured by forming a thin film with a final thickness of 0.1 m by spinner coating) Synthesis example 2. 7 6 The desired product was obtained in the same manner as in Synthesis Example 1.

Yield 42% Elemental analysis CO, N Cu Calculated value/% 82.05 8.27 7.24 4.
10 Actual value/% 80.03 8.41? , 21
4.24 Synthesis Example 3. 6 15 The desired product was obtained in the same manner as in Synthesis Example 1.

Yield 18% Elemental analysis CON H Calculated value/% 59.81 14.50 B, 34
3.28 Actual value/% 80.21 14.01 B
, 52 3.01 Synthesis Example 4. 8 11 The desired product was obtained in the same manner as in Synthesis Example 1.

Yield l9, 7% Elemental analysis CHN Cu Calculated value/% 73.77 3.33 4.85 2.
75 Actual value/% 71.68 3.71 4.83
2. H synthesis example 5. 18 The desired product was obtained in the same manner as in Synthesis Example 1.

Yield 18.4% Elemental analysis CHN Cu Calculated value/% 58.58 5.91 8.82 5.
00 Actual value/% 58.82 5.81 8.80
5.031 mol of ethanol (E t OH) was reacted with 4 mol of ethanol at 130° C. for 3 hours to obtain the following. 2 moles of Li+(QCs Hu)-2 were added to 4 moles of this compound and reacted at 130°C for 2 hours to obtain Li2PcMo0Et)+s. Furthermore, 1 mol of CuCJ12 was added to 1 mol of this compound and reacted in amyl alcohol at 120° C. for 2 hours to obtain the desired product.

Purification was performed in the same manner as in Example 1.

Yield 23.9% Elemental analysis CHN Cu Calculated value/% 80. Q2 11! , 25 8.75
4.98 Actual value/% 60.14 8.20 8. H
4,91 absorption maximum input m a x 810 nm (measured by forming a thin film with a thickness of 0.1 ILm by spinner coating) Synthesis Example 7. 8 28 The desired product was obtained in the same manner as in Synthesis Example 6.

Revenue rate: 33.5% elemental analysis CHN C.

Calculated value/% 87.79 2.82 5.85 2.
97 Actual value/% 88.99 2.85 5.70
2.91 Synthesis Example 8. S23 The target product was obtained in the same manner as in Synthesis Example 6.

Yield l 9.8% Elemental analysis CHN Cu Calculated value/% 75.02 3.91 5.47 3.
10 Actual value/% 73.82 3.93 5.52
3. Of1 synthesis example 9. The desired product was obtained in the same manner as in Synthesis Example 6 of 6 29 .

Yield 28.4% Elemental analysis CHN Fe Calculated value/% 84.18 7.49 7.49 3.
73 Actual value/% 82.94 7.45 7.38
3.84 Synthesis Example 10. 8 30 The desired product was obtained in the same manner as in Synthesis Example 6.

Yield 36.4% Elemental analysis CHN Cu Calculated value/% 80.131 3.93 39.30
2.23 actual value/% 82.90 3.92 39.
10 2.21 4 moles of ethanol (EtOH) and 14
React at 0°C for 2 hours.

Li÷(OC5Hu)-2 moles were added to 4 moles of this compound and reacted at 150°C for 2 hours to form Li2Pc+0Et.
) IG was obtained. Furthermore, 1 mole of this compound contains InCl
Add 31 moles.

The reaction was carried out in amyl alcohol at 130°C for 1 hour to obtain the desired product. After cooling this reaction product to 100°C,
Dilute with ethanol (E t OH), warm to room temperature, and filter.
The filtered material was washed with EtOH, and further EtOH-H
20 (1:1) solution and dried. The crude product thus obtained was developed with toluene on a silica column, separated and purified to obtain the desired product.

Yield 18.6% Elemental analysis CHN In Actual value 7% 54.52 5.138 7.91 8.
113 absorption maximum input amount ax 830 n layer (measured by forming a thin film with a thickness of 0.1 mm by spinner coating) Synthesis Example 12 The desired product was obtained in the same manner as in Synthesis Example 11.

Yield 23.2% Elemental analysis CHN In Actual value 7% 43.92 3.11 8.88 8.1
34 Synthesis Example 13 S 3B The target product was obtained in the same manner as in Synthesis Example 11.

Yield 28.4% elemental analysis CHN Ga Synthesis! The target object was obtained in the same manner as in (2).

Yield 31.8% Elemental analysis CHN Ga Calculated value 7% 813.25 2.76 5,52 3.
44 actual value/%85.84 2.72 5.58 3
．． 4111 Synthesis Example 15 Su 48 16 moles of β-naphthol and 16 moles of KOH were reacted in quinoline at 140° C. for 1 hour.

Add 161 mol of InciPc (CJL) to this,
It was made to react at 160-180 degreeC for 1 hour.

The obtained reaction product was purified in the same manner as in Synthesis Example 11.

Yield 23.6% Elemental analysis CHN In Calculated value 7% 78.52 3.82 3.82 3.9
1 Actual value/%77.94 3.85 3.88 3.
89 Maximum absorption λ dust a 840 nm (measured by forming a thin film with a thickness of 0.1 IL ■ by spinner coating) Synthesis Example 16 44 The desired product was obtained in the same manner as in Synthesis Example 15.

Yield 28.5% elemental analysis CHN A! L Synthesis The desired product was obtained in the same manner as Synthesis 5.

Yield 22.8% Elemental analysis CHN In calculated value 7% 37.29 3.10 ill. 22
fl, 37 actual value/% 37.11 3.12 8.
21 8.38 Synthesis Example 18, X54 The desired product was obtained in the same manner as in Synthesis Example 15.

Yield 29.4% Elemental analysis CHN In Calculated value 7% 49.15 4.17 B, 49 11
．． 71 actual value/%48.93 4.19 8.51
8.70 The carrier generation layer may be composed only of the above-mentioned 7-talo-cyanine compound, or may further contain azo, indigo, cyanine, perylene dyes and pigments, various resins, oligomers, various additives, etc. May be used as
When mixed, the phthalocyanilla compound is 50 to 100%
It is desirable that it be contained in wt%.

The thickness of the carrier generation layer is preferably 0.03 to io#Lm.

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.

Although the above-mentioned phthalocyanine compounds may be used as the material constituting this layer, TNF-based compounds, hydrazone-based compounds, polyvinylcarbazole (PVK)-based compounds, oxazole-based compounds, dihydroxy compounds, dicarboxylic acid-containing polyesters, etc. are usually used. It will be done.

A specific example is shown below.

(a) 2,5-bis-(4-diethylaminophenyl)
-xadiazole-1,3,4(b) poly-vinyl-
Carbazole (PVK) (C) 1-phenyl-3-[p
-diethylaminostyryl)-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-ethylcarbazole] (k) L-phenylene 3-(p-diethylaminostyryl)-5-(p-diethylaminophenyl) 2Δpyrazoline (n) 2,5-bis-(4-
diethylaminophenyl)-1,3,4-oxadiazole (u) The thickness of this carrier transport layer is preferably 4 to 35 μm.

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

The electrophotographic photoreceptor of the present invention has a carrier generation layer and a carrier transfer layer formed on the electrode, but it does not matter which layer is formed on top of the electrode. It is also possible to provide one layer, etc.

A conventional method can be used to form one image using such a photoreceptor.

■Specific effects of the invention According to the present invention, since the carrier generation layer contains the phthalo or cyanine compound represented by the formula (I) or (II), extremely high An electrophotographic photoreceptor having fastness to light and heat can be obtained.

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

EXAMPLE A carrier generation layer having a thickness of 0.1 pm and consisting of a phthalocyanine compound shown in Table 1 was formed on an aluminum electrode. Furthermore, a thickness of 12IL made of oxazar material is added thereon.
A photoreceptor was prepared by forming a carrier transfer layer of m.

The electrophotographic photoreceptors thus obtained are shown in Samples 1 to 20 as shown in Table 1. Ill and 112.

Table 1 shows the sensitivity at each peak sensitivity wavelength.

Table 1 1 (This invention) Exemplified compound (7) 0.22 (This invention) Exemplified compound (1G) 0.33 (This invention)
Exemplified compound (12) 0.34 (present invention) Exemplified compound (1111) 0.25 (present invention) Exemplified compound (17) 0.46 (present invention) Exemplified compound (
23) 0, 37 (present invention) Exemplary compound (24
) 0, 28 (present invention) Exemplary compound (2B)
0, 39 (present invention) Exemplary compound (27) 0
, 410 (This invention) Exemplary compound (30) 0
, 411 (present invention) Exemplary compound (34) 0 ,
312 (This invention) Exemplary compound (H) 0, 41
3 (This invention) Exemplary compound (39) 0, 314
(This invention) Exemplary compound (44) 0, 215
(This invention) Exemplary compound (48) 0, 318 (
(present invention) Exemplified compound (49) 0, 317 (present invention) Exemplified compound (51) 0, 418 (present invention) Exemplified compound (53) 0, 419 (present invention)
Exemplary compound (55) 0, 220 (present invention)
Exemplary compound (5?) 0 + 3111 (comparison)
Cube None 112 (Comparison) Cu P c C11B None These samples were actually mounted on a laser printer to form an image and evaluate the quality of one image.

As a result, when the samples of the present invention were used, 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 image was 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, characterized in that the carrier generation layer contains a phthalocyanine compound represented by the following formula (I) or formula (II). Electrophotographic photoreceptor. Formula (I) Mk-Pc-(OR_1)_n(Y)_1_
6_-_n Formula (II) Mk-Pc-(X_1-R_2-X_2)_l
(OR_3)_m(Y)_1_6_-_2_l_-_m {In formulas (I) and (II), M represents a hydrogen atom, a metal or metalloid atom, or M_1X. M_1 represents a IIIB metal atom, and X represents a halogen atom. When M is a hydrogen atom or a metal atom, k represents the reciprocal of 1/2 of its valence, and when M is M_1X, it is 1. Pc represents a phthalocyanine nucleus. R_1 and R_3 each represent a substituted or unsubstituted aliphatic group, alicyclic group, aromatic group or heterocyclic group. R_2 represents a substituted or unsubstituted divalent aliphatic group, alicyclic group, aromatic group or heterocyclic group. X_1 and X_2 are O, S, Se, Te, respectively
or NT (T represents a hydrogen atom, an alkyl group or an aryl group). Y represents a hydrogen atom or a halogen atom. n represents a positive integer of 5 to 16, l represents a positive integer of 1 to 8, and m represents a positive integer of 0 to 14}