JP4440176B2 - Electrostatic latent image carrier, method for manufacturing the same, image forming apparatus, image forming method, and process cartridge - Google Patents

Description

  The present invention has a high durability by providing a photosensitive layer having a surface layer having high peel resistance and high wear resistance, uniform high elasticity, and good electrical characteristics, and has a long period of time. Electrostatic latent image carrier (hereinafter sometimes referred to as “photosensitive member” or “electrophotographic photosensitive member”), a method for producing the electrostatic latent image carrier, and the electrostatic latent image carrier. The present invention relates to an image forming apparatus using an image carrier, an image forming method, and a process cartridge.

  The organic photoreceptor (OPC) has, for example, (1) optical characteristics such as light absorption wavelength range and absorption amount, (2) electrical characteristics such as high sensitivity and stable charging characteristics, and (3) It has various advantages such as wide selection range of materials, (4) ease of manufacturing, (5) low cost, and (6) non-toxicity. It is often used in these multifunction devices.

  Recently, the diameter of the photoconductor has been reduced due to the downsizing of the image forming apparatus, and the high speed of the machine and the maintenance-free movement have been added to increase the durability of the photoconductor. The organic photoreceptor (OPC) is generally soft because the surface layer is mainly composed of a low molecular charge transport material and an inert polymer, and when used repeatedly in an electrophotographic process, it is mechanically developed by a developing system or a cleaning system. There is a drawback that wear is likely to occur due to the load. In addition, due to the demand for higher image quality, the cleaning blade's rubber hardness and contact pressure can be increased for the purpose of improving the cleaning performance as the toner particle size is reduced, which also promotes the wear of the photoreceptor. Is a factor. Such wear of the photoreceptor deteriorates electrical characteristics such as sensitivity deterioration and chargeability, and causes abnormal images such as image density reduction and background stains. In addition, scratches in which wear locally occurs result in streak-like stain images due to poor cleaning. Under the present circumstances, the wear and scratches are rate-determined and the life of the photoconductor has been replaced.

In order to increase the durability of the photoreceptor, it is a first problem to reduce the amount of wear. Technologies for improving the abrasion resistance of such a photosensitive layer include (1) using a curable binder for the surface layer (see Patent Document 1), and (2) using a polymer type charge transport material ( Patent Document 2), (3) Inorganic filler dispersed in surface layer (see Patent Document 3), and the like.
Among these techniques, the one using the curable binder (1) has a poor compatibility with the charge transport material, and the residual potential increases due to impurities such as polymerization initiators and unreacted residues. There is a tendency for a decrease to occur easily. In addition, the use of the polymer type charge transport material of (2) can improve the abrasion resistance to some extent, but to fully satisfy the durability required for the organic photoreceptor. Has not reached. In addition, since polymer charge transport materials are difficult to polymerize and purify, and it is difficult to obtain high-purity materials, it is difficult to stabilize electrical characteristics between materials. Furthermore, production problems such as high viscosity of the coating solution may occur. In addition, the dispersion of the inorganic filler (3) exhibits higher wear resistance than a photoreceptor in which a normal low molecular charge transport material is dispersed in an inert polymer. The residual potential increases due to the traps present in the image, and the image density tends to decrease. In addition, when the unevenness of the inorganic filler and the binder resin on the surface of the photoconductor is large, defective cleaning may occur, which may cause toner filming and image flow.
The technologies (1), (2), and (3) sufficiently satisfy the overall durability including the electrical durability and mechanical durability required for the organic photoreceptor. It has not reached.

  Furthermore, Patent Document 4 describes a technique of a protective layer containing a conductive filler in order to improve the electrical characteristics of (1). Although this photoreceptor can suppress an increase in the residual potential due to repeated use, the resistance of the protective layer is low, so that there is a tendency for resolution reduction and image flow to occur in a high humidity environment.

  As a wear-resistant technique for a photosensitive layer that replaces these, a cured charge transport layer containing a monomer having a carbon-carbon double bond, a charge transport agent having a carbon-carbon double bond, and a binder resin may be provided. It has been proposed (see Patent Document 5). This binder resin includes those having a carbon-carbon double bond and having reactivity to the charge transfer agent and those having no double bond and no reactivity. This photoconductor is remarkably compatible with both wear resistance and good electrical properties. However, when a non-reactive binder resin is used, the binder resin and the carbon-carbon double layer are used. The compatibility between the monomer having a bond and the cured product produced by the reaction of the charge transfer agent is poor, phase separation occurs in the surface layer, and a portion having a low wear resistance is formed locally. Or toner external additives and paper dust may be fixed. When these fixings further progress, toner filming is caused, and white spots in the image area may occur due to non-uniformity of light transmission. In this case, the binder resin hinders the curing of the monomer, and what is specifically described as the monomer having the carbon-carbon double bond used in the photoreceptor is a bifunctional one. Such a bifunctional monomer has a small number of functional groups and does not provide a sufficient crosslinking density, and is still unsatisfactory in terms of wear resistance. Further, even when a reactive binder is used, it is difficult to achieve both the binding amount and the crosslinking density of the charge transport agent due to the low number of functional groups contained in the monomer and the binder resin, and the electrical characteristics and The abrasion resistance was not sufficient.

  A photosensitive layer containing a compound obtained by curing a hole transporting compound having two or more chain polymerizable functional groups in the same molecule is also known (see Patent Document 6). Since this photosensitive layer can increase the crosslink density, it has high hardness, but since the bulky hole transporting compound has two or more chain polymerizable functional groups, the cured product is distorted and cured. The reaction tends to be uneven. For this reason, there exists a problem that the restoring force with respect to an external stress falls locally, and a crack and a crack are easy to generate | occur | produce by stress, such as carrier adhesion, by long-term repeated use.

  A photosensitive layer containing a compound obtained by curing a hole transporting compound having only one chain polymerizable functional group in the same molecule is also known (see Patent Document 7). This photosensitive layer suppresses distortion in the cured product by using one chain-polymerizable functional group, but it cannot sufficiently reduce internal stress when cured, and cures as wear progresses. There is a problem that the film peels off and sufficient durability cannot be obtained.

  Accordingly, an electrostatic latent image carrier having a photosensitive layer having a surface layer having high peel resistance and wear resistance, good electrical characteristics, and a highly elastic and homogeneous surface layer, and the electrostatic latent image An image forming method that uses an image carrier, has high durability, and can realize sufficiently high image quality over a long period of time and related technology have not yet been provided, and its rapid development is desired. Currently.

JP 56-48637 A JP-A 64-1728 JP-A-4-281461 JP 2002-6526 A Japanese Patent No. 3194392 JP 2000-66425 A JP 2004-302451 A

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention provides image degradation due to abrasion by providing a photosensitive layer having high peel resistance and abrasion resistance, good electrical characteristics, and a highly elastic and homogeneous surface layer. An electrostatic latent image carrier capable of suppressing and realizing high image quality over a long period of time, a method for producing the electrostatic latent image carrier, and a long life and high performance using the electrostatic latent image carrier An object is to provide a high-performance image forming method, an image forming apparatus, and a process cartridge.

Means for solving the problems are as follows. That is,
<1> A support, and at least a photosensitive layer and a surface layer on the support in this order,
The surface layer contains a cured product of at least a trifunctional or higher functional radical polymerizable compound having no charge transport structure and a radical polymerizable compound having a charge transport structure, and the photosensitive layer and the surface layer It has an adhesive layer between the layers, and the adhesive layer contains at least one obtained by curing a radically polymerizable compound not having a charge transporting structure having a viscosity at 25 ° C. of 1 to 20 mPa · s. An electrostatic latent image carrier.
<2> The electrostatic latent image carrier according to <1>, wherein the radical polymerizable compound having no charge transporting structure is bifunctional.
<3> The adhesive layer is obtained by curing a radical polymerizable compound having no charge transporting structure having a viscosity at 25 ° C. of 1 to 20 mPa · s and a radical polymerizable compound having a charge transporting structure . wherein at least containing a stuff <1> is an electrostatic latent image bearing member according to any one of <2>.
<4> The electrostatic latent image carrier according to <3>, wherein the radical polymerizable compound having a charge transporting structure is monofunctional.
<5> The electrostatic latent image carrier according to any one of <1> to <4>, wherein the adhesive layer has a thickness of 0.1 to 5 μm.
<6> The electrostatic latent image carrier according to any one of <1> to <5>, wherein the photosensitive layer contains a charge generation material, and the charge generation material contains titanyl phthalocyanine.
<7> Titanyl phthalocyanine has at least 9.6 ° ± 0.2 °, 24.0 ° ± 0.2 °, and 27.2 ° ± major peaks with a Bragg angle 2θ in an X-ray diffraction spectrum for Cu—Kα rays. The electrostatic latent image bearing member according to <6>, containing a crystal type at 0.2 °.
<8> The electrostatic latent image carrier according to any one of <1> to <7>, wherein the photosensitive layer is a single-layer type photosensitive layer.
<9> The electrostatic latent image according to any one of <1> to <8>, wherein the photosensitive layer is a laminated photosensitive layer having at least a charge generation layer and a charge transport layer in this order on a support. It is a carrier.
<10> A method for producing an electrostatic latent image carrier according to any one of <1> to <9>,
After forming the photosensitive layer on the support, the adhesive layer coating solution and the surface layer coating solution are sequentially coated on the photosensitive layer, and then the adhesive layer and the surface layer are cured by light irradiation. This is a method for producing an electrostatic latent image carrier.
<11> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a toner image, and the toner In an image forming method including at least a transfer step of transferring an image to a recording medium,
In the image forming method, the latent electrostatic image bearing member is the latent electrostatic image bearing member according to any one of <1> to <9>.
<12> An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a toner image An image forming apparatus having at least developing means for forming the toner image and transfer means for transferring the toner image to a recording medium.
The electrostatic latent image carrier is an electrostatic latent image carrier according to any one of <1> to <9>.
<13> The electrostatic latent image carrier according to any one of <1> to <9>, and at least one unit selected from a charging unit, a developing unit, a transfer unit, a cleaning unit, and a charge eliminating unit. The process cartridge is detachable from the image forming apparatus main body.

The electrostatic latent image carrier of the present invention is obtained by curing a radically polymerizable compound having a trifunctional or higher functional group whose surface layer does not have a charge transporting structure and a radically polymerizable compound having a charge transporting structure by light energy irradiation means. A radical having a surface layer, having an adhesive layer between the photosensitive layer and the surface layer, the adhesive layer having a viscosity of 1 to 20 mPa · s at 25 ° C. By containing at least a polymerizable compound, it is possible to suppress peeling wear, have high durability, and achieve high image quality over a long period of time.
The reason for this is that the surface layer radically polymerized by the irradiation of light energy contracts due to the development of the three-dimensional network structure, and the internal stress becomes very large. As a result, when the wear reaches the inside of the surface layer, a crack is generated due to slight scratches, the crack reaches the charge transport layer, the surface layer is peeled off from the photosensitive layer, and the wear proceeds at once.
In the electrostatic latent image carrier of the present invention, in order to suppress peeling, it is possible to improve the adhesive strength between the surface layer and the charge transport layer by providing an adhesive layer between the surface layer and the charge transport layer. .
On the charge transport layer, a coating solution in which a radical polymerizable compound having a charge transport structure with a viscosity of 1 to 20 mPa · s and a radical polymerizable compound having a charge transport structure is mixed as necessary is added to the adhesive layer. Then, the surface layer coating solution is further applied, and then simultaneously cured by the light energy irradiation means so that the charge transport layer and the surface layer are bonded.
Although the mechanism by which the adhesive layer of the present invention bonds the photosensitive layer and the surface layer is not clearly understood, it is likely that the adhesiveness is improved for the following reasons.
In the adhesive layer of the present invention, the key point is to use a radically polymerizable compound having no low-viscosity charge transport structure in the adhesive layer coating solution. That is, the radically polymerizable compound having a low viscosity can be considered as a kind of solvent, and when it adheres to the surface of the charge transport layer, it is considered that it is embedded in the charge transport layer while dissolving the charge transport layer. On the other hand, in order to give wear resistance to the surface layer, a radical polymerizable compound having a charge transport structure having three or more functional groups is used. The trifunctional or higher-functional radical polymerizable compound used here has a very high viscosity and cannot sufficiently penetrate into the charge transport layer. However, it can be cross-linked simultaneously with the adhesive layer embedded in the charge transport layer to form the charge transport layer. It is considered that the anchoring effect is obtained and the surface layer can be bonded to the charge transport layer.

  An image forming apparatus according to the present invention includes an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using toner. Developing means for developing a visible image by development, transfer means for transferring the visible image to a recording medium, fixing means for fixing the transfer image transferred to the recording medium, and the electrostatic latent image carrier The electrostatic latent image carrier is the electrostatic latent image carrier of the present invention. In the image forming apparatus of the present invention, since the electrostatic latent image bearing member of the present invention is used as the electrostatic latent image bearing member, it has high scratch resistance and wear resistance, and has a surface in a high humidity environment. The resistance does not decrease, and an image with high durability and high image quality can be formed over a long period of time even in a high temperature environment seen in a high-speed process or the like.

  The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image. At least a developing step, a transferring step for transferring the visible image to a recording medium, a fixing step for fixing the transferred image transferred to the recording medium, and a cleaning step for cleaning the electrostatic latent image carrier. The electrostatic latent image carrier is the electrostatic latent image carrier of the present invention. In the image forming method of the present invention, since the electrostatic latent image bearing member of the present invention is used as the electrostatic latent image bearing member, it has high scratch resistance and wear resistance, and has a surface in a high humidity environment. The resistance does not decrease, and an image with high durability and high image quality can be formed over a long period of time even in a high temperature environment seen in a high-speed process or the like.

  The process cartridge of the present invention has at least an electrostatic latent image carrier and developing means for developing a latent image formed on the electrostatic latent image carrier using toner to form a visible image. Since the electrostatic latent image carrier of the present invention is used as the electrostatic latent image carrier, scratch resistance, high wear resistance, surface resistance does not decrease in a high humidity environment, In addition, high durability and high-quality images can be obtained over a long period of time even in high-temperature environments found in high-speed processes, etc., and even when blade cleaning or the like is performed, the wear of the electrostatic latent image carrier is extremely slightly suppressed. The property is also good.

According to the present invention, a conventional problem can be solved, and a radically polymerizable compound having three or more functional groups having no charge transport structure and a radical polymerizable compound having a charge transport structure are cured to have a surface layer. In an electrostatic latent image carrier, by providing an adhesive layer between the surface layer and the photosensitive layer, it is possible to suppress abrupt wear due to peeling of the surface layer from the photosensitive layer and to suppress image deterioration due to it. It becomes.
Therefore, according to the present invention, a highly durable and high performance electrostatic latent image carrier can be efficiently produced, and a high performance capable of outputting a good image over a long period of time by using this electrostatic latent image carrier. In addition, an image forming method, an image forming apparatus, and a process cartridge that are highly reliable can be provided.

(Electrostatic latent image carrier)
The electrostatic latent image carrier of the present invention has a support, and at least a photosensitive layer and a surface layer in this order on the support, and an adhesive layer between the photosensitive layer and the surface layer. In addition, other layers are provided as necessary.

In the first embodiment, the electrostatic latent image carrier has a support, a single-layer type photosensitive layer on the support, and a surface layer on the single-layer type photosensitive layer. An adhesive layer is provided between the surface layer and other layers as required.
In the second embodiment, the latent electrostatic image bearing member includes a support, a stacked photosensitive layer having at least a charge generation layer and a charge transport layer on the support, and the stacked photosensitive layer. It has a surface layer on it, has an adhesive layer between the photosensitive layer and the surface layer, and further has other layers as necessary. In the second embodiment, the charge generation layer and the charge transport layer may be laminated in reverse.

Here, the layer configuration of the electrostatic latent image carrier will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of an electrostatic latent image carrier of the present invention, which has a single layer structure in which a photosensitive layer 233 having a charge generation function and a charge transport function at the same time is provided on a support 231. It is a photoreceptor. In FIG. 1, 238 represents an adhesive layer, and 239 represents a surface layer.
FIG. 2 is a schematic sectional view showing another example of the electrostatic latent image carrier of the present invention. On the support 231, a charge generation layer 235 having a charge generation function and a charge transport having a charge transport material function are shown. The photosensitive member has a laminated structure in which the layer 237 is laminated. In FIG. 2, reference numeral 238 denotes an adhesive layer, and 239 denotes a surface layer.

<Surface layer>
The surface layer contains a cured product of at least a trifunctional or higher-functional radical polymerizable compound having no charge transporting structure and a radical polymerizable compound having a charge transporting structure, and further contains other components as necessary. It contains.

-Trifunctional or higher radical polymerizable compound having no charge transport structure-
Examples of the trifunctional or higher functional radical polymerizable compound having no charge transport structure include hole transport structures such as triarylamine, hydrazone, pyrazoline, and carbazole, such as condensed polycyclic quinone, diphenoquinone, cyano group, and the like. It means a monomer having no electron transport structure such as an electron-withdrawing aromatic ring having a nitro group and having three or more radical polymerizable functional groups. Such a radical polymerizable functional group may be any group as long as it has a carbon-carbon double bond and is capable of radical polymerization.

  Examples of these radical polymerizable functional groups include (1) 1-substituted ethylene functional groups or (2) 1,1-substituted ethylene functional groups shown below.

(1) As 1-substituted ethylene functional group, the functional group represented by the following <Formula 1> is mentioned, for example.
<Formula 1>
CH ₂ = _{CH-X 1} -
However, in the above <Formula 1>, X ₁ represents an arylene group which may have a substituent such as a phenylene group or a naphthylene group; an alkenylene group which may have a substituent, a —CO— group, — COO— group, —CON (R ₁₀ ) — group (where R ₁₀ represents a hydrogen atom; an alkyl group such as a methyl group or an ethyl group; an aralkyl group such as a benzyl group, a naphthylmethyl group or a phenethyl group; a phenyl group or a naphthyl group) Represents an aryl group such as a group) or an S-group.
Examples of these substituents include a vinyl group, a styryl group, a 2-methyl-1,3-butadienyl group, a vinylcarbonyl group, an acryloyloxy group, an acryloylamino group, and a vinyl thioether group.

(2) Examples of the 1,1-substituted ethylene functional group include functional groups represented by the following <Formula 2>.
<Formula 2>
_{CH 2 = C (Y) -X} 2 -
However, in <Formula 2>, Y has a substituent such as an alkyl group which may have a substituent, an aralkyl group which may have a substituent, a phenyl group or a naphthyl group. Aryl group, halogen atom, cyano group, nitro group, methoxy group, ethoxy group and other alkoxy groups, -COOR ₁₁ group (where R ₁₁ is a hydrogen atom, a methyl group optionally having substituents, An alkyl group such as an ethyl group, an aralkyl group such as an optionally substituted benzyl or phenethyl group, an aryl group such as an optionally substituted phenyl group or naphthyl group, or CONR ₁₂ R ₁₃ ( However, R ₁₂ and R ₁₃ may be the same as each other or different, a hydrogen atom, which may have a substituent an alkyl group such as methyl group and an ethyl group, a benzyl group, Nafuchirume Le represents group, aralkyl group which may have a substituent such as a phenethyl group, or a phenyl group, a represents an aryl group which may have a substituent such as naphthyl group).
X ₂ represents the same substituent, single bond, or alkylene group as X _{1 in} <Formula 1>.
Note that at least one of Y and X ₂ represents an oxycarbonyl group, a cyano group, an alkenylene group, or an aromatic ring.
Examples of these substituents include an α-acryloyloxy chloride group, a methacryloyloxy group, an α-cyanoethylene group, an α-cyanoacryloyloxy group, an α-cyanophenylene group, and a methacryloylamino group.

Examples of the substituent further substituted on the substituents for X ₁ , X ₂ , and Y include, for example, a halogen atom, a nitro group, a cyano group; an alkyl group such as a methyl group, an ethyl group; a methoxy group, an ethoxy group An alkoxy group such as a group; an aryloxy group such as a phenoxy group; an aryl group such as a phenyl group or a naphthyl group; an aralkyl group such as a benzyl group or a phenethyl group;
Among these radical polymerizable functional groups, an acryloyloxy group and a methacryloyloxy group are particularly preferable.
As the compound having three or more acryloyloxy groups, for example, a compound having three or more hydroxyl groups in the molecule and acrylic acid (salt), acrylate halide, acrylate ester, ester reaction or ester exchange reaction Can be obtained. A compound having three or more methacryloyloxy groups can be obtained in the same manner. Further, the radical polymerizable functional groups in the monomer having three or more radical polymerizable functional groups may be the same or different from each other.

  The trifunctional or higher functional radical polymerizable compound having no charge transport structure is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trimethylolpropane triacrylate (TMPTA) and trimethylolpropane. Trimethacrylate, trimethylolpropane alkylene-modified triacrylate, trimethylolpropane ethyleneoxy-modified (hereinafter sometimes referred to as “EO-modified”) triacrylate, trimethylolpropane propyleneoxy-modified (hereinafter referred to as “PO-modified”) A) triacrylate, trimethylolpropane caprolactone-modified triacrylate, trimethylolpropane alkylene-modified trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, glycerol epichlorohydrin modified (hereinafter sometimes referred to as “ECH modified”) triacrylate, glycerol EO modified triacrylate, glycerol PO modified triacrylate, tris (acryloxyethyl) Isocyanurate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol caprolactone-modified hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkylated dipentaerythritol pentaacrylate, alkylated dipentaerythritol tetraacrylate, alkylated dipentaerythritol triacrylate , Dimethylolpropane tetraacrylate (DTMPTA), pentaerythritol ester Carboxy tetraacrylate, phosphoric acid EO-modified triacrylate, 2,2,5,5, - such as tetrahydroxy methyl cyclopentanone tetraacrylate and the like. These may be used individually by 1 type and may use 2 or more types together.

The trifunctional or higher functional radical polymerizable compound having no charge transport structure preferably has a functional group ratio (molecular weight / functional group number) of 250 or less in order to form a dense cross-linked bond in the surface layer. When the functional group ratio exceeds 250, the surface layer is soft and wear resistance is somewhat lowered. Therefore, among the monomers exemplified above, monomers having a modifying group such as EO, PO, and caprolactone are extremely long. It is not preferable to use one having a modifying group alone.
Moreover, 20-80 mass% is preferable with respect to the said surface layer whole quantity, and, as for the component ratio of the trifunctional or more radically polymerizable compound which does not have the said charge transport structure, 30-70 mass% is more preferable. When the proportion of the trifunctional or higher functional radical polymerizable compound having no charge transporting structure is less than 20% by mass, the surface layer has a small three-dimensional cross-linking density, and a conventional thermoplastic binder resin is used. In comparison with this, a dramatic improvement in wear resistance may not be achieved, and if it exceeds 80% by mass, the content of the radically polymerizable compound having a charge transporting structure may be reduced, resulting in deterioration of electrical characteristics.

-Radical polymerizable compound with charge transport structure-
The radically polymerizable compound having the charge transporting structure is not particularly limited and may be appropriately selected depending on the intended purpose. However, the radically polymerizable compound having a monofunctional charge transporting structure and bifunctional charge transporting may be used. A radical polymerizable compound having a functional structure, a radical polymerizable compound having a trifunctional charge transporting structure, and the like. Among these, a radical polymerizable compound having a monofunctional charge transporting structure is particularly preferable.
Examples of the radical polymerizable compound having a monofunctional charge transporting structure include hole transporting structures such as triarylamine, hydrazone, pyrazoline, and carbazole, such as condensed polycyclic quinone, diphenoquinone, cyano group, and nitro group. A compound having an electron transport structure such as an electron-withdrawing aromatic ring and having one radical polymerizable functional group. Examples of the radical polymerizable functional group include functional groups represented by the above <Formula 1> or <Formula 2>.
More specifically, those shown for the radically polymerizable compound are mentioned, and acryloyloxy group and methacryloyloxy group are particularly useful. In addition, a triarylamine structure is highly effective as a charge transporting structure, and among these, when a compound represented by the structure represented by the following general formula (1) or the following general formula (2) is used, the sensitivity In addition, the electrical characteristics such as the residual potential are favorably maintained.

In the general formulas (1) and (2), R ₁ has a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or a substituent. Aryl group, cyano group, nitro group, alkoxy group, —COOR ₇ (wherein R ₇ is a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, Or an aryl group which may have a substituent), a carbonyl halide group, CONR ₈ R ₉ (wherein R ₈ and R ₉ may be the same as or different from each other, a hydrogen atom, Represents a halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent.
In the general formula (1) and the general formula (2), Ar ₁ and Ar ₂ may be the same as or different from each other, and represent a substituted or unsubstituted arylene group.
In General Formula (1) and General Formula (2), Ar ₃ and Ar ₄ may be the same as or different from each other, and represent a substituted or unsubstituted aryl group.
In the general formulas (1) and (2), X represents 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, sulfur. Represents an atom or vinylene group.
In the general formulas (1) and (2), Z represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene ether divalent group, or an alkyleneoxycarbonyl divalent group.
m and n represent the integer of 0-3.

In the general formulas (1) and (2), examples of the alkyl group in the substituent of R ₁ include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. These include halogen atoms, nitro groups, cyano groups; alkyl groups such as methyl groups and ethyl groups; alkoxy groups such as methoxy groups and ethoxy groups; aryloxy groups such as phenoxy groups; aryl groups such as phenyl groups and naphthyl groups; It may be substituted with an aralkyl group such as a benzyl group or a phenethyl group.
Of the substituents for R ₁ , a particularly preferred one is a hydrogen atom or a methyl group.

Substituted or unsubstituted Ar ₃ and Ar ₄ are aryl groups, and examples of the aryl groups include condensed polycyclic hydrocarbon groups, non-fused cyclic hydrocarbon groups, and heterocyclic groups.
The condensed polycyclic hydrocarbon group preferably has 18 or less carbon atoms forming a ring, for example, a pentanyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptaenyl group, a biphenylenyl group, an as-indacenyl group. , S-indacenyl group, fluorenyl group, acenaphthylenyl group, preadenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, triphenylyl group, pyrenyl group , Chrycenyl group, naphthacenyl group and the like.
Examples of the non-fused cyclic hydrocarbon group include monovalent groups of monocyclic hydrocarbon compounds such as benzene, diphenyl ether, polyethylene diphenyl ether, diphenyl thioether, and diphenyl sulfone, or biphenyl, polyphenyl, diphenylalkane, diphenylalkene, and diphenyl. A monovalent group of a non-condensed polycyclic hydrocarbon compound such as alkyne, triphenylmethane, distyrylbenzene, 1,1-diphenylcycloalkane, polyphenylalkane or polyphenylalkene, or a ring such as 9,9-diphenylfluorene Examples thereof include monovalent groups of aggregate hydrocarbon compounds.
Examples of the heterocyclic group include monovalent groups such as carbazole, dibenzofuran, dibenzothiophene, oxadiazole, and thiadiazole.

In the general formulas (1) and (2), the aryl group represented by Ar ₃ and Ar ₄ may have a substituent as shown below, for example.
(1) A halogen atom, a cyano group, a nitro group, etc. are mentioned. (2) A linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Yes, these alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. It may have a phenyl group substituted with. Specifically, methyl group, ethyl group, n-butyl group, i-propyl group, t-butyl group, s-butyl group, n-propyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-ethoxyethyl Group, 2-cyanoethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-phenylbenzyl group and the like.

(3) An alkoxy group (—OR ₂ ), and R ₂ represents the alkyl group defined in (2) above. 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, benzyloxy group And a trifluoromethoxy group.
(4) An aryloxy group, and examples of the aryl group include a phenyl group and a naphthyl group. These may contain a C1-C4 alkoxy group, a C1-C4 alkyl group, or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methoxyphenoxy group, and a 4-methylphenoxy group.
(5) Alkyl mercapto group or aryl mercapto group, and specific examples include methylthio group, ethylthio group, phenylthio group, p-methylphenylthio group and the like.

(6) A group represented by the following general formula.
However, in the above formula, R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group as defined above (2) or aryl group. As an aryl group, a phenyl group, a biphenyl group, or a naphthyl group is mentioned, for example, These may contain a C1-C4 alkoxy group, a C1-C4 alkyl group, or a halogen atom as a substituent. . R ₃ and R ₄ may form a ring together.
Specifically, amino group, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (tolyl) amino group, dibenzylamino group, piperidino group, morpholino group , A pyrrolidino group, and the like.

(7) An alkylenedioxy group such as a methylenedioxy group or a methylenedithio group, or an alkylenedithio group.
(8) Substituted or unsubstituted styryl group, substituted or unsubstituted β-phenylstyryl group, diphenylaminophenyl group, ditolylaminophenyl group, and the like.
The arylene group represented by Ar ₁ and Ar ₂ is a divalent group derived from the aryl group represented by Ar ₃ and Ar ₄ .

In the general formulas (1) and (2), X is 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, or a sulfur atom. Represents a vinylene group.
The substituted or unsubstituted alkylene group is a linear or branched alkylene group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Further, it has a phenyl group substituted with a fluorine atom, a hydroxyl group, a cyano group, an alkoxy group having 1 to 4 carbon atoms, a phenyl group or a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. You may do it. Specifically, methylene group, ethylene group, n-butylene group, i-propylene group, t-butylene group, s-butylene group, n-propylene group, trifluoromethylene group, 2-hydroxyethylene group, 2-ethoxy. Examples include ethylene group, 2-cyanoethylene group, 2-methoxyethylene group, benzylidene group, phenylethylene group, 4-chlorophenylethylene group, 4-methylphenylethylene group, 4-biphenylethylene group, and the like.
The substituted or unsubstituted cycloalkylene group is a cyclic alkylene group having 5 to 7 carbon atoms. These cyclic alkylene groups include a fluorine atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. It may have an alkoxy group. Specific examples include a cyclohexylidene group, a cyclohexylene group, and a 3,3-dimethylcyclohexylidene group.
Examples of the substituted or unsubstituted alkylene ether group include ethyleneoxy, propyleneoxy, ethylene glycol, propylene glycol, diethylene glycol, tetraethylene glycol, and tripropylene glycol. These alkylene ether group alkylene groups may have a substituent such as a hydroxyl group, a methyl group, or an ethyl group.

Examples of the vinylene group include those represented by the following general formula.
In the general formula, R ₅ represents a hydrogen atom, an alkyl group (said (2) the same as the alkyl group, as defined), or an aryl group (same as the aryl group represented by Ar ₃ and Ar ₄₎ Represents. a represents 1 or 2; b represents 1-3.

In the general formulas (1) and (2), Z represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene ether divalent group, or an alkyleneoxycarbonyl divalent group.
Examples of the substituted or unsubstituted alkylene group include the same alkylene groups as those described above for X.
Examples of the substituted or unsubstituted alkylene ether divalent group include the divalent group of the alkylene ether group of X.
Examples of the alkyleneoxycarbonyl divalent group include a caprolactone-modified divalent group.

Preferred examples of the radical polymerizable compound having a monofunctional charge transport structure further include compounds represented by the following general formula (3).
However, in the said General formula (3), o, p, and q represent the integer of 0 or 1, respectively. Ra represents a hydrogen atom or a methyl group. Rb and Rc represent a C1-C6 alkyl group with a substituent other than a hydrogen atom, and may be different in a plurality of cases. s and t represent the integer of 0-3. Za represents a single bond, a methylene group, an ethylene group, or a group represented by the following structural formula.
In the general formula (3), a compound in which Rb and Rc are a methyl group or an ethyl group is particularly preferable.

  The radically polymerizable compound having a monofunctional charge transport structure represented by the general formulas (1), (2), and (3) is polymerized by opening a carbon-carbon double bond on both sides. Therefore, in a polymer that does not become a terminal structure, is incorporated in a chain polymer, and is crosslinked by polymerization with a radically polymerizable compound having three or more functional groups, it exists in the main chain of the polymer, and Present in the cross-linked chain between the chain and the main chain (this cross-linked chain has an intermolecular cross-linked chain between one polymer and another polymer, and a site where the main chain is folded in one polymer. And other intramolecular cross-linked chains that are cross-linked with other sites derived from the polymerized monomer at positions away from this in the main chain), but even if they are present in the main chain, Even if present, the triarylamine structure suspended from the chain moiety radiates from the nitrogen atom. Has at least three aryl groups arranged in the direction and is bulky, but is not directly bonded to the chain part, but is suspended from the chain part via a carbonyl group etc. Since these triarylamine structures can be spatially arranged adjacent to each other in the polymer, the structural distortion in the molecule is small, and the surface of the electrostatic latent image carrier is also fixed. In the case of a layer, it is presumed that an intramolecular structure that is relatively free from interruption of the charge transport pathway can be adopted.

Specific examples of the radical polymerizable compound having the monofunctional charge transporting structure are shown below, but are not limited to the compounds having these structures.

Specific examples of the radical polymerizable compound having the bifunctional charge transporting structure are shown below, but are not limited to the compounds having these structures.

Specific examples of the radical polymerizable compound having the trifunctional charge transporting structure are shown below, but are not limited to the compounds having these structures.

  The radical polymerizable compound having the charge transporting structure is important for imparting the charge transport performance of the surface layer, and the content of the radical polymerizable compound having the charge transporting structure is based on the total amount of the surface layer. 20-80 mass% is preferable and 30-70 mass% is more preferable. When the content is less than 20% by mass, the charge transport performance of the surface layer cannot be sufficiently maintained, and deterioration of electrical characteristics such as a decrease in sensitivity and an increase in residual potential may appear after repeated use. If it exceeds 1, the content of the trifunctional monomer having no charge transport structure is lowered, and the crosslink density is lowered, so that high wear resistance may not be exhibited.

  The surface layer contains a cured product of at least a trifunctional or higher-functional radical polymerizable compound having no charge transporting structure and a radical polymerizable compound having a charge transporting structure. Monofunctional radically polymerizable compound, bifunctional radically polymerizable compound, and radically polymerizable oligomer described above for the purpose of imparting functions such as viscosity adjustment at the time, stress relaxation of the surface layer, lower surface energy and reduction of friction coefficient Can be used in combination. Known radical polymerizable compounds and oligomers can be used.

  Examples of the monofunctional radically polymerizable compound include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, and benzyl acrylate. Cyclohexyl acrylate, isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, styrene monomer, and the like.

  Examples of the bifunctional radically polymerizable compound include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1 , 6-hexanediol dimethacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, bisphenol A-EO modified diacrylate, bisphenol F-EO modified diacrylate, neopentyl glycol diacrylate, and the like.

  Examples of the functional monomer include those substituted with fluorine atoms such as octafluoropentyl acrylate, 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl methacrylate, 2-perfluoroisononylethyl acrylate, and the like. Siloxane repeating units described in JP-60503 and JP-B-6-45770: 20-70 acryloyl polydimethylsiloxane ethyl, methacryloyl polydimethylsiloxane ethyl, acryloyl polydimethylsiloxane propyl, acryloyl polydimethylsiloxane butyl, diacryloyl poly Examples thereof include vinyl monomers having a polysiloxane group such as dimethylsiloxane diethyl, acrylates and methacrylates.

  Examples of the radical polymerizable oligomers include epoxy acrylate oligomers, urethane acrylate oligomers, and polyester acrylate oligomers. However, when a large amount of monofunctional and bifunctional radically polymerizable compounds and radically polymerizable oligomers are contained, the three-dimensional cross-linking density of the surface layer is substantially reduced, leading to a decrease in wear resistance. For this reason, 50 mass parts or less are preferable with respect to 100 mass parts of radically polymerizable compounds more than trifunctional, and, as for content of these monomers and oligomers, 30 mass parts or less are more preferable.

The surface layer further contains a photopolymerization initiator for efficiently proceeding with a crosslinking reaction between a tri- or higher functional radical polymerizable compound having no charge transport structure and a radical polymerizable compound having a charge transport structure. can do.
Examples of the photopolymerization initiator include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 4- (2-hydroxyethoxy) phenyl. -(2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenylpropan-1-one Acetophenone-based or ketal-based photopolymerization of 2-methyl-2-morpholino (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, etc. Initiator: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin iso Benzoin ether photopolymerization initiators such as tilether, benzoin isopropyl ether; benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoylphenyl ether, acrylated benzophenone, Benzophenone photopolymerization initiators such as 1,4-benzoylbenzene; thioxanthones such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Photopolymerization initiator; Other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethyl Nzoylphenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9 , 10-phenanthrene, acridine compounds, triazine compounds, and imidazole compounds. In addition, what has a photopolymerization acceleration effect can also be used individually or in combination with the said photoinitiator. Examples include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4,4′-dimethylaminobenzophenone, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The content of the polymerization initiator is preferably 0.5 to 40 parts by mass and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of compounds having radical polymerizability.

The surface layer may further contain additives such as various plasticizers (for the purpose of stress relaxation and adhesion improvement), a leveling agent, and a low molecular charge transport material having no radical reactivity, if necessary. As these additives, known ones can be used, and as the plasticizer, those used in general resins such as dibutyl phthalate and dioctyl phthalate can be used. The amount of the plasticizer used is preferably 20% by mass or less, more preferably 10% by mass or less, based on the total solid content of the surface layer coating solution.
Examples of the leveling agent include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil; polymers or oligomers having a perfluoroalkyl group in the side chain. The amount of the leveling agent used is preferably 3% by mass or less based on the total solid content of the surface layer coating solution.

The surface layer is formed by applying and curing a surface layer coating solution containing at least a trifunctional or higher-functional radical polymerizable compound having no charge transport structure and a radical polymerizable compound having a monofunctional charge transport structure. . When the radically polymerizable compound is a liquid, the surface layer coating liquid can be applied by dissolving other components in the liquid, but if necessary, it is diluted with a solvent and applied.
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; acetic acid Esters such as ethyl and butyl acetate; Ethers such as tetrahydrofuran, dioxane and propyl ether; Halogens such as dichloromethane, dichloroethane, trichloroethane and chlorobenzene; Aromatics such as benzene, toluene and xylene; Methyl cellosolve, ethyl cellosolve and cellosolve Examples include cellosolve such as acetate. These may be used individually by 1 type and may use 2 or more types together.

As a method for forming the surface layer, for example, a dipping method, a spray coating method, a ring coating method, a roll coater method, a gravure coating method, a nozzle coating method, a screen printing method and the like are employed. Among these, the spray coating method and the ring coating method are particularly suitable because they are easy to ensure quality stability in production.
There is no restriction | limiting in particular in the thickness of the said surface layer, According to the objective, it can select suitably, 1-10 micrometers is preferable and 2-5 micrometers is more preferable.

<Adhesive layer>
In the electrostatic latent image carrier of the present invention, an adhesive layer is provided between the photosensitive layer and the surface layer in order to improve the adhesive strength between the photosensitive layer and the surface layer.

As the radical polymerizable compound having no charge transport structure used in the adhesive layer, the same radical polymerizable compound as used in the surface layer can be used. Among these, the adhesiveness between the surface layer and the photosensitive layer is improved by using a radical polymerizable compound having a viscosity at 25 ° C. of 1 to 20 mPa · s for the adhesive layer. Here, if the viscosity is less than 1 mPa · s, the fluidity is very high, so the adhesive layer may not be uniformly formed, and uniform adhesion may not be obtained, and when it exceeds 20 mPa · s. In addition, since the radical polymerizable compound does not sink into the charge transport layer, sufficient adhesive strength may not be obtained.
The number of functional groups of the radical polymerizable compound used in the adhesive layer is preferably bifunctional. Since monofunctional groups have few bonding sites, sufficient adhesive ability may not be obtained. When trifunctional or more functional groups are used, the viscosity becomes high, so that the penetration into the charge transport layer is insufficient, and sufficient adhesive ability cannot be obtained. There is.

  There is no restriction | limiting in particular as a radically polymerizable compound which does not have a charge transportable structure whose viscosity in 25 degreeC is 1-20 mPa * s, Although it can select suitably according to the objective, For example, 1, 6- hexanediol Diacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, tetrahydrofurfuryl acrylate, lauryl acrylate, 2-phenoxyethyl acrylate, isodecyl acrylate, isooctyl acrylate, tridecyl acrylate, 1,3-butanediol diacrylate, 1 , 4-butanediol diacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, tet Lahydrofurfuryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, 2-phenoxyethyl methacrylate, tridecyl methacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol Examples include dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and the like. These may be used individually by 1 type and may use 2 or more types together.

As the radical polymerizable compound having a charge transporting structure in the adhesive layer, the same radical polymerizable compound as used in the surface layer can be used, and a monofunctional one is particularly preferable.
The radical polymerizable compound having the charge transporting structure is important for imparting the charge transporting performance of the adhesive layer, and the content of the radical polymerizable compound having the charge transporting structure is the total amount of the adhesive layer. 20 to 80% by mass is preferable, and 30 to 70% by mass is more preferable. When the content is less than 20% by mass, the charge transport performance of the adhesive layer cannot be sufficiently maintained, and deterioration of electrical characteristics such as a decrease in sensitivity and an increase in residual potential may appear after repeated use. If it exceeds 1, the content of the radically polymerizable compound having no charge transport structure is lowered, and the adhesive strength is lowered, and high wear resistance may not be exhibited.

The adhesive layer is obtained by curing a radically polymerizable compound having a viscosity of at least 25 ° C. and having a charge transport structure of 1 to 20 mPa · s. Initiators may be used.
The photopolymerization initiator may be the same as that used for the surface layer.
You may use the said polymerization initiator 1 type or in mixture of 2 or more types. The content of the polymerization initiator is preferably 0.5 to 40 parts by weight and more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the total content having radical polymerizability.

The adhesive layer is formed by applying a coating liquid containing a radical polymerizable compound having no charge transport structure with a viscosity of at least 25 ° C. of 1 to 20 mPa · s and curing. The coating solution is applied after being diluted with a solvent as necessary. Examples of the solvent used at this time include alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; tetrahydrofuran, dioxane, Examples include ethers such as propyl ether; halogens such as dichloromethane, dichloroethane, trichloroethane and chlorobenzene; aromatics such as benzene, toluene and xylene; cellosolvs such as methyl cellosolve, ethyl cellosolve and cellosolve acetate. These may be used individually by 1 type and may use 2 or more types together.
The dilution ratio with the solvent varies depending on the solubility of the composition, the coating method, and the target film thickness, and is arbitrary. The coating can be performed using a dip coating method, spray coating, bead coating, ring coating method or the like.

As the method for forming the adhesive layer, for example, a dipping method, a spray coating method, a ring coating method, a roll coater method, a gravure coating method, a nozzle coating method, a screen printing method and the like are employed. Among these, the spray coating method and the ring coating method are particularly suitable because they are easy to ensure quality stability in production.
The thickness of the adhesive layer is preferably 0.1 to 5 μm, and more preferably 0.1 to 3 μm. When the thickness is less than 0.1 μm, the surface layer may be peeled off from the photosensitive layer. When the thickness is more than 5 μm, the surface potential of the photoreceptor after exposure becomes high and the image density may be lowered.

<Multi-layer type photosensitive layer>
The multi-layered photosensitive layer has at least a charge generation layer and a charge transport layer in this order, and further includes an intermediate layer and other layers as necessary.

-Charge generation layer-
The charge generation layer includes at least a charge generation material, a binder resin, and further includes other components as necessary.
As the charge generation material, inorganic materials and organic materials can be used.
Examples of the inorganic material include crystalline selenium, amorphous-selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compound, and amorphous-silicon. In amorphous-silicon, dangling bonds that are terminated with hydrogen atoms or halogen atoms, or those that are doped with boron atoms or phosphorus atoms are preferably used.
The organic material is not particularly limited and may be appropriately selected from known materials according to the purpose. For example, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azurenium salt pigments, squaric acid methine Pigment, azo pigment having carbazole skeleton, azo pigment having triphenylamine skeleton, azo pigment having diphenylamine skeleton, azo pigment having dibenzothiophene skeleton, azo pigment having fluorenone skeleton, azo pigment having oxadiazole skeleton, bis Azo pigments having a stilbene skeleton, azo pigments having a distyryl oxadiazole skeleton, azo pigments having a distyryl carbazole skeleton, perylene pigments, anthraquinone or polycyclic quinone pigments, quinoneimine pigments, diphenylmethane and triphenyl Enirumetan pigments, benzoquinone pigments, naphthoquinone pigments, cyanine pigments, azomethine pigments, indigoid pigments, and bisbenzimidazole pigments. These may be used individually by 1 type and may use 2 or more types together.
Among these, phthalocyanines are preferable, and titanyl phthalocyanine is particularly preferable.
The titanyl phthalocyanine has at least 9.6 ° ± 0.2 °, 24.0 ° ± 0.2 °, and 27.2 ° ± major peaks with a Bragg angle 2θ in an X-ray diffraction spectrum of at least Cu—Kα ray. Those having a crystal type of 0.2 ° are particularly preferable as high-sensitivity materials.

There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably, For example, a polyamide resin, a polyurethane resin, an epoxy resin, a polyketone resin, a polycarbonate resin, a silicone resin, an acrylic resin, a polyvinyl butyral resin, polyvinyl Formal resin, polyvinyl ketone resin, polystyrene resin, poly-N-vinyl carbazole resin, polyacrylamide resin, and the like can be given. These may be used individually by 1 type and may use 2 or more types together.
In addition to the binder resin described above, the charge generation layer binder resin may be a polymer charge transport material having a charge transport function, such as (1) an arylamine skeleton, a benzidine skeleton, a hydrazone skeleton, a carbazole skeleton, or a stilbene skeleton. Or a polymer material such as a polycarbonate resin having a pyrazoline skeleton, a polyester resin, a polyurethane resin, a polyether resin, a polysiloxane resin, or an acrylic resin, or (2) a polymer material having a polysilane skeleton.

  Specific examples of the above (1) include JP-A-01-001728, JP-A-01-009964, JP-A-01-013061, JP-A-01-019049, JP-A-01-241559. JP, 04-011627, JP 04-175337, JP 04-183719, JP 04-22514, JP 04-230767, JP 04-320420, JP 05-232727, JP 05-310904, JP 06-234836, JP 06-234837, JP 06-234838, JP 06-234839, JP JP 06-234840, JP 06-234841 A, JP 06-239049 A JP, 06-236050, JP 06-236051, JP 06-295077, JP 07-056374, JP 08-176293, JP 08-208820, JP-A-08-212640, JP-A-08-253568, JP-A-08-269183, JP-A-09-062019, JP-A-09-038883, JP-A-09-71642, JP-A-Hei 9-16442 JP 09-87376, JP 09-104746, JP 09-110974, JP 09-110976, JP 09-157378, JP 09-221544, JP 09-09. No. 227669, JP 09-235367 A, JP 09-241369 Charge transporting polymers described in JP-A 09-268226, JP-A 09-272735, JP-A 09-302084, JP-A 09-302085, JP-A 09-328539, and the like. Materials.

  Specific examples of the above (2) include, for example, those described in JP-A-63-285552, JP-A-05-19497, JP-A-05-70595, JP-A-10-73944, and the like. Examples are polysilylene polymers.

The charge generation layer may contain a low molecular charge transport material.
The low molecular charge transport material includes a hole transport material and an electron transport material.
Examples of the electron transporting material include chloroanil, bromoanil, 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] thiophen-4-one, 1,3,7 -Trinitrodibenzothiophene-5,5-dioxide, diphenoquinone derivatives and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the hole transport material include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives. , Triarylmethane derivatives, 9-styrylanthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, and the like, and other known materials such as bisstilbene derivatives and enamine derivatives. These may be used individually by 1 type and may use 2 or more types together.

As a method for forming the charge generation layer, a vacuum thin film preparation method and a casting method from a solution dispersion system can be mentioned.
As the vacuum thin film production method, for example, a vacuum deposition 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.
As the casting method, the inorganic or organic charge generating material, if necessary, binder resin, tetrahydrofuran, dioxane, dioxolane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, cyclopentanone, anisole, xylene, methyl ethyl ketone It can be formed by dispersing with a ball mill, attritor, sand mill, bead mill or the like using a solvent such as acetone, ethyl acetate, butyl acetate, etc., and applying the solution after diluting the dispersion appropriately. Moreover, leveling agents, such as a dimethyl silicone oil and a methylphenyl silicone oil, can be added as needed. The application can be performed by dip coating, spray coating, bead coating, ring coating, or the like.

  The thickness of the charge generation layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.01 to 5 μm, and more preferably 0.05 to 2 μm.

-Charge transport layer-
The charge transport layer is a layer intended to hold a charged charge and to couple the charge generated and separated in the charge generation layer by exposure to the charged charge held by movement. In order to achieve the purpose of holding the charged charge, it is required that the electric resistance is high. Further, in order to achieve the purpose of obtaining a high surface potential with the charged charge held, it is required that the dielectric constant is small and the charge mobility is good.

  The charge transport layer includes at least a charge transport material, and includes a binder resin and, if necessary, other components.

Examples of the charge transport material include a hole transport material, an electron transport material, and a polymer charge transport material.
Examples of the electron transporting material (electron accepting material) include chloranil, bromanyl, 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-one, 1,3,7-trinitrodibenzothiophene-5,5-dioxide, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the hole transport material (electron donating material) include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, 9- (p-diethylaminostyrylanthracene), 1,1-bis- (4 -Dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives, etc. It is done. These may be used individually by 1 type and may use 2 or more types together.

Examples of the polymer charge transport material include those having the following structure.
Examples of (a) a polymer having a carbazole ring include, for example, poly-N-vinylcarbazole, JP-A-50-82056, JP-A-54-9632, JP-A-54-11737, JP-A-5-11737. Examples thereof include compounds described in JP-A-4-175337, JP-A-4-183719, and JP-A-6-234841.
(B) Examples of the polymer having a hydrazone structure include, for example, JP-A-57-78402, JP-A-61-20953, JP-A-61-296358, JP-A-1-134456, Compounds described in Kaihei 1-179164, JP-A-3-180851, JP-A-3-180852, JP-A-3-50555, JP-A-5-310904, and JP-A-6-234840 Etc. are exemplified.
(C) Examples of the polysilylene polymer include, for example, JP-A-63-285552, JP-A-1-88461, JP-A-4-264130, JP-A-4-264131, and JP-A-4-264132. Examples thereof include compounds described in JP-A-4-264133 and JP-A-4-289867.
(D) As a polymer having a triarylamine structure, for example, N, N-bis (4-methylphenyl) -4-aminopolystyrene, JP-A-1-134457, JP-A-2-282264, Examples thereof include compounds described in Kaihei 2-304456, JP-A-4-133605, JP-A-4-133066, JP-A-5-40350, and JP-A-5-202135.
(E) As other polymers, for example, a formaldehyde condensation polymer of nitropyrene, JP-A-51-73888, JP-A-56-15049, JP-A-6-234363, JP-A-6-234837 And the compounds described in Japanese Patent Publication No.

  In addition to the above, the polymer charge transporting material includes, for example, a polycarbonate resin having a triarylamine structure, a polyurethane resin having a triarylamine structure, a polyester resin having a triarylamine structure, and a triarylamine structure. And a polyether resin. Examples of the polymer charge transporting material include JP-A 64-1728, JP-A 64-13061, JP-A 64-19049, JP-A-4-11627, JP-A 4-116627. JP 2225014, JP 4-230767, JP 4-320420, JP 5-232727, JP 7-56374, JP 9-127713, JP 9-222740. And compounds described in JP-A-9-265197, JP-A-9-211877, JP-A-9-30495, and the like.

  Examples of the polymer having an electron donating group include not only the above-mentioned polymer but also a copolymer with a known monomer, a block polymer, a graft polymer, a star polymer, It is also possible to use a crosslinked polymer having an electron donating group as disclosed in JP-A-109406.

Examples of the binder resin include polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyethylene resin, polyvinyl chloride resin, polyvinyl acetate resin, polystyrene resin, phenol resin, epoxy resin, polyurethane resin, polyvinylidene chloride resin, Alkyd resins, silicone resins, polyvinyl carbazole resins, polyvinyl butyral resins, polyvinyl formal resins, polyacrylate resins, polyacrylamide resins, phenoxy resins, and the like are used. These may be used individually by 1 type and may use 2 or more types together.
The charge transport layer may also contain a copolymer of a crosslinkable binder resin and a crosslinkable charge transport material.

  The charge transport layer can be formed by dissolving or dispersing these charge transport materials and a binder resin in an appropriate solvent, and applying and drying them. In addition to the charge transport material and the binder resin, an appropriate amount of additives such as a plasticizer, an antioxidant, and a leveling agent can be added to the charge transport layer as necessary.

As the solvent used for coating the charge transport layer, the same solvent as the charge generation layer can be used, but a solvent that dissolves the charge transport material and the binder resin well is suitable. These solvents may be used alone or in combination of two or more. The charge transport layer can be formed by the same coating method as that for the charge generation layer.
If necessary, a plasticizer and a leveling agent can be added.
As said plasticizer, what is used as a plasticizer of general resins, such as dibutyl phthalate and dioctyl phthalate, can be used as it is, and the usage-amount is 0-30 with respect to 100 mass parts of said binder resins. About mass parts are preferred.
Examples of the leveling agent include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain. The amount used is 100 parts by mass of a binder resin. About 0 to 1 part by mass is preferable.
There is no restriction | limiting in particular in the thickness of the said charge transport layer, According to the objective, it can select suitably, 5-40 micrometers is preferable and 10-30 micrometers is more preferable.

When the photosensitive layer has a laminated structure, an adhesive layer coating solution containing the radical polymerizable compound of the present invention and a binder resin is applied onto the charge transport layer by spraying, and further contains a radical polymerizable composition. The coating liquid to be applied is applied, dried as necessary, and then cured by light energy irradiation means to form an adhesive layer and a surface layer.
At this time, the thickness of the adhesive layer is preferably 0.05 to 5 μm, and more preferably 0.1 to 1 μm. If the thickness is less than 0.05 μm, a sufficient adhesive effect cannot be obtained, and if it is thicker than 5 μm, the electrical characteristics deteriorate. Moreover, 1-20 micrometers is preferable and, as for the thickness of a surface layer, 2-10 micrometers is more preferable. If the thickness is less than 1 μm, unevenness in durability may occur due to uneven thickness, and if it exceeds 20 μm, the electrical characteristics may deteriorate.

<Single layer type photosensitive layer>
The single-layer type photosensitive layer includes a charge generation material, a charge transport material, and a binder resin, and further includes other components as necessary.
As the charge generation material, the charge transport material, and the binder resin, the same materials as those of the multilayer photosensitive layer can be used.

When a single-layer type photosensitive layer is provided by a casting method, in many cases, such a single-layer type photosensitive layer is obtained by dissolving or dispersing a charge generating substance, a low molecular weight molecule, and a polymer charge transporting substance in a suitable solvent, and applying this. It can be formed by drying. In addition, a plasticizer can be added to the single-layer type photosensitive layer as necessary. Furthermore, as the binder resin that can be used as necessary, the binder resins mentioned in the charge transport layer can be used as they are. In addition, the same binder resin as the charge generation layer may be mixed and used.
Moreover, a plasticizer, a leveling agent, etc. can also be added as needed. As the charge generation material dispersion method, the charge generation material, the charge transport material, the plasticizer, and the leveling agent may be the same as those already described in the charge generation layer and the charge transport layer. As the binder resin, in addition to the binder resin previously mentioned in the section of the charge transport layer, the binder resin mentioned in the charge generation layer may be mixed and used. The polymer charge transporting material can also be used, which is useful in that contamination of the lower photosensitive layer composition into the surface layer can be reduced.

There is no restriction | limiting in particular in the thickness of the said single layer type photosensitive layer, According to the objective, it can select suitably, 5-30 micrometers is preferable and 10-25 micrometers is more preferable.
In the case of a single-layer type photosensitive layer, the adhesive layer coating solution containing the radical polymerizable composition of the present invention and a binder resin is applied on the photosensitive layer by spraying, and then the coating solution containing the radical polymerizable composition. Is applied and dried as necessary, and then cured by light energy irradiation means to form an adhesive layer and a surface layer. At this time, the thickness of the adhesive layer is preferably 0.05 to 5 μm, and more preferably 0.1 to 1 μm. When the thickness is less than 0.05 μm, a sufficient adhesion effect cannot be obtained, and when it exceeds 5 μm, the electrical characteristics are deteriorated. Moreover, 1-20 micrometers is preferable and, as for the thickness of the said surface layer, 2-10 micrometers is more preferable. If the thickness is less than 1 μm, unevenness in durability may occur due to thickness unevenness, and if it exceeds 20 μm, electrical characteristics may deteriorate.
The charge generation material contained in the single-layer type photosensitive layer is preferably 1 to 30% by mass with respect to the total amount of the photosensitive layer. The binder resin contained in the lower layer portion of the photosensitive layer is preferably 20 to 80% by mass of the total amount. The charge transport material is preferably 10 to 70 parts by mass with respect to 100 parts by mass of the binder resin.

<Support>
There is no restriction | limiting in particular as said support body, Although it can select suitably according to the objective, The thing which shows the electroconductivity whose volume resistance is 10 < ¹⁰ > ohm * cm or less is suitable.
The material, shape, and size of the support are not particularly limited, and any of a plate shape, a drum shape, or a belt shape can be used. For example, aluminum, nickel, chromium, nichrome, copper, gold Metals such as silver and platinum, metal oxides such as tin oxide and indium oxide by vapor deposition or sputtering, film or cylindrical plastic, paper coated, or plates made of aluminum, aluminum alloy, nickel, stainless steel, etc. And after making them into a raw pipe by a method such as extruding and drawing, pipes subjected to surface treatment such as cutting, superfinishing, polishing, etc. can be used. Further, an endless nickel belt and an endless stainless steel belt disclosed in JP-A-52-36016 can also be used as a support.

In addition to the above, it is also possible to use a conductive layer formed by dispersing and coating conductive powder in an appropriate binder resin on the support.
Examples of the material of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, or metal oxide such as conductive tin oxide and ITO. Examples thereof include powder. Examples of the binder resin include polystyrene resin, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer. Polymer, polyvinyl acetate resin, polyvinylidene chloride resin, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral resin, polyvinyl formal resin, polyvinyl toluene resin, poly-N-vinyl carbazole resin, acrylic resin , Silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, alkyd resin and the like.
The conductive layer can be formed by applying a coating solution in which the conductive powder and the binder resin are dissolved or dispersed in a solvent on a support. Examples of the solvent include tetrahydrofuran, dichloromethane, methyl ethyl ketone, toluene, and the like.

  In addition, the conductive powder is contained in the cylindrical substrate in polyvinyl chloride resin, polypropylene resin, polyester resin, polystyrene resin, polyvinylidene chloride resin, polyethylene resin, chlorinated rubber, polytetrafluoroethylene fluororesin, or the like. It is also preferable to provide a conductive layer with a heat shrinkable tube.

An undercoat layer may be provided between the support and the photosensitive layer as necessary. The undercoat layer generally comprises a resin as a main component, but these resins are resins having a high solvent resistance with respect to general organic solvents in consideration of applying a photosensitive layer thereon with a solvent. It is preferable.
Examples of the resin include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane resins, melamine resins, phenol resins, alkyd-melamine resins, Examples thereof include a curable resin that forms a three-dimensional network structure, such as an epoxy resin.

In addition, a metal oxide fine powder pigment exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential. Good.
The undercoat layer can be formed using an appropriate solvent and coating method like the photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention. The the undercoat layer, vacuum those provided _Al 2 _{O 3} in the anodic oxidation and, polyparaxylylene (parylene) or the like of the organic substances and _{SiO 2, SnO 2, TiO 2} , ITO, an inorganic material such as CeO ₂ Those provided by the thin film manufacturing method can also be used favorably. In addition, known ones can be used.
There is no restriction | limiting in particular in the thickness of the said undercoat layer, According to the objective, it can select suitably, 0-5 micrometers is preferable.

In the electrostatic latent image carrier of the present invention, the surface layer, photosensitive layer, charge generation layer, charge transport layer are used for the purpose of preventing the decrease in sensitivity and the increase in residual potential, in order to improve the environmental resistance. An antioxidant may be added to each layer such as the undercoat layer.
Examples of the antioxidant include phenolic compounds, paraphenylenediamines, organic sulfur compounds, and organic phosphorus compounds.
Examples of the phenol compound include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-ethyl- 6-t-butylphenol), 4,4′-thiobis- (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), 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-hydroxy Ben ) Benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis (4′-hydroxy-3 ′) -T-butylphenyl) butyric acid] cricol ester, tocopherols and the like.
Examples of the paraphenylenediamines include N-phenyl-N′-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl- Examples include p-phenylenediamine, N, N′-di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine, and the like.
Examples of the hydroquinones include 2,5-di-t-octyl hydroquinone, 2,6-didodecyl hydroquinone, 2-dodecyl hydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methyl. Examples include hydroquinone and 2- (2-octadecenyl) -5-methylhydroquinone.
Examples of the organic sulfur compounds include dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like. .
Examples of the organic phosphorus compounds include triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine, and the like.
These compounds are known as antioxidants such as rubbers, plastics and fats and oils, and commercially available products can be easily obtained.
The addition amount of the antioxidant is preferably 0.01 to 10% by mass with respect to the total mass of the layer to be added.

<Synthesis example of compound having monofunctional charge transport structure>
The compound having a monofunctional charge transport structure in the present invention is synthesized, for example, by the method described in Japanese Patent No. 3164426. One example is shown below.
(1) Synthesis of hydroxy group-substituted triarylamine compound (the following structural formula B) 113.85 g (0.3 mol) of a methoxy group-substituted triarylamine compound (the following structural formula A) and 138 g (0.92 mol) of sodium iodide To this, 240 ml of sulfolane was added and heated to 60 ° C. in a nitrogen stream. In this solution, 99 g (0.91 mol) of trimethylchlorosilane was added dropwise over 1 hour and stirred at a temperature of about 60 ° C. for 4 and a half hours to complete the reaction. About 1.5 L of toluene was added to the reaction solution, cooled to room temperature, and washed repeatedly with water and an aqueous sodium carbonate solution. Thereafter, the solvent was removed from the toluene solution and purified by column chromatography (adsorption medium: silica gel, developing solvent: toluene: ethyl acetate = 20: 1). Cyclohexane was added to the obtained pale yellow oil to precipitate crystals.
Thus, 88.1 g (yield = 80.4%) of white crystals represented by the following structural formula B was obtained. The melting point of the obtained compound was 64.0-66.0 ° C.

(2) Triarylamino group-substituted acrylate compound (the above exemplified compound No. 54)
82.9 g (0.227 mol) of the hydroxy group-substituted triarylamine compound (Structural Formula B) obtained in (1) above was dissolved in 400 ml of tetrahydrofuran, and an aqueous sodium hydroxide solution (NaOH: 12.4 g, Water: 100 ml) was added dropwise. The solution was cooled to 5 ° C., and 25.2 g (0.272 mol) of acrylic acid chloride was added dropwise over 40 minutes. Then, it stirred at 5 degreeC for 3 hours, and reaction was complete | finished. The reaction solution was poured into water and extracted with toluene. This extract was repeatedly washed with an aqueous sodium bicarbonate solution and water. Thereafter, the solvent was removed from the toluene solution and purified by column chromatography (adsorption medium: silica gel, developing solvent: toluene).
N-Hexane was added to the obtained colorless oil to precipitate crystals. Thus, Exemplified Compound No. As a result, 80.73 g (yield = 84.8%) of 54 white crystals were obtained. The melting point of the obtained compound was 117.5 to 119.0 ° C.

(Method for producing electrostatic latent image carrier)
The method for producing an electrostatic latent image carrier of the present invention is a method for producing the electrostatic latent image carrier of the present invention,
After forming the photosensitive layer on the support, the adhesive layer coating solution and the surface layer coating solution are sequentially applied on the photosensitive layer, and then the adhesive layer and the surface layer are cured by light irradiation.

After applying the adhesive layer coating solution and further applying the surface layer coating solution, energy is applied from the outside to cure the adhesive layer and the surface layer at the same time, thereby forming the adhesive layer and the surface layer. Examples of external energy used at this time include heat, light, and radiation. Among these, a light energy irradiation means is preferable. As the energy of light, UV irradiation light sources such as high-pressure mercury lamps and metal halide lamps, which mainly have an emission wavelength in ultraviolet light, can be used, but a visible light source is selected according to the absorption wavelength of radically polymerizable substances and photopolymerization initiators. Is also possible. Others include those that use an electron beam as the radiation energy, but those using light energy are useful because of the ease of reaction rate control and the simplicity of the apparatus.
The irradiation light amount is preferably 50 mW / cm ² or more, and more preferably 1,000 mW / cm ² or less. When the irradiation amount is less than 50 mW / cm ² , it may take time for the curing reaction, and when it exceeds 1,000 mW / cm ² , the progress of the reaction becomes non-uniform and the surface layer may become rough. .

  Here, an example of the manufacturing method of the electrostatic latent image carrier of the present invention will be given. First, the prepared adhesive layer coating solution is applied by spraying or the like on a photoreceptor in which an undercoat layer, a charge generation layer, and the charge transport layer are sequentially laminated on a support such as an aluminum cylinder. Subsequently, the surface layer coating solution is applied by spraying or the like, and then the adhesive layer and the surface layer are simultaneously cured by light energy irradiation means. After the curing is completed, the latent electrostatic image bearing member of the present invention can be obtained by heating at 100 to 150 ° C. for 10 to 30 minutes to reduce the residual solvent.

  The electrostatic latent image carrier of the present invention can be used not only for electrophotographic copying machines but also widely for electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making. In particular, the present invention is preferably used for the most popular image forming method, image forming apparatus, and process cartridge described below.

(Image forming method and image forming apparatus)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step. , Including recycling process, control process, etc.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image carrier of the present invention is used as the electrostatic latent image carrier.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.

The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to the roller, and can be selected according to the specifications and form of the electrophotographic apparatus. In the case of using a magnetic brush, the magnetic brush is composed of, for example, various ferrite particles such as Zn-Cu ferrite as a charging member, and a non-magnetic conductive sleeve for supporting it, and a magnet roll included in the non-magnetic conductive sleeve. . Or when using a brush, for example, as the material of the fur brush, a fur treated with carbon, copper sulfide, metal, or metal oxide is used, and this is wound around a metal or other conductive core. Make it a charger by sticking.
The charger is not limited to the contact charger as described above. However, since an image forming apparatus in which ozone generated from the charger is reduced is obtained, a contact charger is used. preferable.
It is preferable that the charger is disposed in contact or non-contact with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying a direct current and an alternating voltage.
Further, the charging device is a charging roller disposed in close proximity to the electrostatic latent image carrier via a gap tape, and the electrostatic latent image carrier is applied by applying a direct current and an alternating voltage to the charging roller. Those that charge the surface are preferred.
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer, and can be appropriately selected from known ones. For example, the toner or developer is accommodated. Preferred examples include those having at least a developing unit capable of bringing the toner or developer into contact or non-contact with the electrostatic latent image.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer contained in the developing device may be a one-component developer or a two-component developer.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. The intermediate recording medium is used to primarily transfer the visible image onto the intermediate recording medium, and then the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate recording medium using two or more colors, preferably a full color toner as the toner, and a composite transfer image; An embodiment including a secondary transfer step of transferring a transfer image onto a recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer unit includes a primary transfer unit that transfers a visible image onto an intermediate recording medium to form a composite transfer image, and a secondary transfer unit that transfers the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate recording medium is not particularly limited and may be appropriately selected from known recording media according to the purpose. For example, a transfer belt or the like is preferable.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited, and may be appropriately selected from known cleaners as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier. Preferred examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the electrophotographic color toner removed in the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

Here, one mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. FIG. 3 is a schematic diagram illustrating an example of an image forming apparatus.
In this image forming apparatus, a charging charger 3 is used as a means for charging the electrostatic latent image carrier (photoconductor) on the average. As the charging means, a corotron device, a scorotron device, a solid discharge element, a needle electrode device, a roller charging device, a conductive brush device, or the like is used, and a known method can be used.

The configuration of the present invention is effective when a charging unit such as a contact charging method or a non-contact proximity arrangement charging method in which the photoreceptor composition is decomposed by proximity discharge from the charging unit is used. The contact charging method is a charging method in which a charging roller, a charging brush, a charging blade, or the like is in direct contact with a photoreceptor. On the other hand, the proximity charging method is, for example, a type in which the charging roller is arranged in a non-contact state so as to have a gap of 200 μm or less between the photoreceptor surface and the charging means.
10-200 micrometers is preferable and the magnitude | size of the said space | gap has more preferable 10-100 micrometers. If the size of the gap is too large, charging may become unstable, and if it is too small, the surface of the charging member may be contaminated when toner remaining on the photoreceptor is present. .

  An image exposure unit 5 is used to form an electrostatic latent image on a uniformly charged electrostatic latent image carrier (photoconductor) 1. As this light source, for example, fluorescent materials such as fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light emitting diodes (LEDs), semiconductor lasers (LD), and electroluminescence (EL) can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.

A developing unit 6 is used to visualize the electrostatic latent image formed on the photoreceptor 1. Development methods include a one-component development method using a dry toner, a two-component development method, and a wet development method using a wet toner. When the photosensitive member is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. If this is developed with toner of negative (positive) polarity (detection fine particles), a positive image can be obtained, and if developed with toner of positive (negative) polarity, a negative image can be obtained.
Next, a transfer charger 210 is used to transfer the toner image visualized on the photoreceptor onto the recording medium 9. In addition, a pre-transfer charger 7 may be used for better transfer. As these transfer means, a transfer charger, an electrostatic transfer method using a bias roller, a mechanical transfer method such as an adhesive transfer method and a pressure transfer method, and a magnetic transfer method can be used. As the electrostatic transfer method, the charging means can be used.
A separation charger 211 and a separation claw 212 are used as means for separating the recording medium 9 from the photoreceptor 1. As other separation means, electrostatic adsorption induction separation, side end belt separation, tip grip conveyance, curvature separation, and the like are used. As the separation charger 211, the charging means can be used.
A fur brush 214 and a cleaning blade 215 are used to clean the toner remaining on the photoconductor after the transfer. Further, a pre-cleaning charger 213 may be used in order to perform cleaning more efficiently. Other cleaning means include a web method, a magnet brush method, and the like, but each may be used alone or in combination.
Next, a neutralizing unit is used for the purpose of removing the latent image on the photoreceptor as required. As the charge removal means, the charge removal lamp 2 and the charge removal charger are used, and the exposure light source and the charging means can be used respectively.
In addition, known processes can be used for reading, feeding, fixing, paper discharge and the like that are not close to the photoconductor.

Next, another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 4 is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 4. An intermediate transfer body cleaning device 17 for removing residual toner on the intermediate transfer body 50 is disposed in the vicinity of the support roller 15. The intermediate transfer body 50 stretched by the support roller 14 and the support roller 15 is a tandem type in which four image forming means 18 of yellow, cyan, magenta, and black are arranged in parallel and facing each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full color image (color copy) using the tandem image forming apparatus will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem image forming apparatus. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each of the image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem image forming apparatus is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image-corresponding image (L in FIG. 5), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image with each color toner, and the toner image is an intermediate transfer member. The image forming apparatus includes a transfer charger 62 for transferring the image onto 0, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

(Process cartridge)
The process cartridge of the present invention comprises the electrostatic latent image carrier of the present invention and at least one means selected from a charging means, a developing means, a transfer means, a cleaning means, and a charge eliminating means, and further if necessary. It has other means and is detachable from the main body of the image forming apparatus.

Here, as shown in FIG. 6, the process cartridge includes a photosensitive member 101, and at least a charging unit 102, a developing unit 104, a transfer unit 106, a cleaning unit 107, and a discharging unit (not shown). This is an apparatus (part) that includes one and is detachable from the main body of the image forming apparatus.
Referring to the image forming process using the process cartridge shown in FIG. 6, the photosensitive member 101 is charged in the direction of the arrow, charged by the charging means 102, and exposed to exposure means (not shown). An electrostatic latent image is formed. The electrostatic latent image is developed with toner by the developing unit 104, and the toner development is transferred to the recording medium 105 by the transfer unit 106 and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by the cleaning unit 107 and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

  The image forming apparatus of the present invention is configured by integrally combining the above-described electrostatic latent image carrier and components such as a developing device and a cleaning device as a process cartridge, and this unit is detachable from the apparatus main body. You may comprise. Further, at least one of a charger, an image exposure device, a developing device, a transfer or separation device, and a cleaning device is integrally supported together with a photosensitive member to form a process cartridge, and a single unit that is detachable from the apparatus main body, It is good also as a structure which can be attached or detached using guide means, such as a rail of an apparatus main body.

  In the image forming apparatus, the image forming method, and the process cartridge of the present invention, a photosensitive layer having a surface layer having high peeling resistance and wear resistance, good electrical characteristics, and a highly elastic and homogeneous surface layer. Since the provided electrostatic latent image carrier is used, image degradation due to wear can be suppressed, and high-definition and high-quality images can be formed over a long period of time.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example. In the following examples, “part” represents “part by mass”, and “%” represents “% by mass”.

(Synthesis Example 1)
-Synthesis of titanyl phthalocyanine pigment-
292 g of 1,3-diiminoisoindoline and 2000 ml of sulfolane are mixed, and 204 g of titanium tetrabutoxide is added dropwise under a nitrogen stream. After completion of the dropping, the temperature was gradually raised to 180 ° C., and the reaction was carried out by stirring for 5 hours while keeping the reaction temperature between 170 ° C. and 180 ° C. After completion of the reaction, the reaction mixture was allowed to cool and then the precipitate was filtered and washed with chloroform until the powder turned blue.
Next, it was washed several times with methanol, washed several times with hot water at 80 ° C. and then dried to obtain crude titanyl phthalocyanine.
The obtained titanyl phthalocyanine was dissolved in 20 times the amount of concentrated sulfuric acid and added dropwise to 100 times the amount of ice water with stirring, and the precipitated crystals were filtered. Next, washing with water was repeated until the washing solution became neutral, and a wet cake of titanyl phthalocyanine pigment was obtained. The obtained wet cake was thoroughly washed with ion exchange water.
20 g of the obtained wet cake was put into 200 g of 1,2-dichloroethane and stirred for 4 hours. After adding 1000 g of methanol to this and stirring for 1 hour, it filtered and dried and obtained titanyl phthalocyanine powder (this is called "pigment 1").
The X-ray diffraction spectrum of the obtained titanyl phthalocyanine pigment was measured under the following conditions.
<Measurement conditions>
・ X-ray tube: Cu
・ Voltage: 40kV
・ Current: 20mA
Scanning speed: 1 ° / min Scanning range: 3 ° -40 °
・ Time constant: 2 seconds

  An X-ray diffraction spectrum of the titanyl phthalocyanine pigment obtained in Synthesis Example 1 is shown in FIG. From this result, the obtained titanyl phthalocyanine pigment has major peaks with Bragg angle 2θ of at least 9.6 ° ± 0.2 °, 24.0 ° ± 0.2 ° and 27.2 ° ± 0.2 °. It can be seen that it has a crystalline form.

Example 1
-Production of electrostatic latent image carrier-
By coating and drying an undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution in the following composition on an aluminum cylinder having a diameter of 30 mm in sequence, a subbing layer having a thickness of 3.5 μm and a thickness of 0 A charge generation layer having a thickness of 3 μm and a charge transport layer having a thickness of 23 μm were formed.
On the obtained charge transport layer, an adhesive layer coating solution and a surface layer coating solution having the following composition were sprayed successively, a metal halide lamp: 160 W / cm, an irradiation distance: 120 mm, an irradiation intensity: 500 mW / cm ² , an irradiation time. : Light irradiation was performed for 120 seconds.
Next, drying was performed at 130 ° C. for 20 minutes to provide a 0.5 μm thick adhesive layer and a 4 μm thick surface layer. Thus, the electrostatic latent image carrier of Example 1 was produced.

[Undercoat layer coating solution]
・ Alkyd resin (Beckosol 1307-60-EL, manufactured by Dainippon Ink & Chemicals, Inc.) ... 6 parts Melamine resin (Super Becamine G-821-60, manufactured by Dainippon Ink & Chemicals, Inc.) ... 4 parts ・ Titanium oxide ・ ・ ・ 40 parts ・ Methyl ethyl ketone ・ ・ ・ 50 parts

[Charge generation layer coating solution]
-Bisazo pigment represented by the following structural formula (I)-2.5 parts-Polyvinyl butyral (XYHL, manufactured by UCC)-0.5 part-Cyclohexanone-200 parts-Methyl ethyl ketone-80 Part

[Charge transport layer coating solution]
Bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals Ltd.) 10 parts Low charge transport material (D-1) represented by the following structural formula (II) 7 parts Tetrahydrofuran・ ・ ・ 100 parts ・ Tetrahydrofuran solution of 1% silicone oil (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.) ・ ・ ・ 1 part

[Adhesive layer coating solution]
1,4-butanediol diacrylate as a bifunctional radically polymerizable compound having no charge transporting structure (SR213, manufactured by Nippon Kayaku Co., Ltd., functional group number = 2 functional, viscosity at 25 ° C. is 8 mPa · s ) ... 5 parts-Radical polymerizable compound having a monofunctional charge transport structure (Exemplary Compound No. 54) ... 5 parts-1-Hydroxy-cyclohexyl-phenyl-ketone (1) as a photopolymerization initiator Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 0.5 parts Tetrahydrofuran ... 400 parts

[Surface layer coating solution]
Trimethylolpropane triacrylate (KAYARAD TMPTA, manufactured by Nippon Kayaku Co., Ltd., molecular weight: 296, functional group number: trifunctional, molecular weight / functional group number) as a tri- or higher functional radical polymerizable compound having no charge transport structure 99) ··· 10 parts · Radical polymerizable compound having a monofunctional charge transport structure (Exemplified Compound No. 54) · · 10 parts · 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 1 part Tetrahydrofuran ... 100 parts

(Example 2)
-Production of electrostatic latent image carrier-
In Example 1, an electrostatic latent image carrier was produced in the same manner as in Example 1 except that the adhesive layer coating solution was changed to an adhesive layer coating solution having the following composition.
[Adhesive layer coating solution]
Diethylene glycol diacrylate as a bifunctional radically polymerizable compound having no charge transporting structure (SR230, manufactured by Nippon Kayaku Co., Ltd., functional group number = 2 functional, viscosity at 25 ° C. is 12 mPa · s) 5 Part ・ Radically polymerizable compound having monofunctional charge transport structure (Exemplary Compound No. 54) 5 parts ・ 1-Hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, Ciba Specialty Chemicals Co., Ltd.) ... 0.5 parts Tetrahydrofuran ... 400 parts

(Example 3)
-Production of electrostatic latent image carrier-
In Example 1, an electrostatic latent image carrier was produced in the same manner as in Example 1 except that the adhesive layer coating solution was changed to an adhesive layer coating solution having the following composition.
[Adhesive layer coating solution]
・ Tetraethylene glycol diacrylate as a bifunctional radically polymerizable compound having no charge transporting structure (SR268, Nippon Kayaku Co., Ltd., functional group number = 2 functional, viscosity at 25 ° C. is 20 mPa · s). -5 parts-Radical polymerizable compound having a monofunctional charge transport structure (Exemplary Compound No. 54) ... 5 parts-1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, as a photopolymerization initiator) Ciba Specialty Chemicals Co., Ltd.) 0.5 parts Tetrahydrofuran 400 parts

Example 4
-Production of electrostatic latent image carrier-
In Example 1, an electrostatic latent image carrier was produced in the same manner as in Example 1 except that the adhesive layer coating solution was changed to an adhesive layer coating solution having the following composition.
[Adhesive layer coating solution]
Triethylene glycol diacrylate as a bifunctional radically polymerizable compound having no charge transporting structure (SR272, manufactured by Nippon Kayaku Co., Ltd., functional group number = 2 functional, viscosity at 25 ° C. is 15 mPa · s) -5 parts-Radical polymerizable compound having a monofunctional charge transport structure (Exemplary Compound No. 54) ... 5 parts-1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, as a photopolymerization initiator) Ciba Specialty Chemicals Co., Ltd.) 0.5 parts Tetrahydrofuran 400 parts

(Example 5)
-Production of electrostatic latent image carrier-
In Example 1, an electrostatic latent image carrier was produced in the same manner as in Example 1 except that the adhesive layer coating solution was changed to an adhesive layer coating solution having the following composition.
[Adhesive layer coating solution]
Propoxy neopentyl glycol diacrylate as a bifunctional radically polymerizable compound having no charge transporting structure (SR9003, Nippon Kayaku Co., Ltd., functional group number = 2 functional, viscosity at 25 ° C. is 15 mPa · s) ... 5 parts-Radical polymerizable compound having a monofunctional charge transport structure (Exemplary Compound No. 54) ... 5 parts-1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure as a photopolymerization initiator) 184, manufactured by Ciba Specialty Chemicals) ... 0.5 parts Tetrahydrofuran ... 400 parts

(Example 6)
-Production of electrostatic latent image carrier-
In Example 1, an electrostatic latent image carrier was produced in the same manner as in Example 1 except that the adhesive layer coating solution was changed to an adhesive layer coating solution having the following composition.
[Adhesive layer coating solution]
-N-Butyl acrylate as a bifunctional radically polymerizable compound having no charge transporting structure (manufactured by Tokyo Chemical Industry Co., Ltd., number of functional groups = 1 functional, viscosity at 25 ° C. is 0.81 mPa · s) 5 parts-Radical polymerizable compound having a monofunctional charge transport structure (Exemplary Compound No. 54) ... 5 parts-1-Hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, Ciba as a photopolymerization initiator)・ Specialty Chemicals Co., Ltd.) 0.5 parts ・ Tetrahydrofuran 400 parts

(Example 7)
-Production of electrostatic latent image carrier-
In Example 1, an electrostatic latent image carrier was produced in the same manner as in Example 1 except that the adhesive layer coating solution was changed to an adhesive layer coating solution having the following composition.
[Adhesive layer coating solution]
・ Ethoxylated 1,6-hexanediol diacrylate as a bifunctional radically polymerizable compound having no charge transporting structure (SR560, manufactured by Nippon Kayaku Co., Ltd., functional group number = 2 functional, viscosity at 25 ° C. is 24 mPa · S) ··· 5 parts · Radical polymerizable compound having a monofunctional charge transport structure (Exemplary Compound No. 54) ··· 5 parts · 1-Hydroxy-cyclohexyl-phenyl- as a photopolymerization initiator Ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 0.5 parts Tetrahydrofuran ... 400 parts

(Comparative Example 1)
-Production of electrostatic latent image carrier-
In Example 1, an electrostatic latent image carrier was prepared in the same manner as in Example 1 except that the adhesive layer was not provided and only the surface layer coating solution was spray-coated on the charge transport layer.

<Actual paper passing test>
About each electrostatic latent image carrier of Examples 1 to 7 and Comparative Example 1 produced as described above, using an image forming apparatus (manufactured by Ricoh Co., Ltd., imagio Neo270, 655 nm semiconductor laser as an image exposure light source), An actual sheet passing test (A4 size, manufactured by NBS Ricoh Co., My Paper, charging potential at start-700 V) was performed on 100,000 sheets, and wear characteristics, in-machine potential, and image evaluation (S3 chart evaluation) were performed. The results are shown in Table 3, Table 4, and Table 5.

* In Table 5, streak image evaluation criteria: ◎ → very good, ○ → good, △ → locally generated, x → generated over the entire image

(Example 8)
-Production of electrostatic latent image carrier-
By applying and drying an undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition in sequence on an aluminum cylinder having a diameter of 30 mm, an undercoat layer having a thickness of 1.0 μm. A 3 μm charge generation layer and a 23 μm thick charge transport layer were formed. On this charge transport layer, an adhesive layer coating solution and a surface layer coating solution having the following composition were spray-coated in succession, a metal halide lamp: 160 W / cm, irradiation distance: 120 mm, irradiation intensity: 500 mW / cm ² , irradiation time: 120 Light irradiation was performed under the condition of seconds. Next, drying was performed at 130 ° C. for 20 minutes to provide an adhesive layer having a thickness of 0.03 μm and a surface layer having a thickness of 4 μm. Thus, an electrostatic latent image carrier of Example 8 was produced.

[Undercoat layer coating solution]
Titanium oxide: 40 parts Alcohol-soluble nylon: 32 parts Methanol: 400 parts Isopropanol: 160 parts

[Charge generation layer coating solution]
-Titanyl phthalocyanine powder synthesized in Synthesis Example 1-4 parts-Polyvinyl butyral (S-REC BM-S, manufactured by Sekisui Chemical Co., Ltd.)-2 parts-Methyl ethyl ketone-150 parts

[Charge transport layer coating solution]
Bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals Ltd.) 10 parts Low charge transport material (D-1) represented by the following structural formula (II) 7 parts Tetrahydrofuran・ ・ ・ 100 parts ・ Tetrahydrofuran solution of 1% silicone oil (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.) ・ ・ ・ 1 part

[Adhesive layer coating solution]
1,4-butanediol dimethacrylate as a bifunctional radical polymerizable compound having no charge transporting structure (SR214, Nippon Kayaku Co., Ltd., functional group number = 2 functional, viscosity at 25 ° C. is 7 mPa · s ) ... 5 parts-Radical polymerizable compound having a monofunctional charge transport structure (Exemplary Compound No. 105) ... 5 parts-1-hydroxy-cyclohexyl-phenyl-ketone (1) as a photopolymerization initiator Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 0.5 parts Tetrahydrofuran ... 400 parts

[Surface layer coating solution]
Dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., molecular weight: 536, functional group number: 5.5 functional, molecular weight / functional Number of radicals = 97)... 10 parts. Radical polymerizable compound having a monofunctional charge transport structure (Exemplary Compound No. 105)... 10 parts. 1-Hydroxy-cyclohexyl-phenyl as a photopolymerization initiator. -Ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 1 part Tetrahydrofuran ... 100 parts

Example 9
-Production of electrostatic latent image carrier-
In Example 8, an electrostatic latent image carrier was produced in the same manner as in Example 8 except that the adhesive layer coating solution was changed to the following composition.
[Surface layer coating solution]
Diethylene glycol dimethacrylate as a bifunctional radically polymerizable compound having no charge transporting structure (SR231E, manufactured by Nippon Kayaku Co., Ltd., functional group number = 2 functional, viscosity at 25 ° C. is 8 mPa · s) 5 Part ・ Radically polymerizable compound having monofunctional charge transport structure (Exemplary Compound No. 105) 5 parts ・ 1-Hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, Ciba Specialty Chemicals Co., Ltd.) ... 0.5 parts Tetrahydrofuran ... 400 parts

(Example 10)
-Production of electrostatic latent image carrier-
In Example 8, an electrostatic latent image carrier was produced in the same manner as in Example 8, except that the adhesive layer coating solution was changed to an adhesive layer coating solution having the following composition.
[Adhesive layer coating solution]
Tetraethylene glycol dimethacrylate as a bifunctional radically polymerizable compound not having a charge transporting structure (SR209, manufactured by Nippon Kayaku Co., Ltd., number of functional groups = 2 functional, viscosity at 25 ° C. is 14 mPa · s) -5 parts-Radical polymerizable compound having a monofunctional charge transport structure (Exemplified Compound No. 105) ... 5 parts-1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, as a photopolymerization initiator) Ciba Specialty Chemicals Co., Ltd.) 0.5 parts Tetrahydrofuran 400 parts

(Example 11)
-Production of electrostatic latent image carrier-
In Example 8, an electrostatic latent image carrier was produced in the same manner as in Example 8, except that the adhesive layer coating solution was changed to an adhesive layer coating solution having the following composition.
[Adhesive layer coating solution]
Triethylene glycol dimethacrylate as a bifunctional radically polymerizable compound not having a charge transporting structure (SR205, manufactured by Nippon Kayaku Co., Ltd., functional group number: bifunctional, viscosity at 25 ° C. is 11 mPa · s) -5 parts-Radical polymerizable compound having a monofunctional charge transport structure (Exemplified Compound No. 105) ... 5 parts-1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, as a photopolymerization initiator) Ciba Specialty Chemicals Co., Ltd.) 0.5 parts Tetrahydrofuran 400 parts

(Example 12)
-Production of electrostatic latent image carrier-
In Example 8, an electrostatic latent image carrier was produced in the same manner as in Example 8, except that the adhesive layer coating solution was changed to an adhesive layer coating solution having the following composition.
[Adhesive layer coating solution]
・ Neopentyl glycol dimethacrylate as a bifunctional radical polymerizable compound having no charge transporting structure (SR248, Nippon Kayaku Co., Ltd., functional group number = 2 functional, viscosity at 25 ° C. is 8 mPa · s). -5 parts-Radical polymerizable compound having a monofunctional charge transport structure (Exemplified Compound No. 105) ... 5 parts-1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, as a photopolymerization initiator) Ciba Specialty Chemicals Co., Ltd.) 0.5 parts Tetrahydrofuran 400 parts

(Example 13)
-Production of electrostatic latent image carrier-
In Example 8, an electrostatic latent image carrier was produced in the same manner as in Example 8, except that the thickness of the adhesive layer was 0.05 μm.

(Example 14)
-Production of electrostatic latent image carrier-
In Example 8, an electrostatic latent image carrier was produced in the same manner as in Example 8, except that the thickness of the adhesive layer was 6 μm.

(Comparative Example 2)
-Production of electrostatic latent image carrier-
In Example 8, an electrostatic latent image carrier was produced in the same manner as in Example 8, except that the adhesive layer was not provided and only the surface layer coating solution was spray-coated on the charge transport layer.

<Actual paper passing test>
Each electrostatic latent image carrier of Examples 8 to 14 and Comparative Example 2 produced as described above was used using an image forming apparatus (manufactured by Ricoh Co., Ltd., imagio Neo 270, 780 nm semiconductor laser as an image exposure light source). An actual sheet passing test of 100,000 sheets (A4 size, manufactured by NBS Ricoh, MyPaper, charging potential at start-700 V) was performed, and wear characteristics, in-machine potential, and image evaluation (S3 chart evaluation) were performed. The results are shown in Table 6, Table 7, and Table 8.

* In Table 8, streak image evaluation criteria: ◎ → very good, ○ → good, △ → locally generated, x → generated over the entire image

  From the results of Tables 3 to 8, it is recognized that Examples 1 to 14 have excellent wear resistance and excellent image quality without generation of a squeeze image even when 100,000 sheets are passed. On the other hand, in Comparative Examples 1 and 2, abrupt wear was observed due to peeling wear, and as a result, a streak image was generated on the entire surface of 50,000 sheets.

  An image forming method, an image forming apparatus, and a process cartridge using an electrostatic latent image carrier of the present invention are a full color copying machine, a full color laser printer, and a full color plain paper using a direct or indirect electrophotographic multicolor image developing system. Widely used for fax machines.

FIG. 1 is a schematic sectional view showing an example of the electrostatic latent image carrier of the present invention. FIG. 2 is a schematic sectional view showing another example of the electrostatic latent image carrier of the present invention. FIG. 3 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 4 is a schematic explanatory view showing an example of carrying out the image forming method of the present invention by the image forming apparatus (tandem color image forming apparatus) of the present invention. FIG. 5 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG. FIG. 6 is a schematic view showing an example of the process cartridge of the present invention. FIG. 7 is an X-ray diffraction spectrum of the titanyl phthalocyanine pigment used in the examples.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrostatic latent image carrier 2 Static elimination lamp 3 Charger charger 4 Eraser 5 Image exposure part 6 Development unit 7 Charger before transfer 8 Registration roller 9 Transfer paper 10 Photosensitive body (photosensitive drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 discharge tray 58 corona charger 60 cleaning device 61 developing device 62 transfer charger 63 photoconductor cleaning device 64 static eliminator 70 static elimination lamp 71 cleaning blade 72 support member 80 transfer roller 90 cleaning device 95 transfer paper 210 transfer charger 211 separation charger 212 Separation claw 213 Charger before cleaning 214 Fur brush 215 Cleaning blade 101 Photosensitive drum 102 Charging device 103 Exposure 104 Developing device 105 Recording medium DESCRIPTION OF SYMBOLS 106 Transfer device 107 Cleaning blade 231 Support body 233 Photosensitive layer 235 Charge generation layer 237 Charge transport layer 238 Adhesive layer 239 Surface layer 100 Image forming apparatus 120 Tandem type developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Image forming apparatus body 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)

Claims (13)

A support, and at least a photosensitive layer and a surface layer in this order on the support;
The surface layer contains a cured product of at least a trifunctional or higher-functional radical polymerizable compound having no charge transport structure and a radical polymerizable compound having a charge transport structure, and the photosensitive layer and the surface layer The adhesive layer has at least a cured product of a radical polymerizable compound having no charge transporting structure whose viscosity at 25 ° C. is 1 to 20 mPa · s. An electrostatic latent image carrier. 2. The electrostatic latent image carrier according to claim 1, wherein the radically polymerizable compound having no charge transporting structure is bifunctional. Adhesive layer, and that the viscosity at 25 ° C. to cure the no radical-polymerizable compound a charge transport structure is 1 to 20 mPa · s, and that by curing a radical polymerizable compound having a charge transport structure The electrostatic latent image carrier according to claim 1, which is contained at least. The electrostatic latent image carrier according to claim 3, wherein the radical polymerizable compound having a charge transporting structure is monofunctional.   The electrostatic latent image carrier according to claim 1, wherein the adhesive layer has a thickness of 0.1 to 5 μm.   6. The electrostatic latent image carrier according to claim 1, wherein the photosensitive layer contains a charge generating material, and the charge generating material contains titanyl phthalocyanine.   Titanyl phthalocyanine has at least 9.6 ° ± 0.2 °, 24.0 ° ± 0.2 ° and 27.2 ° ± 0.2 major peaks with Bragg angle 2θ in the X-ray diffraction spectrum for Cu—Kα rays. The electrostatic latent image carrier according to claim 6, which contains a crystal form at a temperature.   The electrostatic latent image carrier according to claim 1, wherein the photosensitive layer is a single-layer type photosensitive layer.   9. The electrostatic latent image carrier according to claim 1, wherein the photosensitive layer is a laminated photosensitive layer having at least a charge generation layer and a charge transport layer in this order on a support. A method for producing the electrostatic latent image carrier according to any one of claims 1 to 9,
After forming the photosensitive layer on the support, the adhesive layer coating solution and the surface layer coating solution are sequentially coated on the photosensitive layer, and then the adhesive layer and the surface layer are cured by light irradiation. A method for producing an electrostatic latent image carrier. An electrostatic latent image forming step for forming an electrostatic latent image on the electrostatic latent image carrier, a developing step for developing the electrostatic latent image with toner to form a toner image, and recording the toner image In an image forming method including at least a transfer step of transferring to a medium,
10. The image forming method according to claim 1, wherein the latent electrostatic image bearing member is the latent electrostatic image bearing member according to claim 1. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a toner image In an image forming apparatus having at least developing means and transfer means for transferring the toner image to a recording medium,
An image forming apparatus, wherein the latent electrostatic image bearing member is the latent electrostatic image bearing member according to claim 1.   An electrostatic latent image carrier according to any one of claims 1 to 9, and at least one unit selected from a charging unit, a developing unit, a transfer unit, a cleaning unit, and a charge eliminating unit, A process cartridge which is detachable.