Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
  • G03G5/07—Polymeric photoconductive materials
  • G03G5/071—Polymeric photoconductive materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • G03G5/072—Polymeric photoconductive materials obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising pending monoamine groups
  • G03G5/073—Polymeric photoconductive materials obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising pending monoamine groups comprising pending carbazole groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
  • C08F26/12—N-Vinyl-carbazole
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/18—Introducing halogen atoms or halogen-containing groups
  • C08F8/20—Halogenation

Definitions

• An electrophotographic photosensitive material comprises a polymer containing a chlorine and bromine substituted 9-vinylcarbazole unit.
• the present invention relates to electrophotographic photosensitive materials.
• many organic compounds have been known as photoconductive materials for electrophotographic photosensitive materials, and some compounds have been known to have fairly high photosensitivity. Nevertheless in the existing state of things it can be said that examples wherein organic photoconductive materials are used as an electrophotographic photosensitive material are extremely few. Compared with inorganic photoconductive materials, the organic photoconductive materials have many superior performances providing extremely useful application techniques in the technical fields of electrophotography or photosensitive materials.
• organic photoconductive materials despite with those characteristics excellent in many points have been unable to contribute sufficiently up to the present time in the technical field of electrophotography is due to its low sensitivity.
• its sensitivity is remarkably lower than that of selenium and zinc oxide, the well known photosensitive materials.
• An object of the present invention is to provide a high photosensitivity organic electrophotographic photosensitive materials to enhance the industrial value of electrophotographic sensitive materials remarkably.
• Another object of the present invention is to provide a novel means in respect of synthesizing techniques of organic photoconductive materials by developing a manufacturing method for new organic photoconductive materials.
• the other object of the present invention is to provide stable organic photoconductive materials free from deterioration in photosensitivity with elapsed time during long term preservation.
• Still another object of the present invention is to provide organic photoconductive materials easy to handle at the time of manufacture.
• Still another object of the present invention is to provide electrophotographic photosensitive materials having high photosensitivity equivalent to or higher than inorganic photoconductive materials by applying various sensitizing means.
• an electrophotographic photosensitive material which comprises a polymer having a chlorine and bromine substituted 9-vinylcarbazole unit.
• polymer containing a chlorine and bromine substituted 9-vinylcarbazole unit includes a polymer containing both a chlorine substituted 9-vinylcarbazole unit and a bromine substituted 9-vinylcarbazole unit, a polymer containing both a chlorine and bromine substituted 9-vinylcarbazole unit and a chlorine or bromine substituted 9-vinylcarbazole unit, and a polymer containing a chlorine and bromine substituted 9-vinylcarbazole unit, a chlorine substituted 9-vinylcarbazole unit and a bromine substituted 9-vinylcarbazole unit as well as a polymer containing only a chlorine and bromine substituted 9-vinylcarbazole unit as a halogenated 9-vinylcarbazole unit.
• the polymer containing a chlorine and bromine substituted 9-vinylcarbazole unit may be prepared by various methods. For example, a chlorine substituted poly-9- vinylcarbazole is brominated, or a bromine substituted poly-9-vinylcarbazole is chlorinated, or a chlorine and bromine substituted 9-vinylcarbazole is polymerized or copolymerized with other monomer.
• Photosensitivity of the polymer of this invention mainly depends on chlorine content.
• the bromine content affects the photosensitivity.
• the chlorine and bromine substituted poly-N-vinylcarbazole without bringing about surface potential drop maintains outstanding photosensitivity, and at the same time, is excellent in the applicability to coloring matter sensitizing methods, and particularly to the so-called free radical sensitising method disclosed in US. application Ser. No. 843,809, filed July 22, 1969 and US. application Ser. 858,540, filed Sept. 16, 1969 applied for by these applicants, that is, the sensitizing methods characterized by causing free radicals produced by irradiation of radiation to act upon organic photoconductive materials, moreover by combining with those sensitizing methods, it is possible to obtain high sensitivity exceeding the inorganic photoconductive material systems.
• the chlorine and bromine substituted poly-N-vinyl carbazole of the present invention may be prepared by means of successive halogenation of poly-N-vinylcarbazole, or polymerization of a chlorine and bromine substituted 9-vinylcarbazole.
• poly-N vinylcarbazole can be chlorinated approximately quantitatively and up to optional substitutability (until nCl4) by using as solvents aliphatic hydrocarbon halides such as methylene chloride, chloroform, and 1,2-dichloroethane, or aromatic hydrocarbons such as benzene and chlorobenzene and adding sulfuryl chloride, and the substitution positions are mainly at first at 8-position, next '6-position, then l-position and under normal conditions it is inferable from the infra-red spectrum that 1, 3, 6 and 8 tetra substitute is obtainable finally.
• aliphatic hydrocarbon halides such as methylene chloride, chloroform, and 1,2-dichloroethane
• aromatic hydrocarbons such as benzene and chlorobenzene and adding sulfuryl chloride
• reaction solution was violently stirred into a large amount of methanol causing polymers to precipitate, and further dissolved in chlorobenzene, and the methanol precipitation was repeated twice.
• Chlorination is possible by introducing chlorine gas under attentive control of conditions, besides using sulf-ury chloride as described above. For instance, introduction of fine current of chlorine gas at a temperature close to -5 C. stirring with high velocity etc., but in the cases where not so little amount of chlorine substitution is to be made respecting halogenated poly-N-vinylcarbazole of which the number of substitution of halogen atoms n is near 1.5 and above, or poly-3,6-dihalogen substituted- N-vinylcarbazole, high reproducibility is obtained comparatively with ease. In such a case temperature close to room temperature will sufficiently serve for reaction.
• a method either to cause N-bromimide and peroxides to react in chlorobenzene or cause bromine to react in pyridine is suitable.
• bromine atoms substitute mainly at first at 3-position, then at 6-position.
• N-brornimides N-bromosuccinic acid imide, N- bromo-l, 1'-dimethylsuccinic acid imide, N-bromocaprolactam, N-bromophthalimide, and as peroxides, benzoyl peroxide, lauroyl peroxide etc. are suitable.
• chlorine and bromine substituted poly-N-vinylcarbazole (X) was obtained from 1 mol. of chlorinated poly-N-vinylcarbazole (III) which was synthesized by the synthesis Example 1 and 0.5 mol. of N-bromosuccinic imide and lauroyl peroxide; also chlorine and bromine substituted poly-N-vinylcarbazole (XI) was obtained from 1 mol. of chlorinated poly-N-vinylcarbazole (IV) and 1 mol. of N-bromosuccinic imide and lauroyl peroxide.
• TAB LE 3 Total Chlorine and bromine substituted halogen, poly-N-vinylcarbazole percent 'nCl 'nBr 11.
• succinimide produced as a by-product was filtrated and again returned into the reaction vessel and attaching a dropping funnel to the 4-port flask and calcium chloride pipe to the reflux condenser respectively, and cooled the internal temperature to 0 C. and drop methylene chloride v./v. percent solution of sulfuryl chloride.
• the reaction mixture was stirred for one hour and the reaction mixture was poured into a large amount of methanol and the separated polymer was filtrated and again dissolved in chlorobenzene, to precipitate with methanol and dry in a vacuum, and 4.1 g. of white polymer (XIII) was obtained.
• Infrared spectrum of polymer of (XVI) is similar to that of 1,3,6,8-tetrachlorocarbazole (M.P. 213 C.) produced by passing a calculated quantity of chlorine gas in carbon disulfide and under reflux to carbazole and that of chlorinated poly-N-vinylcarbazole (VIII). Accordingly carbazole having halogen substitution positions at 1, 3, 6 and 8 positions is considered to constitute the main ingredient and, by bromination succeeding chlorination, bromine atoms are considered to substitute firstly at l-position then at 8-position.
• a polymer containing a chlorine and bromine substituted 9-vinylcarbazole unit may be obtained by polymerizing various chlorine and bromine substituted 9-vinylcarbazole. Or also by copolymerizing with other monomers.
• chlorine and bromine substituted 9-vinylcarbazole there are preferably mentioned monochloromonobromo-9lvinylcarbazole and dichloromonobromo-9-vinylcarbazole.
• This process is characterized by giving extremely powerful sensitizing effects to organic photoconductive materials and to some of organic photoconductive materials it gives a sensitivity enabling to constitute a sensitive material with high sensitivity equivalent to or higher than that of the well-known coloring matter sensitized zinc oxide and selenium.
• the coloring matter sensitizing means is to add spectral characteristic to organic photoconductive materials
• the Lewis acid sensitization is a sensitization effect based upon the appearance of C-T band (spectral adsorption sensitivity region due to complex formation) due to the growth of complex of donoracceptor between the organic photoconductive materials
• the free radical sensitization means is considered to be a structural sensitization effect wherein extremely active free radicals produced by irradiation of radiation energy bombard the organic photoconductive materials forming a sensitizing center partially.
• brominated poly-9-vinylcarbazole is improved in its photosensitivity against poly-9-vinylcarbazole, but its practicality is discounted because of the fact that it cannot expect adequate sensitization effects in application of sensitization means for practical use, and that particularly the free radical sensitization means which is most powerful and effective for providing practically usable organic photosensitive materials cannot be adequately applied thereto.
• brominated poly-9-vinylcarbazole is unstable tending to respond to heat and long term preservation and cause debromination so that it has low commercial value.
• polymers of the present invention which contain a chlorine and bromine substituted 9-vinylcarbazole unit provides photosensitive materials having a great commercial value in the following points.
• the said polymers have sufliciently overcome the defects of the conventional brominated poly- 9-vinylcarbazole and iodized poly-9-vinylcarbazole in practical applications, in addition, the largest characteristic is that it is extremely excellent in applicability to sensitization means which brings about a practical value of organic photosensitive material.
• chlorinated poly-9-vinylcarbazole is extremely excellent in application value to free radical sensitization, and a chlorine and bromine substituted poly-9-vinylcarbazole has markedly improved sensitization efficiency for coloring matter sensitization as is clarified by comparison examples and examples described later, and is able to provide sensitive materials with elevated sensitivity usable without reducing free radical sensitization elfect even in combined utilization of free radical sensitization means and coloring matter sensitization means.
• Halogen atom content shows number of chlorine and bromine atoms contained per vinylcarbazole ring g 2.0 Chlorobenzene ml 40
• free radical sensitization shows specific sensitivity obtained by adding 10 ml. of carbon tetrabromide to the solution before applying to the film base, and putting it into a hard glass Erlenmeyer flask and while stirring applied photochemical reaction treatment at a distance of 10 cm. with a w. high pressure mercury arc lamp for 5 minutes and then allowed to stand in dark place for 24 hours then applied to the film base, and coloring matter sensitization shows the specific sensitivity in the case where application to film base was made after adding 2.0 mg. of Crystal Violet to the above mentioned solution.
• Free radical sensitization plus coloring matter sensitization shows the specific sensitivity in the case where the above mentioned solution whereto 100 mg. of carbon tetrabromide and 2.0 mg. of Crystal Violet had been added was applied to the film base after undergoing a photochemical reaction treatment similar to that described respecting free radical sensitization.
• Value of specific sensitivity was decided as 100 when the sample polymer was poly-9-vinylcarbazole and was expressed as a reciprocal of exposure amount required to attenuate the charge potential to its by exposure.
• the exposure light source is a tungsten lamp and the initial charge voltage was approximately 500 v. for each sample.
• Free radical sensitization Halogen plus content Free Coloring coloring radical matter matter
• a chlorine and bromine substituted poly-9- vinylcarbazole of the present invention provides sensitive materials with high sensitivity when subjected to free radical sensitization and coloring matter sensitization.
• the above-mentioned polymer may be used in a form of self-supporting material such as thin film or textile, or in a form of a thin layer on an electroconductive support for electrophotographic photosensitive material.
• the polymer solution may be applied to a glass plate followed by peeling the coating after drying to obtain a self-supporting film, or the polymer melt is extruded to form fibers followed by wearing them, or the polymer solution is coated on an electronductive support.
• an additive for adjusting photographic property such as sensitizer and an additive for adjusting physical property of film such as plasticizer and opaque-imparting agent.
• Lewis acids for example, polynitro compounds such as 1,3,5-trinitrobenzene, picric acid, S-nitroacenaphthene and 2,4,7-trinitrofluorenone, carboxylic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and salicyclic acid, sulfonic acid such as benzene sulfonic acid and p-toluene sulfonic acid, sulfonic acid chloride such as p-toluene sulfonyl chloride, and optical sensitizer such as Crystal Violet, Malachite Green, Methylene Blue, Brilliant Green, Meth'ylene Blue, Quinizaline.
• polynitro compounds such as 1,3,5-trinitrobenzene, picric acid, S-nitroacenaphthene and 2,4,7-trinitrofluorenone
• carboxylic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and salicyclic
• plasticizers there may be mentioned dibutylphthalate, dioctylphthalate, tricresylphosphate and polyphenyl chloride.
• free radical formers particularly effective for the polymer containing a chlorine and bromine substituted 9-vinylcarbazole unit of this invention there may be mentioned polyhalogen compounds such as iodoform, carbon tetrabromide, bromoform, bromotrichloromethane and hexachloroethane.
• aromatic amines there may be mentioned 9-vinylcarbazole, 3 chloro 9 vinylcarbazole, 3-bromo-9-vinylcarbazole, diphenylamine, and triphenylamine.
• leuco Malachite Green and leuco Crystal Violet As leuco form of coloring matters, there may be mentioned leuco Malachite Green and leuco Crystal Violet.
• a solution of these components in benzene or monochlorobenzene is irradiated with a high pressure mercury lamp to cause a reaction and then coated on a support such as aluminum plate, paper and film followed by drying to form a photosensitive plate.
• the free radical sensitizing method may be used together with conventional optical sensitization and Lewis acid sensitization.
• the radiation energy source may be appropriately selected depending upon free radical former and solvent used. Any source may be used which can produce a free radical from the free radical former in the sensitizing treatment system.
• a light source capable of emitting a large amount of ultraviolet ray such as mercury lamp (low pressure, high pressure, and super high pressure), metal halide lamp and xenon lamp, is preferred.
• Amount of free radical former preferably ranges from one to 30% by weight of the basis of polymer, but not restricted to said range.
• the electrophotographic photosensitive material according to this invention can be used for producing images by using conventional charging and developing means such as corona discharging, magnet brush development, and electrophoresis development.
• EXAMPLE 2 0n solvent-proof (coated polyvinyl alcohol approximately 2 g./m. processed paper weighing 60 g./m. coated a photosensitive solution mainly consisting of various chlorine and bromine substituted poly-N-vinylcarbazole shown in the following Table 6 and after drying in a vacuum prepared electrophotographic sensitive paper. Photosensitivity and image definition of these sensitive paper are shown in Table 6. In this example the above mentioned sensitive solution were made according to three diiferent prescriptions to investigate performance of chlorine and bromine substituted poly-N-vinylcarbazole.
• a photosensitive solution was prepared in the following manner applying the prescription for free radical sensitization in the sensitizing method column in Table 6.
• nBr 0.48 trinitrofluorenone.
• (XV) .. ⁇ nC1 2.0 ⁇ Free radical 25 75 Clear.
• nBr 0.81 2l1$ltll2h on.
• (XVII)...- . ⁇ nCl 3.0 ⁇ Free radical 23 81 Clear.
• nBr 1.70 sensitization.
• ⁇ nCl 2.0 do 23 70 Do.
• Luvican M-170 is trade name of Badische Anilin und Soda Fabrik.
• Photosensitive plates prepared in this manner were mounted on a rotary electrometer and were charged negatively, then exposure was made with tungsten lamp, and the reciprocals of exposure time necessary to attenuate the potential to A and to were decided as the value of photosensitivity, and the result of comparison of the sens1t1vity is shown in the following table.
• As the potential at starting time approximately 500 v. was chosen respecting each sample.
• This laminate type cylinder is able to form images by means of various processes.
• An electrophotographic photosensitive material which comprises a polymer containing a chlorine and bromine substituted poly-9-vinylcarbazole containing at least 0.2 atom of each of chlorine and bromine per one 9-vinylcarbazole ring and the sum of chlorine atom and bromine atom per one 9-vinylcarbazole ring being 0.4 atom to 4.0 atoms.
• chlorinated and brominated 9-vinylcarbazole is at least one of monochloromonobromo-9-vinylcarbazole and dichloro-monobromo-9- vinylcarbazole.
• dichloro-monobromo-9- vinylcarbazole is at least one of 1,3-dich1oro-6-bromo-9- vinylcarbazole and 1,6-dichloro-3-bromo-9-vinylcarbazole.
• An electrophotographic photosensitive material ac- 16 cording to claim 8 in which the vinyl monomer is 9-vinylcarbazole.
• sensitizing agent is a combination of a sensitizing dye and a Lewis acid.
• An electrophotographic photosensitive material which comprises a polymer containing a chlorine and bromine substituted 9-vinylcarbazole repeating unit containing at least 0.2 atom of each of chlorine and bromine per one 9-vinyl carbazole ring and the sum of chlorine atom and bromine atom per one 9-vinyl carbazole ring being 0.4 atom to 4.0 atom which has been subjected to photochemical reaction treatment by applying a radiation energy thereto in the presence of a free radical former capable of producing a free radical when irradiated by a radiation energy.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• General Chemical & Material Sciences (AREA)
• Photoreceptors In Electrophotography (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Indole Compounds (AREA)

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Cited By (6)

• 1969
  • 1969-07-18 JP JP44056806A patent/JPS495066B1/ja active Pending
• 1970
  • 1970-07-15 US US55215A patent/US3705031A/en not_active Expired - Lifetime
  • 1970-07-15 US US55216A patent/US3702764A/en not_active Expired - Lifetime
  • 1970-07-17 DE DE2035664A patent/DE2035664B2/de active Granted
  • 1970-07-17 BE BE753620A patent/BE753620A/xx unknown
  • 1970-07-17 GB GB3479370A patent/GB1329101A/en not_active Expired

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