JP2006133748A - Electrophotographic photoreceptor, image forming method, image forming apparatus, and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having high wear resistance, capable of maintaining high image quality with few image defects and less liable to cause image defects such as white spots. <P>SOLUTION: The electrophotographic photoreceptor has a layer including a cured material obtained by radical-polymerizing a radical polymerizing monomer having three or more radical polymerizing groups per molecule and a compound represented by formula (1): B<SB>1</SB>-Ar<SB>1</SB>-CH=CH-Ar<SB>2</SB>-B<SB>2</SB>wherein Ar<SB>1</SB>represents a mono- or divalent group comprising an aromatic hydrocarbon skeleton; Ar<SB>2</SB>represents a mono- or divalent group comprising an aromatic hydrocarbon skeleton having one or more tertiary amino groups or a mono- or divalent group comprising a heterocyclic compound skeleton having one or more tertiary amino groups; one of B<SB>1</SB>and B<SB>2</SB>is H; and the other is acryloyloxy, methacryloyloxy, vinyl, alkyl which may have a substituent or alkoxy which may have a substituent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention has extremely high wear resistance during repeated use and can maintain a high image quality with few image defects over a long period of time. High and highly durable electrophotographic photosensitive member (hereinafter also referred to as "photosensitive member", "electrostatic latent image carrier", "image carrier"), and image forming method using the electrophotographic photosensitive member The present invention relates to an image forming apparatus and a process cartridge.

  In recent years, organic photoconductors (OPCs) have good performance and are widely used in copying machines, facsimiles, laser printers, and composite machines in place of inorganic photoreceptors because of various advantages. The reasons for this are, 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) selection of materials. Examples include a wide range, (4) ease of production, (5) low cost, and (6) non-toxicity.

Recently, in order to reduce the size of the image forming apparatus, the diameter of the photoconductor has been reduced, and further, the high speed of the machine and the maintenance-free movement have been added, so that the photoconductor is highly durable. ing. From this point of view, organic photoreceptors are generally soft because the charge transport layer is mainly composed of a low molecular charge transport material and an inert polymer, and when used repeatedly in an electrophotographic process, a development system or a cleaning system There is a drawback that wear is likely to occur due to the mechanical load due to.
In addition, due to the demand for higher image quality, the toner particles have been made smaller in size, and in association with this, in order to improve the cleaning property, the rubber hardness of the cleaning blade and the contact pressure must be increased. The This is also one of the factors that promote the wear of the photoreceptor. 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.

  Accordingly, various improvements have been made for the purpose of improving the wear resistance of the organic photoreceptor. For example, a material using a curable binder in the charge transport layer (see Patent Document 1), a material using a polymer type charge transport material (see Patent Document 2), or a material in which an inorganic filler is dispersed in the charge transport layer (Patent Document) Reference 3), a polyfunctional acrylate monomer cured product (see Patent Document 4), a monomer having a carbon-carbon double bond, a charge transport material having a carbon-carbon double bond, and a binder resin A charge transporting layer formed using a coating liquid (see Patent Document 5), and a compound obtained by curing a hole transporting compound having two or more chain polymerizable functional groups in the same molecule. (See Patent Document 6).

Although these improvements have improved the wear resistance of the organic photoreceptor compared to conventional products, new problems have arisen. Conventional photoreceptors are refaced (renewed surface) due to wear even if foreign matter adheres to the surface, scratches, etc., and image defects do not reoccur forever. However, the photoconductor with improved wear resistance as described above will remain indefinitely once a strong foreign matter is attached or scratched on the surface, and image defects will continue to occur.
Particularly in recent years, due to the demand for higher image quality and energy saving, the particle size of the toner is reduced and the softening temperature is lowered, and in order to ensure its fluidity, inorganic fine particles such as silica are often added to the toner. ing. There is a problem that such silica particles stick to the surface of the organophotoreceptor during the development process, and a wax component of the toner accumulates around the surface of the organophotoreceptor and cannot be developed, resulting in white spot image defects.

  Therefore, the abrasion resistance during repeated use is extremely high, and high image quality with few image defects can be maintained over a long period of time, white spot-like image defects are unlikely to occur, surface smoothness at the initial stage and over time is high, and high Durable electrophotographic photoreceptors and related technologies have not yet been obtained, and it is desired to provide them promptly.

JP 56-48637 A JP-A 64-1728 JP-A-4-281461 Japanese Patent No. 3262488 Japanese Patent No. 3194392 JP 2000-66425 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention has extremely high wear resistance during repeated use and can maintain a high image quality with few image defects over a long period of time. It is an object of the present invention to provide a highly durable and highly durable electrophotographic photosensitive member, and an image forming method, an image forming apparatus, and a process cartridge using the electrophotographic photosensitive member.

Means for solving the problems are as follows. That is,
<1> At least a layer containing a cured product obtained by radical polymerization of a radical polymerizable monomer having three or more radical polymerizable groups in the molecule and a compound represented by the following structural formula (1) An electrophotographic photosensitive member characterized by the above.
_{B 1 -Ar 1 -CH = CH-} Ar 2 -B 2 ··· structural formula (1)
However, in the structural formula (1), Ar ₁ is a monovalent group composed of an aromatic hydrocarbon skeleton which may have a substituent and an aromatic hydrocarbon skeleton which may have a substituent. Any one of the following divalent groups. Ar ₂ represents a monovalent group composed of an aromatic hydrocarbon skeleton having at least one tertiary amino group, a divalent group composed of an aromatic hydrocarbon skeleton having at least one tertiary amino group, and at least one 3 It represents either a monovalent group consisting of a heterocyclic compound skeleton having a secondary amino group or a divalent group consisting of a heterocyclic compound skeleton having at least one tertiary amino group. One of B ₁ and B ₂ may be a hydrogen atom, and the other may have an acryloyloxy group, a methacryloyloxy group, a vinyl group, an alkyl group that may have a substituent, and a substituent. It represents any one group selected from good alkoxy groups.
<2> The cured product obtained by radical polymerization of a radical polymerizable monomer having three or more radical polymerizable groups in the molecule, the compound represented by the structural formula (1), and a photopolymerization initiator. The electrophotographic photosensitive member according to <1>.
<3> The electrophotographic photoreceptor according to any one of <1> to <2>, wherein the compound represented by the structural formula (1) is an acrylate compound represented by the following structural formula (2). is there.
However, in said structural formula (2), R < ₁ > and R < ₂ > represents either the alkyl group which may have a substituent, the alkoxy group which may have a substituent, and a halogen atom. Ar ₃ and Ar ₄ may be the same as or different from each other, and may be an aryl group that may have a substituent, an arylene group that may have a substituent, and a substituent. It represents any of the benzyl groups that may have. B _{1 to} B ₄ are any one group selected from an acryloyloxy group, a methacryloyloxy group, a vinyl group, an alkyl group which may have a substituent, and an alkoxy group which may have a substituent. And only one of B _{1 to} B ₄ is present. l represents an integer of 0 to 5, and m represents an integer of 0 to 4.
<4> The electrophotographic photoreceptor according to any one of <1> to <2>, wherein the compound represented by the structural formula (1) is an acrylate compound represented by the following structural formula (3). is there.
However, in said structural formula (3), R < ₁ > -R < ₄ > represents either the alkyl group which may have a substituent, the alkoxy group which may have a substituent, and a halogen atom. B ₁ .about.B ₄ represents the same meaning as _B 1 .about.B ₄ of structure (2), of the _B 1 .about.B _4, only any one is present. l, n, and o represent an integer of 0 to 5, and m represents an integer of 0 to 4.
<5> The electrophotographic photoreceptor according to any one of <1> to <2>, wherein the compound represented by the structural formula (1) is a compound represented by the following structural formula (4).
However, in the structural formula (4), Ar ₁ and Ar ₂ may be the same as or different from each other, may have an alkylene group which may have a substituent, and have a substituent. Or an arylene group which may be substituted or a heterocyclic group which may have a divalent substitution. Ar ₅ , Ar ₆ , Ar ₇ , and Ar ₈ may be the same as or different from each other, and have a hydrogen atom, an alkyl group that may have a substituent, or a substituent. Represents an aralkyl group which may be substituted, an aryl group which may have a substituent, and a heterocyclic group which may have a substituent, and Ar ₅ and Ar ₆ may form a cyclic structure. Good. B ₁ , B ₅ , B ₆ , B ₇ , and B ₈ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and the B ₁ , B ₅ , B ₆ , B ₇ , and B ₈ Only one of them exists.
<6> The electrophotographic photosensitive member according to any one of <1> to <2>, wherein the compound represented by the structural formula (1) is a compound represented by the following structural formula (5).
However, in the structural formula (5), Ar ₅ , Ar ₆ , Ar ₇ , and Ar ₈ may be the same as or different from each other, and may have a hydrogen atom or a substituent. Any one of a good alkyl group, an aralkyl group which may have a substituent, an aryl group which may have a substituent, and a heterocyclic group which may have a substituent, and Ar ₅ and A ring structure may be formed with Ar ₆ . B ₁ , B ₂ , B ₅ , B ₆ , B ₇ , and B ₈ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and the B ₁ , B ₂ , B ₅ , B ₆ , Only one of B ₇ and B ₈ exists. R ₁ and R ₂ are any of an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, and a halogen atom. To express. The X ring and the Y ring represent a cyclic structure that may be present by bonding to an adjacent benzene ring. l represents an integer of 0 to 5, and m represents an integer of 0 to 4.
<7> The electrophotographic photosensitive member according to any one of <1> to <2>, wherein the compound represented by the structural formula (1) is a compound represented by the following structural formula (6).
However, in said structural formula (6), R < ₁ >, R < ₂ >, R < ₃ >, R < ₄ > and R < ₅ > are the alkyl group which may have a substituent, and the aralkyl group which may have a substituent. Represents an optionally substituted alkoxy group and a halogen atom. B ₁ , B ₂ , B ₅ , B ₆ , and B ₈ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and the B ₁ , B ₂ , B ₅ , B ₆ , and B ₈ Only one of them exists. The X ring and the Y ring represent a cyclic structure that may be present by bonding to an adjacent benzene ring. l, q, r, and s represent an integer of 0 to 5, and m represents an integer of 0 to 4.
<8> The electrophotographic photosensitive member according to any one of <1> to <2>, wherein the compound represented by the structural formula (1) is a compound represented by the following structural formula (7).
However, in the structural formula (7), Ar ₁ and Ar ₉ may be the same as or different from each other, and have an alkylene group or a substituent that may have a substituent. It represents either an arylene group which may be substituted or a heterocyclic group which may have a divalent substituent. R ₂ represents any of an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, and a halogen atom. R ₆ and R ₇ may be the same or different from each other, and may be a hydrogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or a substituent. Represents an alkoxy group which may have a group, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, and a halogen atom; and R ₆ and R ₇ may combine to form a Z ring. m represents an integer of 0 to 3, and t represents an integer of 0 to 2. B ₁ , B ₂ , and B ₉ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and only one of B ₁ , B ₂ , and B ₉ exists.
<9> The electrophotographic photosensitive member according to any one of <1> to <2>, wherein the compound represented by the structural formula (1) is a compound represented by the following structural formula (8).
However, in the structural formula (8), Ar ₉ may have an alkylene group which may have a substituent, an arylene group which may have a substituent, and a divalent substituent. Represents any good heterocyclic group. R ₁ and R ₂ are any of an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, and a halogen atom. To express. R ₆ and R ₇ may be the same or different from each other, and may be a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituted group. Represents an alkoxy group which may have a group, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, and a halogen atom, and R ₆ and R _7. To form a Z ring. l represents an integer of 0 to 5, and m represents an integer of 0 to 3. B ₁ , B ₂ , and B ₉ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and only one of B ₁ , B ₂ , and B ₉ exists.
<10> The electrophotographic photosensitive member according to any one of <1> to <2>, wherein the compound represented by the structural formula (1) is a compound represented by the following structural formula (9).
However, in said structural formula (9), R < ₁ >, R < ₂ >, and R < ₈ > have the alkyl group which may have a substituent, the aralkyl group which may have a substituent, and a substituent. It represents either an optionally substituted alkoxy group or a halogen atom. l and u represent an integer of 0 to 5, and m represents an integer of 0 to 3. B ₁ , B ₂ , and B ₉ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and only one of B ₁ , B ₂ , and B ₉ exists.
<11> The electrophotographic photosensitive member according to any one of <1> to <10>, wherein the cured product has a gel fraction of 95% or more.
<12> The electrophotographic photosensitive member according to any one of <1> to <11>, wherein the gel fraction of the cured product is 97% or more.
<13> A radical polymerizable monomer having three or more radical polymerizable groups in the molecule, a radical polymerizable monomer having three radical polymerizable groups in the molecule, and 5 to 6 radical polymerizable groups in the molecule. The electrophotographic photosensitive member according to any one of <1> to <12>, wherein the electrophotographic photosensitive member is a mixture with a radically polymerizable monomer.
<14> The mixing mass ratio (A: B) of the radical polymerizable monomer (A) having three or more radical polymerizable groups in the molecule and the compound (B) represented by the structural formula (1) is: The electrophotographic photosensitive member according to any one of <1> to <13>, which is 9: 1 to 1: 9.
<15> The electrophotographic photosensitive member according to any one of <1> to <14>, wherein the layer containing the cured product is an outermost surface layer of the electrophotographic photosensitive member.
<16> A support, and at least a charge generation layer, a charge transport layer, and a crosslinkable charge transport layer in this order on the support, wherein the crosslinkable charge transport layer is the outermost surface layer. 15>.
<17> The electrophotographic photosensitive member according to <16>, wherein the cross-linked charge transport layer has a thickness of 3 to 10 μm.
<18> An electrophotographic photosensitive member, an electrostatic latent image forming unit for forming an electrostatic latent image on the electrophotographic photosensitive member, and developing the electrostatic latent image with toner to form a visible image. Development means, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transfer image transferred to the recording medium,
An electrophotographic photosensitive member according to any one of <1> to <17>, wherein the electrophotographic photosensitive member is an image forming apparatus.
<19> An electrostatic latent image forming step of forming an electrostatic latent image on an electrophotographic photosensitive member, a developing step of developing the electrostatic latent image with toner to form a visible image, and the visible A transfer step of transferring the image to the recording medium, and a fixing step of fixing the transfer image transferred to the recording medium,
The electrophotographic photosensitive member is an electrophotographic photosensitive member according to any one of <1> to <17>.
<20> Development for developing a visible image by developing the electrophotographic photosensitive member according to any one of <1> to <17> and an electrostatic latent image formed on the electrophotographic photosensitive member with a toner. And a process cartridge that is detachable from the main body of the image forming apparatus.

The electrophotographic photoreceptor of the present invention is a cured product obtained by radical polymerization of at least a radical polymerizable monomer having three or more radical polymerizable groups in the molecule and a compound represented by the following structural formula (1). It has a layer containing.
_{B 1 -Ar 1 -CH = CH-} Ar 2 -B 2 ··· structural formula (1)
However, in the structural formula (1), Ar ₁ is a monovalent group composed of an aromatic hydrocarbon skeleton which may have a substituent and an aromatic hydrocarbon skeleton which may have a substituent. Any one of the following divalent groups. Ar ₂ represents a monovalent group composed of an aromatic hydrocarbon skeleton having at least one tertiary amino group, a divalent group composed of an aromatic hydrocarbon skeleton having at least one tertiary amino group, and at least one 3 It represents either a monovalent group consisting of a heterocyclic compound skeleton having a secondary amino group or a divalent group consisting of a heterocyclic compound skeleton having at least one tertiary amino group. One of B ₁ and B ₂ may be a hydrogen atom, and the other may have an acryloyloxy group, a methacryloyloxy group, a vinyl group, an alkyl group that may have a substituent, and a substituent. It represents any one group selected from good alkoxy groups.

In the electrophotographic photoreceptor of the present invention, while maintaining excellent wear resistance and electrical characteristics, the external additive in the extremely hard toner such as silica fine particles is prevented from sticking into the photoreceptor, and white spots Image defects can be reduced. The reason can be considered as follows.
The surface layer of a conventional photoreceptor is a thermoplastic resin in which a low molecular charge transport agent is dispersed, and is softer than inorganic fillers such as silica, and is thought to be easily pierced upon contact. For this reason, it is necessary to increase the surface hardness. In this case, even if it is changed to a polymer charge transporting resin that excludes the dispersion of the low molecular charge transporting agent, it is not improved, and a crosslinked resin with an increased crosslinking density is required. It is advantageous.
On the other hand, in order to exhibit good electrical characteristics as an electrophotographic photoreceptor, it is necessary to incorporate a charge transporting component into the crosslinked film. In general, the charge transporting component has a bulky structure having a triarylamine structure, has a molecular weight larger than that of a normal polymerizable monomer, and originally has a high crosslinking density due to mixing of the charge transporting component, A sufficient crosslinking density was not obtained.
Therefore, an attempt has been made to form a highly crosslinked product by using a polyfunctional monomer as the polymerizable monomer and further having a polyfunctional polymerizable group in the charge transporting component. However, in the state where a bulky charge transport component is contained, a cross-linked body having a large strain is formed, so that there is a problem that a crack is generated or a brittle film is formed. For this reason, it is conceivable to introduce a flexible group between the radical polymerizable group and the charge transporting structure, but this is contrary to the increase in hardness.
In addition, when a polymerizable group is added to the triphenylamine structure which is the minimum unit of the triarylamine structure, the charge mobility is insufficient and the photoreceptor is inferior in electrical characteristics. Therefore, as the skeleton of the charge transporting structure, a structure having a suitably conjugated length is preferable, but this is contrary to the improvement of the crosslinking density.

Thus, in a situation where it is difficult to satisfy all the characteristics, in the present invention, the (meth) acrylic acid ester having a specific structure represented by the structural formula (1) functioning as a charge transporting component to be used. It is characterized by using a compound or a vinyl compound. The (meth) acrylic acid ester compound or vinyl compound having a specific structure represented by the structural formula (1) is a tertiary amine compound having a stilbene-type conjugated structure, and has a structure excellent in hole mobility. Yes. It has one acryloyloxy group, methacryloyloxy group or vinyl group having high radical polymerizability in the molecule, and rapidly gels during radical polymerization and does not cause excessive crosslinking strain. In addition, the double bond of the stilbene structure part in the molecule partially participates in the polymerization, and further, the polymerization reaction is lower than the acryloyloxy group, methacryloyloxy group, or vinyl group, so that a time difference occurs in the crosslinking reaction. The distortion is not maximized. In addition, since the number of cross-linking reactions per molecular weight can be increased due to the use of double bonds in the molecule, the cross-linking density can be increased. In addition, the degree of polymerization of this double bond can be adjusted by the crosslinking conditions (polymerization reaction conditions), and an optimum crosslinked film can be easily produced.
Furthermore, since the double bond of the stilbene structure in the molecule is originally low in polymerizability, it reacts in large numbers on the surface side where a large amount of radicals are generated during light irradiation, and forms a cured product with a smaller number of reactions as it enters the interior. There are features. A cured product having such a crosslink density gradient can be formed to a thickness of 2 to 15 μm. As a result, the surface layer is extremely hard and does not get scratched, etc., and the soft lower layer part is prevented from peeling off compared to the cured product, and the properties that make the cured product firmly adhere to the lower layer are compatible with each other. To obtain practical advantages. This makes it possible to form a strong coating layer with extremely high hardness without the coating layer being easily peeled off.
In this case, in particular, when a mixture of a trifunctional monomer and a 5-6 functional monomer is used as the radical polymerizable monomer, the double bond of the stilbene structure in the molecule is added to the curing reaction, thereby smoothing the surface. It is possible to form a cured product that combines the properties, the high surface hardness, and the better wear resistance of the entire cured product.
Such cross-linking participation in radical polymerization is a unique feature of the (meth) acrylate compound or vinyl compound represented by the structural formula (1) used in the present invention. This does not occur in the α-phenylstilbene type structure.

  From the above, it is possible to form a film having a very high crosslink density while maintaining good electrical characteristics and without causing cracks and the like, thereby satisfying various characteristics of the photoreceptor and silica. It is possible to prevent fine particles and the like from sticking to the photoreceptor, and to reduce white spot image defects.

  In this case, the gel fraction of the cured product is preferably 95% or more, and more preferably 97% or more. As a result, it is possible to provide a long-life photoconductor with further improved wear resistance and few image defects. In addition, as the radical polymerizable monomer, those having three or more radical polymerizable groups in the molecule effectively contribute to the expression of wear resistance and scratch resistance, but in order to further improve the characteristics, It is conceivable to use a polyfunctional monomer having 5 to 6 or more radically polymerizable groups. However, the combination of the compound responsible for the charge transporting property and the monomer causes deformation of the film during curing, resulting in a cured coating with poor surface smoothness in many cases. The deformation of the film becomes a streak-like undulation or a dimple-like unevenness, and causes a height difference of several μm. Even if the photoreceptor having such a surface is excellent in abrasion resistance or the like, streak-like cleaning defects are likely to occur due to the blade cleaning property of the toner, which is a practical problem. In the case of the compound having charge transport ability represented by the structural formula (1) used in the present invention, surface smoothness is obtained by using a mixture of a trifunctional monomer and a 5-6 functional monomer as a radical polymerizable monomer. Thus, it is possible to provide a photoconductor that is extremely resistant to abrasion and scratching.

  Therefore, it is possible to provide an image forming method, an image forming apparatus, and a process cartridge that achieve high image quality over a long period of time by using the electrophotographic photosensitive member of the present invention having the above-described configuration.

  According to the present invention, conventional problems can be solved, abrasion resistance during repeated use is extremely high, and high image quality with few image defects can be maintained over a long period of time. It is possible to provide an electrophotographic photosensitive member that is less likely to occur, has high surface smoothness in the initial stage and over time, and is highly durable, and an image forming method, an image forming apparatus, and a process cartridge using the electrophotographic photosensitive member.

(Electrophotographic photoreceptor)
The electrophotographic photosensitive member of the present invention is obtained by radical polymerization of at least a radical polymerizable monomer having three or more radical polymerizable groups in a molecule and a (meth) acrylic acid ester compound or vinyl compound having a specific structure. It has a layer containing a cured product, and further has other layers as necessary.

<Layer containing cured product>
The layer containing the cured product contains at least a radical polymerizable monomer having three or more radical polymerizable groups in the molecule, a compound represented by the following structural formula (1), and preferably a photopolymerization initiator. It contains a cured product obtained by radical polymerization, and further contains other components as necessary.

_{B 1 -Ar 1 -CH = CH-} Ar 2 -B 2 ··· structural formula (1)
However, in the structural formula (1), Ar ₁ is a monovalent group composed of an aromatic hydrocarbon skeleton which may have a substituent and an aromatic hydrocarbon skeleton which may have a substituent. Any one of the following divalent groups. Ar ₂ represents a monovalent group composed of an aromatic hydrocarbon skeleton having at least one tertiary amino group, a divalent group composed of an aromatic hydrocarbon skeleton having at least one tertiary amino group, and at least one 3 It represents either a monovalent group consisting of a heterocyclic compound skeleton having a secondary amino group or a divalent group consisting of a heterocyclic compound skeleton having at least one tertiary amino group. One of B ₁ and B ₂ may be a hydrogen atom, and the other may have an acryloyloxy group, a methacryloyloxy group, a vinyl group, an alkyl group that may have a substituent, and a substituent. It represents any one group selected from good alkoxy groups.

Ar ₁ in the structural formula (1) represents a monovalent group or a divalent group composed of a substituted or unsubstituted aromatic hydrocarbon skeleton. Examples of the monovalent group or divalent group comprising the aromatic hydrocarbon skeleton include benzene, naphthalene, phenanthrene, biphenyl, 1,2,3,4-tetrahydronaphthalene and the like.
Examples of the substituent of the aromatic hydrocarbon skeleton include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a benzyl group, and a halogen atom. These alkyl groups or alkoxy groups may further have a halogen atom or a phenyl group as a substituent.
The alkyl group is preferably one having 1 to 12 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, 2-ethylhexyl group, heptyl group, An octyl group, a nonyl group, etc. are mentioned.
As said alkoxy group, a C1-C12 thing is preferable, For example, a methoxy group, an ethoxy group, an isopropoxy group, 2-ethylhexyloxy group etc. are mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Ar ₂ in the structural formula (1) is a monovalent or divalent group composed of an aromatic hydrocarbon skeleton having at least one tertiary amino group, or a heterocyclic compound skeleton having at least one tertiary amino group. Represents a monovalent group or a divalent group. Here, the aromatic hydrocarbon skeleton having a tertiary amino group is preferably represented by the following structural formula (10).

Ar ₁₀ in the structural formula (10) represents a substituted or unsubstituted aryl group.
R ₁₀ and R ₁₁ in the structural formula (10) represent an acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkenyl group. h represents an integer of 1 to 3.
Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.
The alkyl group of R ₁₀ and R ₁₁ is the same as Ar _{1 in the} structural formula (1).
Examples of the aryl group of R ₁₀ and R ₁₁ include a phenyl group, a naphthyl group, a biphenylyl group, a terphenylyl group, a pyrenyl group, a fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, and a triphenylenyl group. And a group represented by the following structural formula (11) in addition to the chrycenyl group.

However, in the structural formula (11), B represents —O—, —S—, —SO—, —SO ₂ —, —CO—, a group represented by the following structural formula (12), and the following structural formula. It represents one of the groups represented by (13).
R ²² in the structural formula (13) represents a hydrogen atom, a substituted or unsubstituted alkyl group defined by Ar ₁ in the structural formula (1), or a substituted or unsubstituted aryl group defined by R _10. I represents an integer of 1 to 12, and j represents an integer of 1 to 3.

R ²¹ in the structural formula (11) represents a hydrogen atom, defined substituted or unsubstituted alkyl group in Ar ₁ of the structural formula (1), an alkoxy group, a halogen atom, a substituted or previously defined R ₁₀ An unsubstituted aryl group, an amino group, a nitro group, or a cyano group is represented.
Examples of the alkoxy group of R ²¹ include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, 2-hydroxy Examples include ethoxy group, 2-cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
Examples of the halogen atom for R ²¹ in the structural formula (11) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the amino group R ²¹ in the structural formula (11) include a diphenylamino group, a ditolylamino group, a dibenzylamino group, and a 4-methylbenzyl group.

Examples of the aryl group of Ar ₁₀ in the structural formula (10) include a phenyl group, a naphthyl group, a biphenylyl group, a terphenylyl group, a pyrenyl group, a fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, and an anthryl group. Group, triphenylenyl group, chrysenyl group.
Ar ₁₀ , R ₁₀ , and R ₁₁ may have an alkyl group, an alkoxy group, or a halogen atom defined as Ar ₁ in the structural formula (1) as a substituent.

Examples of the heterocyclic compound skeleton having a tertiary amino group of Ar ₂ in the structural formula (1) include pyrrole, pyrazole, imidazole, triazole, dioxazole, indole, isoindole, indoline, benzimidazole, benzotriazole, Examples include heterocyclic compounds having an amine structure such as benzisoxazine, carbazole, and phenoxazine. These may have an alkyl group, an alkoxy group, or a halogen atom defined as Ar ₁ as a substituent.

As B ₁ and B _{2 in} the structural formula (1), one of them is a hydrogen atom and the other is an acryloyloxy group, a methacryloyloxy group, a vinyl group, an alkyl group which may have a substituent, And any one group selected from alkoxy groups which may have a substituent.
As the alkyl group and alkoxy group, the same groups as those in Ar ₁ of the structural formula (1) are used. As the substituent in the alkyl group and alkoxy group, an acryloyloxy group, a methacryloyloxy group, and a vinyl group are used. Can be mentioned.

Here, as a compound represented by the said Structural formula (1), the acrylic ester compound represented by following Structural formula (2) is mentioned suitably.
However, in said structural formula (2), R < ₁ > and R < ₂ > represents either the alkyl group which may have a substituent, the alkoxy group which may have a substituent, and a halogen atom. Ar ₃ and Ar ₄ may be the same as or different from each other, and may be an aryl group that may have a substituent, an arylene group that may have a substituent, and a substituent. It represents any of the benzyl groups that may have. B _{1 to} B ₄ are any one selected from an acryloyloxy group, a methacryloyloxy group, a vinyl group, an alkyl group that may have a substituent, and an alkoxy group that may have a substituent. Represents a group, and only one of B _{1 to} B ₄ is present. l represents an integer of 0 to 5, and m represents an integer of 0 to 4.

The same alkyl group, alkoxy group and halogen atom as R ₁ , R ₂ , Ar ₃ and Ar _{4 in} the structural formula (2) are the same as those in Ar ₁ .
The aryl group in the structural formula (2) is the same as the aryl group defined by R ₁₀ and R ₁₁ . An arylene group is a divalent group derived from the aryl group.
As the alkyl group and alkoxy group of B _{1 to} B ₄ in the structural formula (2), the same groups as in Ar ₁ of the structural formula (1) are used, and the substituents in the alkyl group and alkoxy group are the same. Includes an acryloyloxy group, a methacryloyloxy group, and a vinyl group.

Moreover, it is preferable that the compound represented by the said Structural formula (1) is an acrylate compound represented by following Structural formula (3).
However, in said structural formula (3), R < ₁ > -R < ₄ > represents either the alkyl group which may have a substituent, the alkoxy group which may have a substituent, and a halogen atom. B ₁ .about.B ₄ represents the same meaning as _B 1 .about.B ₄ of structure (2), of the _B 1 .about.B _4, only any one is present. l, n, and o represent an integer of 0 to 5, and m represents an integer of 0 to 4.
R _{1 to} R ₄ in the structural formula (3) are the same as R ₁ and R _{2 in} the structural formula (2).

The compound represented by the structural formula (1) is preferably a compound represented by the following structural formula (4).
However, in the structural formula (4), Ar ₁ and Ar ₂ may be the same as or different from each other, may have an alkylene group which may have a substituent, and have a substituent. Or an arylene group which may be substituted or a heterocyclic group which may have a divalent substitution. Ar ₅ , Ar ₆ , Ar ₇ , and Ar ₈ may be the same as or different from each other, and have a hydrogen atom, an alkyl group that may have a substituent, or a substituent. Represents an aralkyl group which may be substituted, an aryl group which may have a substituent, and a heterocyclic group which may have a substituent, and Ar ₅ and Ar ₆ may form a cyclic structure. Good. B ₁ , B ₅ , B ₆ , B ₇ , and B ₈ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and the B ₁ , B ₅ , B ₆ , B ₇ , and B ₈ Only one of them exists.

Examples of the alkylene group of Ar ₁ and Ar ₂ in the structural formula (4) include an ethylene group, a propylene group, a butylene group, an amylene group, and a hexylene group.
Examples of the heterocyclic group represented by Ar ₁ and Ar ₂ in the structural formula (4) include a 2-furyl group, a 2-thienyl group, a 5-methyl-2-thienyl group, a 2-pyridyl group, and 4-phenyl-2. -A pyridyl group etc. are mentioned.

The compound represented by the structural formula (1) is preferably a compound represented by the following structural formula (5).
However, in the structural formula (5), Ar ₅ , Ar ₆ , Ar ₇ , and Ar ₈ may be the same as or different from each other, and may have a hydrogen atom or a substituent. Any one of a good alkyl group, an aralkyl group which may have a substituent, an aryl group which may have a substituent, and a heterocyclic group which may have a substituent, and Ar ₅ and A ring structure may be formed with Ar ₆ . B ₁ , B ₂ , B ₅ , B ₆ , B ₇ , and B ₈ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and the B ₁ , B ₂ , B ₅ , B ₆ , Only one of B ₇ and B ₈ exists. R ₁ and R ₂ are any of an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, and a halogen atom. To express. The X ring and the Y ring represent a cyclic structure that may be present by bonding to an adjacent benzene ring. l represents an integer of 0 to 5, and m represents an integer of 0 to 4.
The X ring and the Y ring represent a cyclic structure which may be present by bonding to an adjacent benzene ring. For example, benzene, naphthalene, cyclopentene, cyclohexene, cycloheptene, 1,3-cyclohexadiene, thiophene, benzo [ b] Thiophene, furan, pyridine, pyrazine, pyrimidine, pyridazine, indole and the like.
As the alkyl group, alkoxy group, araryl group, aryl group, and halogen atom in the structural formula (5), those similar to the above structural formula (1) can be used.

The compound represented by the structural formula (1) is preferably a compound represented by the following structural formula (6).
However, in said structural formula (6), R < ₁ >, R < ₂ >, R < ₃ >, R < ₄ > and R < ₅ > are the alkyl group which may have a substituent, and the aralkyl group which may have a substituent. Represents an optionally substituted alkoxy group and a halogen atom. B ₁ , B ₂ , B ₅ , B ₆ , and B ₈ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and the B ₁ , B ₂ , B ₅ , B ₆ , and B ₈ Only one of them exists. The X ring and the Y ring represent a cyclic structure that may be present by bonding to an adjacent benzene ring. l, q, r, and s represent an integer of 0 to 5, and m represents an integer of 0 to 4.
As the X ring and the Y ring, those similar to the above structural formula (5) can be used.
As the alkyl group, alkoxy group, aralkyl group, and halogen atom in the structural formula (6), those similar to the structural formula (1) can be used.

Moreover, it is preferable that the compound represented by the said Structural formula (1) is a compound represented by following Structural formula (7).
However, in the structural formula (7), Ar ₁ and Ar ₉ may be the same as or different from each other, and have an alkylene group or a substituent that may have a substituent. It represents either an arylene group which may be substituted or a heterocyclic group which may have a divalent substituent. R ₂ represents any of an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, and a halogen atom. R ₆ and R ₇ may be the same or different from each other, and may be a hydrogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or a substituent. Represents an alkoxy group which may have a group, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, and a halogen atom; and R ₆ and R ₇ may combine to form a Z ring. m represents an integer of 0 to 3, and t represents an integer of 0 to 2. B ₁ , B ₂ , and B ₉ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and only one of B ₁ , B ₂ , and B ₉ exists.

The compound represented by the structural formula (1) is preferably a compound represented by the following structural formula (8).
However, in the structural formula (8), Ar ₉ may have an alkylene group which may have a substituent, an arylene group which may have a substituent, and a divalent substituent. Represents any good heterocyclic group. R ₁ and R ₂ are any of an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, and a halogen atom. To express. R ₆ and R ₇ may be the same or different from each other, and may be a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituted group. Represents an alkoxy group which may have a group, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, and a halogen atom, and R ₆ and R _7. To form a Z ring. l represents an integer of 0 to 5, and m represents an integer of 0 to 3. B ₁ , B ₂ , and B ₉ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and only one of B ₁ , B ₂ , and B ₉ exists.

The compound represented by the structural formula (1) is preferably a compound represented by the following structural formula (9).
However, in said structural formula (9), R < ₁ >, R < ₂ >, and R < ₈ > have the alkyl group which may have a substituent, the aralkyl group which may have a substituent, and a substituent. It represents either an optionally substituted alkoxy group or a halogen atom. l and u represent an integer of 0 to 5, and m represents an integer of 0 to 3. B ₁ , B ₂ , and B ₉ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and only one of B ₁ , B ₂ , and B ₉ exists.
As the alkyl group, alkoxy group, aralkyl group, and halogen atom in the structural formula (9), those similar to the above structural formula (1) can be used.

  Specific examples of the compound represented by the structural formula (1) and the compounds represented by the structural formulas (2) to (9) are shown below, but are not limited thereto. Et represents an ethyl group.

  Here, the compounds represented by the structural formulas (1) to (9) can be easily synthesized, for example, by the following production method.

[Synthesis of diethyl 2-hydroxybenzylphosphonate]
In a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, 38.4 g of 2-hydroxybenzyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 80 ml of o-xylene were placed, and triethyl phosphite ( 62.8 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added dropwise at 80 ° C., and the reaction was further carried out at the same temperature for 1 hour. Thereafter, the produced ethanol, the solvent o-xylene, and unreacted triethyl phosphite were removed by distillation under reduced pressure to obtain 66 g of diethyl 2-hydroxybenzylphosphonate (yield 90%). The boiling point of the obtained compound was 120.0 ° C./1.5 mmHg.

[Synthesis of 2-hydroxy-4 ′-(di-para-tolylamino) stilbene]
In a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, 14.8 g of potassium tert-butoxide and 50 ml of tetrahydrofuran were placed, and 9.90 g of diethyl 2-hydroxybenzylphosphonate and 4- ( A solution of 5.44 g of (di-para-tolylamino) benzaldehyde dissolved in tetrahydrofuran was slowly added dropwise at room temperature, and then reacted at the same temperature for 2 hours. Thereafter, water was added under water cooling, and 2N hydrochloric acid aqueous solution was added for acidification. Tetrahydrofuran was removed by an evaporator, and the crude product was extracted with toluene. The toluene phase was washed with water, an aqueous sodium hydrogen carbonate solution and saturated brine in this order, and dehydrated by adding magnesium sulfate. After filtration, toluene was removed to obtain an oily crude product. Subsequently, after column purification with silica gel, crystallization was performed in hexane to obtain 5.09 g of 2-hydroxy-4 ′-(di-para-tolylamino) stilbene (yield 72%, melting point 136.0). ˜138.0 ° C.).

[Synthesis of 4 ′-(di-para-tolylamino) stilben-2-yl acrylate]
In a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, 14.9 g of 2-hydroxy-4 ′-(di-para-tolylamino) stilbene, 100 ml of tetrahydrofuran, and a 12% strength by weight aqueous sodium hydroxide solution 21 Then, 5.17 g of acrylic acid chloride was added dropwise at 5 ° C. over 30 minutes under a nitrogen stream. Then, it was made to react at the same temperature for 3 hours. The reaction solution was poured into water, extracted with toluene, concentrated and subjected to column purification with silica gel. The obtained crude product was recrystallized with ethanol to obtain 13.5 g of yellow needle-like crystal 4 ′-(di-para-tolylamino) stilben-2-yl acrylate (Exemplary Compound No. 2). Rate 79.8%, melting point 104.1-105.2 ° C.). The results of elemental analysis are shown in Table 1 below.

As described above, by reacting a 2-hydroxybenzylphosphonic acid ester derivative with various amino-substituted benzaldehyde derivatives, a number of 2-hydroxystilbene derivatives are synthesized and subjected to acrylation or methacrylation. Acrylic ester compounds can be synthesized.

[Synthesis of diethyl 4-methoxybenzylphosphonate]
4-Methoxybenzyl chloride and triethyl phosphite were reacted at 150 ° C. for 5 hours. Thereafter, excess triethyl phosphite and by-product ethyl chloride were removed by distillation under reduced pressure to synthesize diethyl 4-methoxybenzylphosphonate.

[Synthesis of 4-methoxy-4 ′-(di-para-tolylamino) stilbene]
Equimolar diethyl 4-methoxybenzylphosphonate and 4- (di-para-tolylamino) benzaldehyde were dissolved in N, N-dimethylformamide, and tert-butoxypotassium was added little by little while stirring under water cooling. After stirring at room temperature for 5 hours, water was added to make the mixture acidic and a crude product of the desired product was obtained. Subsequently, 4-methoxy-4 ′-(di-para-tolylamino) stilbene, which is the target product, was synthesized by purification by silica gel column chromatography.

[Synthesis of 4-hydroxy-4 ′-(di-para-tolylamino) stilbene]
4-Methoxy-4 ′-(di-para-tolylamino) stilbene and 2 equivalents of sodium ethanethiolate were dissolved in N, N-dimethylformamide and reacted at 130 ° C. for 5 hours. Then, it was cooled and opened in water, neutralized with hydrochloric acid, and the target product was extracted with ethyl acetate. The extract was washed with water, dried and evaporated to give a crude product. Subsequently, 4-hydroxy-4 '-(di-para-tolylamino) stilbene, which was the target product, was synthesized by purification by silica gel column chromatography.

[Synthesis of 4 ′-(di-para-tolylamino) stilben-4-yl acrylate]
Next, 4 ′-(di-para-tolylamino) stilben-4-yl acrylate, which was the target product, was synthesized in the same manner as in the acrylation of the 2-hydroxystilbene derivative.
As described above, a number of 4-hydroxystilbene derivatives are synthesized by reacting 4-hydroxybenzylphosphonic acid ester derivatives with various amino-substituted benzaldehyde derivatives, and demethylated and acrylated or methacrylated. A variety of acrylic ester compounds can be synthesized.

[Synthesis of diethyl 3-methoxybenzylphosphonate]
Except for using 3-methoxybenzyl chloride, diethyl 3-methoxybenzylphosphonate was synthesized in the same manner as in the phosphonation of diethyl 4-methoxybenzylphosphonate.

(Preparation of 3-methoxy-4 ′-(di-para-tolylamino) stilbene)
3-Methoxy-benzoate in the same manner as the stilbeneization of 4-methoxy-4 ′-(di-para-tolylamino) stilbene except that diethyl 3-methoxybenzylphosphonate and 4- (di-para-tolylamino) benzaldehyde are used. 4 '-(Di-para-tolylamino) stilbene was obtained.

[Synthesis of 3-hydroxy-4 ′-(di-para-tolylamino) stilbene]
3-hydroxy-4 'in the same manner as the demethylation of 4-hydroxy-4'-(di-para-tolylamino) stilbene except that 3-methoxy-4 '-(di-para-tolylamino) stilbene is used. -(Di-para-tolylamino) stilbene was synthesized.

[Synthesis of 4 ′-(di-para-tolylamino) stilben-3-yl acrylate]
The target 4 ′-(di-para-tolylamino) stilben-3-yl acrylate was synthesized in the same manner as the acrylation of the 2-hydroxystilbene derivative.
As described above, a number of 3-hydroxystilbene derivatives are synthesized by reacting 3-hydroxybenzylphosphonic acid ester derivatives with various amino-substituted benzaldehyde derivatives, and demethylated and acrylated or methacrylated. A variety of acrylic ester compounds can be synthesized.

[Synthesis of 4- [phenyl (4-styrylphenyl) amino] benzaldehyde]
4.63 parts by mass of N, N-dimethylformamide was placed in a toluene solvent, and 8.83 parts by mass of phosphorus oxychloride was slowly added dropwise under ice cooling to prepare a Vilsmeier reagent. Thereto was added dropwise a toluene solution of 10 parts by mass of 4-N, N-diphenylaminostilbene and allowed to react at 80 ° C. for 4 hours. After cooling, 18 parts by mass of ethyl acetate was added and stirred, and then neutralized by opening in water, and the target product was extracted with ethyl acetate. Then, it refine | purified by the column chromatography by a silica gel, and 5 mass parts of 4- [phenyl (4-styrylphenyl) amino] benzaldehyde which is a target object was synthesize | combined.

[Synthesis of 4- [phenyl (4-styrylphenyl) amino] benzyl alcohol]
Under ice-cooling, 5.4 parts by mass of lithium aluminum hydride was added to a tetrahydrofuran solvent, and a tetrahydrofuran solution of 50 parts by mass of 4- [phenyl (4-styrylphenyl) amino] benzaldehyde was slowly added dropwise and reacted at room temperature for 2 hours. It was. Thereafter, water and an aqueous alkaline solution were added, followed by filtration and evaporation of the solvent to obtain a crude product. Furthermore, it recrystallized with the hexane-ethyl acetate mixed solvent, and 45.2 mass parts of 4- [phenyl (4-styrylphenyl) amino] benzyl alcohol which is a target object was obtained. The melting point was 107-109.5 ° C.

[Synthesis of 4- [phenyl (4-styrylphenyl) amino] benzyl acrylate]
To a tetrahydrofuran solution of 20 parts by mass of 4- [phenyl (4-styrylphenyl) amino] benzyl alcohol, 8 parts by mass of triethylamine is added, and 6.7 parts by mass of a tetrahydrofuran solution of acrylic acid chloride is added dropwise under water cooling, and the mixture is stirred at room temperature for 3 hours. Reacted. Then, after adding toluene and washing with water, the solvent was distilled off to obtain a crude product. Subsequently, the residue was purified by column chromatography using silica gel to obtain 22 parts by mass of 4- [phenyl (4-styrylphenyl) amino] benzyl acrylate which is the target product.
As described above, various acrylate compounds can be synthesized by formylating various aminostilbene compounds, reducing and alcoholating them, and finally performing acrylation or methacrylation.

[Synthesis of N- (1,1-diphenylethenyl-2-yl) -N- (4′-hydroxy-4-styrylphenyl) aniline]
N- (1,1-diphenylethenyl-2-yl) -N- (4′-methoxy-4-styrylphenyl) aniline 3.0 parts by mass and sodium ethanethiolate 2.6 parts by mass It was dissolved in 60 ml of dimethylformamide and reacted at 135 ° C. for 5 hours. Then, it was cooled and opened in water, neutralized with hydrochloric acid, and the target product was extracted with ethyl acetate. The extract was washed with water, dried and evaporated to give a crude product. Subsequently, purification was performed by column chromatography using silica gel to synthesize N- (1,1-diphenylethenyl-2-yl) -N- (4′-hydroxy-4-styrylphenyl) aniline which was the target product.

[Synthesis of N- (1,1-diphenylethenyl-2-yl) -N- (4′-acryloyloxy-4-styrylphenyl) aniline (Exemplary Compound No. 23)]
To a tetrahydrofuran solution of 2.0 parts by mass of N- (1,1-diphenylethenyl-2-yl) -N- (4′-hydroxy-4-styrylphenyl) aniline was added 0.7 part by mass of triethylamine, and room temperature. Then, a tetrahydrofuran solution of 0.6 g of acrylic acid chloride was added dropwise and reacted at room temperature for 30 minutes. Then, after adding ethyl acetate and washing with water, the solvent was distilled off to obtain a crude product. Subsequently, the product is purified by column chromatography on silica gel, and the target product N- (1,1-diphenylethenyl-2-yl) -N- (4′-acryloxy-4-styrylphenyl) aniline is obtained as 1. Two parts by mass were synthesized (amorphous).

[Synthesis of 1,2,3,3a, 4,8b-hexahydro-4-phenyl-7- (4′-hydroxy) styrylcyclopent [b] indole]
1,3,3,3a, 4,8b-hexahydro-4-phenyl-7- (4′-methoxy) styrylcyclopent [b] indole (6.3 parts by mass) and sodium ethanethiolate (4.3 parts by mass) , N-dimethylformamide was dissolved in 100 ml and reacted at 135 ° C. for 9 hours. Then, it was cooled and opened in water, neutralized with hydrochloric acid, and the target product was extracted with ethyl acetate. The extract was washed with water, dried and evaporated to give crude crystals. Next, recrystallization from a mixed solvent of water / ethanol and 1,2,3,3a, 4,8b-hexahydro-4-phenyl-7- (4′-hydroxy) styrylcyclopent [b] indole which is the target product 3.2 parts by mass were synthesized.

[Synthesis of 1,2,3,3a, 4,8b-hexahydro-4-phenyl-7- (4′-acryloyloxy) styrylcyclopent [b] indole (the above exemplified compound No. 71))
1,2,3,3a, 4,8b-Hexahydro-4-phenyl-7- (4′-hydroxy) styrylcyclopent [b] indole In a tetrahydrofuran solution of 3.0 parts by mass, 1.3 parts by mass of triethylamine was added. In addition, a tetrahydrofuran solution of 1.5 g of acrylic acid chloride was added dropwise at room temperature and reacted at room temperature for 30 minutes. Then, after adding ethyl acetate and washing with water, the solvent was distilled off to obtain a crude product. Subsequently, the product is purified by column chromatography on silica gel to obtain the target 1,2,3,3a, 4,8b-hexahydro-4-phenyl-7- (4′-acryloxy) styrylcyclopent [b] indole. Of 3.1 parts by weight (yellow crystals, melting point 132.0-133.5 ° C.).

  The compound represented by the structural formula (1) is important for imparting charge transport performance to the cured product, and its content is preferably 20 to 80% by mass, and preferably 30 to 70% by mass with respect to the entire cured product. Is more preferable. When the content is less than 20% by mass, the charge transport performance 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. In some cases, the content of the radical polymerizable monomer having three or more radical polymerizable groups in the molecule is lowered, resulting in a decrease in the crosslink density, and the intended characteristics of the present invention may not be exhibited.

-Radical polymerizable monomer having 3 or more radical polymerizable groups in the molecule-
Examples of the radical polymerizable monomer having three or more radical polymerizable groups in the molecule include hole transporting structures such as triarylamine, hydrazone, pyrazoline, and carbazole, such as condensed polycyclic quinone, diphenoquinone, and cyano group. And a monomer having no electron transport structure (or a group showing an electron transport structure) such as an electron-withdrawing aromatic ring having a nitro group and having three or more radically polymerizable functional groups. The radical polymerizable functional group is not particularly limited as long as it has a carbon-carbon double bond and can be radically polymerized. Examples of these radical polymerizable functional groups include 1-substituted ethylene functional groups and 1,1-substituted ethylene functional groups shown below.

(1) As the 1-substituted ethylene functional group, for example, a functional group represented by the following structural formula (14) is preferably exemplified.
^{_{CH 2 = CH-X 1 -}} ··· structural formula (14)
However, in the structural formula (14), X ¹ represents an arylene group such as a phenylene group optionally having a substituent, an naphthylene group, an alkenylene group optionally having a substituent, a —CO— group, —COO— group, —CON (R ¹⁰ ) — group (where R ¹⁰ is 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, Represents an aryl group such as a naphthyl group) or an S-group.
Specific examples of these substituents include vinyl, styryl, 2-methyl-1,3-butadienyl, vinylcarbonyl, acryloyloxy, acryloylamide, and vinylthioether groups.

(2) As the 1,1-substituted ethylene functional group, for example, a functional group represented by the following structural formula (15) is preferably exemplified.
^{_{CH 2 = C (Y) -X}} 2 - ···· structural formula (15)
However, in the structural formula (15), Y represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, a phenyl group which may have a substituent, or naphthyl. An aryl group such as a group, an alkoxy group such as a halogen atom, a cyano group, a nitro group, a methoxy group or an ethoxy group, a —COOR ¹¹ group (where R ¹¹ is a hydrogen atom, a methyl group optionally having a substituent) , An alkyl group such as an ethyl group, an optionally substituted benzyl, an aralkyl group such as a phenethyl group, an optionally substituted phenyl group, an aryl group such as a naphthyl group, or CONR ¹² R ¹³ (wherein, R ¹² and R ¹³ are hydrogen atoms, which may have a substituent an alkyl group such as methyl group and ethyl group, which may have a substituent group benzyl group, naphthylmethyl group, there Aralkyl group, or a substituent a phenyl group which may have a phenetyl group, an aryl group such as a naphthyl group, may be the same or different from one another), also, X ² is the structural formula (14 ) Represents the same substituent, single bond, and alkylene group as X ^1. However, at least one of Y and X ² is an oxycarbonyl group, a cyano group, an alkenylene group, and 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.
In addition, examples of the substituent further substituted with the substituent for X and Y include an alkyl group such as a halogen atom, a nitro group, a cyano group, a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, Examples thereof include aryloxy groups such as phenoxy group, aryl groups such as phenyl group and naphthyl group, aralkyl groups such as benzyl group and phenethyl group.
Among these radical polymerizable functional groups, an acryloyloxy group and a methacryloyloxy group are particularly useful, and a compound having three or more acryloyloxy groups includes, for example, a compound having three or more hydroxyl groups in the molecule. It can be obtained by an ester reaction or a transesterification reaction using acrylic acid (salt), acrylic acid halide, and acrylic ester. 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.

  The radical polymerizable monomer having three or more radical polymerizable groups in the molecule is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trimethylolpropane triacrylate (TMPTA) and trimethylol. Propane trimethacrylate, trimethylolpropane alkylene-modified triacrylate, trimethylolpropane ethyleneoxy-modified (hereinafter referred to as EO modification) triacrylate, trimethylolpropylenepropyleneoxy-modified (hereinafter referred to as EO modification) triacrylate, trimethylolpropane caprolactone-modified triacrylate Acrylate, trimethylolpropane alkylene-modified trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glyce Triacrylate, glycerol epichlorohydrin modified (hereinafter 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 Ethoxytetraacrylate, phosphoric acid EO modified tri Acrylate, 2,2,5,5, - tetramethyl-hydroxymethyl cyclopentanone tetraacrylate, and the like, which may be used alone or in combination of two or more thereof.

As the radical polymerizable monomer having three or more radical polymerizable groups in the molecule, the ratio of the molecular weight to the number of functional groups in the monomer (molecular weight) in order to form a dense crosslink in the layer containing the cured product. / Number of functional groups) is preferably 250 or less. When the ratio exceeds 250, the layer containing the cured product is soft and wear resistance is somewhat lowered. Therefore, among the monomers exemplified above, among monomers having a modifying group such as EO, PO, and caprolactone, It is not preferable to use a compound having a long modifying group alone.
The content ratio of the radically polymerizable monomer having three or more radically polymerizable groups in the molecule differs depending on the electrical properties and abrasion resistance required by the process used, and cannot be generally specified. 20-80 mass% is preferable with respect to the whole thing, and 30-70 mass% is more preferable. Essentially, it depends on the proportion of the radically polymerizable monomer having three or more radically polymerizable groups in the molecule in the solid content of the coating liquid. When the monomer component is less than 20% by mass, the three-dimensional cross-linking density of the layer containing the cured product is small, and a drastic improvement in wear resistance is not achieved as compared with the case of using a conventional thermoplastic binder resin. On the other hand, if it exceeds 80% by mass, the content of the charge transporting compound is lowered, and the electrical characteristics are deteriorated. The range of 30 to 70% by mass is most preferable.

  The mixing mass ratio (A: B) of the radically polymerizable monomer (A) having three or more radically polymerizable groups in the molecule and the compound (B) represented by the structural formula (1) is: 9: 1 to 9: 1 are preferable, and 8: 2 to 2: 8 are more preferable. If the ratio of the radical polymerizable monomer (A) is too large, the charge transportability is lowered, causing a decrease in sensitivity and an increase in exposure potential. In particular, when the thickness of the layer containing the cured product is as thick as 3 μm or more. The function as a photoconductor may not be achieved, and if the proportion of the radical polymerizable monomer (A) is too small, a dramatic wear resistance may not be achieved due to a decrease in the crosslinking density.

-Photopolymerization initiator-
The photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acetophenone photopolymerization initiators, ketal photopolymerization initiators, benzoin ether photopolymerization initiators, and benzophenones. System photopolymerization initiator, thioxanthone photopolymerization initiator, and other photopolymerization initiators. These polymerization initiators may be used alone or in a combination of two or more.

Examples of the acetophenone photopolymerization initiator or ketal photopolymerization initiator include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 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, 2-methyl-2-morpholino (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, etc. Is mentioned.
Examples of the benzoin ether photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, and benzoin isopropyl ether.
Examples of the benzophenone photopolymerization initiator include benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoylphenyl ether, acrylated benzophenone, 1,4- Examples include benzoylbenzene.
Examples of the thioxanthone photopolymerization initiator include 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and the like.
Examples of the other photopolymerization initiator include ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, and bis (2,4,6-trimethylbenzoyl). ) Phenylphosphine oxide, bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10-phenanthrene, acridine compound, triazine compound, imidazole compound, etc. Is mentioned.
In addition, the compound which has a photopolymerization promotion effect can also be used individually or in combination with the said photoinitiator. Examples thereof include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4,4′-dimethylaminobenzophenone, and the like.

  The content of the photopolymerization initiator is preferably 0.5 to 40 parts by mass, and 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of radical polymerizable monomers having three or more radical polymerizable groups in the molecule. More preferred.

  In addition to the radically polymerizable monomer having three or more radically polymerizable groups in the molecule, the compound represented by the structural formula (1), and the photopolymerization initiator, the layer containing the cured product may be coated. Monofunctional radical polymerizable monomer, bifunctional radical polymerizable monomer, functional monomer, and radical for the purpose of imparting functions such as viscosity adjustment at the time, stress relaxation of the cross-linked charge transport layer, low surface energy and friction coefficient reduction A polymerizable oligomer can be used in combination.

Examples of the monofunctional radical monomer include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, and cyclohexyl. Examples include acrylate, isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, and styrene monomer.
Examples of the bifunctional radically polymerizable monomer 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 a fluorine atom 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 polydimethyl Examples thereof include vinyl monomers having a polysiloxane group such as siloxane diethyl, acrylates and methacrylates.
Examples of the radical polymerizable oligomer include epoxy acrylate, urethane acrylate, and polyester acrylate oligomers.

  When a large amount of monofunctional and bifunctional radically polymerizable monomers and radically polymerizable oligomers are contained, the three-dimensional cross-linking density of the cured product is substantially reduced, leading to deterioration of properties. Therefore, the content of these monomers and oligomers is preferably 50 parts by mass or less and more preferably 30 parts by mass or less with respect to 100 parts by mass of the radical polymerizable monomer having three or more radical polymerizable groups in the molecule.

Next, a method for forming a layer containing the cured product will be described.
The layer containing the cured product contains a radical polymerizable monomer having three or more radical polymerizable groups in the molecule, a compound represented by the structural formula (1), and preferably a photopolymerization initiator. The coating liquid to be prepared is prepared, and the coating liquid is applied to the surface of the photoreceptor, and then light irradiation according to the absorption wavelength of the photopolymerization initiator is performed to polymerize.

When the polymerizable monomer is a liquid, the coating liquid can be applied by dissolving other components in the liquid, but if necessary, it is diluted with a solvent and applied.
Examples of the solvent 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 and propyl ether. Ethers, halogens such as dichloromethane, dichloroethane, trichloroethane and chlorobenzene, aromatics such as benzene, toluene and xylene, and cellosolves such as methyl cellosolve, ethyl cellosolve and cellosolve acetate. These solvents may be used alone or in combination of two or more. The dilution ratio with the solvent varies depending on the solubility of the composition, the coating method, and the desired thickness, and is arbitrary. The application can be performed by dip coating, spray coating, bead coating, ring coating, or the like.

  Further, the coating liquid may contain additives such as various plasticizers (for the purpose of stress relaxation and adhesion improvement), leveling agents, and low molecular charge transport materials having no radical reactivity as required. As these additives, known additives can be used, and as plasticizers, those used in general resins such as dibutyl phthalate and dioctyl phthalate can be used, and the amount used is the total solid content of the coating liquid. 20 mass% or less is preferable with respect to 10 mass% or less. Moreover, as leveling agents, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, polymers or oligomers having a perfluoroalkyl group in the side chain can be used, and the amount used is based on the total solid content of the coating liquid. The amount is preferably 3% by mass or less.

After application of the coating solution, a drying step is optionally performed and curing is performed by light irradiation.
For light irradiation, 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. Is possible. Irradiation light amount is 50 mW / cm ² or more, preferably 2000 mW / cm ² or less, it takes time for the curing reaction is less than 50 mW / cm ^2. If it is higher than 2000 mW / cm ^2, the progress of the reaction becomes non-uniform, and local flaws are generated on the surface of the cross-linked charge transport layer, and many unreacted residues and reaction termination ends are generated. In addition, internal stress increases due to rapid crosslinking, which causes cracks and film peeling.
Moreover, nitrogen substitution may be performed during light irradiation to prevent polymerization inhibition due to oxygen.
Further, the light irradiation may be performed continuously, or may be performed intermittently in a plurality of times.

  Electron beam irradiation can also be used as a similar means of light irradiation. However, those using light energy are preferred because of easy reaction rate control and simple apparatus. In the case of electron beam irradiation, it is not necessary to use a photopolymerization initiator.

The greater the amount of light irradiation, the higher the gel fraction of the cured product, and a more insoluble and infusible state. In order to achieve the object of the present invention, the gel fraction of the cured product is preferably 95% or more, and more preferably 97% or more.
Here, the gel fraction can be obtained from Equation 1 below by immersing the cured product in a highly soluble organic solvent such as tetrahydrofuran for 5 days and measuring the amount of mass loss.
<Formula 1>
Gel fraction (%) = 100 × (amount of cured substance after immersion drying / initial mass of cured product)

In order to form a cured product having a gel fraction of 95% or more, it is preferable to irradiate an integrated irradiation energy of 10 J / cm ² or more. It is particularly preferable to cure to a gel fraction of 97% or more. By increasing the gel fraction, it is possible to prevent further piercing of silica or the like. In this case, it is preferable to irradiate the integrated irradiation energy of 20 J / cm ² or more.

  As described above, the curing of the cured product used in the present invention requires an order of magnitude of irradiation energy as compared with a normal photo-curing resin. This is because cleavage of the photoinitiator is hindered because the (meth) acrylic acid ester compound or vinyl compound represented by the structural formula (1) has a large light absorption property. However, in the present invention, it is expected that the light absorption to the compound represented by the structural formula (1) is also related to the participation of the double bond in the stilbene structure, and the coating solution composition and the light irradiation Due to the combined influence of conditions, it is possible to provide a photoreceptor that has a very high crosslinking density and can prevent white spot-like image defects.

  After curing by light irradiation, annealing is performed at 80 to 150 ° C., and it is used as an electrophotographic photosensitive member. The annealing time is about 1 minute to 60 minutes.

The layer structure of the electrophotographic photoreceptor of the present invention is not particularly limited, but the layer containing the cured product is preferably the outermost layer. This is because the compound represented by the structural formula (1) is preferably formed on the surface of a negatively charged organic photoconductor because of the hole transport property.
As a typical configuration of the negatively charged organic photoconductor, at least a charge generation layer and a charge transport layer are sequentially laminated on a support, and the cured product can be contained in the charge transport layer. However, in this case, since the thickness of the charge transport layer is limited by curing conditions, it is preferable to have a photoreceptor structure in which a crosslinkable charge transport layer is further laminated on the charge transport layer. Most preferred is a layer containing a cured product.

  The thickness of the cross-linked charge transport layer as the layer containing the cured product is preferably 3 to 10 μm, and more preferably 3 to 7 μm. When the thickness exceeds 10 μm, cracks and film peeling are likely to occur, and radical polymerization initiation due to photocleavage of the photopolymerization initiator is less likely to occur in the deep part, making it difficult to form a film with a high crosslinking density. . On the other hand, when the thickness is less than 3 μm, the radical polymerization reaction is susceptible to oxygen inhibition, that is, the surface in contact with the atmosphere is not easily cross-linked due to the influence of radical trapping by oxygen, and becomes non-uniform and wear resistant. And uneven wear tends to occur. In addition, mixing of the lower layer charge transport layer component occurs during the application of the crosslinkable charge transport layer. Furthermore, if the coating thickness of the crosslinkable charge transport layer is thin, contaminants spread throughout the layer, resulting in inhibition of the curing reaction and a decrease in crosslink density. For these reasons, the cross-linked charge transport layer can form a high-density cross-linked body with a thickness of 3 μm or more, thereby preventing white spots. In addition, a decrease in thickness due to wear in repeated use tends to cause local chargeability and sensitivity fluctuations, and the thickness of the crosslinkable charge transport layer is preferably 3 μm or more from the viewpoint of extending the life.

  The electrophotographic photoreceptor has at least a charge generation layer, a charge transport layer, and a cross-linked charge transport layer in this order on a support, and further includes an intermediate layer and other layers as necessary. It becomes. The crosslinkable charge transport layer is a layer containing the cured product of the present invention.

  Here, FIG. 1 is a schematic sectional view showing an example of the layer structure of the electrophotographic photosensitive member of the present invention. This electrophotographic photoreceptor has a laminated structure in which a charge generation layer 2 having a charge generation function, a charge transport layer 3 having a charge transport function, and a cross-linked charge transport layer 4 are laminated in this order on a support 1. This is a photoreceptor.

-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 generating substance, 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, phosphorus atoms, or the like are preferably used.
The organic material is not particularly limited and can be appropriately selected from known materials according to the purpose. Examples thereof include phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azulenium salt pigments, methine squaric acid. 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 and naphthoquinone pigments, cyanine and azomethine pigments, indigoid pigments, and bisbenzimidazole pigments. These may be used individually by 1 type and may use 2 or more types together.

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 resins, polyvinyl ketone resins, polystyrene resins, poly-N-vinyl carbazole resins, polyacrylamide resins and the like can be mentioned. 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 polycarbonate, polyester, polyurethane, polyether, polysiloxane, or acrylic resin having a pyrazoline skeleton, 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 08-21640 A, JP 08-253568 A, JP 08-269183 A, JP 09-062019 A, JP 09-038883 A, JP 09-71642 A, JP 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 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. 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, and optionally 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 that has been 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, 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] 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. . 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.
Examples of the polymer (b) 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 Examples of 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 can 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 may 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 the charge generation layer 35.
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. A mass part is appropriate.
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 appropriate.
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.

-Support-
The support is not particularly limited as long as it has a volume resistance of 10 ¹⁰ Ω · cm or less, and can be appropriately selected according to the purpose. For example, aluminum, nickel, chromium, nichrome, copper Metals such as gold, silver and platinum; metal oxides such as tin oxide and indium oxide deposited or sputtered on a film or cylindrical plastic, paper, or aluminum, aluminum alloy, nickel, stainless steel, etc. And a tube subjected to surface treatment such as cutting, super-finishing, 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, those in which conductive powder is dispersed in an appropriate binder resin and coated on the support can also be used as the support of the present invention.
Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, or metal oxide powder such as conductive tin oxide and ITO. Etc. The binder resin used at the same time includes polystyrene resin, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate. Copolymer, polyvinyl acetate resin, polyvinylidene chloride resin, polyarylate resin, phenoxy resin, polycarbonate resin, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral resin, polyvinyl formal resin, polyvinyl toluene resin, poly-N-vinyl carbazole, Thermoplastic, thermosetting resin, or photocurable resin such as acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, alkyd resin, and the like can be given.
The conductive layer can be provided by dispersing and applying these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, toluene and the like.

  Furthermore, it is electrically conductive by a heat shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon (registered trademark) on a suitable cylindrical substrate. Those provided with a conductive layer can also be used favorably as the support of the present invention.

In the electrophotographic photoreceptor of the present invention, an intermediate is provided between the charge transport layer and the cross-linked charge transport layer for the purpose of suppressing mixing of charge transport layer components into the cross-linked charge transport layer or improving adhesion between the two layers. It is possible to provide a layer. For this reason, as the intermediate layer, those that are insoluble or hardly soluble in the crosslinking type charge transport layer coating solution are suitable, and generally a binder resin is used as a main component. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As the method for forming the intermediate layer, the coating method is employed.
The thickness of the intermediate layer is not particularly limited and can be appropriately selected according to the purpose, and is preferably 0.05 to 2 μm.

In the electrophotographic photoreceptor of the present invention, an undercoat layer can be provided between the support and the photosensitive layer. The undercoat layer generally comprises a resin as a main component. However, considering that the photosensitive layer is applied with a solvent thereon, these resins are resins having a high solvent resistance with respect to general organic solvents. Is desirable. 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, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. In order to prevent moire and reduce residual potential, the undercoat layer is added with a fine powder pigment of a metal oxide such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, or indium oxide. be able to.
For the undercoat layer, an anodized layer of Al ₂ O ₃ , an organic material such as polyparaxylylene (parylene), or an inorganic material such as SiO ₂ , SnO ₂ , TiO ₂ , ITO, or CeO ₂ is vacuumed. Those provided by the thin film manufacturing method can also be used favorably. In addition, known ones can be used.
The undercoat layer can be formed using an appropriate solvent and coating method as in the above-described 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.
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 electrophotographic photosensitive member of the present invention, in order to improve environmental resistance, in particular, for the purpose of preventing a decrease in sensitivity and an increase in residual potential, the cross-linked charge transport layer, the charge transport layer, the charge generation layer, An antioxidant may be added to each layer such as the undercoat layer and the intermediate layer.

  Examples of the antioxidant include phenolic compounds, paraphenylenediamines, hydroquinones, organic sulfur compounds, and organic phosphorus compounds. These may be used individually by 1 type and may use 2 or more types together.

  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-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy Benzyl) 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- 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. And 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. It is done.
Examples of the organic phosphorus compounds include triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine, and the like.

In addition, these compounds are known as antioxidants, such as rubber | gum, a plastic, and fats and oils, and a commercial item can be obtained easily.
There is no restriction | limiting in particular in the addition amount of the said antioxidant, According to the objective, it can select suitably, 0.01-10 mass% is preferable with respect to the total mass of the layer to add.

(Image forming method and image forming apparatus)
The image forming apparatus of the present invention comprises at least an electrophotographic photosensitive member, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and other components appropriately selected as necessary. Means, for example, cleaning means, static elimination 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 cleaning step, a charge removal step, and a recycling step. 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 electrophotographic photosensitive member.
The electrophotographic photosensitive member is not particularly limited with respect to the material, shape, structure, size, and the like, and can be appropriately selected from known ones. Preferred examples of the shape include a drum shape.
As the electrophotographic photosensitive member, the electrophotographic photosensitive member of the present invention can be used.

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

The charging can be performed, for example, by applying a voltage to the surface of the electrophotographic photosensitive member 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 roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the electrophotographic photosensitive member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can perform imagewise exposure on the surface of the electrophotographic photosensitive member charged by the charger, and can be appropriately selected according to the purpose. However, 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 are exemplified.
In the present invention, an optical backside system that performs imagewise exposure from the backside of the electrophotographic photosensitive member may be employed.
In addition, when the image forming apparatus is used as a copying machine or a printer, image exposure is performed by irradiating a photosensitive member with reflected light or transmitted light from a document, or by reading a document with a sensor and converting the laser into a signal. This is performed by irradiating light to the photosensitive member by scanning the beam, driving the LED array, or driving the liquid crystal shutter array.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using a toner or a developer to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using a toner or a developer, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using, for example, toner or developer, and can be appropriately selected from known ones. Preferable examples include at least a developing unit capable of applying toner or developer to the electrostatic latent image in contact or non-contact.
The toner is not particularly limited and may be appropriately selected depending on the intended purpose. However, a fine one is preferable, the volume average particle diameter of the toner is preferably 3 to 10 μm, and the average circularity of the toner is 0.90. ~ 0.99 is preferred.

  For the developing device, a dry development system is usually used. Further, it may be a single color developing device or a multicolor developing device, and has, for example, a stirrer for charging the toner or developer by frictional stirring and a rotatable magnet roller. And the like.

  In the developing device, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. Since the magnet roller is disposed in the vicinity of the electrophotographic photosensitive member, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted by the electrophotographic photosensitive member. Move to the surface. As a result, the electrostatic latent image is developed with toner to form a visible image with toner on the surface of the electrophotographic photosensitive member.

  The developer accommodated in the developing device is a developer containing toner, but the developer may be a one-component developer or a two-component developer. As the toner, a commonly used toner can be used.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, 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 transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the electrophotographic photosensitive member with the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means and the secondary transfer means) includes at least a transfer device that peels and charges the visible image formed on the electrophotographic photosensitive member toward the recording medium. preferable. 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.

-Fixing process and fixing means-
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 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.

-Cleaning process and cleaning means-
The cleaning step is a cleaning step of cleaning the electrophotographic photosensitive member using a cleaning unit.
Examples of the cleaning means include a cleaning blade, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrophotographic photosensitive member, 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 electrophotographic photosensitive member. For example, a neutralization lamp is preferably used. Can be mentioned.

The recycling step is a step of recycling the electrophotographic toner removed by 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, an aspect of the image forming apparatus of the present invention will be described with reference to FIG.
FIG. 2 is a schematic diagram for explaining the image forming apparatus of the present invention, and modifications as described later also belong to the category of the present invention.
The electrophotographic photosensitive member 201 includes a photosensitive layer including a charge generation layer, a charge transport layer, and a cross-linked charge transport layer in this order on a support. The photosensitive member 201 has a drum shape, but may be a sheet shape or an endless belt shape. In FIG. 2, reference numeral 204 denotes an eraser.
A charging charger 203 is used as charging means for charging the photosensitive member 201 on the average. As the charging charger, 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.
In the present invention, it is particularly 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. Here, the contact charging method is a charging method in which a charging roller, a charging brush, a charging blade, or the like directly contacts the photoconductor. 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 surface of the photoreceptor and the charging unit. If this gap is too large, the charging tends to become unstable, and if it is too small, the surface of the charging member may be contaminated when toner remaining on the photoreceptor exists. is there. Therefore, the gap is preferably 10 to 200 μm, more preferably 10 to 100 μm.

  Next, an image exposure unit 205 is used to form an electrostatic latent image on the uniformly charged photoconductor 201. As the light source, all luminescent materials such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an 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.

  Next, the developing unit 206 is used to visualize the electrostatic latent image formed on the photoconductor 201. 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 photoconductor 201 onto the recording medium 209. Further, a pre-transfer charger 207 may be used in order to perform transfer more satisfactorily. 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.

  Next, a separation charger 211 and a separation claw 212 are used as means for separating the recording medium 209 from the photoreceptor 201. 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.

  Next, a fur brush 214 and a cleaning blade 215 are used to clean the toner remaining on the photoconductor 201 after 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, a charge removal lamp 202 and a 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.

  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. An image forming apparatus 100 shown in FIG. 3 includes a photosensitive drum 10 as the electrophotographic photosensitive member (hereinafter also referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and the exposure unit. An exposure device 30, a developing device 40 as the developing device, an intermediate transfer member 50, a cleaning device 60 as the cleaning device having a cleaning blade, and a static elimination lamp 70 as the static elimination device.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Some of the three rollers 51 also function as transfer bias rollers that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is formed between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is arranged between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 3, for example, the charging roller 20 uniformly charges the photosensitive drum 10. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  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 image forming apparatus 100 shown in FIG. 4 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 3, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and the like around the photoconductor 10. Except for the fact that the cyan developing unit 45C is disposed directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 4, the same components as those in FIG. 3 are denoted by the same reference numerals.

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. 5 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. 5. 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. 6), 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 paper 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 includes at least the electrophotographic photosensitive member of the present invention and a developing unit that develops an electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a visible image. In addition, other means such as a charging means, a developing means, a transfer means, a cleaning means, and a static elimination means are provided as necessary.
The developing means includes at least a developer container that contains toner or developer, and a developer carrier that carries and transports the toner or developer contained in the developer container. Furthermore, a layer thickness regulating member for regulating the thickness of the toner layer to be carried may be provided.
The process cartridge of the present invention can be detachably provided in various image forming apparatuses, and is preferably detachably provided in the above-described image forming apparatus of the present invention.

Here, for example, as shown in FIG. 7, the process cartridge includes a photoreceptor 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and other units as necessary. It has. In FIG. 7, reference numeral 103 denotes exposure by exposure means, and 105 denotes a recording medium.
Next, the image forming process using the process cartridge shown in FIG. 7 will be described. The photosensitive member 101 is rotated on the surface by charging by the charging unit 102 and exposure 103 by the exposure unit (not shown) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the exposure 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 108 and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by the cleaning unit 107, further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

  As an image forming apparatus of the present invention, the electrophotographic photosensitive member and components such as a developing unit and a cleaning unit are integrally combined as a process cartridge, and this unit is configured to be detachable from the apparatus main body. May be. Further, at least one selected from a charger, an image exposure device, a developing device, a transfer separator, and a cleaning device is integrally supported together with the electrophotographic photosensitive member to form a process cartridge, and is detachably attached to the apparatus main body. One unit may be detachable using guide means such as a rail of the apparatus main body.

  An image forming method, an image forming apparatus, and a process cartridge according to the present invention include a laminated type photoreceptor having a cross-linked charge transport layer on the surface that has extremely high wear resistance and scratch resistance and is unlikely to cause cracks or film peeling. It 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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example. In addition, all "parts" used in an Example represent a mass part.

Example 1
-Production of electrophotographic photoreceptor-
On an aluminum cylinder having a diameter of 30 mm, an undercoat layer coating solution having the following composition, a charge generation layer coating solution having the following composition, and a charge transporting layer coating solution having the following composition are sequentially applied and dried. An undercoat layer of 3.5 μm, a charge generation layer having a thickness of 0.2 μm, and a charge transport layer having a thickness of 18 μm were formed.
On the obtained charge transport layer, a cross-linked charge transport layer coating solution having the following composition was spray-coated and naturally dried for 20 minutes, and then a metal halide lamp: 160 W / cm, irradiation distance: 110 mm, irradiation intensity: 750 mW / The coating film was cured by light irradiation under conditions of cm ² and irradiation time: 240 seconds. Subsequently, it dried at 130 degreeC for 20 minute (s), and provided the 5.0 micrometer-thick bridge | crosslinking type charge transport layer. Thus, the electrophotographic photosensitive member of Example 1 was produced.

[Composition of 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

[Composition of charge generation layer coating solution]
Polyvinyl butyral (XYHL, manufactured by UCC): 0.5 part Cyclohexanone: 200 parts Methyl ethyl ketone: 80 parts Bisazo pigment represented by the following structural formula (I): 2.4 Part
2- [2-Hydroxy-3- (2-chlorophenyl) carbamoyl-1-naphthylazo] -7- [2-hydroxy-3- (3-methylphenyl) carbamoyl-1-naphthylazo] fluoren-9-one

[Composition of charge transport layer coating solution]
Bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals Ltd.) ... 10 parts Tetrahydrofuran: 100 parts Tetrahydrofuran solution of 1% by weight silicone oil (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)・ ・ ・ 0.2 part ・ Low molecular charge transport material represented by structural formula (II) below: 7 parts
[4- (2,2-diphenylvinyl) phenyl] -di-para-tolylamine

[Composition of crosslinking type charge transport layer coating solution]
・ Trimethylolpropane triacrylate (KAYARAD TMPTA, Nippon Kayaku Co., Ltd., molecular weight: 296, functional group number: trifunctional, molecular weight / functional group number = 99)... 10 parts ・ Represented by the above structural formula (1) Compound (Exemplary Compound No. 12 represented by the following structural formula): 10 parts
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 1 part as a photopolymerization initiator Tetrahydrofuran ... 100 parts

(Example 2)
-Production of electrophotographic photoreceptor-
In Example 1, Exemplified Compound No. 12 is exemplified compound No. 1 represented by the following structural formula. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that it was replaced with 14.

(Example 3)
-Production of electrophotographic photoreceptor-
In Example 1, Exemplified Compound No. 12 is exemplified compound No. 1 represented by the following structural formula. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that it was replaced with 13.

Example 4
-Production of electrophotographic photoreceptor-
In Example 1, Exemplified Compound No. 12 is exemplified compound No. 1 represented by the following structural formula. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that it was replaced with 11.

(Example 5)
-Production of electrophotographic photoreceptor-
In Example 1, the electron irradiation conditions were changed to the metal halide lamp: 160 W / cm, the irradiation distance: 110 mm, the irradiation intensity: 750 mW / cm ² , and the irradiation time: 360 seconds. A photographic photoreceptor was prepared.

(Example 6)
-Production of electrophotographic photoreceptor-
In the same manner as in Example 1, except that the light irradiation conditions were changed to a metal halide lamp: 160 W / cm, irradiation distance: 120 mm, irradiation intensity: 500 mW / cm ² , and irradiation time: 60 seconds. A photographic photoreceptor was prepared.

(Example 7)
-Production of electrophotographic photoreceptor-
In the same manner as in Example 1, except that the light irradiation conditions were changed to a metal halide lamp: 160 W / cm, irradiation distance: 120 mm, irradiation intensity: 500 mW / cm ² , and irradiation time: 120 seconds. A photographic photoreceptor was prepared.

(Example 8)
-Production of electrophotographic photoreceptor-
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the thickness of the crosslinkable charge transport layer was changed to 1 μm.

Example 9
-Production of electrophotographic photoreceptor-
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the thickness of the cross-linked charge transport layer was 3 μm.

(Example 10)
-Production of electrophotographic photoreceptor-
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the thickness of the crosslinkable charge transport layer was changed to 7 μm.

(Example 11)
-Production of electrophotographic photoreceptor-
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the thickness of the crosslinkable charge transport layer was changed to 10 μm.

(Example 12)
-Production of electrophotographic photoreceptor-
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the thickness of the cross-linked charge transport layer was 12 μm.

(Comparative Example 1)
-Production of electrophotographic photoreceptor-
In Example 1, Exemplified Compound No. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 12 was replaced with a compound represented by the following structural formula.
Acrylic acid 2- [4- (di-para-tolylamino) phenyl] ethyl ester

(Comparative Example 2)
-Production of electrophotographic photoreceptor-
In Example 1, Exemplified Compound No. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 12 was replaced with a compound represented by the following structural formula.
2-methylacrylic acid 4- {2- [4- (di-para-tolylamino) phenyl] ethyl} phenyl ester

(Comparative Example 3)
-Production of electrophotographic photoreceptor-
In Example 1, Exemplified Compound No. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 12 was replaced with a compound represented by the following structural formula.
Acrylic acid 4 '-(di-para-tolylamino) biphenyl-4-yl ester

(Comparative Example 4)
-Production of electrophotographic photoreceptor-
In Example 1, Exemplified Compound No. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 12 was replaced with a compound represented by the following structural formula.
Acrylic acid 4- {2- [4- (di-para-tolylamino) phenyl] -1-phenylvinyl} phenyl ester

(Comparative Example 5)
-Production of electrophotographic photoreceptor-
In Example 1, Exemplified Compound No. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 12 was replaced with a compound represented by the following structural formula.
Acrylic acid 4-[(4-acryloyloxymethylphenyl) -para-tolylamino] benzyl ester

<Observation of surface state>
About each produced electrophotographic photoreceptor of Examples 1-12 and Comparative Examples 1-5, the external appearance was observed visually and the presence or absence of the crack and film | membrane peeling was judged. The results are shown in Table 2.

<Measurement of gel fraction of cross-linked charge transport layer>
Further, the gel fraction of the cross-linked charge transport layer of each electrophotographic photoreceptor was determined. The gel fraction was determined by applying a crosslinked charge transport layer coating solution directly onto an aluminum support in the same manner as in each Example and Comparative Example, and irradiating and drying the film under the same conditions in a tetrahydrofuran solution at 25 ° C. It was immersed for 5 days, and was calculated from the following formula 1 from the mass residual ratio of the gel. The results are shown in Table 2.
<Formula 1>
Gel fraction (%) = 100 × (amount of cured substance after immersion drying / initial mass of cured product)

<Paper test>
Next, among the electrophotographic photoreceptors of Examples 1 to 12 and Comparative Examples 1 to 5, except for the photoreceptor of Comparative Example 5 in which cracks occurred during the formation of the cross-linked charge transport layer, these photosensitive materials prepared in the same manner. And a toner containing a silica external additive (volume average particle diameter = 9.5 μm, average circularity = 0.91), a sheet passing test of 100,000 A4 sheets was performed as follows.
First, the photosensitive member was mounted on a process cartridge, and the initial dark portion potential was set to −700 V with a modified machine of an image forming apparatus (Imagio Neo 270 manufactured by Ricoh Co., Ltd.) using a 655 nm semiconductor laser as an image exposure light source. Then, the thickness of all layers after the initial and 50,000 copies were measured, and the amount of wear was calculated from the difference. Further, the image after copying 50,000 sheets was observed, and the number of white spots per unit area was counted from the solid image portion. The results are shown in Table 3.

From the results in Table 3, each of the electrophotographic photoreceptors of Examples 1 to 12 has excellent wear resistance among organic photoreceptors having excellent wear resistance, and can output an image with few defects. In particular, it is recognized that white spots caused by the sticking of silica hardly occur and that the image has sufficient image stability even when used for a long time.
In particular, a cured product having a gel fraction of 95% or more gives an excellent organic photoreceptor with almost no image defects. Further, the cured product of the present invention having a gel fraction of 97% or more gives an excellent organic photoreceptor having excellent abrasion resistance and almost no image defects. It can also be seen that when the thickness of the cross-linked charge transport layer is in the range of 3 to 10 μm, an excellent organic photoreceptor having excellent wear resistance and no image defects is obtained.

(Example 13)
-Production of electrophotographic photoreceptor-
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the crosslinkable charge transport layer coating solution in Example 1 was changed to a crosslinkable charge transport layer coating solution having the following composition.
[Composition of crosslinking type charge transport layer coating solution]
Trimethylolpropane triacrylate (KAYARA DTMPTA, Nippon Kayaku Co., Ltd., molecular weight: 296, functional group number: trifunctional, molecular weight / functional group number = 99) ... 7.5 parts Dipentaerythritol hexaacrylate (KAYARAD DPHA) Manufactured by Nippon Kayaku Co., Ltd., molecular weight: 552, number of functional groups: 5.5, molecular weight / number of functional groups = 100)... 2.5 parts Exemplified Compound No. 12) ... 10 parts
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals) ... 1 part as a photopolymerization initiator Tetrahydrofuran ... 120 parts

(Example 14)
-Production of electrophotographic photoreceptor-
In Example 13, Exemplified Compound No. An electrophotographic photosensitive member was produced in the same manner as in Example 13 except that Example 12 was changed to Exemplified Compound No. 14 represented by the following structural formula.

(Example 15)
-Production of electrophotographic photoreceptor-
In Example 13, Exemplified Compound No. An electrophotographic photosensitive member was produced in the same manner as in Example 13 except that Example 12 was changed to Exemplified Compound No. 23 represented by the following structural formula.

(Example 16)
-Production of electrophotographic photoreceptor-
In Example 13, Exemplified Compound No. An electrophotographic photosensitive member was produced in the same manner as in Example 13 except that Example 12 was changed to Exemplified Compound No. 66.

(Comparative Example 6)
-Production of electrophotographic photoreceptor-
In Example 13, Exemplified Compound No. An electrophotographic photosensitive member was produced in the same manner as in Example 13 except that 12 was replaced with a compound represented by the following structural formula.
Acrylic acid 4 '-(di-para-tolylamino) biphenyl-4-yl ester

<Observation of surface state>
Next, when the surfaces of the obtained electrophotographic photosensitive members of Examples 13 to 16 and Comparative Example 6 were observed with a 50 × microscope, in Examples 13 to 16, a smooth surface such as a mirror surface was obtained. It was. On the other hand, in Comparative Example 6, fine irregularities were observed on one surface of the photoreceptor surface. When the unevenness of the film was measured with a surface roughness meter, the surface average roughness was 0.2 μm in Examples 13 to 16, but 1.1 μm in Comparative Example 6.
The photosensitive layer of the photoreceptor obtained in Example 13 was peeled off, a thin-film oblique cut section was prepared by an ultramicrotome, and the stretched section was doubled with a stilbene structure in the direction of the section of the film using a microscopic Raman spectrum measuring apparatus. The amount of residual bond was measured. As a result, the residual amount is about 5% on the surface of the photoreceptor, and the residual amount gradually increases toward the inside. At the deepest part of the cured product (depth of 5 μm), the double bond residual amount of the stilbene structure is 50%. From this result, it can be seen that the cross-linking reaction of the double bond in the stilbene structure has an inclined distribution. Since the number of crosslinks on the surface side is large and decreases as it enters the inside, it is possible to form a characteristic cured coating layer having mechanical property distribution that is harder on the surface side and softer on the back side.

  Next, various characteristics of each of the electrophotographic photosensitive members of Examples 13 to 16 and Comparative Example 6 were evaluated in the same manner as in Examples 1 to 12 and Comparative Examples 1 to 5. The results are shown in Tables 4 and 5.

  From the results of Tables 4 and 5, each of the electrophotographic photoreceptors of Examples 13 to 16 uses a mixture of a trifunctional radical polymerizable monomer and a 5 to 6 functional radical polymerizable monomer, and is smooth. It is possible to provide a photoreceptor that can be surface-coated, has a high gel fraction, and is more excellent in wear resistance. In addition, it is possible to provide a photoconductor that maintains smoothness even after printing a large number of sheets, has few white spots, and is excellent in image stability.

<Measurement of surface hardness of photoreceptor>
The surface hardness of each of the electrophotographic photoreceptors of Examples 13 to 16 and Comparative Example 6 was measured under the following conditions using a micro hardness tester (Fisgerscope H-100). The results are shown in Table 6.
[Measurement conditions]: Vickers indenter, indentation load 9.8 mN

From the results of Table 6, each of the electrophotographic photoreceptors of Examples 13 to 16 has a harder surface property than that of Comparative Example 6. Therefore, it can be seen that it is possible to provide a photoconductor that is not easily scratched and has excellent long-term image stability.

  The electrophotographic photosensitive member of the present invention can be applied to general electrophotographic apparatuses such as copying machines, laser printers, LED printers, and liquid crystal shutter printers, and further displays, recordings, and light printings using electrophotographic technology. It can be widely applied to image forming apparatuses such as plate making and facsimile.

FIG. 1 is a schematic sectional view showing an example of the layer structure of the electrophotographic photosensitive member of the present invention. FIG. 2 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 3 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 4 is a schematic explanatory view showing another example of carrying out the image forming method of the present invention by the image forming apparatus of the present invention. FIG. 5 is a schematic explanatory view showing an example in which the image forming method of the present invention is implemented by the image forming apparatus (tandem color image forming apparatus) of the present invention. 6 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG. FIG. 7 is a schematic explanatory view showing an example of the process cartridge of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support body 2 Charge generation layer 3 Charge transport layer 4 Crosslinkable charge transport layer 10 Photoreceptor (photoreceptor 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 100 image forming device 101 photoconductor DESCRIPTION OF SYMBOLS 102 Charging means 103 Exposure means 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem type developer 130 Document table 142 Feed roller 143 Paper bank 144 Paper feeding cassette 145 Separating roller 146 Paper feeding path 147 Conveying roller 148 Paper feeding path 150 Image forming apparatus main body 200 Paper feeding table 201 Photoconductor 202 Discharge lamp 203 Charger charger 204 Eraser 205 Image exposure unit 206 Developing unit 207 Pre-transfer charger 208 Registration roller 209 Recording medium 210 Transfer charger 211 Separation charger 212 Separation claw 213 Charger before cleaning 214 Fur brush 215 Cleaning blade 300 Scanner 400 Automatic document feeder (ADF)

Claims (20)

It has a layer containing a cured product obtained by radical polymerization of at least a radical polymerizable monomer having three or more radical polymerizable groups in a molecule and a compound represented by the following structural formula (1). An electrophotographic photoreceptor.
_{B 1 -Ar 1 -CH = CH-} Ar 2 -B 2 ··· structural formula (1)
However, in the structural formula (1), Ar ₁ is a monovalent group composed of an aromatic hydrocarbon skeleton which may have a substituent and an aromatic hydrocarbon skeleton which may have a substituent. Any one of the following divalent groups. Ar ₂ represents a monovalent group composed of an aromatic hydrocarbon skeleton having at least one tertiary amino group, a divalent group composed of an aromatic hydrocarbon skeleton having at least one tertiary amino group, and at least one 3 It represents either a monovalent group consisting of a heterocyclic compound skeleton having a secondary amino group or a divalent group consisting of a heterocyclic compound skeleton having at least one tertiary amino group. One of B ₁ and B ₂ may be a hydrogen atom, and the other may have an acryloyloxy group, a methacryloyloxy group, a vinyl group, an alkyl group that may have a substituent, and a substituent. It represents any one group selected from good alkoxy groups.   The cured product is obtained by radical polymerization of a radical polymerizable monomer having three or more radical polymerizable groups in the molecule, the compound represented by the structural formula (1), and a photopolymerization initiator. The electrophotographic photosensitive member described. The electrophotographic photosensitive member according to claim 1, wherein the compound represented by the structural formula (1) is an acrylate compound represented by the following structural formula (2).
However, in said structural formula (2), R < ₁ > and R < ₂ > represents either the alkyl group which may have a substituent, the alkoxy group which may have a substituent, and a halogen atom. Ar ₃ and Ar ₄ may be the same as or different from each other, and may be an aryl group that may have a substituent, an arylene group that may have a substituent, and a substituent. It represents any of the benzyl groups that may have. B _{1 to} B ₄ are any one selected from an acryloyloxy group, a methacryloyloxy group, a vinyl group, an alkyl group that may have a substituent, and an alkoxy group that may have a substituent. Represents a group, and only one of B _{1 to} B ₄ is present. l represents an integer of 0 to 5, and m represents an integer of 0 to 4. The electrophotographic photoreceptor according to claim 1, wherein the compound represented by the structural formula (1) is an acrylate compound represented by the following structural formula (3).
However, in said structural formula (3), R < ₁ > -R < ₄ > represents either the alkyl group which may have a substituent, the alkoxy group which may have a substituent, and a halogen atom. B ₁ .about.B ₄ represents the same meaning as _B 1 .about.B ₄ of structure (2), of the _B 1 .about.B _4, only any one is present. l, n, and o represent an integer of 0 to 5, and m represents an integer of 0 to 4. The electrophotographic photoreceptor according to claim 1, wherein the compound represented by the structural formula (1) is a compound represented by the following structural formula (4).
However, in the structural formula (4), Ar ₁ and Ar ₂ may be the same as or different from each other, may have an alkylene group which may have a substituent, and have a substituent. Or an arylene group which may be substituted or a heterocyclic group which may have a divalent substitution. Ar ₅ , Ar ₆ , Ar ₇ , and Ar ₈ may be the same as or different from each other, and have a hydrogen atom, an alkyl group that may have a substituent, or a substituent. Represents an aralkyl group which may be substituted, an aryl group which may have a substituent, and a heterocyclic group which may have a substituent, and Ar ₅ and Ar ₆ may form a cyclic structure. Good. B ₁ , B ₅ , B ₆ , B ₇ , and B ₈ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and the B ₁ , B ₅ , B ₆ , B ₇ , and B ₈ Only one of them exists. The electrophotographic photosensitive member according to claim 1, wherein the compound represented by the structural formula (1) is a compound represented by the following structural formula (5).
However, in the structural formula (5), Ar ₅ , Ar ₆ , Ar ₇ , and Ar ₈ may be the same as or different from each other, and may have a hydrogen atom or a substituent. Any one of a good alkyl group, an aralkyl group which may have a substituent, an aryl group which may have a substituent, and a heterocyclic group which may have a substituent, and Ar ₅ and A ring structure may be formed with Ar ₆ . B ₁ , B ₂ , B ₅ , B ₆ , B ₇ , and B ₈ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and the B ₁ , B ₂ , B ₅ , B ₆ , Only one of B ₇ and B ₈ exists. R ₁ and R ₂ are any of an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, and a halogen atom. To express. The X ring and the Y ring represent a cyclic structure that may be present by bonding to an adjacent benzene ring. l represents an integer of 0 to 5, and m represents an integer of 0 to 4. The electrophotographic photosensitive member according to claim 1, wherein the compound represented by the structural formula (1) is a compound represented by the following structural formula (6).
However, in said structural formula (6), R < ₁ >, R < ₂ >, R < ₃ >, R < ₄ > and R < ₅ > are the alkyl group which may have a substituent, and the aralkyl group which may have a substituent. Represents an optionally substituted alkoxy group and a halogen atom. B ₁ , B ₂ , B ₅ , B ₆ , and B ₈ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and the B ₁ , B ₂ , B ₅ , B ₆ , and B ₈ Only one of them exists. The X ring and the Y ring represent a cyclic structure that may be present by bonding to an adjacent benzene ring. l, q, r, and s represent an integer of 0 to 5, and m represents an integer of 0 to 4. The electrophotographic photosensitive member according to claim 1, wherein the compound represented by the structural formula (1) is a compound represented by the following structural formula (7).
However, in the structural formula (7), Ar ₁ and Ar ₉ may be the same as or different from each other, and have an alkylene group or a substituent that may have a substituent. It represents either an arylene group which may be substituted or a heterocyclic group which may have a divalent substituent. R ₂ represents any of an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, and a halogen atom. R ₆ and R ₇ may be the same or different from each other, and may be a hydrogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or a substituent. Represents an alkoxy group which may have a group, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, and a halogen atom; and R ₆ and R ₇ may combine to form a Z ring. m represents an integer of 0 to 3, and t represents an integer of 0 to 2. B ₁ , B ₂ , and B ₉ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and only one of B ₁ , B ₂ , and B ₉ exists. The electrophotographic photosensitive member according to claim 1, wherein the compound represented by the structural formula (1) is a compound represented by the following structural formula (8).
However, in the structural formula (8), Ar ₉ may have an alkylene group which may have a substituent, an arylene group which may have a substituent, and a divalent substituent. Represents any good heterocyclic group. R ₁ and R ₂ are any of an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, and a halogen atom. To express. R ₆ and R ₇ may be the same or different from each other, and may be a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituted group. Represents an alkoxy group which may have a group, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, and a halogen atom, and R ₆ and R _7. To form a Z ring. l represents an integer of 0 to 5, and m represents an integer of 0 to 3. B ₁ , B ₂ , and B ₉ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and only one of B ₁ , B ₂ , and B ₉ exists. The electrophotographic photosensitive member according to claim 1, wherein the compound represented by the structural formula (1) is a compound represented by the following structural formula (9).
However, in said structural formula (9), R < ₁ >, R < ₂ >, and R < ₈ > have the alkyl group which may have a substituent, the aralkyl group which may have a substituent, and a substituent. It represents either an optionally substituted alkoxy group or a halogen atom. l and u represent an integer of 0 to 5, and m represents an integer of 0 to 3. B ₁ , B ₂ , and B ₉ represent the same meaning as B _{1 to} B _{4 in} the structural formula (2), and only one of B ₁ , B ₂ , and B ₉ exists.   The electrophotographic photosensitive member according to claim 1, wherein the cured product has a gel fraction of 95% or more.   The electrophotographic photosensitive member according to claim 1, wherein the cured product has a gel fraction of 97% or more.   A radical polymerizable monomer having three or more radical polymerizable groups in the molecule, a radical polymerizable monomer having three radical polymerizable groups in the molecule, and a radical polymerization having 5 to 6 radical polymerizable groups in the molecule. The electrophotographic photosensitive member according to claim 1, which is a mixture with a functional monomer.   The mixing mass ratio (A: B) between the radical polymerizable monomer (A) having three or more radical polymerizable groups in the molecule and the compound (B) represented by the structural formula (1) is 9: 1. The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is in a range of ˜1: 9.   The electrophotographic photosensitive member according to claim 1, wherein the layer containing the cured product is an outermost surface layer of the electrophotographic photosensitive member.   The support, and at least a charge generation layer, a charge transport layer, and a cross-linked charge transport layer in this order are provided on the support, and the cross-linkable charge transport layer is an outermost surface layer. Electrophotographic photoreceptor.   The electrophotographic photosensitive member according to claim 16, wherein the cross-linked charge transport layer has a thickness of 3 to 10 μm. An electrophotographic photosensitive member; an electrostatic latent image forming unit that forms an electrostatic latent image on the electrophotographic photosensitive member; and a developing unit that develops the electrostatic latent image with toner to form a visible image. A transfer means for transferring the visible image to a recording medium; and a fixing means for fixing the transfer image transferred to the recording medium.
An image forming apparatus, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to claim 1. An electrostatic latent image forming step of forming an electrostatic latent image on the electrophotographic photosensitive member; a developing step of developing the electrostatic latent image with toner to form a visible image; and recording the visible image A transfer step of transferring to a medium, and a fixing step of fixing the transfer image transferred to the recording medium,
The image forming method according to claim 1, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to claim 1. 18. An electrophotographic photosensitive member according to claim 1, and at least developing means for developing an electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a visible image. A process cartridge which is detachable from the main body of the image forming apparatus.