CA1120306A - Photosensitive material containing an organic polymeric photoconductor, phthalocyanine derivative and an electron acceptor polycyclic aromatic nitro compound - Google Patents
Photosensitive material containing an organic polymeric photoconductor, phthalocyanine derivative and an electron acceptor polycyclic aromatic nitro compoundInfo
- Publication number
- CA1120306A CA1120306A CA000294897A CA294897A CA1120306A CA 1120306 A CA1120306 A CA 1120306A CA 000294897 A CA000294897 A CA 000294897A CA 294897 A CA294897 A CA 294897A CA 1120306 A CA1120306 A CA 1120306A
- Authority
- CA
- Canada
- Prior art keywords
- phthalocyanine
- photosensitive material
- layer
- nitro compound
- aromatic nitro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Photoreceptors In Electrophotography (AREA)
Abstract
S F E C I F I C A T I O N
To All Whom It May Concern:
BE IT KNOW THAT we, To u Nakazawa, Keiichi Nagahashi and Tatsuo Aizawa residlng at 10-10. 3-chome.
Ikuno Higashi, Ikuno-ku. Osaka-shi, Osaka-fu, Japan.
212-3, HasHimotos Kaizuka-shi. Osaka-fu, Japan and 6-34. Kuwazu-cho. Higashi-Sumiyoshi-ku, Osaka-shi, Osaka-fu, Japan, respectively, have invented certain new and useful improvements in:
" LAMINATED PHOTOSENSITIVE MATERIAL FOR ELECTRO-PHOTOGRAPHY ", of which the following is a specification.
Abstract of the Disclosure In a laminated photosensitive material for electrophotography. an intermediate layer comprising, incorporated in a binder. phthalocyanine or a phthalo-cyanine derivative and a polycyclic aromatic nitro compound at a specific ratio is formed on an electrically conductive substrate, and a top layer comprising an organic polymeric photoconductor and the above poly-cyclic aromatic nitro compound at a specific ratio is laminated on the intermediate layer. In this photosen-sitive material, the dark decay speed is controlled in a range suitable for application to the repeated copying operation and the residual potential left on the exposure area can be reduced to a negligible level.
Accordingly, occurrence of fogging is prevented and the toner transfer efficiency is improved. Further, this photosensitive material has improved mechanical, chemical and electric durabilities, and therefore, the life of the photosensitive material is remarkably prolonged.
- 1' -
To All Whom It May Concern:
BE IT KNOW THAT we, To u Nakazawa, Keiichi Nagahashi and Tatsuo Aizawa residlng at 10-10. 3-chome.
Ikuno Higashi, Ikuno-ku. Osaka-shi, Osaka-fu, Japan.
212-3, HasHimotos Kaizuka-shi. Osaka-fu, Japan and 6-34. Kuwazu-cho. Higashi-Sumiyoshi-ku, Osaka-shi, Osaka-fu, Japan, respectively, have invented certain new and useful improvements in:
" LAMINATED PHOTOSENSITIVE MATERIAL FOR ELECTRO-PHOTOGRAPHY ", of which the following is a specification.
Abstract of the Disclosure In a laminated photosensitive material for electrophotography. an intermediate layer comprising, incorporated in a binder. phthalocyanine or a phthalo-cyanine derivative and a polycyclic aromatic nitro compound at a specific ratio is formed on an electrically conductive substrate, and a top layer comprising an organic polymeric photoconductor and the above poly-cyclic aromatic nitro compound at a specific ratio is laminated on the intermediate layer. In this photosen-sitive material, the dark decay speed is controlled in a range suitable for application to the repeated copying operation and the residual potential left on the exposure area can be reduced to a negligible level.
Accordingly, occurrence of fogging is prevented and the toner transfer efficiency is improved. Further, this photosensitive material has improved mechanical, chemical and electric durabilities, and therefore, the life of the photosensitive material is remarkably prolonged.
- 1' -
Description
11203~6 Background of -the Invention (1) Field of the Invention:
This inv~ntion relates ~o a photosensitive material for eLec~rophotography, which has a novel laminate strlctlre. More particularly, the invention relates tG a ].amirlated ~hotosensitive material for electro-~h~tr~r-.ihv, which comprises an electrically conductive substra e, an intermediate layer formed on the substrate and a top iayer lamina-ted cn said intermediate layer, wherein the intermediate layer comprises, incorporated in a binder, (A) phthalocyanine or a phthalocyanine derivative and (B) a polycyclic arom~tic nitro compound at an (A)/(B) mixing weight ratio of from 10/5 to 10/40 and the top layer comprises ~C) an organic polymeric photoconductor and (B) said polycyclic aromatic nitro compound at a (C)/(B) mixing weight ratio of from 6/1 to lt6.
This inv~ntion relates ~o a photosensitive material for eLec~rophotography, which has a novel laminate strlctlre. More particularly, the invention relates tG a ].amirlated ~hotosensitive material for electro-~h~tr~r-.ihv, which comprises an electrically conductive substra e, an intermediate layer formed on the substrate and a top iayer lamina-ted cn said intermediate layer, wherein the intermediate layer comprises, incorporated in a binder, (A) phthalocyanine or a phthalocyanine derivative and (B) a polycyclic arom~tic nitro compound at an (A)/(B) mixing weight ratio of from 10/5 to 10/40 and the top layer comprises ~C) an organic polymeric photoconductor and (B) said polycyclic aromatic nitro compound at a (C)/(B) mixing weight ratio of from 6/1 to lt6.
(2) Description of the Prior Art:
In the art of electrophotography, there is broadly adopted a process comprising charging a photosensitive material provided with a photoconductive layer by corona discharge or the like, exposing the photosensitive material imagewise to actinic rays to form-an electro-static latent image on the surface of the photoconductive layer, applying a developer to the surface of the photoconductive layer to form a toner image corresponding to said electrostatic latent image and transferring said toner image formed on the surface of the photoconductive layer ontc, a copying paper. In this conventional process, after the transfer of the toner image, the photosensi+i.ve m~terial is fed to the cleaning step ~.rhere the residual toner is removed. and it is then fed to the above-mentloned charging step and subsequent steps again.
An electrophotographic photosensitlve material -t`,at is used repeatedly in the above-mentioned electro-photographic process is required to have some special : 10 properti,es d,i,fferent from properties required of a photosensitive material of the type where a toner is directly fixed on the photosensitive layerO More specifically, in order to prevent fogging in the repeated copying operation and prolong the life of the photoscnsitive material. it is necessary that the photosensitive material of the former type should have a relatively quick dark decay ( the property ,, that the surface potential of the non-e~pos~d area of the photosensi.tivt layer decays relatively quickly in the dark ) and a residual potèntial as low as negligible ( the property that the potenti.al lef~t on the exposed ar-ea of the photosensitive layer is as low as negligible ).
When the residual potential of the photosensitive material is high. it already causes fogging at the tr~nsfer step. Further, in this case or in the case ~, where the dark decay speed of the photosensitive material is low, electrostatic charges on the electro-static image formed on the sur~ace of the photosensitive _ 3 _ 1~Z030~i ~aterial or electrostatic charges generated for other r~iasor are left on the surface of the photosensitive ~ terial even after the tran fer and cleaning steps, arml they are ~raclually accumulated and cause fogging at -the next cycle o. the copying operationO Further, accumulation of charges results in electric deteriora-t on of the photoconductive layer. Moreover, if the dark decay speed is lo-~, even after the transfer step, toner par~icles are electrostatically attracted to the surface of the photosensitive material by a relatively strong attracting force and therefore, the efficiency of transfer of the toner to a copying paper is relatively low and the surface of the photosensitive material rnust be wiped strongly to remove the residual toner from the surface of the photosensitive material. As a result9 the surface of the photosensitive material is readily and quickly damaged and the life of the photosensitive material is shortened.
The photcsensitive material of this repeatedly used type is also required to have a highly enhanced mechanical, electric or chemical durabilityO Namely, since the photosensitive material of -this type under-goes repeatedly the discharge or irradiation treatment and receives repeatedly friction with a magnetic brush or cleaning member, the photoconductive layer of the photosensitive material is readily mechanically dama~ed or electrically or chemically deteriorated.
~oreover9 such a trouble as peeling of the photoconductive 1~20306 layer frol~ the electrically conductive substrate is r~a~ ly caused while the photosensitive material is U S ~
~s the su~stance for fo~.lng a photoconductive lay~r o~ a phctosc-nsitive mat;erial, there are known various organic and lnorganic photoconductors. Among these kno~ photoconductors, phthalocyanine and phthalocyani.ne de~ri~atives have been noted as substances va uable for manufacture of photosensitive materials for electrophotography because their chemical and electric durabili.ties are exc~llent and they are easily available and cheapO
Photosensitive materials for electrophotography including phthalocyanine or its derivative as a photoconductor, however, fail to satisfy the foregoing requirements sufficiently. For example, a photosensitive material comprising a photoconductive layer composed of a di~spersion of phthalocyanine or its derivative in an electrically insulating binder, which is forrned on an electr~cally conductive substrate, is still defective in that the value of the surface potential at the charging step is generally low, the rising speed of th~ surface potential is low, the residual potential at the exposure step is still at a level that cannot be ncglected and the sp~ed of reduction of the potential in the non-exposed area, namely the dark decay speed, is lowO
--` ` llZ0306 Brief Summary of the Invention We found that when an intermediate lsyer comprising, incorporated in a binder, (A) phthalocyanine or phthalocyanine derivative and (B) a polycyclic aromatic nitro compound at a specific ratio is formed on an electrically conductive substrate and a top layer comprising (C) an organic polymeric photoconductor and (B) said polycyclic aromatic nitro compound at a specific ratio is formed on the intermediate layer, the dark decay speed of the resulting photosensitive material is controlled in a range suitable for application to the repeated copying operation and the residual potential can be reduced to a negligible level, whereby occurrence of fogging can be prevented, the toner transfer efficiency can be improved and the life of the photo-sensitive material can be prolonged. It also was found that a photosensitive material having this laminate structure is excellent in mechanical, chemical and elec-tric turabilities.
More specifically, in accordance with this invention, there is provided a laminated photosensitive material for electrophotography, which comprises an electrically conductive substrate, an intermediate layer formed on the substrate and a top layer laminated on said intermediate layer, wherein the intermediate layer comprises, incorporated in a binder, (A) phthalo-cyanine derivative and (B) a polycyclic aromatic nitro compound at an (A)/(B) mixing weight ratio of from 1~0306 10/5 to 10/40 and ~he top layer comprises (C) an organic polymeric photoconductor and (B) said polycyclic aromatic nitro compound at a ~C)/~B) mixing weight ratio of from 6/1 to 1/6.
Detailed Description of the Preferred Embotiments In this invention, as the phthalocyanine or phthalocyanine derivative tA) constituting the intermetiate layer of the laminated photosensitive material, there can be used phthalocyanine and all of known phthalocyanine derivatives having photoconductivity, for example, aluminum phthalocyanine, aluminum poly-chlorophthalocyanine, antimony phthalocyanine, barium phthalocyanine, beryllium phthalocyanine, cadmium hexadecachlorophthalocyanine, catmium phthalocyanine, cerium phthalocyanine, chromium phthalocyanine, cobalt phthalocyanine, cobalt chlorophthalocyanine, copper 4-aminophthalocyanine, copper bromochloro-phthalocyanine, copper 4-chlorophthalocyanine, copper 4-nitrophthalocyanine, copper phthalocyanine, phthalo-cyanine sulfonate, copper polychlorophthalocyanine, deuterio phthalocyanine, dysprosium phthalocyanine, erbium phthalocyanine, europium phthalocyanine, gadolinium phthalocyanine, gallium phthalocyanine, germanium phthalocyanine, holmium phthalocyanine, indium phthalocyanine, iron phthalocyanine, iron polyhalophthalocyanine, lanthanum phthalocyanine, lead phthalocyanine, lead polychlorophthalocyanine, cobalt hexaphenylphthalocyanine, copper pentaphenylphthalocya-,X
nine, lithium phthalocyanine, ruthenium phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, mercury phthalocyanine, molybdenum phthalocyanine, neodium phthalocyanine, nickel phthalocyanine, nickel polyhalophthalocyanine, osmium phthalocyanine, palladium phthalocyanine, palladium chlorophthalocyanine, alkoxy-phthalocyanine, alkylaminophthalocyanine, alkylmer-captophthalocyanine, aryloxyphthalocyanine, arylmer-captophthalocyanine, copper phthalocyanine piperidine, cycloalkylaminophthalocyanine, dialkylaminophthalocyanine, diaralkylaminophthalocyanine, dicycloalkylaminophthalo-cyanine, hexadecahydrophthalocyanine, imidomethylphthalo-cyanine, 1,2-naphthalocyanine, 2,3-naphthalocyanine, octa-azophthalocyanine, sulfur phthalocyanine, tetra-azophthalocyanine, tetra-4-acetylaminophthalocyanine, tetra-4-aminobenzoylphthalocyanine, tetra-4-aminophthalo-cyanine, tetrachloromethylphthalocyanine, tetra-diazophthalocyanine, tetra-4,4-dimethylocta-azophthalo-cyanine, tetra-4,5-diphenylene-oxide-phthalocyanine, tetra-4,5-diphenylocta-azophthalocyanine, tetra-(6-methylbenzothiazoyl)phthalocyanine, tetra-p-methyl-phenylaminophthalocyanine, tetramethylphthalocyanine, tetranaphthotriazolylphthalocyanine, tetra-4-naphthyl-phthalocyanine, tetra-4-nitrophthalocyanine, tetra-perinaphthylene-4,5-octa-azophthalocyanine, tetra-2,3-phenylene-oxide-phthalocyanine, tetra-4-phenylocta-azophthalocyanine, tetraphenylphthalocyanine, tetraphenylphthalocyanine-tetracarboxylic acid, ~Q306 tetraprl~rylphthalocyanine tetr2bariumcarboxylate, t~trap~enylphthalocyanine-tetra-4-trifllloromethyl-mercaptophthalocyanine, tetr~pyridine-phthalocyanine, tetra-4-trifluoromethylmercaptophthalocyanine, tetra-4-trif~uoromethylphthalocyan ne-4~5-thionaphthene-octa-azophthalocyanine, platinum phthalocyanine.
pot ssium phthalocyanine. rhodium phthalocyanine, sainariur~! phthalocyanine. silver phthalocyanine, silicon phthal(jcyanine, sodium phthalocyanine. sulfonated phthalocyanlne, thorium phthalocyanine. thulium phthalo-cyanine, tin chlorophthalocyanine, tin phthalocyanine, titanium phthalocyanine. uranium phthalocyanine.
vanadium phthalocyanine. ytteribium phthalocyanine.
zinc chlorophthalocyanine, zinc phthalocyanine, and dimers. trimers, oligomers. polymers and copolymers thereof.
Phthalocyanine and phthalocyanine derivatives that are easily available and are especially suitable for attaining the ob,jects of the present invention include metal-free phthalocyanine and their nuclear substitution derivatives. for example, halogen-substituted derivatives~
In this invention. as the organic polymeric photoconductor (C) constituting the top layer, there can be used any of organic polymeric substances having photoconductivity, for example, poly-N-vinylcarbazole.
poly-N-acrylphenothiazine. poly-N-(~-acryloxyethyl)-phenothiazine, poly-N-(2-acryloxypropyl)-phenothiazine, _ g _ 1~Z03Q6 poly-~T-all~lcarbazole9 poly-N-2-~cryloxy-2-methyl-N-etnyl^~rDaz~le, poly-N-(2-p-vinylbenzoylethyl)-carbazole, poly-N-propenylcarb~zole~ poly-N-2-methyl.~cryloxapropylcarbazole~ poly-N-acrylcarbazole, p~.ly-~r-vinyl-p-(N-carbaz~l)toluene, poly(vinylanisolace-tophenone), pol.yindene ~nd other kno~;n photoconductive organic polymeric substances~ Polymeric photoconductors that are easily available and are suitable for attainiing the objects of this invention include poly-N-vinyl-carbazole and nuclear substitution derivatives thereof,for example, halogen- and all~yl-substituted derivatives.
As the polycyclic aromatic nitro compound to be combined with the phthaloxy~nine or phthalocyanine derivative (A) and the organic polymeric photoconduc~tor (C) in the intermediate layer and top layer of the laminated photosensitive material of this invention, there can be used any of polycyclic aromatic compounds having at least one nitro group substituted on the cucleus, for ex~mple, 2,4-dinitro-1-chloronaphhtalene, 1,4-dinitronaphthalene, 1,5-dinitronaphthQlene,
In the art of electrophotography, there is broadly adopted a process comprising charging a photosensitive material provided with a photoconductive layer by corona discharge or the like, exposing the photosensitive material imagewise to actinic rays to form-an electro-static latent image on the surface of the photoconductive layer, applying a developer to the surface of the photoconductive layer to form a toner image corresponding to said electrostatic latent image and transferring said toner image formed on the surface of the photoconductive layer ontc, a copying paper. In this conventional process, after the transfer of the toner image, the photosensi+i.ve m~terial is fed to the cleaning step ~.rhere the residual toner is removed. and it is then fed to the above-mentloned charging step and subsequent steps again.
An electrophotographic photosensitlve material -t`,at is used repeatedly in the above-mentioned electro-photographic process is required to have some special : 10 properti,es d,i,fferent from properties required of a photosensitive material of the type where a toner is directly fixed on the photosensitive layerO More specifically, in order to prevent fogging in the repeated copying operation and prolong the life of the photoscnsitive material. it is necessary that the photosensitive material of the former type should have a relatively quick dark decay ( the property ,, that the surface potential of the non-e~pos~d area of the photosensi.tivt layer decays relatively quickly in the dark ) and a residual potèntial as low as negligible ( the property that the potenti.al lef~t on the exposed ar-ea of the photosensitive layer is as low as negligible ).
When the residual potential of the photosensitive material is high. it already causes fogging at the tr~nsfer step. Further, in this case or in the case ~, where the dark decay speed of the photosensitive material is low, electrostatic charges on the electro-static image formed on the sur~ace of the photosensitive _ 3 _ 1~Z030~i ~aterial or electrostatic charges generated for other r~iasor are left on the surface of the photosensitive ~ terial even after the tran fer and cleaning steps, arml they are ~raclually accumulated and cause fogging at -the next cycle o. the copying operationO Further, accumulation of charges results in electric deteriora-t on of the photoconductive layer. Moreover, if the dark decay speed is lo-~, even after the transfer step, toner par~icles are electrostatically attracted to the surface of the photosensitive material by a relatively strong attracting force and therefore, the efficiency of transfer of the toner to a copying paper is relatively low and the surface of the photosensitive material rnust be wiped strongly to remove the residual toner from the surface of the photosensitive material. As a result9 the surface of the photosensitive material is readily and quickly damaged and the life of the photosensitive material is shortened.
The photcsensitive material of this repeatedly used type is also required to have a highly enhanced mechanical, electric or chemical durabilityO Namely, since the photosensitive material of -this type under-goes repeatedly the discharge or irradiation treatment and receives repeatedly friction with a magnetic brush or cleaning member, the photoconductive layer of the photosensitive material is readily mechanically dama~ed or electrically or chemically deteriorated.
~oreover9 such a trouble as peeling of the photoconductive 1~20306 layer frol~ the electrically conductive substrate is r~a~ ly caused while the photosensitive material is U S ~
~s the su~stance for fo~.lng a photoconductive lay~r o~ a phctosc-nsitive mat;erial, there are known various organic and lnorganic photoconductors. Among these kno~ photoconductors, phthalocyanine and phthalocyani.ne de~ri~atives have been noted as substances va uable for manufacture of photosensitive materials for electrophotography because their chemical and electric durabili.ties are exc~llent and they are easily available and cheapO
Photosensitive materials for electrophotography including phthalocyanine or its derivative as a photoconductor, however, fail to satisfy the foregoing requirements sufficiently. For example, a photosensitive material comprising a photoconductive layer composed of a di~spersion of phthalocyanine or its derivative in an electrically insulating binder, which is forrned on an electr~cally conductive substrate, is still defective in that the value of the surface potential at the charging step is generally low, the rising speed of th~ surface potential is low, the residual potential at the exposure step is still at a level that cannot be ncglected and the sp~ed of reduction of the potential in the non-exposed area, namely the dark decay speed, is lowO
--` ` llZ0306 Brief Summary of the Invention We found that when an intermediate lsyer comprising, incorporated in a binder, (A) phthalocyanine or phthalocyanine derivative and (B) a polycyclic aromatic nitro compound at a specific ratio is formed on an electrically conductive substrate and a top layer comprising (C) an organic polymeric photoconductor and (B) said polycyclic aromatic nitro compound at a specific ratio is formed on the intermediate layer, the dark decay speed of the resulting photosensitive material is controlled in a range suitable for application to the repeated copying operation and the residual potential can be reduced to a negligible level, whereby occurrence of fogging can be prevented, the toner transfer efficiency can be improved and the life of the photo-sensitive material can be prolonged. It also was found that a photosensitive material having this laminate structure is excellent in mechanical, chemical and elec-tric turabilities.
More specifically, in accordance with this invention, there is provided a laminated photosensitive material for electrophotography, which comprises an electrically conductive substrate, an intermediate layer formed on the substrate and a top layer laminated on said intermediate layer, wherein the intermediate layer comprises, incorporated in a binder, (A) phthalo-cyanine derivative and (B) a polycyclic aromatic nitro compound at an (A)/(B) mixing weight ratio of from 1~0306 10/5 to 10/40 and ~he top layer comprises (C) an organic polymeric photoconductor and (B) said polycyclic aromatic nitro compound at a ~C)/~B) mixing weight ratio of from 6/1 to 1/6.
Detailed Description of the Preferred Embotiments In this invention, as the phthalocyanine or phthalocyanine derivative tA) constituting the intermetiate layer of the laminated photosensitive material, there can be used phthalocyanine and all of known phthalocyanine derivatives having photoconductivity, for example, aluminum phthalocyanine, aluminum poly-chlorophthalocyanine, antimony phthalocyanine, barium phthalocyanine, beryllium phthalocyanine, cadmium hexadecachlorophthalocyanine, catmium phthalocyanine, cerium phthalocyanine, chromium phthalocyanine, cobalt phthalocyanine, cobalt chlorophthalocyanine, copper 4-aminophthalocyanine, copper bromochloro-phthalocyanine, copper 4-chlorophthalocyanine, copper 4-nitrophthalocyanine, copper phthalocyanine, phthalo-cyanine sulfonate, copper polychlorophthalocyanine, deuterio phthalocyanine, dysprosium phthalocyanine, erbium phthalocyanine, europium phthalocyanine, gadolinium phthalocyanine, gallium phthalocyanine, germanium phthalocyanine, holmium phthalocyanine, indium phthalocyanine, iron phthalocyanine, iron polyhalophthalocyanine, lanthanum phthalocyanine, lead phthalocyanine, lead polychlorophthalocyanine, cobalt hexaphenylphthalocyanine, copper pentaphenylphthalocya-,X
nine, lithium phthalocyanine, ruthenium phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, mercury phthalocyanine, molybdenum phthalocyanine, neodium phthalocyanine, nickel phthalocyanine, nickel polyhalophthalocyanine, osmium phthalocyanine, palladium phthalocyanine, palladium chlorophthalocyanine, alkoxy-phthalocyanine, alkylaminophthalocyanine, alkylmer-captophthalocyanine, aryloxyphthalocyanine, arylmer-captophthalocyanine, copper phthalocyanine piperidine, cycloalkylaminophthalocyanine, dialkylaminophthalocyanine, diaralkylaminophthalocyanine, dicycloalkylaminophthalo-cyanine, hexadecahydrophthalocyanine, imidomethylphthalo-cyanine, 1,2-naphthalocyanine, 2,3-naphthalocyanine, octa-azophthalocyanine, sulfur phthalocyanine, tetra-azophthalocyanine, tetra-4-acetylaminophthalocyanine, tetra-4-aminobenzoylphthalocyanine, tetra-4-aminophthalo-cyanine, tetrachloromethylphthalocyanine, tetra-diazophthalocyanine, tetra-4,4-dimethylocta-azophthalo-cyanine, tetra-4,5-diphenylene-oxide-phthalocyanine, tetra-4,5-diphenylocta-azophthalocyanine, tetra-(6-methylbenzothiazoyl)phthalocyanine, tetra-p-methyl-phenylaminophthalocyanine, tetramethylphthalocyanine, tetranaphthotriazolylphthalocyanine, tetra-4-naphthyl-phthalocyanine, tetra-4-nitrophthalocyanine, tetra-perinaphthylene-4,5-octa-azophthalocyanine, tetra-2,3-phenylene-oxide-phthalocyanine, tetra-4-phenylocta-azophthalocyanine, tetraphenylphthalocyanine, tetraphenylphthalocyanine-tetracarboxylic acid, ~Q306 tetraprl~rylphthalocyanine tetr2bariumcarboxylate, t~trap~enylphthalocyanine-tetra-4-trifllloromethyl-mercaptophthalocyanine, tetr~pyridine-phthalocyanine, tetra-4-trifluoromethylmercaptophthalocyanine, tetra-4-trif~uoromethylphthalocyan ne-4~5-thionaphthene-octa-azophthalocyanine, platinum phthalocyanine.
pot ssium phthalocyanine. rhodium phthalocyanine, sainariur~! phthalocyanine. silver phthalocyanine, silicon phthal(jcyanine, sodium phthalocyanine. sulfonated phthalocyanlne, thorium phthalocyanine. thulium phthalo-cyanine, tin chlorophthalocyanine, tin phthalocyanine, titanium phthalocyanine. uranium phthalocyanine.
vanadium phthalocyanine. ytteribium phthalocyanine.
zinc chlorophthalocyanine, zinc phthalocyanine, and dimers. trimers, oligomers. polymers and copolymers thereof.
Phthalocyanine and phthalocyanine derivatives that are easily available and are especially suitable for attaining the ob,jects of the present invention include metal-free phthalocyanine and their nuclear substitution derivatives. for example, halogen-substituted derivatives~
In this invention. as the organic polymeric photoconductor (C) constituting the top layer, there can be used any of organic polymeric substances having photoconductivity, for example, poly-N-vinylcarbazole.
poly-N-acrylphenothiazine. poly-N-(~-acryloxyethyl)-phenothiazine, poly-N-(2-acryloxypropyl)-phenothiazine, _ g _ 1~Z03Q6 poly-~T-all~lcarbazole9 poly-N-2-~cryloxy-2-methyl-N-etnyl^~rDaz~le, poly-N-(2-p-vinylbenzoylethyl)-carbazole, poly-N-propenylcarb~zole~ poly-N-2-methyl.~cryloxapropylcarbazole~ poly-N-acrylcarbazole, p~.ly-~r-vinyl-p-(N-carbaz~l)toluene, poly(vinylanisolace-tophenone), pol.yindene ~nd other kno~;n photoconductive organic polymeric substances~ Polymeric photoconductors that are easily available and are suitable for attainiing the objects of this invention include poly-N-vinyl-carbazole and nuclear substitution derivatives thereof,for example, halogen- and all~yl-substituted derivatives.
As the polycyclic aromatic nitro compound to be combined with the phthaloxy~nine or phthalocyanine derivative (A) and the organic polymeric photoconduc~tor (C) in the intermediate layer and top layer of the laminated photosensitive material of this invention, there can be used any of polycyclic aromatic compounds having at least one nitro group substituted on the cucleus, for ex~mple, 2,4-dinitro-1-chloronaphhtalene, 1,4-dinitronaphthalene, 1,5-dinitronaphthQlene,
3-nitro-N-butylc~rb~zole, 4-nitrobiphenyl, 4,4'-dinitrobiphenyl, l-chloro-4-nitroanthraquinone, 2,7-dinitroanthraquinone, 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, 9-dicyanomethylene-2,4,7-trinitrofluorenone and 4-nitroacen~phthene.
Polycyclic arom~tic nitro compounds th~t are suitable for ~tt~ining the objects of this invention include trinitrofluorenone ~nd tetranitrofluorenone.
In ~he lamin~ted photosensitive materi~l of this inveation, it is important th~t the phthalocyanine or phthalocy~nine derivative (A) and the polycyclic aromatic nitro cornpound (B) should be incorporated in ~ binder ~t an (A)/(B) ~eight r~tio of from 10/5 to 10/40, prefer~b]y from 10/7 to 10/14.
It is known that the phthPlocyanine or phthalocya-nine deriv~tive (A) is used in combination with the polycyclic ~romqtic nitro compound ~B) for ~n inter-mediate l~yer of ~ l~min~ted photosensitive plate In 1~nown photosensitive m~teri~ls, however, the polycyclic ~romatic compound is used in an ~mount much sm~ller than the ~mount specified in this invention.
When the polycyclic ~romPtic nitro compound is used in an amount smaller than the ~mount specified in this invention, ~s will be app~rent from CompQr~tive Example 1 and Table 1 given hereinafter, the dark dec~y speed is too low ~nd the residu~l potential is ~t a level that cannot be neglected. Therefore, in this photoconductive layer, fogging is re~dily caused ~t the high-speed repeated copying oper~tion and the residual potential is accumulated, and since a large load is imposed on the photoconductive layer ~t the cleanin3 step, the resist?nce to the copying operation ( the frequency of the repeated copying oper~tion that the photosensitive materi~l can resist ) is drastically lowered. When the polycyclic ~romatic compound is used in an amount l~rger th~n the amount specified in 112~3~
this invention, as will be a}ip~rent from Comparative Example 2 and T~ble 1 given hereinafter, the residual potenti~l can be reduced substantially to zero, but the dark decay speed is too high ~nd the primary surface potential ( surface potential of the photo-sensitive material after ch~rging but before exposure ) i.5 low, and it is difficult to obtain a copied image having high contrast and desnity. In contrast, if the mixing ratio of the polycyclic ~romatic nitro compound to the phthalocyanine or phthalocyanine derivative is adjusted within the ~bove-mentioned range according to this invention, at the high-speed repeated copying operation, the residual potential can be reduced to a negligible level while maintaining the primary surface potential at a high level, ~nd the d~rk decay speed can be controlled so that the potential is abruptly lowered during a period ranging from the toner transfer step to the point of initiation of the cleaning opera-tion. Therefore, according to this invention, it is possible to attain effects of improving th~ toner image transfer efficiency, facilit~ting the cleaning operation, preventing occurrence of fogging and impro-ving the resistance to the co~pying operation concurrently.
This functional effect th~t when the polycyclic aromatic nitro compound is combined with the phthalo-cyanine or phthalocyanine derivative at the above-mentioned specific mixing r~tio, the polycyclic aromatic nitro compound actS as a dark dec~y speed controlling 1i20306 ~oent for the phthalocy~nine or phthalocyanine deriva-tive is a novel effect found by us for the first time.
As the binder for dispersing therein the phthalo-cyanine or phthalocyanine derivative and the polycyclic aromatic nitro compound, there cen be used any of known polymeric binders, especi~lly electrically insulating binders. More specific~lly, there can be used, for exarnple, acrylic resins such as polyacrylic acid esters, polymethacrylic acid esters, acrylic acid/methacrylic acid ester copolymers, acrylic acid/styrene copolymers and maleic anhydride/styrene/methacrylic acid ester copolymers, vinyl aromatic polymers such as polystyrene ~nd poly-methylstyrene, vinyl chloride resins such as vinyl chloride/vinyl acetate copolymers, partially saponified vinyl chloride/vinyl acetate copolymers, partially saponified and acetalized vinyl chloride/
vinyl acetate copolymers and vinyl chloride/vinyl acetate/maleic anhydride copolymers, vinyl ester polymers such as polyvinyl acetate, butadiene copolymers such as styrene/butadiene copolymers and acrylonitrile/
styrene/b-~tadiene copolymers, olefin resins such as ethylene/vinyl acetate copolymers, ethylene/acrylic ~cid copolymers ~nd ionomers, polyester resins such as ethylene!butylene-terephthalate/isophthalate, polyamide and copolyamide resins, polycarbonate resins, unsaturated polyester resins, urethane resins such as ~crylic urethane, epoxy resins, phenol-formaldehyde resins, xylene resins and melamine-formaldehyde resins. These ' ,~
~ - 13 -~2~06 binders may be used singly or in the form of a mixture of two or more of them. It is preferred that the electric resistance (volume resistivity) of the binder used be at least 1 x 1011 ~-cm. In order to attain the objects of this invention, it is especially preferred to use an acrylic resin as a hinder.
The amount used of the binder is not particularly critical in this invention, but in general, it is preferred that the binter be used in an amount of 30 to 1000 parts by weight, especially 50 to 300 parts by weight, per 100 parts by weight of the phthalocyanine or phthalo-cyanine derivative (A).
In this invention, it is very important that a top layer comprising the above-mentioned organic poly-meric photocontuctor (C) and polycyclic aromatic nitro compound (B) at a specific mixing ratio should be laminated on the intermediate layer (first photo-conductive layer) comprising the above-mentioned phthalocyanine or phthalocyanine derivative, polycyclic aromatic nitro compound and binder. More specifically, in case of a photosensitive plate formed by laminating a photoconductive layer comprising the above-mentioned phthalocyanine or phthalocyanine derivative, polycyclic aromatic nitro compound and binter in the form of a mono-layer on an electrically contuctive substrate, as will be apparent from Comparative Example 3 and Table 1 given hereinafter, the primary surface potential (the surface potential of the photosensitive material after - llZQ306 charging but before exposure) is considerably low, the rising speet of the surface potential is low and the sensitivity expressed by the half life (seconds) of light decay is considerably low. Thus, this com-parative photosensitive material is still insufficient in various points. In contrast, when a layer (second photoconductive layer) comprising the above-mentioned organic polymeric photoconductor (C) and polycyclic aromatic nitro compound (B) is disposed on the inter-mediate layer (first photoconductive layer) formed on the electrically conductive substrate according to this invention, the foregoing properties can be remarkably improved without any bad influence on dark decay characteristics, which will readily be understood when results of Comparative Example 3 are compared with results of Examples of this invention.
It also is very important that in the top layer of the photosensitive material of this invention, the organic polymeric photoconductor (C) should be combinet with the polycyclic aromatic nitro compound ; (B) at a (C)/(B) mixing weight ratio of from 6/1 to 1/6, especially from 1/1.7 to 1/2.2.
It is known that a polymeric photoconductor as an electron donor and a polycyclic aromatic nitro compound as an electron acceptor form a complex and a sensitized photoconductive layer can be formed from these two compounds. This invention is in agreement with this known technique in the point that a sensitized .
_ 15 -llZ~3~6 photoconductive layer is formet by using these two components. However, in this invention, not only from the viewpoint of the sensitivity but also from the viewpoints of the residual potential and the charge characteristics of the laminated photosensitive material, the above-mentioned specific mixing ratio of the polycyclic aromatic nitro compound to the polymeric photoconductor should be selected in this invention. This is one of important features of this invention. More specifically, when the amount of the polycyclic aromatic nitro compound incorporated in the top layer is smaller than the above amount specified in this invention, the sensitivity is reduced and further, as will be apparent from Comparative Example S
and Table 1 given hereinafter, during the repeated copying operation the residual potential is accumulated on the surface of the photosensitive material, causing fogging, electric deterioration of the photoconductive layer and drastic reduction of the resistance to the copying operation. In contrast, when the amount of the polymeriG photoconductor is larger than the amount specified in this invention, as will be apparent from Comparative Example 6 and Table 1 given hereinafter, the primary surface potential is drastically reduced and the rising speed of the surface potential is low.
Accordingly, it is difficult to obtain satisfactory copied images. In contrast, when the organic polymeric photoconductor is combined with the polycyclic aromatic ~lZQ306 nitro compound at the above-mentioned specific weight ratio according to this invention, the charge charac-teristics of the surface of the photoconductive layer can be controlled so that the residual potential can be reduced to a level that can be neglected while elevating the primary surface potential and the speed of rising of the surface potential by charging to suffi-ciently high levels and bad influences owing to accumul-ation of the residual potential can be effectively eliminated.
In this invention, it is preferred that a silicone oil be incorporated in the top layer comprising the organic polymeric photoconductor and, the polycyclic aromatic nitro compound. We found that when a silicone oil is incorporated in the top layer, during the exposure and developing steps the dark decay speed can be maintained at a relatively low level and at the subsequent transfer or cleaning step the dark decay speed can be elevated at an extremely high level to thereby reduce drastically the residual potential on the non-exposed area. According to this preferred embodiment, accumulation of charges can be effectively prevented and there can be attained prominent effects of preventing occurrence of fogging, improving the toner transfer efficiency, preventing occurrence of insulation breakdown and improving the adaptability to the cleaning operation. Still further, in this preferred em~odiment, the coating operation can be remarkably ~Z~3Q~i facilitated and the smoothness of the coating layer can be prominently improved.
As the silicone oil that can be used in this invention, there can be mentioned, for exa~ple, polydimethylsiloxane, polymethylphenylsiloxane, polyhydrodiene-methylsiloxane, polymethylaminopropyl-siloxane, their copolymers, and dimethylsiloxane/ethyl-ene oxide block copolymers. Polydimethylsiloxane is especially preferred because it is easily available and is suitable for attaining the objects of this invention.
The amount incorporated of the silicone oil may be changed in a broad range, but in general, in order to attain the objects of this invention advantageously, it is preferred that the silicone oil be incorporated in an amount of 1 to 30 parts by weight, especially 5 to 17 parts by weight, per 100 parts by weight of the organic polymeric photoconductor (~).
In this invention, a foil or plate of copper, aluminum, silver, t;n or iron, which is formed into a sheet or drum, is used as the electrically conductive substrate. Further, a product formed by depositing such metal in the form of a thin film on a plastic film or the like by vacuum dcposition, non-eloctroly~ic pluting or like means can be uscd as the electrically conductive substrate.
In general, the luminated photosensitive material of this lnv0ntion is prepared by a process comprising coating a binder solution containing the phthalocyanine X
or phthalocyanine derivative (A) and the polycyclic aromatic nitro compound (B) at the above-mentioned specific ratio on an electrically conductive substrate such as mentioned above to form an intermediate layer, drying the so coated intermediate layer, coating a liquid composition comprising the organic polymeric photoconductor (C) and the polycyclic aromatic nitro compound (B) at the above-mentioned specific ratio on the intermediate layer, and drying the coating according to need.
As the solvent for preparing a coating co~position for the intermediate layer, there can be used, for example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, cyclic ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methylethyl ketone, methylisobutyl ketone and cyclohexanone, alcohols such as diacetone alcohol and ethylene glycol isobutyl ether, and alicyclic hydrocarbons such as cyclohexane. These solvents may be used singly or in the form of a mixture of two or more of them.
In general, a coating composition for forming the intermediate layer is prepared by dissolving a binder such as mentioned above in one or more of the above-mentioned organic solvents, dispersing or dissolving the phthalocyanine or phthalocyanine derivative and the polycyclic aromatic nitro compound into the binder solution, and homogenizing the resulting dispersion or solution. From the viewpoint of the adaptability to 1~2~30~;
the coating operation, it is generally preferred that the solid concentration of this coating composition be 1 to 80% by weight, especially 5 to 30% by weight.
A top layer-forming coating composition is pre-pared by dissolving the organic polymeric photoconductor (C) and polycyclic aromatic nitro compound (B) in one or more of the above-mentioned organic solvents to form a complex of the two components.
In general, it is preferred that this coating composition be applied to the intermediate layer at a solid concentration of 1 to 80% by weight, especially 5 to 30% by weight. The coated composition is ordinarily dried at a temperature of 10 to 180C.
to form a top layer.
In the above process, a complex is formed from the organic polymeric photoconductor (C) and the polycyclic aromatic nitro compound (B) in the coating solution. In this invention, it also is possible to adopt a process in which a solution of the organic polymeric photoconductor (C) and a solution of the polycyclic aromatic nitro compound (B) are prepared separately, the respective solutions are coated on the intermediate layer in this order or reverse order and a complex is formed directly on the intermediate layer.
In forming the top layer, it is preferred that the following be taken into consideration. Namely, it is preferred to select as the solvent of the top ll;~Q30~;
layer-forming coating composition a solvent that does not substantially dissolve the binder constituting the intermediate layer. Of course, it is permissible to use a solvent capable of substantially dissolving the intermediate layer for the top layer-forming coating composition. In this case, however, it is preferred that the top layer-forming composition be solidified within 5 minutes, especially 1 minute.
In the laminated photosensitive material of this invention, it is preferred that the thickness of the intermediate layer be 1 to 40 ~t especially 3 to 6 ~J
and that the thickness of the top layer be 1 to 40 ~, especially 3 to 7 ~. If the thickness of the inter-mediate layer is smaller than 1 ~, the primary surface potential or rising speed thereof is often too low, and if the thickn,ess of the intermediate layer is larger than 40 ~, the residual potential is at a level that cannot be neglected and occurrence of fogging or reduction of the resistance to the copying operation is readily caused. When the thickness of the top layer is smaller than 1 ~, the primary surface potential or rising speed thereof is often too low, and when the thickness of the top layer is larger than 40 ~, the sensitivity, i.e., the light decay speed, is reduced and insulation breakdown is readily caused.
In the laminated photosensitive material of this invention, as described hereinbefore, electric charac-teristics and photoconductive characteristics at the X
l~Z~)306 repea~ed copying operation can be remarkably improved, and furthermore, mechanical properties such as the peel resistance can be prominently improved. More speci-fically, although in case of a photosensitive material formed by applying a photoconductive layer comprising the above-mentioned phthalocyanine or phthalocyanine derivative, polycyclic aromatic nitro compound and binder in the form of a mono-layer to a metal substrate, the photoconductive layer is readily peeled off at a pressure-sensitive tape peel test described hereinaf~er, in case of the laminated photosensitive material of this invention, peeling of the photoconductive layer is not caused at all at the same test. Further, since the polymeric photoconductor is present on the surface layer, the abrasion resistance is enhanced. Thus, it will readily be understood that in the laminated photosensitive material of this invention, also the mechanical properties are remarkably improved.
The laminated photosensitive material of this invention is especially valuable and useful as a photosensitive material for an electrophotographic copying machin0 in which the surface of the photosensi-tive material is negatively charged and the photo-sensitive material is used repeatedly for the copying operation using all the rays in the visible region.
This invention will now be described in detail by reference to the following Examples that by no means limit the scope of the invention.
~1~0306 Example l In 4.4 g of toluene were homogeneously dissolved 0.3 g of Phthalocyanine Blue (Heliogen Blue 7800 manufactured by BASF AG.), 0.3 g of 2,4,7-trinitro-9-fluorenone and l.0 g of an acrylic resin (Paraloid*
A-21 manufactured by Rohm ~ Haas Co., solid content =
30%), and the solution was coated on an aluminum plate so that the dry thickness of the coating was 5 ~.
Thus, an intermediate layer was formed.
In 190 g of tetrahydrofuran were homogeneously dissolved lO g of poly-N-vinylcarbazole (hereinafter referred to as "PVK") (Luvican* Ml70 manufactured by BASF AG.), 1 g of a silicone oil (KF 96 manufactured by Shinetsu Kagaku Kogyo ~. K.) and 20 g of 2,4,7-trinitro-9-fluorenone, and the solution was coated as a top layer on the above phthalocyanine layer so that the dry thickness of the entire coating (inclusive of the phthalocyanine layer was lO ~. Thus, a photosensi-tive plate of the present invention was prepared.
The photosensîtive plate obtained in Example l was tested by using a tester of the negative charging-exposure-developing-transfer-fixing type. Clear images having a high resolving power were obtained.
Scores of thousands of prints could be obtained when the copying operation was repeated by using this photosensitive plate.
Electric characteristics of the photosensitive plate obtained in Example l were examined by using an *Trademark - 23 -llZ0306 electrostatic i~per analyzer manufactured by Kawaguchi Denki K.~. to obt~in results shown in Table 1.
Exam~le 2 In 7.3 g of methylethy1 ketone were uniformly dispersed and dissolved 0.3 g of Phthalocyanine Blue ( Heliogen Blue 7800 manufactured by BASF AG. ), 0.3 g of 2,4,7-trinitro-9-fluorenone, 0.3 g of an epoxy resin ( Epikote~1009 manufactured by Shell Chemical Co. ) and 0.015 g of a curing agent ( Epicure~manufac-tured by Shell Chemical Co. ), and the resultingcomposition was coated on an ~luminum pl~te and dried at 180C. in an oven for 30 minutes to thermally cure the epo~y resin. The thickness of the coating after curing was 5 ~.
Then, 10 g of poly-N-vinylcarbazole ~ Tuvica1*210 manufactured by Takasago ~oryo K. K. ), 1 g of a sili-cone oil ( KF 96 manufactured by Shinetsu K~gaku Kogyo K. K. ) and 20 g of 2,4,7-trinitro-9-fluorenone were homogeneously dissolved in 190 g of tetrahydrofuran, ~nd the solution was coated~ on the phthalocyanine layer so that the dry thickness of the entire coating ( inclusive of the phthalocyanine layer ) was 10 ~.
When this photosensitive plate was used for the photocopying operation in the same manner as described in Example 1, scores of thousands of clear prints having a high resolving power could be obtained.
Ex~mple 3 In 5 g of toluene were homogeneously dispersed ~d e ~
and dissolved 0.3 g of Phthalocyanine Blue (Heliogen Blue 7800 manufactured by BASF AG.), 0.3 g of 2,4,7-trinitro-9-fluorenone and 0.6 g of an unsaturated polyester resin (U-PICA* AGS-260-A92 manufactured by Toyo Boseki K. K., solid content = 50%), and the composition was coated on an aluminum plate and heated at 180C. in an oven for 1 hour to thermally cure the unsaturated polyester resin. The thickness of the coat-ing after curing was 5 ~.
A PVK layer was laminated on the so formed phthalocyanine layer in the same manner as in Example 1.
When the resulting photosensitive plate was tested in the same manner as described in Example 1, scores of thousands of clear prints could be obtained and the copied images had a very high resolving power.
ExamFle 4 In 6 g of toluene were homogeneously dispersed and dissolved 0.3 g of Phthalocyanine Blue (Heliogen Blue 7800 manufactured by BASF AG.), 0.3 g of 2,4,7-trinitro-9-fluorenone and 0.3 g of a polystyrene resin (D-150 manufactured by Esso Standard Petroleum K. K.), and the composition was coated on an aluminum plate so that the dry thickness of the coating was 5 ~.
A PVK layer was laminated on this phthalocyanine layer in the same manner as described in Example 1.
When the resulting photosensitive plate was tested in the same manner as described in Example, scores of thousands of clear prints could be obtained and copied *Trade~ark - 25 -1~203~)6 images had a very high resolving pOWer.
E~mple 5 In 5 g ~f toluene were homogeneously dispersed ~nd dissolved 0.3 g of Phthalocyanine Blue ( Heliogen Blue 7800 manuf~ctured by BAS~ AG. ), 0.3 g of 2,4,7-trinitro-9-fluorenone and 0.6 g of a silicone resin ( ES 1001 m~nufactured by Shinetsu Kagaku Kogyo K. K., solid content - 50 % ), ~nd the composition was coated on an aluminum plate so th~t the dry thickness of the coating was 5 ~.
A PVK layer was laminated on this phthalocyanine layer in the s~me manner as described in Example 1.
When the resulting photosensitive plate was tested in the same manner as described in Example 1, ~cores of thousands of clear prints could be obtained and copied images had a high resolving power.
Example 6 : In 3.4 g of toluene were homogeneously dispersed and dissolved 0 3 g of Phthalocyanine Blue ( Heliogen ~lue 7800 m~nufactured by BASF ), 0.3 g of 2,4,7-trinitro-9-fluorenone and 5 g of an acrylic resin ( Paraloid A-21 manufactured by Rhom & Haas Co. ), and the composition was coated on an aluminum plate so th~t the dry thickness of the co~ting was 8 ~.
25 . Then, 10 g of polyvinylcarbazole ( Luvican M170 ,~
manufactured by BASF AG. ), 1 g of a silicone oil ( KF 96 manufactured by Shinetsu Kogaku Kogyo K. K. ) and 20 g of 2,4,7-trinitro-9-fluorenone were homoge-:
~ - 26 -.~ .
1~20306 neously dissolved in 190 g of tetrahydrofuran, and the solution was coated on the phthalocyanine layer so that the dry thickness of the entire coating (inclusive of the phthalocyanine layer ) was 10 ~.
When the 50 preparet photosensitive plate was tested in the same manner as described in Example 1 except that the polarity of charging was changed to the positive polarity, scores of thousands of clear prints could be obtained and copied images had a very high resolving power.
Comparative Example 1 In 4.4 g of toluene were homogeneously dispersed and dissolved 0.3 8 of Phthalocyanine Blue tHeliogen Blue 7800 manufactured by BASP AG.), 0.03 g of 2,4,7-trinitro-9-fluorenone and 1.0 g of an acrylic resin Paraloid A-21 manufactured by Rhom ~ Haas Co., solid content ~ 30%), and the composition was coated on an aluminum plate so that the dry thickness of the coating was 5 ~.
Then, 10 g of poly-N-vinylcarbazole tLuvican M170 manufactured by BASF AG.), 1 g of a silicone oil (KP 96 manufactured by Shinetsu Kagaku Kogyo K. K.~
and 20 g of 2,4,7-trinitro-9-fluorenone were homogene-ously dissolved in 190 g of tetrahydrofuran. The resulting solution was coated as a top layer on the phthalocyanine layer so that the dry thickness of the entire coating (inclusive of the phthalocyanine layer) was 10 ~. The resulting photosensitive plate were 1~203~
tested in the same manner as described in Example 1 to obtain results shown in Table 1.
Comparative Example 2 In 4.4 g of toluene were homogeneously dispersed and dissolved 0.3 g of Phthalocyanine Blue (Heliogen Blue 7800 manufactured by BASF AG.), 2.0 g of 2,4,7-trinitro-9-fluorenone and 1.0 g of an acrylic resin ~Paraloid A-21 manufactured by Rhom ~ Haas Co.), and the composition was coated on an aluminum plate so that the dry thickness of the coating was 5 ~.
In the same manner as described in Co~parative Example 1, a top layer was formed on the so formed phthalocyanine layer. The resulting photosensitive plate was tested in the same manner as described in Example 1 to obtain results shown in Table 1.
Comparative ExamPle 3 In 6 g of toluene were homogeneously dispersed and dissolved 0.3 g of Phthalocyanine Blue (Heliogen Blue 7800 manufactured by BASF AG.), 0.3 g of 2,4,7-trinitro-9-fluorenone and 3.5 g of an acrylic resin (PR-1112D manufactured Mitsubishi Kasei K. K., solid content = 40%), and the composition was coated on an aluminum plate so that the dry thickness of the coating was 10 ~.
The so obtained photosensitive plate was tested in the same manner as described in Example 1 except that the charging polarity was changed to the positive polarity. Obtained results are shown in Table 1.
_ 28 -Comparative Ex~mPle 4 In 190 g of tetrahydrofuran were homogeneously dissolved 10 g of poly-N-vinylcarbazole ( Luvican M170 manufactured by BASF AG. ) and 20 g of 2,4,7-trinitro-9-fluorenone, and the solution was coated on an aluminum plate so that the dry thickness of the coating was 10 ~.
The so obtained photosensitive plate was tested in the same manner as described in Example 1 to obtain results shown in Table 1.
Com~arative Example 5 In 6 g of toluene were homogeneously dispersed and dissolved 0.3 g of Phthalocyanine Blue ( Heliogen Blue 7800 manufactured by BASF AG ), 0 3 g of 2,4,7-trinitro-9-fluorenone and 0.3 g of a polystyrene resin ( D-150 manufactured by Esso Standard Petroleum K. K, ), and the composi~lon was coated on an aluminum plate so that the dry thickness of the coating was 5 Thus, an intermediate l~yer was formed.
Then, 10 g of poly-N-vinyl carbazole ( Luvican M170 manufactured by BASF AG. ), 1 g of a silicone oil ( KF 96 manufactured by Shinetsu Kagaku Kogyo K. K, ) and 1 g of 2,4,7-trinitro-9-fluorenone were homogen~-ously dissolved in 190 g of tetrahydrofuran, and the solution was coated as a top layer on the phthalocya-nine layer so th~1; the dry thickness of the entire coating ( inclusive of the phthalocyanine layer ) was 10 ~. .
The so obtained photosensitive plate was tested in the same manner as described in Example 1 to o~tain results shown in Table 1.
Comparative Example 6 In the same manner as described in Comparative Ex~mple 5, an intermediate layer having a thickness of 5 ~ was prepared. Then, 10 g of poly-N-vinylcarbazole ( Luvican M170 manufactured by BASF AG. ), 1 g of a sili-cone oil ( KF 96 manufactured by Shinetsu Kagaku Kogyo K. K. ) and 63 g of 2,4,7~trinitro-9-fluorenone were homogeneously dissolved in 190 g of tetrahydrofuran.
The resulting solution was coated as a top layer on the phthalocyanine layer so that the dry thickness of the entire coating ( inclusive of the phthalocyanine layer ~ was 10 ~.
The so obtained photosensitive plate was tested in the same manner as described in Example 1 to obtain results shown in Table 1.
~lZ~306 a~ ~ ~ u~
~ ~ O ~ ~ a x O ~ ~, o ,e , ~ ~
U~ V ~
~ ~ I
1 ~ ~ ~ ~ a x x a J ~ ~ ~ X
d O
V
~ ~D
~ a <J X O O ~ O O O ~ o ~ a V ,~
hr~ ~ O X ~I ~ <3 a) ~o ~ ,, ~ O
a~
~ ~ ~ I
a) ~ V
;~ ~ ~ X XO O ~ ~ ~ ~
~ ~g~l .
~3 V ~1 a x O X X <J O X ~ ~ ~ ~D ~ O
, ~o I
V ~
a O O O O O O O O
~ ~ o ~ o o o ~ o~
al ~ ~ ~ .~ ~, P~ O h ~1 o d rl 0 o a, h P~ ~) ~ h ~ O _~ uq t~ a~ o bO ~ ~! ~ O
O ~0 s~ h ~) ~ y ,~ ~ 0 a~
C ~ ~, a) ~ ~! ~1 0 c~ 1 ~ ~ O ~ u~ 0 0 a~ o ~ o ~ ~,~
I ~ Oq hn 0 ~I C O rt ~: h u~ X ~ h .u~ h ~ a) ~,q ~ rl O h ~ ~¦
V O
l~Z03~6 Notes Sharpness:
Reproducibility of fine lines, meshes, half-tones ~nd small letters, which was evaluated according to the following scale:
O s good A s slightly bad X : bad Densitys The density of the image area ( non-exposed area ), which was evaluated ~ccording to the following scale:
~s dense ~s slightly thin X s thin Foggings Contamination o~ the bac~ground in the non-lmage area ( exposure area ), which was evaluated ~ccording to the following sCale~
~ s not observed ~s slight X s conspicuous Cleaning Propertys Easiness in removing the toner left ~n the photosensitive plate after tran~fer, which was evaluated according to the ~ollowing scales O : very easy A : slightly difficult .
X s difficult 1~Z0306 Resistance to Copying Operation:
The number of good quality prints obtained at the repeated copying operation. which was evaluated according to the following sc~le:
o : ~ore than 20000 prints 1000 - 20000 prints X s less than 1000 prints Color Image Quality~
Reproducibility at printing of a color chart, which was evaluated ~ccording to the following scale:
o : good reproducibility X : no reproducibility ( especially red ) Transfer Efficiencys The ratio of the toner transferred to copying p~per after development, which wPs evaluated according to the following scales O s more than 80 % of the toner was transferred ~s 50 to 80 % of the toner was transferred X s less than 50 % of the toner was transferred Conditions ~or Me~surements by Electrostatic Paper Analyzers Lights 40 Lux Charge~ 5 KV ( negative ) ( positive in Compara-tive Example 3 ) Sensitivitys quantity of light ( Lux-sec ) at which the potential just before exposure decayed to 1/2, which was determined according the Qtatic method 1~0306 Initial potential: saturation ch~rge voltage ( V ) as determined according to the sbdtic method Charge quQntitys saturation voltage ( V ) observed when charging was effected for 10 seconds, which was determlned according to the dynamic method Re~idual potentialt voltage ( Y ) observed 3 seconds after exposure, whlch was deter-mined according to the static method D~rk decays average value of the potentlal decay ( V/sec ) o~er a period of 3 seconds from charge-o~f, which wa~ determined according to the static method Adhesivene~ss The sdhesion strength of the photosensitive layer to the alumlnum sub~trate ( the peel resistance observed when ~n pressure-sensitive adhesive tape was applled to the photosensltive layer and the tape was then peeled off ), which ~as evsluated according to the following scales s strong ~: ordinary X s we~k Example 7 A photosensitive plate w~ prepared in the s~me manner as described in Example 1 except that 2,4,7-- ~4 -1 ~a~3c~6 trinitro-9-fluorenone used in Example 1 was replaced by the same amount of 2,4,5,7-tetranitrofluorenone.
When this photosensitive plate was tested in the same manner as described in Example 1, clear prints similar to these obtained in Example 1 were obtained with a high resistance to the copying operation.
Example 8 A photosensitive plate was prep~red in the same manner as described in Example 1 except that Cyanine Blue BB ( copper phthalocyanine manufactured by Dai-Nippon Ink K. K. ) was used instead of Heliogen Blue 7800. When this photosensitive plate was tested in the same manner a8 described in Example 1, clear prints ~imilar to those obtained in Example 1 were o~tained 5 wlth a high re~istance to the copying operation.
x~mple 9 An intermediate layer wa~ prepared in the same manner a~ described in Example 1. Then, 10 g o~ poly-N-vinylphenothiazine, 1 g of ~ silicone oil ( KF 96 m~nufac~ured by Shinetsu Kag~ku Kogyo K. K. ) and 20 g of 2,4,7-trlnitro-9Lfluorenone were homogeneously dissolved in 190 g of tetr~hydrofuran, and the ~olution was coated as a top layer on the intermediate phthalo-cyanine layer so that the dry thickness of the entire coating ( inclusive of the phthalQcyanine layer ) was 10 ~. When the 80 prepared photosensitive plate was tested in the same manner as in Example 1, clear prints could be obtained with a high resistance to the printing operation.
Polycyclic arom~tic nitro compounds th~t are suitable for ~tt~ining the objects of this invention include trinitrofluorenone ~nd tetranitrofluorenone.
In ~he lamin~ted photosensitive materi~l of this inveation, it is important th~t the phthalocyanine or phthalocy~nine derivative (A) and the polycyclic aromatic nitro cornpound (B) should be incorporated in ~ binder ~t an (A)/(B) ~eight r~tio of from 10/5 to 10/40, prefer~b]y from 10/7 to 10/14.
It is known that the phthPlocyanine or phthalocya-nine deriv~tive (A) is used in combination with the polycyclic ~romqtic nitro compound ~B) for ~n inter-mediate l~yer of ~ l~min~ted photosensitive plate In 1~nown photosensitive m~teri~ls, however, the polycyclic ~romatic compound is used in an ~mount much sm~ller than the ~mount specified in this invention.
When the polycyclic ~romPtic nitro compound is used in an amount smaller than the ~mount specified in this invention, ~s will be app~rent from CompQr~tive Example 1 and Table 1 given hereinafter, the dark dec~y speed is too low ~nd the residu~l potential is ~t a level that cannot be neglected. Therefore, in this photoconductive layer, fogging is re~dily caused ~t the high-speed repeated copying oper~tion and the residual potential is accumulated, and since a large load is imposed on the photoconductive layer ~t the cleanin3 step, the resist?nce to the copying operation ( the frequency of the repeated copying oper~tion that the photosensitive materi~l can resist ) is drastically lowered. When the polycyclic ~romatic compound is used in an amount l~rger th~n the amount specified in 112~3~
this invention, as will be a}ip~rent from Comparative Example 2 and T~ble 1 given hereinafter, the residual potenti~l can be reduced substantially to zero, but the dark decay speed is too high ~nd the primary surface potential ( surface potential of the photo-sensitive material after ch~rging but before exposure ) i.5 low, and it is difficult to obtain a copied image having high contrast and desnity. In contrast, if the mixing ratio of the polycyclic ~romatic nitro compound to the phthalocyanine or phthalocyanine derivative is adjusted within the ~bove-mentioned range according to this invention, at the high-speed repeated copying operation, the residual potential can be reduced to a negligible level while maintaining the primary surface potential at a high level, ~nd the d~rk decay speed can be controlled so that the potential is abruptly lowered during a period ranging from the toner transfer step to the point of initiation of the cleaning opera-tion. Therefore, according to this invention, it is possible to attain effects of improving th~ toner image transfer efficiency, facilit~ting the cleaning operation, preventing occurrence of fogging and impro-ving the resistance to the co~pying operation concurrently.
This functional effect th~t when the polycyclic aromatic nitro compound is combined with the phthalo-cyanine or phthalocyanine derivative at the above-mentioned specific mixing r~tio, the polycyclic aromatic nitro compound actS as a dark dec~y speed controlling 1i20306 ~oent for the phthalocy~nine or phthalocyanine deriva-tive is a novel effect found by us for the first time.
As the binder for dispersing therein the phthalo-cyanine or phthalocyanine derivative and the polycyclic aromatic nitro compound, there cen be used any of known polymeric binders, especi~lly electrically insulating binders. More specific~lly, there can be used, for exarnple, acrylic resins such as polyacrylic acid esters, polymethacrylic acid esters, acrylic acid/methacrylic acid ester copolymers, acrylic acid/styrene copolymers and maleic anhydride/styrene/methacrylic acid ester copolymers, vinyl aromatic polymers such as polystyrene ~nd poly-methylstyrene, vinyl chloride resins such as vinyl chloride/vinyl acetate copolymers, partially saponified vinyl chloride/vinyl acetate copolymers, partially saponified and acetalized vinyl chloride/
vinyl acetate copolymers and vinyl chloride/vinyl acetate/maleic anhydride copolymers, vinyl ester polymers such as polyvinyl acetate, butadiene copolymers such as styrene/butadiene copolymers and acrylonitrile/
styrene/b-~tadiene copolymers, olefin resins such as ethylene/vinyl acetate copolymers, ethylene/acrylic ~cid copolymers ~nd ionomers, polyester resins such as ethylene!butylene-terephthalate/isophthalate, polyamide and copolyamide resins, polycarbonate resins, unsaturated polyester resins, urethane resins such as ~crylic urethane, epoxy resins, phenol-formaldehyde resins, xylene resins and melamine-formaldehyde resins. These ' ,~
~ - 13 -~2~06 binders may be used singly or in the form of a mixture of two or more of them. It is preferred that the electric resistance (volume resistivity) of the binder used be at least 1 x 1011 ~-cm. In order to attain the objects of this invention, it is especially preferred to use an acrylic resin as a hinder.
The amount used of the binder is not particularly critical in this invention, but in general, it is preferred that the binter be used in an amount of 30 to 1000 parts by weight, especially 50 to 300 parts by weight, per 100 parts by weight of the phthalocyanine or phthalo-cyanine derivative (A).
In this invention, it is very important that a top layer comprising the above-mentioned organic poly-meric photocontuctor (C) and polycyclic aromatic nitro compound (B) at a specific mixing ratio should be laminated on the intermediate layer (first photo-conductive layer) comprising the above-mentioned phthalocyanine or phthalocyanine derivative, polycyclic aromatic nitro compound and binder. More specifically, in case of a photosensitive plate formed by laminating a photoconductive layer comprising the above-mentioned phthalocyanine or phthalocyanine derivative, polycyclic aromatic nitro compound and binter in the form of a mono-layer on an electrically contuctive substrate, as will be apparent from Comparative Example 3 and Table 1 given hereinafter, the primary surface potential (the surface potential of the photosensitive material after - llZQ306 charging but before exposure) is considerably low, the rising speet of the surface potential is low and the sensitivity expressed by the half life (seconds) of light decay is considerably low. Thus, this com-parative photosensitive material is still insufficient in various points. In contrast, when a layer (second photoconductive layer) comprising the above-mentioned organic polymeric photoconductor (C) and polycyclic aromatic nitro compound (B) is disposed on the inter-mediate layer (first photoconductive layer) formed on the electrically conductive substrate according to this invention, the foregoing properties can be remarkably improved without any bad influence on dark decay characteristics, which will readily be understood when results of Comparative Example 3 are compared with results of Examples of this invention.
It also is very important that in the top layer of the photosensitive material of this invention, the organic polymeric photoconductor (C) should be combinet with the polycyclic aromatic nitro compound ; (B) at a (C)/(B) mixing weight ratio of from 6/1 to 1/6, especially from 1/1.7 to 1/2.2.
It is known that a polymeric photoconductor as an electron donor and a polycyclic aromatic nitro compound as an electron acceptor form a complex and a sensitized photoconductive layer can be formed from these two compounds. This invention is in agreement with this known technique in the point that a sensitized .
_ 15 -llZ~3~6 photoconductive layer is formet by using these two components. However, in this invention, not only from the viewpoint of the sensitivity but also from the viewpoints of the residual potential and the charge characteristics of the laminated photosensitive material, the above-mentioned specific mixing ratio of the polycyclic aromatic nitro compound to the polymeric photoconductor should be selected in this invention. This is one of important features of this invention. More specifically, when the amount of the polycyclic aromatic nitro compound incorporated in the top layer is smaller than the above amount specified in this invention, the sensitivity is reduced and further, as will be apparent from Comparative Example S
and Table 1 given hereinafter, during the repeated copying operation the residual potential is accumulated on the surface of the photosensitive material, causing fogging, electric deterioration of the photoconductive layer and drastic reduction of the resistance to the copying operation. In contrast, when the amount of the polymeriG photoconductor is larger than the amount specified in this invention, as will be apparent from Comparative Example 6 and Table 1 given hereinafter, the primary surface potential is drastically reduced and the rising speed of the surface potential is low.
Accordingly, it is difficult to obtain satisfactory copied images. In contrast, when the organic polymeric photoconductor is combined with the polycyclic aromatic ~lZQ306 nitro compound at the above-mentioned specific weight ratio according to this invention, the charge charac-teristics of the surface of the photoconductive layer can be controlled so that the residual potential can be reduced to a level that can be neglected while elevating the primary surface potential and the speed of rising of the surface potential by charging to suffi-ciently high levels and bad influences owing to accumul-ation of the residual potential can be effectively eliminated.
In this invention, it is preferred that a silicone oil be incorporated in the top layer comprising the organic polymeric photoconductor and, the polycyclic aromatic nitro compound. We found that when a silicone oil is incorporated in the top layer, during the exposure and developing steps the dark decay speed can be maintained at a relatively low level and at the subsequent transfer or cleaning step the dark decay speed can be elevated at an extremely high level to thereby reduce drastically the residual potential on the non-exposed area. According to this preferred embodiment, accumulation of charges can be effectively prevented and there can be attained prominent effects of preventing occurrence of fogging, improving the toner transfer efficiency, preventing occurrence of insulation breakdown and improving the adaptability to the cleaning operation. Still further, in this preferred em~odiment, the coating operation can be remarkably ~Z~3Q~i facilitated and the smoothness of the coating layer can be prominently improved.
As the silicone oil that can be used in this invention, there can be mentioned, for exa~ple, polydimethylsiloxane, polymethylphenylsiloxane, polyhydrodiene-methylsiloxane, polymethylaminopropyl-siloxane, their copolymers, and dimethylsiloxane/ethyl-ene oxide block copolymers. Polydimethylsiloxane is especially preferred because it is easily available and is suitable for attaining the objects of this invention.
The amount incorporated of the silicone oil may be changed in a broad range, but in general, in order to attain the objects of this invention advantageously, it is preferred that the silicone oil be incorporated in an amount of 1 to 30 parts by weight, especially 5 to 17 parts by weight, per 100 parts by weight of the organic polymeric photoconductor (~).
In this invention, a foil or plate of copper, aluminum, silver, t;n or iron, which is formed into a sheet or drum, is used as the electrically conductive substrate. Further, a product formed by depositing such metal in the form of a thin film on a plastic film or the like by vacuum dcposition, non-eloctroly~ic pluting or like means can be uscd as the electrically conductive substrate.
In general, the luminated photosensitive material of this lnv0ntion is prepared by a process comprising coating a binder solution containing the phthalocyanine X
or phthalocyanine derivative (A) and the polycyclic aromatic nitro compound (B) at the above-mentioned specific ratio on an electrically conductive substrate such as mentioned above to form an intermediate layer, drying the so coated intermediate layer, coating a liquid composition comprising the organic polymeric photoconductor (C) and the polycyclic aromatic nitro compound (B) at the above-mentioned specific ratio on the intermediate layer, and drying the coating according to need.
As the solvent for preparing a coating co~position for the intermediate layer, there can be used, for example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, cyclic ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methylethyl ketone, methylisobutyl ketone and cyclohexanone, alcohols such as diacetone alcohol and ethylene glycol isobutyl ether, and alicyclic hydrocarbons such as cyclohexane. These solvents may be used singly or in the form of a mixture of two or more of them.
In general, a coating composition for forming the intermediate layer is prepared by dissolving a binder such as mentioned above in one or more of the above-mentioned organic solvents, dispersing or dissolving the phthalocyanine or phthalocyanine derivative and the polycyclic aromatic nitro compound into the binder solution, and homogenizing the resulting dispersion or solution. From the viewpoint of the adaptability to 1~2~30~;
the coating operation, it is generally preferred that the solid concentration of this coating composition be 1 to 80% by weight, especially 5 to 30% by weight.
A top layer-forming coating composition is pre-pared by dissolving the organic polymeric photoconductor (C) and polycyclic aromatic nitro compound (B) in one or more of the above-mentioned organic solvents to form a complex of the two components.
In general, it is preferred that this coating composition be applied to the intermediate layer at a solid concentration of 1 to 80% by weight, especially 5 to 30% by weight. The coated composition is ordinarily dried at a temperature of 10 to 180C.
to form a top layer.
In the above process, a complex is formed from the organic polymeric photoconductor (C) and the polycyclic aromatic nitro compound (B) in the coating solution. In this invention, it also is possible to adopt a process in which a solution of the organic polymeric photoconductor (C) and a solution of the polycyclic aromatic nitro compound (B) are prepared separately, the respective solutions are coated on the intermediate layer in this order or reverse order and a complex is formed directly on the intermediate layer.
In forming the top layer, it is preferred that the following be taken into consideration. Namely, it is preferred to select as the solvent of the top ll;~Q30~;
layer-forming coating composition a solvent that does not substantially dissolve the binder constituting the intermediate layer. Of course, it is permissible to use a solvent capable of substantially dissolving the intermediate layer for the top layer-forming coating composition. In this case, however, it is preferred that the top layer-forming composition be solidified within 5 minutes, especially 1 minute.
In the laminated photosensitive material of this invention, it is preferred that the thickness of the intermediate layer be 1 to 40 ~t especially 3 to 6 ~J
and that the thickness of the top layer be 1 to 40 ~, especially 3 to 7 ~. If the thickness of the inter-mediate layer is smaller than 1 ~, the primary surface potential or rising speed thereof is often too low, and if the thickn,ess of the intermediate layer is larger than 40 ~, the residual potential is at a level that cannot be neglected and occurrence of fogging or reduction of the resistance to the copying operation is readily caused. When the thickness of the top layer is smaller than 1 ~, the primary surface potential or rising speed thereof is often too low, and when the thickness of the top layer is larger than 40 ~, the sensitivity, i.e., the light decay speed, is reduced and insulation breakdown is readily caused.
In the laminated photosensitive material of this invention, as described hereinbefore, electric charac-teristics and photoconductive characteristics at the X
l~Z~)306 repea~ed copying operation can be remarkably improved, and furthermore, mechanical properties such as the peel resistance can be prominently improved. More speci-fically, although in case of a photosensitive material formed by applying a photoconductive layer comprising the above-mentioned phthalocyanine or phthalocyanine derivative, polycyclic aromatic nitro compound and binder in the form of a mono-layer to a metal substrate, the photoconductive layer is readily peeled off at a pressure-sensitive tape peel test described hereinaf~er, in case of the laminated photosensitive material of this invention, peeling of the photoconductive layer is not caused at all at the same test. Further, since the polymeric photoconductor is present on the surface layer, the abrasion resistance is enhanced. Thus, it will readily be understood that in the laminated photosensitive material of this invention, also the mechanical properties are remarkably improved.
The laminated photosensitive material of this invention is especially valuable and useful as a photosensitive material for an electrophotographic copying machin0 in which the surface of the photosensi-tive material is negatively charged and the photo-sensitive material is used repeatedly for the copying operation using all the rays in the visible region.
This invention will now be described in detail by reference to the following Examples that by no means limit the scope of the invention.
~1~0306 Example l In 4.4 g of toluene were homogeneously dissolved 0.3 g of Phthalocyanine Blue (Heliogen Blue 7800 manufactured by BASF AG.), 0.3 g of 2,4,7-trinitro-9-fluorenone and l.0 g of an acrylic resin (Paraloid*
A-21 manufactured by Rohm ~ Haas Co., solid content =
30%), and the solution was coated on an aluminum plate so that the dry thickness of the coating was 5 ~.
Thus, an intermediate layer was formed.
In 190 g of tetrahydrofuran were homogeneously dissolved lO g of poly-N-vinylcarbazole (hereinafter referred to as "PVK") (Luvican* Ml70 manufactured by BASF AG.), 1 g of a silicone oil (KF 96 manufactured by Shinetsu Kagaku Kogyo ~. K.) and 20 g of 2,4,7-trinitro-9-fluorenone, and the solution was coated as a top layer on the above phthalocyanine layer so that the dry thickness of the entire coating (inclusive of the phthalocyanine layer was lO ~. Thus, a photosensi-tive plate of the present invention was prepared.
The photosensîtive plate obtained in Example l was tested by using a tester of the negative charging-exposure-developing-transfer-fixing type. Clear images having a high resolving power were obtained.
Scores of thousands of prints could be obtained when the copying operation was repeated by using this photosensitive plate.
Electric characteristics of the photosensitive plate obtained in Example l were examined by using an *Trademark - 23 -llZ0306 electrostatic i~per analyzer manufactured by Kawaguchi Denki K.~. to obt~in results shown in Table 1.
Exam~le 2 In 7.3 g of methylethy1 ketone were uniformly dispersed and dissolved 0.3 g of Phthalocyanine Blue ( Heliogen Blue 7800 manufactured by BASF AG. ), 0.3 g of 2,4,7-trinitro-9-fluorenone, 0.3 g of an epoxy resin ( Epikote~1009 manufactured by Shell Chemical Co. ) and 0.015 g of a curing agent ( Epicure~manufac-tured by Shell Chemical Co. ), and the resultingcomposition was coated on an ~luminum pl~te and dried at 180C. in an oven for 30 minutes to thermally cure the epo~y resin. The thickness of the coating after curing was 5 ~.
Then, 10 g of poly-N-vinylcarbazole ~ Tuvica1*210 manufactured by Takasago ~oryo K. K. ), 1 g of a sili-cone oil ( KF 96 manufactured by Shinetsu K~gaku Kogyo K. K. ) and 20 g of 2,4,7-trinitro-9-fluorenone were homogeneously dissolved in 190 g of tetrahydrofuran, ~nd the solution was coated~ on the phthalocyanine layer so that the dry thickness of the entire coating ( inclusive of the phthalocyanine layer ) was 10 ~.
When this photosensitive plate was used for the photocopying operation in the same manner as described in Example 1, scores of thousands of clear prints having a high resolving power could be obtained.
Ex~mple 3 In 5 g of toluene were homogeneously dispersed ~d e ~
and dissolved 0.3 g of Phthalocyanine Blue (Heliogen Blue 7800 manufactured by BASF AG.), 0.3 g of 2,4,7-trinitro-9-fluorenone and 0.6 g of an unsaturated polyester resin (U-PICA* AGS-260-A92 manufactured by Toyo Boseki K. K., solid content = 50%), and the composition was coated on an aluminum plate and heated at 180C. in an oven for 1 hour to thermally cure the unsaturated polyester resin. The thickness of the coat-ing after curing was 5 ~.
A PVK layer was laminated on the so formed phthalocyanine layer in the same manner as in Example 1.
When the resulting photosensitive plate was tested in the same manner as described in Example 1, scores of thousands of clear prints could be obtained and the copied images had a very high resolving power.
ExamFle 4 In 6 g of toluene were homogeneously dispersed and dissolved 0.3 g of Phthalocyanine Blue (Heliogen Blue 7800 manufactured by BASF AG.), 0.3 g of 2,4,7-trinitro-9-fluorenone and 0.3 g of a polystyrene resin (D-150 manufactured by Esso Standard Petroleum K. K.), and the composition was coated on an aluminum plate so that the dry thickness of the coating was 5 ~.
A PVK layer was laminated on this phthalocyanine layer in the same manner as described in Example 1.
When the resulting photosensitive plate was tested in the same manner as described in Example, scores of thousands of clear prints could be obtained and copied *Trade~ark - 25 -1~203~)6 images had a very high resolving pOWer.
E~mple 5 In 5 g ~f toluene were homogeneously dispersed ~nd dissolved 0.3 g of Phthalocyanine Blue ( Heliogen Blue 7800 manuf~ctured by BAS~ AG. ), 0.3 g of 2,4,7-trinitro-9-fluorenone and 0.6 g of a silicone resin ( ES 1001 m~nufactured by Shinetsu Kagaku Kogyo K. K., solid content - 50 % ), ~nd the composition was coated on an aluminum plate so th~t the dry thickness of the coating was 5 ~.
A PVK layer was laminated on this phthalocyanine layer in the s~me manner as described in Example 1.
When the resulting photosensitive plate was tested in the same manner as described in Example 1, ~cores of thousands of clear prints could be obtained and copied images had a high resolving power.
Example 6 : In 3.4 g of toluene were homogeneously dispersed and dissolved 0 3 g of Phthalocyanine Blue ( Heliogen ~lue 7800 m~nufactured by BASF ), 0.3 g of 2,4,7-trinitro-9-fluorenone and 5 g of an acrylic resin ( Paraloid A-21 manufactured by Rhom & Haas Co. ), and the composition was coated on an aluminum plate so th~t the dry thickness of the co~ting was 8 ~.
25 . Then, 10 g of polyvinylcarbazole ( Luvican M170 ,~
manufactured by BASF AG. ), 1 g of a silicone oil ( KF 96 manufactured by Shinetsu Kogaku Kogyo K. K. ) and 20 g of 2,4,7-trinitro-9-fluorenone were homoge-:
~ - 26 -.~ .
1~20306 neously dissolved in 190 g of tetrahydrofuran, and the solution was coated on the phthalocyanine layer so that the dry thickness of the entire coating (inclusive of the phthalocyanine layer ) was 10 ~.
When the 50 preparet photosensitive plate was tested in the same manner as described in Example 1 except that the polarity of charging was changed to the positive polarity, scores of thousands of clear prints could be obtained and copied images had a very high resolving power.
Comparative Example 1 In 4.4 g of toluene were homogeneously dispersed and dissolved 0.3 8 of Phthalocyanine Blue tHeliogen Blue 7800 manufactured by BASP AG.), 0.03 g of 2,4,7-trinitro-9-fluorenone and 1.0 g of an acrylic resin Paraloid A-21 manufactured by Rhom ~ Haas Co., solid content ~ 30%), and the composition was coated on an aluminum plate so that the dry thickness of the coating was 5 ~.
Then, 10 g of poly-N-vinylcarbazole tLuvican M170 manufactured by BASF AG.), 1 g of a silicone oil (KP 96 manufactured by Shinetsu Kagaku Kogyo K. K.~
and 20 g of 2,4,7-trinitro-9-fluorenone were homogene-ously dissolved in 190 g of tetrahydrofuran. The resulting solution was coated as a top layer on the phthalocyanine layer so that the dry thickness of the entire coating (inclusive of the phthalocyanine layer) was 10 ~. The resulting photosensitive plate were 1~203~
tested in the same manner as described in Example 1 to obtain results shown in Table 1.
Comparative Example 2 In 4.4 g of toluene were homogeneously dispersed and dissolved 0.3 g of Phthalocyanine Blue (Heliogen Blue 7800 manufactured by BASF AG.), 2.0 g of 2,4,7-trinitro-9-fluorenone and 1.0 g of an acrylic resin ~Paraloid A-21 manufactured by Rhom ~ Haas Co.), and the composition was coated on an aluminum plate so that the dry thickness of the coating was 5 ~.
In the same manner as described in Co~parative Example 1, a top layer was formed on the so formed phthalocyanine layer. The resulting photosensitive plate was tested in the same manner as described in Example 1 to obtain results shown in Table 1.
Comparative ExamPle 3 In 6 g of toluene were homogeneously dispersed and dissolved 0.3 g of Phthalocyanine Blue (Heliogen Blue 7800 manufactured by BASF AG.), 0.3 g of 2,4,7-trinitro-9-fluorenone and 3.5 g of an acrylic resin (PR-1112D manufactured Mitsubishi Kasei K. K., solid content = 40%), and the composition was coated on an aluminum plate so that the dry thickness of the coating was 10 ~.
The so obtained photosensitive plate was tested in the same manner as described in Example 1 except that the charging polarity was changed to the positive polarity. Obtained results are shown in Table 1.
_ 28 -Comparative Ex~mPle 4 In 190 g of tetrahydrofuran were homogeneously dissolved 10 g of poly-N-vinylcarbazole ( Luvican M170 manufactured by BASF AG. ) and 20 g of 2,4,7-trinitro-9-fluorenone, and the solution was coated on an aluminum plate so that the dry thickness of the coating was 10 ~.
The so obtained photosensitive plate was tested in the same manner as described in Example 1 to obtain results shown in Table 1.
Com~arative Example 5 In 6 g of toluene were homogeneously dispersed and dissolved 0.3 g of Phthalocyanine Blue ( Heliogen Blue 7800 manufactured by BASF AG ), 0 3 g of 2,4,7-trinitro-9-fluorenone and 0.3 g of a polystyrene resin ( D-150 manufactured by Esso Standard Petroleum K. K, ), and the composi~lon was coated on an aluminum plate so that the dry thickness of the coating was 5 Thus, an intermediate l~yer was formed.
Then, 10 g of poly-N-vinyl carbazole ( Luvican M170 manufactured by BASF AG. ), 1 g of a silicone oil ( KF 96 manufactured by Shinetsu Kagaku Kogyo K. K, ) and 1 g of 2,4,7-trinitro-9-fluorenone were homogen~-ously dissolved in 190 g of tetrahydrofuran, and the solution was coated as a top layer on the phthalocya-nine layer so th~1; the dry thickness of the entire coating ( inclusive of the phthalocyanine layer ) was 10 ~. .
The so obtained photosensitive plate was tested in the same manner as described in Example 1 to o~tain results shown in Table 1.
Comparative Example 6 In the same manner as described in Comparative Ex~mple 5, an intermediate layer having a thickness of 5 ~ was prepared. Then, 10 g of poly-N-vinylcarbazole ( Luvican M170 manufactured by BASF AG. ), 1 g of a sili-cone oil ( KF 96 manufactured by Shinetsu Kagaku Kogyo K. K. ) and 63 g of 2,4,7~trinitro-9-fluorenone were homogeneously dissolved in 190 g of tetrahydrofuran.
The resulting solution was coated as a top layer on the phthalocyanine layer so that the dry thickness of the entire coating ( inclusive of the phthalocyanine layer ~ was 10 ~.
The so obtained photosensitive plate was tested in the same manner as described in Example 1 to obtain results shown in Table 1.
~lZ~306 a~ ~ ~ u~
~ ~ O ~ ~ a x O ~ ~, o ,e , ~ ~
U~ V ~
~ ~ I
1 ~ ~ ~ ~ a x x a J ~ ~ ~ X
d O
V
~ ~D
~ a <J X O O ~ O O O ~ o ~ a V ,~
hr~ ~ O X ~I ~ <3 a) ~o ~ ,, ~ O
a~
~ ~ ~ I
a) ~ V
;~ ~ ~ X XO O ~ ~ ~ ~
~ ~g~l .
~3 V ~1 a x O X X <J O X ~ ~ ~ ~D ~ O
, ~o I
V ~
a O O O O O O O O
~ ~ o ~ o o o ~ o~
al ~ ~ ~ .~ ~, P~ O h ~1 o d rl 0 o a, h P~ ~) ~ h ~ O _~ uq t~ a~ o bO ~ ~! ~ O
O ~0 s~ h ~) ~ y ,~ ~ 0 a~
C ~ ~, a) ~ ~! ~1 0 c~ 1 ~ ~ O ~ u~ 0 0 a~ o ~ o ~ ~,~
I ~ Oq hn 0 ~I C O rt ~: h u~ X ~ h .u~ h ~ a) ~,q ~ rl O h ~ ~¦
V O
l~Z03~6 Notes Sharpness:
Reproducibility of fine lines, meshes, half-tones ~nd small letters, which was evaluated according to the following scale:
O s good A s slightly bad X : bad Densitys The density of the image area ( non-exposed area ), which was evaluated ~ccording to the following scale:
~s dense ~s slightly thin X s thin Foggings Contamination o~ the bac~ground in the non-lmage area ( exposure area ), which was evaluated ~ccording to the following sCale~
~ s not observed ~s slight X s conspicuous Cleaning Propertys Easiness in removing the toner left ~n the photosensitive plate after tran~fer, which was evaluated according to the ~ollowing scales O : very easy A : slightly difficult .
X s difficult 1~Z0306 Resistance to Copying Operation:
The number of good quality prints obtained at the repeated copying operation. which was evaluated according to the following sc~le:
o : ~ore than 20000 prints 1000 - 20000 prints X s less than 1000 prints Color Image Quality~
Reproducibility at printing of a color chart, which was evaluated ~ccording to the following scale:
o : good reproducibility X : no reproducibility ( especially red ) Transfer Efficiencys The ratio of the toner transferred to copying p~per after development, which wPs evaluated according to the following scales O s more than 80 % of the toner was transferred ~s 50 to 80 % of the toner was transferred X s less than 50 % of the toner was transferred Conditions ~or Me~surements by Electrostatic Paper Analyzers Lights 40 Lux Charge~ 5 KV ( negative ) ( positive in Compara-tive Example 3 ) Sensitivitys quantity of light ( Lux-sec ) at which the potential just before exposure decayed to 1/2, which was determined according the Qtatic method 1~0306 Initial potential: saturation ch~rge voltage ( V ) as determined according to the sbdtic method Charge quQntitys saturation voltage ( V ) observed when charging was effected for 10 seconds, which was determlned according to the dynamic method Re~idual potentialt voltage ( Y ) observed 3 seconds after exposure, whlch was deter-mined according to the static method D~rk decays average value of the potentlal decay ( V/sec ) o~er a period of 3 seconds from charge-o~f, which wa~ determined according to the static method Adhesivene~ss The sdhesion strength of the photosensitive layer to the alumlnum sub~trate ( the peel resistance observed when ~n pressure-sensitive adhesive tape was applled to the photosensltive layer and the tape was then peeled off ), which ~as evsluated according to the following scales s strong ~: ordinary X s we~k Example 7 A photosensitive plate w~ prepared in the s~me manner as described in Example 1 except that 2,4,7-- ~4 -1 ~a~3c~6 trinitro-9-fluorenone used in Example 1 was replaced by the same amount of 2,4,5,7-tetranitrofluorenone.
When this photosensitive plate was tested in the same manner as described in Example 1, clear prints similar to these obtained in Example 1 were obtained with a high resistance to the copying operation.
Example 8 A photosensitive plate was prep~red in the same manner as described in Example 1 except that Cyanine Blue BB ( copper phthalocyanine manufactured by Dai-Nippon Ink K. K. ) was used instead of Heliogen Blue 7800. When this photosensitive plate was tested in the same manner a8 described in Example 1, clear prints ~imilar to those obtained in Example 1 were o~tained 5 wlth a high re~istance to the copying operation.
x~mple 9 An intermediate layer wa~ prepared in the same manner a~ described in Example 1. Then, 10 g o~ poly-N-vinylphenothiazine, 1 g of ~ silicone oil ( KF 96 m~nufac~ured by Shinetsu Kag~ku Kogyo K. K. ) and 20 g of 2,4,7-trlnitro-9Lfluorenone were homogeneously dissolved in 190 g of tetr~hydrofuran, and the ~olution was coated as a top layer on the intermediate phthalo-cyanine layer so that the dry thickness of the entire coating ( inclusive of the phthalQcyanine layer ) was 10 ~. When the 80 prepared photosensitive plate was tested in the same manner as in Example 1, clear prints could be obtained with a high resistance to the printing operation.
Claims (7)
1. A laminated photosensitive material for electrophotography, which comprises an electrically conductive substrate, an intermediate layer formed on the substrate and a top layer laminated on said inter-mediate layer, wherein the intermediate layer comprises, incorporated in a binder, (A) phthalocyanine or a phthslocyanine derivative and (B) a polycyclic aromatic nitro compound at an (A)/(B) mixing weight ratio of from 10/5 to 10/40 and the top layer comprises (C) an organic polymeric photoconductor and (B) said polycyclic aromatic nitro compound at a (C)/(B) mixing weight ratio of from 6/1 to 1/6.
2. A laminated photosensitive material as set forth in claim 1 wherein the organic polymeric photo-conductor (C) is polyvinyl carbazole or a nuclear substitution derivative thereof.
3. A laminated photosensitive material as set forth in claim 1 wherein the poly cyclic aromatic nitro com-pound (B) is at least one member selected from the group consisting of trinitrofluorenone and tetranitrofluore-none.
4. A laminated photosensitive material as set forth in claim 1 wherein the phthalocyanine or phthalocyanine derivative (A) is at least one member selected from the group consisting of metal-free phthalocyanines and nuclear substitution derivatives thereof.
5. A laminated photosensitive material as set forth in claim 1 wherein the binder is an acrylic resin,
6. A laminated photosensitive material as set forth in claim 1 wherein the top layer further comprises a silicone oil in an amount of 1 to 30 parts by weight per 100 parts by weight of the organic polymeric photoconductor (C).
7. A laminated photosensitive material as set forth in claim 1 wherein the intermediate layer has a thickness of 1 to 40 µ and the top layer has a thickness of 1 to 40 µ.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000294897A CA1120306A (en) | 1978-01-13 | 1978-01-13 | Photosensitive material containing an organic polymeric photoconductor, phthalocyanine derivative and an electron acceptor polycyclic aromatic nitro compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000294897A CA1120306A (en) | 1978-01-13 | 1978-01-13 | Photosensitive material containing an organic polymeric photoconductor, phthalocyanine derivative and an electron acceptor polycyclic aromatic nitro compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1120306A true CA1120306A (en) | 1982-03-23 |
Family
ID=4110525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000294897A Expired CA1120306A (en) | 1978-01-13 | 1978-01-13 | Photosensitive material containing an organic polymeric photoconductor, phthalocyanine derivative and an electron acceptor polycyclic aromatic nitro compound |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1120306A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113711007A (en) * | 2019-04-24 | 2021-11-26 | 株式会社岛津制作所 | Method for determining generation source of fine particles in atmosphere |
-
1978
- 1978-01-13 CA CA000294897A patent/CA1120306A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113711007A (en) * | 2019-04-24 | 2021-11-26 | 株式会社岛津制作所 | Method for determining generation source of fine particles in atmosphere |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3573906A (en) | Electrophotographic plate and process | |
| US4226928A (en) | Laminated photosensitive material for electrophotography | |
| US4388392A (en) | Laminated photosensitive plate for electrophotography having an electron donative polymer and phenanthrene charge transport layer | |
| US3869285A (en) | Plate-making master and method for producing a printing plate which does not require dampening water | |
| US4214907A (en) | Photosensitive material for electrophotography having a polyvinyl carbazole derivative, phthalocyanine, and an electron-acceptor | |
| US4547447A (en) | Photosensitive members for electrophotography containing phthalocyanine | |
| US4748099A (en) | Process for forming printing plate using an electrophotographic material for obtaining toner image | |
| US4030923A (en) | Mixture of binder materials for use in connection with a charge transport layer in a photoconductor | |
| JP3244246B2 (en) | Electrophotographic photoreceptor and electrophotographic apparatus | |
| US3723110A (en) | Electrophotographic process | |
| CA1120306A (en) | Photosensitive material containing an organic polymeric photoconductor, phthalocyanine derivative and an electron acceptor polycyclic aromatic nitro compound | |
| CA1119449A (en) | Photosensitive material containing an organic polymeric photoconductor, phthalocyanine derivative and an electron acceptor polycyclic aromatic nitro compound | |
| JP2565400B2 (en) | Electrophotographic photoreceptor using styrene-maleic anhydride copolymer as polymer binder | |
| US5320922A (en) | Electrophotographic photosensitive member and apparatus using same | |
| CA1127900A (en) | Photoconductive composition containing an organic polymeric photoconductor, an aromatic polycyclic nitro compound and a phthalocyanine | |
| JP3684044B2 (en) | Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus having the electrophotographic photoreceptor | |
| JPH1165141A (en) | Electrophotographic photoreceptor and process cartridge and electrophotographic apparatus each having this photoreceptor | |
| US4076528A (en) | Xerographic binder plate | |
| US4055420A (en) | Single phase organic photoconductive composition | |
| JP3697038B2 (en) | Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus having the electrophotographic photoreceptor | |
| JPH0715581B2 (en) | Electrophotographic photoreceptor | |
| JP3684043B2 (en) | Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus having the electrophotographic photoreceptor | |
| JP3535698B2 (en) | Electrophotographic photoreceptor, process cartridge having the electrophotographic photoreceptor, and electrophotographic apparatus | |
| JPS60249153A (en) | Laminate type electrophotographic sensitive body | |
| JP2879372B2 (en) | Electrophotographic photoreceptor, electrophotographic apparatus provided with the electrophotographic photoreceptor, and facsimile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |