JP2013029779A - Image holding body for image forming apparatus, process cartridge, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image holding body for an image forming apparatus having a low variation in residual potential due to repeated usage.SOLUTION: The image holding body for an image forming apparatus comprises a supporting body and a photosensitive layer containing a compound represented by the following general formula (I) on the supporting body.

Description

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

  A photoreceptor having a photosensitive layer containing an organic photoconductive compound as a main component is compared with a photoreceptor containing an inorganic photoconductor (such as selenium, zinc oxide, cadmium sulfide or silicon), which has been conventionally used, as a main component. Therefore, it has been actively researched with many advantages such as being relatively easy to manufacture, inexpensive, easy to handle, and excellent thermal stability.

  In particular, the charge generation function and the charge transport function of the photoconductor are assigned to separate functional layers, the former material having the generation function is used as the charge generation layer, and the latter material having the transport function is used as the charge transport layer. A photoreceptor having a laminated type function separation type photosensitive layer to be contained has already been put into practical use.

  Among these, tetraarylbenzidine compounds have been actively studied as photoconductive compounds because of their high charge mobility (see, for example, Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5). .

U.S. Pat. No. 4,047,948 US Pat. No. 4,299,897 Japanese Patent Laid-Open No. 61-132955 Japanese Patent Laid-Open No. 62-26749 JP-A-3-138654

  An object of the present invention is to provide an image carrier for an image forming apparatus in which a change in residual potential due to repeated use is low as compared with the invention described in Patent Document 1.

The above problem is solved by the following means. That is,
The invention according to claim 1
An image carrier for an image forming apparatus, comprising: a support; and a photosensitive layer containing a compound represented by the following general formula (I) on the support.

In general formula (I), each R ¹ independently represents a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms, and Ar represents a substituted or unsubstituted phenyl group, substituted or unsubstituted Monovalent polynuclear aromatic hydrocarbon group having 2 to 10 unsubstituted aromatic rings, substituted or unsubstituted monovalent condensed aromatic hydrocarbon group having 2 to 10 aromatic rings, or substituted or unsubstituted Represents a monovalent aromatic heterocyclic group, and each n independently represents 0 or more and 7 or less.

The invention according to claim 2
An image carrier for an image forming apparatus, comprising: a support; and a photosensitive layer containing a compound represented by the following general formula (II-1) on the support.

In General Formula (II-1), each Y ¹ independently represents a substituted or unsubstituted divalent hydrocarbon group, A ¹ represents a group represented by the following General Formula (II-2), R ² is independently a hydrogen atom, a monovalent polynuclear aromatic hydrocarbon group having 2 or more and 10 or less substituted or unsubstituted aromatic rings, or a monovalent condensation having 2 or more and 10 or less substituted or unsubstituted aromatic rings. Aromatic hydrocarbon group, substituted or unsubstituted monovalent linear hydrocarbon group having 1 to 6 carbon atoms, or substituted or unsubstituted monovalent branched hydrocarbon group having 2 to 10 carbon atoms Represents. Each m independently represents an integer of 1 to 5, and p represents an integer of 5 to 5,000.

  In general formula (II-2), Ar represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon group having 2 to 10 aromatic rings, and a substituted or unsubstituted aromatic ring number. It represents a monovalent condensed aromatic hydrocarbon group of 2 or more and 10 or less, or a substituted or unsubstituted monovalent aromatic heterocyclic group, and n independently represents 0 or more and 7 or less.

The invention according to claim 3
An image holding body for an image forming apparatus according to claim 1 or 2, a charging unit for charging the image holding body for an image forming apparatus, and exposing the charged image holding body for an image forming apparatus to electrostatic An exposure unit that forms a latent image, a developing unit that develops the electrostatic latent image to form a toner image, a transfer unit that transfers the toner image to a transfer target, and the image carrier for the image forming apparatus are cleaned. A process cartridge having at least one selected from cleaning means.

The invention according to claim 4
An image holding member for an image forming apparatus according to claim 1, a charging means for charging the image holding member for an image forming apparatus, and the charged image holding member for an image forming apparatus are exposed and statically exposed. An image forming apparatus comprising: an exposure unit that forms an electrostatic latent image; a developing unit that develops the electrostatic latent image to form a toner image; and a transfer unit that transfers the toner image to a transfer target.

According to the first aspect of the present invention, there is provided an image carrier for an image forming apparatus in which the variation of the residual potential due to repeated use is lower than that of the invention described in Patent Document 1.
According to the second aspect of the present invention, there is provided an image carrier for an image forming apparatus in which the variation of the residual potential due to repeated use is lower than that of the invention described in Patent Document 1.
According to the third aspect of the present invention, there is provided a process cartridge that is excellent in fine line reproducibility by repeated use when used in an image forming apparatus as compared with the invention described in Patent Document 1.
According to the invention of claim 4, an image forming apparatus is provided that is superior in thin line reproducibility by repeated use as compared with the invention described in Patent Document 1.

1 is a schematic cross-sectional view of an image carrier for an image forming apparatus according to a first embodiment. FIG. 6 is a schematic cross-sectional view of an image carrier for an image forming apparatus according to a second embodiment. It is a schematic cross section of an image carrier for an image forming apparatus according to a third embodiment. 1 is a schematic configuration diagram of an image forming apparatus according to an embodiment. It is a schematic block diagram of the process cartridge which concerns on embodiment.

Hereinafter, preferred embodiments of the present invention will be described.
In this embodiment, an image carrier for an image forming apparatus is provided by using at least one of a compound represented by the following general formula (I) and a compound represented by the following general formula (II-1) as a charge transport material. Is done. That is, an image carrier for an image forming apparatus in which a photosensitive layer is formed on a support (for example, a conductive support), the photosensitive layer comprising a compound represented by the following general formula (I) and the following general formula (II): -1) at least one of the compounds shown.
The conductive support in the present embodiment has a surface volume resistivity of less than 10 ⁷ Ω · cm, measured based on JIS K 7194 “Resistivity Test Method by Conductive Plastic 4-Probe Method”. Refers to the support. That is, the conductive support may be a support formed of a conductive material having a volume resistivity measured based on the above method of less than 10 ⁷ Ω · cm. The support body which has the formed conductive layer may be sufficient.

  The photosensitive layer in the image carrier for the image forming apparatus is a single layer type photosensitive layer containing the charge generating material and the charge transporting material in the same layer, or a layer containing the charge generating material and a layer containing the charge transporting material are adjacent to each other. Any of the function-separated photosensitive layers provided separately, and contains at least one of a compound represented by the following general formula (I) and a compound represented by the following general formula (II-1) as a charge transport material. It is something to be made.

  As the charge generation material, a known charge generation material such as oxytitanium phthalocyanine, chlorogallium phthalocyanine, or hydroxygallium phthalocyanine can be used. The image carrier for an image forming apparatus may be provided with a protective layer on the outermost surface (position farthest from the conductive support). In this case, the protective layer has a charge transport property. It preferably comprises a crosslinkable silicone resin.

(Image carrier for image forming apparatus)
The image carrier for an image forming apparatus according to the exemplary embodiment includes, on a support, a photosensitive layer containing at least one of a compound represented by the following general formula (I) and a compound represented by the following general formula (II-1). Is an image holding body for an image forming apparatus.

<Compound represented by formula (I)>
Hereinafter, the compound represented by the following general formula (I) will be described in detail.

In general formula (I), each R ¹ independently represents a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms, and Ar represents a substituted or unsubstituted phenyl group, substituted or unsubstituted Monovalent polynuclear aromatic hydrocarbon group having 2 to 10 unsubstituted aromatic rings, substituted or unsubstituted monovalent condensed aromatic hydrocarbon group having 2 to 10 aromatic rings, or substituted or unsubstituted Represents a monovalent aromatic heterocyclic group, and each n independently represents 0 or more and 7 or less.

R ¹ in the general formula (I) will be described.
As described above, R ¹ in general formula (I) each independently represents a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms.
The alkyl groups represented by R ¹ each independently preferably have 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.
The alkyl group represented by R ¹ is linear or branched, and is preferably a linear alkyl group from the viewpoint of maintaining crystallinity and solubility.

In the general formula (I), when the alkyl group represented by R ¹ has a substituent, examples of the substituent include an aryl group and a heterocyclic group.
The aryl group as the substituent preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group, a toluyl group, and a naphthyl group.
The heterocyclic group as the substituent represents a group having a ring containing an element other than carbon and hydrogen (that is, a heterocyclic ring). The number of atoms (Nr) constituting the ring skeleton of the heterocyclic ring is preferably 5 or 6. The type and number of atoms (heterogeneous atoms) other than carbon atoms constituting the ring skeleton are not particularly limited, and for example, a sulfur atom, a nitrogen atom, an oxygen atom, a selenium atom, a silicon, a phosphorus atom, and the like are preferably used. The skeleton may contain two or more kinds of heteroatoms, and may contain two or more kinds of heteroatoms.

Examples of the 5-membered heterocyclic ring include thiophene, pyrrole, furan, imidazole, oxazole, selenophene, thiazole, thiadiazole, pyrazole, isoxazole, isothiazole, silole, or the 3rd and 4th carbons of the above compound with nitrogen. A substituted heterocycle is preferably used. Other examples of the aromatic heterocycle having a 5-membered heterocycle include benzothiophene, benzimidazole, and indole.
As the 6-membered heterocyclic ring, pyridine, pyrimidine, pyrazine, and piperazine are preferably used.

  The heterocyclic group as the substituent includes those in which the heterocyclic ring is substituted with an aromatic ring, and those in which the aromatic ring is substituted with a heterocyclic ring.

Specific examples of the alkyl group represented by R ¹ in the general formula (I) include a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, an n-hexyl group, and an n-octyl group. A methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, an n-hexyl group, or an n-octyl group, preferably a methyl group or a butyl group, Group or butyl group is more preferable from the viewpoint of ease of production and maintaining crystallinity, and methyl group is more preferable from the viewpoint of availability.

R ¹ is a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms. Within this range, there is little influence on the ionization potential and charge transportability due to the difference in the type of the alkyl group. .
Further, a plurality of R ¹ present in the general formula (I) may be the same or different, but are preferably the same from the viewpoint of production.

Ar in the general formula (I) will be described.
In general formula (I), Ar represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon group having 2 to 10 aromatic rings, and a substituted or unsubstituted aromatic ring number of 2. It represents a monovalent condensed aromatic hydrocarbon group of 10 or less or a substituted or unsubstituted monovalent aromatic heterocyclic group.

  Here, the “polynuclear aromatic hydrocarbon group” and the “condensed aromatic hydrocarbon group” are groups in which two or more rings selected from the group consisting of an aromatic ring composed of carbon and hydrogen and a heterocyclic ring described later are present. Yes, specifically:

The “polynuclear aromatic hydrocarbon group” means that there are two or more rings selected from the group consisting of an aromatic ring composed of carbon and hydrogen and a heterocyclic ring described later, and the rings are bonded by a carbon-carbon bond. Represents a hydrocarbon group. Specifically, a hydrocarbon group in which carbons constituting an aromatic ring are directly bonded by a carbon-carbon bond, or aromatic rings are connected by a carbon chain having 1 to 18 carbon atoms (an alkyl chain or an alkylene chain). The hydrocarbon group etc. which are made are mentioned.
Specific examples of the polynuclear aromatic hydrocarbon group include biphenyl, terphenyl, stilbene, and triphenylethylene. The “polynuclear aromatic hydrocarbon group” is a substituent composed of a polynuclear aromatic hydrocarbon group, and examples thereof include a substituent composed of biphenyl, that is, a biphenylene group.
The ring constituting the polynuclear aromatic hydrocarbon group may be a condensed aromatic hydrocarbon group described later or an aromatic heterocycle. Specific examples of the condensed aromatic hydrocarbon group and the aromatic heterocyclic ring constituting the polynuclear aromatic hydrocarbon group include the same compounds as the specific examples described later.

  In addition, the “condensed aromatic hydrocarbon group” includes two or more rings selected from the group consisting of an aromatic ring composed of carbon and hydrogen and a heterocyclic ring described later, and these rings are adjacently bonded. Represents a hydrocarbon group sharing a pair of carbon atoms. Specific examples include naphthalene, anthracene, phenanthrene, pyrene, perylene, and fluorene. The “condensed aromatic hydrocarbon group” is a substituent composed of a condensed aromatic hydrocarbon group, and examples thereof include a substituent composed of naphthalene, that is, a naphthyl group.

The “aromatic heterocycle” represents an aromatic ring containing an element other than carbon and hydrogen. The aromatic heterocyclic group is a substituent composed of an aromatic heterocyclic ring.
Examples of the number of atoms (Nr) constituting the ring skeleton of the aromatic heterocyclic ring include Nr = 5 or Nr = 6. Further, the type and number of atoms (heterogeneous atoms) other than carbon atoms constituting the ring skeleton are not limited. Examples of the hetero atom include a sulfur atom, a nitrogen atom, an oxygen atom, a selenium atom, a silicon atom, and a phosphorus atom. In addition, the aromatic heterocycle may contain two or more heteroatoms in the ring skeleton, and may contain two or more heteroatoms.

In particular, as a heterocyclic ring having a ring skeleton structure of Nr = 5 (that is, a 5-membered ring structure), for example, thiophene, thiofin, pyrrole, furan, imidazole, oxazole, selenophene, thiazole, thiadiazole, pyrazole, isoxazole, isothiazole , Silole, or a heterocyclic ring obtained by further substituting the 3- and 4-position carbons with nitrogen. Examples of the heterocyclic ring having a 5-membered ring structure include benzothiophene, benzimidazole, indole and the like in addition to the above.
Examples of the heterocyclic ring having a ring skeleton structure of Nr = 6 (that is, a 6-membered ring structure) include pyridine, pyrimidine, pyrazine, piperazine and the like.

Examples of the substituent for substituting the phenyl group, polynuclear aromatic hydrocarbon group, condensed aromatic hydrocarbon group, or aromatic heterocyclic group include a hydrogen atom, an alkyl group, an alkoxy group, a phenoxy group, an aryl group, and an aralkyl. A group, a substituted amino group, a halogen atom, and the like. Among them, for example, a hydrogen atom, an alkyl group, an alkoxy group, and the like can be given.
As said alkyl group, a C1-C10 thing is mentioned, for example, Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group etc. are mentioned, for example.
Examples of the alkoxy group include those having 1 to 10 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
As said aryl group, a C6-C20 thing is mentioned, for example, Specifically, a phenyl group, a toluyl group, etc. are mentioned, for example.
Examples of the aralkyl group include those having 7 to 20 carbon atoms, and specific examples include a benzyl group and a phenethyl group.
Examples of the substituent of the substituted amino group include an alkyl group, an aryl group, and an aralkyl group, and specific examples of the alkyl group, the aryl group, and the aralkyl group are as described above. Specific examples of the substituted amino group include a diphenylamino group.

Among the above, Ar in the general formula (I) is preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted polynuclear aromatic hydrocarbon group from the viewpoint of mobility and ease of handling. Or a substituted or unsubstituted polynuclear aromatic hydrocarbon group not containing an unsubstituted phenyl group or a condensed aromatic hydrocarbon group and an aromatic heterocycle, and a carbon constituting the substituted or unsubstituted phenyl group or aromatic ring. A substituted or unsubstituted polynuclear aromatic hydrocarbon group in which they are directly bonded by a carbon-carbon bond is more preferable.
The number of aromatic rings in Ar in the general formula (I) is preferably 1 or more and 6 or less, more preferably 1 or more and 3 or less, and more preferably 1 or 2 from the viewpoint of compatibility with the resin and ease of synthesis. Further preferred. That is, as Ar in the general formula (I), a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group is more preferable. A substituted biphenyl group or an unsubstituted terphenyl group is more preferred.

N in the general formula (I) will be described.
N in general formula (I) is 0 or more and 7 or less each independently. The two n's in general formula (I) may be the same or different, but are preferably the same from the viewpoint of production. N in the general formula (I) is preferably small from the viewpoint of charge transport properties, but if n is too small, the charge mobility is lowered due to the influence of the dipole moment of the carbonyl group, and is preferably 1 or more and 3 or less. 1 is most preferred.

  Since the compound represented by the general formula (I) has a dibenzothiophene dioxide skeleton, it is considered that the compound has good charge transportability and good compatibility with the resin.

Hereinafter, specific compounds 1 to 30 of the dibenzothiophene dioxide compound represented by the general formula (I) (compounds of specific compound number 1 to specific compound number 30 in the following table) are shown below, but are not limited thereto. Is not to be done.
Note that R ¹ , Ar, and n in the specific examples 1 to 30 mean R ¹ , Ar, and n in the general formula (I).

<Method for producing compound represented by formula (I)>
Hereafter, the manufacturing method of the compound shown by general formula (I) is demonstrated concretely.
In the present embodiment, for example, a coupling reaction of a halogen compound represented by the following general formula (III) and an acetamide compound represented by the following general formula (IV) with a copper catalyst is performed, or the following general formula (V): A diarylamine represented by the following general formula (VII) is obtained by performing a coupling reaction of the acetamide compound represented by the formula and the halogen compound represented by the following general formula (VI) with a copper catalyst.

  Next, a diarylamine represented by the following general formula (VII) and a dihalogen compound represented by the following general formula (VIII) are subjected to a coupling reaction with a copper catalyst, whereby the dibenzothiophene oxide compound represented by the general formula (I) is obtained. can get.

In the general formula (III), ^{R 1} is the same as ^{R 1} in the general formula (I), G represents a chlorine atom, a bromine atom, or iodine atom. In general formula (IV), Ar is the same as Ar in general formula (I), and Ac represents an acetyl group.

In the general formulas (V) and (VI), R ¹ , Ac, Ar, and G are the same as described above.

In general formula (VII), Ar and R ¹ are the same as described above.

  In general formula (VIII), G is the same as described above.

In the above coupling reaction, for example, 1.0 equivalent or more of the halogen compound represented by the general formula (III) or (VI) is added to 1 equivalent of the acetamide compound represented by the general formula (IV) or (V). It is used in an equivalent amount or less, preferably 1.0 equivalent or more and 1.2 equivalent or less.
Examples of the copper catalyst used in the coupling reaction include copper powder, cuprous oxide, copper sulfate, and the like. Moreover, the said copper catalyst is 0.001 mass part or more and 3 mass parts or less with respect to 1 mass part of acetamide compounds shown by general formula (IV) or (V), Preferably it is 0.01 mass part or more and 2 mass parts Used in the following.

  In the coupling reaction, a base is used. Specific examples of the base to be used include potassium phosphate, sodium carbonate, potassium carbonate and the like. The base is used in an amount of, for example, 0.5 equivalents or more and 3 equivalents or less, preferably 0.7 equivalents or more and 2 equivalents or less, with respect to 1 equivalent of the acetamide compound represented by the general formula (IV) or (V).

  In the coupling reaction, a solvent may be used or a solvent may not be used. When a solvent is used, examples of the solvent used include high-boiling water-insoluble hydrocarbon solvents such as n-tridecane, tetralin, p-cymene and terpinolene, and high-boiling halogens such as o-dichlorobenzene and chlorobenzene. System solvents and the like. The solvent is, for example, from 0.1 parts by weight to 3 parts by weight, and preferably from 0.2 parts by weight to 2 parts by weight with respect to 1 part by weight of the acetamide compound represented by the general formula (IV) or (V). Used in range.

  In addition, the above reaction is efficiently performed in a temperature range of, for example, 100 ° C. or higher and 300 ° C. or lower, preferably 150 or higher and 270 ° C. or lower, more preferably 180 ° C. or higher and 230 ° C. or lower, in an inert gas atmosphere such as nitrogen or argon. It is preferable to carry out the reaction while stirring and further to remove water generated during the reaction.

After completion of the reaction, the reaction mixture is cooled as necessary, and then added with a solvent such as methanol, ethanol, n-octanol, ethylene glycol, propylene glycol, or glycerin, and a base such as sodium hydroxide or potassium hydroxide. Disassemble.
The amount of the solvent used in the hydrolysis is, for example, 0.5 parts by mass or more and 10 parts by mass or less, preferably 1 part by mass or more and 5 parts by mass with respect to 1 part by mass of the acetamide compound represented by the general formula (IV) or (V). The mass part or less is mentioned. Moreover, the usage-amount of the base in the said hydrolysis is 0.2 mass part or more and 5 mass parts or less with respect to 1 mass part of acetamide compounds shown by general formula (IV) or (V), Preferably it is 0.3 mass. Part or more and 3 parts by weight or less.

In addition, the hydrolysis reaction is performed, for example, after the coupling reaction is performed, the solvent and the base are directly added to the reaction solution, and used at 50 ° C. or higher in an inert gas atmosphere such as nitrogen or argon. It is carried out with stirring in a temperature range below the boiling point of the solvent.
In this case, since a carboxylate is generated and solidified by a coupling reaction, for example, a solvent having a boiling point of 150 ° C. or higher is used as a solvent in order to increase the reaction temperature.

  After completion of the hydrolysis reaction, the reaction product is poured into water and further neutralized with hydrochloric acid or the like to liberate the diarylamine compound represented by the general formula (VII). In the post-treatment of this hydrolysis reaction, in order to liberate the diarylamine compound represented by the general formula (VII) by pouring into water and then neutralizing with hydrochloric acid or the like, for example, water-soluble ethylene glycol, It is particularly preferable to add propylene glycol or glycerin.

  After the diarylamine compound represented by the general formula (VII) is liberated, it is then washed and, if necessary, dissolved in a solvent, followed by purification with silica gel, alumina, activated clay, activated carbon, column or the like. Alternatively, a treatment such as adding these adsorbents to the solution to adsorb unnecessary components is performed. Further, the recrystallization may be performed by recrystallization from a solvent such as acetone, ethanol, ethyl acetate, and toluene, or the same recrystallization operation may be performed after esterification to an alkyl ester such as methyl ester or ethyl ester. .

  Next, the diarylamine compound represented by the general formula (VII) obtained above and the dihalogen compound represented by the general formula (VIII) are subjected to a coupling reaction with a copper catalyst, and a methyl ester or an ethyl ester, if necessary. The compound represented by the general formula (I) is obtained by esterification into an alkyl ester of

  In the coupling reaction of the diarylamine compound represented by the general formula (VII) and the dihalogen compound represented by the general formula (VIII), for example, 1 equivalent per 1 equivalent of the diarylamine compound represented by the general formula (VII) A dihalogen compound represented by the general formula (VIII) is used in an amount of 0.5 to 5 equivalents, preferably 1.7 to 4 equivalents.

  Examples of the copper catalyst used in the coupling reaction include copper powder, cuprous oxide, copper sulfate, and the like. The copper catalyst is used in an amount of 0.001 to 3 parts by weight, preferably 0.01 to 2 parts by weight, based on 1 part by weight of the diarylamine compound represented by the general formula (VII). It is done.

  In the coupling reaction, a base is used, and specific examples of the base to be used include potassium phosphate, sodium carbonate, potassium carbonate and the like. The base is used in an amount of, for example, 1 equivalent to 6 equivalents, preferably 1.4 equivalents to 4 equivalents, relative to 1 equivalent of the diarylamine compound represented by the general formula (VII).

  In the coupling reaction, a solvent is used as necessary. Examples of the solvent used include high-boiling water-insoluble hydrocarbon solvents such as n-tridecane, tetralin, p-cymene, and terpinolene, and o -High-boiling halogen solvents such as dichlorobenzene and chlorobenzene. The solvent is used in a range of, for example, 0.1 parts by mass to 3 parts by mass, preferably 0.2 parts by mass to 2 parts by mass with respect to 1 part by mass of the diarylamine compound represented by the general formula (VII). Is done.

  In addition, the above reaction is efficiently performed in a temperature range of, for example, 100 ° C. or more and 300 ° C. or less, preferably 150 or more and 270 ° C. or less, more preferably 180 ° C. or more and 250 ° C. or less in an inert gas atmosphere such as nitrogen or argon. It is preferable to carry out the reaction while stirring and further to remove water generated during the reaction.

  After completion of the reaction, for example, the reaction product is dissolved in a solvent such as toluene, isopar, or n-tridecane, and unnecessary substances are removed by washing with water or filtration as necessary. Further, silica gel, alumina, activated clay is further removed. Alternatively, column purification is performed with activated carbon or the like, or these adsorbents are added to the solution, and unnecessary portions are adsorbed. Furthermore, for example, purification may be performed by recrystallization from a solvent such as ethanol, ethyl acetate, or toluene.

  Further, the compound represented by the general formula (I) may be synthesized in an amination reaction using a palladium catalyst. That is, as a synthesis method of the compound represented by the general formula (I), for example, a diarylamine compound represented by the general formula (VII) and a dihalogen compound represented by the general formula (VIII) are converted into tertiary phosphines, A method of synthesis by reacting in the presence of a palladium compound and a base is also included.

  The amount of the diarylamine represented by the general formula (VII) in the amination reaction using the palladium catalyst is, for example, 0.1 mol in terms of molar ratio with respect to 1 part by mass of the dihalogen compound represented by the general formula (VIII). The range is 5 parts by mass or more and 4.0 parts by mass or less, and more preferably 0.8 part by mass or more and 2.0 parts by mass or less.

The tertiary phosphines are not particularly limited, and examples thereof include triphenylphosphine, tri (tertiary-butyl) phosphine, tri (p-tolylphosphine), tri (m-tolylphosphine), triisobutylphosphine, Tertiary alkyl phosphines such as tricyclohexylphosphine and triisopropylphosphine can be mentioned, and tri (tertiary-butyl) phosphine is preferable.
Although the usage-amount of the said tertiary phosphine is not specifically limited, For example, 0.5 times mole or more and 10 times mole or less are mentioned with respect to a palladium compound, More preferably, it is 2.0 times with respect to a palladium compound. It is the range of more than mol and less than 8.0 times mol.

The palladium compound is not particularly limited. For example, a divalent palladium compound such as palladium acetate (II), palladium chloride (II), palladium bromide (II), palladium trifluoroacetate (II), etc. , Zero-valent palladium compounds such as tris (dibenzylideneacetone) dipalladium (0), (dibenzylideneacetone) dipalladium (0), tetrakis (triphenylphosphine) palladium (0), palladium-carbon and the like. Particularly preferred are palladium acetate and trisdibenzylideneacetone dipalladium (0).
Although the usage-amount of the said palladium compound is not specifically limited, For example, 0.001 mol% or more and 10 mol% or less are mentioned in conversion of palladium with respect to the dihalogen compound shown by general formula (VIII). Preferably, it is 0.01 mol% or more and 5.0 mol% or less in terms of palladium.

The base is not particularly limited, and examples thereof include potassium carbonate, rubidium carbonate, cesium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, tertiary-butoxy potassium, tertiary-butoxy sodium, sodium. A metal, potassium metal, potassium hydride etc. are mentioned, Preferably it is a rubidium carbonate and a tertiary-butoxy sodium.
The amount of the base used is, for example, in the range of 0.5 or more and 4.0 or less, more preferably 1.0 or more and 2.5 or less with respect to the dihalogen compound represented by the general formula (VIII). It is a range.

  The amination reaction is performed, for example, in an inert solvent. The solvent used may be any solvent that does not significantly inhibit this reaction, for example, an aromatic hydrocarbon solvent such as benzene, toluene, xylene and mesitylene, an ether solvent such as diethyl ether, tetrahydrofuran and dioxane, Acetonitrile, dimethylformamide, dimethyl sulfoxide and the like can be mentioned. Of these, more preferred are aromatic hydrocarbon solvents such as toluene and xylene.

  The amination reaction is performed, for example, under normal pressure (atmospheric pressure) or an inert gas atmosphere such as nitrogen or argon, but may be performed under pressurized conditions. As reaction temperature, the range of 20 to 300 degreeC is mentioned, for example, More preferably, it is the range of 50 to 180 degreeC. Although reaction time changes with reaction conditions, what is necessary is just to select from the range of several minutes (specifically 5 minutes) or more and 20 hours or less, for example.

After the amination reaction, for example, the reaction solution is poured into water and stirred. If the reaction product is a crystal, the crude product is obtained by filtration through suction filtration. If the reaction product is an oily product, a crude product can be obtained by extraction with a solvent such as ethyl acetate or toluene. The composition organism thus obtained is subjected to treatment such as column purification with, for example, silica gel, alumina, activated clay, activated carbon, or the like, or these adsorbents are added to the solution to adsorb unnecessary components. Further, when the reaction product is a crystal, it is purified by recrystallization from a solvent such as hexane, methanol, acetone, ethanol, ethyl acetate, or toluene.
However, the synthesis method in the present embodiment is not limited to these.

<Compound containing a structural unit represented by the general formula (II-3) (polyester)>
Hereinafter, the compound containing the structural unit represented by the following general formula (II-3) will be described in detail.
In this embodiment, a polyester represented by the following general formula (II-1) is used as a compound containing a structural unit represented by the following general formula (II-3).

In General Formula (II-3), Y ¹ each independently represents a substituted or unsubstituted divalent hydrocarbon group, m represents an integer of 1 to 5, and A ¹ represents General Formula (II) below. -2) is represented.

  In general formula (II-2), Ar represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon group having 2 to 10 aromatic rings, and a substituted or unsubstituted aromatic ring number. It represents a monovalent condensed aromatic hydrocarbon group of 2 or more and 10 or less, or a substituted or unsubstituted monovalent aromatic heterocyclic group, and n independently represents 0 or more and 7 or less.

The polyester containing the structural unit represented by the general formula (II-3) includes the structural unit A ¹ derived from the benzobisthiazole compound represented by the general formula (I). Further, since the polyester containing the structural unit represented by the general formula (II-3) is a polymer, such as N, N′-diphenyl-N, N′-di (m-tolyl) benzidine which is a low molecular compound. Higher heat resistance than charge transport materials.
Therefore, the polyester containing the structural unit represented by the general formula (II-3) is suitable for use in an image carrier for an image forming apparatus.
Furthermore, a polymer including the structural unit A ¹ derived from the compound represented by the general formula (I) is synthesized by converting the polymer including the structural unit represented by the general formula (II-3) into an ester structure. Easy to manufacture.

Hereinafter, Formula (II-3) will be described in detail.
In General Formula (II-3), Y ¹ each independently represents a substituted or unsubstituted divalent hydrocarbon group.
The divalent hydrocarbon group represented by Y ¹ is a divalent alcohol residue, and is an alkylene group, (poly) ethyleneoxy group, (poly) propyleneoxy group, arylene group, divalent heterocyclic group or A combination of these is preferred.

The divalent hydrocarbon group represented by Y ¹ is preferably a linking group having a small number of carbon atoms from the viewpoint of compatibility with the resin and charge transportability. Specifically, a range of 1 to 18 carbon atoms is preferable, and a range of 1 to 6 carbon atoms is more preferable.
The divalent hydrocarbon group represented by Y ¹ is preferably a linking group having a small dipole moment from the viewpoint of charge transportability. Specifically, a linking group containing no atoms other than carbon atoms and hydrogen atoms (for example, oxygen atom, nitrogen atom, sulfur atom, etc.) is preferable.
That is, the divalent hydrocarbon group represented by Y ¹ is preferably an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 18 carbon atoms, and an alkylene group having 1 to 6 carbon atoms. More preferred.
Further, the divalent hydrocarbon group represented by Y ¹ is more preferably a group having a small steric bulk from the viewpoint of compatibility with the resin. Examples of the divalent hydrocarbon group having a small steric bulk height include groups having no ring structure, and specific examples include alkylene groups having 1 to 10 carbon atoms. 1 or more and 5 or less alkylene group is still more preferable. In addition to the compatibility with the resin, an alkylene group having 2 carbon atoms is most preferable from the viewpoint of easy synthesis of a polymer compound having a large molecular weight.

Specific examples of Y ¹ in the general formula (II-3) include groups selected from the following formulas (1) to (8).

In formulas (1) and (2), d and e each independently represent an integer of 1 or more and 10 or less.
In formulas (5) and (6), R ⁴ and R ⁵ are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, substituted Alternatively, it represents an unsubstituted aralkyl group or a halogen atom.
In formulas (5) and (6), f and g each represent an integer of 0, 1, or 2, h and i each represent 0 or 1, and V is selected from the following formulas (9) to (29) Represents a group.

In formula (9), b represents an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4.
In formula (15), each R ⁶ independently represents a hydrogen atom, an alkyl group, or a cyano group.
In formulas (26) and (29), R ⁷ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted group Alternatively, it represents an unsubstituted aralkyl group or a halogen atom.
In formulas (15), (16), and (25) to (29), each c independently represents an integer of 0 or more and 10 or less, preferably 0 or more and 6 or less, more preferably 1 or more. Represents an integer of 3 or less.

A plurality of Y ¹ present in the compound containing the structural unit represented by formula (II-3) may be the same or different, but are preferably the same from the viewpoint of production.

  In general formula (II-3), m represents an integer of 1 or more and 5 or less. M is preferably an integer of 1 or more and 3 or less, and more preferably an integer of 1 or more and 2 or less from the viewpoint of achieving high molecular weight. Further, from the viewpoint of improving the electrical characteristics of the image carrier for an image forming apparatus, m is most preferably 1 in the general formula (II-3).

In General Formula (II-3), A ¹ represents a group represented by the following General Formula (II-2).

  In general formula (II-2), Ar represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon group having 2 to 10 aromatic rings, and a substituted or unsubstituted aromatic ring number. It represents a monovalent condensed aromatic hydrocarbon group of 2 or more and 10 or less, or a substituted or unsubstituted monovalent aromatic heterocyclic group, and n independently represents 0 or more and 7 or less.

Ar and n in the general formula (II-2) have the same meanings as Ar and n in the general formula (I), respectively, and preferred ranges thereof are also the same.
A plurality of A ¹ present in the compound containing the structural unit represented by the general formula (II-3) may all be the same or two or more types may be included.

Examples of the polyester including the structural unit represented by the general formula (II-3) include a polyester represented by the following general formula (II-1) and a polyester represented by the following general formula (II-4). . Since both of them contain the structural unit A ¹ derived from the general formula (I) (that is, the group represented by the general formula (II-2)), the charge transportability is good and the compatibility with the resin is also good. And suitable for an image carrier for an image forming apparatus.

The polyester represented by the following general formula (II-1) has A ¹ as a carboxylic acid residue, and in the polyester represented by the following general formula (II-4), A ¹ and Z ¹ are carboxylic acid. As a residue. Thus, polyester represented by the following general formula (II-1) is excellent in terms of ease of synthesis, polyester represented by the following Formula (II-4), further images by carboxylic acid residues Z ¹ combined It can be suitable for an image carrier for a forming apparatus.

In General Formula (II-1), each Y ¹ independently represents a substituted or unsubstituted divalent hydrocarbon group, A ¹ represents a group represented by General Formula (II-2), and R 1 ² is independently a monovalent polynuclear aromatic hydrocarbon group having a substituted or unsubstituted aromatic ring number of 2 to 10, and a monovalent condensed aromatic carbon group having a substituted or unsubstituted aromatic ring number of 2 to 10. A hydrogen group, a substituted or unsubstituted monovalent linear hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted monovalent branched hydrocarbon group having 2 to 10 carbon atoms, or a hydrogen atom Represents. Each m independently represents an integer of 1 to 5, and p represents an integer of 5 to 5,000.
That in the general formula ^{(II-1), Y 1} , A 1, and m, ^{Y 1, A} 1 in the general formula (II-3), and m and are each synonymous.

In the general formula ^{(II-4), Y 1} , A 1, m, and ^{p, Y 1, A 1, m} , and p respectively have the same meanings in the general formula (II-1). Each R ⁸ independently represents a group represented by —O— (Y ¹ —O) _m —H or —O— (Y ¹ —O) _m —CO—Z ¹ —CO—OR ² . Here, R ² has the same meaning as R ² in General Formula (II-1), and m has the same meaning as m in General Formula (II-1). Z ¹ represents a divalent hydrocarbon group (that is, a carboxylic acid residue).

In general formulas (II-1) and (II-4), p represents an integer of 5 or more and 5,000 or less. In consideration of solubility in a general solvent when used as a coating composition (coating solution), p is preferably an integer of 5 or more and 2000 or less, and 5 or more from the viewpoint of ease of synthesis. It is more preferably an integer of 600 or less, and further preferably an integer of 5 or more and 500 or less from the viewpoint of molecular dispersibility Mw / Mn.
If p is in the range of 5 or more and 5,000 or less, the ionization potential is hardly affected by the number of p, and it is estimated that the fluctuation is about 0.1 eV at most.

In general formula (II-1), each R ² is independently a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon group having 2 to 10 aromatic rings, or a substituted or unsubstituted aromatic ring having 2 or more. 10 or less monovalent condensed aromatic hydrocarbon group, substituted or unsubstituted monovalent linear hydrocarbon group having 1 to 6 carbon atoms, substituted or unsubstituted monovalent hydrocarbon group having 2 to 10 carbon atoms A branched hydrocarbon group or a hydrogen atom is represented. ^{R 2} contained in the group represented by ^{R 8} in Formula (II-4) is also the same as ^{R 2} in Formula (II-1).

Among the above, R ² is preferably a hydrogen atom or a phenyl group, and more preferably a hydrogen atom from the viewpoint of cost reduction and ease of production.

Two R ² in the general formulas (II-1) and (II-4) may be the same or different, but are preferably the same from the viewpoint of production. Two R ⁸ in the general formula (II-4) may be the same or different, but are preferably the same from the viewpoint of production.

Z ¹ in the general formula (II-4) represents a divalent carboxylic acid residue.
Specifically, it is the same as the divalent linking group exemplified for Y ¹ in formula (II-3), and the preferred range is also the same. The plurality of Z ¹ in the general formula (II-4) may be the same or different, but are preferably the same from the viewpoint of production.

A plurality of A ¹ in general formula (II-1) and general formula (II-4) may be the same or different, but are preferably the same from the viewpoint of production.
Moreover, although several m in general formula (II-1) and general formula (II-4) may be the same or different, it is preferable that it is the same from a viewpoint on manufacture.

The polyester containing the structural unit derived from the compound represented by the general formula (I) such as the general formula (II-1) or the general formula (II-4) has a weight average molecular weight Mw in the range of 5000 to 300,000. Some are preferable, and generally considering the solubility in a solvent when used as a coating solution, the weight average molecular weight is preferably 10,000 or more and 200,000 or less, and more preferably 30,000 or more and 150,000 or less.
The weight average molecular weight is an average molecular weight in terms of polystyrene measured by gel permeation chromatography (carrier: tetrahydrofuran).

Hereinafter, specific polymers 1 to 30 of the polyester represented by the general formula (II-1) (namely, specific polyesters 1 to 30) are shown, but this embodiment is not limited to these specific examples. .
The numbers in the column of monomer in the specific example the polymer (column of "structure number of A ¹ ') corresponds to the specific examples the compounds No. of the compound represented by the general formula (I). Hereinafter, specific examples (compounds) assigned with respective numbers, for example, the structure of A ¹ assigned with the number 15 means a structure derived from the specific example compound 15.
Further, ^Y 1, m, p, and ^{R 2} in the specific example polymer, ^Y 1, m, p, respectively, in formula (II-1), and represents the ^{R 2.}

<Method for producing compound represented by formula (II-1)>
The method for synthesizing the polyester containing the structural unit represented by the general formula (II-3) is used by combining known methods according to the desired structure. Although the synthesis method is not particularly limited, an example of a synthesis method of dibenzothiophene oxide-containing polyester used for the image carrier for an image forming apparatus of the present embodiment will be described below.

  The polyester represented by the general formula (II-1) is a known monomer described in the following general formula (I-3), for example, in the 4th edition Experimental Chemistry Course Vol. 28 (Maruzen, 1992). It is obtained by polymerizing by the method.

In the general formula (I-3), A ¹ represents a partial structure derived from at least one selected from the compounds represented by the general formula (I), and A ¹ in the general formula (II-1) It is synonymous with. A ² represents a hydroxyl group, a halogen atom, or —O—R ⁹ , and R ⁹ represents an alkyl group, a substituted or unsubstituted aryl group, or an aralkyl group.
That is, the polyester represented by the general formula (II-1) is synthesized as follows.

1) In the case where A ² is a hydroxyl group For example, an equivalent amount of a dihydric alcohol represented by HO— (Y ¹ —O) _m —H is mixed with the compound represented by the general formula (I-3), and an acid catalyst is used. To polymerize. Incidentally, ^{Y 1} represents a divalent alcohol residue, the same meaning as ^{Y 1} in the general formula (II-1). m represents an integer of 1 to 5, and has the same meaning as m in formula (II-1).

As the acid catalyst, those used for ordinary esterification reaction such as sulfuric acid, toluenesulfonic acid, trifluoroacetic acid and the like are used, and are monomers (that is, compounds represented by the general formula (I-3), and so on. ) 1 / 10,000 parts by mass to 1/10 parts by mass, preferably 1 / 1,000 to 1/50 parts by mass with respect to 1 part by mass.
In order to remove water generated during the polymerization, it is preferable to use a solvent azeotropic with water. Examples of the solvent azeotropic with water include toluene, chlorobenzene, 1-chloronaphthalene, and the like, and 1 part by weight or more and 100 parts by weight or less, preferably 2 parts by weight or more and 50 parts by weight or less with respect to 1 part by weight of the monomer. Used in the following ranges.
Although reaction temperature is set according to conditions, in order to remove the water produced | generated during superposition | polymerization, it is preferable to make it react at the boiling point of a solvent.

When the solvent is not used after completion of the reaction, it is dissolved in a solvent to be dissolved. When a solvent is used, the reaction solution is dropped as it is in a poor solvent in which alcohols such as methanol and ethanol and polymers such as acetone are difficult to dissolve, to precipitate the polyester, and after separating the polyester, Wash with organic solvent and dry.
Further, if necessary, the reprecipitation treatment in which the polyester is precipitated by dissolving in an organic solvent and dropping in a poor solvent may be repeated. The reprecipitation treatment is preferably carried out with efficient stirring with a mechanical stirrer or the like. The solvent for dissolving the polyester in the reprecipitation treatment is used in the range of 1 part by mass to 100 parts by mass, preferably 2 parts by mass to 50 parts by mass with respect to 1 part by mass of the polyester. The poor solvent is used in an amount of 1 to 1,000 parts by weight, preferably 10 to 500 parts by weight, based on 1 part by weight of the polyester.

2) In the case where A ² is halogen, for example, an equivalent amount of a dihydric alcohol represented by HO— (Y ¹ —O) _m —H is mixed with the compound represented by the general formula (I-3), and pyridine, triethylamine, etc. Polymerization is performed using an organic basic catalyst. Incidentally, ^{Y 1} represents a divalent alcohol residue, the same meaning as ^{Y 1} in the general formula (II-1). m represents an integer of 1 to 5, and has the same meaning as m in formula (II-1).

The organic basic catalyst is used in the range of 1 equivalent to 10 equivalents, preferably 2 equivalents to 5 equivalents, relative to 1 equivalent of the monomer (that is, the compound represented by the general formula (I-3)).
Examples of the solvent include methylene chloride, tetrahydrofuran (THF), toluene, chlorobenzene, 1-chloronaphthalene, and the like, and 1 part by mass or more and 100 parts by mass or less, preferably 2 parts by mass or more and 50 parts by mass or more with respect to 1 part by mass of the monomer. It is used in the range of parts or less.
The reaction temperature is set according to the conditions. After the polymerization, reprecipitation treatment is performed as described above, and purification is performed.

Moreover, when using dihydric alcohols with high acidity, such as bisphenol, an interfacial polymerization method may be used. That is, after adding a dihydric alcohol to water and adding and dissolving an equivalent base, polymerization is carried out by adding a monomer solution equivalent to the dihydric alcohol while stirring vigorously. Under the present circumstances, water is used in 1 mass part or more and 1,000 mass parts or less with respect to 1 mass part of dihydric alcohol, Preferably it is 2 mass parts or more and 500 mass parts or less. Examples of the solvent for dissolving the monomer include methylene chloride, dichloroethane, trichloroethane, toluene, chlorobenzene, 1-chloronaphthalene and the like.
The reaction temperature is set according to the conditions, and a phase transfer catalyst such as an ammonium salt or a sulfonium salt may be used to promote the reaction. The phase transfer catalyst is used in the range of 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass with respect to 1 part by mass of the monomer.

3) When A ² is —O—R ^{9 To} the compound represented by the general formula (I-3), an excess of a dihydric alcohol represented by HO— (Y ¹ —O) _m —H is added, and sulfuric acid is added. It is synthesized by transesterification by heating using inorganic acid such as phosphoric acid, titanium alkoxide, acetate or carbonate such as calcium or cobalt, oxide of zinc or lead as a catalyst. Incidentally, ^{Y 1} represents a divalent alcohol residue, the same meaning as ^{Y 1} in the general formula (II-1). m represents an integer of 1 to 5, and has the same meaning as m in formula (II-1).

The dihydric alcohol is used in the range of 2 equivalents to 100 equivalents, preferably 3 equivalents to 50 equivalents, relative to 1 equivalent of the monomer (compound represented by formula (I-3)).
The catalyst is used in a range of 1 / 10,000 parts by weight to 1 part by weight, preferably 1 / 1,000 parts by weight to 1/2 parts by weight with respect to 1 part by weight of the monomer.

The reaction is carried out at a reaction temperature of 200 ° C. or higher and 300 ° C. or lower. After completion of the transesterification from —O—R ⁹ to —O— (Y ¹ —O) _m —H, HO— (Y ¹ —O) _m — In order to promote polymerization due to elimination of H, the reaction is preferably performed under reduced pressure. Also, ^HO- (Y 1 _-O) using a high-boiling solvent 1-chloronaphthalene azeotropic and m -H, under normal pressure (atmospheric pressure) ^HO- the (Y 1 _-O) m -H You may make it react, removing azeotropically.

Moreover, you may synthesize | combine polyester as follows.
In each of the above cases, a compound represented by the following general formula (I-4) was produced by adding an excess of a dihydric alcohol and reacting, and then the compound was represented by the above general formula (I-3). The polyester represented by the general formula (II-1) is obtained by reacting with a divalent carboxylic acid or a divalent carboxylic acid halide, etc., in place of the monomer.

In General Formula (I-4), A ¹ represents a partial structure derived from at least one selected from the compounds represented by General Formula (I), and has the same meaning as A ¹ in General Formula (II-1). It is. Y ¹ represents a divalent alcohol residue, the same meaning as ^{Y 1} in the general formula (II-1). m represents an integer of 1 to 5, and has the same meaning as m in the general formula (II-1).

In addition, a molecule may be introduced into the terminal of the polyester. In that case, the following method is mentioned. That is, when A ² is a hydroxyl group, the terminal-introducing compound monocarboxylic acid is copolymerized, or the electron-transporting compound after the polymerization reaction of the polymer is charged and reacted for introduction.

Further, when A ² is a halogen, or copolymerizing mono-acid chloride end-introducing compound, after the polymerization reaction of the polymer, it is introduced by reacting charged with mono-acid chloride terminal introducing compound. When A ² is —O—R ⁹ , the terminal introduction compound monoester is copolymerized, or after the polymerization reaction of the polymer, the terminal introduction compound monoester is charged and reacted.

In the image carrier for an image forming apparatus of this embodiment, as described above, at least one of the compound represented by the general formula (I) and the compound represented by the general formula (II-1) is included in the photosensitive layer. . In addition, since at least one of the compound represented by the general formula (I) and the compound represented by the general formula (II-1) has a high charge transport property, the charge injection property from the charge generation layer (especially positive charge) It is considered that the injectability of the liquid is improved. As a result, for example, the charge-up phenomenon is unlikely to occur, the residual potential fluctuation due to repeated use is reduced, and it is considered that excellent environmental maintainability is exhibited.
In the image carrier for an image forming apparatus of the present embodiment, since at least one of the compound represented by the general formula (I) and the compound represented by the general formula (II-1) is excellent in compatibility with the resin, The film thickness unevenness of the photosensitive layer is reduced. As a result, it is considered that the fluctuation of the residual potential due to repeated use of the image carrier is reduced.
Furthermore, since the image forming apparatus and the process cartridge according to the present embodiment use the image carrier for the image forming apparatus according to the present embodiment, good image quality can be obtained over a long period of time, and the environmental load is reduced and the cost is greatly reduced. It also becomes.

<Configuration of image carrier for image forming apparatus>
Hereinafter, the configuration of the image carrier for the image forming apparatus of the present embodiment will be described.
The image carrier for an image forming apparatus according to the exemplary embodiment is an image carrier for an image forming apparatus having a photosensitive layer on a support, and the compound represented by the above general formula (I) and the general formula are provided in the photosensitive layer. It contains at least one of the compounds represented by (II-1).
1 to 3 are schematic cross-sectional views showing first to third embodiments of the image carrier for an image forming apparatus according to this embodiment, respectively.
In either case, the image carrier 1 for an image forming apparatus is cut along the stacking direction of the conductive support 2 and the photosensitive layer 3.

  The image carrier 1 for an image forming apparatus according to the first and second embodiments shown in FIGS. 1 and 2 includes a function-separated type photosensitive layer in which a charge generation material and a charge transport material are contained in different layers. It is. That is, in the photosensitive layer 3, a layer containing a charge generation material (charge generation layer 5) and a layer containing a charge transport material (charge transport layer 6) are formed separately and laminated so that they are adjacent to each other. ing.

  On the other hand, the image carrier 1 for an image forming apparatus according to the third embodiment shown in FIG. 3 includes a single-layer type photosensitive layer in which the charge generation material and the charge transport material are contained in the same layer. That is, a charge generation / transport layer 8 containing a charge generation material and a charge transport material is formed in the photosensitive layer 3.

  More specifically, in the image carrier 1 for an image forming apparatus according to the first embodiment, the undercoat layer 4, the charge generation layer 5, and the charge transport layer 6 are laminated in this order on the conductive support 2. In the image carrier 1 for an image forming apparatus according to the second embodiment, a photosensitive layer 3 is configured. On the conductive support 2, an undercoat layer 4, a charge generation layer 5, a charge transport layer 6, and a protective layer are formed. The layer 7 is laminated in this order to constitute the photosensitive layer 3. In the image carrier 1 for an image forming apparatus according to the third embodiment, the undercoat layer 4 and the charge generation / transport layer 8 are laminated in this order on the conductive support 2 to form the photosensitive layer 3. ing.

  In addition, although illustration is abbreviate | omitted, as a deformation | transformation aspect of 2nd Embodiment, the aspect which reversed the lamination | stacking order of the charge generation layer 5 and the charge transport layer 6 in 2nd Embodiment, or a deformation | transformation aspect of 3rd Embodiment Another example is a mode in which the protective layer 7 used in the second embodiment is formed on the charge generation / transport layer 8 of the third embodiment.

  As the conductive support 2, aluminum is used in a drum shape, a sheet shape, a plate shape, or the like, but is not limited thereto. The conductive support 2 may be subjected to anodic oxidation treatment, boehmite treatment, honing treatment or the like.

  As shown in FIGS. 1 to 3, an undercoat layer 4 is provided in a region sandwiched between the conductive support 2 and the photosensitive layer 3 or a region sandwiched between the conductive support 2 and the charge generation / transport layer 8. As the undercoat layer 4, an organic zirconium compound such as a zirconium chelate compound, a zirconium alkoxide compound, or a zirconium coupling agent; an organic titanium compound such as a titanium chelate compound, a titanium alkoxide compound, or a titanate coupling agent; an aluminum chelate compound, or In addition to organoaluminum compounds such as aluminum coupling agents; antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxide compounds, aluminum Titanium alkoxide compound or aluminum zirconium alkoxide compound Organometallic compounds such is used. In particular, an organic zirconium compound, an organic titanyl compound, or an organic aluminum compound is preferably used.

  Also, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyl Triethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, or β-3,4-epoxycyclohexyl A silane coupling agent such as trimethoxysilane is further contained.

Furthermore, polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, polyester, phenol resin, vinyl chloride- A known binder resin such as vinyl acetate copolymer, epoxy resin, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, or polyacrylic acid may be further contained. These mixing ratios are set as necessary.
Further, an electron transporting pigment can be mixed or dispersed in the undercoat layer 4.

  Examples of the electron transporting pigment include organic pigments such as perylene pigments, bisbenzimidazole perylene pigments, polycyclic quinone pigments, indigo pigments, and quinacridone pigments described in JP-A-47-30330. Further, organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as cyano group, nitro group, nitroso group, or halogen atom, and inorganic pigments such as zinc oxide or titanium oxide. Among these pigments, a perylene pigment, a bisbenzimidazole perylene pigment, a polycyclic quinone pigment, zinc oxide, or titanium oxide is preferable.

  In addition, the surface of these pigments may be surface-treated with the above coupling agent or binder. The content of the electron transporting pigment is 95% by weight or less, preferably 90% by weight or less, based on the total amount of the undercoat layer 4.

  As a method of mixing or dispersing the electron transporting pigment in the undercoat layer 4, a conventional method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like is applied. Mixing and dispersion are carried out in an organic solvent, and the organic solvent can be used as long as it dissolves an organometallic compound or resin and does not cause gelation or aggregation when an electron transporting pigment is mixed or dispersed. Anything is used.

The thickness of the undercoat layer 4 is preferably 0.1 μm or more and 30 μm or less, and more preferably 0.2 μm or more and 25 μm or less.
The coating method used when the undercoat layer 4 is provided is a normal coating method such as blade coating method, Mayer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, or curtain coating method. Use the method.

  The undercoat layer 4 is obtained by drying the coating film formed by applying the composition for forming the undercoat layer containing the above components, and the drying is usually performed at a temperature at which the solvent can be evaporated to form a film. . In particular, it is preferable to form the undercoat layer 4 because the substrate subjected to the acidic solution treatment and the boehmite treatment tends to have insufficient defect concealing power.

  The charge generation material contained in the charge generation layer 5 is an azo pigment such as bisazo or trisazo; a fused aromatic pigment such as dibromoanthanthrone; a perylene pigment, a pyrrolopyrrole pigment, or a phthalocyanine pigment. Although metal and metal-free phthalocyanine pigments are particularly preferred. Among these, hydroxygallium phthalocyanine disclosed in JP-A-5-263007 and JP-A-5-279951, chlorogallium phthalocyanine disclosed in JP-A-5-98181, JP-A-5-140472 and Dichlorotin phthalocyanine disclosed in JP-A-5-140473 or titanyl phthalocyanine disclosed in JP-A-4-189873 and JP-A-5-43813 is particularly preferable.

The charge generation layer 5 is formed by mixing a charge generation material and a binder resin. Such a binder resin is selected from a wide range of insulating resins, and also includes poly-N-vinylcarbazole and polyvinyl. It may be selected from organic photoconductive polymers such as anthracene, polyvinylpyrene, or polysilane. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin. Insulating resin such as, but not limited to, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, or polyvinyl pyrrolidone resin. These binder resins are used alone or in combination of two or more.
The insulating resin in the present embodiment is an insulating resin whose volume resistivity measured based on JIS K 7194 “Resistivity testing method of conductive plastic by four-probe method” is 10 ¹² Ω · cm or more. Point to.

The blending ratio (weight ratio) of the charge generation material and the binder resin is preferably in the range of 10: 1 to 1:10, more preferably 8: 3 to 3: 8.
In addition, as a method for dispersing them, a normal method such as a ball mill dispersion method, an attritor dispersion method, or a sand mill dispersion method is used. At this time, the condition that the crystal form of the charge generation material is not changed by the dispersion is required. . Incidentally, it has been confirmed that the crystal form does not change before dispersion for any of the dispersion methods used in this embodiment.

  Further, at the time of dispersion, it is effective to make the particles of the charge generating material 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less.

  The thickness of the charge generation layer 5 is preferably 0.1 μm or more and 5 μm or less, more preferably 0.2 μm or more and 2.0 μm or less. In addition, as a coating method used when the charge generation layer 5 is provided, the blade coating method, the Meyer bar coating method, the spray coating method, the dip coating method, the bead coating method, the air knife coating method, the curtain coating method, etc. Use the method.

As the charge transport layer 6, a layer formed by a known technique is used except that it contains at least one of the compound represented by the general formula (I) and the compound represented by the general formula (II-1). obtain.
If the charge transport layer 6 contains at least one of the compound represented by the general formula (I) and the compound represented by the general formula (II-1), the charge transport layer 6 contains other charge transport materials, binder resins, and the like. May be formed. When the compound represented by the general formula (I) is used and the compound represented by the general formula (II-1) is not used, the compound represented by the general formula (I) is dispersed in a binder resin or the like. It is desirable to use them. When the compound represented by the general formula (II-1) is used, the charge transport layer 6 can be formed without using other resins, but from a low cost viewpoint, it is used by mixing with other resins. It is desirable.
Other charge transport materials include, for example, quinone compounds such as p-benzoquinone, chloranil, bromanyl, anthraquinone; tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, and xanthone compounds. , Benzophenone compounds, cyanovinyl compounds, ethylene compounds, etc., triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazones Other charge transport materials such as a hole transporting compound such as a series compound may be mentioned, but are not limited thereto.

In the total amount of the charge transport layer 6, the content of the compound represented by the general formula (I) and the compound represented by the general formula (II-1) is preferably 5% by mass or more and 70% by mass or less, more preferably 10%. It is 20 mass% or more, More preferably, it is 20 mass% or more and 50 mass% or less.
When a compound other than the compound represented by the general formula (I) and the compound represented by the general formula (II-1) is used as a charge transport material, the total amount of the charge transport material is represented by the general formula (I). The content of the compound shown and the compound shown by the general formula (II-1) is preferably 1% by mass or more, and more preferably 5% by mass or more.

  When a binder resin is used for the charge transport layer 6, examples of the binder resin include polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene. -Butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene -Alkyd resins, poly-N-vinylcarbazole, polysilane, or polymer charge transport materials such as polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820. It is done. These binder resins are used alone or in combination of two or more. The blending ratio (weight ratio) between the charge transport material and the binder resin is preferably 10: 1 to 1:10, more preferably 8: 3 to 3: 8.

The thickness of the charge transport layer 6 is preferably 5 μm or more and 50 μm or less, more preferably 10 μm or more and 30 μm or less.
As a coating method, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method is used.

Moreover, you may add additives, such as antioxidant, a light stabilizer, and a heat stabilizer, in a photosensitive layer.
Moreover, you may contain an at least 1 sort (s) of electron-accepting substance.

  The image carrier for an image forming apparatus according to this embodiment may include a protective layer 7 (surface layer), but the protective layer 7 is preferably a high-strength protective layer (high-strength surface layer). As this high-strength protective layer, conductive particles are dispersed in a binder resin, lubricating particles such as fluorine resin and acrylic resin are dispersed in a normal charge transport layer material, hard coat such as silicone and acrylic An agent or the like is used. The high-strength protective layer preferably has a charge transporting property and contains a siloxane resin having a crosslinked structure.

The protective layer 7 may be used by mixing other coupling agents and fluorine compounds. As this compound, various silane coupling agents and commercially available silicone hard coat agents are used.
Adjustment of the coating liquid used for forming the protective layer 7 may be performed without a solvent, or a solvent may be used as necessary.

  Although the reaction temperature and time vary depending on the type of raw material, it is usually 0 to 100 ° C., preferably 10 to 70 ° C., particularly preferably 15 to 50 ° C. The reaction time is not particularly limited, but the reaction time is preferably in the range of 10 minutes to 100 hours.

  Examples of the curing catalyst include a protic acid such as hydrochloric acid, acetic acid, phosphoric acid, or sulfuric acid, a base such as ammonia or triethylamine, an organic tin compound such as dibutyltin diacetate, dibutyltin dioctoate, or stannous oxalate, tetra- Organotitanium compounds such as n-butyl titanate or tetraisopropyl titanate, organoaluminum compounds such as aluminum tributoxide or aluminum triacetylacetonate, iron salts, manganese salts, cobalt salts, zinc salts or zirconium salts of organic carboxylic acids However, metal compounds are preferred, metal acetylacetonate or acetylacetate is preferred, and aluminum triacetylacetonate is particularly preferred.

The amount of the curing catalyst used is set as necessary, but is preferably 0.1% by weight or more and 20% by weight or less, and preferably 0.3% by weight or more and 10% by weight or less with respect to the total amount of materials containing hydrolyzable silicon substituents. More preferably, it is less than wt%.
The curing temperature is set as required, but is set to 60 ° C. or higher, more preferably 80 ° C. or higher in order to obtain a desired strength. The curing time is set as required, but is preferably 10 minutes to 5 hours.
It is also effective to maintain a high humidity state after the curing reaction. Further, depending on the application, surface treatment is performed using hexamethyldisilazane, trimethylchlorosilane, or the like to make it hydrophobic.

It is preferable to add an antioxidant to the protective layer 7 of the image carrier for the image forming apparatus.
Further, a resin that dissolves in alcohol may be added to the protective layer 7 of the image carrier for the image forming apparatus.
Furthermore, various particles may be added to the protective layer 7. They may be used alone or in combination. Examples of the particles include silicon-containing particles, fluorine-based particles, and semiconductive metal oxide particles.
Further, an oil such as silicone oil can be added to the protective layer 7.

In the case of a single-layer type photosensitive layer, the single-layer type photosensitive layer includes the charge generation material, the charge transport material (the compound represented by the general formula (I) of the present embodiment, and the general formula (II-1)). And at least one of the compounds shown) and a binder resin. The charge transport material may contain a polymer charge transport material. As the binder resin, those listed as binder resins used for the charge generation layer 5 and the charge transport layer 6 are used. The content of the charge generating material in the single-layer type photosensitive layer is from 10% by weight to 85% by weight, preferably from 20% by weight to 50% by weight. The content of the charge transport material in the single-layer type photosensitive layer is preferably 5% by weight or more and 50% by weight or less.
The above-mentioned thing is used for the solvent and coating method used for application | coating. The film thickness of the single layer type photosensitive layer is preferably 5 μm or more and 50 μm or less, and more preferably 10 μm or more and 40 μm or less.

(Image forming device)
The image forming apparatus according to the present embodiment includes the above-described image carrier for the image forming apparatus according to the present embodiment, a charging device that charges the image carrier for the image forming apparatus, and the charged image carrier for the image forming apparatus. An exposure device that forms an electrostatic latent image by exposing the toner, a developing device that develops the electrostatic latent image to form a toner image, and a transfer device that transfers the toner image to a transfer target. It is characterized by.
FIG. 4 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of the image forming apparatus of the present embodiment.
An image forming apparatus 200 shown in FIG. 4 is connected to the image holding apparatus for image forming apparatus 207 of the present embodiment, a charging apparatus 208 for charging the image holding apparatus for image forming apparatus 207 by a contact charging method, and the charging apparatus 208. The image forming apparatus image carrier 207 charged by the power source 209 and the charging apparatus 208 is exposed to form an electrostatic latent image, and the electrostatic latent image formed by the exposure apparatus 210 is made of toner. A developing device 211 that develops a toner image, a transfer device 212 that transfers the toner image formed by the developing device 211 to the transfer target 500, a cleaning device 213, a static eliminator 214, and a fixing device 215. Prepare.

The charging device 208 shown in FIG. 4 applies a voltage to the image carrier by bringing a contact charging member (for example, a charging roll) into contact with the surface of the image carrier 207 for the image forming apparatus, and charges the surface of the image carrier. It is something to be made.
As the contact-type charging member, a roller-shaped member in which an elastic layer, a resistance layer, a protective layer and the like are provided on the outer peripheral surface of the core material is preferably used. The shape of the contact-type charging member may be any of the above-described roller shape, brush shape, blade shape, pin electrode shape, and the like, and is selected according to the specifications and form of the image forming apparatus.

As the core material of the roller-shaped contact-type charging member, a conductive material such as iron, copper, brass, stainless steel, aluminum, or nickel is used. In addition, a resin molded product in which conductive particles are dispersed is used. As the material of the elastic layer, a conductive or semiconductive material, for example, a rubber material in which conductive particles or semiconductive particles are dispersed is used. As the material of the resistance layer and the protective layer, conductive particles or semiconductive particles are dispersed in a binder resin, and the resistance is controlled.
When charging the image carrier using these contact-type charging members, a voltage is applied to the contact-type charging member. The applied voltage may be either a DC voltage or a DC voltage superimposed with an AC voltage. .
Instead of the contact-type charging member in FIG. 4, a non-contact type corona charging device such as corotron or scorotron is also used. These are selected according to the specifications and form of the image forming apparatus.

  As the exposure apparatus 210, an optical system apparatus or the like that exposes a light source such as a semiconductor laser, an LED (light emitting diode), a liquid crystal shutter, or the like on the surface of the image carrier for the image forming apparatus in a desired image manner.

  As the developing device 211, a conventionally known developing device using a regular or reversal developer such as a one-component system or a two-component system is used. The shape of the toner used in the developing device 211 is not particularly limited, but a spherical toner is preferable.

  Examples of the transfer device 212 include a roller-type contact charging member, a contact-type transfer charger using a belt, a film, a rubber blade, or the like, or a scorotron transfer charger or a corotron transfer charger using corona discharge. Can be mentioned.

  The cleaning device 213 is for removing residual toner adhering to the surface of the image holding member for the image forming apparatus after the transfer process, and the image holding member for the image forming device thus cleaned has the above-mentioned image formation. Used repeatedly in the process. As the cleaning device, a cleaning blade, brush cleaning, roll cleaning, or the like is used. Of these, it is preferable to use a cleaning blade. Examples of the material for the cleaning blade include urethane rubber, neoprene rubber, and silicone rubber.

Although the above embodiment has one image forming unit, an image forming apparatus according to another embodiment is a tandem type image forming apparatus having a plurality of image forming units.
For example, when there are four image forming units, each developing device of the four image forming units uses, for example, four color component toners of yellow, magenta, cyan, and blank. The tandem image forming apparatus includes a belt that is common to the four image forming units and conveys a recording material, a conveyance device that conveys the belt, a toner supply device that supplies a toner image to each developing device, and a color toner. A fixing device for fixing the image to the recording material is preferably provided.

  Further, the image forming apparatus of the present embodiment preferably has a mechanism for supplying only the toner alone when the image carrier is used for 200000 cycles or more, further 250,000 cycles, or 300000 cycles or more.

(Process cartridge)
The process cartridge according to the present embodiment includes at least the image carrier for an image forming apparatus according to the above-described embodiment, and a charging device that charges the image carrier for the image forming apparatus. An exposure device that exposes an image carrier to form an electrostatic latent image, a developing device that develops the electrostatic latent image to form a toner image, a transfer device that transfers the toner image to a transfer target, and the image And at least one selected from a cleaning device for cleaning the image carrier for the forming apparatus.

FIG. 5 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of a process cartridge including an image carrier for an image forming apparatus according to this embodiment.
The process cartridge 300 includes an image holder 207 for an image forming apparatus, a charging device 208, a developing device 211, a cleaning device (cleaning means) 213, an opening 218 for exposure, and an opening 217 for discharge exposure. They are combined and integrated using mounting rails 216.
The process cartridge 300 is used for an image forming apparatus main body including a transfer device 212 that transfers a toner image formed by the developing device 211 to the transfer target 500, a fixing device 215, and other components not shown. The image forming apparatus is configured together with the image forming apparatus main body.
Although the present embodiment has been described above, the present embodiment can be variously modified and changed within the scope of the gist.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.
In this example, for identification of the target product, ¹ H-NMR spectrum (solvent: CDCl ₃ , Varian Inc., UNITY-300, 300 MHz), and IR spectrum (Fourier transform infrared spectrophotometry by KBr method). A meter (Horiba, Ltd., FT-730, resolution 4 cm ⁻¹ ) was used.
Furthermore, in this example, the molecular weight of the polymer was measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8120GPC).

(Synthesis of the compound represented by the general formula (I) or (II-1))
[Synthesis Example 1-Synthesis of Specific Example Compound 6]
500 ml of acetanilide (25.0 g), methyl 4-iodophenylpropionate (64.4 g), potassium carbonate (38.3 g), copper sulfate pentahydrate (2.3 g), n-tridecane (50 ml) The flask was placed in a flask and heated and stirred at 230 ° C. for 20 hours under a nitrogen stream. After completion of the reaction, potassium hydroxide (15.6 g) dissolved in ethylene glycol (300 ml) was added, heated under reflux for 3.5 hours under a nitrogen stream, and then cooled to room temperature (25 ° C.). The mixture was poured into 1 L of distilled water and neutralized with hydrochloric acid to precipitate crystals. The crystals were collected by suction filtration, washed with water, and transferred to a 1 L flask. Toluene (500 ml) was added thereto, heated to reflux, water was removed by azeotropy, then a solution of concentrated sulfuric acid (1.5 ml) in methanol (300 ml) was added, and the mixture was heated to reflux for 5 hours under a nitrogen stream. After the reaction, extraction with toluene was performed, and the organic phase was washed with pure water. Subsequently, after drying with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and recrystallization from hexane gave 36.5 g of DAA-1 below.

  Next, in a 500 ml three-necked flask, 30% aqueous hydrogen peroxide (34.0 g) was added dropwise over 20 minutes to a mixture of dibenzothiophene (18.4 g) and acetic acid (200 ml), and magnetized at 90 ° C. for 9 hours. Stir. After completion of the reaction, the reaction mixture was poured into an ice bath (600 ml) and extracted with chloroform (800 ml). The organic layer was washed successively with water (200 ml), saturated aqueous iron sulfate solution (80 ml), 10% sodium carbonate (100 ml), water (200 ml) and saturated brine (200 ml), and dried over calcium chloride. The organic solvent was distilled off to obtain colorless crystals. This was recrystallized (chloroform 150 ml, ethanol 200 ml) to obtain 18.2 g of dibenzothiophene dioxide.

In a 500 ml three-necked flask, dibenzothiophene dioxide dioxide (18 g) was dissolved in sulfuric acid (250 ml), and N-bromosuccinimide (29.6 g) was added. After stirring at 25 ° C. for 18 hours, the reaction solution was slowly poured into ice water (800 ml), the deposited precipitate was suction filtered, and washed with water (200 ml), 10% NaOH aqueous solution (100 ml), and water (200 ml). And dried with calcium chloride. Recrystallization from chloroform (700 ml) gave 20.1 g of 3,7-dibromodibenzothiophene dioxide.

  Under a nitrogen atmosphere, in a 200 ml three-necked flask, DAA-1 (8.0 g), 3,7-dibromodibenzothiophene dioxide (5.2 g), palladium (II) acetate (150 mg), rubidium carbonate (19.6 g). And dissolved in 50 ml of xylene. Tri-tert-butylphosphine (420 mg) was quickly added, and the mixture was heated and refluxed magnetically stirred for 9 hours under a nitrogen atmosphere. After confirming the disappearance of the DAA-1 spot by TLC (hexane / ethyl acetate = 3/1), it was cooled to room temperature (25 ° C.). After removing inorganic substances by Celite suction filtration, washing was carried out in the order of dilute hydrochloric acid 100 ml, water 200 ml × 3, saturated saline 200 ml × 1 in this order. After drying over anhydrous sodium sulfate, purification was performed by silica gel column chromatography (hexane / toluene = 3/1), followed by vacuum drying at 70 ° C. for 18 hours to obtain Specific Example Compound 6 (4.8 g).

It was confirmed that the obtained compound was the specific example compound 6 by ¹ H-NMR spectrum measurement and IR spectrum measurement.

[Synthesis Example 2-Synthesis of Specific Example Polymer 10]
Using 1.0 g of the specific example compound 6 obtained in Synthesis Example 1, 10 ml of ethylene glycol and 0.02 g of tetrabutoxytitanium were placed in a 50 ml three-necked eggplant flask, and the mixture was heated and stirred at 200 ° C. for 5 hours in a nitrogen atmosphere.
After confirming by TLC that the specific example compound 6 as a raw material had reacted and disappeared, the pressure was reduced to 50 Pa and the mixture was heated to 210 ° C. while distilling off ethylene glycol, and the reaction was continued for 6 hours.

Thereafter, the mixture was cooled to room temperature (25 ° C.), dissolved in 50 ml of tetrahydrofuran, insoluble matter was filtered through a 0.5 μl polytetrafluoroethylene (PTFE) filter, the filtrate was distilled off under reduced pressure, and then 300 ml of monochlorobenzene. It was dissolved in 1N-HCl 300 ml and water 500 ml × 3 in this order. The monochlorobenzene solution was distilled off under reduced pressure to 30 ml and dropped into ethyl acetate / methanol = 1/3: 800 ml to reprecipitate the polymer.
The obtained polymer was filtered, washed with methanol, and then vacuum dried at 60 ° C. for 16 hours to obtain 0.5 g of a polymer [specific example polymer 10].

When the molecular weight of this polymer was measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8120GPC), the weight average molecular weight Mw = 5.6 × 10 ⁴ (in terms of styrene), Mw / Mn = 2. The polymerization degree p determined from the molecular weight of the low-molecular compound as a raw material was 78.

[Synthesis Example 3-Synthesis of Specific Example Compound 7]
4-methylacetanilide (21.0 g), methyl 4-iodophenylpropionate (64.4 g), potassium carbonate (38.3 g), copper sulfate pentahydrate (2.3 g), n-tridecane (50 ml). The mixture was placed in a 500 ml three-necked flask and heated and stirred at 230 ° C. for 15 hours under a nitrogen stream. After completion of the reaction, potassium hydroxide (15.6 g) dissolved in ethylene glycol (300 ml) was added, heated under reflux for 3.5 hours under a nitrogen stream, and then cooled to room temperature (25 ° C.). The mixture was poured into 1 L of distilled water and neutralized with hydrochloric acid to precipitate crystals. The crystals were collected by suction filtration, washed with water, and transferred to a 1 L flask. Toluene (500 ml) was added thereto, heated to reflux, water was removed by azeotropy, then a solution of concentrated sulfuric acid (1.5 ml) in methanol (300 ml) was added, and the mixture was heated to reflux for 5 hours under a nitrogen stream. After the reaction, extraction with toluene was performed, and the organic phase was washed with pure water. Next, after drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and recrystallization from hexane gave 34.1 g of DAA-2 below.

  Under a nitrogen atmosphere, in a 200 ml three-necked flask, DAA-2 (8.0 g), 3,7-dibromodibenzothiophene dioxide (5.2 g), palladium (II) acetate (150 mg), rubidium carbonate (19.6 g). And dissolved in 50 ml of xylene. Tri-tert-butylphosphine (420 mg) was quickly added, and the mixture was heated and refluxed magnetically stirred for 9 hours under a nitrogen atmosphere. After confirming the disappearance of the DAA-2 spot by TLC (hexane / ethyl acetate = 3/1), it was cooled to room temperature (25 ° C.). After removing inorganic substances by Celite suction filtration, washing was carried out in the order of dilute hydrochloric acid 100 ml, water 200 ml × 3, saturated saline 200 ml × 1 in this order. After drying over anhydrous sodium sulfate, purification was performed by silica gel column chromatography (hexane / toluene = 3/1), followed by vacuum drying at 70 ° C. for 18 hours to obtain Specific Example Compound 7 (5.1 g).

It was confirmed by ¹ H-NMR spectrum measurement and IR spectrum measurement that the obtained compound was the specific example compound 7.

[Synthesis Example 4-Synthesis of Specific Example Polymer 12]
Using 1.0 g of the specific example compound 7 obtained in Synthesis Example 3, 10 ml of ethylene glycol and 0.02 g of tetrabutoxytitanium were placed in a 50 ml three-necked eggplant flask, and the mixture was heated and stirred at 200 ° C. for 5 hours in a nitrogen atmosphere.
After confirming by TLC that the specific compound 7 as a raw material had reacted and disappeared, the pressure was reduced to 50 Pa and the mixture was heated to 210 ° C. while distilling off ethylene glycol, and the reaction was continued for 6 hours.

Thereafter, the mixture was cooled to room temperature (25 ° C.), dissolved in 50 ml of tetrahydrofuran, insoluble matter was filtered through a 0.5 μl polytetrafluoroethylene (PTFE) filter, the filtrate was distilled off under reduced pressure, and then 300 ml of monochlorobenzene. It was dissolved in 1N-HCl 300 ml and water 500 ml × 3 in this order. The monochlorobenzene solution was distilled off under reduced pressure to 30 ml and dropped into ethyl acetate / methanol = 1/3: 800 ml to reprecipitate the polymer.
The obtained polymer was filtered, washed with methanol, and then vacuum dried at 60 ° C. for 18 hours to obtain 0.5 g of a polymer [specific example polymer 12].

When the molecular weight of this polymer was measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8120GPC), the weight average molecular weight Mw = 5.4 × 10 ⁴ (in terms of styrene), Mw / Mn = 2. And the degree of polymerization p determined from the molecular weight of the low molecular weight compound as the raw material was 72.

[Synthesis Example 5-Synthesis of Specific Example Compound 17]
1-acetamidonaphthalene (25.0 g), methyl 4-iodophenylpropionate (64.4 g), potassium carbonate (38.3 g), copper sulfate pentahydrate (2.3 g), n-tridecane (50 ml) The mixture was placed in a 500 ml three-necked flask and heated and stirred at 230 ° C. for 18 hours under a nitrogen stream. After completion of the reaction, potassium hydroxide (15.6 g) dissolved in ethylene glycol (300 ml) was added, heated under reflux for 3.5 hours under a nitrogen stream, and then cooled to room temperature (25 ° C.). The mixture was poured into 1 L of distilled water and neutralized with hydrochloric acid to precipitate crystals. The crystals were collected by suction filtration, washed thoroughly with water, and transferred to a 1 L flask. Toluene (500 ml) was added thereto, heated to reflux, water was removed by azeotropy, concentrated methanol (1.5 ml) in methanol (300 ml) was added, and the mixture was heated to reflux for 5 hours under a nitrogen stream. After the reaction, extraction with toluene was performed, and the organic layer was sufficiently washed with pure water. Subsequently, after drying with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and 36.5 g of DAA-3 was obtained by recrystallization from hexane.

  Under a nitrogen atmosphere, in a 200 ml three-necked flask, DAA-3 (9.2 g), 3,7-dibromodibenzothiophene dioxide (5.2 g), palladium (II) acetate (150 mg), rubidium carbonate (19.6 g). And dissolved in 50 ml of xylene. Tri-tert-butylphosphine (420 mg) was quickly added, and the mixture was heated and refluxed magnetically stirred for 9 hours under a nitrogen atmosphere. After confirming the disappearance of the DAA-3 spot by TLC (hexane / ethyl acetate = 3/1), it was cooled to room temperature (25 ° C.). After removing inorganic substances by Celite suction filtration, washing was carried out in the order of dilute hydrochloric acid 100 ml, water 200 ml × 3, saturated saline 200 ml × 1 in this order. After drying over anhydrous sodium sulfate, purification was performed by silica gel column chromatography (hexane / toluene = 3/1), followed by vacuum drying at 70 ° C. for 19 hours to obtain Specific Example Compound 17 (5.6 g).

It was confirmed by ¹ H-NMR spectrum measurement and IR spectrum measurement that the obtained compound was the specific example compound 17.

[Synthesis Example 6-Synthesis of Specific Example Polymer 20]
Using 1.0 g of the specific example compound 17 obtained in Synthesis Example 5, 10 ml of ethylene glycol and 0.02 g of tetrabutoxytitanium were placed in a 50 ml three-necked eggplant flask and stirred with heating at 200 ° C. for 5 hours in a nitrogen atmosphere.
After confirming by TLC that the specific compound 17 as a raw material reacted and disappeared, the pressure was reduced to 50 Pa and the mixture was heated to 210 ° C. while distilling off ethylene glycol, and the reaction was continued for 6 hours.

Thereafter, the mixture was cooled to room temperature (25 ° C.), dissolved in 50 ml of tetrahydrofuran, insoluble matter was filtered through a 0.5 μl polytetrafluoroethylene (PTFE) filter, the filtrate was distilled off under reduced pressure, and then 300 ml of monochlorobenzene. It was dissolved in 1N-HCl 300 ml and water 500 ml × 3 in this order. The monochlorobenzene solution was distilled off under reduced pressure to 30 ml and dropped into ethyl acetate / methanol = 1/3: 800 ml to reprecipitate the polymer.
The obtained polymer was filtered, washed with methanol, and then vacuum-dried at 60 ° C. for 16 hours to obtain 0.7 g of a polymer [specific example polymer 20].

When the molecular weight of this polymer was measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8120GPC), the weight average molecular weight Mw = 5.7 × 10 ⁴ (in terms of styrene), Mw / Mn = 2. The polymerization degree p determined from the molecular weight of the low molecular weight compound as the raw material was 69.

Synthesis Example 7 Synthesis of Specific Compound 19
4- (2-thienyl) acetanilide (30.0 g), methyl 4-iodophenylpropionate (28.5 g), potassium carbonate (13.6 g), copper sulfate pentahydrate (2.0 g), 1,2 -Dichlorobenzene (50 ml) was placed in a 500 ml three-necked flask and heated and stirred at 230 ° C for 20 hours under a nitrogen stream. After completion of the reaction, potassium hydroxide (15.6 g) dissolved in ethylene glycol (300 ml) was added, heated under reflux for 3.5 hours under a nitrogen stream, and then cooled to room temperature (25 ° C.). The mixture was poured into 1 L of distilled water and neutralized with hydrochloric acid to precipitate crystals. The crystals were collected by suction filtration, washed with water, and transferred to a 1 L flask. Toluene (500 ml) was added thereto, heated to reflux, water was removed by azeotropy, then a solution of concentrated sulfuric acid (1.5 ml) in methanol (300 ml) was added, and the mixture was heated to reflux for 5 hours under a nitrogen stream. After the reaction, extraction with toluene was performed, and the organic phase was washed with pure water. Next, after drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and recrystallization from hexane gave 17.9 g of DAA-4.

  Under a nitrogen atmosphere, in a 200 ml three-necked flask, DAA-4 (10.1 g), 3,7-dibromodibenzothiophene dioxide (5.2 g), palladium (II) acetate (150 mg), rubidium carbonate (19.6 g). And dissolved in 50 ml of xylene. Tri-tert-butylphosphine (420 mg) was quickly added, and the mixture was heated and refluxed magnetically stirred for 9 hours under a nitrogen atmosphere. After confirming disappearance of the DAA-4 spot by TLC (hexane / ethyl acetate = 3/1), it was cooled to room temperature (25 ° C.). After removing inorganic substances by Celite suction filtration, washing was carried out in the order of dilute hydrochloric acid 100 ml, water 200 ml × 3, saturated saline 200 ml × 1 in this order. After drying over anhydrous sodium sulfate, purification was performed by silica gel column chromatography (hexane / toluene = 3/1), followed by vacuum drying at 70 ° C. for 17 hours to obtain Specific Example Compound 19 (6.2 g).

¹ H-NMR spectrum measurement and IR spectrum measurement confirmed that the obtained compound was the specific example compound 19.

[Synthesis Example 8-Synthesis of Specific Example Polymer 22]
Using 1.0 g of the specific example compound 19 obtained in Synthesis Example 7, 10 ml of ethylene glycol and 0.02 g of tetrabutoxytitanium were placed in a 50 ml three-necked eggplant flask, and the mixture was heated and stirred at 200 ° C. for 5 hours in a nitrogen atmosphere.
After confirming by TLC that the specific compound 19 as a raw material had reacted and disappeared, the pressure was reduced to 50 Pa and the mixture was heated to 210 ° C. while distilling off ethylene glycol, and the reaction was continued for 6 hours.

Thereafter, the mixture was cooled to room temperature (25 ° C.), dissolved in 50 ml of tetrahydrofuran, insoluble matter was filtered through a 0.5 μl polytetrafluoroethylene (PTFE) filter, the filtrate was distilled off under reduced pressure, and then 300 ml of monochlorobenzene. It was dissolved in 1N-HCl 300 ml and water 500 ml × 3 in this order. The monochlorobenzene solution was distilled off under reduced pressure to 30 ml and dropped into ethyl acetate / methanol = 1/3: 800 ml to reprecipitate the polymer.
The obtained polymer was filtered, washed with methanol, and then vacuum dried at 60 ° C. for 16 hours to obtain 0.6 g of a polymer [specific example polymer 22].

When the molecular weight of this polymer was measured by gel permeation chromatography (GPC) (HLC-8120GPC, manufactured by Tosoh Corporation), the weight average molecular weight Mw = 4.1 × 10 ⁴ (in terms of styrene), Mw / Mn = 2. The degree of polymerization p determined from the molecular weight of the low molecular weight compound as the raw material was 55.

[Synthesis Example 9-Synthesis of Specific Example Compound 23]
Under nitrogen atmosphere, 2-iodo-9,9-dimethylfluorene (31.8 g), methyl 4-acetaminophenylpropionate 20.0 g, potassium carbonate 18.8 g, copper sulfate pentahydrate 1.2 g, tridecane 15 ml Was placed in a 300 ml three-necked flask and stirred with heating at 200 ° C. for 13 hours under a nitrogen stream. After this reaction, 150 ml of ethylene glycol and 7.6 g of potassium hydroxide were added, heated under reflux for 5 hours under a nitrogen stream, cooled to room temperature (25 ° C.), poured into 150 ml of distilled water, and neutralized with hydrochloric acid. Then, crystals were precipitated. This was filtered, washed thoroughly with water, and then transferred to a 500 ml flask. To this, 500 ml of toluene was added and heated to reflux, water was removed azeotropically, 100 ml of methanol and 1.0 ml of concentrated sulfuric acid were added, and the mixture was heated to reflux for 5 hours under a nitrogen stream. After the reaction, extraction with toluene was performed, and the organic layer was sufficiently washed with distilled water. Subsequently, after drying with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and 25 g of DAA-5 was obtained by recrystallization from hexane.

  Under a nitrogen atmosphere, in a 200 ml three-necked flask, DAA-5 (11.2 g), 3,7-dibromodibenzothiophene dioxide (5.2 g), palladium (II) acetate (150 mg), rubidium carbonate (19.6 g). And dissolved in 50 ml of xylene. Tri-tert-butylphosphine (420 mg) was quickly added, and the mixture was heated and refluxed magnetically stirred for 9 hours under a nitrogen atmosphere. After confirming the disappearance of the DAA-5 spot by TLC (hexane / ethyl acetate = 3/1), it was cooled to room temperature (25 ° C.). After removing inorganic substances by Celite suction filtration, washing was carried out in the order of dilute hydrochloric acid 100 ml, water 200 ml × 3, saturated saline 200 ml × 1 in this order. After drying over anhydrous sodium sulfate, purification was performed by silica gel column chromatography (hexane / toluene = 3/1), followed by vacuum drying at 70 ° C. for 15 hours to obtain the specific compound 23 (6.0 g).

¹ H-NMR spectrum measurement and IR spectrum measurement confirmed that the obtained compound was the specific example compound 23.

Synthesis Example 10 Synthesis of Specific Example Polymer 23
Using 1.0 g of the specific example compound 23 obtained in Synthesis Example 9, 10 ml of ethylene glycol and 0.02 g of tetrabutoxytitanium were placed in a 50 ml three-necked eggplant flask and stirred with heating at 200 ° C. for 5 hours in a nitrogen atmosphere.
After confirming by TLC that the specific compound 23 as a raw material had reacted and disappeared, the pressure was reduced to 50 Pa and the mixture was heated to 210 ° C. while distilling off ethylene glycol, and the reaction was continued for 6 hours.

Thereafter, the mixture was cooled to room temperature (25 ° C.), dissolved in 50 ml of tetrahydrofuran, insoluble matter was filtered through a 0.5 μl polytetrafluoroethylene (PTFE) filter, the filtrate was distilled off under reduced pressure, and then 300 ml of monochlorobenzene. It was dissolved in 1N-HCl 300 ml and water 500 ml × 3 in this order. The monochlorobenzene solution was distilled off under reduced pressure to 30 ml and dropped into ethyl acetate / methanol = 1/3: 800 ml to reprecipitate the polymer.
The polymer obtained was filtered, washed with methanol, and then vacuum dried at 60 ° C. for 16 hours to obtain 0.7 g of a polymer [specific example polymer 23].

When the molecular weight of this polymer was measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8120GPC), the weight average molecular weight Mw = 6.6 × 10 ⁴ (in terms of styrene), Mw / Mn = 2. The polymerization degree p determined from the molecular weight of the low-molecular compound as the raw material was 69.

Synthesis Example 11 Synthesis of Specific Example Compound 15
Under a nitrogen atmosphere, 3-bromobiphenyl (23 g), methyl 4-acetaminophenylpropionate 20 g, potassium carbonate 18.8 g, copper sulfate pentahydrate 1.1 g, and tridecane 20 ml were placed in a 300 ml three-necked flask and a nitrogen stream Under stirring at 200 ° C. for 24 hours. After this reaction, 150 ml of ethylene glycol and 6.5 g of potassium hydroxide were added, heated under reflux for 3 hours under a nitrogen stream, cooled to room temperature (25 ° C.), poured into 150 ml of distilled water, and neutralized with hydrochloric acid. Then, crystals were precipitated. This was filtered, washed thoroughly with water, and then transferred to a 500 ml flask. To this, 500 ml of toluene was added and heated to reflux, water was removed azeotropically, 100 ml of methanol and 1.0 ml of concentrated sulfuric acid were added, and the mixture was heated to reflux for 5 hours under a nitrogen stream. After the reaction, extraction with toluene was performed, and the organic layer was sufficiently washed with distilled water. Subsequently, after drying with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and 25 g of DAA-6 was obtained by recrystallization from hexane.

  Under a nitrogen atmosphere, in a 200 ml three-necked flask, DAA-6 (9.9 g), 3,7-dibromodibenzothiophene dioxide (5.2 g), palladium (II) acetate (150 mg), rubidium carbonate (19.6 g). And dissolved in 50 ml of xylene. Tri-tert-butylphosphine (420 mg) was quickly added, and the mixture was heated and refluxed magnetically stirred for 9 hours under a nitrogen atmosphere. After confirming disappearance of the DAA-6 spot by TLC (hexane / ethyl acetate = 3/1), the mixture was cooled to room temperature (25 ° C.). After removing inorganic substances by Celite suction filtration, washing was carried out in the order of dilute hydrochloric acid 100 ml, water 200 ml × 3, saturated saline 200 ml × 1 in this order. After drying over anhydrous sodium sulfate, purification was performed by silica gel column chromatography (hexane / toluene = 3/1), followed by vacuum drying at 70 ° C. for 15 hours to obtain Specific Example Compound 15 (5.2 g).

¹ H-NMR spectrum measurement and IR spectrum measurement confirmed that the obtained compound was the specific example compound 15.

Synthesis Example 12 Synthesis of Specific Example Polymer 18
Using 1.0 g of the specific example compound 15 obtained in Synthesis Example 11, 10 ml of ethylene glycol and 0.02 g of tetrabutoxytitanium were placed in a 50 ml three-necked eggplant flask, and the mixture was heated and stirred at 200 ° C. for 5 hours in a nitrogen atmosphere.
After confirming by TLC that the above-mentioned specific compound 15 as a raw material reacted and disappeared, the pressure was reduced to 50 Pa and the mixture was heated to 210 ° C. while distilling off ethylene glycol, and the reaction was continued for 6 hours.

Thereafter, the mixture was cooled to room temperature (25 ° C.), dissolved in 50 ml of tetrahydrofuran, insoluble matter was filtered through a 0.5 μl polytetrafluoroethylene (PTFE) filter, the filtrate was distilled off under reduced pressure, and then 300 ml of monochlorobenzene. It was dissolved in 1N-HCl 300 ml and water 500 ml × 3 in this order. The monochlorobenzene solution was distilled off under reduced pressure to 30 ml and dropped into ethyl acetate / methanol = 1/3: 800 ml to reprecipitate the polymer.
The obtained polymer was filtered, washed with methanol, and then vacuum dried at 60 ° C. for 16 hours to obtain 0.6 g of a polymer [specific example polymer 18].

When the molecular weight of this polymer was measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8120GPC), the weight average molecular weight Mw = 5.1 × 10 ⁴ (in terms of styrene), Mw / Mn = 2. And the degree of polymerization p determined from the molecular weight of the low molecular weight compound as the raw material was 67.

(Preparation of image carrier for image forming apparatus)
[Example 1]
A solution comprising 10 parts by mass of a zirconium compound (Orgatechs ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 1 part by mass of a silane compound (A1110, manufactured by Nihon Unicar), 40 parts by mass of i-propanol and 20 parts by mass of butanol on an aluminum substrate. The film was applied by a dip coating method and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.6 μm. On top of this, chlorogallium phthalocyanine crystals with strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 7.4 °, 16.6 °, 25.5 ° and 28.3 ° in the X-ray diffraction spectrum. 1 part by mass is mixed with 1 part by mass of polyvinyl butyral resin (S-REC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts by mass of n-butyl acetate, and after being treated with a glass shaker for 1 hour and dispersed, it is obtained. The obtained coating solution was applied onto the undercoat layer by a dip coating method and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer.
Next, 2 parts by mass of the specific compound 6 obtained as described above and 3 parts by mass of a bisphenol (Z) polymer compound (viscosity average molecular weight: 40,000) having the following structure are added to 35 parts by mass of chlorobenzene. After heating and dissolving, the temperature was returned to room temperature (25 ° C.). This coating solution was applied onto the charge generation layer by dip coating, and heated at 130 ° C. for 60 minutes to form a charge transport layer having a thickness of 20 μm.

[Example 2 to Example 12]
Instead of the specific example compound 6 used in Example 1, a specific example polymer 10, a specific example compound 7, a specific example polymer 12, a specific example compound 17, a specific example polymer 20, a specific example compound 19, a specific example polymer 22, a specific example An image carrier for an image forming apparatus was produced in the same manner as in Example 1 except that Example Compound 23, Specific Example Polymer 23, Specific Example Compound 15 and Specific Example Polymer 18 were used.

[Example 13]
Instead of the chlorogallium phthalocyanine crystal used in Example 1, 7.5 °, 9.9 °, 12.5 °, 16.3 ° of the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum, An image carrier for an image forming apparatus was produced in the same manner as in Example 1 except that hydroxygallium phthalocyanine crystals having strong diffraction peaks at 18.6 °, 25.1 °, and 28.3 ° were used.

[Comparative Example 1]
An image carrier for an image forming apparatus was produced by the method described in Example 1 except that the compound (X) having the following structure was used in place of the specific example compound 6 used in Example 1.

[Comparative Example 2]
An image carrier for an image forming apparatus was produced by the method described in Example 1 except that the compound (XI) (p = 52) having the following structure was used instead of the specific example compound 6 used in Example 1. .

[Comparative Example 3]
An image carrier for an image forming apparatus was produced by the method described in Example 1, except that the compound (XII) having the following structure was used in place of the specific example compound 6 used in Example 1.

[Comparative Example 4]
An image carrier for an image forming apparatus was produced by the method described in Example 1 except that the compound (XIII) (p = 55) having the following structure was used instead of the specific compound 6 used in Example 1. .

(Evaluation)
In order to evaluate the electrophotographic characteristics using the image carriers for the image forming apparatuses obtained in the above examples and comparative examples, an electrostatic copying paper test apparatus (electrostatic analyzer EPA-8100, manufactured by Kawaguchi Electric Co., Ltd.) Was used, and was charged with a corona discharge of -6 KV in an environment of 20 ° C. and 40% RH. Then, the tungsten lamp was changed to a monochromatic light of 800 nm using a monochromator, and 1 μW on the surface of the photoreceptor. Irradiation was carried out after adjusting to / cm ² .
Then, the surface potential V ₀ (V) on the surface of the photoreceptor immediately after charging, and the half-exposure amount E1 / 2 (erg / cm ² ) at which the surface potential becomes 1/2 × V _O (V) by light irradiation on the surface of the photoreceptor. Was measured (initial characteristics). Thereafter, 10 lux of white light was irradiated for 1 second, and the residual potential VRP (V) remaining on the surface of the photoreceptor was measured (initial characteristics).
Furthermore, V ₀ , E1 / 2, and VRP after repeating the above charging, exposure (monochromatic light at 800 nm, exposure amount is half exposure amount), and irradiation with white light (10 lux) 1000 times, and Fluctuations ΔV ₀ , ΔE1 / 2 and ΔVRP were evaluated (stability and durability).

Next, an image forming apparatus was produced using the image carrier for the image forming apparatus obtained in the above examples and comparative examples. As elements other than the image carrier for the image forming apparatus, those mounted on a printer Documenter C6550I manufactured by Fuji Xerox were used.
Each image forming apparatus was subjected to an image forming test for 10,000 sheets (image density 10%, cyan 100%) in an environment of 28 ° C. and 75% RH. In this test condition, the process of each cartridge is performed as usual, but toners of cartridges other than cyan are not used (supplied). After the test, toner cleaning properties (charger contamination and image quality deterioration due to poor cleaning) and image quality (process black 1 dot line oblique 45 degree fine line reproducibility) were evaluated. The cleaning method and image quality evaluation methods and evaluation criteria are as follows, and Table 1 shows the obtained results.

The cleaning property was evaluated visually and evaluated based on the following evaluation criteria.
○: Good △: Partially (about 10% or less of the whole) streak-like image quality defect ×: Widely streak-like image quality defect

The image quality was judged using a magnifying glass and evaluated based on the following evaluation criteria.
A: Good B: Partially defective (no problem in practical use)
C: Defect (thin lines are not reproduced)

  From the above results, it can be seen that the image carrier for the image forming apparatus obtained in this example has a lower residual potential variation due to repeated use than in the comparative example. It can also be seen that the image obtained by the image forming apparatus having the image carrier for the image forming apparatus has good image quality.

DESCRIPTION OF SYMBOLS 1 Image carrier for image forming apparatuses 2 Conductive support 3 Photosensitive layer 4 Subbing layer 5 Charge generation layer 6 Charge transport layer 7 Protective layer 8 Charge generation / transport layer 200 Image forming apparatus 207 Image carrier for image forming apparatus 208 Charging device 209 Power source 210 Exposure device 211 Development device 212 Transfer device 213 Cleaning device 214 Static eliminator 215 Fixing device 216 Mounting rail 217 Opening portion 218 for static elimination exposure Opening portion 300 for exposure Process cartridge 500 Transfer object

Claims (4)

An image carrier for an image forming apparatus, comprising: a support; and a photosensitive layer containing a compound represented by the following general formula (I) on the support.

[In General Formula (I), each R ¹ independently represents a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms, Ar represents a substituted or unsubstituted phenyl group, Or a monovalent polynuclear aromatic hydrocarbon group having 2 to 10 unsubstituted aromatic rings, a monovalent condensed aromatic hydrocarbon group having 2 to 10 substituted or unsubstituted aromatic rings, or substituted or unsubstituted Of the monovalent aromatic heterocyclic group, and n independently represents 0 or more and 7 or less. ] An image carrier for an image forming apparatus, comprising: a support; and a photosensitive layer containing a compound represented by the following general formula (II-1) on the support.

[In General Formula (II-1), each Y ¹ independently represents a substituted or unsubstituted divalent hydrocarbon group, A ¹ represents a group represented by the following General Formula (II-2), R ² each independently represents a hydrogen atom, a monovalent polynuclear aromatic hydrocarbon group having 2 to 10 substituted or unsubstituted aromatic rings, or a monovalent polyvalent aromatic hydrocarbon group having 2 to 10 substituted or unsubstituted aromatic rings. Condensed aromatic hydrocarbon group, substituted or unsubstituted monovalent linear hydrocarbon group having 1 to 6 carbon atoms, or substituted or unsubstituted monovalent branched hydrocarbon group having 2 to 10 carbon atoms Represents a group. Each m independently represents an integer of 1 to 5, and p represents an integer of 5 to 5,000. ]

[In the general formula (II-2), Ar represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon group having 2 to 10 aromatic rings, a substituted or unsubstituted aromatic group. It represents a monovalent condensed aromatic hydrocarbon group having 2 to 10 rings, or a substituted or unsubstituted monovalent aromatic heterocyclic group, and n independently represents 0 or more and 7 or less. ]   An image holding body for an image forming apparatus according to claim 1 or 2, a charging unit for charging the image holding body for an image forming apparatus, and exposing the charged image holding body for an image forming apparatus to electrostatic An exposure unit that forms a latent image, a developing unit that develops the electrostatic latent image to form a toner image, a transfer unit that transfers the toner image to a transfer target, and the image carrier for the image forming apparatus are cleaned. A process cartridge having at least one selected from cleaning means.   An image holding member for an image forming apparatus according to claim 1, a charging means for charging the image holding member for an image forming apparatus, and the charged image holding member for an image forming apparatus are exposed and statically exposed. An image forming apparatus comprising: an exposure unit that forms an electrostatic latent image; a developing unit that develops the electrostatic latent image to form a toner image; and a transfer unit that transfers the toner image to a transfer target.