JPS5930541A - Electrophotographic receptor and its manufacture - Google Patents

Abstract

PURPOSE:To obtain a photoreceptor suitable for semiconductor laser beams, by forming a thin film of a phthalocyanine compd. contg. a metal of group IV on a conductive substrate, bringing it into contact with a shifting agent to form a charge generating layer, and forming a charge transfer layer on this layer. CONSTITUTION:A thin org. film contg. a phthalocyanine compd. contg. a metal of group IV, such as Ti, is formed on a conductive substrate. A shifting agent selected from a group of benzophenone derivs., benzyl derivs., dibenzyl ketone derivs., diphenyl derivs., benzene derivs. substd. by at least one nitro, cyano, acetyl, or aldehyde group, naphthalene derivs., acenaphthene derivs., and acenapthylene derivs. is dissolved in a solvent, and brought into contact with said thin org. film to form a charge generating layer. Then, a charge transfer layer comprising a charge transfer agent and binder is formed on that layer, thus obtaining the entitled photoreceptor having high sensitivity to light in a near IR region.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photoreceptor for semiconductor lasers that absorbs in the near-infrared region.

In recent years, the development of semi-rod lasers has been remarkable, and small and stable laser oscillators have become available at low cost and are beginning to be used as light sources for electrophotography.

However, when used in such a device, the wavelength of semiconductor laser light used as a light source is limited to a relatively long wavelength.

The reason why a semiconductor laser capable of emitting short wavelength light is used as a light source for electrophotography is that Li& deviation is problematic in terms of lifespan, output, etc.

Therefore, it is inappropriate to use conventionally used photoreceptors that absorb in the relatively short wavelength region for semiconductor lasers, and a photoreceptor that absorbs in the near-infrared region is required.

As an inorganic compound, S
e, ``re, CdS, and ZnO are known, and polyvinylcarbazole is known as an organic compound.Since both these inorganic compounds and organic compounds have insufficient sensitivity on the long wavelength side, they cannot be used near the above. There are problems in using it for semiconductor laser light having a center wavelength in the infrared region.Inorganic compounds also have a strong 7.ili property.

As semiconductor laser technology progresses, the emergence of a photoreceptor that overcomes the above-mentioned drawbacks and is highly sensitive to light in the near-infrared region, is non-toxic, and has abrasive properties has been awaited.

The present invention has been made in view of the above-mentioned current situation, and its purpose is to provide a novel electrophotographic light source that is sensitive to light in the near-infrared region, non-toxic, and durable, and a method for manufacturing the same.
Ji - To serve.

As a result of diligent efforts, the present inventors succeeded in developing such a light source for electrophotography, resulting in the present invention.

That is, the present invention provides a phthalocyanine compound containing a group (III) metal provided on a "carriage substrate" 2, a benzophenone derivative, a benzyl derivative, a dibenzyl ketone derivative, a diphenyl derivative, any one substituent, a nitro group, a cyanogen benzene derivatives, which are groups, acetyl groups, aldehyde groups,
naphthalene derivatives, acenaphthene derivatives, acenaphthene 1
7 composed of an organic film consisting of one or more shifting agents selected from the group consisting of /N derivatives.
1. A charge-transfer layer comprising a charge-generating layer and a charge-transfer layer comprising a charge-transfer agent and a binder is formed thereon.
This paper relates to a laminated type electrophotographic photoreceptor, and has been known for its first manufacturing method, i.e., conductor'c1 (in which an organic thin film containing a phthalocyanine compound containing a Group 1 V metal is disposed on a substrate and dissolved in a solvent). pen/phenone derivatives, benzyl derivatives, 'hair'; ketone derivatives, diphenyl derivatives, At-force) benzene derivatives in which one substituent is a nitro group, cyano group, acetyl group, or aldehyde group ,
A charge generation layer is formed by contacting with one or more shifting agents selected from the group consisting of naphthalene derivatives, acenaphthene derivatives, and acenaphthylene derivatives; and second, a charge transfer agent and a binder. The present invention relates to a method for manufacturing a laminated electrophotographic photoreceptor characterized by forming a charge transfer layer.

The present invention will be explained in detail below.

Group Ⅰ metals of the present invention are -ri, Sn and/or p.
b and the phthalocyanine compounds containing this include titanium phthalocyanine (TiP c ), monochlorotitanium phthalocyanine ('l''1CeP
c), monochlorotitanium phthalocyanine monochloride (1"1C (J
PcC:5), tin phthalocyanine (SnPc), monochlorotin phthalocyanine (SnC51'c), monochlorotin phthalocyanine monochloride (SnCePcCe), which has one of the benzene rings chlorinated,
Phthalocyanine (pbc6), monochlorinated phthalocyanine (Pb to jPc), monochlorinated phthalocyanine monochloride (Pb(J!PcCJ)) in which one of the benzene rings is chlorinated.

The shifting agent used in the present invention is a compound that shifts the absorption wavelength of a phthalocyanine compound containing a group 11V metal to the longer wavelength side by contacting the compound. The shifting agents include specific benzophenone derivatives, benzyl derivatives, and dibenzyl derivatives!・Choose from 29 acenaphthylene derivatives, benzene derivatives, naphthalene derivatives, acenaphthene derivatives, and acenaphthylene derivatives in which any one substituent is a nitro group, cyano group, acetyl group, or aldehyde group, one building or Two or more types are used in combination.

A benzophenone derivative is a compound represented by the general formula (11).

(Here, it, ~R1o are hydrogen atoms, the number of carbon atoms is 1
-10 alkyl group, alkoxy group having 1 to 10 carbon atoms, 1q halogen group, hydroxyl group, nitro group, cyan group, acedel group, aldehyde group, carboxyl group or -COC
ut1m1 and n is 1-10. It is assumed that In is an ester group having an integer of 3 to 20. ) A benzyl derivative is a compound represented by the general formula (2).

(Here, 1 (1~R, o is a hydrogen atom, number of carbon atoms is 1~
Represented by 10 alkyl groups, alkoxy groups, halogen atoms, hydroxyl groups, 21,4 groups, amino groups, cyano groups, acetyl groups, carboxyl groups, or -COCn Hm, excellent! It is assumed that 1 is 1 1 "" I Olm is an ester group of an integer from 3 to 20. ) A dibenzyl ketone derivative is a compound represented by the general formula (3).

(Here, R, ~ and 10 are hydrogen atoms, and the number of carbon atoms is 1-10
an alkyl group, an alkoxy group of mt to 10 carbon atoms, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an acetyl group, a carboxyl group or -CO111
m is 1, and n is l to l Q, and II+ is 3 to 20
shall be an integer of ester groups. ) A diphenyl derivative is a compound represented by the general formula (4).

(Here, at least one of ttl and it10 is a nitro group, cyan group, acetyl group, aldehyde group, carboxyl group, or -COC: n1 is a hydrogen atom, and the carbon atom is an alkyl group of Ql-10, a carbon atom)・; Represented by an alkoxy group having 1 to 10 atoms, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an acetyl group, a carboxyl group, or -COCnllm, and -J n is 1 to 10,
1 m or 8 to 20 ester groups. ) A benzene derivative is a compound represented by the general formula (5) or (6).

4 R.

(Here, at least one of R and #R6 is a nitro group, a cyan group, an acetyl group, or an aldehyde group,
Others are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups, nologen groups, hydroxyl groups, nitro groups, cyano groups, acetyl groups, or aldehyde groups. Here, n in the side chain ester group is l -10゜m is 8
~2(1)'li number, R, -R, is a hydrogen atom, a carbon atom number 1-1 (l alkyl group, alkoxy group, halogen atom, hydroxyl group, nitro thread, dir) group, acetyl group or a carboxyl group. ) A naphthalene derivative is a compound represented by the general formula (7).

(Here, at least one of R and ~R8 is a nitro group, a cyano group, an acetyl group, or an aldehyde group,
The others are hydrogen atoms, alkyl groups with 1-10 carbon atoms, alkoxy groups with 1-10 carbon atoms, halogen atoms, hydroxyl groups, cyano groups, acetyl groups, aldehyde groups, or -COCnl1m1 It is assumed that II is an ester group where l-IQSm is an integer of 3 to 2 degrees. ) Acenaphthene derivatives are compounds represented by general formula (8).

(Here, at least one of R1 to R is represented by a nitro group, a cyano group, an acetyl group, or a, and n is 1 to 1.
0, m is an integer of 8 to 20, and the others are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to IO carbon atoms, halogen atoms, hydroxyl groups, nitro groups, Cyan group, acetyl group, aldehyde group,
It is a carboxyl group or an ester group represented by -COCnHm, where n is an integer of 11 to 10 and m is an integer of 8 to 20. ) The acenaphthylene derivative is a compound represented by the general formula (9).

(Here, at least one of R1-R8 is a nitro group, a cyano group, an acetyl group, an aldehyde group, a carboxyl group, or -C (JCnl-1m is represented by a convex shape, and n is 1 to 1O1in is 8 to 20 is an ester group which is an integer of , and the others are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, halogen + sx atoms, hydroxyl groups, nitro groups, cyan groups, acetyl groups , aldehyde group, ]J ruboxyl h
(Or it is represented by -〇〇Cn11m, and !1 is an ester group with an integer of 11 to IQ, and m is an integer of 8 to 20.) Further, as a specific example of the above compound as a shifting agent, , benzoic acid, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl benzoate, P-
Hydroxybenzoic acid, ethyl P-hydroxybenzoate,
Ethyl P-hydroxybenzoate, propyl P-hydroxybenzoate, butyl P-hydroxybenzoate, phenyl P-hydroxybenzoate/Lz, m-hydroxybenzoic acid, methyl nl-hydroxybenzoate, ethyl '1n-hydroxybenzoate , In-propyl hydroxybenzoate, butyl m-hydroxybenzoate, phenyl in-hydroxybenzoate, salicylic acid, methyl salicylate, ethyl salicylate, propyl salicylate, butyl salicylate, phenyl salicylate, phenylacetic acid, methyl phenylacetate, ethyl phenylacetate, Propyl phenylacetate, methyl phenylacetate, phenyl phenylacetate, nitrobenzene, P-dinitrobenzene, n1-dinitrobenzene, 0-dinitrobenzene, benzaldehyde, benzonitrile, p-7 talonitrile, m-phthalonitrile, 0
-phthalonitrile, terephthalic acid, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate,
Dibutyl terephthalate, diphenyl terephthalate, P-
Methylbenzoic acid, methyl P-methylbenzoate, ethyl P-methylbenzoate, propyl P-methylbenzoate, P-
Butinope P-methylbenzoate, phenyl methylbenzoate,
m-methylbenzoic acid, methyl m-methylbenzoate, m-
Ethyl methylbenzoate, pyropyl In-methylbenzoate, butyl In-methylbenzoate, phenyl In-methylbenzoate, 0-methylbenzoic acid, methyl 0-methylbenzoate, 0-methylbenzor1 diethyl, O-methylbenzoate propyl acid, butyl 0-methylbenzoate, nψphenyl 0-methylbenzoate, acetophenone, p-methylacetophenone, m-ethylacetophenone, 0-methylacetophenone, P-ethylacetophenone, m-ethylacetophenone, 0-ethylacetophenone,) )−
Propylacetophenone, lll-propylacetophenone, 0-propylacetophenone, P-butylacetophenone, m-butylacetophenone, 0-butylacetophenone, P-phenylacetophenone, 1n-phenylacetophenone, O/-phenylacetophenone,
Benzophenone, 4-methylbenzophenone, 4-ethylbenzophenone, 4-propylbenzophenone, 4-
-j thylbenzophenone, 4-phenylbenzophenone, 2.2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-5-chlorobenzophenone, 2.4-dihydroxybenzophenone, 4.4'
-dichlorobenzophenone, 2-hydroxy-4-methoxybenzophenone, 4-dobcyclo-2-hydroxy-benzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2.2'-dihydroxy-4-methoxybenbenzophenone, 2. 2',4.4'-tetrahydroxybenzophenone, 2-hydroxy-4-
Methoxy-5-sulfopenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone,
2-Hydroxy-4-chlorobenzophenone, 4-(hydroxy)benzylbenzonitrile, diphenyl, 0-
Hydroxydiphenyl, 4-nitrodiphenyl, 4-cyanodiphenyl, 1)-cumylphanol, phenol 2.5-dimethylxylenol, 5-nitroacenaphthene, 5-cyanoacenaphthene, 5-acetylacenaphdene, 5-nitro Acenaphthylene, 5-cyanoacenaphthylene, 5-a7tylacenaphthylene, 2-nitronaphthalene, 2-cyanonaphthalene, 2-acetonaphthalene, 2-nitrophenanthrene, 2-cyanophenanthrene, 2-acetyl phenanthrene, 2-nitropyrene,
2-cyanobilene 7.2-7 cetylpyrene, 2-nitrotriphenylene, 2-cyanotriphenylene, 2-acetyltriphenylene, 1-nitrofluoran-sol, ■-
Cyanofluoranthene, l-acetylfluoranthene l-cyanobenzanthracene, l-acetobenzanthracene, benzyl, 4-methylbenzyl, 4-hydroxybenzyl, 4-nitrobenzyl, 4-cyanobenzyl, 4-acetylbenzyl, di Benzyl ketone, 4,
Examples include 4'-(dimethyl)dibenzyl ketone.

The laminated photoreceptor of the present invention comprises a flexible substrate, a charge generation layer formed by contacting a phthalocyanine compound containing a Group Ⅰ metal with a shift agent, and a charge generation layer made of 0 +', 'Tll5IG; It is composed of a 1×1 charge transfer layer coated with a coating solution obtained by dissolving a transfer agent and a binder in a solvent. In addition to the method of forming a charge-generating layer using a shifting agent and then forming a charge-transfer layer, for example, a phthalocyanine compound containing a group V metal is vacuum-deposited on a conductive plate, and then the second layer is formed. It is also possible to simultaneously form a charge generation layer having an absorption peak in the near-infrared region and a charge transfer layer by applying a coating solution obtained by dissolving a charge transfer agent, a binder, and a shifting agent in a solvent. However, such a method is also included within the scope of the present invention.

In order to form the organic membrane of the phthalocyanine compound containing Group (1) metal of the present invention, a vacuum deposition method or a spin cord method may be used. In the former case, L (
It is obtained by heating a phthalocyanine compound to 400-500°C under a high vacuum of 1'-5~t 0-Jl/L/ ('l'orr); in the latter case, the phthalocyanine compound is heated to 400-500°C. , using a coating solution obtained by dissolving in a solvent such as amide, the number of revolutions is 8.000 to 7.0.
Obtained by spin-coaching ink at 0 Orpm.

Both coating methods have advantages and disadvantages, and the latter is superior in terms of simplicity, while the former is superior in terms of absorbance of the obtained thin film, and a thin film with a large absorption IV can be easily obtained.

In the present invention, the following methods are available as method T in which an organic thin film of a phthalocyanine compound containing a group (1) metal is brought into contact with a shifting agent.

One method is to apply the shifting agent uniformly to its soluble solvent.
This is a method of dipping the organic thin film provided on the conductive substrate in the solvent.

Other methods include a method in which this solvent is uniformly sprayed onto the organic HB>> and a method in which the shifting agent is evaporated under reduced pressure to uniformly contact the organic HB. Note that 4 in this solution of the shifting agent
'1 degree is o, a ~3QwL%, preferably 1.0~1
0.0W 1%.

The structure of the electrophotographic photoreceptor used as the charge generation layer of the present invention is as described above, but the charge transfer layer is designed to transfer charges generated in the charge generation layer to the surface of the PA layer type electrophotography photoreceptor. It is preferable to use one that can absorb light in the near-infrared region, and one that can sufficiently pass through semiconductor laser light that absorbs in the near-infrared region.

There is a method of coating the charge transfer layer on the charge generation layer using a spin coater, doctor blade, etc. In other words, the charge transfer layer and its binder are dissolved in both solvents. This method involves applying a coating liquid.

The charge transfer agent "C" used in the charge transfer layer may be one having pole conductivity, such as carbazole, N-ethylcarbazole, 13-(N-medy-N-phenylhydrazone) meg-9-ethylcarbazole, or tri-carbazole. Phenylmethane, fluorene, 1,2-benzofluorene,
2.3-benzofluorene, 2.5-bis(4-diethylaminophenyl)-1,8°4-oxadiazole,
p-(dimethylamino)stilbene, pyrazoline, l-
Phenyl-8-(p-diethylaminophenyl)pyrazoline, ■-(2-pyridyl)-8-(p-diethylaminophenyl)pyrazoline, 3°8'-bis(1,5-diphenyl-2-pyrazoline), 3. 8'-bis(1,4
, 5-triphenyl-2-pyrazoline), 8,3'-bis(l, 5-diphenyl-4,5-dimethyl-2-pyrazoline), and the like.

Binders used in the charge transfer layer include polyvinylcarbazole, polyvinylpyrazoline, polyvinylpyrene, polyvinyl chloride, polystyrene, ethylene-vinyl acetate copolymer, hinyl chloride-vinyl acetate copolymer, and styrene-vinyl acetate copolymer.
Examples include butadiene copolymers, polycarbonates, polyesters, polyamides, methylpentene polymers, polysulfones, polyethersulfones, epoxy+silicone, 1 resin, acrylic resins, silicone resins, and the like.

Examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1: 5Xl of titanium phthalocyanine (TiPc)
(approximately 400 to 5
It was heated to 00°C and vacuum deposited onto a glass substrate. When measuring the film thickness with a crystal vibrating film thickness meter (manufactured by Japan Vacuum Technology),
It was l 8 Q nm. UV-V I S Spec 1
When the absorption curve was measured using a trometer (Shimadzu UV210Δ), the maximum absorption wavelength was 72Q nm.The substrate was dipped in a trichlorethylene solution in which 1 wL% of penzophenone was uniformly dissolved.
When Q, 51-1 was dried at 100° C., it was found that the maximum absorption wavelength shifted to <825 n sn as shown in FIG.

Example 1 Titanium phthalocyanine was dissolved in 5Xl()-6 Torr(T
The film was heated in a vacuum of 78M on the aluminum vapor-deposited substrate while monitoring with a quartz-crystal film thickness meter so that the film thickness became l l 0111TI.

This was dipped in a trichlorethylene solution containing 1 wt% of benzophenone, and after air-drying,
Dry at 511°C.

Next, the base was applied using a coating l+M prepared by dissolving 1-phenyl-5-(+3-diethylaminostyryl)-5-(p-diethylaminostyryl)pyrazoline in 51 parts, polycarbonate in 51 parts, and 90 parts of tetrahydrofuran.

Using an electrostatic charging test device (manufactured by Kawaguchi?li 8G),
The laminated photoreceptor was negatively charged with a 7KV corona exposure. After that, a 500'vVXe lamp (manufactured by Wacom) was used.
The light attenuation of the surface potential of the photoreceptor was measured by using an external light source as a monochromatic light source using a monochromator (manufactured by Jobin Yvon), and attaching j(aC) from an external 19-light manual section.

As a result, when m-color light of f33 Q n rn in the near-infrared region was used, the half-life exposure (the product of the time when the city position remaining 4-tap rotation becomes negative and the light intensity) was 1.2 μJ/lri.

Comparative Example 1 A sample similar to the titanium phthalocyanine of Example 1 was prepared by vacuum evaporating copper phthalocyanine (type 13) on an aluminum evaporation/substrate at 5 X l O'' Torr. When the optical attenuation of the surface potential was measured under the same conditions, the law of half-exposure to 33 Qnm monochromatic light was 0.
．． 5111. 1/F or more, and the sensitivity +i was significantly worse than that of the titanium phthalocyanine of Example 1.

Copper phthalocyanine was vacuum deposited on a glass substrate and the absorption curve was measured.
The city electrode was formed by vacuum deposition. The electrode-1- was subjected to short-time dipping* (dipping) of trichlorethylene containing titanium % in the same manner as in Example 1.
) by drying Q, 5 II at °C.
A small flow cell was formed.

A voltage of 3 cm was applied between the above electrodes, a 500 WX e lamp (manufactured by Wacom) was used as the light source, and a monochromatic light of 880 nm was irradiated with a monochromator (manufactured by Gino (manufactured by N. Yvon)) to measure the photocurrent in °C. >'i L, 1.2 X L
O-” It was A.

Departure I example 2 tti pole spacing of 300 μIn on a glass substrate? J.

The electrodes were made of gold vapor, and secondly, Example 1 was made of IIK. +111 method of light'@11 style/[1! When the sample was determined, it was found to be 5X10-13A.

[Brief explanation of drawings]

Figure 1 shows the relationship between jll & luminous intensity (0 to 2 Abs) and wavelength of the same vacuum vaporized film of Example 1 of the present invention after vacuum deposition +154 and shift and other agent treatment of titanium phthalocyanine. This is what is shown. Are both figures 1 and 2 true of the copper phthalocyanine of Comparative Example 1? and Steam'It
This figure shows the relationship between IIK absorbance (0 to 2 Abg) and wave deflection.

Claims (1)

[Scope of Claims] ■) A phthalocyanine compound containing a Group ■ metal on a conductive substrate, as well as benzophenone derivatives, benzyl derivatives, dibenzyl ketone derivatives, diphenyl derivatives, in which any one substituent is a nitro group, a cyano group, acedel group, aldehyde group benzene derivatives, naphthalene derivatives,
A charge generation layer composed of L'i + IQ is formed, and a charge generation layer is formed with 161B selected from the group consisting of acenaphthene derivatives and acenaphthylene derivatives, or two or more shifting agents; A laminated electrophotographic photoreceptor comprising a charge transfer layer comprising a binder and a binder. 2) A benzophenone derivative, a benzyl derivative, a dibenzyl ketone derivative, a diphenyl derivative prepared by dissolving an organic thin film containing a phthalocyanine compound containing a group (III) metal on a conductive substrate, in which one of the substituents is 1 selected from the group consisting of benzene derivatives, naphthalene derivatives, acenaphthene derivatives, and acenaphthylene derivatives, which are cyano groups, acetyl groups, and aldehyde groups.
Electric charge generation upon contact with the ridge or two or more types of shifting agents 11☆
and on top of that? 1. A method for producing a laminated electrophotographic photoreceptor, which comprises forming an r1 cargo transfer layer comprising a cargo transfer agent and a binder. 8) The laminated electrophotographic photoreceptor according to claim 1, characterized in that the WIV group metal is Ti, Sn and/or Pb.