JPH09311490A - Image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure especially superior wear resistance for an electrophotographic photoreceptor and to also ensure superior durability, stability and photosensitivity by incorporating a high molecular electric charge transferring material having a specified structure into a layer of the photoreceptor positioned farthest from the substrate on the surface side when the photoreceptor is set in an electrophotographic device using a dry contact developing means. SOLUTION: A high molecular electric charge transferring material represented by the formula is incorporated into a layer of an electrophotographic photoreceptor positioned farthest from the substrate on the surface side when the photoreceptor is set in an electrophotographic device using a dry contact developing means. In the formula, each of R'1 -R'3 is optionally substd. alkyl or halogen, R'4 is H or optionally substd. alkyl, each of R1 and R2 is optionally substd. aryl, each of (o), (p) and (q) is an integer of 0-4, the ratio of k:j is (0.1-1):(0-0.9), (n) is an integer of 5-5,000 as the number of repeating units and X is a divalent aliphatic group, a divalent alicyclic group, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member and an image forming apparatus using the same, and more particularly, an image forming apparatus using a dry contact developing means using a long-life electrophotographic photosensitive member and powder toner. Regarding The electrophotographic photosensitive member of the present invention and the image forming apparatus using the same are applied to a copying machine, a facsimile, a laser printer, a direct digital plate making machine and the like.

[0002]

2. Description of the Related Art An image forming apparatus using an electrophotographic photoconductor, which is applied to a copying machine, a facsimile, a laser printer, a direct digital plate making machine, etc., includes at least an electrophotographic photoconductor, a primary charging means, and an image exposure device. And a developing unit, and a unit for transferring a toner image onto an image carrier (transfer paper), a fixing unit, and a cleaning unit for cleaning the surface of the electrophotographic photosensitive member.

Here, the developing means in the electrophotographic technique is roughly divided into a dry developing means and a wet developing means.

The dry developing means is the most commonly used developing means in an electrophotographic apparatus in view of easiness of maintenance and the like, and is a method of using electro-detection fine particles (toner) made of powder. The dry developing means, depending on the type of the developer, is a dry two-component type in which the developer is a toner and a carrier (toner carrier particles) and other additives, and a dry one-component type in which the carrier is not included but a toner and other additives. It is divided into two. Separately from this, the contact developing means in which the developer directly contacts the photoconductor to attach the toner to the electrostatic latent image on the photoconductor, and the toner carrier such as the carrier or the developing roller directly contacts the photoconductor. However, it can be classified into non-contact developing means in which toner flies in a minute gap between the toner carrier and the photoconductor and adheres to the electrostatic latent image on the photoconductor.

The non-contact developing means has the merit that mechanical damage to the photoconductor is smaller than that of the contact developing means, but in principle it is difficult to develop high density toner such as solid areas on the surface of the photoconductor. Also, in order to obtain stable developing characteristics, it is necessary to have a control technology for the toner layer on the toner carrier and a bias control technology for applying a bias between the toner carrier and the photoconductor in order to stably fly the toner. There are disadvantages.

On the other hand, the contact developing means is superior in stability of image quality to the non-contact developing means. However, on the contrary, since the toner carrier such as the carrier and the developing roller is in direct contact with the surface of the photosensitive member, there is a problem that mechanical damage (wear and scratches) to the photosensitive member is large.

On the other hand, the basic characteristics required for an electrophotographic photoreceptor in electrophotography are that it can be charged to an appropriate potential in a dark place. There is little dissipation of charges in a dark place. What can be done is mentioned.

In addition to these characteristics, long-term reliability, low pollution, low cost, etc. are also required.

Conventionally, as a photoconductor used in an electrophotographic apparatus, a photoconductive layer containing selenium or a selenium alloy as a main component is provided on a conductive support, or an inorganic photoconductive material such as zinc oxide or cadmium sulfide. It is generally known that the above is dispersed in a binder and one using an amorphous silicon-based material, but in recent years, the cost is low, the degree of freedom in designing the photoconductor is high, and there is no pollution. Organic photoreceptors have been widely used due to their properties.

For an organic electrophotographic photosensitive member, a photoconductive resin typified by PVK (polyvinylcarbazole), P
VK-TNF (2,4,7-trinitrofluorenone)
A charge-transfer complex type represented by, a pigment dispersion type represented by a phthalocyanine-binder, a function-separated type photoconductor using a combination of a charge-generating substance and a charge-transporting substance, and the like are known. Photoreceptors are receiving attention.

The mechanism of electrostatic latent image formation in this function-separated type photoconductor is that, when the photoconductor is charged and then irradiated with light, the light passes through the transparent charge transport layer and is caused by the charge generating substance in the charge generating layer. The charge-generating substance that has been absorbed and absorbs light generates charge carriers, which are injected into the charge-transporting layer and move in the charge-transporting layer according to the electric field generated by charging, so that the charge on the surface of the photoconductor is removed. By neutralizing, an electrostatic latent image is formed. It is known and useful in the function-separated type photoreceptor to use a combination of a charge transport substance having an absorption mainly in the ultraviolet region and a charge generating substance having an absorption mainly in the visible region.

Most of the charge transporting substances have been developed as low molecular weight compounds, but since the low molecular weight compounds have no film-forming property by themselves, they are usually used by being dispersed and mixed in an inert polymer. However, the charge transport layer composed of the low molecular weight charge transport material and the inactive polymer is generally soft and has a drawback that the film is easily scraped by repeated use in the Carlson process.

Further, the charge transport layer having this structure has a limit in charge mobility, which has been an obstacle to speeding up or downsizing of the electrophotographic apparatus. This is because the content of the low molecular weight charge transport material is usually 50% by weight or less. That is, the charge mobility can certainly be increased by increasing the content of the low-molecular weight charge transport material, but at the same time, the film-forming property is deteriorated.

In order to overcome these problems, attention has been paid to a polymer type charge transport material, for example, Japanese Patent Laid-Open No. 51-73888.
JP, JP-A-54-8527, JP-A-54-1
1737, JP-A-56-150749, JP-A-57-78402, and JP-A-63-28555.
No. 2, JP-A No. 1-1728, and JP-A No. 1-19.
No. 049, Japanese Patent Laid-Open No. 3-50555, and the like.

However, the photosensitivity of the photoconductor in which the charge transport layer composed of the polymer charge transport material and the charge generation layer are combined is remarkably inferior to the case where the above-mentioned low molecular charge transport material is used. The improvement of was strongly desired.

[0016]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electrophotographic photosensitive member which is suitable for an electrophotographic device using a dry contact developing means, and an image forming apparatus which is a combination thereof. In particular, it is an object to provide an organic electrophotographic photoreceptor having excellent abrasion resistance, durability, stability and photosensitivity, and an image forming apparatus by electrophotography using a dry contact developing means using the same. And

[0017]

[Means for Solving the Problems] We have solved the problems of abrasion resistance and low mobility of charge gallbladder when a conventional organic photoreceptor and an electrophotographic apparatus using a dry contact developing means are combined. As a result of diligent study to achieve the above, in an electrophotographic apparatus using a dry contact developing means, an electrophotographic photosensitive member used in the electrophotographic apparatus is provided in at least one layer from the surface side farthest from the conductive support. It has been clarified that the above object can be achieved by using the electrophotographic photoreceptor containing the polymer charge transport material having the specific structure of the present invention.

That is, when the polymer charge transporting material has the specific structure of the present invention, it is highly resistant to wear caused by contact with a dry developer or a toner carrier and mechanical hazards such as a cleaning blade. And the photosensitivity of the photoconductor is very good by using the polymer charge transport material having the specific structure of the present invention, which is useful for designing an electrophotographic image forming apparatus having a dry contact developing means. It turned out that a big merit is obtained.

The present invention will be described below with reference to the drawings. 1 and 5 and 6 show examples of schematic sectional views of the electrophotographic photoreceptor of the present invention and a dry contact development electrophotographic apparatus using the same. The dry contact developing means further includes a two-component developer composed of a carrier made of magnetic powder or glass powder and a toner, a non-magnetic one-component developer, and a magnetic one-component developer. It can be divided into those to be used.

FIG. 1 shows an example of an image forming apparatus having a dry contact developing means using a two-component developer. Compared with the one-component developer type developing means, the dry contact developing means using the two-component developer has advantages such as good solid image reproducibility, less environmental fluctuation, and stable image quality.
It is generally used as a developing device for black and white and color.

In FIG. 1, (101) is a photosensitive drum which rotates in the direction of the arrow, and a charging device (1
02), image exposure from exposure device (103), developing device (104), two-component developer (105), developer stirring roller (106), developing sleeve (107), magnetic carrier brush (108), toner tank (109), a toner supply roller (110), a transfer body (111), a transfer charger (112), a separation charger (113), a cleaning unit (114), a discharge lamp (115), a fixing device (116), etc. are provided. ing.

Here, the exposure by the image exposure device (103) is performed by analog image exposure in which reflected light of a copy original is emitted through a lens or a mirror, an electric signal from a computer or the like, or an image sensor such as CCD of the copy original. Any of digital image exposure in which an electric signal or the like read and converted in step 1 is reproduced as an optical image by a laser beam, an LED array, or the like may be used.

The electrostatic latent image formed on the surface of the photosensitive drum (101) by being charged and exposed to an image is a developing device (10).
In 4), toner adheres and is visualized. That is, in the developing device (104), the developer stirring roller (10
The magnetic carrier and the toner, which are agitated by 6) and attracted by the electrostatic attraction by frictional charging, are carried to the surface of the photoconductor by the rotating developing sleeve (107) to form a magnetic carrier brush (108) to form the photoconductor drum (108). 101) In contact with the surface, the toner selectively adheres to the electrostatic latent image portion. At this time, for the purpose of controlling or improving the toner adhesion amount and stability, the developing sleeve (107) and the photosensitive drum (1
01) with a linear velocity difference, or the developing sleeve (107)
A contrivance such as applying a DC or AC bias to the device is made.

Further, in the example of FIG. 1, only one developing device is displayed, but in the case of a multi-color image device or a full-color image device, a necessary number of developing devices are arranged around the photoconductor. .

The toner used as a constituent element of the two-component developer (105) contains a thermoplastic resin as a main component,
If necessary, a colorant and a polarity control agent for controlling the charging ability are added to the composition.

Examples of the thermoplastic binder resin include polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-chlorostyrene copolymer, and styrene-
Propylene copolymer, styrene-butadiene copolymer,
Styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-
Acrylic ester copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer,
Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer (styrene-methyl methacrylate copolymer, styrene-methacrylic acid) Ethyl acrylate copolymer, styrene-butyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, etc.), styrene-α-chloromethyl acrylate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer, etc. Styrene resin (styrene or homopolymer containing styrene substitution), vinyl chloride resin, styrene-vinyl acetate copolymer, rosin-modified maleic acid resin, epoxy resin, polyester resin, polyethylene, polypropylene, ionomer resin , Polyurethane resin, keto Resins, ethylene - ethyl acrylate copolymer, xylene resin, waxes such as hot-melt resin and natural or synthetic waxes such as polyvinyl butyral. These are used alone or as a mixture.

As the colorant, carbon black (eg, channel black, acetylene black, lamp black, etc.), nigrosine dye, aniline blue, chalco oil blue, phthalocyanine blue, chrome yellow, ultramarine blue, quinoline yellow, methylene blue chloride, monastral. Blue, malachite green oxalate, rose bengal, monastral red, sudan black BM and the like can be mentioned.

The carrier holds the toner by electrostatic force and conveys it to the surface of the photosensitive member. Iron powder, nickel powder, ferrite powder, glass beads, etc. having a particle size of about 50 to 300 μm are used. Magnetic powder is generally used because it is easy to control the retention and transportation of the carrier.

In addition, a coating layer may be provided on the surface of the carrier for the purpose of preventing the toner from adhering (spenting).

Polyolefin resins such as polyethylene, polypropylene, chlorinated polyethylene, and chlorosulfonated polyethylene as the resin for this coating layer; polyvinyl and polyvinylidene resins such as polystyrene, acrylic resins (eg polymethylmethacrylate), polyacrylonitrile, Polyvinyl acetate,
Polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinylcarbazole, polyvinyl ether, and polyvinyl ketone; vinyl chloride-vinyl acetate copolymers; styrene-acrylic acid copolymers; silicone resins such as straight silicone resins having organosiloxane bonds. Or a modified product thereof (for example, a modified product with an alkyd resin, polyester, epoxy resin, polyurethane, etc.); Fluorine resin such as polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene polyamide; polyester,
Examples thereof include polyethylene terephthalate, polyurethane, polycarbonate; amino resins such as urea-formaldehyde resin; epoxy resin and the like. Of these, acrylic resins, silicone resins or modified products thereof, and fluororesins, particularly silicone resins or modified products thereof, are preferable from the viewpoint of preventing the spent toner from adhering to the carrier.

Further, a fluidizing agent such as silica fine powder, a metal oxide such as titanium oxide and aluminum oxide, an abrasive such as silicon carbide, a lubricant such as fatty acid metal salt and the like are added to the two-component developer. In some cases.

FIG. 5 shows an example of a dry contact development type image forming apparatus using a non-magnetic one-component developer. The dry contact developing method using the non-magnetic one-component developer does not require a device for detecting and controlling the toner concentration as in the two-component developer, and a small-sized and low-cost developing device can be designed. It has the feature. Further, since the toner has high transparency, it can be used as a developing device for color.

In FIG. 5, reference numeral (501) is a photosensitive drum which rotates in the direction of the arrow, and the charging device (5
02), image exposure from the exposure device (503), developing device (504), non-magnetic one-component developer (505), developer stirring roller (506), toner supply roller (507), toner carrying roller (508). , Transfer body (511), transfer charger (512), cleaning unit (51
4), a charge eliminating lamp (515), a fixing device (516) and the like are provided.

Image exposure by the exposure device (503) is analog image exposure in which reflected light of a copy original is emitted through a lens or a mirror, an electric signal from a computer or the like, or an image sensor such as CCD of the copy original. Any of digital image exposure in which an electric signal or the like read and converted in step 1 is reproduced as an optical image by a laser beam, an LED array or the like may be used.

The electrostatic latent image formed on the surface of the photoconductor by being charged and exposed to an image is visualized with toner attached thereto in the developing device (504). That is, the developing device (5
The toner supplied to the toner carrier roller (508) by the toner supply roller (507) in the surface 04) is attracted to the surface of the toner carrier roller (508) by electrostatic attraction due to frictional charging, and the surface of the photosensitive drum (501). The toner is transported to and comes into contact with the toner, and the toner selectively adheres to the electrostatic latent image portion. At this time, for the purpose of controlling or improving the toner adhesion amount and stability, a linear velocity difference is provided between the toner carrying roller (508) and the photoconductor drum (501), or the toner carrying roller (508) and the toner supplying roller. A measure such as applying a DC or AC bias to (507) is made.

In such a developing device, the toner carrying roller is required to have a toner holding ability and an appropriate resistance for applying a developing bias, and in the case where the photoconductor does not elastically deform in a drum shape, Further, in order to secure a sufficient contact area between the surface of the photoconductor and the toner carrying roller, appropriate elasticity [rubber hardness of 40 degrees (JIS A) or less] is required.

As a material for such a toner carrying roller, there are a resin material (plastomer) and a rubber material (elastomer) as the organic polymer materials generally used, and specific examples thereof include polyvinyl chloride and Polyvinyl butyral, polyvinyl alcohol, polyvinylidene chloride, polyvinyl acetate, polyvinyl formal and other vinyl resins; polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer and other polystyrene resins; polyethylene, ethylene-vinyl acetate Polyethylene resin such as copolymers;
Acrylic resins such as polymethylmethacrylate, polymethylmethacrylate-styrene copolymer; polyacetal, polyamide, cellulose, polycarbonate, phenoxy resin, polyester, fluororesin, polyurethane, phenol resin, urea resin, melamine resin, epoxy resin, unsaturated Resin materials such as polyester resin and silicone resin; natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, chloroprene rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, nitrile rubber, acrylic rubber,
Examples of rubber materials include urethane rubber, polysulfide rubber, silicone rubber, fluororubber, and silicone-modified ethylene-propylene rubber.

Materials for imparting conductivity to these materials include metal powders such as Ni and Cu; furnace black, lamp black, thermal black, acetylene black,
Carbon black such as channel black; conductive oxides such as tin oxide, zinc oxide, molybdenum oxide, antimony oxide and potassium titanate; electroless plated products such as titanium oxide and mica plated; graphite;
Examples include inorganic fillers such as metal fibers and carbon fibers, and surfactants. These electroconductivity-imparting agents are added when the organic polymer is insulative, but have a medium resistance (from 10 ² to 10 ²⁾ such as polyamide, chloroprene rubber, epichlorohydrin rubber, nitrile rubber, acrylic rubber and urethane rubber.
It is not always necessary to add it to organic polymers capable of having a region of 10 ¹² Ω · cm).

By using the above materials, the resistance value is adjusted to an appropriate value, and the toner carrying roller is used. Also,
It is not a single layer, but a plurality of materials having different laminated structures and different resistance values are mixed for use in order to improve the characteristics.

In the example of FIG. 5, only one developing device is displayed, but in the case of a multi-color image device or a full-color image device, a necessary number of developing devices are arranged around the photoconductor. .

The toner of the non-magnetic one-component developer also contains a thermoplastic resin as a main component, and if necessary, a colorant and a polarity control agent for controlling the charging ability are added thereto.

As the binder resin and colorant for this toner, the same materials as those for the above-mentioned two-component toner are used. In addition to the above-mentioned components, the toner may also contain various plasticizers (dibutyl phthalate, dioctyl phthalate, etc.) and resistance adjusters (in addition to the above components) for the purpose of adjusting the thermal properties, electrical properties, and physical properties of the toner. Auxiliary agents such as tin oxide, lead oxide, antimony oxide) may be added. As additives other than the toner of the non-magnetic one-component developer, TiO ₂ , Al ₂ O ₃ and S added for the purpose of improving the fluidity of the toner.
Examples thereof include iO ₂ .

Further, FIG. 6 shows an example of a dry contact development type image forming apparatus using a magnetic one-component developer. The dry contact developing method using a magnetic one-component developer has the same characteristic as that using a non-magnetic one-component developer, which makes it possible to design a developing device that is small and low in cost. Since it contains a body, the toner retention and transport properties are superior to those using a non-magnetic one-component developer. However, since it generally contains an opaque magnetic material, it is difficult to apply it to those using a color toner which is required to have color reproducibility and color developability.

In FIG. 6, reference numeral (601) denotes a belt-shaped photosensitive member which rotates in the direction of the arrow, and the charging device (602), the image exposure from the exposure device (603), the developing device (604), Magnetic one-component developer (605), developer stirring roller (606), toner supply roller (607), magnetic toner carrying roller (608), transfer body (611), transfer charger (612), cleaning unit (6)
14), a discharge lamp (615), a fixing device (616), and the like.

Image exposure by the exposure device (603) is analog image exposure in which reflected light of a copy original is emitted through a lens or a mirror, an electric signal from a computer or the like, or an image sensor such as CCD of the copy original. Any of digital image exposure in which an electric signal or the like read and converted in step 1 is reproduced as an optical image by a laser beam, an LED array or the like may be used.

The electrostatic latent image formed on the surface of the photoconductor by being charged and exposed to an image is visualized in the developing device (604) with toner attached. That is, the developing device (6
The toner supplied to the toner carrier roller (608) by the toner supply roller (607) in 04) is attracted to the surface of the toner carrier roller (608) by electrostatic attraction due to frictional charging, or is magnetic as a toner carrier. When the body is used, it is carried to the surface of the photoconductor (601) and held in contact with it while being held by the magnetic force, and the toner selectively adheres to the electrostatic latent image portion. At this time, for the purpose of controlling or improving the toner adhesion amount and stability, a linear velocity difference is provided between the toner carrying roller (608) and the photoconductor (601),
Toner carrying roller (608) and toner supply roller (6)
07) is devised such as applying a DC or AC bias.

In such a developing device, the toner carrying roller is required to have an adequate resistance for applying a toner holding ability (magnetic force) and a developing bias, and in the case where the photosensitive member is drum-shaped and is not elastically deformed. In addition,
Elasticity [rubber hardness of 40 degrees (JIS
A) and below] is also required.

As the material of such a toner carrying roller, the same material as the toner carrying roller in the image forming apparatus of the non-magnetic one-component developing system described above is used. Also,
As the material for imparting conductivity to these materials, the same materials as those for the toner carrying roller in the above-mentioned non-magnetic one-component developing system are used.

Further, as the magnetic substance powder contained in the toner carrying roller for holding the magnetic one-component toner, metal powder such as cobalt, iron and nickel; aluminum, cobalt, copper, iron, lead, nickel, magnesium,
Tin, zinc, gold, silver, selenium, titanium, tungsten,
And a metal such as zirconium and a mixture thereof; a metal oxide such as iron oxide and nickel oxide and a metal compound containing the same; a ferromagnetic ferrite and a mixture thereof.

Using the above materials, the resistance value is adjusted to an appropriate value and the toner carrying roller is used. Also,
It is not a single layer, but a plurality of materials having different laminated structures and different resistance values are mixed for use in order to improve the characteristics.

The toner of the magnetic one-component developer is composed of a thermoplastic resin and a magnetic powder as main components, to which a colorant and a polarity control agent for controlling chargeability are added, if necessary. ing.

As the binder resin and colorant for this toner, the same materials as those for the above-mentioned two-component toner are used. As the magnetic powder, metal powder such as cobalt, iron and nickel; aluminum, cobalt, copper, iron, lead, nickel, magnesium, tin, zinc, gold, silver, selenium,
Examples thereof include metals such as titanium, tungsten, and zirconium and mixtures thereof; metal oxides such as iron oxide and nickel oxide and metal compounds containing the same; ferromagnetic ferrites and mixtures thereof.

Further, in addition to the above components, the toner may contain various plasticizers (dibutyl phthalate, dioctyl phthalate, etc.), resistance, etc. for the purpose of adjusting the thermal characteristics, electrical characteristics, physical characteristics, etc. of the toner. Auxiliary agents such as regulators (tin oxide, lead oxide, antimony oxide, etc.) may be added. As additives other than the toner of the magnetic one-component developer, TiO ₂ , A added for the purpose of improving the fluidity of the toner.
1 ₂ O ₃ , SiO _{2 and the} like can be mentioned.

Next, the electrophotographic photosensitive member used in the present invention will be described with reference to the drawings. FIG. 2 is a cross-sectional view of an electrophotographic photosensitive member used in the present invention, in which a photosensitive layer (23) is formed on a conductive support (21).
FIG. 3 is a cross-sectional view showing another constitution of the electrophotographic photosensitive member used in the present invention, which is a photosensitive layer comprising a charge generating layer (31) and a charge transporting layer (33) on a conductive support (21). (23) is formed. FIG. 4 is a cross-sectional view showing still another constitution of the electrophotographic photosensitive member used in the present invention, in which a conductive support (21) and a photosensitive layer (2) are provided.
The undercoat layer (25) is formed between the charge generation layer (31) and the charge generation layer (3).

Next, the polymer charge transport material used in the present invention will be described. As the polymer charge transport material used in the present invention, polymer charge transport materials represented by the following general formulas 1 to 10 are effectively used. The polymer charge transport materials represented by the general formulas 1 to 10 are exemplified below, and specific examples are shown.

[0056]

Embedded image In the formula, R ₁ , R ₂ , and R ₃ are each independently a substituted or unsubstituted alkyl group or halogen atom, R ₄ is a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₅ and R ₆ are substituted or unsubstituted. Substituted aryl groups, o, p and q each independently represent an integer of 0 to 4, k and j represent compositions, and 0.1 ≦
k ≦ 1, 0 ≦ j ≦ 0.9, and n represents the number of repeating units and is an integer of 5 to 5000. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula.

[0057]

Embedded image In the formula, R ₁₀₁ and R ₁₀₂ each independently represent a substituted or unsubstituted alkyl group, aryl group or halogen atom.
l and m are integers of 0 to 4; Y is a single bond;
2, a linear, branched or cyclic alkylene group, -O
-, - S -, - SO -, - SO 2 -, - CO -, - CO
-O-Z-O-CO- (in the formula, Z represents an aliphatic divalent group), or

[0058]

Embedded image (In the formula, a represents an integer of 1 to 20, b represents an integer of 1 to 2000, and R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or aryl group.). Here, R ₁₀₁ and R ₁₀₂ , and R ₁₀₃ and R ₁₀₄ may be the same or different.

Specific examples of the general formula 1 R ₁ , R ₂ and R ₃ each independently represent a substituted or unsubstituted alkyl group or a halogen atom. Specific examples thereof include the following. It may be the same or different.

The alkyl group is preferably C ₁ -C ₁₂
In particular, it is a C _{1 to} C ₈ , more preferably a C _{1 to} C ₄ linear or branched alkyl group, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, a C _{1 to} C ₄ alkoxy group, It may contain a phenyl group or a phenyl group substituted with a halogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-
Butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl group,
2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4
-Methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R ₄ represents a hydrogen atom or a substituted or unsubstituted alkyl group,
Specific examples of the alkyl group include R ₁ , R ₂ and R ₃ described above.
And the same. R ₅ and R ₆ represent a substituted or unsubstituted aryl group (aromatic hydrocarbon group and unsaturated heterocyclic group), and specific examples thereof include the following, which may be the same or different. May be.

As the aromatic hydrocarbon group, a phenyl group,
As the condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] Cycloheptenylidenephenyl group, and the non-condensed polycyclic group includes biphenylyl group and terphenylyl group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The above aryl group may have the following groups as a substituent. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) Alkyl group. As the alkyl group, the above R ₁ ,
The same as R ₂ and R ₃ can be mentioned.

(3) Alkoxy group (-OR ₁₀₅ ). Examples of the alkoxy group (-OR ₁₀₅ ) include those in which R ₁₀₅ is the alkyl group defined in the above (2), and specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group and an i- group.
Propoxy group, t-butoxy group, n-butoxy group, s-
Examples thereof include butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group and trifluoromethoxy group. (4) An aryloxy group. As an aryloxy group,
Examples of the aryl group include those having a phenyl group and a naphthyl group. This is a C ₁ -C ₄ alkoxy group, C ₁
An alkyl group or a halogen atom -C ₄ may contain a substituent group. Specifically, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxypheninoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group, etc. Is mentioned.

(5) Substituted mercapto group or aryl mercapto group. Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group and a p-methylphenylthio group. (6) An alkyl-substituted amino group. Examples of the alkyl-substituted amino group include those whose alkyl group is the alkyl group defined in the above (2), and specifically, include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group,
Examples thereof include N, N-dibenzylamino group. (7) Acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group and a benzoyl group.

When the diol compound having a triarylamino group represented by the following general formula (A) is polymerized by the phosgene method, the transesterification method or the like, the structural portion represented by X is
It is introduced into the main chain by using the diol compound of the following general formula (B) together. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. The structural portion represented by X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (A) and a bischloroformate derived from the following general formula (B). To be done. In this case, the polycarbonate produced is an alternating copolymer.

[0067]

Embedded image Specific examples of the diol compound of the general formula (B) include the following. 1,3-propanediol, 1,4
-Butanediol, 1,5-pentanediol, 1,6
-Hexanediol, 1,8-octanediol, 1,
10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol, poly Aliphatic diols such as tetramethylene ether glycol and 1,4-cyclohexanediol,
1,3-cyclohexanediol, cyclohexane-
Examples include cycloaliphatic diols such as 1,4-dimethanol.

As the diol having an aromatic ring,
4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2 -Bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-
Bis (4-hydroxyphenyl) cyclopentane, 2,
2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylsulfone,
4'-dihydroxydiphenylsulfoxide, 4,4 '
-Dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide,
4,4'-dihydroxydiphenyl oxide, 2,2-
Bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) xanthene, ethylene glycol-bis (4-hydroxybenzoate), diethylene glycol- Bis (4-hydroxybenzoate), triethylene glycol-bis (4
-Hydroxybenzoate), 1,3-bis (4-hydroxyphenyl) -tetramethyldisiloxane, phenol-modified silicone oil and the like.

[0069]

Embedded image In the formula, R ₇ and R ₈ are substituted or unsubstituted aryl groups, A
r ₁ , Ar ₂ and Ar ₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1.

Specific examples of the general formula 2 R ₇ and R ₈ represent a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different. The aromatic hydrocarbon group is a phenyl group, the condensed polycyclic group is a naphthyl group,
Pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-
2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, biphenylyl group as a non-condensed polycyclic group,
Terphenylyl group, or

[0071]

Embedded image (Where W is -O-, -S-, -SO-, -SO
Represents _2- , -CO- or the following divalent group. )

[0072]

Embedded image

[0073]

Embedded image

[0074]

[Chemical 21]

[0075]

Embedded image Represents

Examples of the heterocyclic group include thienyl group, benzothienyl group, furyl group, benzofuranyl group and carbazolyl group. The arylene group represented by Ar ₁ , Ar ₂ and Ar ₃ includes the divalent group of the aryl group represented by R ₇ and R ₈ and may be the same or different. The above-mentioned aryl group and arylene group may have the following groups (1) to (7) as substituents. Also,
These substituents have the same meanings as R ₁₀₆ , R ₁₀₇ and R ₁₀₈ in the above general formula.

(1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) Alkyl group. The alkyl group is preferably C
₁ -C ₁₂ especially more preferably C ₁ -C ₁₈ linear or branched alkyl group of C ₁ -C _4, these alkyl groups may further fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄ Alkoxy group, phenyl group, or halogen atom, C ₁ ~
It may contain a phenyl group substituted with a C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples thereof include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group and a 4-phenylbenzyl group.

(3) Alkoxy group (-OR ₁₀₉ ). As the alkoxy group (—OR ₁₀₉ ), R ₁₀₉ represents the alkyl group defined in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-
Examples thereof include butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group and trifluoromethoxy group. (4) An aryloxy group. As an aryloxy group,
Examples of the aryl group include those having a phenyl group and a naphthyl group. This is a C ₁ -C ₄ alkoxy group, C ₁
An alkyl group or a halogen atom -C ₄ may contain a substituent group. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be

(5) Substituted mercapto group or aryl mercapto group. Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group and a p-methylphenylthio group. (6) An alkyl-substituted amino group represented by the following formula.

[0080]

Embedded image In the formula, R ₁₁₀ and R ₁₁₁ each independently represent an alkyl group or an aryl group defined in the above (2). Examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group. These are C _{1 to} C ₄ alkoxy groups and C ₁ to
It may contain a C ₄ alkyl group or a halogen atom as a substituent. It may also form a ring in cooperation with the carbon atom on the aryl group. Specific examples of the alkyl-substituted amino group include a diethylamino group, an N-methyl-N-phenylamino group, an N, N-diphenylamino group, an N, N-di (p-tolyl) amino group, a dibenzylamino group, Examples thereof include a piperidino group, a morpholino group, and a julolidyl group.

(7) Methylenedioxy group, alkylenedioxy group such as methylenedithio group, alkylenedithio group and the like.

When the diol compound having a triarylamino group represented by the following general formula (C) is polymerized by the phosgene method, the transesterification method or the like, the structural portion represented by X is
It is introduced into the main chain by using the diol compound of the following general formula (B) together. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. The structural portion of X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group represented by the following general formula (C) and a bischloroformate derived from the following general formula (B). . In this case, the polycarbonate produced is an alternating copolymer.

[0083]

Embedded image As the diol compound of the general formula (B), the same ones as in the general formula 1 can be mentioned.

[0084]

Embedded image In the formula, R ₉ and R ₁₀ are substituted or unsubstituted aryl groups,
Ar ₄ , Ar ₅ and Ar ₆ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1.

Specific examples of the general formula 3 R ₉ and R ₁₀ represent a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different. The aromatic hydrocarbon group is a phenyl group, the condensed polycyclic group is a naphthyl group,
Pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-
2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, biphenylyl group as a non-condensed polycyclic group,
And a terphenylyl group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₄ , Ar ₅ and Ar ₆ include the divalent groups of the aryl groups represented by R ₉ and R ₁₀ , which may be the same or different. The above-mentioned aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) Alkyl group. The alkyl group is preferably
C ₁ -C ₁₂ especially C ₁ -C _8, more preferably C ₁ -C
_{4 is} a straight chain or branched chain alkyl group, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, and C _1-
A C ₄ alkoxy group, a phenyl group, or a halogen atom,
It may contain a phenyl group substituted with a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples thereof include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group and a 4-phenylbenzyl group.

(3) Alkoxy group (-OR ₁₁₂ ). The alkoxy group (-OR _112), include those R _{11 2} is an alkyl group as defined above (2), specifically, methoxy group, ethoxy group, n- propoxy group, i- propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) Aryloxy group. Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. This is a C ₁ -C ₄ alkoxy group, C ₁
An alkyl group or a halogen atom -C ₄ may contain a substituent group. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be

(5) Substituted mercapto group or arylmercapto group. Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group and a p-methylphenylthio group.

(6) Alkyl-substituted amino group. As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specifically, a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group,
Examples thereof include N, N-dibenzylamino group. (7) acyl group; specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

When the diol compound having a triarylamino group represented by the following general formula (D) is polymerized by the phosgene method, the transesterification method or the like, the structural portion represented by X is:
It is introduced into the main chain by using the diol compound of the following general formula (B) together. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. The structural portion of X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group represented by the following general formula (D) and a bischloroformate derived from the following general formula (B). . In this case, the polycarbonate produced is an alternating copolymer.

[0092]

[Chemical formula 26] As the diol compound of the general formula (B), the same ones as in the general formula 1 can be mentioned.

[0093]

Embedded image In the formula, R ₁₁ and R ₁₂ are substituted or unsubstituted aryl groups,
Ar ₇ , Ar ₈ and Ar ₉ are the same or different arylene groups, p
Represents an integer of 1 to 5. X, k, j and n are the same as in the case of the general formula 1.

Specific Examples of General Formula 4 R ₁₁ and R ₁₂ represent a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different. The aromatic hydrocarbon group is a phenyl group, the condensed polycyclic group is a naphthyl group,
Pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-
2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, biphenylyl group as a non-condensed polycyclic group,
And a terphenylyl group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₇ , Ar ₈ and Ar ₉ include the divalent groups of the aryl groups represented by R ₁₁ and R ₁₂ , which may be the same or different. The above-mentioned aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) Alkyl group. The alkyl group is preferably
C ₁ -C ₁₂ especially C ₁ -C _8, more preferably C ₁ -C
_{4 is} a straight chain or branched chain alkyl group, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, and C _1-
A C ₄ alkoxy group, a phenyl group, or a halogen atom,
It may contain a phenyl group substituted with a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples thereof include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group and a 4-phenylbenzyl group.

(3) Alkoxy group (-OR ₁₁₃ ). Examples of the alkoxy group (-OR ₁₁₃ ) include those in which R ₁₁₃ is an alkyl group defined in the above (2), and specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and t. -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like. (4) An aryloxy group. As an aryloxy group,
Examples of the aryl group include a phenyl group and a naphthyl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group,
4-methoxyphenoxy group, 4-chlorophenoxy group,
6-methyl-2-naphthyloxy group and the like can be mentioned.

(5) Substituted mercapto group or aryl mercapto group. Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group and a p-methylphenylthio group. (6) An alkyl-substituted amino group. Examples of the alkyl-substituted amino group include those whose alkyl group is defined in (2) above, and specifically include dimethylamino group, diethylamino group, N-methyl-N-propylamino group,
Examples thereof include N, N-dibenzylamino group. (7) Acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group and a benzoyl group.

When the diol compound having a triarylamino group represented by the following general formula (E) is polymerized by the phosgene method, the transesterification method or the like, the structural portion represented by X is
It is introduced into the main chain by using the diol compound of the following general formula (B) together. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. The structural portion of X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group represented by the following general formula (E) and a bischloroformate derived from the following general formula (B). . In this case, the polycarbonate produced is an alternating copolymer.

[0099]

Embedded image As the diol compound of the general formula (B), the same ones as in the general formula 1 can be mentioned.

[0100]

[Chemical 29] In the formula, R ₁₃ and R ₁₄ are a substituted or unsubstituted aryl group,
Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are the same or different arylene groups,
X ₁ and X ₂ represent a substituted or unsubstituted ethylene group, or a substituted or unsubstituted vinylene group. X, k, j and n are the same as in the case of the general formula 1.

Specific Examples of General Formula 5 R ₁₃ and R ₁₄ represent a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different. The aromatic hydrocarbon group is a phenyl group, the condensed polycyclic group is a naphthyl group,
Pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-
2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, biphenylyl group as a non-condensed polycyclic group,
And a terphenylyl group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₁₀ , Ar ₁₁ and Ar ₁₂ include the divalent groups of the aryl groups represented by R ₁₃ and R ₁₄ , which may be the same or different.
The above-mentioned aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) Alkyl group. The alkyl group is preferably a C _{1 to} C _12, especially a C _{1 to} C ₈ , more preferably a C _{1 to} C ₄ linear or branched alkyl group, and these alkyl groups further include a fluorine atom and a hydroxyl group. ,
Cyano group, C ₁ -C ₄ alkoxy group, phenyl group, or halogen atom, C ₁ -C ₄ alkyl group, or C ₁ -C ₄
It may also contain a phenyl group substituted with an alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n
-Butyl group, i-butyl group, trifluoromethyl group, 2
-Hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4
-Chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like can be mentioned.

(3) Alkoxy group (-OR ₁₁₄ ). Examples of the alkoxy group (-OR ₁₁₄ ) include those in which R ₁₁₄ is an alkyl group defined in the above (2), and specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group and a t group. -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) Aryloxy group. Examples of the aryloxy group include those having a phenyl group or a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group,
Examples thereof include a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group and a 6-methyl-2-naphthyloxy group.

(5) Substituted mercapto group or aryl mercapto group. Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group and a p-methylphenylthio group.

(6) Alkyl-substituted amino group. Examples of the alkyl-substituted amino group include those whose alkyl group is the alkyl group defined in the above (2), and specific examples thereof include dimethylamino group, diethylamino group, N-methyl-N-propylamino group, N, N. -Dibenzylamino group and the like. (7) Acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group and a benzoyl group.

The structural portion of X ₁ and X ₂ represents a substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylene group, and the substituent includes a cyano group, a halogen atom, a nitro group, the above R ₁₃ , The aryl group of R _{14 and} the alkyl group of the above (2) can be mentioned.

When the diol compound having a triarylamino group represented by the following general formula (F) is polymerized by the phosgene method, the transesterification method or the like, the structural portion represented by X is
It is introduced into the main chain by using the diol compound of the following general formula (B) together. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. The structural portion of X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group represented by the following general formula (F) and a bischloroformate derived from the following general formula (B). . In this case, the polycarbonate produced is an alternating copolymer.

[0109]

Embedded image As the diol compound of the general formula (B), the same ones as in the general formula 1 can be mentioned.

[0110]

[Chemical 31]

In the formula, R ₁₅ , R ₁₆ , R ₁₇ , and R ₁₈ are substituted or unsubstituted aryl groups, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ , and A.
r ₁₆ is the same or different arylene group, Y ₁ , Y ₂ , and Y ₃ are a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, They represent a sulfur atom or a vinylene group and may be the same or different. X, k, j
And n are the same as in general formula 1.

Specific Examples of General Formula 6 R ₁₅ , R ₁₆ , R ₁₇ , and R _{18 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, and they are the same. May also be different.

As the aromatic hydrocarbon group, a phenyl group,
As the condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] Cycloheptenylidenephenyl group, and the non-condensed polycyclic group includes biphenylyl group and terphenylyl group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

Further, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆
Examples of the arylene group represented by are the divalent groups of the above aryl groups represented by R ₁₅ , R ₁₆ , R ₁₇ , and R ₁₈ , which may be the same or different.

The above aryl group and arylene group may have the following groups as a substituent. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) Alkyl group. The alkyl group is preferably
C ₁ -C ₁₂ especially C ₁ -C _8, more preferably C ₁ -C
_{4 is} a straight chain or branched chain alkyl group, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, and C _1-
A C ₄ alkoxy group, a phenyl group, or a halogen atom,
It may contain a phenyl group substituted with a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples thereof include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group and a 4-phenylbenzyl group.

(3) Alkoxy group (-OR ₁₁₅ ). Examples of the alkoxy group (-OR ₁₁₅ ) include those in which R ₁₁₅ is an alkyl group defined in the above (2), and specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a t. -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) Aryloxy group. Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. This is a C ₁ -C ₄ alkoxy group, C ₁
An alkyl group or a halogen atom -C ₄ may contain a substituent group. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be

The structural portion of Y ₁ , Y ₂ and Y ₃ is a single bond,
It represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group, which may be the same or different.

Examples of the alkylene group include a divalent group derived from the alkyl group shown in the above (2). Specific examples thereof include a methylene group, an ethylene group, a 1,3-propylene group and a 1,4 group. -Butylene group, 2-methyl-1,3-propylene group, difluoromethylene group, hydroxyethylene group, cyanoethylene group, methoxyethylene group, phenylmethylene group, 4-methylphenylmethylene group, 2,2-
Examples thereof include a propylene group, a 2,2-butylene group and a diphenylmethylene group.

As the cycloalkylene group, 1,1-
Cyclopentylene group, 1,1-cyclohexylene group,
A 1,1-cyclooctylene group etc. can be mentioned.

Examples of the alkylene ether group include a dimethylene ether group, a diethylene ether group, an ethylenemethylene ether group, a bis (triethylene) ether group and a polytetramethylene ether group.

When the diol compound having a triarylamino group represented by the following general formula (G) is polymerized by the phosgene method, the transesterification method or the like, the structural portion represented by X is
It is introduced into the main chain by using the diol compound of the following general formula (B) together. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. The structural portion of X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group represented by the following general formula (G) and a bischloroformate derived from the following general formula (B). . In this case, the polycarbonate produced is an alternating copolymer.

[0123]

Embedded image As the diol compound of the general formula (B), the same ones as in the general formula 1 can be mentioned.

[0124]

[Chemical 33] In the formula, R ₁₉ and R ₂₀ represent a hydrogen atom or a substituted or unsubstituted aryl group, and R ₁₉ and R ₂₀ may form a ring. Ar ₁₇ , Ar ₁₈ and Ar ₁₉ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1.

Specific Examples of General Formula 7 R ₁₉ and R _{20 each} represent a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As the condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] Cycloheptenylidenephenyl group, and the non-condensed polycyclic group includes biphenylyl group and terphenylyl group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

When R ₁₉ and R ₂₀ form a ring, 9
-Fluorididene, 5H-dibenzo [a, d] cycloheptenylidene and the like. In addition, Ar ₁₇ , Ar ₁₈
And R ₁₉ and R ₂₀ are arylene groups represented by Ar ₁₉ and Ar _19.
Examples of the divalent group of the aryl group shown in 1) may be the same or different.

The above aryl group and arylene group may have the following groups as a substituent. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) Alkyl group. The alkyl group is preferably
C ₁ -C ₁₂ especially C ₁ -C _8, more preferably C ₁ -C
_{4 is} a straight chain or branched chain alkyl group, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, and C _1-
A C ₄ alkoxy group, a phenyl group, or a halogen atom,
It may contain a phenyl group substituted with a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples thereof include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group and a 4-phenylbenzyl group.

(3) Alkoxy group (-OR ₁₁₆ ). Examples of the alkoxy group (—OR ₁₁₆ ) include those in which R ₁₁₆ is an alkyl group defined in the above (2), and specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group and a t group. -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) Aryloxy group. Examples of the aryloxy group include those having a phenyl group or a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group,
Examples thereof include a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group and a 6-methyl-2-naphthyloxy group.

(5) Substituted mercapto group or aryl mercapto group. Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group and a p-methylphenylthio group. (6) An alkyl-substituted amino group. Examples of the alkyl-substituted amino group include those whose alkyl group is defined in (2) above, and specifically include dimethylamino group, diethylamino group, N-methyl-N-propylamino group,
Examples thereof include N, N-dibenzylamino group. (7) Acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group and a benzoyl group.

When the diol compound having the triarylamino group of the following general formula (H) is polymerized by the phosgene method, the transesterification method or the like, the structural portion of X is used together with the diol compound of the following general formula (B). It is thus introduced into the main chain. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer.
The structural portion of X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (H) and a bischloroformate derived from the following general formula (B). . In this case, the polycarbonate produced is an alternating copolymer.

[0133]

Embedded image As the diol compound of the general formula (B), the same ones as in the general formula 1 can be mentioned.

[0134]

Embedded image In the formula, R ₂₁ is a substituted or unsubstituted aryl group, A
r ₂₀ , Ar ₂₁ , Ar ₂₂ , and Ar ₂₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1.

Specific Examples of General Formula 8 R ₂₁ represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As the condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] Cycloheptenylidenephenyl group, and the non-condensed polycyclic group includes biphenylyl group and terphenylyl group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

Further, Ar ₂₀ , Ar ₂₁ , Ar ₂₂ and Ar ₂₃
Examples of the arylene group represented by are the divalent groups of the aryl group represented by R ₂₁ , and they may be the same or different.
The above-mentioned aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group.

(2) Alkyl group. As the alkyl group,
Preferably, it is a C _{1 to} C _12, especially a C _{1 to} C ₈ , more preferably a C _{1 to} C ₄ linear or branched alkyl group,
These alkyl groups are further substituted with a fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄ alkoxy group, a phenyl group, or a halogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. It may also contain a phenyl group.
Specifically, a methyl group, an ethyl group, an n-propyl group, i
-Propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group Group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.

(3) Alkoxy group (-OR ₁₁₇ ). Examples of the alkoxy group (-OR ₁₁₇ ) include those in which R ₁₁₇ is an alkyl group defined in the above (2), and specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and t. -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) Aryloxy group. Examples of the aryloxy group include those having a phenyl group or a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group,
Examples thereof include a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group and a 6-methyl-2-naphthyloxy group.

(5) Substituted mercapto group or aryl mercapto group. Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group and a p-methylphenylthio group.

(6) Alkyl-substituted amino group. The alkyl-substituted amino group represents an alkyl group as defined in (2) above. Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, an N, N-dibenzylamino group, and the like. (7) Acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group and a benzoyl group.

When the diol compound having a triarylamino group of the following general formula (J) is polymerized by the phosgene method, the transesterification method or the like for the structural portion of X, the diol compound of the following general formula (B) is used in combination. It is thus introduced into the main chain. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer.
In addition, the structural portion X includes a diol compound having a triarylamino group represented by the following general formula (J) and the following general formula (B).
It is also introduced into the repeating unit by a polymerization reaction with bischloroformate derived from. In this case, the polycarbonate produced is an alternating copolymer.

[0144]

Embedded image As the diol compound of the general formula (B), the same ones as in the general formula 1 can be mentioned.

[0145]

Embedded image In the formula, R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are substituted or unsubstituted aryl groups, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ and Ar _28.
Represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1.

Specific examples of the general formula 9 R ₂₂ , R ₂₃ , R ₂₄ and R _{25 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following and are the same. May also be different.

As the aromatic hydrocarbon group, a phenyl group,
As the condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] Cycloheptenylidenephenyl group, and the non-condensed polycyclic group includes biphenylyl group and terphenylyl group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

Further, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ ,
And the arylene group represented by Ar ₂₈ includes R ₂₂ ,
The divalent group of the aryl group represented by R ₂₃ , R ₂₄ , and R ₂₅ can be mentioned, and they may be the same or different. The above-mentioned aryl group and arylene group may have the following groups as substituents.

(1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) Alkyl group. The alkyl group is preferably
C ₁ -C ₁₂ especially C ₁ -C _8, more preferably C ₁ -C
_{4 is} a straight chain or branched chain alkyl group, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, and C _1-
A C ₄ alkoxy group, a phenyl group, or a halogen atom,
It may contain a phenyl group substituted with a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples thereof include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group and a 4-phenylbenzyl group.

(3) Alkoxy group (-OR ₁₁₈ ). Examples of the alkoxy group (-OR ₁₁₈ ) include those in which R ₁₁₈ is an alkyl group defined in the above (2), and specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and t. -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) Aryloxy group. Examples of the aryloxy group include those having a phenyl group or a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group,
Examples thereof include a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group and a 6-methyl-2-naphthyloxy group.

(5) Substituted mercapto group or aryl mercapto group. Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group and a p-methylphenylthio group.

(6) Alkyl-substituted amino group. Examples of the alkyl-substituted amino group include those whose alkyl group is the alkyl group defined in the above (2), and specific examples thereof include dimethylamino group, diethylamino group, N-methyl-N-propylamino group, N, N. -Dibenzylamino group and the like. (7) Acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group and a benzoyl group.

When the diol compound having a triarylamino group represented by the following general formula (L) is polymerized by the phosgene method, the transesterification method or the like, the structural portion represented by X is
It is introduced into the main chain by using the diol compound of the following general formula (B) together. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. The structural portion X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following general formula (L) and a bischloroformate derived from the following general formula (B). . In this case, the polycarbonate produced is an alternating copolymer.

[0155]

Embedded image As the diol compound of the general formula (B), the same ones as in the general formula 1 can be mentioned.

[0156]

Embedded image In the formula, R ₂₆ and R ₂₇ are substituted or unsubstituted aryl groups,
Ar ₂₉ , Ar ₃₀ and Ar ₃₁ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1.

Specific Examples of General Formula 10 R ₂₆ and R ₂₇ represent a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As the condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] Cycloheptenylidenephenyl group, and the non-condensed polycyclic group includes biphenylyl group and terphenylyl group. Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene group represented by Ar ₂₉ , Ar ₃₀ and Ar ₃₁ includes the divalent groups of the aryl groups represented by R ₂₆ and R ₂₇ , which may be the same or different. The above-mentioned aryl group and arylene group may have the following groups as substituents.

(1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) Alkyl group. The alkyl group is preferably
C ₁ -C ₁₂ especially C ₁ -C _8, more preferably C ₁ -C
_{4 is} a straight chain or branched chain alkyl group, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, and C _1-
A C ₄ alkoxy group, a phenyl group, or a halogen atom,
It may contain a phenyl group substituted with a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i
-Butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group,
Examples thereof include a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group and a 4-phenylbenzyl group.

(3) Alkoxy group (-OR ₁₁₉ ). Examples of the alkoxy group (—OR ₁₁₉ ) include those in which R ₁₁₉ is an alkyl group defined in the above (2), and specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and t. -Butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(4) Aryloxy group. Examples of the aryloxy group include those having a phenyl group or a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group,
Examples thereof include a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group and a 6-methyl-2-naphthyloxy group.

(5) Substituted mercapto group or aryl mercapto group. Specific examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group and a p-methylphenylthio group. (6) An alkyl-substituted amino group. Examples of the alkyl-substituted amino group include those whose alkyl group is defined in (2) above, and specifically include dimethylamino group, diethylamino group, N-methyl-N-propylamino group,
Examples thereof include N, N-dibenzylamino group. (7) Acyl group. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group and a benzoyl group.

When the diol compound having a triarylamino group of the following general formula (M) is polymerized by the phosgene method, the transesterification method or the like, the structural portion of X is used together with the diol compound of the following general formula (B). It is thus introduced into the main chain. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer.
In addition, the structural portion X includes a diol compound having a triarylamino group represented by the following general formula (M) and the following general formula (B).
It is also introduced into the repeating unit by a polymerization reaction with bischloroformate derived from. In this case, the polycarbonate produced is an alternating copolymer.

[0165]

Embedded image As the diol compound of the general formula (B), the same ones as in the general formula 1 can be mentioned.

The conductive support (21) has a volume resistance of 10 ¹⁰ Ω or less, such as aluminum, nickel, chromium, nichrome, copper, silver, gold, platinum,
Metals such as iron, oxides such as tin oxide and indium oxide coated on film or cylindrical plastic, paper, etc. by vapor deposition or sputtering, or plates of aluminum, aluminum alloy, nickel, stainless steel, etc. D. I. , I. I. It is possible to use a tube or the like which has been subjected to surface treatment by cutting, superfinishing, polishing or the like after forming a raw tube by a method such as extrusion, drawing or the like.

The photosensitive layer (23) in the present invention may be a single layer type or a laminated type, but here, for convenience of explanation, the laminated type will be described first. First, the charge generation layer (31) will be described. The charge generation layer (31) is a layer containing a charge generation substance as a main component, and a binder resin may be used if necessary. As the charge generation substance, an inorganic material and an organic material can be used. Examples of the inorganic material include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, and amorphous silicon. As amorphous silicon, a material obtained by terminating a dangling bond with a hydrogen atom or a halogen atom, or a material doped with a boron atom, a phosphorus atom, or the like is preferably used.

On the other hand, known materials can be used as the organic material. For example, phthalocyanine-based pigments such as metal phthalocyanine and metal-free phthalocyanine, azurenium salt pigment, squaric acid methine pigment, azo pigment having a carbazole skeleton, azo pigment having a triphenylamine skeleton, azo pigment having a diphenylamine skeleton, dibenzothiophene skeleton Having azo pigment, azo pigment having fluorenone skeleton, azo pigment having oxadiazole skeleton, azo pigment having bisstilbene skeleton, azo pigment having distyryl oxadiazole skeleton, azo pigment having distyryl carbazole skeleton, perylene Series pigments, anthraquinone series or polycyclic quinone series pigments, quinone imine series pigments, diphenylmethane and triphenylmethane series pigments, benzoquinone and naphthoquinone series pigments, cyanine and azomethine series pigments, Goido based pigments, and bisbenzimidazole pigments. These charge generating substances can be used alone or as a mixture of two or more.

As the binder resin used as necessary in the charge generation layer (31), polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral,
Polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, polyacrylamide and the like are used. These binder resins can be used alone or as a mixture of two or more kinds. In addition to the above-mentioned binder resins as the binder resin for the charge generation layer, the polymer charge transporting substances of the general formulas 1 to 10 described above are preferably used. Is mentioned.

Next, the polymer charge transport material used in the present invention will be described. As the polymer charge transport material used in the present invention, known polymer charge transport materials can be used.

For example, (a) a polymer having a carbazole ring in its main chain and / or side chain. For example, a polymer of poly-N-vinylcarbazole, of N-acrylamidomethylcarbazole disclosed in JP-A-50-82056. Polymer, halogenated poly-N-vinylcarbazole described in JP-A-54-9632, poly-N-acrylamidomethylcarbazole and poly-N-acrylamidomethylcarbamoylalkylcarbazole described in JP-A-54-11737, Japanese Patent Laid-Open No. Hei 4
No. 183719, a specific dihydroxy compound having a carbazole structure, that is, bis [N-hydroxyaryl (or -hydroxyhetero) -N-aryl]
Examples include carbazole-based polycarbonates and compounds obtained by reacting an amino-substituted carbazole or a bisphenol compound with a carbonate-forming compound. (B) Polymer having hydrazone structure in main chain and / or side chain For example, it is produced by dehydrochlorination condensation of chloromethylated polystyrene and 4-hydroxybenzylidenebenzylphenylhydrazone described in JP-A-57-78402. Polystyrene having a hydrazone structure
For example, polystyrene compounds having a 4-hydrazone side chain structure generated by dehydration condensation of poly (4-formylstyrene) and 1,1-diarylhydrazine described in Japanese Patent No. 50555 are exemplified. (C) Polysilylene polymer For example, poly (methylphenylsilylene), poly (n-propylmethylsilylene) -1-methylphenylsilylene or poly (n-propylmethylsilylene) described in JP-A-63-285552, Kaihei 5-1949
-(Si (R ₁ ) (R ₂ ))-described in Japanese Patent Publication No. 7

[0172]

Embedded image A polysilane compound having a repeating unit of (R ₁ , R ₂ ,
R ₃ and R ₄ are exemplified by compounds of H, halogen, ether group, substituted alkyl group, etc.). (D) Polymer having a tertiary amine structure in the main chain and / or side chain, for example, N, N-bis (4-methylphenyl) -4-aminopolystyrene, JP-A-1-13061, and JP-A-1-13061. General formula described in JP-A 1-19049

[0173]

Embedded image (Where Ar and Ar ′ are aryl, Z is carbazole-
4,7-diyl group, Furuorenin group, a phenylene group, a pyrenediyl group, 4,4'-biphenylene divalent unsaturated cyclic group such as a group, R and R 'is -CH ₂ individually -, - (CH ₂ )
_{2 -, - (CH 2)} 3 - and _{- (CH 2) 4 -,} R " is -CO-
Or _{-CO-O-C 6 H 4} -Y-C 6 H 4 -O-CO- (Y
It is _{-O -, - CH 2 -,} - S -, - C (Me) 2 - , etc.), m
Represents 0 or 1, and n represents 5 to 5000. ), JP-A-1
-1728 JP described _{R- [OAO-CH 2 -CH (} OR) -CH 2 -O-B
_{-O-CH 2 -CH (OR)} -CH 2] m- (R is H, -Me, -Et, m is 4-1
000 and A are -Ar-N (Ar ')-[Z]-[N (Ar')-.
Ar] n- (Z is carbazole-4,7-diyl group, fluorenylene group, phenylene group, pyrenediyl group, 4,
A divalent unsaturated cyclic group such as a 4′-biphenylene group, Ar,
Ar 'is an aryl group), B has the same meaning as A or -Ar
-V-Ar (V is _{-CH 2 -, - O -,} - S -, - C (M
e) _2-, etc.). ) Having an arylamine-containing polyhydroxyether resin described in JP-A-5-66598.

[0174]

Embedded image (N ₁ is 1 to 10, n ₂ is 0 to 4, n ₃ is 0 to 5, m is 0
(Co) polymer of (meth) acrylic acid ester having the structure of 1 to 1) described in JP-A-5-40350.
Structural unit

[0175]

Embedded image (R ₁ and R ₂ are alkyl, aryl, aralkyl, A
r ₁ , Ar ₂ and Ar ₃ are divalent aromatic residues, l is an integer of 0 or more, m is an integer of 1 or more, n is an integer of 2 or more, and p is 3 to
Compounds having an integer of 6) are exemplified. (E) Other Polymers For example, a formaldehyde condensation polymer of nitropyrene, a polymer of a 6-vinyl indolo [2,3-b] quinoxaline derivative described in JP-A-51-73888, JP-A-56-150749. 1,1-bis (4
Examples thereof include formaldehyde condensation resin compounds of -dibenzylaminophenyl) propane.

The polymer having an electron-donating group used in the present invention is not limited to the above-mentioned polymers, but also copolymers of known monomers, block polymers, graft polymers, star polymers, and For example, as disclosed in JP-A-3-109406,

[0177]

Embedded image It is also possible to use a cross-linked polymer having an electron donating group.

The low molecular weight charge transporting substances that can be used in combination with the charge generating layer (31) include hole transporting substances and electron transporting substances.

Examples of the electron transporting substance include chloranil, bromanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone, 2,
4,8-Trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophene-4
On, 1,3,7-trinitrodibenzothiophene-
Electron accepting substances such as 5,5-dioxide are exemplified. These electron transport materials can be used alone or as a mixture of two or more kinds.

Examples of the hole-transporting substance include the electron-donating substances shown below, which are preferably used. For example, oxazole derivative, oxadiazole derivative, imidazole derivative, triphenylamine derivative, 9-
(P-diethylaminostyrylanthracene), 1,1
-Bis- (4-dibenzylaminophenyl) propane,
Styryl anthracene, styryl pyrazoline, phenylhydrazone, α-phenylstilbene derivative, thiazole derivative, triazole derivative, phenazine derivative,
Examples include acridine derivatives, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives and the like. These hole transport materials can be used alone or as a mixture of two or more kinds.

The method for forming the charge generation layer (31) includes
The vacuum thin film forming method and the casting method from a solution dispersion system are largely cited. As the former method, a vacuum evaporation method, a glow discharge decomposition method, an ion plating method, a sputtering method, a reactive sputtering method, a CVD method, or the like is used, and the above-mentioned inorganic material and organic material can be favorably formed.

In order to form the charge generation layer by the casting method described later, the above-mentioned inorganic or organic charge generation substance is used together with a binder resin, if necessary, with a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane or butanone. It can be formed by dispersing with a ball mill, an attritor, a sand mill or the like, and appropriately diluting the dispersion liquid and applying it. The coating can be performed by a dip coating method, a spray coating method, a bead coating method, or the like. The thickness of the charge generation layer provided as described above is appropriately about 0.01 to 5 μm, and preferably 0.05 to 2 μm.

Next, the charge transport layer (33) will be described. The charge transport layer (33) is a layer containing a polymer charge transport material as a main component, and can be formed by dissolving or dispersing the polymer charge transport material in a suitable solvent, and applying and drying the solution. As the polymer charge transport substance, any known material may be used as long as it is a polymer charge transport substance having a mobility of 1 × 10 ⁻⁵ cm ² / V · sec or more under an electric field of 3 × 10 ⁵ V / cm. However, a polycarbonate having a triarylamine structure in its main chain and / or side chain is effectively used. The polymer charge transport materials of the above general formulas 1 to 10 are particularly preferably used. Further, if necessary, an appropriate binder resin, low molecular weight charge transport material, plasticizer or leveling agent may be added.

As the binder resin which can be used in combination with the charge transport layer (33), polycarbonate (bisphenol A
Type, bisphenol Z type), polyester, methacrylic resin, acrylic resin, polyethylene, vinyl chloride, vinyl acetate, polystyrene, phenol resin, epoxy resin, polyurethane, polyvinylidene chloride, alkyd resin, silicone resin, polyvinyl carbazole, polyvinyl butyral, polyvinyl Formal, polyacrylate, polyacrylamide, phenoxy resin, etc. are used. These binders can be used alone or as a mixture of two or more kinds.

As the low molecular weight charge transporting material which can be used in combination with the charge transporting layer (33), the same ones as described in the explanation of the charge generating layer (31) can be used. The film thickness of the charge transport layer (33) is suitably 20 μm or less, preferably 15 μm or less. The reason for this is that the resolution of the electrostatic latent image (reproducibility of the original) is improved as described above, and the resolution is lowered when the film thickness is 20 μm or more. Regarding the resolution, the thinner the film thickness, the better results are obtained, but since the abrasion of the photosensitive layer also affects the electrostatic fatigue characteristics, by examining the lower limit value of the film thickness that can be experimentally set in advance, It can be arbitrarily set within the above range. Further, in the present invention, a plasticizer or a leveling agent may be added to the charge transport layer (33).

As the plasticizer, those used as a plasticizer for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount thereof is 0 to 30 parts by weight with respect to 100 parts by weight of the binder resin. The degree is appropriate. As the leveling agent, silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, etc., and polymers or oligomers having a perfluoroalkyl group in the side chain are used, and the amount thereof is 0 based on 100 parts by weight of the binder resin. About 1 part by weight is suitable.

Next, the case where the photosensitive layer (23) has a single layer structure will be described. When a single-layer photosensitive layer is provided by the casting method, most of them include a function-separated type comprising a charge generating substance, a low molecular weight substance and a high molecular weight charge transporting substance. That is,
The above-mentioned materials can be used for the charge generating substance and the charge transporting substance. If necessary, a plasticizer or a leveling agent can be added. Further, as the binder resin which can be used as necessary, the binder resin mentioned above in the charge transport layer (33) is used as it is, or the binder resin mentioned in the charge generation layer (31) is mixed and used. May be. The film thickness of the single-layer photoconductor is 5-100 μm.
m is suitable, and preferably about 10 to 40 μm.

The electrophotographic photosensitive member used in the present invention includes
An undercoat layer (2) is provided between the conductive support (21) and the photosensitive layer (23) [in the case of a laminated type, the charge generation layer (31)].
5) can be provided. The undercoat layer (25) is provided for the purpose of improving the adhesiveness, preventing moire, improving the coatability of the upper layer, and reducing the residual potential. The undercoat layer (25) generally contains a resin as a main component,
Considering that the photosensitive layer is coated thereon with a solvent, it is desirable that these resins have high solubility resistance to general organic solvents. As such a resin, polyvinyl alcohol, casein, water-soluble resin such as sodium polyacrylate, copolymerized nylon, alcohol-soluble resin such as methoxymethylated nylon, polyurethane, melamine resin, alkyd-melamine resin, epoxy resin, etc. Curable resins that form a three-dimensional network structure are exemplified. In addition, titanium oxide, silica, alumina,
A metal oxide exemplified by zirconium oxide, tin oxide, indium oxide, or the like, or a fine powder of metal sulfide, metal nitride, or the like may be added. These undercoat layers can be formed using an appropriate solvent and a coating method as in the case of the above-described photosensitive layer.

Further, a metal oxide layer formed by a sol-gel method or the like using a silane coupling agent, a titanium coupling agent, a chromium coupling agent or the like is also useful as the undercoat layer of the photoreceptor of the present invention. is there. In addition to the above, the undercoat layer of the present invention is provided with Al ₂ O ₃ by anodic oxidation, organic substances such as polyparaxylene (parylene), SiO, SnO ₂ , TiO ₂ , ITO, CeO _{2 and the} like. It is also possible to favorably use the above-mentioned inorganic substance provided by the vacuum thin film forming method. The thickness of the undercoat layer is suitably from 0 to 5 μm.

Further, in the present invention, an antioxidant may be added for the purpose of improving the environment resistance, particularly for the purpose of preventing a decrease in sensitivity and an increase in residual potential. The antioxidant may be added to any layer containing an organic substance, but good results can be obtained by adding it to a layer containing a charge transporting substance. The following may be mentioned as antioxidants that can be used in the present invention.

Monophenol compounds 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5- The-t-
Butyl-4-hydroxyphenyl) propionate and the like.

Bisphenol compounds 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-
Ethyl-6-t-butylphenol), 4,4'-thiobis- (3-methyl-6-t-butylphenol),
4,4'-butylidene bis- (3-methyl-6-t-butylphenol) and the like.

Polymer Phenolic Compound 1,1,3-Tris- (2-methyl-4-hydroxy-)
5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-
4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis (4'-hydroxy) -3′-t-butylphenyl) butyric acid] glycol ester, tocophenols and the like.

Para-phenylenediamines N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-
Phenylenediamine, N, N'-di-isopropyl-p
-Phenylenediamine, N, N'-dimethyl-N, N '
-Di-t-butyl-p-phenylenediamine and the like.

Hydroquinones 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t
-Octyl-5-methylhydroquinone, 2- (2-octadecenyl) -5-methylhydroquinone and the like.

Organic Sulfur Compounds Dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate and the like.

Organic Phosphorus Compounds Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine and the like.

These compounds are known as antioxidants for rubber, plastics, oils and fats, and are easily available as commercial products. The amount of the antioxidant added in the present invention is 0.1-10 with respect to 100 parts by weight of the charge transport material.
It is 0 part by weight, preferably 2 to 30 parts by weight.

[0199]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. In the examples, all parts used are parts by weight, and the repeating unit n of the polymer charge transporting material used is the weight average molecular weight (M
The range was 100 ± 20 calculated from w).

Example 1 A coating liquid for an undercoat layer, a coating liquid for a charge generating layer, and a coating liquid for a charge transport layer, each having the following composition, were successively applied and dried on an φ80 mm aluminum drum to form a coating solution. An electrophotographic photosensitive member of the present invention was obtained by forming an undercoat layer of 5 μm, a charge generation layer of 0.2 μm, and a charge transport layer of 25 μm.

[Coating liquid for undercoat layer] Alkyd resin 6 parts (Beckosol 1307-60-EL, manufactured by Dainippon Ink and Chemicals) Melamine resin 4 parts (Super Beckamine G-821-60, Dainippon Ink and Chemicals) Manufactured) Titanium oxide 40 parts Methyl ethyl ketone 200 parts [Coating liquid for charge generation layer] Trisazo pigment of the following structure 2.5 parts

[0202]

Embedded image Polyvinyl butyral (UCC: XYHL) 0.25 parts Cyclohexanone 200 parts Methyl ethyl ketone 80 parts

[Coating Liquid for Charge Transport Layer] 10 parts of polymeric charge transport material having the following structure

[0204]

Embedded image 100 parts of methylene chloride

Example 2 An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Example 1 except that the polymer charge transporting material used in the charge transporting layer in Example 1 was changed to the one having the following structure. .

[0206]

Embedded image

Example 3 An electrophotographic photosensitive member of the present invention was prepared in exactly the same manner as in Example 1 except that the polymer charge transporting material used in the charge transporting layer in Example 1 was changed to the one having the following structure. .

[0208]

Embedded image

Example 4 An electrophotographic photosensitive member of the present invention was prepared in exactly the same manner as in Example 1 except that the polymer charge transporting material used in the charge transporting layer in Example 1 was changed to the one having the following structure. .

[0210]

Embedded image

Example 5 An electrophotographic photosensitive member of the present invention was prepared in exactly the same manner as in Example 1 except that the polymer charge transporting material used in the charge transporting layer in Example 1 was changed to the one having the following structure. .

[0212]

[Chemical 51]

Example 6 An electrophotographic photosensitive member of the present invention was prepared in the same manner as in Example 1 except that the polymer charge transporting material used in the charge transporting layer in Example 1 was changed to the one having the following structure. .

[0214]

Embedded image

Example 7 An electrophotographic photoreceptor of the present invention was prepared in exactly the same manner as in Example 1 except that the polymer charge transporting material used in the charge transporting layer in Example 1 was changed to the one having the following structure. .

[0216]

Embedded image

Example 8 An electrophotographic photosensitive member of the present invention was prepared in exactly the same manner as in Example 1 except that the polymer charge transporting material used in the charge transporting layer in Example 1 was changed to the one having the following structure. .

[0218]

Embedded image

Example 9 An electrophotographic photosensitive member of the present invention was prepared in exactly the same manner as in Example 1 except that the polymer charge transporting material used in the charge transporting layer in Example 1 was changed to the one having the following structure. .

[0220]

Embedded image

Example 10 An electrophotographic photosensitive member of the present invention was prepared in exactly the same manner as in Example 1 except that the polymer charge transporting material used in the charge transporting layer in Example 1 was changed to the one having the following structure. .

[0222]

Embedded image

Comparative Example 1 The same procedure as in Example 1 was carried out except that the charge transport layer coating solution in Example 1 was changed to the one having the following structure. [Coating Liquid for Charge Transport Layer] Bisphenol A-type Polycarbonate 10 parts (Teijin: Panlite K1300) 10 parts of low molecular charge transport material having the following structure

[0224]

Embedded image 100 parts of methylene chloride

After mounting the electrophotographic photosensitive members of Examples 1 to 10 and Comparative Example 1 produced as described above, the evaluation was performed as follows.

[Evaluation method of actual machine running characteristics] Up to 100,000 sheets of paper can be passed for each photoconductor by using a commercially available dry contact development type digital copying machine (two-component development method) Imagio 420V [manufactured by Ricoh Co., Ltd.] I went. During the paper passing test and after the paper passing test, the potential characteristics of the photoconductor, the image quality characteristics, and the abrasion loss of the photosensitive layer were evaluated at appropriate times.

Dark part potential: photoconductor surface potential when moved to the developing portion position after primary charging Light part potential: image exposure (solid exposure) after primary charging,
Photoreceptor surface potential when moved to the developing section position Image quality: Comprehensive evaluation of solid density, fine line reproducibility, abnormal image, etc. Abrasion amount: Photosensitive layer film thickness reduction amount due to actual machine running Table 1 shows the evaluation results.

[0228]

[Table 1-1]

[0229]

[Table 1-2]

[0230]

[Table 1-3]

[0231]

[Table 1-4]

As is clear from Table 1, the electrophotographic photoconductor and the dry contact development type image forming apparatus (two-component development type) using the electrophotographic photoconductor of the present invention are excellent in charging property and photosensitivity, and have excellent electrical characteristics. With little deterioration and little wear of the photosensitive layer, a high quality hard copy can be obtained stably for a long period of time. On the other hand, in the comparative example, the one using the conventional electrophotographic photosensitive member using the low-molecular-weight charge transport material has a lower initial photosensitivity than the examples, and the film thickness is largely reduced in the continuous use. It can be seen that the characteristics and the image characteristics are greatly deteriorated in a short period of time, and the image forming apparatus having high durability and high reliability is clearly inferior to the image forming apparatus of the present invention.

Example 11 An undercoat layer coating liquid, a charge generation layer coating liquid, and a charge transport layer coating liquid having the same composition as in Example 1 were successively applied and dried on a φ30 mm aluminum drum. Due to 3.5μ
m undercoat layer, 0.2 μm charge generation layer, and 30 μm charge transport layer were formed to obtain the electrophotographic photoreceptor of the present invention.

Example 12 Example 11 was repeated except that the polymer charge transporting material used in the charge transporting layer in Example 11 was changed to the one having the structure of Example 2.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 13 Example 11 except that the polymer charge transporting material used in the charge transporting layer in Example 11 was changed to the one having the structure of Example 3.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 14 Example 11 was repeated except that the polymer charge transporting material used in the charge transporting layer in Example 11 was changed to the one having the structure of Example 4.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 15 Example 11 was repeated except that the polymer charge transporting material used in the charge transporting layer in Example 11 was changed to the structure of Example 5.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 16 Example 11 except that the polymer charge transporting material used in the charge transporting layer in Example 11 was changed to that of the structure of Example 6.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 17 Example 11 was repeated except that the polymer charge transporting material used in the charge transporting layer in Example 11 was changed to the structure of Example 7.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 18 Example 11 was repeated except that the polymer charge transporting material used in the charge transporting layer in Example 11 was changed to the structure of Example 8.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 19 Example 11 was repeated except that the polymer charge transporting material used in the charge transporting layer in Example 11 was changed to the one having the structure of Example 9.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 20 Example 1 was repeated except that the polymer charge transporting material used in the charge transporting layer in Example 11 was changed to the structure of Example 10.
An electrophotographic photosensitive member of the present invention was prepared in exactly the same manner as 1.

Comparative Example 2 The procedure of Example 11 was repeated, except that the coating liquid for charge transport layer in Example 11 was changed to the structure of Comparative Example 1.

After mounting the electrophotographic photosensitive members of Examples 11 to 20 and Comparative Example 2 prepared as described above, the evaluation was performed as follows.

[Actual machine running characteristics evaluation method] Commercial dry contact development type printer (non-magnetic one-component development type) L
With P-6000 [manufactured by Ricoh Co., Ltd.], a paper passing test was performed on each of the photoconductors up to 50,000 sheets. During the paper passing test and after the paper passing test, the potential characteristics of the photoconductor, the image quality characteristics, and the abrasion loss of the photosensitive layer were evaluated at appropriate times.

Dark part potential: photoconductor surface potential when moved to the developing portion position after primary charging Bright part potential: image exposure (solid exposure) after primary charging,
Photoreceptor surface potential when moved to the developing unit position Image quality: Comprehensive evaluation of solid density, fine line reproducibility, abnormal image, etc. Abrasion amount: Photosensitive layer film thickness reduction amount due to actual machine running Table 2 shows the evaluation results.

[0247]

[Table 2-1]

[0248]

[Table 2-2]

[0249]

[Table 2-3]

As is clear from Table 2, the electrophotographic photoconductors of Examples 11 to 20 of the present invention and the dry contact development type image forming apparatus (non-magnetic one-component development type) using the same were found to have chargeability and It has excellent photosensitivity, little deterioration of electrical characteristics, and little abrasion of the photosensitive layer, and a hard copy of high image quality can be stably obtained for a long period of time. On the other hand, in the comparative example,
In the case of using the conventional electrophotographic photosensitive member using the low-molecular charge transport material, the initial photosensitivity is low as compared with the examples,
It can be seen that in continuous use, the film thickness is greatly reduced, the electrical characteristics and the image characteristics are greatly deteriorated in a short period of time, and the image forming apparatus having high durability and high reliability is obviously inferior to that of the embodiment.

Example 21 A coating liquid for an undercoat layer, a coating liquid for a charge generation layer and a coating liquid for a charge transport layer, which had the same composition as in Example 1, were sequentially applied and dried on a Ni belt having a diameter of 60 mm. Thus, an undercoat layer of 3.5 μm, a charge generation layer of 0.2 μm, and a charge transport layer of 30 μm were formed to obtain the electrophotographic photosensitive member of the present invention.

Example 22 Example 21 except that the polymer charge transporting material used in the charge transporting layer in Example 21 was changed to the one having the structure of Example 2.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 23 Example 21 except that the polymer charge transporting material used in the charge transporting layer in Example 21 was changed to the one having the structure of Example 3.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 24 Example 21 except that the polymer charge transporting material used for the charge transporting layer in Example 21 was changed to that of the structure of Example 4.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 25 Example 21 except that the polymer charge transporting material used in the charge transporting layer in Example 21 was changed to that of the structure of Example 5.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 26 Example 21 except that the polymer charge transport material used in the charge transport layer in Example 21 was changed to that of the structure of Example 6.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 27 Example 21 except that the polymer charge transporting material used in the charge transporting layer in Example 21 was changed to the structure of Example 7.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 28 Example 21 except that the polymer charge transporting material used in the charge transporting layer in Example 21 was changed to the structure of Example 8.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 29 Example 21 except that the polymer charge transporting material used in the charge transporting layer in Example 21 was changed to the structure of Example 9.
An electrophotographic photosensitive member according to the present invention was prepared in exactly the same manner as.

Example 30 Example 2 was repeated except that the polymer charge transporting material used in the charge transporting layer in Example 21 was changed to that of Example 10.
An electrophotographic photosensitive member of the present invention was prepared in exactly the same manner as 1.

Comparative Example 3 The procedure of Example 21 was repeated, except that the coating liquid for the charge transport layer in Example 21 was changed to the same as that of Comparative example 1.

After mounting the electrophotographic photosensitive members of Examples 21 to 30 and Comparative Example 3 prepared as described above, the evaluation was performed as follows.

[Actual machine running characteristics evaluation method] Commercially available dry contact development type printer (magnetic one-component development type) SP
-2000 [manufactured by Ricoh Co., Ltd.], each paper was subjected to a paper passing test up to 50,000 sheets. During the paper passing test and after the paper passing test, the potential characteristics of the photoconductor, the image quality characteristics, and the abrasion loss of the photosensitive layer were evaluated at appropriate times.

Dark part potential: photoconductor surface potential when moved to the developing portion position after primary charging Light part potential: image exposure (solid exposure) after primary charging,
Photoreceptor surface potential when moved to the developing section position Image quality: Comprehensive evaluation of solid density, fine line reproducibility, abnormal image, etc. Abrasion amount: Photosensitive layer film thickness reduction amount due to actual machine running Table 3 shows the evaluation results.

[0265]

[Table 3-1]

[0266]

[Table 3-2]

[0267]

[Table 3-3]

As is clear from Table 3, the electrophotographic photoconductors of Examples 21 to 30 of the present invention and the dry contact development type image forming apparatus (non-magnetic one-component development type) using the electrophotographic photoconductors were found to have chargeability and It has excellent photosensitivity, little deterioration of electrical characteristics, and little abrasion of the photosensitive layer, and a hard copy of high image quality can be stably obtained for a long period of time. On the other hand, in the comparative example,
In the case of using the conventional electrophotographic photosensitive member using the low-molecular charge transport material, the initial photosensitivity is low as compared with the examples,
It can be seen that in continuous use, the film thickness is greatly reduced, the electrical characteristics and the image characteristics are greatly deteriorated in a short period of time, and the image forming apparatus having high durability and high reliability is obviously inferior to that of the embodiment.

[0269]

As described above in detail and concretely, by using the electrophotographic photoreceptor of the present invention having excellent photosensitivity and abrasion resistance, high-performance and highly reliable dry contact development can be achieved. A system image forming apparatus can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of an image forming apparatus of the present invention.

FIG. 2 is a sectional view showing a configuration of an electrophotographic photosensitive member used in the image forming apparatus of the present invention.

FIG. 3 is a cross-sectional view showing another configuration of the electrophotographic photosensitive member used in the image forming apparatus of the present invention.

FIG. 4 is a cross-sectional view showing still another configuration of the electrophotographic photosensitive member used in the image forming apparatus of the present invention.

FIG. 5 is a schematic view showing another example of the image forming apparatus of the present invention.

FIG. 6 is a schematic view showing still another example of the image forming apparatus of the present invention.

[Explanation of symbols]

 21 conductive support 23 photosensitive layer 25 undercoat layer 31 charge generation layer 33 charge transport layer 101 photoconductor drum 102 charging device 103 exposure device 104 developing device 105 two-component developer 106 developer stirring roller 107 developing sleeve 108 magnetic carrier brush 109 Toner Tank 110 Toner Supply Roller 111 Transfer Body 112 Transfer Charger 113 Separation Charger 114 Cleaning Unit 115 Electrification Lamp 116 Fixing Device 501 Photosensitive Drum 502 Charging Device 503 Exposure Device 504 Developing Device 505 Non-Magnetic One-Component Developer 506 Developer Stirring Roller 507 Toner supply roller 508 Toner carrying roller 511 Transfer body 512 Transfer charger 513 Separation charger 514 Cleaning unit 515 Static elimination lamp 516 Fixing device 601 belt-shaped photosensitive body 602 a charging device 603 exposure device 604 developing device 605 magnetic one-component developer 606 developer stirring roller 607 the toner supply roller 608 magnetic toner-carrying roller 611 transfer member 612 transfer charger 614 cleaning unit 615 removing lamp 616 fixing device

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Hiroshi Nagame 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Jun Aoto 1-3-6 Nakamagome, Ota-ku, Tokyo In stock company Ricoh (72) Inventor Tatsuya Niimi 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh stock company (72) Inventor Hiroshi Tamura 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72) Inventor Eri Toshi, Nakatamagome 1-3-6, Ota-ku, Tokyo Inside Ricoh Co., Ltd.

Claims (13)

[Claims] 1. At least a charging means, an image exposing means,
In an image forming apparatus having a developing unit, a transfer unit, a fixing unit, and a cleaning unit, the developing unit is a dry contact developing unit using at least powder toner, and the electrophotographic photosensitive member used in the present image forming apparatus is An image forming apparatus comprising a polymer charge transporting material represented by the following general formula 1 in at least one layer on the outermost surface side farthest from a conductive substrate. Embedded image In the formula, R ₁ , R ₂ , and R ₃ are each independently a substituted or unsubstituted alkyl group or halogen atom, R ₄ is a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₅ and R ₆ are substituted or unsubstituted. Substituted aryl groups, o, p and q each independently represent an integer of 0 to 4, k and j represent compositions, and 0.1 ≦
k ≦ 1, 0 ≦ j ≦ 0.9, and n represents the number of repeating units and is an integer of 5 to 5000. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula. Embedded image In the formula, R ₁₀₁ and R ₁₀₂ each independently represent a substituted or unsubstituted alkyl group, aryl group or halogen atom.
l and m are integers of 0 to 4; Y is a single bond;
2, a linear, branched or cyclic alkylene group, -O
-, - S -, - SO -, - SO 2 -, - CO -, - CO
--O--Z--O--CO-- (wherein Z represents an aliphatic divalent group) or: (In the formula, a represents an integer of 1 to 20, b represents an integer of 1 to 2000, and R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or aryl group.). Here, R ₁₀₁ and R ₁₀₂ , and R ₁₀₃ and R ₁₀₄ may be the same or different. 2. An electrophotographic photosensitive member used in the image forming apparatus contains a polymer charge-transporting substance represented by the following general formula 2 in at least one layer on the outermost surface side farthest from the conductive substrate. An image forming apparatus characterized by being a thing. Embedded image In the formula, R ₇ and R ₈ are substituted or unsubstituted aryl groups, A
r ₁ , Ar ₂ and Ar ₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1. 3. An electrophotographic photosensitive member used in the image forming apparatus contains a polymer charge transporting substance represented by the following general formula 3 in at least one layer on the outermost surface side farthest from the conductive substrate. An image forming apparatus characterized by being a thing. Embedded image In the formula, R ₉ and R ₁₀ are substituted or unsubstituted aryl groups,
Ar ₄ , Ar ₅ and Ar ₆ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1. 4. An electrophotographic photosensitive member used in the image forming apparatus contains a polymer charge transport substance represented by the following general formula 4 in at least one layer on the outermost surface side farthest from the conductive substrate. An image forming apparatus characterized by being a thing. [Chemical 6] In the formula, R ₁₁ and R ₁₂ are substituted or unsubstituted aryl groups,
Ar ₇ , Ar ₈ and Ar ₉ are the same or different arylene groups, p
Represents an integer of 1 to 5. X, k, j and n are the same as in the case of the general formula 1. 5. An electrophotographic photosensitive member used in the image forming apparatus contains a polymer charge transporting material represented by the following general formula 5 in at least one layer on the outermost surface side farthest from the conductive substrate. An image forming apparatus characterized by being a thing. [Chemical 7] In the formula, R ₁₃ and R ₁₄ are a substituted or unsubstituted aryl group,
Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are the same or different arylene groups,
X ₁ and X ₂ represent a substituted or unsubstituted ethylene group, or a substituted or unsubstituted vinylene group. X, k, j and n are the same as in the case of the general formula 1. 6. An electrophotographic photosensitive member used in the image forming apparatus contains a polymer charge transport substance represented by the following general formula 6 in at least one layer on the outermost surface side farthest from the conductive substrate. An image forming apparatus characterized by being a thing. Embedded image In the formula, R ₁₅ , R ₁₆ , R ₁₇ , and R ₁₈ are substituted or unsubstituted aryl groups, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ , and Ar ₁₆ are the same or different arylene groups, and Y ₁ , Y ₂ , and Y ₃ are They represent a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom or a vinylene group and may be the same or different. X, k, j and n are the same as in the case of the general formula 1. 7. An electrophotographic photosensitive member used in the image forming apparatus contains a polymer charge-transporting substance represented by the following general formula 7 in at least one layer on the outermost surface side farthest from the conductive substrate. An image forming apparatus characterized by being a thing. Embedded image In the formula, R ₁₉ and R ₂₀ represent a hydrogen atom or a substituted or unsubstituted aryl group, and R ₁₉ and R ₂₀ may form a ring. Ar ₁₇ , Ar ₁₈ and Ar ₁₉ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1. 8. An electrophotographic photosensitive member used in the image forming apparatus contains a polymer charge transport substance represented by the following general formula 8 in at least one layer on the outermost surface side farthest from the conductive substrate. An image forming apparatus characterized by being a thing. Embedded image In the formula, R ₂₁ is a substituted or unsubstituted aryl group, A
r ₂₀ , Ar ₂₁ , Ar ₂₂ , and Ar ₂₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1. 9. An electrophotographic photosensitive member used in the image forming apparatus contains a polymer charge transport substance represented by the following general formula 9 in at least one layer on the outermost surface side farthest from the conductive substrate. An image forming apparatus characterized by being a thing. Embedded image In the formula, R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are substituted or unsubstituted aryl groups, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ and Ar _28.
Represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1. 10. An electrophotographic photosensitive member used in the image forming apparatus contains a polymer charge-transporting substance represented by the following general formula 10 in at least one layer on the outermost surface side farthest from the conductive substrate. An image forming apparatus characterized by being a thing. [Chemical 12] In the formula, R ₂₆ and R ₂₇ are substituted or unsubstituted aryl groups,
Ar ₂₉ , Ar ₃₀ and Ar ₃₁ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1. 11. The image forming apparatus according to claim 1, wherein the dry contact developing means using at least powder toner is magnetic one-component developing means. 12. The image forming apparatus according to claim 1, wherein the dry contact developing means using at least powder toner is a non-magnetic one-component developing means. 13. The image forming apparatus according to claim 1, wherein the dry contact developing means using at least powder toner is a two-component developing method using a magnetic carrier. .