JPS63115173A - Photoconductive composition - Google Patents

Abstract

PURPOSE:To enhance storage stability and sensitization efficiency by using a photoconductive composition containing a photoconductor, a binder resin, and a sensitizing dye composed of an aromatic ring, hetero ring, or a ring formed by a aliphatic chain. CONSTITUTION:The photoconductive composition contains the photoconductor, a binder resin, and the sensitizing dye represented by the formula shown on the right in which Z is O, S, Se, or the like; Q is an atomic group necessary to form an optionally substituted pyrane, benzopyrane, or the like, or an N- containing hetero ring; each of Y1 and Y2 is H, an aliphatic or aromatic group; p is 0 or 1; each of R1-R7 is H, halogen or the like; R8 is H or an aliphatic group; each of X1-X3 is H, alkyl, or the like; A<-> is an anion; and r is 1 or 2.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a photoconductive composition comprising a photoconductor dispersed in a binder resin, in which the photoconductor is spectrally sensitized with a novel dye. TECHNICAL FIELD The present invention relates to photoconductive compositions.

[Conventional technology]

Many spectral enhancing dyes are already known in electrophotographic photosensitive layers of photoconductor-resin dispersion systems. There are various properties required of these spectral enhancing dyes, including good adhesion to the photoconductor, high exacerbation efficiency, and not lowering the resistance of the electrophotographic photosensitive layer in the dark more than necessary. This is a particularly important point. Examples of dyes that meet these requirements are U.S. Pat. Nos. 3,052,540 and 311,059
No. 1, No. 3125447, No. 3128179, No. 3
No. 132942, No. 3241959 and No. 3121
No. 008 and British Patent No. 1,093,823.

On the other hand, spectral enhancing dyes for red light or infrared light are described in U.S. Pat. No. 3,619,154 and U.S. Pat.
For example, cyanine dyes, particularly polymethine dyes with long methine chains (eg, 5 or more), are mainly used for spectral sensitization for wavelengths of 700 nm or more.

(Problems to be Solved by the Invention) However, these dyes are generally easy to decompose (decompose significantly during the storage of the dye or during the manufacturing process and storage of the electrophotographic photosensitive layer, resulting in a decrease in performance, which is a major practical problem). There were drawbacks. Harata et al. stated that sensitizing dyes for red or infrared light are more unstable than sensitizing dyes for shorter wavelength light (visible light). ("Industrial Chemistry Magazine")
Volume 66, No. 2, page 26 (I963)). In particular, this instability is due to the fact that the methine chain in the sensitizing dye is long (and tends to increase), so it has a practical effect of showing spectral sensitization, especially for long wavelength light of 750 nm or more (e.g., semiconductor laser light). The emergence of stable dyes is desired.

Furthermore, it is desired that dyes with high sensitization efficiency to long wavelength light as described above be developed.

Therefore, an object of the present invention is to provide a photoconductor-resin dispersion type photoconductive multi-component composition which has excellent storage stability and contains a spectral sensitizing dye with high exacerbation efficiency.

Another object of the present invention is to provide a photoconductive composition that can be used as a photoreceptor for electrophotography using a laser as a light source.

A further object of the present invention is to provide a photoconductive composition containing a novel dye as a spectral sensitizer, which is colorless and transparent, has absorption in far-infrared to near-infrared, and provides high sensitization efficiency. It is in.

[Means for solving problems]

The above object of the present invention is to provide a photoconductive composition containing a photoconductor, a sensitizing dye, and a binder resin, wherein the sensitizing dye is a compound represented by the following general formula (I). It has been found that this can be achieved with photoconductive compositions.

General formula (I) (AO)r-1 In formula (I), Z is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or:? NR, (wherein R9 represents an aliphatic group).

Q is an atom necessary to form pyran, benzopyran, naphthopyran, thiopyran, benzothiopyran, naphthothiopyran, selenapyran, benzoselenapyran, naphthoselenapyran, ternapyran, penzoternapyran or naphthoternabilan, which may be substituted. group or a group of atoms necessary to form an optionally substituted heterocycle containing a nitrogen atom.

Yl and Y2 are the same or different and each represents a hydrogen atom, an aliphatic group or an aromatic group. p represents 0 or ■.

Ra, Rg, Rs, Rs, Ra, R%, R4
% and R9 are the same or different, and each represents a hydrogen atom, a halogen atom, or a monovalent organic residue, or R is Rz, Rg and R, R, and R4, R4 and Rs,
At least one combination of Rs and R6 and Rh and R1 forms a ring made of a substituted or unsubstituted aromatic ring, heterocycle, or aliphatic chain.

R3 represents a hydrogen atom or an aliphatic group.

X+, Xz and X are the same or different, and each represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group,
Represents a substituted or unsubstituted amino group or halogen atom, and/or Xl and XZ, X.

and X, and/or X+ and X form a fused 6-membered ring.

AO represents an anion.

γ represents 1 or 2, provided that r is 1 when the dye forms an inner salt.

Each substituent in the compound represented by general formula (I) is preferably the substituent shown below.

or represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or "-N Ra (wherein R9 represents a substituted or unsubstituted alkyl group, an alkenyl group, or an aralkyl group, preferably having 1 to 18 carbon atoms. ), when z is an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom, Q is
Optionally substituted pyran, benzopyran, naphthopyran, thiopyran, benzothiopyran, naphthopyran,
Represents the atomic group necessary to form selenapyran, benzoselenapyran, naphthoselenapyran, ternaviran, penzoternapyran or naphthoselenapyran.

When Z is ≧N-R, Q represents a nonmetallic atomic group necessary to form a 5- or 6-membered nitrogen atom-containing heterocycle, and the ring is, for example, a thiazole nucleus (e.g., thiazole , 4-methylthiazole, 4-phenylthiazole, 5
-Methylthiazole, 5-phenylthiazole, 4.5
-dimethylthiazole, 4,5-diphenylthiazole, 4,(2-chenyl)thiazole, etc.), benzothiazole nuclei (e.g. benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7- Chlorobenzothiazo-, 4-methylbenzothiazole, 5-methylbenzothiazole, 6
-Methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-trifluoromethylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-ethoxybenzothiazole, 5 -Carboxybenzothiazole, 5-cyanobenzothiazole, 5-fluorobenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5.6-
cymethoxybenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, etc.), naphthothiazole nuclei (e.g. naphtho-(I,2-d)thiazole, nand(2,1-d)thiazole, nat(2,
3-d) Thiazole, 5-methoxynaphtho(2,1-d)
) thiazole, 5-ethoxynaphtho(2,1-d)thiazole, 8-methoxynaphtho(I,2-d)thiazole, 7-methoxynaphtho(I,2-d)thiazole, etc.),
Oxazole nucleus (e.g. 4-methyloxazole, 5-
Methyloxazole, 4-phenyloxazole, 4.
5-diphenyloxazole, 4-ethyloxazole, 4.5-dimethyloxazole, 5-phenyloxazole, etc.), benzoxazole nuclei (e.g. benzoxazole, 5, chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5.6-dimethylbenzoxazole, 4.6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole, 5-fluorobenzoxazole,
6-medoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazole core (e.g., nut (I, 2-d
) oxazole, naphtho(2,1-d)oxazole,
naphtho(2°3-d)oxazole, etc.), selenazole nuclei (e.g. selenazole, 4-methylselenazole, 4
-phenylselenazole, 4,5-diphenylselenazole, etc.), benzoselenazole core (e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole,
5-phenylbenzoselenazole, etc.), naphthoselenazole cores (e.g. naphtho(I,2-d) selenazole, naphtho(2°1-d) selenazole, naphtho(2,3-d)
) selenazole, etc.), imidazole nucleus (e.g. 1-ethylimidazole, 1-benzylimidazole, etc.), benzimidazole nucleus (e.g. 1,3-diethylbenzimidazole, 1,3-diethyl-5,6-dichlorobenzimidazole, 1. 3-diethyl-5-trifluoromethyl-6-chlorobenzimidazole, 1,3-diethyl-5-cyano-6-chlorobenzimidazole, etc.)
, naphthoimidazole nucleus (e.g. IH-naphtho(2,3
-d) imidazole, etc.), thiazoline nuclei (e.g., thiazoline, 4-methylthiazoline, 4-phenylthiazoline, etc.), imidazoquinoline nuclei (e.g., IH-imidazo(4-phenylthiazoline, etc.),
, 5-b) quinoline, etc.), imidazo(4,5-b) quinoxaline core (e.g. 1,3-diethylimidazo(4,5
-b) Quinoxaline, 1,3-diallylimidazo(4,
5-b) Quinoxaline, 1,3-diphenylimidazo (
4,5-b) Quinoxaline, 6-chloro-L3-diethyl-imidazo(4,5-b)quinoxaline, 6-chloro-1,3-diallylimidazo(4,5-b)quinoxaline, 6,7-dichloro -1,3-diphenylimidazo(
4,5-b) quinoxaline, etc.), oxazoline nucleus (for example, 5,5-dimethyloxazoline, etc.), isoxazole nucleus (for example, 5-methylisoxazole, etc.), benzisoxazole nucleus (for example, benzisoxazole, etc.), 3. 3-dialkylindolenine nucleus (e.g. 3.3
-dimethylindolenine, 3.3.5-trimethylindolenine, 5-chloro-3,3-dimethylindolenine, 5-ethoxycarbonyl-3,3-dimethylindolenine, 5-carboxy-3,3-dimethylindolenine renin, 5-sulfo-3,3-dimethylindolenine, etc.) 2-pyridine nucleus (e.g., lysine, 5-methylpyridine, etc.), 4-pyridine nucleus (e.g., pyridine, etc.), 2-quinoline nucleus (e.g., 6-nitoxyquinoline, etc.) , 6-ethylquinoline, 6-chloroquinoline, 8-fluoroquinoline, etc.), 4-quinoline core (e.g. 8-methylquinoline, 8-fluoroquinoline, etc.),
Fluoroquinoline, 6-chloroquinoline, etc.), 1-isoquinoline core (eg, isoquinoline, etc.) are preferred.

R is an unsubstituted alkyl group having 18 or less carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group,
Octyl group, decyl group, dodecyl group, octadecyl group,
(vinylmethyl group, cyclohexyl group, etc.) or substituted alkyl group (substituents include, for example, carboxy group, sulfo group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom), hydroxy group, carbon number 8 The following alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy groups having 8 or less carbon atoms (e.g. methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.) , an aryloxy group of the formula having 10 or less carbon atoms (e.g. phenoxy group,
P-)lyloxy group, etc.), acyloxy group having 3 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), acyl group having 8 or less carbon atoms (e.g. acetyl group,
propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (e.g. carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N.

N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), aryl groups having 10 or less carbon atoms (e.g. phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.) An alkyl group having 18 or less carbon atoms substituted with, etc.) is preferable.

Substituents for Q include halogen atoms (e.g. chlorine atoms,
bromine atom, etc.), optionally substituted alkyl groups having 1 to 22 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, chloromethyl group, cyanomethyl group, hydroxyethyl group) groups, etc.), alkoxy groups having 1 to 20 carbon atoms (e.g., methoxy, ethoxy, propoxy, butyloxy, hexyloxy, tesyloxy, etc.), optionally substituted aralkyl groups having 7 to 22 carbon atoms (e.g. benzyl group, phenethyl group, etc.), an optionally substituted aryl group having 6 to 22 carbon atoms (e.g. phenyl group, tolyl group, naphthyl group, chlorophenyl group, dichlorophenyl group, butylphenyl group,
Methoxyphenyl group, ethoxyphenyl group, hydroxyphenyl group N.

N-dimethylaminophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, cyanophenyl group, methanesulfonylphenyl group, etc.), hydroxyl group, cyano group, alkyloxycarbonyl group having 1 to 22 carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group having 6 to 22 carbon atoms (e.g. phenyloxycarbonyl group, chlorophenyloxycarbonyl group, tolyloxycarbonyl group, butylphenyloxycarbonyl group, methoxyphenyloxy carbonyl group, etc.), C1-C22 alkanesulfonyl group (e.g., methanesulfonyl group, ethanesulfonyl group, propanesulfonyl group, butanesulfonyl group, hexylsulfonyl group, etc.), C6-C22 arylsulfonyl group (e.g., benzene). sulfonyl group, etc.), an optionally substituted amino group having 1 to 28 carbon atoms (e.g., amino group, N-methylamino group, N,N-dimethylamino group, N
-ethylamino group, N, N-diethylamino group, N, N
-propylamino group, N.

N-dibutylamino group, N-methyl-N-phenylamino group, N-phenylamino group, N-benzylamino group, etc.).

Y and Y2 may be the same or different, and each represents a hydrogen atom, an optionally substituted alkyl group having 1 to 22 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group). group, octyl group, decyl group, dodecyl group, tetrodecyl group, etc.), optionally substituted cycloalkyl group having 5 to 22 carbon atoms (e.g. cyclopentyl group, cyclohexyl group, etc.), optionally substituted carbon number 7
~22 aralkyl groups (e.g. benzyl group, phenethyl group, etc.), optionally substituted aryl groups having 6 to 22 carbon atoms (e.g. phenyl group, tolyl group, butylphenyl group, chlorophenyl group, dichlorophenyl group, methoxyphenyl group) group, naphthyl group, bromophenyl group, cyanophenyl group, methanesulfonylphenyl group, N,N-dimethylaminofluoronylphenyl group, N,N-dimethylaminophenyl group, N,N-dibutylaminophenyl group,
methoxycarbonylphenyl group, ethoxycarbonylphenyl group, etc.).

R8 preferably represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group).

x, , Xi and Preferably, the alkoxy group is an alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.). XI, Xi, x unsubstituted or substituted amino group or may be different, hydrogen atom, carbon number 1-
4 lower alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, etc.) and acyl groups having 2 to 8 carbon atoms (for example, acetyl group, propionyl group, benzoyl group, etc.) are preferable.

It is also preferable that R1° and R11 are connected to each other to form a 5-membered ring or a 6-membered ring. Furthermore, R16 and/or RI1 may be bonded to the benzene ring of the benzopyrylium ring to form a condensed ring.

R+, Rz, Rs, Rs, R& and R7 may be the same or different, and each represents a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), or a monovalent organic residue. represent. Monovalent organic residues can be selected from a wide variety of groups, but in particular alkyl groups (methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-amyl, n-hexyl, n-octyl, 2-ethylhexyl, t-octyl, etc.), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, chlorophenyl, nitrophenyl, dimethylaminophenyl, α-naphthyl, β-naphthyl, etc.), substituted or unsubstituted aralkyl groups (benzyl, 2-phenylethyl, 2-phenyl-1-methylethyl, bromobenzyl, 2-bromophenyl) ethyl, methylbenzyl, methoxybenzyl, nitrobenzyl), acyl groups (acetyl, propionyl, butyryl, valeryl, benzoyl, triooyl, naphthoyl, phthaloyl, furoyl, etc.), substituted or unsubstituted amino groups (amino, dimethylamino, diethylamino,
dipropylamino, acetylamino, benzoylamino, etc.), substituted or unsubstituted styryl groups (styryl, dimethylaminostyryl, diethylaminostyryl, dipropylaminostyryl, methoxystyryl, ethoxystyryl, methylstyryl, etc.), nitro group, hydroxy group, Carboxyl group, cyano group or substituted or unsubstituted arylazo group (phenylazo, α-naphthylazo, β
-naphthylazo, dimethylaminophenylazo, chlorophenylazo, nitrophenylazo, methoxyphenylazo, tolylazo, etc.).

Also, R3 and R,, R, and R3, R3 and R4, R4 and Rs
, Rs and R1, R, and R7 may form a ring consisting of a substituted or unsubstituted aromatic ring, heterocycle, or aliphatic chain.

Examples of aromatic rings formed include benzene, naphthalene, chlorobenzene, bromobenzene, methylbenzene, ethylbenzene, methoxybenzene, and ethoxybenzene, and examples of heterocycles formed include furan ring, benzofuran ring, and virol ring. , thiophene ring, pyridine ring, quinoline ring, thiazole ring, etc.
Aliphatic chains include groups such as dimethylene, trimethylene, and tetramethylene.

These heterocyclic or aliphatic chain rings include halogen atoms (chlorine, bromine, iodine), alkyl groups (methyl, ethyl, propyl, butyl, etc.), alkoxy groups (
methoxy, ethoxy, butoxy), amino group, etc.

On the other hand, when R3, R2, and R do not contribute to the formation of such a ring,
3, R4, R3, R6 and R1 are a hydrogen atom, a halogen atom (chlorine atom, bromine atom, iodine atom) or a monovalent organic residue (same as the above-mentioned preferred examples).

AO represents an anion, specifically chloride, bromide, iosito, thiocyanate, perchlorate,
Preferred are paratoluenesulfonate, tetrafluoroborate, and the like. γ represents 1 or 2, and when the dye forms an internal salt, γ is 1.

Specific examples of the compound of general formula (I) used in the present invention are listed below, but the invention is not limited to these compounds.

Compound (I) C120aO Compound (2) cao,e Compound (3) BF4θ CHx Compound (4) Compound (5) Compound (6) C61(S Compound (7) 5ra Compound (9) Compound (I1) Compound (I2 ) N CH3CH38F40 Compound (I5) Compound 9J (I6) F9 Compound (I7) F 40 The polymethine dye of the present invention can be produced using a conventionally known method.That is, substituted pyrylium salts can be prepared using, for example, J -Kuthan, Advancesin
Heterocyclic Chemistry No. 34
Vol. 146 (I983), U.S. Patent No. 42837
No. 5 or R-J-Murry, j Org,
It can be produced according to the synthesis method described in Chem+ 4 L 5235 (I982) and the like.

Further, quaternary salts of heterocycles containing a nitrogen atom include, for example, G
'F'Duffin Advances in
It can be produced according to the synthesis method described in Heterocyclic Chemistry, Volume 3, Page 1 (I964).

The compound represented by the general formula (I) is, for example, a pyrylium salt having an active methyl group or a quaternary salt of a heterocycle synthesized as described above, as shown in the following reaction formula (I), and 4-methylthiocoumarin. Intermediate CP obtained by reaction with derivative
) and 1-formyl azulene compounds.

Reaction formula (I) (A○L-I X'1 intermediate (P) where Z, Q, p, Xr, Xt, A and r in the above formula
is as defined in general formula (I).

The dye of the present invention is T, HoJames f4 rThe
Theory of the Photography
c ProcessJ 4th edition (Macmillan P
Publishing New York, 1977
Published in 2013) and F. M. Harn+en rThe Cy
anine Dyes and Re1ated Co
s+poundsJ (John Wikey & 5
Ans Inc., New York.

(published in 1964).

The polymethine dyes of formula (I) of the present invention are used as sensitizers in inorganic and organic photoconductive materials to improve the photoconductivity and sensitivity properties of various photoconductive materials.

As the inorganic photoconductive substance, zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, etc. can be used. Examples of organic photoconductive substances include polymeric substances.
The following (I) to (5) can be mentioned.

(I) Polyvinylcarbazole and its derivatives described in Japanese Patent Publication No. 34-10966, (2) Japanese Patent Publication No. 43-1
Polyvinylpyrene, polyvinylanthracene, poly-2 described in JP-A No. 8674 and Japanese Patent Publication No. 43-19192
-vinyl-4-(4'-dimethylaminophenyl)-5
-vinyl polymers such as phenyl-oxazole and poly-3-vinyl-N-ethylcarbazole; (3) polyacenaphthylene, polyindene, and copolymers of acenaphthylene and styrene described in Japanese Patent Publication No. 19193-1973; (4) Condensation resins such as pyrene-formaldehyde resin, brompyrene-formaldehyde resin, and ethylcarbazole-formaldehyde resin described in Japanese Patent Publication No. 56-13940, (5) Japanese Patent Publication No. 56-90833, 56-16155
Various triphenylmethane polymers described in Publication No. 0.

Examples of low molecular weight compounds include the following (6) to (I8).

(6) Triazole derivatives described in US Pat. No. 3,112,197, etc.; (7) Oxadiazole derivatives, described in US Pat. No. 3,189,447, etc.;
Imidazole derivatives described in Publication No. 16096, etc. (9) U.S. Patent No. 3615402, U.S. Patent No. 382098
No. 9, No. 3542544, Special Publication No. 45-555, No. 10983-1983, Japanese Patent Publication No. 93224-1971,
JP-A-55-17105, JP-A-56-4148,
JP-A-55-108667, JP-A-55-15695
No. 3, polyarylalkane derivatives described in JP-A No. 56-36656, publications, etc., (I0) U.S. Pat. No. 3,180,729, U.S. Pat.
No. 46, JP-A-55-88064, JP-A-55-88
No. 065, JP-A-49-105537, JP-A-55-
No. 51086, JP-A-56-80051, JP-A-56
-88141, JP-A-57-45545, JP-A-5
Pyrazoline derivatives and pyrazolone derivatives described in No. 4-112637, JP-A-55-74546, publications, etc.

(I1) U.S. Patent No. 3,615,404, Special Publication No. 5
1-10105, JP-A-54-83435, JP-A-54-110836, JP-A-54-119925,
Phenyldiamine derivatives described in Japanese Patent Publication No. 46-3712, Japanese Patent Publication No. 47-28336, publications, etc. (I2) U.S. Patent No. 3567450, Japanese Patent Publication No. 49-3
5702, West German Patent (DAS)” 1110518, U.S. Patent No. 3180703, U.S. Patent No. 32405
No. 97, U.S. Patent No. 3,658,520, U.S. Patent No. 42
No. 32103, U.S. Patent No. 4175961, U.S. Patent No. 4012376, JP-A-55-144250, JP-A-56-119132, JP-A-39-27577, JP-A-56-22437 specifications, publications, etc. The arylamine derivatives described, (I3) the amino-substituted chalcone derivatives described in U.S. Pat. No. 3,526,501, (I4) the N,N-vicarbasil derivatives described in U.S. Pat. No. 3,542,546, etc., (I5) the U.S. Pat. Oxazole derivatives described in Japanese Patent No. 3257203, (I6) Styryl anthracene derivatives described in Japanese Patent Application Laid-Open No. 56-46234, etc., (I7) Fluorenone described in Japanese Patent Application Laid-Open No. 54-110837, etc. Derivative, (I8) U.S. Patent No. 3,717,462, JP-A-54-54
9143 (corresponding to U.S. Patent No. 415098), JP 55-52063, JP 55-52064, JP 55-46760, JP 55-85495, JP 57-11350 No., Japanese Patent Publication No. 57-14874
Vidrazone derivatives disclosed in Patent No. 9, Publication No. 1, etc.

Two or more of these photoconductive substances may be used in combination depending on the case.

Among these photoconductive materials are poly-N-vinylcarbazole; triarylamines such as tri-p-tolylamine and triphenylamine; 4,4'-bis(diethylamine)-2°2'-dimethyltriphenyl; Boarylmethane such as methane; and 3-(4
-dimethylaminophenyl)-1,5-diphenyl-2
-Unsaturated heterocycle-containing compounds represented by pyrazoline derivatives such as pyrazoline are preferably used.

The photoconductive composition of the present invention containing the polymethine dye of formula (I) of the present invention as a sensitizer can be obtained by dissolving these dyes, a photoconductive substance, and a binder resin in an organic solvent.

This can be applied and dried on a conductive support by a commonly used method such as spin coating, blade coating, knife coating, reverse roll coating, dip coating, rod bar coating or spray coating, and used as a photoreceptor. In addition to being usable as a photosensitive N (photoconductive layer) in a single-stone type electrophotographic photosensitive material, it can also be used as a charge carrier generation layer in a functionally separated electrophotographic photosensitive material having two layers: a charge carrier generation layer and a charge carrier transport layer. It can be used as

The photoconductive composition of the present invention can also be used in photoelectrophoresis by producing particles from the organic solvent solution using a mini-spray device or the like, and dispersing the particles in an insulating solution. .

The photoconductive composition of the present invention can be applied as a photoconductive layer in the image pickup tube of a red-body or infrared-sensitive video camera, or over a one-dimensional or two-dimensional array of semiconductor circuits for known signal transfer or scanning. It can be used as a photoconductive layer sensitive to red light or infrared rays of a solid-state image sensor having a light-receiving layer (semiconductive layer).

The method of using the sensitizing dye when used as an ordinary electrophotographic photoreceptor in the present invention may be according to a conventionally known method, which involves dispersing the photoconductor in a binder resin and then adding a dye solution. Particularly convenient methods include placing the photoconductor in advance in a dye solution, adsorbing the dye, and then dispersing it in a binder resin. The amount of sensitizing dye used in the present invention varies over a wide range depending on the degree of exacerbation required. That is, it can be used in an amount of 0.0001 to 20.0 parts by weight, preferably in a range of 0.001 to 10.0 parts by weight, based on 100 parts by weight of the photoconductor.

The sensitizing dyes used in the present invention can be contained in the photosensitive layer singly or in combination of two or more.

Depending on the purpose, the sensitizing dye of the present invention may also be used with other conventionally known spectral sensitizing dyes (for example, rose bengal, eosin,
Needless to say, it can be used in combination with

In addition, acid anhydrides and the like are sometimes added to zinc oxide, which is one of the photoconductors, to promote spectral sensitization, but in the present invention, the stability of the sensitizing dye of the present invention is sufficient. It is advantageous in that various conventionally known additives for electrophotographic photosensitive layers can be used in combination.

As the binder that can be combined, all conventionally known binders can be used. Typical examples include vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-butyl methacrylate copolymer, polymethacrylate, polyacrylate, polyvinyl acetate, polyvinyl butyral, alkyd resin, silicone resin, and epoxy resin. , epoxy ester resin, polyester resin, etc.

It is also possible to combine it with an aqueous acrylic emulsion or an acrylic ester emulsion.

For examples of specific polymeric materials useful as binders, see Research Disclosure.
H Disclosure), Volume 109, Pages 61-67, under the title "Electrophotographic Elements, Materials and Methods".

Generally, sensitizing dyes are susceptible to oxidation, and therefore, it is desirable to avoid using them together with catalyst compounds that promote oxidation.

For example, among vinyl polymerization initiators, care must be taken when using peroxides such as benzoyl peroxide, and organic acid salts of noble metals that promote hardening of unsaturated fatty acids. Regarding this point, even the sensitizing dye used in the present invention requires the same level of consideration as conventional sensitizing dyes, but conventional polymethine dyes cannot be used in combination with these oxidation promoters. However, the problem was that it disintegrated in a short period of time. However, when the dye of formula (I) of the present invention is used, its stability is significantly improved.

Generally, the amount of binder present in the photoconductive compositions of the present invention is variable. Typically, a useful amount of binder, based on the total amount of the photoconductive material and binder mixture, is about Within the range of 10 to about 90% by weight.

The electrophotographic photosensitive layer according to the present invention can be provided on a conventionally known support. Generally speaking, the support for the electrophotographic photosensitive layer is preferably electrically conductive, and metal plates, 4
Plastic films provided with a conductive layer (for example, those provided with a thin layer of aluminum, palladium, indium oxide, tin oxide, cuprous iodide), paper treated to be conductive, etc. are often used. Polymers containing quaternary ammonium salts (for example, polyvinylbenzyltrimethylammonium chloride, US Pat. No. 4,108,802) can be used as conductive treatment agents for paper.
No. 4118231; No. 4126467; No. 41
A polymer containing quaternary nitrogen in the main chain as described in No. 37217,
U.S. Patent No. 4,070,189; Japanese Patent Application Publication No. 54-20977
Quaternary salt polymer latex etc. described in sclosure #1625 B), polystyrene sulfonate salts, colloidal alumina, etc. are well known, and are usually used in combination with polyvinyl alcohol, styrene-butadiene latex, gelatin, casein, etc. There are many.

The organic solvent used for dispersion is a volatile hydrocarbon solvent with a boiling point of 200°C or less, especially dichloromethane,
Chloroform, 1. Preferred are halogenated hydrocarbons having 1 to 3 carbon atoms, such as 2-dichloroethane, tetrachloroethane, dichloropropane or trichloroethane.

Various solvents used in coating compositions and mixtures of the above solvents, such as other chlorobenzenes, aromatic hydrocarbons such as toluene, xylene or benzene, ketones such as acetone or 2-butanone, ethers such as tetrahydrofuran, and methylene chloride. is also available. The solvent is added in an amount of 1 to 100 g, preferably 5 to 20 g, per 1 g of dye, photoconductive material and other additives.

The coating thickness of the photoconductive composition of the present invention on a suitable support is:
Can vary widely. Typically, coatings can be applied within the range of about 10 microns to about 300 microns (before drying). The preferred range of coating thickness before drying is approximately 5
It was found to be in the range of 0 microns to about 150 microns. However, useful results can be obtained even outside this range. The dry thickness of this coating may range from about 1 micron to about 50 microns.

Furthermore, as another mode of use of the composition of the present invention, it is also possible to incorporate an exacerbating agent into particles used for photoelectrophoresis to obtain images by photoelectrophoresis. The particles used in the photoelectrophoresis method are produced using a mini-spray device from a solution consisting of a photoconductive substance such as the aforementioned poly-N-vinylcarbazole and the aggravating agent of the present invention. These particles can also be used in insulating liquids containing saturated hydrocarbons such as decane, dodecane, octane, paraffin, isooctane, etc.
Preferably Isopar E1 Isopar H1 Isopar G
(manufactured by Esso Chemical Co., Ltd., trade name) or the like to form a dispersion liquid, which is used for photoelectrophoresis. Isopar E, Isopar H, and
Isopar G contains 99.9.99 saturated hydrocarbons, respectively.
．． 3 and 99.8% by weight, and 0.05.0, 2, and 0.2% by weight of aromatic hydrocarbons, respectively. However, Isopar H contains 0.5% by weight or less of olefin. The respective boiling points are 115℃~142℃ and 174℃~
189°C and 158°C to 177°C. The amount of particles in the dispersion is between 0.5 and 10% by weight, preferably between 1 and 3% by weight, based on the dispersion.

Regarding the photoelectrophoresis method and its equipment, see 45-2 Japanese Patent Publication.
No. 0640.

Necessary additives may be appropriately added to the photoconductive layer and particles to improve the properties of the photoconductive layer and particles.

In the photoelectrophoresis method described above, for example, an electrically insulating binder component can also be present in the photoconductive composition of the present invention. Preferred binders used in making the photoconductive compositions of the present invention are film-forming, hydrophobic polymeric binders with fairly high dielectric strength and good electrical insulation properties. A typical example of such a substance is as follows. Natural resins such as vinyl resins, gelatin, cellulose ester derivatives, cellulose nitrate; Polycondensates including polyesters and polycarbonates; Silicone resins; Alkyd resins including styrene-alkyd resins; Paraffin; and various mineral waxes. .

Generally, the amount of binder in the photoconductive compositions of the present invention can vary, and typically useful amounts of binder are from about 10 to about 90% by weight, based on the total amount of the photoconductor and binder mixture. is within the range of

When producing photoconductive particles, a charge control agent and a dispersion stabilizer may also be added, especially a copolymer of lauryl methacrylate and styrene (copolymerization ratio of 4 to 4), which has the functions of both charge control and dispersion stabilization. 2:1) or a copolymer of 2-ethylhexyl methacrylate and styrene (copolymerization ratio 4:2 to 1), etc. are advantageously used.

In addition to the above-mentioned dispersion stabilizer, the photoconductive composition of the present invention generally contains a plasticizer such as chlorinated diphenyl, dimethyl phthalate, and an epoxy resin (trade name Epicote) to improve flexibility and strength. It is also possible to add up to 60 parts by weight, preferably 10 to 40 parts by weight, per 100 parts by weight of photoconductive material.

In addition, in order to improve the strength, JP-A-58-65438
No., JP-A-58-65439, JP-A-58-1022
No. 39, JP-A-58-102240, JP-A-58-1
Urea compounds, thiourea compounds, carbonylamine compounds, thiocarbonylamine compounds, which are respectively described in No. 07544 and JP-A-58-129434,
A chemical aggravating agent such as a sulfonylamine compound or a dicarbonylamine compound may also be added in an amount of 1 to 100 parts by weight, preferably 3 to 50 parts by weight, based on 100 parts by weight of the photoconductive material.

Examples 1 to 5 Poly-N-vinylcarbazole (trade name Rubican 170
, manufactured by BASF, 18.25°C, in THF) 5g, 1st
Dye 35■, 3.3'-', of specific compound examples shown in the table;
Nitrobenzanilide 30■ and methylene chloride'
It was dissolved in 15 ml of ethylene chloride and 12 ml of ethylene chloride to prepare a photosensitive solution.

This photosensitive solution was applied to a conductive transparent support (a polyethylene terephthalate support of I00 μm with a surface resistance 1
03Ω) to obtain an organic thin film having an irradiation layer of about 4 μm.

This organic thin film was heated to 400V by +5kV corona discharge.
The exposure amount required to attenuate the potential by 1/2, that is, the half-reduction exposure amount E, /2 (erg/cIl)
was measured.

As a light source, a carillium aluminum-arsenic semiconductor laser (oscillation wavelength: 830 parts m) was used.

The results are shown in Table 1.

Table 1 Examples Specific compound examples El/□ (erg/ad
)1 (I) 50. 22
(2) 52.13 (
3) 49. 24 (5)
51.25 (7)
49.5 Example 6 Organic photoconductive substance: 5 g of 4,4'-bis(diethylamino)-2,2'-dimethyltriphenylmethane, 5 g of bisphenol A polycarbonate (manufactured by GE, trade name: Lexan 121), compound Dye 4 of specific example (I)
0■, Anilide compound 0 of the following structural formula as a chemical aggravator
．． 2g to 30ml of methylene chloride! and 30 ml of ethylene chloride to prepare a photosensitive solution. An organic thin film was prepared in the same manner as in Example 1, and seven Ets were measured.
E17, is 53. 2 (er g/cj).

(Anilide compound) Examples 7 to 16 As an organic photoconductive substance, 5 g of 4,4'-bis(diethylamino)-2,2'-dimethyltriphenylmethane and polycarbonate of bisphenol A (manufactured by GE, trade name: Lexan) 121) 5g, specific examples of compounds shown in Table 2, dye 40■, 0.2g of the anilide compound used in Example 6 as a chemical aggravator, and methylene chloride 3Qm
1 and 30 ml of ethylene chloride to prepare a photosensitive solution. An M'S film was produced in the same manner as in Example 1.

The photoconductor produced in this way was measured using a paper analyzer 5.
Using P-428 (manufactured by Kawaguchi Electric Co., Ltd.), the sample was corona charged at 15 kV using a static lid method, held in a dark place for 30 seconds, and then exposed to light at 1 lux to examine the charging characteristics.

The charging characteristics include the initial charging potential (vO) and how much the potential after 30 seconds of dark decay is maintained with respect to the initial potential (vO), that is, the dark charge retention wheel (DRR (
%) and E17t similar to Example 1 were measured. The results are shown in Table 2.

Table 2 Example 17 and Comparative Example A 100 parts of fine particulate zinc oxide (average particle size 0.5 to 1 μm, 5azex2000 manufactured by Sakai Chemical Co., Ltd.) (all parts mean parts by weight), acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd.) Dianal LROO9・) 30 parts of 40% by weight toluene solution, 60 parts of toluene, and a specific example of the compound of the present invention (I1
) was mixed with 8 parts of a dye solution containing a 1.0×10 −' mol/1 methanol solution and kneaded in a porcelain ball mill for 2 hours to prepare a dispersion.

This dispersion was coated on aluminum foil with a dry film thickness of approximately 8 cm.
An electrophotographic photoreceptor (a) was prepared by applying the coating to a thickness of .mu.m and then drying it in a constant temperature bath at 50.degree. C. for 2 hours.

On the other hand, photoreceptor A was prepared in exactly the same manner as above except that Comparative Compound A below was used instead of Compound (I6) above.

(Comparative Compound A) Regarding the above two types of photoreceptors, spectral reflectance measurements were performed, and spectral photographs were taken by ordinary electrophotography using a liquid developer containing carbon black as a toner.

As a result of the spectroscopy, it was found that the electrophotographic photosensitive layer containing compound (I6) not only responds in the intrinsic photosensitive range of ZnO around a wavelength of 380 nm, but also has sensitivity due to spectral sensitization in the wavelength range corresponding to the spectral reflectance mentioned above. showed that.

On the other hand, in the electrophotographic photosensitive layer containing the comparative compound, no response other than the response in the specific photosensitive range of ZnO was observed; that is, the electrophotographic photosensitive layer containing the comparative compound A was not spectrally sensitized. It became clear that there was no.

On the other hand, this photoreceptor was heated to 140 kW by corona discharge at 16 KV.
The exposure amount required for charging to 0V and attenuating the potential to 1/2, that is, the half-reduction exposure amount E r/z (erg
/c11) was measured.

As a light source, a galylium-aluminum-arsenic semiconductor laser (oscillation wavelength: 830 nm) was used.

El of the electrophotographic photoreceptor of the present invention using compound (I6)
/l was 58 (erg/cd), and the photoreceptor using comparative compound A showed no photosensitivity at all.

The above results were due to the fact that Comparative Compound A disappeared due to decomposition due to its instability, and such decomposition occurred when preparing a dispersion of the composition by adding zinc oxide, etc. and a pigment in advance, and then placing it in a ball mill. It is presumed that because the mixture was kneaded for 2 hours, the dye decomposed during that time. On the other hand, it can be seen that the sensitizing dye of the present invention exists stably even under such conditions and exhibits a spectral sensitizing effect.

Example 18 Using the two types of compounds shown in Example 17, an electrophotographic photosensitive layer was prepared by a method different from that in Example 1.

100 parts of fine particulate zinc oxide (average particle size 0.5 to 1 μm, 5azex2000 manufactured by Sakai Chemical Co., Ltd.), styrenated alkyd resin (Styresol #42 manufactured by Nippon Reichhold Co., Ltd.)
35 parts of a 25% toluene solution of 50.) and 40 parts of toluene were mixed and kneaded in a porcelain hole mill for 2 hours to prepare a white dispersion. Add polyisocyanate resin (Parnock D-750 manufactured by Nippon Reichhold Co., Ltd.) to this dispersion.
0) 15 parts of a 25% by weight butyl acetate solution was added and stirred well for 3 minutes.
10 parts of each seed methanol solution were added and stirred well. This 2
Each type of dispersion was applied onto aluminum foil to a dry film thickness of 10 μm, and then placed in a constant temperature bath at 50°C for 1 hour.
After drying for 5 hours, two types of electrophotographic materials were obtained. Here, regarding the two types of materials, Comparative Compound A and Compound (I
The materials having an electrophotographic photosensitive layer containing 6) are named Comparative Sample B and Sample (2), respectively.

Spectral reflectance and spectral sensitivity by electrophotography were measured for these two types of samples. Two types of samples were stored for one week at 50°C and 80% RH.The absorbance at the maximum absorption wavelength was measured in the spectral reflectance wavelength range of 700 nm to 85 Qnm, and the absorbance after the accelerated test was determined by the absorbance immediately after manufacturing. The stability was estimated using the divided value as the stability value. Stability values are listed in Table 1, with stability values closer to 1 indicating more stable. In addition, the maximum reflectance of the comparative sample immediately after production was around the wavelength of 800 nm (corresponding to the absorption maximum wavelength of the comparative compound) and around the wavelength of 380 nm (Z
However, after the accelerated test, the maximum reflectance around the wavelength of 800 nm disappeared and the spectral absorbance curve became flat, and the spectral absorbance curve became flat at the wavelength of 38 nm.
Only a maximum reflectance near 0 nm was observed. This fact indicates that the comparative compound in the electrophotographic photosensitive layer disappeared under the accelerated test conditions in Table 2.

Separately, for sample #1, the degree of spectral exacerbation immediately after manufacture and after the accelerated test was measured in the same manner as in Example 9.
A spectral sensitization ratio almost equivalent to the above stability value was obtained.

In other words, it was revealed that in both Sample #1, the desired spectral enhancement was achieved to almost the same extent by the compound immediately after production and after the accelerated test, respectively.

〔Effect of the invention〕

The photoconductive composition of the present invention is a highly sensitive photoreceptor that exhibits a sufficient sensitizing effect. In particular, the dye group of the present invention, which deteriorates in the long wavelength range of 750 nm or more, can have significantly higher sensitivity and greatly improved stability compared to conventional electrophotographic photoreceptors for lasers.

That is, the present invention overcomes the drawback that conventional electrophotographic photosensitive layers containing cyanine dyes cannot withstand long-term storage by using the sensitizing dyes having the characteristic skeleton structure as described above. Not only has the decomposition of the sensitizing dye been reduced during the production of the photosensitive layer, but the photosensitive layer can also be used under harsh test conditions such as 50°C and 80% R, H (relative humidity). In comparison, it has a remarkable effect in that it shows very good stability. In particular, it has much greater stability than conventionally used red or infrared sensitizing dyes.

Since the dye is highly stable, the method of using the sensitizing dye in the present invention does not require consideration such as setting special dispersion mixing conditions or carefully selecting the timing of addition. It has the advantage of being simple and stabilizing the quality and performance of the photosensitive material. In addition, when inorganic photoconductors such as zinc oxide, titanium oxide, zinc sulfide, and cadmium sulfide are used as photoconductors, the coexistence of these photoconductors with sensitizing dyes may cause damage, especially under light irradiation. Conventionally known sensitizing dyes tend to be easily decomposed, and in particular when using red light to infrared ray sensitizing dyes, restrictions such as carrying out photosensitive layer manufacturing work in a dark place are required. It is also a significant effect of the present invention that such limitations are significantly overcome.

Procedural amendment December 16, 1986

Claims (1)

[Scope of Claims] A photoconductive composition containing a photoconductor, a sensitizing dye, and a binder resin, characterized in that the sensitizing dye is a compound represented by the following general formula [I] Photoconductive composition general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (I), Z is an oxygen atom, sulfur atom, selenium atom, tellurium atom, or ▲There are mathematical formulas, chemical formulas, tables, etc. ▼
(However, R_9 represents an aliphatic group.) Q is an atomic group necessary to form pyran, benzopyran, naphthopyran, thiopyran, benzothiopyran, naphthothiopyran, selenapyran, benzoselenapyran, naphthoselenapyran, ternapyran, benzoternapyran or naphthoternapyran, which may be substituted; Alternatively, it represents an atomic group necessary to form an optionally substituted heterocycle containing a nitrogen atom. Y_1 and Y_2 are the same or different and each represents a hydrogen atom, an aliphatic group, or an aromatic group. p represents 0 or I. R_1, R_2, R_3, R_4, R_5, R_6, and R_7 are each the same or different, and each is a hydrogen atom,
Represents a halogen atom or a monovalent organic residue, or R
_1 and R_2, R_2 and R_3, R_3 and R_4, R_
The combination of at least one of the combinations of 4 and R_5, R_5 and R_6, and R_6 and R_7 forms a substituted or unsubstituted ring consisting of an aromatic ring, a heterocycle, or an aliphatic chain. R_8 represents a hydrogen atom or an aliphatic group. X_1, X_2 and X_3 are each the same or different,
Each represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a substituted or unsubstituted amino group, or a halogen atom, and/or X_1 and X_2, X_2 and X_3
and/or X_1 and X_3 form a fused 6-membered ring. A^■ represents an anion. γ represents 1 or 2. However, when the dye forms an inner salt, r is 1.