JP2015045692A - Photoreceptor, image forming apparatus, and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoreceptor that has excellent durability, and can suppress an increase in the potential of an exposure part and the occurrence of density unevenness.SOLUTION: A photoreceptor 10A has a single-layer photoreceptor 2 and a protective layer 3 sequentially laminated on a conductive support 1, and the protective layer 3 is formed by curing a composition including a tri- or more functional radical polymerizable compound having no charge transport structure, a radical polymerizable compound having a charge transport structure, a compound having a specific structure with oxidation gas resistance, and a compound having a specific structure suppressing photodecomposition.

Description

  The present invention relates to a photoreceptor, an image forming apparatus, and a process cartridge.

  In an image forming method using an image forming apparatus, an image is formed by subjecting a photoconductor to steps such as a charging step, an exposure step, a development step, and a transfer step. In recent years, organic photoreceptors are widely used as photoreceptors.

  With the rapid progress of full color and high speed in an image forming apparatus, durability is demanded for an organic photoreceptor.

  In Patent Document 1, at least a charge generation layer, a hole transport layer, and a hole transport protective layer are sequentially laminated on a conductive support, and the protective layer irradiates at least a radical polymerizable hole transport compound with active energy rays. Discloses an electrophotographic photoreceptor comprising a three-dimensional crosslinked film obtained by chain polymerization. At this time, the protective layer contains an oxazole compound represented by the general formula (1) or the general formula (2).

  However, when it is left for a long time after repeated use, the resistance value of the surface of the photoconductor in the vicinity of the charger may decrease. In this case, when the apparatus is restarted, the charged potential and the potential after exposure are lowered, and the density unevenness of the image may occur. In addition, the potential of the exposed portion may increase.

  In view of the above-described problems of the related art, an object of one embodiment of the present invention is to provide a photoconductor that has excellent durability and can suppress an increase in potential of an exposed portion and occurrence of density unevenness.

  One embodiment of the present invention is a photosensitive member in which a photosensitive layer and a protective layer are sequentially laminated on a conductive support, and the protective layer has a trifunctional or higher functional radical polymerization property having no charge transporting structure. A compound, a radically polymerizable compound having a charge transporting structure, and a general formula

（式中、Ｒ_１及びＲ_２は、それぞれ独立に、置換基により置換されていてもよいアルキル基、置換基により置換されていてもよいアラルキル基、置換基により置換されていてもよい１価の脂肪族複素環基又は置換基により置換されていてもよい１価の芳香族基であり、Ｒ_１及びＲ_２は、互いに結合して環を形成してもよく、ｎは、１以上３以下の整数である。）
で表される化合物又は一般式

(In the formula, R ₁ and R ₂ are each independently an alkyl group optionally substituted by a substituent, an aralkyl group optionally substituted by a substituent, or a monovalent optionally substituted by a substituent. An aliphatic heterocyclic group or a monovalent aromatic group which may be substituted by a substituent, R ₁ and R ₂ may be bonded to each other to form a ring, and n is 1 or more and 3 The following integers.)
Or a compound represented by the general formula

（式中、Ｒ_１及びＲ_２は、それぞれ独立に、置換基により置換されていてもよいアルキル基、置換基により置換されていてもよいアラルキル基又は置換基により置換されていてもよい１価の芳香族基であり、Ｒ_１及びＲ_２は共同で環を形成してもよく、Ａｒは、置換基により置換されていてもよい２価の芳香族基であり、Ｘは、単結合又は炭素数が１以上４以下のアルキレン基である。）
で表される化合物と、一般式

(In the formula, R ₁ and R ₂ are each independently an alkyl group optionally substituted by a substituent, an aralkyl group optionally substituted by a substituent, or a monovalent optionally substituted by a substituent. R ₁ and R ₂ may form a ring together, Ar is a divalent aromatic group optionally substituted by a substituent, and X is a single bond or (It is an alkylene group having 1 to 4 carbon atoms.)
And a compound represented by the general formula

（式中、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子又は炭素数が１以上４以下のアルキル基であり、Ｙは、ビニレン基、炭素数が６以上１４以下のアリーレン基又は２，５−チオフェンジイル基である。）
で表される化合物又は一般式

(Wherein R ₃ and R ₄ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y is a vinylene group, an arylene group having 6 to 14 carbon atoms, or 2, 5-thiophenediyl group.)
Or a compound represented by the general formula

（式中、Ａｒ_１及びＡｒ_２は、それぞれ独立に、炭素数が６以上１４以下のアリール基であり、Ｙは、炭素数が６以上１４以下のアリーレン基であり、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子又はメチル基である。）
で表される化合物を含む組成物を硬化して形成されている。

(In the formula, Ar ₁ and Ar ₂ are each independently an aryl group having 6 to 14 carbon atoms, Y is an arylene group having 6 to 14 carbon atoms, and R ₃ and R ₄ are And each independently a hydrogen atom or a methyl group.)
It is formed by curing a composition containing a compound represented by:

  According to one embodiment of the present invention, it is possible to provide a photoconductor that is excellent in durability and can suppress an increase in potential of an exposed portion and occurrence of density unevenness.

It is sectional drawing which shows an example of a photoreceptor. It is sectional drawing which shows the other example of a photoreceptor. 1 is a schematic diagram illustrating an example of an image forming apparatus. It is the schematic which shows the other example of an image forming apparatus. It is the schematic which shows an example of a process cartridge. It is an LC-MS spectrum of a compound (1-33). It is an infrared absorption spectrum of a compound (1-33). It is a ¹ H-NMR spectrum of the compound (1-33). It is an LC-MS spectrum of a compound (1-36). It is an infrared absorption spectrum of a compound (1-36). It is a ¹ H-NMR spectrum of the compound (1-36). It is an LC-MS spectrum of a compound (1-52). It is an infrared absorption spectrum of a compound (1-52). It is a ¹ H-NMR spectrum of the compound (1-52). It is a MS spectrum of a compound (2-2). It is an infrared absorption spectrum of a compound (2-2). It is a MS spectrum of a compound (2-3). It is an infrared absorption spectrum of a compound (2-3). It is a MS spectrum of a compound (2-6). It is an infrared absorption spectrum of a compound (2-6). 2 is an X-ray diffraction spectrum of Y-type titanyl phthalocyanine.

  Next, the form for implementing this invention is demonstrated.

  In the photoreceptor, a photosensitive layer and a protective layer are sequentially laminated on a conductive support, and other layers are further formed as necessary.

  The protective layer includes a trifunctional or higher functional radical polymerizable compound having no charge transport structure, a radical polymerizable compound having a charge transport structure, and a compound represented by the general formula (1) or the general formula (2). And a composition containing a compound represented by general formula (3) or a compound represented by general formula (4).

  When a high-quality image required for commercial printing is formed, the photoreceptor is required to have potential stability between printed sheets so that the exposure potential is constant over time. For this purpose, it is important to suppress the film thickness and homogeneity of the protective layer and the generation of charge traps in the protective layer in the photoreceptor.

  In general, the protective layer is formed by radical polymerization by irradiating a composition containing a tri- or higher functional radical polymerizable compound having no charge transport structure and a radical polymerizable compound having a charge transport structure with active energy rays. Let it be formed. At this time, irradiation with active energy rays generates a photodegradation product of a radical polymerizable compound having a charge transporting structure, and this product becomes a charge trap, thereby repeatedly increasing the potential of the exposed portion over time. I think that.

  On the other hand, the compound represented by the general formula (3) or the compound represented by the general formula (4) is used to suppress the photodecomposition of the radical polymerizable compound having a charge transporting structure, thereby protecting the compound. It is considered that the generation of charge traps in the layer can be suppressed, and the increase in potential of the exposed portion over time can be suppressed (see Patent Document 1).

  The mechanism by which the compound represented by the general formula (3) or the compound represented by the general formula (4) suppresses the photodegradation of a radical polymerizable compound having a charge transporting structure is unknown, but is excited by active energy rays. The radically polymerizable compound in a state and the compound represented by the general formula (3) or the compound represented by the general formula (4) form an intermolecular exciton aggregate (Exciplex), which is deactivated. By doing so, it is considered that the photodecomposition of the radical polymerizable compound is suppressed.

  By the way, it is known that the increase in the potential of the exposed portion gradually increases when the photosensitive member is used for a long time. This may be due to an increase in charge traps due to the decomposition product of the charge transport structure. As factors that cause the decomposition of the charge transporting structure, the oxidizing gas generated in the charging process and the light energy irradiated in the exposure process or the charge removal process can be considered.

  On the other hand, the compound represented by the general formula (1) or the compound represented by the general formula (2) exhibits an effect of suppressing decomposition by an oxidizing gas, and is represented by the general formula (3). Or it is thought that the compound represented by General formula (4) is exhibiting the effect which suppresses decomposition | disassembly by light energy.

The mechanism by which the compound represented by the general formula (1) or the compound represented by the general formula (2) suppresses the decomposition of the charge transporting structure by the oxidizing gas is unknown, but the general formula —NR ₁ R ₂
Since the group represented by is a basic group, the neutralization effect with respect to oxidizing gas is estimated. At this time, the oxidizing gas is considered to be a causative substance of concentration unevenness.

In addition, the anthryl group in the compound represented by the general formula (1) and the general formula -Ar-N = in the compound represented by the general formula (2)
Is known to be a functional group having excellent charge transporting ability (see Takahashi et al., Journal of Electrophotographic Society, Vol. 25, No. 3, p. 16, 1986). ) Or the compound represented by the general formula (2) is a compound having a high charge transporting ability.

  In addition, the mechanism by which the compound represented by the general formula (3) or the compound represented by the general formula (4) suppresses the decomposition of the charge transporting structure due to light energy is unknown. This is considered to be because the active state leading to the decomposition of the sex structure is deactivated.

[Compound represented by general formula (1)]
The compound represented by the general formula (1) can be synthesized by the method described in Maruzen Co., Ltd., 4th edition, Experimental Chemistry Course, Vol. 20, pages 284-286. That is, it can be synthesized by subjecting poly (chloromethyl) anthracene and secondary amine to a substitution reaction in a solvent in the presence of a base.

ポリ（クロロメチル）アントラセンとアミンを反応させる温度は、通常、０〜１５０℃程度であり、５０〜１３０℃程度であることが好ましい。

The temperature at which poly (chloromethyl) anthracene and amine are reacted is usually about 0 to 150 ° C, and preferably about 50 to 130 ° C.

  Although it does not specifically limit as a base, Sodium hydrogencarbonate, potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, cesium hydroxide, triethylamine, diazabicycloundecene, etc. are mentioned.

  Examples of the solvent include, but are not limited to, water, ethanol, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide and the like.

  In addition, the compound represented by the general formula (1) is a method described in AFAbdel-Magid et al., J. Org. Chem., Vol. 61, No. 11, 3849-3862 (1996). , ER Burkhardt et al., Tetrahedron. Lett., Vol. 49, No. 35, 5152-5155 (2008). That is, it can be synthesized by reacting anthracene polycarbaldehyde and a secondary amine in a solvent in the presence of a reducing agent.

アントラセンポリカルボアルデヒドとアミンを反応させる温度は、通常、−５０〜１００℃程度であり、室温〜５０℃程度であることが好ましい。

The temperature at which the anthracene polycarbaldehyde reacts with the amine is usually about −50 to 100 ° C. and preferably about room temperature to 50 ° C.

  The reducing agent is not particularly limited, but lithium aluminum hydride, lithium borohydride, sodium borohydride, sodium bis (2-methoxyethoxy) aluminum hydride, sodium cyanoborohydride, sodium triacetoxyborohydride, formic acid , Borane-tetrahydrofuran complex, borane-N, N-diethylaniline complex, methyl sulfide borane, 5-ethyl-2-methylpyridine borane and the like. Of these, sodium cyanoborohydride, sodium triacetoxyborohydride, and 5-ethyl-2-methylpyridine borane are preferable.

  Examples of the solvent include, but are not limited to, methanol, ethanol, isopropyl alcohol, acetonitrile, tetrahydrofuran, dichloroethane, dichloromethane, 1,4-dioxane, toluene, xylene, anisole and the like.

  In addition, when making anthracene polycarbaldehyde and an amine react, in order to make reaction rate high, you may add an acid.

  Although it does not specifically limit as an acid, Acetic acid, hydrochloric acid, a sulfuric acid, p-toluenesulfonic acid etc. are mentioned.

The alkyl group in R ₁ and R _2, but not limited to, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc. undecanyl group.

  Examples of the substituent of the alkyl group include alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, pyridine, quinoline, thiophene, furan, oxazole, And monovalent aromatic heterocyclic groups derived from aromatic heterocyclic compounds such as oxadiazole and carbazole, and monovalent aliphatic heterocyclic groups derived from aliphatic heterocyclic compounds such as pyrrolidine, piperidine, and piperazine. It is done.

The aralkyl group in R ₁ and R ₂ is not particularly limited, and examples thereof include a benzyl group, a phenethyl group, a cumyl group, and a naphthylmethyl group.

  Aralkyl group substituents include the above alkyl groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups and other alkoxy groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms and other halogen atoms, pyridine, quinoline, thiophene , Monovalent aromatic heterocyclic groups derived from aromatic heterocyclic compounds such as furan, oxazole, oxadiazole, carbazole, etc., monovalent aliphatic heterocyclic groups derived from aliphatic heterocyclic compounds such as pyrrolidine, piperidine, piperazine, etc. A cyclic group etc. are mentioned.

The monovalent aliphatic heterocyclic group in R ₁ and R ₂ is not particularly limited, and examples thereof include groups derived from aliphatic heterocyclic compounds such as pyrrolidine, piperidine, piperazine and the like.

  Examples of the substituent for the monovalent aliphatic heterocyclic group include alkoxy groups such as the above alkyl groups, methoxy groups, ethoxy groups, propoxy groups, and butoxy groups, and halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. , Monovalent aromatic groups derived from aromatic compounds such as benzene, biphenyl, naphthalene, anthracene, fluorene, pyrene, pyridine, quinoline, thiophene, furan, oxazole, oxadiazole, and carbazole.

The monovalent aromatic group in R ₁ and R ₂ is not particularly limited, but aromatic compounds such as benzene, biphenyl, naphthalene, anthracene, fluorene, pyridine, quinoline, thiophene, furan, oxazole, oxadiazole, and carbazole. The group derived from is mentioned.

  Although it does not specifically limit as a substituent of a monovalent | monohydric aromatic group, Alkoxy groups, such as said alkyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. And monovalent aliphatic heterocyclic groups derived from aliphatic heterocyclic compounds such as pyrrolidine, piperidine and piperazine.

The heterocyclic group formed by combining R ¹ and R ² with each other is not particularly limited, and examples thereof include a pyrrolidino group, a piperidino group, a piperazino group, and a morpholyl group.

  Although it does not specifically limit as a compound represented by General formula (1), Compound (1-1)-(1-57) etc. are mentioned, You may use 2 or more types together.

なお、表中、Ｒ_１とＲ_２の間に仕切りが無い場合は、Ｒ_１及びＲ_２が互いに結合して環を形成していることを意味する。

In the table, when the partition between the R ₁ and R ₂ is absent, it means that R ₁ and R ₂ are bonded to each other to form a ring.

  Content of the compound represented by General formula (1) in a protective layer is 0.1-10 mass% normally, and it is preferable that it is 0.5-5 mass%. When the content of the compound represented by the general formula (1) in the protective layer is less than 0.1% by mass, the potential of the exposed portion may increase. May decrease.

[Compound represented by formula (2)]
The compound represented by the general formula (2) has the chemical formula

で表されるピペラジンと、一般式

And piperazine represented by the general formula

（式中、Ｚは、ハロゲン原子である。）
で表されるハロゲン化合物を、有機金属触媒及び塩基の存在下、溶媒中で反応させることにより合成することができる。

(In the formula, Z is a halogen atom.)
Can be synthesized by reacting in a solvent in the presence of an organometallic catalyst and a base.

  The temperature at which piperazine reacts with the halogen compound is usually about −50 to 250 ° C., preferably about room temperature to 150 ° C.

  Examples of the solvent include, but are not limited to, methanol, ethanol, isopropyl alcohol, acetonitrile, tetrahydrofuran, dichloroethane, dimethylformamide, dimethyl sulfoxide, dichloromethane, 1,4-dioxane, toluene, xylene, anisole and the like.

  The organometallic catalyst is not particularly limited, but copper, bis (tri-tert-butylphosphine) palladium (0), bis (tricyclohexylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), etc. Is mentioned.

  Examples of the base include, but are not limited to, potassium carbonate, sodium hydroxide, triethylamine, diisopropylethylamine and the like.

The alkyl group in R ₁ and R _2, but not limited to, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc. undecanyl group.

  Examples of the substituent of the alkyl group include alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, pyridine, quinoline, thiophene, furan, oxazole, And monovalent aromatic heterocyclic groups derived from aromatic heterocyclic compounds such as oxadiazole and carbazole, and monovalent aliphatic heterocyclic groups derived from aliphatic heterocyclic compounds such as pyrrolidine, piperidine, and piperazine. It is done.

The aralkyl group in R ₁ and R ₂ is not particularly limited, and examples thereof include a benzyl group, a phenethyl group, a cumyl group, and a naphthylmethyl group.

  As the substituent of the aralkyl group, alkoxy groups such as the above alkyl group, methoxy group, ethoxy group, propoxy group, butoxy group, fluorine atom, chlorine atom, bromine atom, halogen atom of iodine atom, pyridine, quinoline, thiophene, Monovalent aromatic heterocyclic groups derived from aromatic heterocyclic compounds such as furan, oxazole, oxadiazole and carbazole, and monovalent aliphatic heterocyclic rings derived from aliphatic heterocyclic compounds such as pyrrolidine, piperidine and piperazine Groups and the like.

The monovalent aromatic group in R ₁ and R ₂ is not particularly limited, but aromatic compounds such as benzene, biphenyl, naphthalene, anthracene, fluorene, pyridine, quinoline, thiophene, furan, oxazole, oxadiazole, and carbazole. The group derived from is mentioned.

  Although it does not specifically limit as a substituent of a monovalent | monohydric aromatic group, Alkoxy groups, such as said alkyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. And monovalent aliphatic heterocyclic groups derived from aliphatic heterocyclic compounds such as pyrrolidine, piperidine and piperazine.

The heterocyclic group formed by combining R ¹ and R ² with each other is not particularly limited, and examples thereof include a pyrrolidino group, a piperidino group, a piperazino group, and a morpholyl group.

  The divalent aromatic group in Ar is not particularly limited, but groups derived from aromatic compounds such as benzene, biphenyl, naphthalene, anthracene, fluorene, pyridine, quinoline, thiophene, furan, oxazole, oxadiazole, and carbazole are included. Can be mentioned.

  Although it does not specifically limit as a substituent of a bivalent aromatic group, Alkoxy groups, such as said alkyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. And monovalent aliphatic heterocyclic groups derived from aliphatic heterocyclic compounds such as pyrrolidine, piperidine and piperazine.

  Although it does not specifically limit as a C1-C4 alkylene group in X, A methylene group, ethylene group, a propylene group, a butylene group etc. are mentioned.

  Although it does not specifically limit as a compound represented by General formula (2), Compound (2-1)-(2-32) etc. are mentioned, You may use together 2 or more types.

保護層中の一般式（２）で表される化合物の含有量は、通常、０．１〜１０質量％であり、０．５〜５質量％であることが好ましい。保護層中の一般式（１）で表される化合物の含有量が０．１質量％未満であると、露光部の電位が上昇することがあり、１０質量％を超えると、感光体の耐久性が低下することがある。

Content of the compound represented by General formula (2) in a protective layer is 0.1-10 mass% normally, and it is preferable that it is 0.5-5 mass%. When the content of the compound represented by the general formula (1) in the protective layer is less than 0.1% by mass, the potential of the exposed portion may increase. May decrease.

[Compound represented by formula (3)]
The alkyl group of indicated number of carbon atoms in R ₃ and _{R 4} are 1-4, but are not limited to, methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, Examples thereof include a tert-butyl group.

  The arylene group having 6 to 14 carbon atoms in Y is not particularly limited, but o-phenylene group, p-phenylene group, 1,4-naphthalenediyl group, 2,6-naphthalenediyl group, and 9,10-anthracene. Examples include a diyl group, a 1,4-anthracenediyl group, a 4,4′-biphenyldiyl group, and a 4,4′-stilbenediyl group.

  Although it does not specifically limit as a compound represented by General formula (3), The compound etc. which are described in Unexamined-Japanese-Patent No. 2012-032631 etc. are mentioned, You may use 2 or more types together. Among these, compounds (3-1) to (3-4) are preferable.

電荷輸送性構造を有するラジカル重合性化合物に対する一般式（３）で表される化合物の質量比は、通常、０．００５〜０．３であり、０．０２〜０．１であることが好ましい。電荷輸送性構造を有するラジカル重合性化合物に対する一般式（３）で表される化合物の質量比が０．００５未満であると、露光部の電位が上昇することがあり、０．３を超えると、感光体の耐久性が低下することがある。

The mass ratio of the compound represented by the general formula (3) to the radically polymerizable compound having a charge transporting structure is usually 0.005 to 0.3, and preferably 0.02 to 0.1. . When the mass ratio of the compound represented by the general formula (3) to the radically polymerizable compound having a charge transporting structure is less than 0.005, the potential of the exposed portion may increase. The durability of the photoreceptor may be reduced.

[Compound represented by the general formula (4)]
The aryl group having 6 to 14 carbon atoms in Ar ₁ and Ar ₂ is not particularly limited, and examples thereof include a phenyl group, a 4-methylphenyl group, a 4-tert-butylphenyl group, a naphthyl group, and a biphenylyl group.

  The arylene group having 6 to 14 carbon atoms in Y is not particularly limited, but o-phenylene group, p-phenylene group, 1,4-naphthalenediyl group, 2,6-naphthalenediyl group, and 9,10-anthracene. Examples include a diyl group, a 1,4-anthracenediyl group, a 4,4′-biphenyldiyl group, and a 4,4′-stilbenediyl group.

  Although it does not specifically limit as a compound represented by General formula (4), The compound etc. which are described in Unexamined-Japanese-Patent No. 2012-032631 are mentioned, You may use 2 or more types together. Among these, compounds (4-1) to (4-2) are preferable.

電荷輸送性構造を有するラジカル重合性化合物に対する一般式（４）で表される化合物の質量比は、通常、０．００５〜０．３であり、０．０２〜０．１であることが好ましい。電荷輸送性構造を有するラジカル重合性化合物に対する一般式（４）で表される化合物の質量比が０．００５未満であると、露光部の電位が上昇することがあり、０．３を超えると、感光体の耐久性が低下することがある。

The mass ratio of the compound represented by the general formula (4) to the radically polymerizable compound having a charge transporting structure is usually 0.005 to 0.3, preferably 0.02 to 0.1. . When the mass ratio of the compound represented by the general formula (4) to the radically polymerizable compound having a charge transporting structure is less than 0.005, the potential of the exposed portion may increase. The durability of the photoreceptor may be reduced.

[Radically polymerizable compound having 3 or more functional groups having no charge transport property]
A trifunctional or higher-functional radical polymerizable compound having no charge transporting property includes a hole transporting structure such as a triarylamine structure, a hydrazone structure, a pyrazoline structure, a carbazole structure, or a condensed polycyclic quinone, diphenoquinone, cyano group, nitro group It means a compound that does not have an electron transporting structure such as an aromatic ring structure substituted by an electron withdrawing group such as a group and has three or more radically polymerizable groups.

  The radical polymerizable group is a group having a carbon-carbon double bond and capable of radical polymerization, and is preferably an acryloyloxy group or a methacryloyloxy group.

  A compound having three or more acryloyloxy groups can be synthesized, for example, by subjecting a compound having three or more hydroxyl groups and an acrylate, an acrylate halide or an acrylate ester to an ester reaction or a transesterification reaction. .

  A compound having three or more methacryloyloxy groups can be synthesized in the same manner.

  In addition, the 3 or more radically polymerizable group which the trifunctional or more radically polymerizable compound which does not have charge transportability may have may be the same, or may differ.

  Although it does not specifically limit as a radically polymerizable compound more than trifunctional which does not have charge transportability, A trimethylol propane triacrylate (TMPTA), a trimethylol propane trimethacrylate, an ethyleneoxy modification (EO modification) trimethylol propane triacrylate , Propyleneoxy modified (PO modified) trimethylolpropane triacrylate, caprolactone modified trimethylolpropane triacrylate, HPA modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH modified glycerol Triacrylate, EO-modified glycerol triacrylate, PO-modified glycerol triacrylate Tris (acryloxyethyl) isocyanurate, dipentaerythritol hexaacrylate (DPHA), caprolactone modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkyl modified dipentaerythritol pentaacrylate, alkyl modified dipentaerythritol tetraacrylate, alkyl Modified dipentaerythritol triacrylate, dimethylolpropane tetraacrylate (DTMPTA), pentaerythritol ethoxytetraacrylate, EO modified phosphoric acid triacrylate, 2,2,5,5-tetrahydroxymethylcyclopentanone tetraacrylate, etc. Two or more kinds may be used in combination.

[Radically polymerizable compound having a charge transporting structure]
The radical polymerizable compound having a charge transporting structure is a hole transporting structure such as a triarylamine structure, a hydrazone structure, a pyrazoline structure, or a carbazole structure, or a condensed polycyclic quinone, diphenoquinone, cyano group, nitro group, etc. It means a compound having an electron transporting structure such as an aromatic ring structure having an electron withdrawing group and having a radical polymerizable group.

  The radical polymerizable group is a group having a carbon-carbon double bond and capable of radical polymerization, and is preferably an acryloyloxy group or a methacryloyloxy group, and more preferably an acryloyloxy group. .

  The radical polymerizable compound having a charge transporting structure preferably has one radical polymerizable group, that is, is monofunctional from the viewpoint of electrostatic characteristics.

  The monofunctional radically polymerizable compound having a charge transporting structure preferably has a triarylamine structure, and has a general formula

（式中、Ｒ_１は、水素原子、ハロゲン基、置換基により置換されていてもよいアルキル基、置換基により置換されていてもよいアラルキル基、置換基により置換されていてもよいアリール基、シアノ基、ニトロ基、アルコキシ基、一般式
−ＣＯＯＲ_２
（式中、Ｒ_２は、水素原子、置換基により置換されていてもよいアルキル基、置換基により置換されていてもよいアラルキル基又は置換基により置換されていてもよいアリール基である。）
で表される基、ハロカルボニル基、又は、一般式
−ＣＯＮＲ_３Ｒ_４
（式中、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子、ハロゲン基、置換基により置換されていてもよいアルキル基、置換基により置換されていてもよいアラルキル基又は置換基により置換されていてもよいアリール基である。）
で表される基であり、Ａｒ_１は、置換基により置換されていてもよい二価の芳香族基であり、Ａｒ_２及びＡｒ_３は、それぞれ独立に、置換基により置換されていてもよい一価の芳香族基であり、Ｘは、単結合又は一般式
−Ｙ−Ａｒ_４−
（式中、Ｙは、単結合、置換基により置換されていてもよいアルキレン基、置換基により置換されていてもよいシクロアルキレン基、置換基により置換されていてもよいアルキレンオキシ基、オキシ基、チオ基又はビニレン基であり、Ａｒ_４は、置換基により置換されていてもよい二価の芳香族基である。）
で表される基であり、Ｚは、置換基により置換されていてもよいアルキレン基、置換基により置換されていてもよいアルキレンオキシ基、アルキレンオキシカルボニル基であり、ｎは、０〜３の整数である。）
で表される化合物がさらに好ましい。

(In the formula, R ₁ represents a hydrogen atom, a halogen group, an alkyl group which may be substituted with a substituent, an aralkyl group which may be substituted with a substituent, an aryl group which may be substituted with a substituent, Cyano group, nitro group, alkoxy group, general formula -COOR ₂
(In the formula, R ₂ represents a hydrogen atom, an alkyl group which may be substituted with a substituent, an aralkyl group which may be substituted with a substituent, or an aryl group which may be substituted with a substituent.)
Or a halocarbonyl group represented by the general formula —CONR ₃ R ₄
(Wherein R ₃ and R ₄ are each independently substituted with a hydrogen atom, a halogen group, an alkyl group optionally substituted with a substituent, an aralkyl group optionally substituted with a substituent, or a substituent. An aryl group that may be present.)
Ar ₁ is a divalent aromatic group that may be substituted with a substituent, and Ar ₂ and Ar ₃ may each independently be substituted with a substituent. A monovalent aromatic group, X is a single bond or a general formula —Y—Ar ₄ —.
Wherein Y is a single bond, an alkylene group which may be substituted with a substituent, a cycloalkylene group which may be substituted with a substituent, an alkyleneoxy group which may be substituted with a substituent, or an oxy group. , A thio group or a vinylene group, and Ar ₄ is a divalent aromatic group which may be substituted with a substituent.)
Z is an alkylene group which may be substituted with a substituent, an alkyleneoxy group which may be substituted with a substituent, or an alkyleneoxycarbonyl group, and n is 0-3. It is an integer. )
Is more preferable.

Examples of the alkyl group for R ₁ include a methyl group, an ethyl group, a propyl group, and a butyl group. Further, examples of the aralkyl group in R ₁ include a benzyl group, a phenethyl group, and a naphthylmethyl group. Furthermore, examples of the aryl group in R ₁ include a phenyl group and a naphthyl group. Examples of the alkoxy group for R ₁ include a methoxy group, an ethoxy group, and a propoxy group.

Examples of the substituent in R ₁ include halogen groups, nitro groups, cyano groups, alkyl groups such as methyl groups and ethyl groups, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, phenyl groups and naphthyl groups. And aryl groups such as benzyl group and phenethyl group.

R ₁ is preferably a hydrogen atom or a methyl group.

Examples of the monovalent aromatic group in Ar ₂ and Ar ₃ include a monovalent condensed polycyclic hydrocarbon group, a monovalent non-condensed cyclic hydrocarbon group, and a monovalent heterocyclic group.

  The monovalent condensed polycyclic hydrocarbon group includes a pentanyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptaenyl group, a biphenylenyl group, an as-indacenyl group, an s-indacenyl group, a fluorenyl group, an acenaphthylenyl group, and a preadenyl group. Acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylyl group, pyrenyl group, chrysenyl group, naphthacenyl group and the like. The monovalent condensed polycyclic hydrocarbon group preferably has 18 or less carbon atoms constituting the ring.

  Monovalent non-condensed cyclic hydrocarbon groups include groups derived from monocyclic hydrocarbon compounds such as benzene, diphenyl ether, polyethylene diphenyl ether, diphenyl thioether, diphenyl sulfone, biphenyl, polyphenyl, diphenylalkane, diphenylalkene, diphenylalkyne. , Groups derived from non-condensed polycyclic hydrocarbon compounds such as triphenylmethane, distyrylbenzene, 1,1-diphenylcycloalkane, polyphenylalkane and polyphenylalkene, and ring-assembled hydrocarbons such as 9,9-diphenylfluorene Examples include groups derived from compounds.

  Examples of the heterocyclic group include aromatic heterocyclic groups derived from aromatic heterocyclic compounds such as carbazole, dibenzofuran, dibenzothiophene, oxadiazole, and thiadiazole.

The substituents for Ar ₂ and Ar ₃ are shown below.

[1] Halogen atom, cyano group, nitro group [2] Alkyl group The carbon number of the alkyl group is usually 1 to 12, preferably 1 to 8, and more preferably 1 to 4. The alkyl group is a fluoro group, a hydroxyl group, a cyano group, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, a halogen group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. It may be substituted with a substituted phenyl group.

  As the alkyl group, methyl group, ethyl group, n-butyl group, isopropyl group, t-butyl group, s-butyl group, n-propyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-ethoxyethyl group 2-cyanoethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-phenylbenzyl group and the like.

[3] Alkoxy group The alkyl group in the alkoxy group is the same as the alkyl group in [2].

  Alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, n-butoxy, s-butoxy, isobutoxy, 2-hydroxyethoxy, benzyloxy, trifluoro A methoxy group etc. are mentioned.

[4] Aryloxy group Examples of the aryl group in the aryloxy group include a phenyl group and a naphthyl group. The aryloxy group may be substituted by an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or a halogen group.

  Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methoxyphenoxy group, and a 4-methylphenoxy group.

[5] Alkyl mercapto group or aryl mercapto group Examples of the alkyl mercapto group include a methylthio group and an ethylthio group. Examples of the aryl mercapto group include a phenylthio group and a p-methylphenylthio group.

[6] Amino group optionally substituted by a substituent The amino group optionally substituted by a substituent has the general formula —NR ₁ R _2.
[Wherein, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group or an aryl group in [2], and R ₁ and R ₂ may jointly form a ring. ]
It is represented by

Examples of the aryl group in R ₁ and R ₂ include a phenyl group, a biphenylyl group, and a naphthyl group. The aryl group is an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or a halogen group. May be substituted.

  Examples of the amino group optionally substituted by a substituent include an amino group, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-ditolylamino group, dibenzylamino group, Examples include a piperidino group, a morpholino group, a pyrrolidino group, and the like.

[7] Alkylenedioxy group or alkylenedithio group Examples of the alkylenedioxy group include a methylenedioxy group. Examples of the alkylenedithio group include a methylenedithio group.

[8] Others Examples include a styryl group that may be substituted with a substituent, a β-phenylstyryl group that may be substituted with a substituent, a diphenylaminophenyl group, a ditolylaminophenyl group, and the like.

Examples of the divalent aromatic group for Ar ₁ and Ar ₄ include groups derived from the monovalent aromatic group for Ar ₂ and Ar ₃ .

  Carbon number of the alkylene group in Y is 1-12 normally, 1-8 are preferable and 1-4 are more preferable. The alkylene group is a fluoro group, a hydroxyl group, a cyano group, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, a halogen group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. It may be substituted with a substituted phenyl group.

  Examples of the alkylene group include methylene group, ethylene group, n-butylene group, isopropylene group, t-butylene group, s-butylene group, n-propylene group, trifluoromethylene group, 2-hydroxyethylene group, and 2-ethoxyethylene. Group, 2-cyanoethylene group, 2-methoxyethylene group, benzylidene group, phenylethylene group, 4-chlorophenylethylene group, 4-methylphenylethylene group, 4-biphenylylethylene group and the like.

  Carbon number of the cycloalkylene group in Y is 5-7 normally. The cycloalkylene group may be substituted with a fluoro group, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

  Examples of the cycloalkylene group include a cyclohexylidene group, a cyclohexylene group, and a 3,3-dimethylcyclohexylidene group.

The alkyleneoxy group for Y is represented by the chemical formula —CH ₂ CH ₂ O—.
A group represented by the formula: —CH ₂ CH ₂ CH ₂ O—
A group represented by the general formula _{- (OCH 2 CH 2) n} O-
(In the formula, n is an integer of 1 to 4.)
A group represented by the formula:-(OCH ₂ CH ₂ CH ₂ ) _m O-
(In the formula, m is an integer of 1 to 4.)
The group etc. which are represented by these are mentioned.

  The alkyleneoxy group may be substituted with a substituent such as a hydroxyl group, a methyl group, or an ethyl group.

As the vinylene group for Y, the general formula — (C (R ₁ ) ═CH) _n —
(In the formula, R ₁ represents a hydrogen atom, an alkyl group (similar to the alkyl group in the above [2]), or a divalent aromatic group (the divalent aromatic group in Ar ₂ and Ar ₃ described above). And n is 1 or 2.)
A group represented by the formula: —C (R ₂ ) ═CH— (CH═CH) _m —
(In the formula, R ₂ represents a hydrogen atom, an alkyl group (similar to the alkyl group in the above [2]), or a divalent aromatic group (the divalent aromatic group in Ar ₂ and Ar ₃ described above) And m is an integer of 1 to 3.)
The group etc. which are represented by these are mentioned.

  The alkylene group for Z is the same as the alkylene group for Y.

  The alkyleneoxy group in Z is the same as the alkyleneoxy group in Y.

  Examples of the alkyleneoxycarbonyl group for Z include a caprolactone-modified group.

  A monofunctional radically polymerizable compound having a charge transporting structure has a general formula

（式中、Ｒ_１は、水素原子又はメチル基であり、Ｒ_２及びＲ_３は、それぞれ独立に、置換基により置換されていてもよい炭素数が１〜６のアルキル基であり、Ｚは、単結合、メチレン基、エチレン基、化学式
−ＣＨ_２ＣＨ_２Ｏ−
で表される基、化学式
−ＣＨ（ＣＨ_３）ＣＨ_２Ｏ−
で表される基、又は、化学式

(In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently an alkyl group having 1 to 6 carbon atoms which may be substituted by a substituent, and Z is , Single bond, methylene group, ethylene group, chemical formula —CH ₂ CH ₂ O—
A group represented by the formula: —CH (CH ₃ ) CH ₂ O—
Or a group represented by the chemical formula

で表される基であり、ｏ、ｐ及びｑは、それぞれ独立に、０又は１であり、ｓ及びｔは、それぞれ独立に、０〜３の整数である。）
で表される化合物であることが好ましい。

O, p, and q are each independently 0 or 1, and s and t are each independently an integer of 0 to 3. )
It is preferable that it is a compound represented by these.

R ₂ and R ₃ are preferably each independently a methyl group or an ethyl group.

  The mass ratio of the radical polymerizable compound having a charge transport function to the trifunctional or higher functional radical polymerizable compound having no charge transport function is usually 0.5 to 2.0, and 0.8 to 1.4. Preferably there is. When the mass ratio of the radical polymerizable compound having a charge transport function to the trifunctional or higher functional radical polymerizable compound having no charge transport function is less than 0.5, the electrostatic characteristics of the photoreceptor may be lowered. If it exceeds 2.0, the durability of the photoreceptor may be lowered.

  The composition may further contain a polymerization initiator as necessary in order to allow the curing reaction to proceed efficiently.

  The thermal polymerization initiator is not particularly limited, but 2,5-dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, benzoyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2 , 5-di (peroxybenzoyl) hexyne-3, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide and other peroxide initiators, azobisisobutyl nitrile, Examples include azo initiators such as azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, azobisisobutylamidine hydrochloride, 4,4′-azobis-4-cyanovaleric acid, and two or more of them may be used in combination.

  The photopolymerization initiator is not particularly limited, but is 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-phenylpropane-1 Acetophenone-based or ketal-based light such as 2-one, 2-methyl-2-morpholino (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime Polymerization initiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin ether photopolymerization initiators such as sobutyl ether and benzoin isopropyl ether, benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoylphenyl ether, acrylated benzophenone, Benzophenone photopolymerization initiators such as 1,4-benzoylbenzene, thioxanthone light such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone A polymerization initiator etc. are mentioned, You may use 2 or more types together.

  Other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenyl Examples include phosphine oxide, bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10-phenanthrene, acridine compound, triazine compound, imidazole compound, and the like. It is done.

  The composition may further contain a compound having an effect of promoting photopolymerization instead of or together with the photopolymerization initiator.

  The compound having a photopolymerization accelerating effect is not particularly limited, but triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4,4 ′ -Dimethylamino benzophenone etc. are mentioned.

  The mass ratio of the polymerization initiator to the total amount of the compound having a radical polymerizable group is usually 0.005 to 0.4, and preferably 0.01 to 0.2.

  The composition preferably further includes inorganic particles and / or organic particles, and more preferably further includes inorganic particles. Thereby, the durability of the photoreceptor can be improved.

  Although it does not specifically limit as a material which comprises organic particle, A fluororesin, such as polytetrafluoroethylene, a silicone resin, etc. are mentioned, You may use 2 or more types together.

  The material constituting the inorganic particles is not particularly limited, but metals such as copper, tin, aluminum, indium, silicon oxide, tin oxide, aluminum oxide, zinc oxide, titanium oxide, indium oxide, antimony oxide, bismuth oxide, etc. A metal oxide, potassium titanate, amorphous carbon, etc. are mentioned, You may use 2 or more types together. Among these, metal oxides are preferable from the viewpoint of electrostatic characteristics, and silicon oxide (colloidal silica), aluminum oxide (colloidal alumina), and titanium oxide are more preferable.

  The average primary particle size of the inorganic particles and / or organic particles is usually 0.01 to 0.5 μm. When the average primary particle size of the inorganic particles and / or organic particles is less than 0.01 μm, the durability of the photoreceptor may be lowered, and when it exceeds 0.5 μm, the light transmittance of the protective layer is lowered. Sometimes.

  Content of the inorganic particle and / or organic particle in a protective layer is 5-50 mass% normally, and it is preferable that it is 5-30 mass%. When the content of the inorganic particles and / or organic particles in the protective layer is less than 5% by mass, the durability of the photoconductor may decrease. When the content exceeds 30% by mass, the electrostatic characteristics of the photoconductor deteriorates. Or the light transmittance of the protective layer may be reduced.

  The inorganic particles may be surface-treated with a surface treatment agent. Thereby, the dispersibility of the inorganic particle in a protective layer can be improved.

  Although it does not specifically limit as a surface treating agent, Titanate coupling agent, aluminum coupling agent, zircoaluminate coupling agent, higher fatty acid, aluminum oxide, titanium dioxide, zirconium dioxide, silicone resin, aluminum stearate, etc. And two or more of them may be used in combination.

  The treatment amount of the surface treatment agent with respect to the inorganic particles is usually 3 to 30% by mass, and preferably 5 to 20% by mass. When the treatment amount of the surface treatment agent with respect to the inorganic particles is less than 3% by mass, the dispersibility of the inorganic particles in the protective layer may be reduced, and when it exceeds 30% by mass, the electrostatic characteristics of the photoreceptor are deteriorated. Sometimes.

  When the protective layer contains inorganic particles, the protective layer may further contain a surfactant.

  The mass ratio of the surfactant to the inorganic particles is usually 0.005 to 0.3, and preferably 0.01 to 0.15. If the mass ratio of the surfactant to the inorganic particles is less than 0.005, the dispersibility of the inorganic particles in the protective layer may be reduced, and if it exceeds 0.3, the residual potential may be increased.

  The composition may further contain a plasticizer, a leveling agent, a charge transport material and the like.

  Although it does not specifically limit as a plasticizer, Dibutyl phthalate, a dioctyl phthalate, etc. are mentioned.

  The content of the plasticizer in the protective layer is usually 20% by mass or less and preferably 10% by mass or less.

  The leveling agent is not particularly limited, and examples thereof 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 content of the leveling agent in the protective layer is usually 3% by mass or less.

  The protective layer includes a trifunctional or higher functional radical polymerizable compound having no charge transport structure, a radical polymerizable compound having a charge transport structure, and a compound represented by the general formula (1) or the general formula (2). And a coating solution in which the compound represented by general formula (3) or the compound represented by general formula (4) is dissolved or dispersed in a solvent, dried, and then externally applied. It can be formed by applying energy and curing.

  The solvent is not particularly limited, but alcohol solvents such as methanol, ethanol, propanol and butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, tetrahydrofuran, dioxane, Ether solvents such as propyl ether, halogen solvents such as dichloromethane, dichloroethane, trichloroethane, chlorobenzene, aromatic solvents such as benzene, toluene, xylene, cellosolv solvents such as methyl cellosolve, ethyl cellosolve, cellosolve acetate, etc. Two or more kinds may be used in combination.

  A method for applying the coating solution is not particularly limited, and examples thereof include a dip coating method, a spray coating method, a bead coating method, and a ring coating method.

  Although it does not specifically limit as external energy, Active energy rays, such as an ultraviolet-ray and an electron beam, a heat | fever, etc. are mentioned. Among these, active energy rays are preferable because the durability of the photoreceptor can be improved.

  It is preferable to apply external energy while cooling in an atmosphere having a low oxygen concentration such as nitrogen gas or rare gas. Thereby, the durability of the photoreceptor can be improved.

  It is also preferable to apply the coating liquid and dry it in an atmosphere having a low oxygen concentration such as nitrogen gas or rare gas.

  The light source used when irradiating the active energy ray is not particularly limited, and a light source that irradiates ultraviolet rays such as a high-pressure mercury lamp or a metal halide lamp can be used, but a light source that irradiates visible light may also be used.

  The temperature of the surface of the coating film when irradiating active energy rays is usually 40 to 170 ° C.

  In addition, it is preferable to control the surface temperature of the coating film using a heat medium.

The irradiation light amount of the active energy ray is usually 50 to 1000 mW / cm ² . If the irradiation amount of the active energy ray is less than 50 mW / cm ² , the time for curing the composition may be long. If it exceeds 1000 mW / cm ² , the photoreceptor may be deformed or the electrical characteristics may be deteriorated. There are things to do.

  The thickness of the protective layer is usually 1 to 30 μm, preferably 2 to 20 μm, and more preferably 4 to 15 μm. When the thickness of the protective layer is less than 1 μm, the durability of the photoreceptor may be lowered, and when it exceeds 30 μm, the residual potential may be increased.

  The photosensitive layer may be a laminated type or a single layer type.

  In the stacked photosensitive layer, a charge generation layer and a charge transport layer are sequentially stacked.

  The charge generation layer contains a charge generation material and may further contain a binder resin or the like.

  The charge generation material is not particularly limited, but as the inorganic material, phthalocyanine series such as crystalline selenium, amorphous selenium, selenium-tellurium compound, selenium-tellurium-halogen compound, selenium-arsenic compound, metal phthalocyanine, metal-free phthalocyanine, etc. Pigment, azulenium salt pigment, squaric acid methine pigment, azo pigment having carbazole skeleton, azo pigment having triphenylamine skeleton, azo pigment having diphenylamine skeleton, azo pigment having dibenzothiophene skeleton, azo pigment having fluorenone skeleton, Azo pigment having oxadiazole skeleton, azo pigment having bis stilbene skeleton, azo pigment having distyryl oxadiazole skeleton, azo pigment having distyrylcarbazole skeleton, perylene pigment, anthraquinone Materials, polycyclic quinone pigments, quinone imine pigments, diphenylmethane pigments, triphenylmethane pigments, benzoquinone pigments, naphthoquinone pigments, cyanine pigments, azomethine pigments, indigoid pigments, bisbenzimidazole pigments, etc. Two or more kinds may be used in combination.

  The binder resin is not particularly limited, and examples thereof include polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, and polyacrylamide. May be.

  The charge generation layer may further contain a charge transport material.

  At this time, the charge transport material may be a polymer charge transport material.

  The method for forming the charge generation layer is not particularly limited, but includes a glow discharge polymerization method, a vacuum deposition method, a CVD method, a sputtering method, a reactive sputtering method, an ion plating method, an accelerated ion injection method, and the like, Examples thereof include casting methods such as dip coating, spray coating, and bead coating.

  When forming a charge generation layer using a casting method, a coating solution in which a charge generation material is dissolved or dispersed in a solvent is used.

  The solvent is not particularly limited, but acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, dichloromethane, dichloroethane, dichloropropane, trichloroethane, trichloroethylene, tetrachloroethane, tetrahydrofuran, dioxolane, dioxane, methanol, ethanol , Isopropyl alcohol, butanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve, ethyl cellosolve, propyl cellosolve, and the like. Among these, tetrahydrofuran, methyl ethyl ketone, dichloromethane, methanol, and ethanol having a boiling point of 40 to 80 ° C. are preferable from the viewpoint of the drying property of the coating film.

  A method for dissolving or dispersing the charge generating substance in the solvent is not particularly limited, and examples thereof include a method using a dispersion medium such as a ball mill, a bead mill, a sand mill, and a vibration mill, and a high-speed liquid collision dispersion method.

  The thickness of the charge generation layer is usually from 0.01 to 5 μm, and preferably from 0.05 to 2 μm. When the thickness of the charge generation layer exceeds 5 μm, the photosensitivity of the photoreceptor may be lowered.

  The charge transport layer includes a charge transport material and a binder resin.

  As the charge transport material, a low molecular charge transport material such as a low molecular hole transport material or a low molecular electron transport material can be used, and a polymer charge transport material may be used as necessary.

  Although it does not specifically limit as a low molecular hole transport material, An oxazole derivative, an oxadiazole derivative, an imidazole derivative, a triphenylamine derivative, 9- (p-diethylaminostyrylanthracene), 1,1-bis- (4-di Benzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives, etc. Two or more kinds may be used in combination.

  Although it does not specifically limit as a polymeric charge transport material, The compound etc. which are shown below are mentioned.

(A) Polymer having carbazole structure For example, poly (N-vinylcarbazole), JP-A-50-82056, JP-A-54-9632, JP-A-54-11737, JP-A-4-11437 Examples thereof include compounds described in JP-A No. 175337, JP-A-4-183719, and JP-A-6-234841.

(B) Polymer having a hydrazone structure For example, JP-A-57-78402, JP-A-61-20953, JP-A-61-296358, JP-A-1-134456, JP-A-1-134456 179164, JP-A-3-180851, JP-A-3-180852, JP-A-3-50555, JP-A-5-310904, JP-A-6-234840, and the like. Is done.

(C) Polysilylene polymer For example, JP-A-63-285552, JP-A-1-88461, JP-A-4-264130, JP-A-4-264131, JP-A-4-264132, Examples thereof include compounds described in Kaihei 4-264133 and JP-A-4-289867.

(D) Polymer having a triarylamine structure For example, N, N-bis (4-methylphenyl) -4-aminopolystyrene, JP-A-1-134457, JP-A-2-282264, JP-A-2- Examples include compounds described in JP-A-304456, JP-A-4-133605, JP-A-4-133066, JP-A-5-40350, and JP-A-5-202135.
Is done.

(E) Other polymers For example, formaldehyde condensation polymer of nitropyrene, JP-A-51-73888, JP-A-56-150749, JP-A-6-234836, JP-A-6-234837 The described compounds and the like are exemplified.

  Examples of the polymer charge transporting material other than the above include polycarbonates having a triarylamine structure, polyurethanes having a triarylamine structure, polyesters having a triarylamine structure, polyethers having a triarylamine structure, and the like.

  Examples of such a polymer charge transport material include, for example, JP-A 64-1728, JP-A 64-13061, JP-A 64-19049, JP-A-4-11627, JP-A-4-11627. JP-A-4-225014, JP-A-4-230767, JP-A-4-320420, JP-A-5-232727, JP-A-7-56374, JP-A-9-127713, JP-A-9- Examples thereof include compounds described in JP-A-9222740, JP-A-9-265197, JP-A-9-211877, JP-A-9-30495, and the like.

  The polymer having an electron transporting structure is not particularly limited, but includes a copolymer of a monomer having an electron transporting structure and a known monomer, a block polymer, a graft polymer, a star polymer, and the like. Can be mentioned.

  Examples of the polymer having an electron transporting structure other than the above include cross-linked polymers having an electron transporting structure described in JP-A-3-109406.

  Although it does not specifically limit as a low molecular electron transport material, A fluorene type compound, a quinone type compound, etc. are mentioned, You may use together 2 or more types.

  The binder resin is not particularly limited, but polycarbonate, polyester, methacrylic resin, acrylic resin, polyethylene, polyvinyl chloride, polyvinyl acetate, polystyrene, phenol resin, epoxy resin, polyurethane, polyvinylidene chloride, alkyd resin, silicone resin, Examples thereof include polyvinyl carbazole, polyvinyl butyral, polyvinyl formal, polyacrylate, polyacrylamide, phenoxy resin, and the like.

  The charge transport layer may be formed by curing a curable binder resin and a curable charge transport material.

  The charge transport layer can be formed by applying a coating solution in which a charge transport material and a binder resin are dissolved or dispersed in a solvent.

  The thickness of the charge transport layer is usually 5 to 100 μm, and preferably 5 to 30 μm.

  The single-layer type photosensitive layer includes a charge generation material, a charge transport material, and a binder resin.

  The single-layer type photosensitive layer can be formed by applying a coating solution in which a charge generating substance, a charge transporting substance and a binder resin are dissolved or dispersed in a solvent and then drying.

  The thickness of the single-layer type photosensitive layer is usually 5 to 100 μm, preferably 5 to 50 μm. When the thickness of the single-layer type photosensitive layer is less than 5 μm, the chargeability of the photoreceptor may be lowered, and when it exceeds 100 μm, the sensitivity of the photoreceptor may be lowered.

The conductive support is not particularly limited as long as it has a volume resistivity of 1 × 10 ¹⁰ Ω · cm or less, but a metal such as Al, Ni, Cr, Cu, Au, Ag, and Pt. And a film or cylindrical plastic, paper, or a plate of aluminum, aluminum alloy, nickel, stainless steel, or the like, which is coated with a metal oxide such as an alloy, tin oxide or indium oxide by vapor deposition or sputtering. Examples include pipes that have been subjected to processing such as cutting, super-finishing, polishing, etc. after extruding and forming a raw pipe by a method such as drawing.

  As the conductive support, an endless nickel belt or an endless stainless steel belt disclosed in JP-A-52-36016 may be used.

  Further, as the conductive support, a nickel foil having a thickness of 50 to 150 μm, and a polyethylene terephthalate film having a thickness of 50 to 150 μm that is conductively processed by vapor-depositing aluminum on the surface may be used.

  Further, a conductive layer in which conductive powder is dispersed in the binder resin may be formed on the surface of the conductive support.

  Although it does not specifically limit as electroconductive powder, Carbon black, acetylene black; Metal powder, such as aluminum, nickel, iron, nichrome, copper, zinc, silver; Metal oxides, such as electroconductive tin oxide and ITO Examples thereof include powders.

  The binder resin is not particularly limited, but polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly (N-vinylcarbazole), acrylic resin, silicone resin, epoxy resin, Examples include melamine resin, urethane resin, phenol resin, alkyd resin, and the like.

  The conductive layer can be formed by applying a coating solution in which conductive powder and binder resin are dissolved or dispersed in a solvent and then drying the coating solution.

  Although it does not specifically limit as a solvent, Tetrahydrofuran, a dichloromethane, methyl ethyl ketone, toluene etc. are mentioned.

  As the conductive support, a cylindrical substrate in which a conductive layer is formed by a heat shrinkable tube containing conductive powder may be used.

  The material constituting the cylindrical substrate is not particularly limited, and examples thereof include polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, and Teflon (registered trademark).

  A subbing layer is further formed between the conductive support and the photosensitive layer for the purpose of improving adhesion between the conductive support and the photosensitive layer, preventing moire, improving coating properties, and reducing residual potential. It may be.

  The undercoat layer contains a binder resin.

  The binder resin is not particularly limited as long as it has resistance to the coating solution applied when forming the photosensitive layer, but water-soluble resins such as polyvinyl alcohol, casein, sodium polyacrylate, copolymer nylon, Examples thereof include curable resins that form a three-dimensional network structure, such as alcohol-soluble resins such as methoxymethylated nylon, polyurethane, melamine resins, alkyd-melamine resins, and epoxy resins.

  The undercoat layer may further contain a powder.

  The material constituting the powder is not particularly limited, and examples thereof include metal oxides such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, and indium oxide, metal sulfides, and metal nitrides.

  The undercoat layer can be formed by applying a coating solution in which a binder resin is dissolved or dispersed in a solvent and then drying it.

  As an undercoat layer other than the above, a metal oxide formed by a sol-gel method using a silane coupling agent, a titanium coupling agent, a chromium coupling agent, etc., an aluminum oxide formed by anodization , Polyparaxylylene (parylene), tin (IV) oxide formed by a vacuum thin film manufacturing method, titanium dioxide, ITO, cerium oxide, and the like.

  The thickness of the undercoat layer is usually 0.1 to 10 μm, and preferably 1 to 5 μm.

  An intermediate layer may be further formed between the photosensitive layer and the protective layer for the purpose of suppressing the mixing of the components of the photosensitive layer into the protective layer or improving the adhesion between the photosensitive layer and the protective layer.

  The intermediate layer includes a binder resin.

  The binder resin is not particularly limited as long as it has resistance to the coating solution applied when forming the protective layer, and examples thereof include polyamide, alcohol-soluble nylon, polyvinyl butyral, and polyvinyl alcohol.

  The intermediate layer can be formed by applying a coating solution in which a binder resin is dissolved or dispersed in a solvent and then drying it.

  The thickness of the intermediate layer is usually 0.05 to 2 μm.

  Each layer of the photosensitive layer, the charge transport layer, the charge generation layer, the undercoat layer, and the intermediate layer may further contain a plasticizer, a leveling agent, an antioxidant, and the like.

  Although it does not specifically limit as a plasticizer, Dibutyl phthalate, a dioctyl phthalate, etc. are mentioned, You may use 2 or more types together.

  Although it does not specifically limit as a leveling agent, Silicone oils, such as a dimethyl silicone oil and a methylphenyl silicone oil; The polymer or oligomer etc. which have a perfluoroalkyl group in a side chain are mentioned.

  Although it does not specifically limit as antioxidant, A phenol type compound, paraphenylenediamine, hydroquinone, an organic sulfur compound, organic phosphorus compounds, a hindered amine, etc. are mentioned.

  FIG. 1 shows an example of the layer structure of the photoreceptor.

  In the photoreceptor 10 </ b> A, a monolayer type photosensitive layer 2 and a protective layer 3 are sequentially laminated on a conductive support 1.

  An undercoat layer may be further formed between the conductive support 1 and the single-layer type photosensitive layer 2.

  Further, an intermediate layer may be further formed between the single-layer type photosensitive layer 2 and the protective layer 3.

  FIG. 2 shows another example of the layer structure of the photoreceptor.

  In the photoreceptor 10 </ b> B, the laminated photosensitive layer 4 and the protective layer 3 are sequentially laminated on the conductive support 1. At this time, in the laminated photosensitive layer 4, the charge generation layer 4a and the charge transport layer 4b are sequentially laminated.

  An undercoat layer may be further formed between the conductive support 1 and the charge generation layer 4a.

  Further, an intermediate layer may be further formed between the charge transport layer 4 b and the protective layer 3.

  Further, in the stacked photosensitive layer 4, the order of stacking the charge generation layer 4a and the charge transport layer 4b may be reversed.

  FIG. 3 shows an example of the image forming apparatus.

  The photoconductor 10 can rotate. Around the photoconductor 10, a charging member 11, a developing member 13, a transfer member 15, a cleaning member 16, and a charge removal member 17 are disposed.

  The cleaning member 16 and the charge removal member 17 may be omitted.

  The operation of the image forming apparatus is basically as follows. The charging member 11 charges the surface of the photoconductor 10 almost uniformly. Next, a laser beam 12 corresponding to the input signal is irradiated by an exposure member (not shown) to form an electrostatic latent image. Further, the electrostatic latent image is developed by the developing member 13 and a toner image is formed on the surface of the photoreceptor 10. Next, the toner image is transferred by the transfer member 15 to the transfer paper P conveyed to the transfer site by the conveyance roller 14. The toner image is fixed on the transfer paper P by a fixing device (not shown). A part of the toner that has not been transferred to the transfer paper P is cleaned by the cleaning member 16. Next, the charge remaining on the surface of the photoreceptor 10 is neutralized by the neutralizing member 17, and the process proceeds to the next cycle.

  The photoconductor 10 has a drum shape, but may have a sheet shape or an endless belt shape.

  As the charging member 11 and the transfer member 15, a corotron, a scorotron, a solid state charger (solid state charger), a roller-shaped charging member, a brush-shaped charging member, or the like can be used.

  As a light source for the exposure member and the charge removal member 17, a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), an electroluminescence (EL), or the like can be used. Among these, a semiconductor laser (LD) or a light emitting diode (LED) is preferable.

  Note that a filter may be used to irradiate only light in a desired wavelength range.

  Although it does not specifically limit as a filter, A sharp cut filter, a band pass filter, a near-infrared cut filter, a dichroic filter, an interference filter, a color temperature conversion filter etc. are mentioned.

  In addition, a transfer process, a cleaning process, a pre-exposure process, and the like using light irradiation may be provided.

  At this time, the charge removal member 17 may be omitted, and the charge removal may be performed by applying a reverse bias in the charging process or the cleaning process.

  When the photosensitive member 10 is charged positively (negatively) and then irradiated with the laser beam 12, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member 10. If a positive (negative) electrostatic latent image is developed with negative (positive) toner, a positive image can be obtained, and if developed with positive (negative) toner, a negative image can be obtained.

  As the cleaning member 16, a cleaning blade, a cleaning brush, or the like can be used, and the cleaning blade and the cleaning brush may be used in combination.

  FIG. 4 shows a tandem full-color electrophotographic apparatus as another example of the image forming apparatus.

  The photoconductors 10C, 10M, 10Y, and 10K have a drum shape, and the photoconductors 10C, 10M, 10Y, and 10K rotate in the direction of the arrow in the drawing. Around the photoreceptors 10C, 10M, 10Y, and 10K, charging members 11C, 11M, 11Y, and 11K, developing members 13C, 13M, 13Y, and 13K, and cleaning members 16C, 16M, 16Y, and 16K are arranged in order of rotation. .

  The developing members 13C, 13M, 13Y, and 13K develop with toners of C (cyan), M (magenta), Y (yellow), and K (black), respectively.

  Image forming units 19 </ b> C, 19 </ b> M, 19 </ b> Y, and 19 </ b> K centering around the photoreceptors 10 </ b> C, 10 </ b> M, 10 </ b> Y, and 10 </ b> K are juxtaposed along the transfer conveyance belt 18.

  The transfer conveyance belt 18 is in contact with the photosensitive members 10C, 10M, 10Y, and 10K between the developing members 13C, 13M, 13Y, and 13K and the cleaning members 16C, 16M, 16Y, and 16K. Further, transfer members 15C, 15M, 15Y, 15K) for applying a transfer bias are arranged on the side of the transfer conveyance belt 18 where the photoreceptors 10C, 10M, 10Y, 10K are not installed. The image forming units 19C, 19M, 19Y, and 19K have the same configuration except that the toner colors of the developing members 13C, 13M, 13Y, and 13K are different.

  The image forming operation is performed as follows.

  First, in the image forming units 19C, 19M, 19Y, and 19K, the photoreceptors 10C, 10M, 10Y, and 10K are charged by the charging members 11C, 11M, 11Y, and 11K that rotate in the accompanying direction. Next, 12C, 12M, 12Y, and 12K are irradiated from exposure members disposed outside the photoreceptors 10C, 10M, 10Y, and 10K, and electrostatic latent images are formed on the photoreceptors 10C, 10M, 10Y, and 10K. Is done. Further, the electrostatic latent image is developed by the developing members 13C, 13M, 13Y, and 13K to form a toner image. The toner images of the respective colors formed on the photoconductors 10C, 10M, 10Y, and 10K are superimposed on the transfer conveyance belt 18.

  The transfer paper P is fed from the tray 20 by the paper feed roller 21, temporarily stopped by the pair of registration rollers 22, and then conveyed to the transfer member 23 in synchronization with the toner images superimposed on the transfer conveyance belt 18. The The toner image superimposed on the transfer conveyance belt 18 is transferred to the transfer paper P by an electric field formed from the transfer bias applied to the transfer member 23 and the potential difference between the transfer conveyance belt 18. The toner image transferred to the transfer paper P is conveyed, fixed on the transfer paper P by the fixing member 24, and discharged to a paper discharge unit (not shown). Further, the toner remaining on the photoreceptors 10C, 10M, 10Y, and 10K without being transferred onto the transfer conveyance belt 18 is collected by the cleaning members 16C, 16M, 16Y, and 16K.

  Note that a drum-shaped intermediate transfer member may be used instead of the transfer conveyance belt 18.

  Further, the order in which the image forming units 19C, 19M, 19Y, and 19K are arranged is not particularly limited.

  Furthermore, a mechanism may be provided that stops the image forming units 19C, 19M, and 19Y when a black-only document is created.

  The image forming units 19C, 19M, 19Y, and 19K may be fixedly incorporated in an image forming apparatus such as a copying machine, a facsimile, or a printer, or may be incorporated in the image forming apparatus in the form of a process cartridge. It may be.

  FIG. 5 shows an example of the process cartridge.

  The process cartridge incorporates the photosensitive member 10, has a charging member 11, a developing member 13, a transfer member 15, and a cleaning member 16, and is detachable from the main body of the image forming apparatus.

  Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples. In addition, a part means a mass part.

[Synthesis of Compound (1-33)]
Chemical formula

で表される９、１０−ビス（クロロメチル）アントラセン５ｇ（１８．１７ｍｍｏｌ）、ジベンジルアミン１０．７ｇ（５４．５１ｍｍｏｌ）、炭酸カリウム６．５ｇ（４７．２４ｍｍｏｌ）及びＮ，Ｎ−ジメチルホルムアミド５０ｍＬを、アルゴン気流下、９０℃で８時間撹拌した。次に、エバポレータを用いて濃縮した後、水１５０ｍＬ及びトルエン２００ｍＬを注ぎ、分液した。さらに、有機層を硫酸マグネシウムで乾燥させた後、濃縮し、粗生成物を得た。次に、トルエン／メタノール混合溶媒（体積比７／３）を用いて、粗生成物を晶析し、化学式

9,10-bis (chloromethyl) anthracene represented by the formula: 10.7 g (54.51 mmol) of dibenzylamine, 6.5 g (47.24 mmol) of potassium carbonate and N, N-dimethylformamide 50 mL was stirred at 90 ° C. for 8 hours under an argon stream. Next, after concentration using an evaporator, 150 mL of water and 200 mL of toluene were poured and separated. Furthermore, the organic layer was dried over magnesium sulfate and then concentrated to obtain a crude product. Next, the crude product was crystallized using a toluene / methanol mixed solvent (volume ratio 7/3), and the chemical formula

で表される化合物（１−３３）の黄色結晶５．８８ｇ（９．８５ｍｍｏｌ）を得た（収率５４．２％）。

The yellow crystal 5.88g (9.85mmol) of the compound (1-33) represented by this was obtained (yield 54.2%).

When compound (1-33) was analyzed using LC-MS, a molecular ion ([M] ⁺ ) peak (m / z = 596.92) was observed (see FIG. 6). In addition, Compound (1-33) was identified from the infrared absorption spectrum (KBr method) (see FIG. 7) and ¹ H-NMR spectrum (see FIG. 8).

[Synthesis of Compound (1-36)]
9, 10-bis (chloromethyl) anthracene 5 g (18.17 mmol), ethylbenzylamine 7.37 g (54.51 mmol), potassium carbonate 6.5 g (47.24 mmol) and N, N-dimethylformamide 50 mL The mixture was stirred at 90 ° C. for 7 hours under an air stream. Next, after concentration using an evaporator, 50 mL of water and 200 mL of toluene were poured and separated. Furthermore, the organic layer was dried over magnesium sulfate and then concentrated to obtain a crude product. Next, the crude product was crystallized using a toluene / methanol mixed solvent (volume ratio 7/3), and the chemical formula

で表される化合物（１−３６）の黄色結晶６．６１ｇ（１３．９８ｍｍｏｌ）を得た（収率７７．０％）。

6.61 g (13.98 mmol) of a yellow crystal of the compound (1-36) represented by the formula (yield 77.0%) was obtained.

When compound (1-36) was analyzed using LC-MS, a molecular ion ([M] ⁺ ) peak (m / z = 472.83) was observed (see FIG. 9). In addition, Compound (1-36) was identified from the infrared absorption spectrum (KBr method) (see FIG. 10) and ¹ H-NMR spectrum (see FIG. 11).

[Synthesis of Compound (1-52)]
9,10-bis (chloromethyl) anthracene 5 g (18.17 mmol), piperidine 4.64 g (54.51 mmol), potassium carbonate 6.5 g (47.24 mmol) and N, N-dimethylformamide 50 mL were added under an argon stream. , And stirred at 90 ° C. for 3 hours. Next, after concentrating using an evaporator, 50 mL of water and 200 mL of toluene were poured and liquid-separated at 60 degreeC. Furthermore, the organic layer was dried over magnesium sulfate and then concentrated to obtain a crude product. Next, the crude product was crystallized using a toluene / methanol mixed solvent (volume ratio 7/3), and the chemical formula

で表される化合物（１−５２）の黄色結晶５．２０ｇ（１３．９６ｍｍｏｌ）を得た（収率７６．８％）。

The yellow crystal 5.20g (13.96mmol) of the compound (1-52) represented by this was obtained (yield 76.8%).

When compound (1-52) was analyzed using LC-MS, a molecular ion ([M] ⁺ ) peak (m / z = 373.08) was observed (see FIG. 12). In addition, Compound (1-52) was identified from an infrared absorption spectrum (KBr method) (see FIG. 13) and a ¹ H-NMR spectrum (see FIG. 14).

[Synthesis of Compound (2-2)]
N-4-bromobenzyl-N, N-dibenzylamine 3.00 g (8.19 mmol), piperazine 0.32 g (3.72 mmol), sodium t-butoxide 1.07 g (11.16 mmol), bis (tri- Tert-butylphosphine) palladium (0) 38.0 mg (0.074 mmol) and toluene 20 mL were stirred under reflux for 3 hours under an argon stream, and then cooled to room temperature. Next, the precipitate was filtered, and the filtrate was collected and concentrated. Further, the mixture was purified using silica gel column chromatography (developing solvent: toluene / ethyl acetate mixed solvent (volume ratio 9/1) and concentrated. Next, the toluene / ethanol mixed solvent (volume ratio 7/3) was added. And recrystallized to obtain 1.78 g (2.71 mmol) of white powder of compound (2-2) (yield 72.8%).

When the compound (2-2) was subjected to mass spectrometry (ionization method: APCI), a molecular ion ([M + H] ⁺ ) peak (m / z = 657.8) was observed (see FIG. 15). Moreover, the compound (2-2) was identified from the infrared absorption spectrum (KBr method) (refer FIG. 16).

[Synthesis of Compound (2-3)]
Instead of 3.00 g (8.19 mmol) of N-4-bromobenzyl-N, N-dibenzylamine, 2.49 g (8.19 mmol) of N-4-bromobenzyl-N-benzyl-N-ethylamine was used. In the same manner as in the compound (2-2), 1.76 g (3.30 mmol) of a white powder of the compound (2-3) was obtained (yield: 88.7%).

When the compound (2-3) was subjected to mass spectrometry (ionization method: APCI), a molecular ion ([M + H] ⁺ ) peak (m / z = 533.7) was observed (see FIG. 17). In addition, Compound (2-3) was identified from the infrared absorption spectrum (KBr method) (see FIG. 18).

[Synthesis of Compound (2-6)]
Except for using 2.49 g (8.19 mmol) of N-4-bromobenzyl-N-ethyl-toluidine instead of 3.00 g (8.19 mmol) of N-4-bromobenzyl-N, N-dibenzylamine. Produced 1.83 g (3.43 mmol) of white powder of compound (2-6) in the same manner as compound (2-2) (yield 92.2%).

When the compound (2-6) was subjected to mass spectrometry (ionization method: APCI), a molecular ion ([M + H] ⁺ ) peak (m / z = 533.8) was observed (see FIG. 19). In addition, Compound (2-6) was identified from the infrared absorption spectrum (KBr method) (see FIG. 20).

[Preparation of coating solution for undercoat layer]
12 parts of alkyd resin solution Beckolite M6401-50 (manufactured by Dainippon Ink and Chemicals), 8 parts of superbecamine G-821-60 (manufactured by Dainippon Ink and Chemicals) of melamine resin solution, titanium oxide CR-EL 40 parts (manufactured by Ishihara Sangyo Co., Ltd.) and 200 parts of methyl ethyl ketone were mixed to obtain an undercoat layer coating solution.

[Preparation of coating solution for charge generation layer]
6 parts of Y-type titanyl phthalocyanine, 4 parts of butyral resin BX-1 (manufactured by Sekisui Chemical Co., Ltd.) and 200 parts of 2-butanone (manufactured by Kanto Chemical Co., Ltd.) were mixed to obtain a coating solution for charge generation layer.

  FIG. 18 shows an X-ray diffraction spectrum of Y-type titanyl phthalocyanine. The X-ray diffraction spectrum was measured under the following conditions.

X-ray tube: Cu
Voltage: 50kV
Current: 30mA
Scanning speed: 2 ° / min
Scanning range: 3-40 °
Time constant: 2s
[Preparation of coating solution for charge transport layer]
Panlite TS-2050 (manufactured by Teijin Chemicals Ltd.) of bisphenol A polycarbonate, chemical formula

で表される低分子電荷輸送物質１０部、テトラヒドロフラン８０部及びシリコーンオイルＫＦ５０−１００ＣＳ（信越化学工業社製）０．１部を混合し、電荷輸送層用塗布液を得た。

10 parts of a low molecular charge transport material represented by the formula, 80 parts of tetrahydrofuran and 0.1 part of silicone oil KF50-100CS (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed to obtain a charge transport layer coating solution.

(Example 1-1)
[Preparation of coating solution for protective layer]
Trifunctional radical polymerizable compound KAYARAD TMPTA (trimethylolpropane triacrylate) (manufactured by Nippon Kayaku Co., Ltd.), 10 parts, chemical formula, having no charge transport structure

で表される電荷輸送性構造を有する単官能のラジカル重合性化合物１０部、化合物（１−３３）０．０２部、化合物（３−２）０．５部、光重合開始剤イルガキュア１８４（１−ヒドロキシシクロヘキシルフェニルケトン）（チバ・スペシャルティ・ケミカルズ製）１部、平均一次粒径が０．３μｍのアルミナ粒子ＡＡ−０３（住友化学工業社製）２部、固形分が５０質量％の不飽和ポリカルボン酸ポリマー溶液ＢＹＫ−Ｐ１０４（ＢＹＫケミー社製）０．０８部及びテトラヒドロフラン１００部を混合し、保護層用塗布液を得た。

10 parts of a monofunctional radically polymerizable compound having a charge transporting structure represented by the formula: 0.02 part of the compound (1-33), 0.5 part of the compound (3-2), Irgacure 184 (1 -Hydroxycyclohexyl phenyl ketone) (manufactured by Ciba Specialty Chemicals), 1 part of alumina particles AA-03 (manufactured by Sumitomo Chemical Co., Ltd.) having an average primary particle size of 0.3 μm, and an unsaturated content of 50% by mass 0.08 part of polycarboxylic acid polymer solution BYK-P104 (manufactured by BYK Chemie) and 100 parts of tetrahydrofuran were mixed to obtain a coating solution for a protective layer.

  An undercoating layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution are sequentially dip-coated on an aluminum drum having a wall thickness of 1.5 mm, a length of 380 mm, and an outer diameter of 100 mm, and then dried to obtain a thickness. A subbing layer having a thickness of 3.5 μm, a charge generation layer having a thickness of 0.2 μm, and a charge transporting layer having a thickness of 25 μm were formed.

Next, the coating liquid for protective layers was spray-coated. At this time, PC-WIDE308 (manufactured by Olympus) was used as the spray gun, and the nozzle tip of the spray gun, the undercoat layer, the charge generation layer, and the charge transport layer were sequentially formed at an atomization pressure of 2.1 kgf / cm ^2. The coating solution for the protective layer was applied from a position where the distance between the laminated aluminum drums was 50 mm. The discharge amount was about 3 cc. Furthermore, in a UV irradiation booth substituted with nitrogen gas so that the oxygen concentration becomes 2% or less, a metal halide lamp with an output of 160 W / cm was irradiated with ultraviolet rays under the following conditions, and then 20 ° C. at 130 ° C. The film was dried for 5 minutes to form a protective layer having a thickness of 3.5 μm to obtain a photoreceptor.

Irradiation distance: 120mm
Irradiation intensity: 700 mW / cm ²
Irradiation time: 120s
(Example 1-2)
A photoconductor was obtained in the same manner as in Example 1-1 except that the addition amount of the compound (1-33) was changed to 0.1 part.

(Example 1-3)
A photoconductor was obtained in the same manner as in Example 1-1 except that the addition amount of the compound (1-33) was changed to 0.4 part.

(Example 1-4)
A photoconductor was obtained in the same manner as in Example 1-1 except that the addition amount of the compound (1-33) was changed to 1.6 parts.

(Example 1-5)
A photoconductor was obtained in the same manner as in Example 1-1 except that the addition amount of the compound (1-33) was changed to 3.0 parts.

(Example 1-6)
A photoconductor was obtained in the same manner as in Example 1-3, except that the addition amount of the compound (3-2) was changed to 0.03 part.

(Example 1-7)
A photoconductor was obtained in the same manner as in Example 1-3, except that the addition amount of the compound (3-2) was changed to 0.1 part.

(Example 1-8)
A photoconductor was obtained in the same manner as in Example 1-3, except that the addition amount of the compound (3-2) was changed to 0.8 part.

(Example 1-9)
A photoconductor was obtained in the same manner as in Example 1-3, except that the addition amount of the compound (3-2) was changed to 2.5 parts.

(Example 1-10)
A photoconductor was obtained in the same manner as in Example 1-3, except that the addition amount of the compound (3-2) was changed to 3.5 parts.

(Example 1-11)
A photoconductor was obtained in the same manner as in Example 1-3 except that the compound (1-36) was used instead of the compound (1-33).

(Example 1-12)
A photoconductor was obtained in the same manner as in Example 1-3 except that the compound (1-52) was used instead of the compound (1-33).

(Example 1-13)
A photoconductor was obtained in the same manner as in Example 1-3 except that the compound (3-1) was used instead of the compound (3-2).

(Example 1-14)
A photoconductor was obtained in the same manner as in Example 1-3 except that the compound (3-3) was used instead of the compound (3-2).

(Example 1-15)
A photoconductor was obtained in the same manner as in Example 1-3 except that the compound (3-4) was used instead of the compound (3-2).

(Example 1-16)
A photoconductor was obtained in the same manner as in Example 1-3 except that the compound (4-1) was used instead of the compound (3-2).

(Example 1-17)
A photoconductor was obtained in the same manner as in Example 1-3 except that the compound (4-2) was used instead of the compound (3-2).

(Example 1-18)
A photoconductor was obtained in the same manner as in Example 1-3 except that alumina particles AA-03 (manufactured by Sumitomo Chemical Co., Ltd.) and unsaturated polycarboxylic acid polymer BYK-P104 (manufactured by BYK Chemie) were not added. It was.

(Example 1-19)
Instead of alumina particles AA-03 (manufactured by Sumitomo Chemical Co., Ltd.), fluororesin particles MPE-056 (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) are used, and unsaturated polycarboxylic acid polymer BYK-P104 (manufactured by BYK Chemie) 0 A photoconductor was obtained in the same manner as in Example 1-3, except that 0.2 part of dispersion aid Modiper F210 (manufactured by NOF Corporation) was used instead of 0.04 part.

(Example 1-20)
Example 1 except that the addition amounts of the trifunctional radical polymerizable compound having no charge transporting structure and the monofunctional radical polymerizable compound having the charge transporting structure were changed to 6 parts and 14 parts, respectively. In the same manner as in No. 3, a photoreceptor was obtained.

(Example 1-21)
Example 1 except that the addition amounts of the trifunctional radically polymerizable compound having no charge transporting structure and the monofunctional radically polymerizable compound having the charge transporting structure were changed to 14 parts and 6 parts, respectively. In the same manner as in No. 3, a photoreceptor was obtained.

(Examples 2-1 to 2-10)
A photoconductor was obtained in the same manner as in Examples 1-1 to 1-10, except that the compound (2-2) was used instead of the compound (1-33).

(Example 2-11)
A photoconductor was obtained in the same manner as in Example 1-3 except that the compound (2-3) was used instead of the compound (1-33).

(Example 2-12)
A photoconductor was obtained in the same manner as in Example 1-3 except that the compound (2-6) was used instead of the compound (1-33).

(Examples 2-13 to 2-21)
A photoconductor was obtained in the same manner as in Example 1-13 to 1-21, except that the compound (2-2) was used instead of the compound (1-33).

(Comparative Example 1)
A photoconductor was obtained in the same manner as in Example 1-3 except that the compound (1-33) was not added.

(Comparative Example 2)
A photoconductor was obtained in the same manner as in Example 1-3 except that the compound (3-2) was not added.

(Comparative Example 3)
Instead of compound (3-2), a chemical formula

で表される化合物を用いた以外は、実施例１−３と同様にして、感光体を得た。

A photoconductor was obtained in the same manner as in Example 1-3 except that the compound represented by formula (1) was used.

(Comparative Example 4)
Instead of compound (3-2), a chemical formula

で表される化合物を用いた以外は、実施例１−３と同様にして、感光体を得た。

A photoconductor was obtained in the same manner as in Example 1-3 except that the compound represented by formula (1) was used.

(Comparative Example 5)
Instead of compound (1-33), the chemical formula

で表される化合物を用いた以外は、実施例１−３と同様にして、感光体を得た。

A photoconductor was obtained in the same manner as in Example 1-3 except that the compound represented by formula (1) was used.

(Comparative Example 6)
Instead of compound (1-33), the chemical formula

で表される化合物を用いた以外は、実施例１−３と同様にして、感光体を得た。

A photoconductor was obtained in the same manner as in Example 1-3 except that the compound represented by formula (1) was used.

(Comparative Example 7)
Instead of compound (1-33), the chemical formula

で表される化合物を用いた以外は、実施例１−３と同様にして、感光体を得た。

A photoconductor was obtained in the same manner as in Example 1-3 except that the compound represented by formula (1) was used.

(Comparative Example 8)
Instead of compound (1-33), the chemical formula

で表される化合物を用いた以外は、実施例１−３と同様にして、感光体を得た。

A photoconductor was obtained in the same manner as in Example 1-3 except that the compound represented by formula (1) was used.

(Comparative Example 9)
Instead of compound (1-33), the chemical formula

で表される化合物を用いた以外は、実施例１−３と同様にして、感光体を得た。

A photoconductor was obtained in the same manner as in Example 1-3 except that the compound represented by formula (1) was used.

  Next, the potential increase, density unevenness, and durability of the exposed portion of the photoreceptor were evaluated.

[Exposure potential rise]
In a normal temperature and humidity environment, a photoconductor is mounted on the black station of a remodeled machine of a full-color printer RICOH Pro C901 (manufactured by Ricoh), and an A4-size halftone test chart with a black monochrome image area ratio of 5% After continuous output, 5 solid images were output continuously. At this time, the potentials of the first and fifth exposed portions, that is, the solid image portions when 5 sheets were continuously output were measured, and the potential increase amount of the exposed portions was calculated. In addition, the case where the amount of potential increase in the exposed portion was less than 5V was evaluated as ◎, the case where it was 5V or more and less than 15V as ◯, and the case where it was 15V or more as ×.

[Density unevenness]
In a 15 ° C, 20% RH environment, install a photoconductor on the black station of a remodeled machine of a full-color printer RICOH Pro C901 (manufactured by Ricoh) (equipped with a charger discharged for 200 hours or more in advance). After outputting 20,000 test charts continuously, the power was turned off and left for 24 hours. Next, the power was turned on, and a 1200 dpi 2by2 black single-color full-surface halftone image was output, and the presence or absence of density unevenness corresponding to the width of the charger was evaluated. In addition, the case where density unevenness did not occur was judged as ◎, the case where slight density unevenness occurred, but when acceptable in practice, ○, and when density unevenness occurred remarkably and was unacceptable, judged as x.

[durability]
In a normal temperature and humidity environment, the photoconductor is mounted on the black station of the remodeled machine of the full color printer RICOH Pro C901 (manufactured by Ricoh), and 200,000 continuous black test charts are output. From this, the wear amount of the protective layer was calculated. The case where the wear amount of the protective layer was less than 2.0 μm was evaluated as ◎, the case where it was 2.0 μm or more and less than 4.0 μm was evaluated as ◯, and the case where it was 4.0 μm or more was determined as ×.

  Tables 16 to 18 show the evaluation results of the potential increase, density unevenness, and durability of the exposed portion of the photoreceptor.

表１６〜１８から、実施例１−１〜１−２１、２−１〜２−２１の感光体は、耐久性に優れ、露光部の電位上昇及び濃度ムラの発生を抑制できることがわかる。

From Tables 16-18, it can be seen that the photoconductors of Examples 1-1 to 1-21, 2-1 to 2-21 are excellent in durability, and can suppress the potential increase and density unevenness in the exposed area.

  On the other hand, since the photoreceptor of Comparative Example 1 does not contain the compound represented by the general formula (1) or (2), the potential of the exposed area is increased.

  Since the photoreceptor of Comparative Example 2 does not contain the compound represented by the general formula (3) or (4), density unevenness occurs.

  Since the photoreceptors of Comparative Examples 3 and 4 do not contain the compound represented by the general formula (3) or (4) but contain the compound represented by the chemical formula (A) or (B), the potential increase in the exposed area In addition, density unevenness occurs.

  The photoreceptors of Comparative Examples 5 to 9 do not contain the compound represented by the general formula (1) or (2), and are represented by the chemical formula (C), (D), (E), (F), or (G). As a result, the potential of the exposed area is increased.

DESCRIPTION OF SYMBOLS 1 Conductive support body 2 Single layer type photosensitive layer 3 Protective layer 4 Laminated type photosensitive layer 4a Charge generation layer 4b Charge transport layer 10 Photoconductor

JP 2012-32631 A

Claims (9)

A photosensitive layer and a protective layer are sequentially laminated on the conductive support,
The protective layer includes a tri- or higher functional radical polymerizable compound having no charge transport structure, a radical polymerizable compound having a charge transport structure, and a general formula

(In the formula, R ₁ and R ₂ are each independently an alkyl group optionally substituted by a substituent, an aralkyl group optionally substituted by a substituent, or a monovalent optionally substituted by a substituent. An aliphatic heterocyclic group or a monovalent aromatic group which may be substituted by a substituent, R ₁ and R ₂ may be bonded to each other to form a ring, and n is 1 or more and 3 The following integers.)
Or a compound represented by the general formula

(In the formula, R ₁ and R ₂ are each independently an alkyl group optionally substituted by a substituent, an aralkyl group optionally substituted by a substituent, or a monovalent optionally substituted by a substituent. R ₁ and R ₂ may form a ring together, Ar is a divalent aromatic group optionally substituted by a substituent, and X is a single bond or (It is an alkylene group having 1 to 4 carbon atoms.)
And a compound represented by the general formula

(Wherein R ₃ and R ₄ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y is a vinylene group, an arylene group having 6 to 14 carbon atoms, or 2, 5-thiophenediyl group.)
Or a compound represented by the general formula

(In the formula, Ar ₁ and Ar ₂ are each independently an aryl group having 6 to 14 carbon atoms, Y is an arylene group having 6 to 14 carbon atoms, and R ₃ and R ₄ are And each independently a hydrogen atom or a methyl group.)
A photoconductor formed by curing a composition containing a compound represented by the formula:   In the protective layer, the content of the compound represented by the general formula (1) or the compound represented by the general formula (2) is 0.1% by mass or more and 10% by mass or less. Item 2. The photoreceptor according to Item 1.   The mass ratio of the compound represented by the general formula (3) or the compound represented by the general formula (4) to the radical polymerizable compound having the charge transporting structure is 0.005 or more and 0.3 or less. The photoreceptor according to claim 1, wherein:   4. The photoreceptor according to claim 1, wherein the radical polymerizable compound having a charge transporting structure has an acryloyloxy group.   The photoconductor according to claim 1, wherein the radical polymerizable compound having a charge transporting structure is monofunctional.   6. The mass ratio of the radical polymerizable compound having a charge transport function to a tri- or higher functional radical polymerizable compound having no charge transport function is 0.5 or more and 2.0 or less. The photoconductor according to any one of the above.   The photoconductor according to claim 1, wherein the composition includes inorganic particles and / or organic particles. A photoconductor according to any one of claims 1 to 7,
Charging means for charging the photoreceptor;
Exposure means for exposing the charged photoreceptor to form an electrostatic latent image;
Developing means for developing the electrostatic latent image formed on the photoreceptor using toner to form a toner image;
An image forming apparatus comprising transfer means for transferring a toner image formed on the photoreceptor to a recording medium.   A process cartridge comprising the photosensitive member according to claim 1.

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