JP5170391B2 - Binder resin for the photosensitive layer of electrophotographic photoreceptors. - Google Patents

Description

The present invention relates to a binder resin for a photosensitive layer of an electrophotographic photosensitive member containing a terminal silicone-modified polycarbonate and an electrophotographic photosensitive member using the binder resin.

At present, electrophotographic technology is widely applied to copying machines, laser beam printers (hereinafter abbreviated as LBP), fax machines, etc. due to its high speed and high image quality.

Conventionally, inorganic photoconductive materials such as selenium, selenium / tellurium alloys, selenium / arsenic alloys, cadmium sulfide have been mainly used as electrophotographic photoreceptors in this electrophotographic technology. However, recently, an electrophotographic photoreceptor using an organic photoconductive substance has been developed from the viewpoint of toxicity, safety, price, productivity, and the like.

There are two types of electrophotographic photoreceptors using an organic photoconductive material: a laminate type divided into a charge generation layer and a charge transport layer and a single layer type in which both layers are mixed. Yes. For the purpose of retaining a low molecular charge transport agent contained in the charge transport layer, various binder resins are usually used and dissolved in a solvent to form a coating film.

Binder resins include vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, and copolymers thereof, various thermoplastic resins such as polycarbonate, polyester, polysulfone, phenoxy resin, epoxy resin, and silicone resin, and thermosetting. Resin has been used. Electrophotographic photoreceptors using these various binder resins can be easily formed into thin films by a cast film forming method, are suitable for mass production, and are relatively inexpensive. Of these various resins, polycarbonate resin has relatively excellent characteristics and is often used (see Patent Reference 1).

Among these, it has been reported that a polycarbonate resin having a silicone chain is effective as a binder resin for an electrophotographic photoreceptor excellent in wear resistance (see Patent Document 2 and Patent Document 3).

On the other hand, with the spread of LBP and digital multi-function peripherals to small-scale offices and general households, various problems due to inadequate maintenance have occurred. Among them, the surface of the outermost layer of the photoconductor is contaminated with dust, fingerprints, oil, cleaning liquid, a large amount of toner, etc. when the photoconductor unit is replaced, and the initial printed image deteriorates so that it cannot be recovered immediately by the cleaning blade. Cases have been reported.

The conventional polycarbonate resin is not sufficient for the contamination that causes deterioration of the initial printed image, and the binder resin having improved stain resistance against dust, fingerprints, oil, cleaning liquid, and a large amount of toner. There was a request.
Japanese Patent Application Laid-Open No. 60-172044 JP-A-5-155999 JP-A-5-306335

  SUMMARY OF THE INVENTION An object of the present invention is to provide a binder resin for a photosensitive layer that has improved stain resistance against dust, fingerprints, oil, cleaning liquid, a large amount of toner and the like that cause deterioration of an initial printed image.

As a result of intensive studies to solve the conventional problems, the present inventors have used a conventional binder resin for an electrophotographic photoreceptor using a binder resin in which a small amount of a specific terminal silicone-modified polycarbonate is added to the photosensitive layer. Compared to the conventional electrophotographic photoreceptor, it has been found that the toner can be removed more easily and it is difficult to get wet with alcohol-based cleaning agents, and it has been found to improve the stain resistance when the photoreceptor unit is replaced, thereby completing the present invention. It was.
That is, the present invention relates to the following binder resin for a photosensitive layer and an electrophotographic photoreceptor using the same.

（Ｒ₆及びＲ₇は炭素数１〜１０のアルキレン基を表し、Ｒ_１〜Ｒ_５は水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１〜９のアルキル基、炭素数１〜５のアルコキシ基又は炭素数６〜１２のアリール基を表す。ｂは１〜１００の整数を表す。）

（２）前記一般式（Ａ）中のＲ_１〜Ｒ_５がメチル基、ブチル基又はフェニル基である（１）記載の感光層用バインダー樹脂。

（３）前記一般式（Ａ）中のＲ_６及びＲ_７が炭素数１〜６のアルキレン基である（１）又は（２）記載の感光層用バインダー樹脂。

（４）前記一般式（Ａ）中のｂが１〜２０である（１）〜（３）いずれかに記載の感光層用バインダー樹脂。

（５）末端変性ポリカーボネート樹脂が、下記一般式（１）で表される繰り返し単位を有する（１）記載の感光層用バインダー樹脂。

（式中、Ｒ₈〜Ｒ₁₁は水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１〜９のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、または炭素数７〜１７のアラルキル基である。（A）は請求項１記載の一般式（A）を表す。ｎは１以上の整数を表す。Ｘは、

であり、Ｒ₁₂、Ｒ₁₃は水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１〜９のアルキル基、炭素数１〜５のアルコキシ基、または炭素数６〜１２のアリール基を表す。さらにＲ₁₂及びＲ₁₃が一緒に結合して、炭素環または複素環を形成する基形成しても良い。aは０〜２０の整数を表す。)
（６）一般式（１）で表される繰り返し単位が、２，２−ビス（４−ヒドロキシフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、１，１−ビス（４−ヒドロキシ−３−メチルフェニル）シクロヘキサン、１，１−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、ビス（４−ヒドロキシフェニル）メタン、又は１，１‘−ビフェニル−４，４’−ジオールから誘導されたものである（５）記載の感光層用バインダー樹脂。
（７）バインダー樹脂が、２，２−ビス（４−ヒドロキシフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、１，１‘−ビフェニル−４，４’−ジオール、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、ビス（４−ヒドロキシフェニル）メタン、又は１，１−ビス（４−ヒドロキシフェニル）エタン由来の構成単位を主構成単位とするポリカーボネート樹脂である（１）記載の感光層用バインダー樹脂。
（８）導電性基体上に感光層を有する電子写真感光体であって、該感光層におけるバインダー樹脂として（１）〜（７）何れか記載の感光層用バインダー樹脂を用いることを特徴とする電子写真感光体。
（９）（８）記載の電子写真感光体を備えている画像形成装置。
(1) A binder resin used for a photosensitive layer of an electrophotographic photosensitive member, having a terminal group represented by the following general formula (A) and having an intrinsic viscosity of 0.05 to 0.50 dl / g A binder resin for a photosensitive layer containing 0.1 to 10.0% by weight of a modified polycarbonate resin.

(R ₆ and R ₇ represent an alkylene group having 1 to 10 carbon atoms, and R _{1 to} R ₅ are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, and a carbon number. Represents an alkoxy group having 1 to 5 or an aryl group having 6 to 12 carbon atoms, and b represents an integer of 1 to 100.)

(2) The binder resin for a photosensitive layer according to (1), wherein R _{1 to} R ₅ in the general formula (A) are a methyl group, a butyl group, or a phenyl group.

(3) The binder resin for a photosensitive layer according to (1) or (2), wherein R ₆ and R ₇ in the general formula (A) are an alkylene group having 1 to 6 carbon atoms.

(4) The binder resin for a photosensitive layer according to any one of (1) to (3), wherein b in the general formula (A) is 1 to 20.

(5) The binder resin for photosensitive layers according to (1), wherein the terminal-modified polycarbonate resin has a repeating unit represented by the following general formula (1).

Wherein R _{8 to} R ₁₁ are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkenyl having 2 to 5 carbon atoms. A group, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, (A) represents the general formula (A) according to claim 1. n represents an integer of 1 or more. Is

R ₁₂ and R ₁₃ are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl having 6 to 12 carbon atoms. Represents a group. Further, R ₁₂ and R ₁₃ may be bonded together to form a group that forms a carbocyclic or heterocyclic ring. a represents an integer of 0 to 20. )
(6) The repeating unit represented by the general formula (1) is 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4- Hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) methane, or 1 The binder resin for photosensitive layers according to (5), which is derived from 1,1′-biphenyl-4,4′-diol.
(7) The binder resin is 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1′-biphenyl-4,4′-diol, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) methane, or 1,1-bis (4-hydroxy) The binder resin for photosensitive layers according to (1), which is a polycarbonate resin having a structural unit derived from phenyl) ethane as a main structural unit.
(8) An electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, wherein the binder resin for a photosensitive layer described in any one of (1) to (7) is used as a binder resin in the photosensitive layer. Electrophotographic photoreceptor.
(9) An image forming apparatus comprising the electrophotographic photosensitive member according to (8).

  The electrophotographic photosensitive member using the binder resin for the photosensitive layer to which a small amount of the specific terminal silicone-modified polycarbonate of the present invention is added can easily remove the toner as compared with the conventional electrophotographic photosensitive member using the binder resin. It exhibits the property that it is difficult to get wet with alcohol-based cleaning agents, and the contamination resistance when the photosensitive unit is replaced is improved. Therefore, it contributes to the stability of the image quality at the initial stage of replacement, and is effective in saving paper and toner, extending the life of the photoreceptor, and improving the replacement workability. Furthermore, since it can be used by adding a small amount of the terminal silicone-modified polycarbonate of the present invention to a conventional binder resin, there is an advantage that it can be produced with almost no change in the electrophotographic photoreceptor production process and materials.

The electrophotographic photoreceptor of the present invention can be used for a single-layer photosensitive layer on a conductive substrate or a functionally separated laminated type, but the properties of the binder resin holding the charge transport material are sufficient. It is preferably used for a charge transport layer of a multi-layer electrophotographic photosensitive member that is easy to exhibit.

Examples of the conductive substrate of the present invention include metal materials such as aluminum, stainless steel, and nickel, polyester films provided with a conductive layer such as aluminum, palladium, tin oxide, and indium oxide on the surface, phenol resin, and paper. It is done.

The charge generation layer of the present invention is formed on a conductive support by a known method. As the charge generation material, for example, organic pigments such as azoxybenzene, disazo, trisazo, benzimidazole, polycyclic quinoline, indigoid, quinacridone, phthalocyanine, perylene, and methine can be used. . These charge generation materials are made of fine particles such as polyvinyl butyral resin, polyvinyl formal resin, silicone resin, polyamide resin, polyester resin, polystyrene resin, polycarbonate resin, polyvinyl acetate resin, polyurethane resin, phenoxy resin, epoxy resin, and various celluloses. Used in a form dispersed in a binder resin.

  The charge transport layer of the present invention is formed by dispersing a charge transport material on the charge generation layer by a known method in a binder resin to which the terminal-modified polycarbonate of the present invention is added. Examples of the charge transport material include polytetracyanoethylene; fluorenone compounds such as 2,4,7-trinitro-9-fluorenone; nitro compounds such as dinitroanthracene; succinic anhydride; maleic anhydride; dibromomaleic anhydride; Triphenylmethane compounds; oxadiazole compounds such as 2,5-di (4-dimethylaminophenyl) -1,3,4-oxadiazole; styryl compounds such as 9- (4-diethylaminostyryl) anthracene Carbazole compounds such as poly-N-vinylcarbazole; pyrazoline compounds such as 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline; 4,4 ′, 4 ″ -tris (N, N-diphenylamino); Triphenylamine, N, N′-bis (3-methylphenyl) -N, N′-bi Amine derivatives such as (phenyl) benzidine; conjugated unsaturated compounds such as 1,1-bis (4-diethylaminophenyl) -4,4-diphenyl-1,3-butadiene; 4- (N, N-diethylamino) benzaldehyde-N Hydrazone compounds such as N-diphenylhydrazone; including indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, pyrazoline compounds, triazole compounds, etc. Examples thereof include nitrogen cyclic compounds, condensed polycyclic compounds, etc. The above charge transport materials may be used alone or in combination.

The terminal-modified polycarbonate of the present invention is a known method used for producing a polycarbonate from bisphenol A and a carbonic acid ester-forming compound, for example, a direct reaction between bisphenols and phosgene (phosgene method), or bisphenols and bisaryl. It can be produced by a method such as transesterification with carbonate (transesterification method).

Specific examples of the raw material bisphenol used in the production of the terminal-modified polycarbonate in the present invention include 1,1′-biphenyl-4,4′-diol, bis (4-hydroxyphenyl) methane, and bis (4-hydroxy). Phenyl) ether, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis ( 4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2 -Bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) silane Clopentane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 1,1-bis (4-hydroxyphenyl) -3 , 3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-allylphenyl) propane, 2,2-bis (4- Hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9- Bis (4-hydroxy-3-methylphenyl) fluorene, 4,4 '-[1,4-phenylene bi (1-methylethylidene)] bisphenol, 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 4,4'-butylidenebis (3-methyl-6-t-butyrylphenol) Etc. are exemplified. Two or more of these may be used in combination. Of these, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, , 1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1′-biphenyl-4,4′- Preferably selected from diols.

On the other hand, examples of the carbonate ester-forming compound include phosgene and bisallyl carbonate such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Two or more of these compounds can be used in combination.

In the phosgene method, the bisphenols and phosgene are usually reacted in the presence of an acid binder and a solvent. Examples of the acid binder include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and examples of the solvent include methylene chloride and chloroform. Further, a tertiary amine catalyst such as triethylamine or a quaternary ammonium salt such as benzyltriethylammonium chloride is used to promote the condensation polymerization reaction. In the present invention, the terminal-modified polycarbonate of the present invention can be obtained by reacting a monochloroformate having a polysiloxane group as a terminal stopper for adjusting the degree of polymerization. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite, or a branching agent such as phloroglucin, isatin bisphenol, or trisphenol ethane may be added. The reaction is usually in the range of 0 to 150 ° C, preferably 5 to 40 ° C. While the reaction time depends on the reaction temperature, it is generally 0.5 min-10 hr, preferably 1 min-2 hr. Further, during the reaction, it is desirable to maintain the pH of the reaction system at 10 or more.

On the other hand, in the transesterification method, bisphenols, bisaryl carbonate, and an alcohol or carbonate having a polysiloxane group are mixed and reacted at high temperature under reduced pressure. Even if they are added at the same time, after reacting bisphenols and bisaryl carbonate first, an alcohol or carbonate having a polysiloxane group is added, or a polycarbonate having a terminal phenolic hydroxyl group previously obtained by the phosgene method is added. A carbonate having a polysiloxane group can be added and reacted. The reaction is usually carried out at a temperature in the range of 150 to 350 ° C., preferably 200 to 300 ° C., and the degree of vacuum is preferably 1 mmHg or less, and the phenol derived from the bisaryl carbonate produced by the transesterification reaction. The product is distilled out of the system. The reaction time depends on the reaction temperature and the degree of reduced pressure, but is usually about 1 to 10 hours. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. Moreover, you may react by adding antioxidant and a branching agent as needed.

As the compound for inducing the structure represented by the general formula (A) which is the terminal group of the terminal-modified polycarbonate of the present invention, specifically,

Etc. The polymerization degrees b and c are preferably 1 to 100 on average, and more preferably 1 to 20. In the terminal-modified polycarbonate resin of the present invention, all terminals have a structure substantially represented by the general formula (A). Although there is a possibility that a terminal that remains phenolic OH remains at a level of several ppm, substantially all terminals have a structure represented by the general formula (A). It should be noted that it can be used in combination with an end stopper having another structure without departing from the gist of the present invention due to required characteristics of the material. Examples of other terminators include known end terminators such as phenols such as phenol, pt-butylphenol and cumylphenol, and chloroformates such as ethyl chloroformate and phenyl chloroformate. It is done. When using a known terminal terminator in combination, it is preferably less than 50 mol%, more preferably less than 20 mol%, relative to the terminator that induces the structure represented by the general formula (A) of the present invention.

The terminal-modified polycarbonate of the present invention has an intrinsic viscosity at 20 ° C. of a 0.5 g / dl solution containing methylene chloride as a solvent at 0.05 to less than 0.50 dl / g, preferably 0.05 to 0.30 dl / g. The average degree of polymerization n calculated from the ratio of the monofunctional compound that derives the general formula (A) to the raw material bisphenol is preferably in the range of 1 to 100, more preferably 5 to 30.

The terminal-modified polycarbonate of the present invention cannot be used alone as a binder resin, but is used by adding to other binder resins. The amount added to the binder resin is 0.1 to 10.0% by weight, more preferably 0.5 to 5.0% by weight, based on the binder resin, in consideration of the water repellency effect and film formability. is there.
When the amount of the terminal-modified polycarbonate of the present invention is too small, the toner desorption effect is lowered. . If the amount is too large, the photoconductor tends to become cloudy.

After mixing with a charge transporting material using the binder resin of the present invention, an electrophotographic photosensitive member is formed by known wet molding such as solution casting, casting, spraying, dip coating (dip method), etc. It is possible. In order for the electrophotographic photosensitive member formed by wet forming to obtain a sufficient film strength, the intrinsic viscosity of the binder resin is preferably 0.40 to 1.5 dl / g.

The mixing ratio of the charge transport material and the binder resin is preferably in the range of 10: 1 to 1:10. The thickness of the charge transport layer is 2 to 100 μm, preferably 5 to 30 μm.

Binder resins include vinyl polymers such as polymethyl methacrylate, polystyrene, polyvinyl chloride, and copolymers thereof, various thermoplastic resins such as polycarbonate, polyester, polysulfone, phenoxy resin, epoxy resin, silicone resin, and thermosetting. In particular, it is preferable to select a polycarbonate having good compatibility with the terminal-modified polycarbonate of the present invention.

When polycarbonate is selected as the binder resin, specifically, 1,1′-biphenyl-4,4′-diol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4- Hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol) -L A; BPA), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3) -Methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1 -Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3-allylphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3) -Methylphenyl) fluorene, 4,4 '-[1,4-phenylenebis (1-methylethylidene) ] Bisphenol, 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 4,4'-butylidenebis (3-methyl-6-t-butyrylphenol), etc. as raw material bisphenol Those synthesized from are preferred. Two or more of these may be used in combination. Among these, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, , 1′-biphenyl-4,4′-diol, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Preferably it is selected from ethane.

Prepolymerization 1
912 g (4.00 mol) of 2,2-bis (4-hydroxyphenyl) propane, 815 g (3.81 mol) of diphenyl carbonate, and 3.5 × 10 ⁻⁵ g (4.2 × 10 ⁻⁷ ) of sodium bicarbonate Mol) was placed in a 3 liter four-necked flask equipped with a stirrer and a distillation apparatus, heated to 220 ° C. in a nitrogen atmosphere, and the degree of vacuum was adjusted to 0.28 mmHg in 1 hour while stirring. The transesterification reaction was carried out for 4 hours. After completion of the reaction, nitrogen was blown into the reactor to return to normal pressure, and the produced polycarbonate was taken out.

The intrinsic viscosity at 20 ° C. of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent of this polymer was 0.21 dl / g. Further, the result of measuring the concentration of the terminal hydroxyl group by a titanium tetrachloride color developing method with a spectrophotometer was 1.21% by weight, and the result of gel permeation chromatography was that the remaining amount of monomer was less than 100 ppm. The results obtained polymer was analyzed by infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, it is polycarbonate having a carbonate bond confirmed.

Prepolymerization 2
The reaction was performed in the same manner as in Prepolymerization 1, except that 1072 g of 1,1-bis (4-hydroxyphenyl) cyclohexane was used instead of 2,2-bis (4-hydroxyphenyl) propane.

Prepolymerization 3
The reaction was carried out in the same manner as in Prepolymerization 1, except that 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane was changed to 1184 g instead of 2,2-bis (4-hydroxyphenyl) propane.

Prepolymerization 4
The reaction was performed in the same manner as in Prepolymerization 1, except that 1024 g of 2,2-bis (4-hydroxy-3-methylphenyl) propane was used instead of 2,2-bis (4-hydroxyphenyl) propane.

Prepolymerization 5
The reaction was performed in the same manner as in Prepolymerization 1, except that 856 g of 1,1-bis (4-hydroxyphenyl) ethane was used instead of 2,2-bis (4-hydroxyphenyl) propane.

Prepolymerization 6
Prepolymerization 1 except that 112 g of 1,1′-biphenyl-4,4′-diol and 680 g of bis (4-hydroxyphenyl) methane were used instead of 2,2-bis (4-hydroxyphenyl) propane. The reaction was performed in the same manner.

Synthesis example 1
Next, 3 liters of methylene chloride, 267 g of bis (2,4-dinitrophenyl) carbonate and a silicone compound having the following structure (hereinafter abbreviated as S1)

308 g was put into a 5 liter beaker and stirred and mixed at room temperature. To this mixed solution, a solution obtained by dissolving 73.7 g of triethylamine in 500 ml of methylene chloride was slowly added dropwise over 1.5 hours to cause a stirring reaction. Further, after stirring for 1 hour, a solution in which 500 g of prepolymerized polycarbonate 500, 73.7 g of triethylamine, and 2.5 g of 4- (dimethylamino) pyridine were dissolved in 3.5 liters of methylene chloride was slowly reacted over 2.5 hours. The solution was added dropwise and mixed with stirring. After further stirring for 3 hours, the reaction solution was washed with 3.5 kg of 1N hydrochloric acid, and then washed four times with 3.5 kg of 0.5N caustic soda solution. Finally, the reaction solution was washed with 3.5 kg of 1N hydrochloric acid and further washed with 7.4 kg of pure water.

  Methylene chloride was removed from the reaction solution with an evaporator, and the residue was washed with 3 liters of methanol and then with 3 liters of hexane. The washed residue was vacuum dried at 40 ° C. to obtain the desired polymer.

The intrinsic viscosity at 20 ° C. of a 0.5 g / dl concentration solution of this polymer using methylene chloride as a solvent was 0.22 dl / g. Further, the result of measurement of the terminal hydroxyl group concentration by the titanium tetrachloride coloring method by a spectrophotometer was less than 0.01% by weight. The results obtained polymer was analyzed by infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, contains further results Si atoms XPS analysis It was confirmed that As a result, it was confirmed that this polymer was a terminal-modified polycarbonate (hereinafter abbreviated as A1) having the following structure.

Synthesis example 2
The reaction was performed in the same manner as in Synthesis Example 1 except that the polycarbonate of prepolymerization 2 was used in place of the polycarbonate of prepolymerization 1 and 230 g of bis (2,4-dinitrophenyl) carbonate was changed to 263 g of S1.

The intrinsic viscosity of the obtained polymer was 0.22 dl / g, and the terminal hydroxyl group concentration measurement result was less than 0.01% by weight. As a result of infrared absorption spectrum and XPS analysis, the polymer had terminal structures having the following structures: It was confirmed to be a modified polycarbonate (hereinafter abbreviated as A2).

Synthesis example 3
Instead of S1, a silicone compound having the following structure (hereinafter abbreviated as S2)

Was synthesized in the same manner as in Synthesis Example 1 except that 264 g of was used.

The intrinsic viscosity of the obtained polymer is 0.21 dl / g, and the terminal hydroxyl group concentration measurement result is less than 0.01% by weight. As a result of infrared absorption spectrum and XPS analysis, this polymer has the following structure: It was confirmed to be a modified polycarbonate (hereinafter abbreviated as A3).

Synthesis example 4
Instead of S1, a silicone compound having the following structure (hereinafter abbreviated as S3)

Was synthesized in the same manner as in Synthesis Example 1 except that 531 g of was used.

The intrinsic viscosity of the obtained polymer was 0.22 dl / g, and the terminal hydroxyl group concentration measurement result was less than 0.01% by weight. As a result of infrared absorption spectrum and XPS analysis, the polymer had terminal structures having the following structures: It was confirmed to be a modified polycarbonate (hereinafter abbreviated as A4).

Synthesis example 5
The reaction was performed in the same manner as in Synthesis Example 1 except that the polycarbonate of prepolymerization 3 was used instead of the polycarbonate of prepolymerization 1, and bis (2,4-dinitrophenyl) carbonate was changed to 207 g and S1 was changed to 237 g.

The intrinsic viscosity of the obtained polymer was 0.22 dl / g, and the terminal hydroxyl group concentration measurement result was less than 0.01% by weight. As a result of infrared absorption spectrum and XPS analysis, the polymer had terminal structures having the following structures: It was confirmed to be a modified polycarbonate (hereinafter abbreviated as A5).

Synthesis Example 6
The reaction was carried out in the same manner as in Synthesis Example 1 except that the polycarbonate of prepolymerization 4 was used in place of the polycarbonate of prepolymerization 1, and 238 g of bis (2,4-dinitrophenyl) carbonate and 274 g of S1 were changed.

The intrinsic viscosity of the obtained polymer is 0.21 dl / g, and the terminal hydroxyl group concentration measurement result is less than 0.01% by weight. As a result of infrared absorption spectrum and XPS analysis, this polymer has the following structure: It was confirmed to be a modified polycarbonate (hereinafter abbreviated as A6).

Synthesis example 7
The reaction was performed in the same manner as in Synthesis Example 1 except that the polycarbonate of prepolymerization 5 was used instead of the polycarbonate of prepolymerization 1, and bis (2,4-dinitrophenyl) carbonate was changed to 288 g and S1 was changed to 333 g.

The intrinsic viscosity of the obtained polymer was 0.23 dl / g, and the terminal hydroxyl group concentration measurement result was less than 0.01% by weight. As a result of infrared absorption spectrum and XPS analysis, the polymer had terminal structures having the following structures: It was confirmed to be a modified polycarbonate (hereinafter abbreviated as A7).

Synthesis Example 8
The reaction was performed in the same manner as in Synthesis Example 1 except that 430 g of the prepolymerized 6 polycarbonate was used instead of the prepolymerized 1 polycarbonate.

The intrinsic viscosity of the obtained polymer was 0.19 dl / g, and the terminal hydroxyl group concentration measurement result was less than 0.01% by weight. As a result of infrared absorption spectrum and XPS analysis, the polymer had terminal structures having the following structures: It was confirmed to be a modified polycarbonate (hereinafter abbreviated as A8).

<Example 1>
10 g of phthalocyanine titanium oxide (ST10 / 10.1 manufactured by SYNTEC Co.), 5 g of phenoxy resin, 5 g of polyvinyl butyral resin, and 100 g of dimethoxyethane are mixed on a polyethylene terephthalate film on which aluminum is deposited to a thickness of about 50 nm. Then, it was coated using a coating liquid that had been pulverized and dispersed, dried, and a charge generation layer having a thickness of about 0.5 μm was provided.

Next, 50 g of N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) benzidine (ST16 / 1.2 manufactured by SYNTEC) was added to 2,2-bis (4-hydroxyphenyl) propane. 49.5 g of a homopolycarbonate binder resin (Mitsubishi Gas Chemical Co., Ltd., Iupilon E-2000, intrinsic viscosity 0.58 dl / g) derived from the above, 0.5 g of A1 obtained in Synthesis Example 1, and 350 g of methylene chloride A coating solution mixed with the above was prepared, applied onto the charge generation layer, air-dried and then dried at 100 ° C. for 8 hours, and a charge transport layer having a thickness of about 20 μm was provided to prepare a multilayer electrophotographic photoreceptor.

Evaluation of this electrophotographic photosensitive member was measured with an EPA-8100 electrostatic charge test apparatus manufactured by Kawaguchi Electric Co., Ltd., and water repellency and wettability by surface contact angle measurement were also evaluated.

Further, the photosensitive drum of a commercially available LBP photosensitive cartridge (LPA3ETC4 manufactured by Epson Corporation) is taken out, the charge transport layer is dissolved in THF, the charge transport agent solution is applied, and a charge transport layer having a thickness of about 20 μm is provided. The photoreceptor was regenerated. The toner in the cartridge was evenly sprinkled on the surface of the regenerated photoreceptor, and the increase in weight due to toner adhesion at the time when the toner no longer fell by shaking was measured.

Further, the reproducing photosensitive drum is mounted on the cartridge, mounted on a commercially available LBP (LP-8600FX manufactured by Epson Corporation), and after a part of the toner in the cartridge is evenly sprinkled on the exposed photosensitive drum surface, After shaking the cartridge lightly to visually confirm that the toner no longer spills, the cartridge was mounted on the LBP main body, continuous white printing was performed, and the number of sheets until the black spot with a major axis of 0.5 mm or more disappeared was visually counted. .

On the other hand, the regenerative photosensitive drum is mounted on a cartridge and mounted on a commercially available LBP (LP-8600FX manufactured by Epson Corporation). The exposed photosensitive drum surface is lightly rubbed with ethanol-containing absorbent cotton, and further dried absorbent cotton After the ethanol was wiped off, continuous black printing was carried out, and the number of sheets until thin unevenness could not be confirmed visually was counted.

<Example 2>
The same operation as in Example 1 was conducted except that A1 was changed to 2.4 g and the binder resin (E-2000) was changed to 47.6 g.

<Example 3>
The same operation as in Example 1 was conducted except that A1 was changed to 0.3 g and the binder resin (E-2000) was changed to 49.7 g.

<Example 4>
The binder resin (E-2000) was changed to a homopolycarbonate derived from 1,1-bis (4-hydroxyphenyl) cyclohexane (Mitsubishi Gas Chemical Co., Ltd., Iupizeta PCZ-200, intrinsic viscosity 0.58 dl / g). The same procedure as in Example 1 was conducted except that A1 was changed to A2 and methylene chloride was changed to toluene.

<Example 5>
The binder resin (E-2000) is converted into 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane and 1,1-bis (4-hydroxyphenyl)- Copolymerized polycarbonate derived from 1-phenylethane (Mitsubishi Gas Chemical Co., Ltd., Iupizeta FPC-A152, intrinsic viscosity 0.96 dl / g) was changed, A1 was changed to A2, and methylene chloride was changed to tetrahydrofuran. Except for this, the same procedure as in Example 1 was performed.

<Example 6>
Binder resin (E-2000) is a copolymerized polycarbonate derived from 2,2-bis (4-hydroxyphenyl) propane and 1,1′-biphenyl-4,4′-diol (Tufzette B, manufactured by Idemitsu Kosan Co., Ltd.) -300, intrinsic viscosity 0.72 dl / g), A1 was changed to A2, and methylene chloride was changed to toluene.

<Example 7>
The same procedure as in Example 1 was performed except that A1 was changed to A3.

<Example 8>
The same procedure as in Example 1 was performed except that A1 was changed to A4.

<Example 9>
The same procedure as in Example 1 was conducted except that A1 was changed to A5 and the binder resin (E-2000) was changed to a polycarbonate resin (hereinafter abbreviated as B5) obtained by the following binder resin polymerization method.
B5 was prepared by adding 24 g (0.12 mol) of bis (4-hydroxyphenyl) methane and 63.8 g (0.28 mol) of 2,2-bis (4-hydroxyphenyl) propane to 1100 ml of a 5 w / w% aqueous sodium hydroxide solution. And 0.1 g of hydrosulfite were dissolved.
To this, 500 ml of methylene chloride was added and stirred, while maintaining at 15 ° C., 60 g of phosgene was blown in over 60 minutes.
After the completion of phosgene blowing, 1.0 g of pt-butylphenol was added as a molecular weight regulator and stirred vigorously to emulsify the reaction solution. After emulsification, 0.4 ml of triethylamine was added and the reaction was carried out at 20 to 25 ° C. for about 1 hour. Stir and polymerize.
After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with water was repeated until the conductivity of the previous solution (aqueous phase) became 10 μS / cm or less. The obtained polymer solution was dropped into warm water maintained at 45 ° C., and the solvent was removed by evaporation to obtain a white powdery precipitate.
The obtained precipitate was filtered and dried at 105 ° C. for 24 hours to obtain a polymer powder.
The intrinsic viscosity at 20 ° C. of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent of this polymer was 0.73 dl / g. The results obtained polymer was analyzed by infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, the polycarbonate resin having a carbonate bond (B5) It was confirmed that.

<Example 10>
The same procedure as in Example 1 was performed except that A1 was changed to A6.

<Example 11>
The same procedure as in Example 1 was performed except that A1 was changed to A7.

<Example 12>
The same procedure as in Example 1 was conducted except that A1 was changed to A8 and the binder resin (E-2000) was changed to a polycarbonate resin (hereinafter abbreviated as B6) obtained by the following binder resin polymerization method.
B6 was prepared by dissolving 85.6 g (0.4 mol) of 1,1-bis (4-hydroxyphenyl) ethane and 0.1 g of hydrosulfite in 1100 ml of a 5 w / w% aqueous sodium hydroxide solution.
To this, 500 ml of methylene chloride was added and stirred, while maintaining at 15 ° C., 60 g of phosgene was blown in over 60 minutes.
After completion of phosgene blowing, 1.3 g of pt-butylphenol was added as a molecular weight regulator and stirred vigorously to emulsify the reaction solution. After emulsification, 0.4 ml of triethylamine was added and the reaction was carried out at 20-25 ° C. for about 1 hour. Stir and polymerize.
After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with water was repeated until the conductivity of the previous solution (aqueous phase) became 10 μS / cm or less. The obtained polymer solution was dropped into warm water maintained at 45 ° C., and the solvent was removed by evaporation to obtain a white powdery precipitate.
The obtained precipitate was filtered and dried at 105 ° C. for 24 hours to obtain a polymer powder.
The intrinsic viscosity at 20 ° C. of a 0.5 g / dl concentration solution of this polymer using methylene chloride as a solvent was 0.81 dl / g. The results obtained polymer was analyzed by infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, the polycarbonate resin having a carbonate bond (B6) It was confirmed that.

<Comparative example 1>
The same procedure as in Example 1 was performed except that A1 was not used.

<Comparative example 2>
The same procedure as in Example 4 was performed except that A2 was not used.

<Comparative Example 3>
Similar to Example 1 except that the polycarbonate having the following structure obtained by the method described in Example 1 of JP-A-5-155999 (inherent viscosity 0.65 dl / g, hereinafter abbreviated as B7) was used instead of A1. I went to.

<Comparative example 4>
The same procedure as in Example 1 was performed except that 0.5 g of S1 described in Synthesis Example 1 was used instead of A1.

(表の記号および言葉の説明)
Ａ１：合成例１の末端変性ポリカーボネート
Ａ２：合成例２の末端変性ポリカーボネート
Ａ３：合成例３の末端変性ポリカーボネート
Ａ４：合成例４の末端変性ポリカーボネート
Ａ５：合成例５の末端変性ポリカーボネート
Ａ６：合成例６の末端変性ポリカーボネート
Ａ７：合成例７の末端変性ポリカーボネート
Ａ８：合成例８の末端変性ポリカーボネート
Ｂ１：三菱ガス化学株式会社製ユーピロンＥ−２０００
Ｂ２：三菱ガス化学株式会社製ユピゼータＰＣＺ−２００
Ｂ３：三菱ガス化学株式会社製ユピゼータＦＰＣ−Ａ１５２
Ｂ４：出光興産株式会社製タフゼットＢ−３００
Ｂ５：実施例９記載のビス（４−ヒドロキシフェニル）メタン／２，２−ビス（４−ヒドロキシフェニル）プロパン共重合ポリカーボネート
B６：実施例１２記載の１，１−ビス（４−ヒドロキシフェニル）エタン型ポリカーボネート
Ｂ７：特開平５−１５５９９９の実施例１記載のグラフトシリコーン型ポリカーボネート
Ｓ１：合成例１記載のシリコーン化合物
初期電位：室温（約２３℃）で感光体フィルムをＤＣ帯電器にて５０μＡ電流が流入するよう調整したときの初期帯電量。
残留電位：室温（約２３℃）で感光体フィルムを露光（除電１０Ｌｕｘ）後、４秒後の残留電位。
水接触角：協和界面科学株式会社製ＤｒｏｐＭａｓｔｅｒ３００で測定。
フィルム外観：目視で判定。
静摩擦係数：新東科学株式会社製ヘイドントライボギアミューズ摩擦計で測定。
トナー付着重量：感光体ドラムにトナーを振りかけて、振っても落ちない量のトナー重量。

(Explanation of table symbols and words)
A1: End-modified polycarbonate A2 of Synthesis Example 1: End-modified polycarbonate A3 of Synthesis Example 2: End-modified polycarbonate A4 of Synthesis Example 3 End-modified polycarbonate A5 of Synthesis Example 4 A5: End-modified polycarbonate A6 of Synthesis Example 5: Synthesis Example 6 Terminal-modified polycarbonate A7: terminal-modified polycarbonate A8 of Synthesis Example 7: terminal-modified polycarbonate B of Synthesis Example 8 B1: Iupilon E-2000 manufactured by Mitsubishi Gas Chemical Company, Inc.
B2: Iupizeta PCZ-200 manufactured by Mitsubishi Gas Chemical Company, Inc.
B3: Iupizeta FPC-A152 manufactured by Mitsubishi Gas Chemical Company, Inc.
B4: Idemitsu Kosan Co., Ltd. Toughzet B-300
B5: Bis (4-hydroxyphenyl) methane / 2,2-bis (4-hydroxyphenyl) propane copolymer polycarbonate described in Example 9
B6: 1,1-bis (4-hydroxyphenyl) ethane type polycarbonate described in Example 12 B7: Grafted silicone type polycarbonate S1 described in Example 1 of JP-A-5-155999: Silicone compound initial potential described in Synthesis Example 1: Initial charge amount when the photoreceptor film is adjusted at room temperature (about 23 ° C.) with a DC charger so that a current of 50 μA flows.
Residual potential: Residual potential after 4 seconds after exposing the photosensitive film at room temperature (about 23 ° C.) (static elimination 10 Lux).
Water contact angle: measured with DropMaster 300 manufactured by Kyowa Interface Science Co., Ltd.
Film appearance: judged visually.
Static friction coefficient: Measured with Haydon Tribogear Muse friction meter manufactured by Shinto Kagaku Co., Ltd.
Toner adhesion weight: The toner weight that does not fall off when the toner is sprinkled on the photosensitive drum.

(表の記号および言葉の説明)


※：５０回印刷後でも黒点、印刷ムラがあった。

(Explanation of table symbols and words)


*: Black spots and uneven printing were observed even after printing 50 times.

Claims (9)

A binder resin used for a photosensitive layer of an electrophotographic photoreceptor, having a terminal group represented by the following general formula (A), and having an intrinsic viscosity of 0.05 to 0.50 dl / g A binder resin for a photosensitive layer containing 0.1 to 10.0% by weight.

(R ₆ and R ₇ represent an alkylene group having 1 to 10 carbon atoms, and R _{1 to} R ₅ are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, and a carbon number. Represents an alkoxy group having 1 to 5 or an aryl group having 6 to 12 carbon atoms, and b represents an integer of 1 to 100.) 2. The binder resin for a photosensitive layer according to claim 1, wherein R _{1 to} R ₅ in the general formula (A) are a methyl group, a butyl group, or a phenyl group. The binder resin for a photosensitive layer according to claim 1 or 2, wherein R ₆ and R ₇ in the general formula (A) are alkylene groups having 1 to 6 carbon atoms. B in the said general formula (A) is 1-20, Binder resin for photosensitive layers of any one of Claims 1-3. The binder resin for a photosensitive layer according to claim 1, wherein the terminal-modified polycarbonate resin has a repeating unit represented by the following general formula (1).

Wherein R _{8 to} R ₁₁ are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkenyl having 2 to 5 carbon atoms. A group, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, (A) represents the general formula (A) according to claim 1. n represents an integer of 1 or more. Is one of the structures shown below,

R ₁₂ and R ₁₃ represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms. . Further, R ₁₂ and R ₁₃ may be bonded together to form a group that forms a carbocyclic or heterocyclic ring. a represents an integer of 0 to 20. ) The repeating unit represented by the general formula (1) is 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3). -Methylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) methane, or 1,1 ' The binder resin for a photosensitive layer according to claim 5, wherein the binder resin is derived from -biphenyl-4,4'-diol. The binder resin is 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1 '-Biphenyl-4,4'-diol, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) methane, or 1,1-bis (4-hydroxyphenyl) ethane The binder resin for a photosensitive layer according to claim 1, which is a polycarbonate resin having a derived structural unit as a main structural unit. An electrophotographic photosensitive member having a photosensitive layer on a conductive substrate, wherein the binder resin for a photosensitive layer according to any one of claims 1 to 7 is used as a binder resin in the photosensitive layer. body. An image forming apparatus comprising the electrophotographic photosensitive member according to claim 8.