JPH05202135A - Acrylic or methacrylic acid ester having new triphenylamine skeleton, new polymer produced therefrom and electrophotographic photoreceptor produced by using the polymer - Google Patents

Abstract

PURPOSE:To provide a new compound useful for electrophotographic photoreceptor having high sensitivity and durability. CONSTITUTION:The compound of formula I [R1 is H or methyl; R2 to R5 are (substituted)alkyl, alkoxy, (substituted)aryl, aryloxy, aralkyloxy, halogen or (substituted)amino; n1 is 1-10; n2 is 1-4; n3 and n4 are 1-5; m and k are 0 or 1], e.g. 1-[2'-(4''-diphenylaminophenyl)ethyl]phenyl methacrylate. The compound of formula I can be produced e.g. by reacting a compound of formula II with a compound of formula III. A polymer expressed by formula IV can be produced by polymerizing the compound of formula I.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel acrylic or methacrylic acid ester, an acrylic or methacrylic acid ester homopolymer or copolymer obtained therefrom, and an electrophotographic photoreceptor using the polymer.

[0002]

2. Description of the Related Art In recent years, organic photoconductors (OPCs) have been used in copying machines,
Mostly used in printers. These OPCs have a structure in which a charge generation layer (CGL) and a charge transfer layer (CTL) are sequentially stacked. CTL is a film obtained by dissolving a low molecular weight charge transfer material (CTM) in a binder resin at a certain concentration. The addition of CTM lowers the mechanical strength inherent in the binder resin, and the CTL film is brittle and has a low tensile strength. This decrease in mechanical strength is considered to be the cause of abrasion, scratches, peeling, cracks and the like of the photoconductor. On the other hand, there have been proposed many photoconductors using a polymer charge transfer agent such as polyvinylcarbazole, polyvinylanthracene, and polyvinylpyrene as a single CTL, but the mechanical strength and electrical characteristics are not sufficient. In addition, M. Stolka, J. PO
LYM. SCI. VOL. Although there is a description of an acrylic polymer in 21,969, the mobility is slow. '89 Japan
HARD COPY P.I. 67 describes a vinyl polymer of hydrazone, but a residual potential is observed. JP-A-1-115915, JP-A-1-141902, JP-A-1
The carbazole polymer described in -141939 has a low sensitivity. JP-A-1-134456, JP-A-1-134445
7, JP-A-1-134462 has good sensitivity, but residual potential and sensitivity change are observed. JP-A-64-9964
Has a reaction limitation.

[0003]

DISCLOSURE OF THE INVENTION The present invention is directed to an acrylic or methacrylic acid ester having a novel triphenylamine skeleton, a novel polymer obtained therefrom, and an acrylic or methacrylic acid ester homopolymer having the novel triphenylamine skeleton. An object of the present invention is to provide a highly sensitive and highly durable electrophotographic photoreceptor containing a polymer or a copolymer in a charge transfer layer.

[0004]

According to the present invention, an acrylic or methacrylic acid ester represented by the following chemical formula 1

[Chemical 1] In the formula, R _{1 is} hydrogen, a methyl group R ₂ , R ₃ , R ₄ , and R _{5 are the} same or different and are substituted;
An unsubstituted linear or branched alkyl group or alkoxy group,
Substituted or unsubstituted aryl group, aryloxy group, aralkyloxy group, halogen, substituted or unsubstituted amino group n ₁ : 1 to 10 integer n ₂ : 1 to 4 integer n ₃ , n ₄ : 1 to 5 Is an integer m, k: 0 or 1, and is a homopolymer or copolymer (I) of an acrylic or methacrylic acid ester having a repeating unit represented by the following chemical formula 2.

[Chemical 2] In the formula, R _{1 is} hydrogen, a methyl group R ₂ , R ₃ , R ₄ , and R _{5 are the} same or different and are substituted;
An unsubstituted linear or branched alkyl group or alkoxy group,
Substituted or unsubstituted aryl group, aryloxy group, aralkyloxy group, halogen, substituted or unsubstituted amino group n ₁ : 1 to 10 integer n ₂ : 1 to 4 integer n ₃ , n ₄ : 1 to 5 In the electrophotographic photoreceptor in which a photoconductive layer is provided on a conductive support, an integer of m, k: 0 or 1 is provided in the photoconductive layer. There is provided an electrophotographic photosensitive member characterized by containing a polymer or a copolymer (I), and further, an electrophotographic photosensitive member in which a charge generating layer and a charge transfer layer are sequentially laminated on a conductive support, An electrophotography characterized by containing an acrylic or methacrylic acid ester copolymer (II) having a repeating unit represented by the following chemical formula 2 and a repeating unit represented by the following chemical formula 3 in the charge transfer layer. Photoconductor

[Chemical 2] In the formula, R _{1 is} hydrogen, a methyl group R ₂ , R ₃ , R ₄ , and R _{5 are the} same or different and are substituted;
An unsubstituted linear or branched alkyl group or alkoxy group,
Substituted or unsubstituted aryl group, aryloxy group, aralkyloxy group, halogen, substituted or unsubstituted amino group n ₁ : 1 to 10 integer n ₂ : 1 to 4 integer n ₃ , n ₄ : 1 to 5 Integer m, k: 0 or 1

[Chemical 3] In the formula, R _{1 is} hydrogen, a methyl group, R _{6 is a} linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group or an aralkyl group, and further, on a conductive support. Charge generation layer,
In an electrophotographic photosensitive member in which a charge transfer layer is sequentially laminated, in the charge transfer layer, a repeating unit represented by the following chemical formula 2,
An electrophotographic photosensitive member containing a cured product of an acrylic or methacrylic acid ester copolymer (III) having an repeating unit represented by the following chemical formula 3 and a repeating unit represented by the following chemical formula 4 with an isocyanate.

[Chemical 2] In the formula, R _{1 is} hydrogen, a methyl group R ₂ , R ₃ , R ₄ , and R _{5 are the} same or different and are substituted;
An unsubstituted linear or branched alkyl group or alkoxy group,
Substituted or unsubstituted aryl group, aryloxy group, aralkyloxy group, halogen, substituted or unsubstituted amino group n ₁ : 1 to 10 integer n ₂ : 1 to 4 integer n ₃ , n ₄ : 1 to 5 Integer m, k: 0 or 1

[Chemical 3] In the formula, R _{1 is} hydrogen or a methyl group R _{6 is a} linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group or an aralkyl group.

[Chemical 4] In the formula, R ₁ : hydrogen, a methyl group n ₅ : an integer of 1 to 10 are provided.

The present invention will be described in detail below. The acrylic or methacrylic acid ester having a triphenylamine skeleton represented by Chemical Formula 1 of the present invention has 4- (N, Ndiphenylamino) benzaldehyde and diethyl-methoxybenzylphosphoric acid as shown in the reaction formula in Table 1 below. The resulting naphthoate was reacted with sodium methylate to synthesize 4-diphenylamino-4′-methoxystilbene, which was hydrogenated, and then the methoxy group was hydrolyzed to OH using a silyl compound, and then acrylic chloride was added under alkaline conditions. Synthesize by reacting.

[Table 1] After the hydrolysis, the alkyleneoxy chain can be extended by reacting it with epichlorohydrin or the like in the presence of alkali.

A homopolymer or copolymer (I) of an acrylic or methacrylic acid ester having a repeating unit represented by the above chemical formula 2 of the present invention is prepared by using the corresponding acrylic or methacrylic acid ester as a monomer and using a monomer such as toluene. It is obtained by dissolving in a solvent and carrying out a polymerization reaction in the presence of a peroxide or an azo type initiator. The homopolymer or copolymer (I) preferably has a molecular weight of 8,000 to 200,000. Next, Table 2 shows examples of homopolymers.

[0007]

[(1) of Table 2]

[(2) of Table 2]

[(2) in Table 2]

[(4) in Table 2]

[(2) in Table 2]

[(2) in Table 2]

[(2) in Table 2]

[(8) in Table 2]

[(2) in Table 2]

These polymers show high mobility, high sensitivity, low electric potential with low residual potential, and good film property. The film can be dissolved in a solvent such as toluene and coated on CGL to provide a single CTL layer. Stolka et al. Reported that a film obtained by substituting triphenylamine for polymethylmethacrylate was fragile, but the polymer of the present invention showed that the distance from the vinyl chain of acrylic was (CnH2nO), phenyl group, (CnH2n).
It is separated by groups such as, and the problem of brittleness and flexibility is solved by the substitution position of the acrylic group. Further, the monomer represented by Chemical formula 1 can be copolymerized with other vinyl monomer such as acrylic or methacrylic acid ester to improve the film characteristics. As such a polymer, an acrylic or methacrylic acid ester having a repeating unit having the triphenylamine skeleton represented by the above Chemical Formula 2 and a repeating unit represented by the above Chemical Formula 3, and a copolymer (II), or further An acrylic or methacrylic acid ester copolymer (III) having a repeating unit represented by the above chemical formula 4 can be mentioned.

As the copolymerizable monomer giving the repeating unit represented by the above chemical formula 3, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, Propyl acrylate, propyl methacrylate, hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, 2,2,2-trifluoroethyl methacrylate, octafluoropentyl methacrylate, heptadecafluoromethacrylate, phenyl methacrylate, methoxyethyl Methacrylate, ethoxyethyl methacrylate, etc. It is below.

These monomers may be copolymerized singly or in a plural number, and in consideration of abrasion resistance as mechanical properties such as film property, flexibility, adhesiveness, compatibility (transparency) and mechanical strength. In terms of hardness, low friction coefficient, surface energy, ozone resistance, light resistance, humidity resistance, electrical characteristics, etc., the type of copolymerized monomer, single or multiple,
Alternatively, the number and ratio thereof are determined, but in the copolymer (II) having the repeating unit represented by the above Chemical formula 2 and the repeating unit represented by the above Chemical formula 3, the copolymer is represented by the following Chemical formula 2 as the raw material. Generally, the amount of the monomer represented by the chemical formula 1 which gives a repeating unit is preferably 30% by weight or more and 90% by weight or less. If it is less than 30% by weight, the sensitivity when used in a photoreceptor is lowered, and if it is more than 90% by weight, the physical properties of the film, such as adhesiveness and flexibility, are deteriorated. As the copolymerization method, solution polymerization using radicals, emulsion polymerization, suspension polymerization to obtain a bead-like polymer, and ionic polymerization using ions such as anions and cations are applied.

As the copolymerizable monomer that gives the repeating unit represented by the above formula 4, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3- Hydroxypropyl methacrylate and the like can be mentioned.

In the copolymer (III) further having a repeating unit having a hydroxy group represented by the chemical formula 4, the monomer represented by the chemical formula 1 as the raw material is
30 to 90% by weight is preferable, 20 to 40% by weight of the monomer giving the repeating unit represented by the chemical formula 3, and 5% of the monomer giving the repeating unit represented by the chemical formula 4.
-20% by weight is preferred. If the amount of the monomer represented by the chemical formula 1 is less than 30% by weight, the sensitivity is lowered when it is used for a photoreceptor, and if it exceeds 90% by weight, the adhesiveness and flexibility are deteriorated. The repeating unit represented by the chemical formula 3 imparts flexibility to the film, and the monomer providing the repeating unit is 20
If it is less than 40% by weight, the film becomes brittle, and if it is more than 40% by weight, it becomes soft and the film properties deteriorate. If the amount of the monomer giving the repeating unit represented by the chemical formula 4 is less than 5% by weight, the adhesiveness is poor, and since the number of reaction sites with the isocyanate compound is small, the film hardness is low and the abrasion resistance is poor. On the other hand, if it is more than 20% by weight, the sensitivity is lowered when it is used for a photoreceptor. In the copolymer (III) with the monomer having a hydroxy group, the mechanical strength of the film can be improved by the cross-linking reaction between the functional group —OH and isocyanate.
The polymerization method is the same as the above-mentioned method.

In the present invention, as the isocyanate used in the crosslinking reaction, known isocyanates can be used.
Illustrative is an isocyanate represented by

R ₇ [(R ₈ ) n ′ (NCO) n ″] In the formula, R _{7 is} an alkyl group having 3 to 20 carbon atoms, and 3 to 3 carbon atoms.
20 alkoxy group, aryl group, aralkyl group, R ₈ : C 3-20 alkyl group, C 3-20 alkoxy group, aryl group, aralkyl group. These groups may be via either directly bonded to R _7, or -NHCO- bond. n ': 0-3 n'': 2-3 are shown.

Specifically, toluylene diisocyanate,
3,3'-dimethyl-1-diphenyl-4,4'-diisocyanate, diphenylmethane 4,4'-diisocyanate, triphenylmethane triisocyanate, and Sumidule L, HL commercially available from Sumitomo Bayer Ltd. , VL, N and other polyisocyanate compounds,
Examples thereof include cross-linked isocyanates such as Takenate 500 commercially available from Takeda Yakuhin and Vernock D-750 commercially available from Dainippon Ink. In the present invention, the isocyanate compound is preferably added in an amount equal to that of the hydroxyl group in the copolymer (III), but of course the amount may be larger or smaller. Generally, 0.05 to 2 parts by weight based on 10 parts by weight of the copolymer (III) is dissolved in an aromatic solvent such as toluene or a ketone solvent such as MEK before coating,
It is dried and cured at 90 to 150 ° C.

Examples of the photosensitive member include a negative charging type photosensitive member having a charge generating layer and a charge transfer layer sequentially stacked, a positive charging type photosensitive member having a charge transfer layer and a charge generating layer sequentially stacked, and a single layer positive charging type photosensitive member. There are layer configurations and the polymers of the present invention are suitable for all of them. As the charge generating material, C.I. I. No. Condensed polycyclic quinone compounds such as 59300 Vat Orange 3, C.I. I.
No. Perylene compounds such as 38001, and azo pigments having a carbazole skeleton (JP-A-53-95033).
No. JP-A-53-1), azo pigments having a styrylstilbene skeleton (described in JP-A No. 53-138229), and azo pigments having a triphenylamine skeleton (JP-A No. 53-1).
No. 32547), an azo pigment having a dibenzothiophene skeleton (described in JP-A-54-21728), an azo pigment having an oxadiazole skeleton (described in JP-A-54-12742), and a fluorenone skeleton. Azo pigments having a bisstilbene skeleton (described in JP-A No. 54-22834), and azo pigments having a bisstilbene skeleton (JP-A No.
No. 4-17733), an azo pigment having a distyryl oxadiazole skeleton (described in JP-A-54-2129), and an azo pigment having a distyryl carbazole skeleton (described in JP-A-54-17734). Described), a triazo pigment having a carbazole skeleton (JP-A-57-19).
5767), an azo pigment having an anthraquinone skeleton (described in JP-A-57-202545),
Examples include metal or metal-free phthalocyanine and squarium dyes.

These charge generating materials may be pulverized and dispersed alone or together with a binder resin by a method such as a ball mill, an attritor or a vibration mill. Methanol as a solvent,
Alcohols such as isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethers such as tetrahydrofuran, dioxane and ethylene glycol dialkyl ether, esters such as ethyl acetate and butyl acetate, halogenated methylene chloride, dichloroethane and chlorobenzene. Examples thereof include hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, and the like, and they can be used as a mixture of two or more kinds thereof. Examples of the binder resin include polyvinyl butyral, polyvinyl acetal, cellulose derivative, phenol resin, epoxy resin, acrylic resin, polyester, silicone resin, polyvinyl acetate and the like. The average particle diameter of the pigment for pulverization and dispersion is preferably 0.3 μm or less.

As the coating method of the charge generating layer, a conventionally known method such as a dipping method, a spray method, a roll method or the like is applied. The film thickness is 0.05 to 5 μm, preferably 0.05 to 1 μm.

When the dispersion does not contain a binder resin, it is preferable to provide an intermediate layer for preventing charge injection from the conductive support. As the intermediate layer binder resin, polyamide, polyacrylanilide, casein,
Examples thereof include vinyl chloride-vinyl acetate-maleic acid copolymers and phenol resins.

CTL is a polymer (I), (II), (II
I) is dissolved in an aromatic hydrocarbon such as toluene, a halogenated hydrocarbon such as methylene chloride, a cyclic ether such as tetrahydrofuran, and applied by a dipping method, a spray method or a roll method to provide a film thickness of 10 to 50 μm. The polymer (I) can also be used in combination with other binder resins, and the binder resins used in combination include polystyrene and styrene-M.
It is used in combination with a resin having a good film property such as MA copolymer, styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, polyMMA, polyester, polycarbonate, polyarylate, polysulfone, and polyphenylene oxide. The mixing ratio is preferably 2 to 10 polymer parts with respect to 10 polymer parts of the polymer (I).

Further, the polymers (I), (II) and (II
It is also possible to dissolve a low molecular weight charge transfer material in I) to form CTL, and as the charge transfer material, a pyrazoline compound, α
-Phenylstilbene compounds, hydrazone compounds,
Examples thereof include diarylmethane compounds, triphenylamine compounds, divinylbenzene compounds, oxadiazole compounds, diaminocarbazole compounds and the like.

Examples will be shown below. Example 1 4-diphenylamino-4'-methoxystilbene 4-diphenylaminobenzaldehyde 54.6 g
(0.2 mol), diethyl-4-methoxybenzylphosphonate 51.6 g (0.2 mol), D.I. M. F
Transfer 250 ml to a 500 ml four-diameter flask and stir 2
57.9 g of 8% sodium methylate was added dropwise at room temperature over 15 minutes, reacted at 50-60 ° C. for 5 hours, diluted with 500 ml of water and acidified with acetic acid, and then filtered off. The wet cake was washed with 100 ml of methanol three times. It was washed and recrystallized with a mixed solvent of ethanol: dioxane. Yellow, needles m. p. 1
70-171.5 ° C, yield 46.2 g (61.3%) 1- (4-diphenylaminophenyl) -2- (4
-Methoxyphenyl) ethane 37.7 g (0.1 mol) of the above stilbene was dissolved in 250 ml of dioxane, 4 g of 5% Pd / C powder was added, and hydrogenated at 2.41 hydrogen. The solvent was removed and an oily, transparent, pale yellow product was obtained. I. Δ from R: 900-10
The absorption of HC = CH at 00 cm ^-1 had disappeared. 1- (4-diphenylaminophenyl) -2- (4
-Hydroxyphenyl) ethane 38.5 g of the above hydrogenated compound, 200 ml of sulfolane,
Add 45 g of NaI and stir at 120 ° C in a four-diameter flask.
Dissolve, cool to 60 ° C., add 2 ml of distilled water, then add 32.6 g of trimethylchlorosilane dropwise over 30 minutes,
React at 60-70 ° C for 3 hours, pour into 500 ml of water,
A brownish tar product is obtained. It is washed several times with 200 ml of water and dissolved in 300 ml of toluene to obtain a brown toluene solution. This is a saturated aqueous solution of sodium sulfite, 100 ml
It was washed twice with to obtain a pale yellow, transparent toluene solution. After dehydration with anhydrous MgSO ₄ , the solvent was removed and the product was chromatographed using silica gel and toluene to obtain a hydrolyzate. Oily substance 31.4 g. I. RνOH3550, 3400cm
^-1 1- [2 '-(4 "-diphenylaminophenyl)
Ethyl] phenyl methacrylate 31.4 g of the above hydrolyzate, 150 ml of dioxane, 2
20 g of 0% sodium hydroxide aqueous solution was taken, cooled to 5 ° C., and 10.8 g of methacryl chloride was added dropwise with stirring.
Keeping the temperature below 10 ° C, after the completion of dropping, react at room temperature for 2 hours, pour into 500 ml of water, extract with 300 ml of toluene, wash twice with 200 ml of water, and then extract the extract with anhydrous MgSO 4.
After dehydration in ₄ , the solvent was removed, and chromatography was performed using silica gel and toluene to obtain a monomer. m. p: 105.5
˜107 ° C., 30 g, I.V. Rν: 3550, 3400c
With disappearance of m ⁻¹ , C = O at 1740 cm ⁻¹ , 950 cm
An absorption of = CH ₂ was observed at ^-1 .

Example 2 1- (4-diphenylaminophenyl) -2-
(4′-3 ″ -Hydroxypropoxyphenyl) ethane 50% of the hydroxy form of Example 1-36.5 g, 20% aqueous sodium hydroxide solution 24 g, dioxane 200 ml.
11.1 g of epichlorohydrin was added to 30 ° C. with heating and stirring.
The mixture was added dropwise for 5 minutes, reacted at 60 ° C. for 5 hours, poured into 500 ml of water, the oil phase was extracted with toluene, washed twice with 200 ml of water, dehydrated with anhydrous MgSO ₄ , and subjected to column chromatography separation with silica gel and a developing solvent of toluene. .. 20 g of anhydrous oily substance was obtained. 47.28% γ- {4- [2- (4-diphenylaminophenyl) ethyl]} phenyloxypropyl methacrylate Dissolve 20 g of the above alcohol precursor in 150 ml of dioxane, take 4 ml of pyridine, cool to 5 ° C., and stir. 5.9 g of methacryl chloride was added dropwise. After dropping, the mixture was reacted for 2 hours, poured into 300 ml of water, extracted with 200 ml of toluene, washed twice with 200 ml of water, dehydrated with anhydrous MgSO ₄ , and subjected to column chromatography separation with silica gel and toluene to obtain 19 g of a colorless oily monomer. .. 82.0%

Example 3 Poly-4- [2 '-(4 "-diphenylaminophenyl) ethyl] phenyl methacrylate (Table 2 Polymer N
o. 26) 25 g of the above monomers, 50 g of toluene, and 0.09 g of azobisisobutylnitrile were added, and the mixture was stirred at room temperature under a nitrogen stream for 1 hour, then at 60 ° C. for 5 hours, 70 ° C. for 2 hours, 80 ° C. for 2 hours, and 100 ° C. The polymerization reaction was carried out for 1 hour. The reaction solution was added dropwise to 2 L of methanol to crystallize the polymer, and the precipitate was washed with 500 ml of acetone, and then the polymer was again added with 300 ml of toluene.
It was dissolved in ml and repeated reprecipitation with 2 L of methanol. Yield 18g (72%)

Example 4 Poly-γ- {4- [2- (4-diphenylaminophenyl) ethyl]} phenyloxypropyl methacrylate (Table 2 polymer No. 43) All polymerizations were carried out in the same manner as in Example 3. But G. P. C
From the results, the molecular weight was obtained in the range of 5,000 to 100,000. It is considered that this is due to steric hindrance of the monomer, electron density of vinyl group, and subtle difference in reaction atmosphere. The difference in molecular weight does not greatly affect the electrical properties, but rather the effects of the substituents and the substitution positions have a large effect.

Example 5 Polymer No. 1 in Table 2 20 g of the monomer of 3, 3 g of n-butyl methacrylate (nBMA), 0.09 g of azobisisobutyronitrile (AIBN), and 63 g of toluene were placed in a four-diameter flask, and nitrogen gas was bubbled at room temperature for 1 hour, and then at 5 ° C. at 5 ° C. The reaction was performed at 70 ° C. for 2 hours and at 80 ° C. for 4 hours. The reaction solution was light brown and viscous. This reaction liquid was diluted with 200 ml of toluene and added dropwise to 2 L of methanol for precipitation. The precipitate was washed with 500 ml of acetone, dissolved again in 200 ml of toluene and reprecipitated with methanol to obtain a polymer.

Example 6 Polymer No. 1 in Table 2 20 g of 19 monomers, 5 g of methyl methacrylate (MMA), 5 g of nBMA, AIBN
0.1 g and 70 g of toluene were placed in a four-diameter flask and a polymer was obtained in the same manner as in Example 5.

Example 7 Polymer No. 20 g of 27 monomers, nBMA5
g, MMA 2 g, 2 hydroxyethyl methacrylate (2HEMA) 3 g, AIBN 0.1 g, toluene 70
g was placed in a four-diameter flask and a polymerization reaction was carried out in the same manner as in Example 5 to obtain a light brown viscous liquid having a solid content of 30%.

Polymer No. 1 in Table 2 35 monomers 20
g, 2 ethylhexyl methacrylate (2HEMA) 5
g, benzyl methacrylate (BzyMA) 4 g, 2 hydroxypropyl methacrylate 4 g, AIBN 0.1
2 g and 77 g of toluene were placed in a four-diameter flask, and Example 5 was used.
A polymerization reaction was carried out in the same manner as in 1. to obtain a light brown viscous liquid having a solid content of 30%. As described above, the copolymers (II) and (II
I) is obtained, but the copolymers of Examples 7 and 8 do not reprecipitate,
The coating liquid was used as it was.

Example 9 The following intermediate layer liquid was coated on a 0.3 mm aluminum plate with a doctor blade and dried at 120 ° C. to form an intermediate layer of 0.3 μm. Polyamide resin (CM-8000, manufactured by Toray Industries, Inc.) 4 parts Methanol 60 parts Butanol 36 parts Next, the following charge generation layer coating liquid was prepared and applied by the blade method, dried at 120 ° C. for 10 minutes, and a film of 0.3 μm was formed. A thick charge emitting layer was provided. [Charge generation layer coating liquid] 22 parts of the compound represented by the following chemical formula 6 Cyclohexanone 440 parts

[Chemical 6] Was pulverized and dispersed in a ball mill for 72 hours, 600 parts of cyclohexanone was added, the mixture was ball-milled again for 3 hours, and then let down with 800 parts of a mixed solvent of cyclohexanone: methyl ethyl ketone = 1: 1 weight ratio to obtain a coating liquid. Then
The following charge transfer layer liquid was prepared on the charge generation layer and applied by a blade method and dried at 120 ° C. for 20 minutes to give a film thickness of 23 μm.
Of the charge transfer layer. No. of Table 2 Polymer of 1 Mn = 23,000 5 parts Toluene 5 parts

Examples 10 to 22 In the same manner as in Example 9, an intermediate layer and a charge generating layer were provided, and then Table 2 was used.
A compound was applied to prepare a photoreceptor.

The electrophotographic photosensitive member produced as described above was used as an electrostatic copying paper test apparatus [SP42 manufactured by Kawaguchi Electric Co., Ltd.].
8 type] was used to evaluate the electrophotographic characteristics under the following conditions (measured in dynamic mode). First for the sample -6K
3. Corona discharge of V is performed for 20 seconds to charge it, the surface potential Vm (Volt) after 20 seconds is measured, the surface potential Vo (Volt) at that time is left for 20 seconds, and then 4. The exposure doses E1 / 2 and E1 / 10 (lux · sec) required to attenuate Vo to 1/2 and 1/10 by irradiating 5 lux of white tungsten light, and the surface potential Vr (Volt after 30 seconds of irradiation) ) Was measured. The results are shown in Table 3.

[0032]

[Table 3]

A photoconductor was prepared in the same manner as in Example 9 for the copolymer (II). The copolymerization components and ratios are shown in Table 4 and the photosensitive characteristics thereof are shown.

[Table 4]

Example 28 Similar to Example 9, 5 parts of the copolymer used in Example 23 and 1 part of the charge transfer material represented by the following chemical formula 7 were provided on the intermediate layer and the charge generation layer, and 10 parts of toluene. And was coated in the same manner as in Example 9 to obtain a photoconductor.

[Chemical 7]

Example 29 Similar to Example 28, an intermediate layer and a charge generation layer were provided, and 5 parts of the copolymer used in Example 24 and 1 part of CTM-1 represented by the above chemical formula 7 were used to transfer charge. A photoconductor was prepared in the same manner as in Example 9 except that the layers were provided.

Example 30 A photoconductor was prepared in the same manner as in Example 9 except that 5 parts of the copolymer used in Example 26 and 1 part of CTM-2 represented by the following chemical formula 8 were used to form the charge transfer layer. ..

[Chemical 8]

Table 5 shows the photosensitivity of the thus obtained photoconductor.

[Table 5]

Example 31 As in Example 9, 5% of a 30% solution obtained by copolymerizing 2HEMA of Example 7 and 0.1 part of toluylene diisocyanate were added to the laminate of the intermediate layer and the charge generation layer, and a blade was added. Method, and dried and cured at 130 ° C. for 30 minutes to form a charge transfer layer.

Example 32 A photoconductor was prepared in the same manner as in Example 31 except that Example 7 was replaced with Example 8.

Photosensitive characteristics of the thus obtained photosensitive member are shown in Table 6.

[Table 6] Even when Examples 31 and 32 were immersed in Isopar H, an isoparaffinic solvent, or a solvent of toluene or methyl ethyl ketone, no elution of the membrane was observed.

[0041]

The acrylic or methacrylic acid ester having the triphenylamine skeleton represented by the chemical formula 1 of the present invention and the chemical formula 2, the chemical formula 2 and the chemical formula 3, or the chemical formula 2, the chemical formula 3 and the chemical formula 4 are represented. The polymer (I), the copolymer (II) and (III) having a repeating unit are novel, and the polymer (I), the copolymer (II) and (III) are novel.
By containing the above-mentioned compound in the charge transfer layer of the electrophotographic photosensitive member, it is possible to obtain a highly sensitive and highly durable photosensitive member.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of 4-diphenylamino-4′-methoxystilbene.

FIG. 2 1- (4-diphenylaminophenyl) -2-
Infrared absorption spectrum of (4-hydroxyphenyl) ethane

FIG. 3 is an infrared absorption spectrum of 4- [2 ′-(4 ″ -diphenylaminophenyl) ethyl] phenyl methacrylate.

FIG. 4 is an infrared absorption spectrum of poly-4- [2 ′-(4 ″ -diphenyl) ethyl] phenymethacrylate.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaomi Sasaki 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd.

Claims (5)

[Claims] 1. An acrylic or methacrylic acid ester represented by the following chemical formula 1. In the formula, R _{1 is} hydrogen, a methyl group R ₂ , R ₃ , R ₄ , and R _{5 are the} same or different and are substituted;
An unsubstituted linear or branched alkyl group or alkoxy group,
Substituted or unsubstituted aryl group, aryloxy group, aralkyloxy group, halogen, substituted or unsubstituted amino group n ₁ : 1 to 10 integer n ₂ : 1 to 4 integer n ₃ , n ₄ : 1 to 5 Integer m, k: 0 or 1 2. A homopolymer or copolymer (I) of an acrylic or methacrylic acid ester having a repeating unit represented by the following chemical formula (2): In the formula, R _{1 is} hydrogen, a methyl group R ₂ , R ₃ , R ₄ , and R _{5 are the} same or different and are substituted;
An unsubstituted linear or branched alkyl group or alkoxy group,
Substituted or unsubstituted aryl group, aryloxy group, aralkyloxy group, halogen, substituted or unsubstituted amino group n ₁ : 1 to 10 integer n ₂ : 1 to 4 integer n ₃ , n ₄ : 1 to 5 Integer m, k: 0 or 1 3. An electrophotographic photosensitive member having a photoconductive layer provided on a conductive support, wherein the acrylic or methacrylic acid ester homopolymer or copolymer (I) according to claim 2 is contained in the photoconductive layer. ) Is contained in the electrophotographic photosensitive member. 4. An electrophotographic photosensitive member comprising a conductive support, and a charge generation layer and a charge transfer layer laminated in this order. In the charge transfer layer, a repeating unit represented by the following chemical formula 2 and a repeating unit represented by the following chemical formula 3. And an acrylic or methacrylic acid ester copolymer (II) having a repeating unit. [Chemical 2] In the formula, R _{1 is} hydrogen, a methyl group R ₂ , R ₃ , R ₄ , and R _{5 are the} same or different and are substituted;
An unsubstituted linear or branched alkyl group or alkoxy group,
Substituted or unsubstituted aryl group, aryloxy group, aralkyloxy group, halogen, substituted or unsubstituted amino group n ₁ : 1 to 10 integer n ₂ : 1 to 4 integer n ₃ , n ₄ : 1 to 5 An integer m, k: 0 or 1 In the formula, R _{1 is} hydrogen or a methyl group R _{6 is a} linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group or an aralkyl group. 5. An electrophotographic photosensitive member comprising a conductive support, on which a charge generation layer and a charge transfer layer are sequentially laminated, and in the charge transfer layer, a repeating unit represented by the following formula 2 and the following chemical formula 3:
An electrophotographic photosensitive member comprising a cured product of an acrylic or methacrylic acid ester copolymer (III) having a repeating unit represented by the formula (4) and an repeating unit represented by the following formula (4) with an isocyanate. [Chemical 2] In the formula, R _{1 is} hydrogen, a methyl group R ₂ , R ₃ , R ₄ , and R _{5 are the} same or different and are substituted;
An unsubstituted linear or branched alkyl group or alkoxy group,
Substituted or unsubstituted aryl group, aryloxy group, aralkyloxy group, halogen, substituted or unsubstituted amino group n ₁ : 1 to 10 integer n ₂ : 1 to 4 integer n ₃ , n ₄ : 1 to 5 An integer m, k: 0 or 1 In the formula, R _{1 is} hydrogen, a methyl group R _{6 is a} linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, or an aralkyl group. In the formula, R ₁ : hydrogen, a methyl group n ₄ : an integer of 1 to 10