JPS62139557A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve lubricity and releasability of the surface of an electrophotographic sensitive body by incorporating a specified silicone type polymer and a polyarylate resin in the electrophotographic sensitive body composed of a photosensitive layer and a nonphotosensitive surface layer. CONSTITUTION:A condensed product of a modified silicone is obtained by reacting the silicone of formula I and/or II with the compound of formula III. In formulae I, II, and III, each of R1-R7 is alkyl or aryl; (n) is an average polymerization degree; each of R8-R10 is H, halogen, alkyl, or aryl; R11 is alkyl or aryl; X is halogen or alkoxy; and (m) is an integer of 1-3. This modified silicone is reacted with a polymerizable functional compound, such as methyl methacrylate, to produce a silicone type comb-shaped graft polymer (SP), and this SP and the polyacrylate type resin are incorporated in the nonphotosensitive surface layer to obtain the electrophotographic sensitive body, thus permitting cleanability and durability to be improved.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to an electrophotographic photoreceptor that can be widely used in the electrophotographic field such as electrophotographic copying machines, laser beam printers, CRT printers, and electrophotographic engraving systems. .

[Prior Art] Inorganic photoconductive materials such as selenium, cadmium sulfide, and zinc oxide have conventionally been used as photoconductive materials for electrophotographic photoreceptors. On the other hand, organic photoconductive materials such as polyvinyl rubber, oxadiazole, and phthalocyanine have advantages over inorganic photoconductive materials such as non-pollution and high productivity, but their low sensitivity has made it difficult to put them into practical use. For this reason, several sensitization methods have been proposed, and the use of a functionally separated photoreceptor in which a charge generation layer and a charge transport layer are laminated is known and put into practical use as an effective method. It goes without saying that the IT electrophotographic photoreceptor is required to have predetermined sensitivity, electrical properties, and optical properties depending on the electrophotographic process to which it is applied. In particular, for photoreceptors that can be used repeatedly, the surface layer of the photoreceptor, that is, the layer furthest from the substrate, is directly exposed to electrical and mechanical external forces such as corona charging, toner development, transfer to paper, and cleaning processing. Since these materials are added, durability against them is required. Specifically, sensitivity and potential drop due to deterioration due to ozone generated during corona charging.

Durability against increased residual potential and surface friction and scratches caused by rubbing is required.

In addition, adhesion of paper powder due to contact with paper is one of the causes of image fading under high humidity conditions, and toner filming and residual toner due to poor cleaning can significantly impair the resulting image. There is a need to form a photoreceptor surface that is not easily contaminated by these substances and is easily removed.

Conventionally, various methods have been proposed to solve the above-mentioned drawbacks. As one such method, the use of polyarylate resin as a binder for the surface layer is being considered. Polyarylate m resin has good abrasion resistance, so it is a sphere that uses polyarylate resin as a binder in the surface layer.
The durability against Shiteng City's basic strength will be greatly improved. However, since the amount of abrasion of the surface layer decreases, cleaning performance of attached paper dust and residual toner becomes poor, and conversely, this causes deterioration of image quality. In order to improve this problem, attempts have been made to impart lubricity and release properties to the surface layer, making it difficult for paper powder and residual toner to adhere to it and making it easier to clean. As a means for this, there is a method of adding a general coating film surface modifier, ie, a leveling agent, silicone oil, etc., and a method of dispersing Teflon powder.

However, these common surface modifiers.

Due to its poor compatibility with the components of the coating liquid to which it is added, it migrates or oozes out onto the surface layer during long-term use, making it difficult to maintain its effect. In addition, when the surface layer itself forms a photoconductive layer, the surface modifier has poor compatibility with the photoconductive substance, and furthermore, it tends to act as a trap for the movement of carriers due to photogeneration, and it is difficult to repeat the electrophotographic process. There was a tendency for the residual charge to increase.

On the other hand, in the surface layer in which Teflon or the like is dispersed, problems such as poor dispersibility, decreased transparency, and trouble in the carrier have occurred.

[Problems to be solved by the invention] The present invention solves the conventional problems and improves the lubricity of the surface.
The object of the present invention is to provide an electrophotographic photoreceptor which has excellent mold release properties, extremely good cleaning properties, excellent eel return durability, and less damage to the surface layer.

Another object of the present invention is to provide an electrophotographic photoreceptor that does not accumulate residual charge during repeated electrophotographic processes and can always produce high-quality images.

[Means for Solving Problems 1 Effect] The electrophotographic photoreceptor of the present invention, which was discovered as a means for achieving the above-mentioned object of the present invention, has a silicone comb-shaped graft polymer and a polymer at least in the area furthest from the substrate. It is characterized by containing an arylate resin.

That is, 1 the present invention provides silicone represented by the following general formula CI) and/or general formula (II) and at least the following general formula (III) in the layer farthest from the substrate.
) Contains a polyarylate resin and a silicone comb-shaped graft polymer obtained by copolymerizing a modified silicone which is a condensation reaction product with a compound represented by () and a compound having a polymerizable functional group. An electrophotographic photoreceptor.

General Formula (I) In the formula, Rt, Rt, Ra, R4 and Rs represent an alkyl group or an aryl group which may have a substituent, and n represents an average degree of polymerization.

General formula (n) R&? HO→SiO=H In the formula, R13 and R7 represent an alkyl group or an aryl group which may have a substituent, and n represents an average degree of polymerization.

In the formula, Ra, R9 and Rho are a hydrogen atom, a norogen atom, an alkyl group or an aryl group which may have a substituent, Ru is a furkyl group or an aryl group which may have a substituent, and X is a Indicates a halogen atom or an alkoxy group which may have a substituent.

m represents an integer of 1 to 3.

The photosensitive layer has a photosensitive layer and a surface layer of a non-photosensitive layer as constituent components, and the layer that is farthest from the substrate is the non-photosensitive surface layer, and the photosensitive layer has a charge generation layer and a charge transport layer. The layer having a laminated structure and the farthest distance from the substrate is the photosensitive layer, and the layer having the photosensitive layer having a laminated structure of a charge generation layer and a charge transport layer as a component and the layer farthest from the substrate is the charge layer. The content of the silicone comb-shaped graft polymer in the layer furthest from the substrate is within the range of 0.01-10% by weight. .

As is known in the art, an electrophotographic photoreceptor has a photosensitive layer on a substrate, and optionally a non-photosensitive subbing layer, an intermediate layer, a surface layer, etc., and the photosensitive layer includes ,
Some have a single layer structure and others have a laminated structure of a charge generation layer and a charge transport layer.

The present invention can be applied to all of these known types of electrophotographic photoreceptors, and at least the layer furthest away from the substrate (hereinafter referred to as the surface layer of the present invention) is 1, for example, the non-photosensitive surface layer, a single layer. The photosensitive layer of the structure, the charge generation layer or the charge transport layer in the photosensitive layer of the Hi layer structure contains the silicone-based comb-shaped graft polymer and the poly-7-rylate resin.

The silicone-based comb-shaped graft polymer used in the present invention is a modified silicone which is a condensation reaction product of silicone represented by general formula (I) and/or general formula (II) and at least a compound represented by general formula (III). It is obtained by copolymerizing silicone and a compound having a polymerizable functional group, and has a structure in which silicone-containing side chain groups are bonded to the main chain in a branched manner.

The compound represented by the above general formula will be explained in detail below.

General formula (H) R(HO-be5iO)--H And in the general formulas (1) and (II), Rz
, Rz, R1, R4, Ry, R6 and R7 are alkyl groups such as methyl, ethyl, propyl, butyl, or heptaryl groups such as phenyl and naphthyl, and have a substituent such as a halogen atom or a lower alkyl group. and preferably a methyl group.

It is a phenyl group.

n indicates the average degree of polymerization, and is in the range of 1 to 1000, preferably in the range of 1O to 500.

In general formula (m), R8, R9 and R+. are hydrogen atoms, halogen atoms such as fluorine, chlorine, bromine, and iodine,
It is an alkyl group such as methyl, ethyl, propyl, or butyl, or a heptalyl group such as phenyl or naphthyl, and may have a substituent such as a halogen atom or a lower alkyl group, and is preferably a hydrogen atom.

R11 is an alkyl group such as methyl, ethyl, propyl, or butyl, or a heptalyl group such as phenyl or naphthyl, which may have a substituent such as a halogen atom, and is preferably a methyl group or a phenyl group.

X is a halogen atom such as fluorine, chlorine, bromine, or iodine, or a flukoxy group such as methoxy, ethoxy, propoxy, or butoxy, and may have a substituent such as a lower alkoxy group, preferably a methoxy group or ethoxy group. base, 2
-methoxy-ethoxy group.

m represents an integer of 1 to 3.

Next, typical examples of the compounds represented by the above general formula will be listed.

Specific example No. of the compound represented by general formula (I),
Structural formula % Formula % CH, CH.

C,Hr CxHt C,H,C)I3 Specific example No. of the compound represented by the general formula (n), Structural formula No. Specific example No. of the compound represented by the structural formula (III), Structural formula % Formula % : OC, H+0111:H□ j (53) CH Yuyumi HS i OC-H
40CHJOC, 0CI(.

OCz H400-Hr (54) CHLsICH-5i-O
C, H40C, HrOC2H40C&H1 OC-Hr HOCH□ (58) C) + Yotomi C-8i-C9■ i CaHr C&H1 replacement OCR.

CH.

(1114) CM knee CH-9i-C sentence CH.

(85) CH,=C-5i-FCJz 0C,H.

C) I, OCR.

(88) CI, ■C-55-0CRJ■ CH3 CJr (70) CI, 5IC-5i OCH
3OCR.

0C YaHtsu QC, Hs OC, To Rma OC4)! .

0C2H40CH.

QC4120C, Hh (8G) CH Engineering 1ICH-9i -OC
The condensation reaction between the silicone represented by the general formula (I) and/or the general formula (II) and at least the compound represented by the general formula (III) can be carried out very easily according to ordinary organic chemical reaction procedures. To obtain a stable modified silicone by suitably controlling the reaction molar ratio and reaction conditions according to the description in JP-A-58-187606, which discloses a method for synthesizing a comb-shaped graft polymer that proceeds smoothly. I can do it.

As a compound having a polymerizable functional group, a polymerizable monomer without a silica atom is also a compound having a polymerizable functional group at the terminal and has a relatively low molecular weight of about 1,000 to lo or ooo. Examples include macromonomers consisting of monomers such as

Examples of polymerizable monomers include olefinic compounds such as low molecular weight linear unsaturated hydrocarbons such as ethylene, propylene, and butylene, vinyl halides such as vinyl chloride and vinyl fluoride, substituted bistyrene acetates, and vinyl and Lysine and other vinyl aromatic compounds such as vinylnaphthalene, acrylic acid, methacrylic acid and their esters, amides and rust conductors of acrylic acid, methacrylic acid including 7-acrylonitrile, N-vinylcarbazole, N-vinylpyrrolidone and N -Vinyl force N-vinyl compounds such as prolactam, vinyl silicon compounds such as vinyltriethoxysilane, and the like. Disubstituted ethylenes can also be used, examples of which include vinylidene fluoride, vinylidene chloride, and the like, as well as maleic anhydride, maleic acid and fumaric acid. In particular, acrylic esters, methacrylic esters, styrene, and the like are preferred from the viewpoint of affinity with polyarylate resins, and the monomers can be used alone or in combination with monomers of 2s or more.

As a polymerization method for silicone-based comb-shaped graft polymers, radical polymerization and ionic polymerization such as solution polymerization, suspension polymerization, and bulk polymerization can be applied, but radical polymerization by solution polymerization is simple and preferred.

The copolymerization ratio is 5 to 9 as the silicone monomer content.
0% by weight is preferred, and 10-70% by weight is more preferred.

The molecular weight of the obtained polymer was 500 as a number average molecular weight.
-100,000. In particular, 1,000 to 50,000 is preferable.

Since the silicone-based comb-shaped graft polymer in the present invention has such a structure, it has excellent compatibility with a coating solution containing a polyarylate-based resin as a binder resin for forming a surface layer in the present invention. Therefore, the coating film obtained has good transparency and has a long-lasting effect without causing migration or oozing onto the surface layer of the present invention, and the silicone-containing branch portion is Since it has excellent interfacial migration properties, surface modification can be achieved by adding a small amount. Furthermore, even if this additive is contained on the surface, there is no accumulation of residual charge due to repeated electrophotographic processes, and stable charging characteristics can be obtained.

The polyarylate resin used in the present invention contains a linear polymer containing one or more repeating units represented by the following general formula (IV).

General formula (17) In the formula, R12 and RlB are each a hydrogen atom.

Alkyl groups such as methyl, ethyl, propyl, butyl,
It represents a 7-aryl group such as phenyl or naphthyl, and may have a substituent such as a halogen atom or a lower alkyl group, or may form a cyclic structure together with the carbon atom bonded between R1 and R13. , specific examples include a cyclohexyl ring and a lactone structure.

x, x2, x3 and x4 are each a hydrogen atom,
Indicates halogen atoms such as fluorine, chlorine, bromine, and iodine; alkyl groups such as methyl, ethyl, propyl, and butyl; alicyclic alkyl groups such as cyclohexyl; heptaryl groups such as phenyl and naphthyl; and flukoxy groups such as methoxy and ethoxy. .

The above polyarylate resin can be obtained, for example, by a general polyarylate resin synthesis method such as the terephthalic acid chloride method using one or more diol compounds represented by the following general formula.

General formula (V) where R11, Rtx, XI, X2, X3 and JC and x
4 has the same meaning as general formula (IT).

Next, typical specific examples of the compound represented by the general formula (V) are shown below.

Compound No. Structural formula %formula%) CH,C)I.

CH3CN.

0H.

(CHa)u CHλ H.J. (CB,)yo C.I.

CH.

(CH,hr II CH (CHJt CH.

CJHwa H.S. CH.

CH.

H.J. CH.

(CHλ) Yu cooc and H5 C.I.

)1. Go -P-OCH3 The amount of silicone graft polymer added is 31% of the solid content of the surface layer! Based on I, 0.01-10% is suitable, especially O,OS ~5%.

If the amount added is less than 0.01, a sufficient surface modification effect cannot be obtained, while if it exceeds 10%, the graft polymer will exist not only on the coating surface but also in the bulk, making it the main component of the surface layer. Compatibility problems with certain resins and photoconductive materials can lead to whitening, and residual charge buildup can occur during repeated electrophotographic processes.

Next, the present invention will be described in detail by taking as an example the case where the photosensitive layer has a laminated structure of a charge generation layer and a charge transport layer, and the surface layer according to the present invention is the charge transport layer.

When producing the electrophotographic photoreceptor of the present invention, a cylindrical cylinder or film made of metal such as aluminum or stainless steel, paper, or plastic is used as the substrate. A subbing layer (adhesion R) having a barrier function and a subbing function can be provided on these substrates.

The undercoat layer is formed to improve the adhesion of the photosensitive layer, improve workability, protect the substrate, cover defects on the substrate, improve charge injection from the substrate, protect the photosensitive layer from electrical breakdown, etc. .

Materials for the undercoat layer include polyvinyl alcohol and poly-N.
- Vinylimidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, copolymerized nylon, glue, gelatin, etc. are known. These are each dissolved in a suitable solvent and applied onto the substrate. What is the film thickness?

It is about 0.2 to 2 minutes.

In the functionally separated photoreceptor, the charge generating substances include selenium, selenium-tellurium, biryllium dyes, thiopyrylium dyes, phthalocyanine dyes, anthonthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, trisazo pigments, disazo pigments, Azo pigments, indigo pigments, quinacridone pigments, asymmetric quinocyanine, chimesyanine, amorphous silicon described in JP-A-54-143645, etc. can be used, and charge transport substances include pyrene, N-ethylcarbazole, N-
Isopropylcarbazole, N-methyl-N-phenylhydrazino-3-methylidene-9-ethylcarbazole, N,N-diphenylhydrazino-3-methylidene-
8-ethylcarbazole, N,N-diphenylhydrazino-3-methylidene-10-ditylphenothiazine,
N,N-diphenylhydrazino-3-methylidene-1O
-Ethylphenoxazine, P-diethylaminobenzaldehyde-N,N-diphenylhydrazone, P-diethylaminobenzaldehyde -N-α-naphthyl-N-phenylhydrazone, P-pyrrolidinobenzaldehyde-
Hydrazones such as N,N-diphenylhydrazone, 1.3゜3-trimethylindolenine-ω-aldehyde-N,N-diphenylhydrazone, P-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone, 2 .5-bis(P-diethylaminophenyl)-
1,3,4-oxadiazole, 1-phenyl-3-(
P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[quinolyl(2
)]-3-(P-diethylaminostyryl) -s -
(p-diethylaminophenyl)pyrazoline, 1-[pyridyl(2)]-3-(P-diethylaminostyryl)
-5-(p-diethylaminophenyl)pyrazoline, 1
-[8-methoxypyridyl(2)]-3-(P-diethylaminostyryl) -5-(P-diethylaminophenylpyrazoline, 1-[pyridyl(3)]-3-(P-
diethyl 7-minostyryl) -5-(P-diethylaminophenyl)pyrazoline, 1-[lepidyl (2)]-3
-CP-diethylaminostyryl) -5-(P-diethylaminophenyl)pyrazoline, 1-[pyridyl(2
)]-3-(P-diethylaminostyryl)-4-methyl-5-(P-diethylaminophenyl)pyrazoline,
l-(pyridyl(2))]-3-(α-methyl-P-diethylaminostyryl)-5-(p-diethylaminophenyl)hilazoline, 1-phenyl-3-(P-diethylaminostyryl)-4-methyl-5 -(P-diethylaminophenyl)pyrazoline, l-phenyl-3-(α-
benzyl-2-diethylaminostyryl)-5-(P
-diethylaminophenyl)pyrazoline, spiropyrazoline and other pyrazolines, 2-(P-diethylaminostyryl)-6-diethylaminobenzthiazole, 2-
Oxazole compounds such as (P-diethylaminophenyl)-4-(P-dimethylaminophenyl)-5-(2-chlorophenyl)oxazole, thiazole compounds such as 2-(P-diethylaminostyryl)-8-diethylaminobenzthiazole , triarylmethane compounds such as bis(4-diethylamino-2-methylphenyl)phenylmethane, 1.1-bis(4-N,N
-diethyl 7minor 2-methylphenyl)butane.

1.1.2. Polyarylalkanes such as 2-tetrakis(4-N,N-dimethylamino-2-methylphenyl)ethane, etc. can be used.

The charge generation layer is prepared by using a homogenizer, an ultrasonic wave, a ball mill, or a vibrating ball mill using the above-mentioned charge generation substance together with a binder resin and a solvent in an amount of 0.3 to 4 times.

It is well-dispersed using methods such as sand milling, attritor, and roll milling, and is formed by coating and drying.

Its thickness is about 0.1 to 1 mm.

The charge transport layer is formed by dissolving the polyarylate resin and silicone comb-shaped graft polymer, which are essential in the present invention, in a solvent together with a charge transport material as a binder, and coating the mixture on the charge generation layer.

The mixing ratio of the charge transport material and the binder resin is 2:1 to 1:1.
It is about 2.

Examples of solvents used include ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, aromatic hydrocarbons such as toluene and xylene, and chlorinated hydrocarbons such as chlorobenzene, chloroform, and carbon tetrachloride. It will be done.

When applying this solution, 1, for example, dip coating method,
Coating methods such as spinner coating method, bead coating method, blade coating method, curtain coating method can be used, and drying time is 10 to 20 minutes.
5 minutes to 0°C, preferably at a temperature in the range of 20-150°C
The drying can be carried out under blow drying or stationary drying for 5 hours, preferably 10 minutes to 2 hours. The thickness of the generated charge transport layer is about 5 to 201L.

The charge transport layer can also contain one of various additives. Additives include diphenyl, diphenyl chloride,
0-terphenyl, P-terphenyl, dibutyl phthalate, dimethyl glycol phthalate, dioctyl phthalate, triphenyl phosphoric acid, methylnaphthalene, benzophenone, chlorinated paraffin, dilaurylthiopropionate, 3,5-dinitrosalicylic acid, various fluorocarbons etc. can be mentioned.

On the other hand, in a functional photoreceptor having a charge generation layer as a surface layer, the polyarylate resin of the present invention and a silicone comb-shaped graft polymer can be used as a binder for a charge generation substance.

Furthermore, even in a single-layer type photoreceptor in which the photoreceptor layer is the surface layer specified in the present invention, polyarylate resin and silicone comb-shaped graft polymer can be used as binders in the photoreceptor layer. When a non-photosensitive surface layer is provided as a protective layer, for example, the polyarylate resin and silicone comb-shaped graft polymer can be used as protective film forming materials.

Hereinafter, the present invention will be explained according to Examples.

Silicone comb-shaped graft polymer used in Examples (
Samples (a) to (0)) were synthesized according to the polymerization method described in JP-A-58-167606 and JP-A-59-126478, which disclose a method for synthesizing comb-shaped graft polymers. Its composition is listed in Table 1.

Table 1 Silicone-based comb-shaped graft polymer composition Modified silicone (a) 1 30 43 (b)
2 30 44 (C)
7 30 45(d) 1
1 300 4B(e) 13
300 53(f) +4
30 54 (g) 22 300
55 (h) 28 30
134(i) 27 30
43(j) 29 300 45
(k) 28 300 53 (cross”
) 35 30 55 (m)
H30H (n) 1 and 28 30 74 Weight ratio 8G/40 (o) 7 and 35 30 81
! JEL 14-ffl Q1'11'In(a)
Methyl methacrylate 30(b) Styrene
20(C) Methyl methacrylate
1O(e) Styrene 30(f)
Styrene 30 (g) Methyl methacrylate 20 (h) Styrene
30(i) Styrene 15(J) Methyl methacrylate 2°(2) Styrene
30 (m) Methyl methacrylate 25 (n) Methyl methacrylate 20 (0) Styrene 25 The structure of the synthesized silicone-based comb-shaped graft polymer was
and sample (h) ← * 4M shi 1-
Pt I ko 1-1 ψ 4 tei - t n; average 30. Pi
, ql ; Positive integer A1/Bt ; 30/
70 (weight ratio) sample (h) n; average 30, P2, (12; positive integer A2 /B
2; 30/70 (!IE:l ratio) (Synthesis of polyarylate resin) Synthesized using the compound represented by the general formula (V) and terephthalic acid chloride. Specifically, 1.0 mol of bisphenols was dissolved in 1 mol of sodium hydroxide aqueous solution, a surfactant was added, and while stirring vigorously, a solution of 1.0 mol of terephthalic acid chloride dissolved in chloroform was added. Add. After continued stirring, the resulting emulsion was poured into acetone to precipitate the polymer, which was thoroughly washed with water.
After separating into three units and drying by heating, a white polymer is obtained.

Example 1 10 parts (parts by weight, the same applies hereinafter) of cutic casein produced by New Sealant were weighed out, dispersed in 90 parts of water, and then dissolved in 1 part of ammonia water. On the other hand, hydroxypropyl methylcellulose resin (trade name Metrose 80)
Dissolve 3 parts of SH50 (manufactured by Shin-Etsu Chemical) in 20 parts of water and make 1
Next, the two were mixed to prepare a coating solution for an undercoat layer. This coating solution was applied to an aluminum cylinder of 80φ x 300mm by dipping method, and dried at 80°C for 10 minutes to form a 2-layer thick subbing layer.
parts, > 6 parts of cellulose acetate butyrate resin (trade name CAB-381, manufactured by Eastman Chemical) and 60 parts of cyclohexanone
The sample was dispersed for 20 hours using a sand mill device using 1φ glass beads. 7,100 parts of methyl ethyl keto was added to this dispersion, and the mixture was applied by dip coating onto the above-mentioned subbing layer.
After heating and drying for 0 minutes, a charge generation layer with a coating weight of 1 g/m2 of O was provided.

Next, add 10 parts of a hydrazone compound having the following structure.

10 parts of a polyarylate resin synthesized according to the synthesis method of the polyarylate resin using the compound of the specific example (84) of the general formula (V) was dissolved in 7100 parts of dichloromethane. To this liquid, 0.2 parts of the silicone-based comb-shaped graft polymers (a) and f) were added as solid content. This solution was applied onto the charge generation layer and dried with hot air at 100° C. for 1 hour to form a charge transport layer with a thickness of 16 μL. This is designated as sample 1.

Similarly, electrophotographic photoreceptors prepared using the silicone comb-shaped graft polymers of Samples N(b) to (0) were designated as Samples 2 to 15.

For comparison, a sample without the silicone comb-shaped graft polymer was prepared in the same manner as above. This will be referred to as comparative sample 1.

Durability evaluation of 30,000 sheets was performed on these samples using an electrophotographic process consisting of -5.5 kV, corona charging, image exposure, dry toner development, toner transfer to plain paper, and cleaning with a urethane rubber blade. . The results are shown below.

Evaluation environment: 32.5° C., RH 90% For samples 1 to 15, stable high-quality images were obtained up to 30,000 sheets.

In comparative sample 1, image deletion occurred after about 500 copies were made.

Example 2 10 parts of a polyarylate resin synthesized using 10 parts of the hydrazone compound used in Example 1 and the compound of specific example (89) of general formula (V) was dissolved in 80 parts of monochlorobenzene. To this liquid, 0.4 parts of silicone-based comb-shaped graft polymer of sample (h) was added as solid content. This solution was applied onto a substrate coated up to the charge generation layer prepared in the same manner as in Example 1, and dried with hot air at 100°C for 1 hour.
A charge transport layer having an IL thickness was formed.

This is designated as sample 16.

For comparison, a sample without the silicone comb-shaped graft polymer was prepared in the same manner as above, and this was designated as Comparative Sample 2.

The durability of these samples was evaluated under the same conditions as in Example 1. The results are shown below.

For sample 16, stable high-quality images were obtained up to 20,000 sheets. In Comparative Sample 2, image deletion occurred after about 500 copies were made.

Example 3 An aluminum cylinder of 80φ x 300mm was used as a base, and polyamide resin (trade name Ami 970M-80) was applied to it.
A 5% methanol solution of 00, Toshi Fuso) was applied by dipping to form a subbing layer with a thickness of 11 L.

Next, 12 parts of a pyrazoline compound having the following structure and 10 parts of the polyarylate resin synthesized in Example 2 were dissolved in 60 parts of monochlorobenzene.

This liquid was dip-coated onto the above-mentioned subbing layer and dried at 100° C. for 1 hour to form a charge transport layer having a final thickness of 14 mm.

Next, 10 parts of the same bisazo pigment used in Example 1 was added to 100 parts of a 10% by weight dioxane solution of the polyarylate resin synthesized in Example 1, and dispersed for 20 hours using a sand mill device using glass beads. did.

One part of the silicone-based comb-shaped graft polymer of sample (C) was added as a solid content to this dispersion. This solution was applied onto the charge transport layer and dried at 100° C. for 20 minutes to form a charge generation layer with a thickness of 2 IL. This will be referred to as trial 817.

For comparison, a sample without the silicone comb-shaped graft polymer was prepared in the same manner as above, and this was used as Comparative Sample 3.
shall be.

The sample thus obtained was attached to an electrophotographic copying machine that has +5.6kV corona charging, image exposure, dry toner development, toner transfer to plain paper, and cleaning steps using a urethane rubber blade, and the environment was set at 32.5°C and RH90.
Durability evaluation was performed on 3,000 sheets.

For sample 17, high-quality images were obtained up to 3,000 copies. In Comparative Sample 3, the toner was fused onto the surface layer after 300 copies, and many black spots appeared on the image.

Example 4 10 parts of the same hydrazone compound used in Example 1 and 10 parts of the polyarylate resin synthesized in Example 2 were dissolved in 60 parts of monochlorobenzene. This solution was applied by dip coating onto the undercoat layer formed in the same manner as in Example 3, and then heated at 100°C for 1 hour.
A charge transport layer of 15 microns was formed after drying for a period of time.

Next, 10 parts of the same bisazo pigment used in Example 3 was added to 100 parts of a 10fi% monochlorobenzene solution of the polyarylate resin synthesized in Example 2, and dispersed for 20 hours using a sand mill device using glass beads. . One part of the silicone-based comb-shaped graft polymer of sample (j) was added to this dispersion as a solid content. This solution was pushed up and applied onto the charge transport layer and dried at 100°C for 20 minutes.
A thick charge generation layer was formed. This is designated as sample 18.

For comparison, a sample without adding the silicone comb-shaped graft polymer was prepared in the same manner as above, and this was designated as Comparative Sample 4.

The stability of these samples was evaluated under the same conditions as in Example 3. For sample 18, high-quality images were obtained up to 2,000 copies. In comparative sample 4, image deletion occurred after about 800 copies were made.

Example 5 Two parts of the polyarylate resin synthesized in Example 1 were dissolved in 727,100 parts of dichlor. Add the silicone comb-shaped graft polymer of sample (e) to this solution at a solid content of 0.15.
added. This solution was spray-coated onto an electrophotographic photoreceptor prepared in the same manner as Sample 6 of Example 1, and heated at 100°C.
It was dried for 5 minutes to form a protective layer of 0.5 JL.

This is designated as sample 19.

Similarly, 2 parts of the polyarylate resin synthesized in Example 2 was dissolved in 100 parts of monochlorobenzene, and sample (i)
of silicone-based comb-shaped graft polymer with a solid content of 0.
Added 5 copies. This solution was spray-coated onto an electrophotographic photoreceptor prepared in the same manner as Comparative Sample 2 of Example 2.
℃ for 5 minutes to form a protective layer of 0.4 islands.

This is designated as sample 20.

These samples were subjected to s, ooo under the same conditions as in Example 1.
The durability of the sheet was evaluated.

For both Samples 19 and 20, high-quality images were obtained up to 5,000 copies.

Comparative Example Comparative Sample 5 is a sample prepared in the same manner as in Example 1, except that 1 part of silicone oil (trade name KF9B, manufactured by Shin-Etsu Silicone Co., Ltd.) was used as a solid content in place of the silicone-based comb-shaped graft polymer. .

Similarly, a sample prepared in the same manner as in Example 4 except for using 1 part of the above silicone oil was designated as Comparative Sample 6. Durability evaluation of these samples was conducted under the same conditions as in Example 3, but there was significant soil blurring, and the degree of fogging increased due to repeated copying. Also, comparative sample 5
When samples No. 8 and No. 6 were observed one month after their preparation, the silicone oil had migrated to the surface layer and stood out in the form of a stain.

On the other hand, samples 1 to 20 to which the silicone-based comb-shaped graft polymer was added showed no such change over time, and exhibited the same appearance and characteristics as the initial stage.

Example 6 (Measurement of potential characteristics) Next, for samples 1 and 16 and comparative sample 5, -5,5
The VL was attached to an electrophotographic copying machine equipped with a kV corona charger and subjected to an empty charge durability test of 30,000 sheets at room temperature, and was exposed to vD potential and 7.5 lux for seconds.
, the fluctuations in potential were measured. The results are shown below.

Table 2 Sample Initial VB after 30,000 sheets durability
(-V) V*(-V) Vn(-
V) Vt, (-V) Comparative sample 3 of the sample to which silicone oil was added as shown in the table above.
It can be seen that the Vm fluctuation after 0.000 sheet durability is very large, whereas the photoreceptor of the present invention has an extremely stable potential during durability.

Example 7 (Measurement of M1 position characteristics) Next, for sample 18 and comparative sample 6, +5.5 kV
We attached it to an electrophotographic copying machine equipped with a corona charger and conducted three empty charge durability tests of 3,000 sheets at room temperature.
V33 part and 7.5 lux, vL after standing for seconds,
Changes in potential were measured. The results are shown below.

Table 3 Initial a, after oooo sheets durability V) (V)
VL, (V) VD (V) Vb
(V) Sample 18 870 180 820 2
10 Comparative sample 8 880 170 825 31
0 As shown in the table above, the variation in V after 3,000 sheets of the sample to which silicone oil was added was extremely large, whereas the photoreceptor of the present invention has an extremely stable potential during durability. .

Example 8 (Frictional Force Test) Next, the frictional force between the urethane blade and the surface layer was measured for the sample and the comparative sample.

The results are shown below (frictional force is expressed as a relative value, with the frictional force of comparative sample 2 as the reference value l) Table 4 Sample Frictional force Sample Frictional force + 0.
25 2 0.293 0.33
4 0.285 0.30 1
3 0.257 0.27 8
0.229 0.38 10 0.2
911 Q, 38 12 0.20
13 0.27 14 0.2515
0.27 1fl O, 1817
0,17180,11 190,28200,12 Comparative sample Frictional force Comparative sample Frictional force 1 0.
99 2 1.003 0.98
4 0.955 0.14 1
3 0.18 As shown in the table above, the photoreceptor of the present invention to which a silicone-based comb-shaped graft polymer was added and the comparative sample to which silicone oil was added had significantly reduced frictional force compared to the sample without the addition. .

However, the comparative sample to which silicone oil was added had poor storage stability and potential stability during durability as described above.

Example 9 Specific examples (88), (92), (93) of general formula (V) were used in place of the polyarylate resin used in Example 1.
, (100), (103), (105), (110), etc. were used, but the same results as in the case of the polyarylate resin of Example 1 were obtained. Ta.

By adding silicone-based comb-shaped graft polymers in this way, the frictional force of the surface layer is reduced, the cleaning performance is improved, and it is difficult for adherents such as toner and paper dust to stick. The combination with arylate resin has excellent durability, little increase in residual potential, and exhibits stable characteristics over a long period of time.

[Effects of the Invention] The electrophotographic photoreceptor of the present invention has excellent lubricity and mold releasability on one surface, extremely good cleaning properties, and excellent green reversal durability, and is effective in eliminating residual charges in the edge reversal electrophotographic process. There is no accumulation and you can always get high quality images.

Claims (7)

[Claims] (1) A condensation reaction product of silicone represented by the following general formula (I) and/or general formula (II) and at least a compound represented by the following general formula (III) is provided at least in the layer farthest from the substrate. An electrophotographic photoreceptor characterized in that it contains a silicone-based comb-shaped graft polymer obtained by copolymerizing a modified silicone and a compound having a polymerizable functional group, and a polyarylate-based resin. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1, R_2, R_3, R_4 and R_5 represent an alkyl group or an aryl group that may have a substituent, and n is the average degree of polymerization. shows. General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R_6 and R_7 represent an alkyl group or an aryl group that may have a substituent, and n represents an average degree of polymerization. General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_8, R_9 and R_1_0 are hydrogen atoms,
A halogen atom, an alkyl group or an aryl group that may have a substituent, R_1_1 represents an alkyl group or an aryl group that may have a substituent, and X represents a halogen atom or an alkoxy group that may have a substituent. , m represents an integer of 1 to 3. (2) The electrophotographic photosensitive material according to claim (1), which has a photosensitive layer and a non-photosensitive surface layer as constituent components, and the layer that is furthest away from the substrate is the non-photosensitive surface layer. body. (3) The electrophotographic photoreceptor according to claim (2), wherein the photosensitive layer has a laminated structure of a charge generation layer and a charge transport layer. (4) The electrophotographic photoreceptor according to claim (1), wherein the layer furthest away from the substrate is a photosensitive layer. (5) The electronic device according to claim (1), which has as a constituent a photosensitive layer having a laminated structure of a charge generation layer and a charge transport layer, and the layer farthest from the substrate is the charge transport layer. Photographic photoreceptor. (6) The electronic device according to claim (1), which has a photosensitive layer having a laminated structure of a charge generation layer and a charge transport layer as a component, and the charge generation layer is the layer furthest away from the substrate. Photographic photoreceptor. (7) The content of the silicone comb-shaped graft polymer in the layer furthest from the substrate is within the range of 0.01 to 10% by weight, according to any one of claims (1) to (6). The electrophotographic photoreceptor described above.