JP3164426B2 - Acrylic or methacrylic acid ester having novel triphenylamine skeleton, novel polymer obtained therefrom, and electrophotographic photoreceptor using the polymer - Google Patents

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 copiers,
Often used in printers. These OPCs have a configuration in which a charge generation layer (CGL) and a charge transfer layer (CTL) are sequentially laminated. In CTL, a low molecular charge transfer material (CTM) is dissolved in a binder resin at a certain concentration to form a film. Addition of CTM lowers the intrinsic mechanical strength of the binder resin, and the CTL film is brittle and has low tensile strength. This decrease in mechanical strength is considered to be the cause of wear, scratches, peeling, cracks, etc. of the photoreceptor. On the other hand, many photoconductors using a polymer charge transfer agent such as polyvinyl carbazole, polyvinyl anthracene, and polyvinyl pyrene as a single CTL have been proposed, but their mechanical strength and electrical properties are not sufficient. M. Stolka, J. et al. PO
LYM. SCI. VOL. 21,969 describes an acrylic polymer, but has a low mobility. '89 JAPAN
HARD COPY P. 67 describes a hydrazone vinyl polymer, but a residual potential is observed. JP-A-1-115915, JP-A-1-141902, JP-A-1
The carbazole polymer described in -141939 has low sensitivity. JP-A-1-134456, JP-A-1-134445
7, JP-A-1-134462 has good sensitivity, but a residual potential and a change in sensitivity are observed. JP-A-64-9964
Has restrictions on the reaction.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to an acrylic or methacrylic ester having a novel triphenylamine skeleton, a novel polymer obtained therefrom, and an acrylic or methacrylic ester having the novel triphenylamine skeleton. An object of the present invention is to provide a high-sensitivity, high-durability electrophotographic photosensitive member containing a coalesced or copolymer in a charge transfer layer.

[0004]

According to the present invention, there is provided an acrylic or methacrylic acid ester represented by the following formula 1.

Embedded image In the formula, R ₁ : hydrogen, methyl group R ₂ , R ₃ , R ₄ , R ₅ : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n ¹ : an integer of ^{1 to} 10 n ² : an integer of 1 to 4 n ³ , n ⁴ : an integer of 1 to 5 m, k: 0 or 1 And an acrylic or methacrylic acid ester homopolymer or copolymer (I) having a repeating unit represented by the following formula (2):

Embedded image In the formula, R ₁ : hydrogen, methyl group R ₂ , R ₃ , R ₄ , R ₅ : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n ¹ : an integer of ^{1 to} 10 n ² : an integer of 1 to 4 n ³ , n ⁴ : an integer of 1 to 5 m, k: 0 or 1 Further, in an electrophotographic photoreceptor having a photoconductive layer provided on a conductive support, the photoconductive layer contains the homopolymer or copolymer (I) of the acrylic or methacrylic acid ester. An electrophotographic photoreceptor is provided, further comprising a charge generation layer and a charge transfer layer sequentially laminated on a conductive support, wherein the charge transfer layer is represented by the following formula (2). And a repeating unit represented by the following chemical formula 3 , and
Which represents a repeating unit represented by Formula 2
Mixture containing 30 to 90% by weight of the monomer to be prepared
Electrophotographic photoreceptor containing an acrylic or methacrylic acid ester copolymer (II) obtained by polymerizing a product

Embedded image In the formula, R ₁ : hydrogen, methyl group R ₂ , R ₃ , R ₄ , R ₅ : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n ¹ : an integer of ^{1 to} 10 n ² : an integer of 1 to 4 n ³ , n ⁴ : an integer of 1 to 5 m, k: 0 or 1

Embedded image In the formula, R ₁ : hydrogen, a methyl group R ₆ : a linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, or an aralkyl group is provided. In an electrophotographic photoreceptor in which a charge generation layer and a charge transfer layer are sequentially laminated, in the charge transfer layer,
A repeating unit represented by the following chemical formula 2, a repeating unit represented by the following chemical formula 3, and a repeating unit represented by the following chemical formula 4, and represented by the following chemical formula 2
To give 30 to 90 weight
Amount that gives a repeating unit represented by the following formula
20 to 40% by weight of the mer
Mono containing 5 to 20% by weight of a monomer giving a unit
Electrophotographic photoreceptor comprising a cured product of an acrylic or methacrylic acid ester copolymer (III) obtained by polymerizing a polymer mixture with an isocyanate

Embedded image In the formula, R ₁ : hydrogen, methyl group R ₂ , R ₃ , R ₄ , R ₅ : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n ¹ : an integer of ^{1 to} 10 n ² : an integer of 1 to 4 n ³ , n ⁴ : an integer of 1 to 5 m, k: 0 or 1

Embedded image In the formula, R ₁ : hydrogen, methyl group R ₆ : linear or branched alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl group, aralkyl group

Embedded image Wherein R _{1 is} hydrogen, methyl group n ⁵ is an integer from 1 to 10.

Hereinafter, the present invention will be described in detail. The acrylic or methacrylic acid ester having a triphenylamine skeleton represented by the above formula 1 of the present invention is obtained by reacting 4- (N, N-diphenylamino) benzaldehyde and diethyl-methoxybenzylphospho as shown in the following reaction formula in Table 1. The compound is reacted under sodium methylate to synthesize 4-diphenylamino-4'-methoxystilbene. After hydrogenation, the methoxy group is hydrolyzed to -OH using a silyl compound, and then acryl chloride is alkalized. Synthesize by reacting.

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

The homopolymer or copolymer (I) of the acrylic or methacrylic ester having a repeating unit represented by the formula (2) of the present invention comprises the above-mentioned corresponding acrylic or methacrylic ester as a monomer, It is obtained by dissolving in a solvent and conducting a polymerization reaction in the presence of a peroxide or an azo-based initiator. The molecular weight of the homopolymer or copolymer (I) is preferably from 8,000 to 200,000. Next, Table 2 shows examples of the homopolymer.

[0007]

[(1) in Table 2]

[(2) in Table 2]

[(3) in Table 2]

[(4) in Table 2]

[(5) in Table 2]

[(6) in Table 2]

[(7) in Table 2]

[(8) in Table 2]

[(9) in Table 2]

These polymers exhibit high mobility, high sensitivity, low residual potential, and good film properties. The film can be provided as a single CTL layer by dissolving in a solvent such as toluene and coating on CGL. Stolka et al. Report that a film obtained by replacing triphenylamine with polymethyl methacrylate is brittle, but the polymer of the present invention has a distance from the acrylic vinyl chain of (CnH2nO), a phenyl group, (CnH2n).
And the like, and the problem of brittleness and flexibility can be solved by the substitution position of the acrylic group. Further, the monomer represented by Chemical Formula 1 can be copolymerized with another vinyl monomer, for example, an acrylic or methacrylic acid ester to improve the film properties. Examples of such a polymer include an acrylic or methacrylic acid ester having a repeating unit having a triphenylamine skeleton represented by Chemical Formula 2 and a repeating unit represented by Chemical Formula 3, and a copolymer (II), or An acrylic or methacrylic acid ester copolymer (III) having a repeating unit represented by the above formula (4).

Examples of the copolymerizable monomer which gives the repeating unit represented by the above formula (3) include 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, heptadecafluoro methacrylate, phenyl methacrylate, methoxyethyl Methacrylate, ethoxyethyl methacrylate, etc. It is below.

[0010] These monomers may be copolymerized singly or in plurals, taking into consideration the film physical properties such as film properties, flexibility, adhesion, compatibility (transparency), and mechanical strength in consideration of wear resistance. In terms of hardness, low friction coefficient, surface energy, ozone resistance, light resistance, humidity resistance, electrical properties, etc.
Alternatively, the number and ratio thereof are determined. In a copolymer (II) having a repeating unit represented by the above formula (2) and a repeating unit represented by the above formula (3), the copolymer (II) is used as the starting material. The monomer represented by the above formula (1) which gives a repeating unit is generally preferably at least 30% by weight and at most 90% by weight. If the amount is less than 30% by weight, the sensitivity is reduced when used for a photoreceptor, and if it is more than 90% by weight, the physical properties of the film, for example, adhesiveness and flexibility are deteriorated. As the copolymerization method, solution polymerization using radicals, emulsion polymerization, suspension polymerization for obtaining a bead polymer, and ionic polymerization using ions such as anions and cations are applied.

The copolymerizable monomer giving a repeating unit represented by the above formula (4) is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, Hydroxypropyl methacrylate and the like.

In the copolymer (III) which further has a repeating unit having a hydroxy group represented by the chemical formula 4, the monomer represented by the chemical formula 1 as a raw material thereof is:
The content of the repeating unit represented by the above formula (3) is preferably from 20 to 40% by weight, and the amount of the monomer providing the repeating unit represented by the above formula (5) is 5 to 90% by weight.
-20% by weight is preferred. If the amount of the monomer represented by Chemical Formula 1 is less than 30% by weight, the sensitivity decreases when the monomer is used for a photoreceptor, and if it exceeds 90% by weight, adhesiveness and flexibility deteriorate. The repeating unit represented by the above formula (3) gives the flexibility of the film, and the monomer giving 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 formula (4) is less than 5% by weight, the adhesiveness is poor, and the number of reactive sites with the isocyanate compound is small, so that the film hardness is low and the abrasion resistance is poor. On the other hand, when the content is more than 20% by weight, the sensitivity decreases when used for a photoreceptor. In the copolymer (III) with the monomer having a hydroxy group, the mechanical strength of the film can be measured by the crosslinking reaction between the functional group -OH and the isocyanate.
The polymerization is carried out in the same manner as described above.

In the present invention, known isocyanates can be used for the crosslinking reaction.
Is exemplified.

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

Specifically, tolylene diisocyanate,
3,3'-dimethyl-1-diphenyl-4,4'-diisocyanate, diphenylmethane 4,4'-diisocyanate, triphenylmethane triisocyanate, and Sumidur L, HL commercially available from Sumitomo Bayer KK , VL, N and other polyisocyanate compounds;
Crosslinked isocyanates such as Takenate 500 commercially available from Takeda Pharmaceutical Co., and Vernock D-750 commercially available from Dainippon Ink. In the present invention, the isocyanate compound is preferably added in the same amount as the hydroxyl group in the copolymer (III), but may be more or less. 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.
Dry and cure at 90-150 ° C.

The photoreceptor includes a negatively charged photoreceptor in which a charge generation layer and a charge transfer layer are sequentially laminated, a positively chargeable photoreceptor in which a charge transfer layer and a charge generation layer are sequentially laminated, and a single layer positively chargeable photoreceptor. There is a layer configuration and the polymers of the invention are adapted to all of them. C.I. I. No. Fused polycyclic quinone compounds such as 59300 Vat Orange 3; I.
No. And azo pigments having a carbazole skeleton (JP-A-53-95033).
Azo pigments having a styrylstilbene skeleton (described in JP-A-53-138229) and azo pigments having a triphenylamine skeleton (described in JP-A-53-1).
32547), azo pigments having a dibenzothiophene skeleton (described in JP-A-54-21728), azo pigments having an oxadiazole skeleton (described in JP-A-54-12742), fluorenone skeleton Azo pigments having a bisstilbene skeleton (described in JP-A-54-22834).
4-17733), an azo pigment having a distyryloxadiazole skeleton (described in JP-A-54-2129), and an azo pigment having a distyrylcarbazole skeleton (described in JP-A-54-17834). Described), triazo pigments having a carbazole skeleton (JP-A-57-19)
No. 5767), an azo pigment having an anthraquinone skeleton (described in JP-A-57-202545),
Metal or metal-free phthalocyanine and squarium dye can be mentioned.

These charge generating materials are used alone or together with a binder resin to be pulverized and dispersed by a method such as a ball mill, an attritor, and 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, ethylene glycol dialkyl ether, esters such as ethyl acetate and butyl acetate, and halogenation such as methylene chloride, dichloroethane and chlorobenzene Examples thereof include hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene, and can also be used as a mixture of two or more of these. Examples of the binder resin include polyvinyl butyral, polyvinyl acetal, a cellulose derivative, a phenol resin, an epoxy resin, an acrylic resin, a polyester, a silicone resin, and polyvinyl acetate. Pulverization and dispersion preferably have an average pigment particle size of 0.3 μm or less.

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

When a binder resin is not contained in the dispersion, an intermediate layer is preferably provided in order to prevent charge injection from the conductive support, and polyamide, polyacrylanilide, casein, and the like are used as the binder resin for the intermediate layer.
Examples thereof include polyvinyl chloride-vinyl acetate-maleic acid copolymer and phenol resin.

CTLs are polymers (I), (II) and (II)
I) is dissolved in an aromatic hydrocarbon such as toluene, a halogenated hydrocarbon such as methylene chloride, or a cyclic ether such as tetrahydrofuran, and applied by a dipping method, a spray method, or a roll method to form a film having a thickness of 10 to 50 μm. The polymer (I) can be used in combination with another binder resin, and the binder resin used in combination is polystyrene, styrene-M
It is used in combination with a resin having good film properties 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 for 10 polymer parts of the polymer (I).

The polymers (I), (II) and (II)
The CTL can also be formed by dissolving a low-molecular charge transfer material in I), and the charge transfer material may be a pyrazoline compound, α
-A phenylstilbene compound, a hydrazone compound,
Examples include a diarylmethane-based compound, a triphenylamine-based compound, a divinylbenzene-based compound, an oxadiazole-based compound, and a diaminocarbazole-based compound.

Examples will be described below. Example 1 44.6 g of 4-diphenylamino-4'-methoxystilbene 4-diphenylaminobenzaldehyde
(0.2 mol), 51.6 g (0.2 mol) of diethyl-4-methoxybenzylphosphonate, D.I. M. F
Transfer 250 ml to a 500 ml four-necked flask,
57.9 g of 8% sodium methylate was added dropwise at room temperature for 15 minutes, reacted at 50-60 ° C. for 5 hours, diluted with 500 ml of water, acidified with acetic acid, filtered, and the wet cake was filtered three times with 100 ml of methanol. It was washed and recrystallized with a mixed solvent of ethanol and dioxane. Yellow, needles m.p. 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 hydrogenation was performed with 2.41 hydrogen. The solvent was removed to obtain an oily, transparent, pale yellow substance. I. From R δ: 900 to 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 in 30 minutes,
React at 60-70 ° C. for 3 hours, pour into 500 ml of water,
A brown tar 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. 100 ml of a saturated aqueous solution of sodium sulfite
, And a pale yellow, transparent toluene solution was obtained. After dehydration over anhydrous MgSO ₄ , the solvent was removed, and the residue was chromatographed using silica gel and toluene to obtain a hydrolyzate. 31.4 g of oily substance. I. RνOH 3550, 3400cm
^-1 1- [2 '-(4 "-diphenylaminophenyl)
[Ethyl] phenyl methacrylate 31.4 g of the above hydrolyzate, 150 ml of dioxane, 2
20 g of a 0% aqueous sodium hydroxide solution was taken, cooled to 5 ° C., and 10.8 g of methacryl chloride was added dropwise with stirring.
The temperature was kept at 10 ° C. or lower. After the completion of the dropwise addition, the mixture was reacted at room temperature for 2 hours, poured into 500 ml of water, extracted with 300 ml of toluene, washed twice with 200 ml of water, and extracted with anhydrous MgSO 4.
After dehydration in ₄ and removal of the solvent, chromatography separation was performed using silica gel and toluene to obtain a monomer. m. p: 105.5
~ 107 ° C, 30 g, I.V. Rν: 3550, 3400c
C = O at 1740 cm ^-1 with disappearance of m ^-1 , 950 cm
= Absorption of CH ₂ were observed to ^-1.

Example 2 1- (4-diphenylaminophenyl) -2-
(4′-3 ″ -Hydroxypropoxyphenyl) ethane 36.5 g of the hydroxy compound of Example 1, 24 g of a 20% aqueous sodium hydroxide solution, and 200 ml of dioxane were added to 50
While heating and stirring at 11.degree. C., 11.1 g of epichlorohydrin was added to 30.
After the reaction at 60 ° C. for 5 hours, the mixture was 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 separated by silica gel and column chromatography with a developing solvent toluene. . 20 g of anhydrous oil was obtained. 47.28% γ- {4- [2- (4-diphenylaminophenyl) ethyl]} phenyloxypropyl methacrylate 20 g of the above alcohol precursor is dissolved in 150 ml of dioxane, 4 ml of pyridine is taken, cooled to 5 ° C. and stirred. Methacryl chloride (5.9 g) 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 separated by silica gel and column chromatography with 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 monomer, 50 g of toluene and 0.09 g of azobisisobutylnitrile were added, and the mixture was stirred at room temperature for 1 hour under a nitrogen stream, then at 60 ° C for 5 hours, at 70 ° C for 2 hours, at 80 ° C for 2 hours, and at 100 ° C. The polymerization reaction was performed 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.
The solution was dissolved in 2 ml of methanol, and reprecipitation was repeated with 2 L of methanol. Yield 18 g (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. Is G. P. C
As a result, a molecular weight of 5,000 to 100,000 was obtained. This is thought to be due to steric hindrance of the monomer, electron density of the vinyl group, and subtle differences in the reaction atmosphere. The difference in the molecular weight does not significantly affect the electrical properties, but rather the effects of the substituents and substitution positions.

Example 5 Polymer No. 2 in Table 2 20 g of the monomer of No. 3, n-butyl methacrylate (nBMA) 7 g, azobisisobutyronitrile (AIBN) 0.09 g, and toluene 63 g were placed in a four-necked flask, and nitrogen gas was bubbled at room temperature for 1 hour. The reaction was carried out at 70 ° C. for 2 hours and at 80 ° C. for 4 hours. The reaction solution was light brown and viscous. The reaction solution was diluted with 200 ml of toluene, and dropped into 2 L of methanol to precipitate. 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. 2 in Table 2 20 g of 19 monomer, 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. 2 shown in Table 2 20 g of monomer 27, 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 subjected to a polymerization reaction in the same manner as in Example 5 to obtain a pale brown viscous liquid having a solid content of 30%.

The polymer Nos. 35 monomers 20
g, 2 ethylhexyl methacrylate (2HEMA) 5
g, benzyl methacrylate (BzyMA) 4 g, 2-hydroxypropyl methacrylate 4 g, AIBN 0.1
Example 5 5 g of 2 g and 77 g of toluene were placed in a four-diameter flask.
A polymerization reaction was carried out in the same manner as described above to obtain a pale brown viscous liquid having a solid content of 30%. As described above, the copolymers (II) and (II)
Although I) was obtained, the copolymers of Examples 7 and 8 did not reprecipitate,
The coating solution was used as it was.

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

Embedded image Was ground and dispersed in a ball mill for 72 hours, and 600 parts of cyclohexanone was added. After ball milling for 3 hours again, the mixture was let down with 800 parts of a mixed solvent of cyclohexanone: methyl ethyl ketone = 1: 1 by weight to obtain a coating liquid. Then
The following charge transfer layer liquid was prepared on the charge generation layer, applied by a blade method, dried at 120 ° C. for 20 minutes, and had a thickness of 23 μm.
Was provided. No. of Table 2 Polymer 1 Mn = 23,000 5 parts Toluene 5 parts

Examples 10 to 22 As in Example 9, an intermediate layer and a charge generation layer were provided, and
Were coated to prepare a photoreceptor.

The electrophotographic photosensitive member prepared as described above is used as an electrostatic copying paper tester [SP42 manufactured by Kawaguchi Electric Co., Ltd.]
8 type], and the electrophotographic characteristics were evaluated under the following conditions (measured in a dynamic mode). First, the sample is -6K
3. Perform corona discharge of V for 20 seconds to charge, measure the surface potential Vm (Volt) after 20 seconds, leave in a dark place for further 20 seconds, measure the surface potential Vo (Volt) at that time, and then 4. Exposure amounts E1 / 2 and E1 / 10 (lux · sec) required to irradiate 5 lux of white tungsten light to reduce Vo to 1/2 and 1/10, and a surface potential Vr (Volt) 30 seconds after irradiation ) Was measured. Table 3 shows the results.

[0032]

[Table 3]

A photoreceptor was prepared in the same manner as in Example 9 for the copolymer (II). Table 4 shows the copolymer components and ratios, and shows the photosensitive characteristics.

[Table 4]

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

Embedded image

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

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

Embedded image

Table 5 shows the photosensitive characteristics of the obtained photosensitive members.

[Table 5]

Example 31 In the same manner as in Example 9, the intermediate layer and the charge generating layer were laminated, and 5 parts of a 30% solution of 2HEMA copolymerized in Example 7 and 0.1 part of toluylene diisocyanate were added. Coating was carried out by a method, and drying and curing were performed at 130 ° C. for 30 minutes to provide a charge transfer layer.

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

Table 6 shows the photosensitive characteristics of the obtained photoreceptor.

[Table 6] When Examples 31 and 32 were immersed in Isopar H, an isoparaffin-based solvent, or a solvent of toluene or methyl ethyl ketone, no elution of the film was observed.

[0041]

According to the present invention, an acrylic or methacrylic ester having a triphenylamine skeleton represented by the above formula (1), and represented by the above formula (2), (2) and (3), or (2), (3) and (4) The polymer (I), copolymer (II), and (III) having a repeating unit is a novel polymer (I), copolymer (II), and (III)
Is contained in the charge transfer layer of the electrophotographic photoreceptor, whereby there is an effect that a photoreceptor having high sensitivity and high durability can be obtained.

[Brief description of the drawings]

FIG. 1. 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] phenylmethacrylate

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masaomi Sasaki 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 20 / 36 C07C 217/80 C07C 219/34 G03G 5/06-5/07 CA, REGISTRY (STN)

Claims (5)

(57) [Claims] 1. An acrylic or methacrylic acid ester represented by the following chemical formula 1. In the formula, R ₁ : hydrogen, methyl group R ₂ , R ₃ , R ₄ , R ₅ : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n ¹ : an integer of ^{1 to} 10 n ² : an integer of 1 to 4 n ³ , n ⁴ : an integer of 1 to 5 m, k: 0 or 1 2. An acrylic or methacrylic acid ester homopolymer or copolymer (I) having a repeating unit represented by the following chemical formula (2): In the formula, R ₁ : hydrogen, methyl group R ₂ , R ₃ , R ₄ , R ₅ : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n ¹ : an integer of ^{1 to} 10 n ² : an integer of 1 to 4 n ³ , n ⁴ : an integer of 1 to 5 m, k: 0 or 1 3. An electrophotographic photoreceptor having a photoconductive layer provided on a conductive support, wherein the photoconductive layer comprises a homopolymer or copolymer (I) of the acrylic or methacrylic acid ester according to claim 2. An electrophotographic photoreceptor characterized by containing: 4. An electrophotographic photosensitive member in which a charge generation layer and a charge transfer layer are sequentially laminated on a conductive support, wherein the charge transfer layer contains a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3). Which consists of repeating units
2. A compound according to claim 1, which gives a repeating unit represented by:
Containing 30 to 90% by weight of a monomer represented by the formula:
An electrophotographic photoreceptor comprising an acrylic or methacrylic acid ester copolymer (II) obtained by polymerizing a polymer mixture . Embedded image In the formula, R ₁ : hydrogen, methyl group R ₂ , R ₃ , R ₄ , R ₅ : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n ¹ : integer of 10 to 10 n ² : integer of 1 to 4 n ³ , n ⁴ : integer of 1 to 5 m, k: 0 or 1 ] In the formula, R ₁ : hydrogen, methyl group R ₆ : linear or branched alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl group, aralkyl group 5. An electrophotographic photoreceptor in which a charge generation layer and a charge transfer layer are sequentially laminated on a conductive support, wherein the charge transfer layer contains a repeating unit represented by the following formula (2) and a compound represented by the following formula (3).
And a repeating unit represented by the following chemical formula 4, and a repeating unit represented by the following chemical formula 2
2. The product represented by the formula (1) according to claim 1, which gives a unit.
30 to 90% by weight of the mer
20 to 40% by weight of a monomer giving a unit,
A monomer which gives a repeating unit represented by the formula:
An electrophotographic photoreceptor comprising an isocyanate cured product of an acryl or methacrylic ester copolymer (III) obtained by polymerizing a monomer mixture containing 1% by weight . Embedded image In the formula, R ₁ : hydrogen, methyl group R ₂ , R ₃ , R ₄ , R ₅ : hydrogen, the same or different,
Substituted, unsubstituted linear or branched alkyl or alkoxy group, substituted, unsubstituted aryl group, aryloxy group,
Aralkyloxy group, halogen, substituted or unsubstituted amino group n ¹ : integer of 10 to 10 n ² : integer of 1 to 4 n ³ , n ⁴ : integer of 1 to 5 m, k: 0 or 1 ] In the formula, R ₁ : hydrogen, methyl group R ₆ : linear or branched alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl group, aralkyl group In the formula, R ₁ : hydrogen, methyl group n ⁵ : an integer of 1 to 10