JP5261870B2 - Method for producing amine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellent method with which an amine compound utilized for electronic materials can inexpensively be produced with slight impurities adversely affecting electrical characteristics. <P>SOLUTION: The method for producing the amine compound is carried out as follows. A raw material amine compound is reacted with a halogen compound in the presence of metallic copper and a tertiary phosphorus compound. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a method for producing an amine compound, an amine compound produced thereby, and an electrophotographic photosensitive member, a cartridge, and an image forming apparatus using the amine compound.

  Generally, as a charge transport medium used in an electrophotographic photosensitive member, there are a case where a polymer charge transport material is used and a case where a low molecular charge transport compound is dispersed and dissolved in a binder polymer. Many organic compounds have been proposed as these charge transport materials. In particular, many compounds having a triarylamine structure have excellent electrophotographic characteristics compared to other compounds such as easy molecular design and high hole mobility, and many proposals have been disclosed thereafter. .

  However, even in an electrophotographic photoreceptor using these triarylamine compounds as a charge transport material, the sensitivity characteristics are not always sufficient, and potential fluctuations during repeated use, in a low or high humidity environment. There are still points to be improved such as image defects.

  The characteristics of the electrophotographic photosensitive member are influenced not only by the structure of the charge transport material but also by the manufacturing method thereof. In particular, it has been found that the influence of the manufacturing method of the charge transport material appears strongly with respect to the change in the residual potential and the image characteristics. There is a point that cannot be explained only by the purity of the charge transporting material and the presence of impurities, and a method for producing an arylamine compound having excellent electrophotographic characteristics is urgently required.

  In addition, not only the charge transport material of an electrophotographic photoreceptor, but also an electronic material such as an organic electroluminescence (EL) element, there is a strong demand for a method for producing an arylamine compound having excellent light emission characteristics.

  In general, an amine compound such as an arylamine compound used for an electronic material is usually synthesized by a condensation reaction between a corresponding aryl halide and an amine compound.

  For example, a method of synthesizing from a corresponding iodobenzene and an amine compound using a copper catalyst (Ullmann reaction) is known, but these reactions use a large amount of copper catalyst and require a high reaction temperature. However, because the reaction time is long, the yield of the arylamine compound as a product is lowered, and at the same time, coloring impurities and decomposition products that adversely affect the electrophotographic characteristics are produced as a by-product, so that the produced arylamine is produced. There was a problem that separation and purification of the compound from the reaction system became difficult, and purification required high costs.

  As an improved method, a method of synthesizing an arylamine compound using a phosphine ligand and copper iodide has been reported (see Non-Patent Document 1). In order to use the obtained arylamine compound as an electronic material, purification is relatively difficult.

  Moreover, although the synthesis method of the arylamine compound using a quaternary phosphonium compound and a copper catalyst is reported (refer patent document 1), in addition to using expensive copper salt compared with metallic copper, this method is used. In order to use the obtained arylamine compound as an electronic material, purification is relatively difficult and it cannot be said that it is an industrially advantageous method.

  In recent years, synthesis examples of amine compounds using platinum group catalysts such as palladium have been reported. However, there are problems of noble metal resources, costs, etc., and this is still not satisfactory as an industrial production method. .

International Publication No. 2004-24670 Pamphlet Chemical Communications, 2003, p. 2460

  The present invention has been made to solve the above problems. That is, an object of the present invention is to provide an excellent amine compound production method capable of producing an amine compound that is excellent in electrical characteristics and can be suitably used in an electronic material at low cost and in high yield, and An amine compound obtained thereby, and an electrophotographic photosensitive member, a cartridge, and an image forming apparatus using the amine compound are provided.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors use economically inexpensive metallic copper together with a tertiary phosphorus compound when producing an amine compound by reacting a raw material amine compound with a halogen compound. Thus, the present invention was completed by finding that an amine compound can be produced at a relatively low cost without impairing the reaction yield, and that the obtained amine compound has excellent electrical characteristics and can be used effectively as an electronic material. It was.

That is, the gist of the present invention resides in a method for producing an amine compound, characterized in that a secondary amine compound and an aryl halide are reacted in the presence of metallic copper and a trialkyl phosphorus compound or a triaryl phosphorus compound. Item 1).
Here, the reaction is preferably performed in the presence of a base (claim 2) .

  According to the method for producing an amine compound of the present invention, it is possible to produce an amine compound that is excellent in electrical characteristics and can be suitably used as an electronic material such as an electrophotographic material at a relatively low cost and in a high yield. In addition, by using the amine compound obtained by this production method, an electrophotographic photosensitive member having high durability, excellent in electrical characteristics, image forming characteristics, etc., and excellent in stability of characteristics when repeatedly used, A photoconductor cartridge and an image forming apparatus can be realized.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following descriptions, and can be implemented with appropriate modifications without departing from the gist of the present invention.

[I. Method for producing amine compound)
In the method for producing an amine compound of the present invention, an amine compound is synthesized by reacting a raw material amine compound and a halogen compound in the presence of metallic copper and a tertiary phosphorus compound. Furthermore, it is preferable that a base coexists during the reaction.

The reaction mechanism in the production method of the present invention is not clear, but is presumed as follows.
That is, during the reaction, metallic copper functions as a reaction catalyst, and the tertiary phosphorus compound seems to be useful for accelerating the reaction rate and suppressing side reactions. Further, the base is effective for trapping acid in the reaction process and controlling side reactions, and metal alkoxide is considered to be effective for improving the reaction rate.

<Raw material amine compound>
The amine compound used as a raw material in the present invention (this may be referred to as “raw material amine compound” in the present specification) is not particularly limited, but is usually a primary or secondary amine compound.

  The type of hydrocarbon group bonded to the nitrogen atom of the amine is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an arylalkyl group, and an alkylaryl group. In the case of a secondary amine compound, the two hydrocarbon groups of the amine nitrogen atom may be the same or different. Further, these hydrocarbon groups may be bonded to each other to form a ring. The number of carbon atoms of each hydrocarbon group is usually 1 or more, and usually 20 or less, preferably 15 or less.

Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, a pyrenyl group, a fluorenyl group, and an anthryl group.
Examples of the alkyl group include a chain alkyl group and a cyclic alkyl group, and any of them may be used. Examples of chain alkyl groups include methyl group, ethyl group, propyl group (n-propyl group, i-propyl group), butyl group (n-butyl group, t-butyl group, isobutyl group, s-butyl group). , A pentyl group (such as n-pentyl group), a hexyl group (such as n-hexyl group) and the like. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group. Further, these chain alkyl groups and cyclic alkyl groups may be bonded.
Examples of the alkenyl group and alkynyl group include groups obtained by converting one or more carbon-carbon bonds on the hydrocarbon chain as a double bond or a triple bond in the above exemplified alkyl group. Specific examples include a vinyl group (ethenyl group) and a propenyl group (1-propenyl group, 2-propenyl group).
Examples of the arylalkyl group include groups in which the above-exemplified alkyl groups are substituted with one or more aryl groups exemplified above. Specific examples include a benzyl group and a phenylethyl group.
Examples of the alkylaryl group include groups in which the above-exemplified aryl groups are substituted with one or more alkyl groups exemplified above. Specifically, a tolyl group (o-tolyl group, m-tolyl group, p-tolyl group), a xylyl group (3,4-xylyl group, etc.), etc. are mentioned.

  These hydrocarbon groups may further have a substituent without departing from the spirit of the present invention. The type of the substituent is not particularly limited as long as it does not depart from the gist of the present invention. Examples thereof include a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.); hydroxyl group; nitro group; cyano group; Oxy group; carboxyl group; sulfonic acid group; amino group; alkyl group; alkenyl group; alkynyl group; aryl group; heterocyclic group (sulfur-containing heterocyclic group, oxygen-containing heterocyclic group, nitrogen-containing heterocyclic group, etc.); Group; aryloxy group; alkylthio group; arylthio group; carboxylic acid ester group; sulfonic acid ester group; substituted silyl group (trimethylsilyl group and the like); substituted amino group; amide group and the like. In addition, when said hydrocarbon group has these substituents, it is preferable that carbon number of the whole substituted hydrocarbon group including the substituent becomes in the said prescription | regulation range.

Among these, from the viewpoint of improving the electrical properties of the amine compound to be produced, the raw material amine compound is preferably an arylamine compound having an aryl group or alkylaryl group as a hydrocarbon group, that is, an aniline derivative is particularly preferable.
However, the above is merely an example, and the raw material amine compound used for the reaction may be appropriately selected in consideration of the structure of the amine compound to be produced and the halogen compound to be used in combination.

<Halogen compounds>
The type of the halogen compound used in the present invention is not particularly limited, but is usually a halogenated hydrocarbon in which a halogen atom is bonded to a hydrocarbon group.

The kind of halogen atom is not particularly limited. Examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a bromine atom or an iodine atom is preferable.
The number of halogen atoms per molecule of the halogen compound is not particularly limited and may be 1 or 2 or more, but is preferably 1 to 3 from the viewpoint of practicality of the resulting amine compound as an electronic material. When the number of halogen atoms per molecule is 2 or more, the plurality of halogen atoms may be the same or different from each other, but are preferably the same from the viewpoint of ease of production of the compound.

  The kind of hydrocarbon group is not particularly limited. Examples of monovalent hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups, arylalkyl groups, alkylaryl groups, arylalkylaryl groups, alkylarylalkyl groups, and the like. Examples of the divalent or higher valent hydrocarbon group include those obtained by omitting one or more hydrogen atoms from the above monovalent hydrocarbon group. The carbon number of each hydrocarbon group is usually 1 or more and usually 30 or less, preferably 20 or less.

Specific examples of the aryl group, alkyl group, alkenyl group, alkynyl group, arylalkyl group, and alkylaryl group include the same groups as those exemplified above for the raw material amine compound.
Specific examples of the alkylarylalkyl group include groups in which the above-exemplified arylalkyl groups are further substituted by one or more alkyl groups exemplified above.
Specific examples of the arylalkylaryl group include groups in which the above-exemplified alkylaryl groups are further substituted with one or more aryl groups exemplified above.
Moreover, as a bivalent hydrocarbon group, the bivalent group induced | guided | derived by omitting one more hydrogen atom from these monovalent exemplary groups is preferable.

  Among them, from the viewpoint of improving the electrical characteristics of the amine compound to be produced, the monovalent hydrocarbon group is particularly preferably an aryl group, an arylalkyl group, or an arylalkylaryl group, and the divalent hydrocarbon group is Groups derived from these groups are preferred.

  These hydrocarbon groups may further have a substituent without departing from the spirit of the present invention. The type of the substituent is not particularly limited as long as it does not depart from the gist of the present invention. Examples thereof include the same groups as those exemplified above for the raw material amine compound.

That is, as the halogen compound, an iodinated hydrocarbon or a brominated hydrocarbon is preferable, and an aryl iodide derivative or an aryl bromide derivative is particularly preferable.
However, the above is just an example, and the halogen compound used for the reaction may be appropriately selected in consideration of the structure of the amine compound to be produced and the raw material amine compound to be used in combination.

<Relationship between raw material amine compound and halogen compound>
The combination of the raw material amine compound and the halogen compound is not particularly limited, and an appropriate combination may be selected according to the structure of the desired amine compound. For example, when producing a triarylamine compound exemplified later, examples of preferable combinations include a combination of a diarylamine compound and an aryl monohalide, a combination of a diarylamine compound and an aryl dihalide, an arylamine compound and an aryl monohalide And combinations of (di) alkylamine compounds and alkyl halides.

  Moreover, the usage ratio of the raw material amine compound and the halogen compound is selected so as to be an appropriate equivalent ratio according to the structures of the raw material amine compound and the halogen compound and the structure of the target amine compound.

<Metal copper>
Although it does not specifically limit as metallic copper used for this invention, Copper powder is preferable and an electrolytic copper powder is preferable from an economical reason. Among copper powders, those treated with stearic acid or the like for surface activation are also preferably used.

  The amount of metallic copper used is a value in terms of simple metal equivalent to 1 mole equivalent of halogen of the halogen compound, and is usually 0.01 mole equivalent or more, preferably 0.1 mole equivalent or more, more preferably 0.3 mole equivalent or more, The range is usually 2 molar equivalents or less, preferably 1.5 molar equivalents or less. If the amount of metallic copper used is too small, the effects due to the use of metallic copper do not appear remarkably and a sufficient reaction rate may not be obtained. On the other hand, if the amount of metallic copper used is too large, it will not be possible to obtain an improvement in reaction rate and yield commensurate with the amount used, and stirring of the reaction system will be difficult, and labor and cost at the time of disposal, It is not preferable also in terms of crude product purification efficiency.

<Tertiary phosphorus compound>
The type of tertiary phosphorus compound used in the present invention is not particularly limited as long as it is a compound in which three organic groups are bonded to a phosphorus atom.

Examples of organic groups bonded to the phosphorus atom include aryl groups, alkyl groups, alkenyl groups, alkynyl groups, heterocyclic groups (sulfur-containing heterocyclic groups, oxygen-containing heterocyclic groups, nitrogen-containing heterocyclic groups, etc.), condensed poly A cyclic group, an alkoxy group, an aryloxy group; an alkylthio group; an arylthio group; a substituted silyl group (such as a trimethylsilyl group); The number of carbon atoms of the organic group per organic group is usually 1 or more, and usually 30 or less, preferably 10 or less.
Especially, as an organic group, an aryl group or an alkyl group is preferable. Specific examples of the aryl group and the alkyl group include the same groups as those exemplified above for the raw material amine compound.

  The three organic groups bonded to the phosphorus atom may be the same or different from each other, but are preferably the same from the viewpoint of ease of production. That is, as the tertiary phosphorus compound, triarylphosphine (triarylphosphorus compound) or trialkylphosphine (trialkylphosphorus compound) is preferable.

  Of these, triarylphosphine is preferable in view of electrical characteristics and image forming characteristics of the amine compound to be produced as an electronic material. Specific examples of triarylphosphine include triphenylphosphine, tri (o-tolyl) phosphine, tri (p-tolyl) phosphine and the like. Of these, triphenylphosphine is preferable because it can be produced industrially in large quantities and is inexpensive.

  On the other hand, trialkylphosphine is preferable from the viewpoint of improving the reaction rate, but it may adversely affect the electrical properties of amine compounds that are rarely produced. Specific examples include tri-n-butylphosphine, tri-t-butylphosphine, tricyclohexylphosphine, and the like. Among these, tricyclohexylphosphine is preferable in terms of electrical characteristics and handling, and tri-n-butylphosphine is preferable in terms of reactivity.

  The amount of the tertiary phosphorus compound used is a value in terms of simple metal equivalent to 1 mole equivalent of halogen in the halide, and is usually 0.001 mole equivalent or more, preferably 0.01 mole equivalent or more, more preferably 0.1 mole equivalent or more. In addition, it is usually in the range of 1 molar equivalent or less, preferably 0.5 molar equivalent or less. When the amount of the tertiary phosphorus compound used is too small, the effect of using the tertiary phosphorus compound does not appear remarkably, and there is a possibility that a sufficient reaction rate cannot be obtained. On the other hand, if the amount of the tertiary phosphorus compound used is too large, the reaction rate and yield corresponding to the amount used cannot be improved, and it is also preferable in terms of labor and cost at the time of disposal, the efficiency of purification of the crude product, etc. Absent.

<Base>
In the production method of the present invention, a base is preferably allowed to coexist in the reaction system. The type of base is not particularly limited, but various metal salts are usually used.

Metal salts are divided into inorganic salts and organic salts.
Inorganic salts include alkali metal inorganic salts and other general metal inorganic salts, but alkali metal inorganic salts are preferred. Examples of the alkali metal inorganic salt include potassium carbonate, sodium carbonate, cesium carbonate, tripotassium phosphate, trisodium phosphate, sodium hydroxide, potassium hydroxide and the like.

However, from the viewpoint of improving the reaction rate, organic salts are preferred, and metal alkoxides are particularly preferred.
Examples of the metal alkoxide include those containing alkali metals and those containing other general metals, but those containing alkali metals are preferred. Examples include sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, lithium methoxide, lithium ethoxide, lithium tert-butoxide, sodium phenoxide, potassium phenoxide, Examples thereof include lithium phenoxide. Among these, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferable. Among these, sodium tert-butoxide or potassium tert-butoxide is more preferable from the viewpoint of improving the reaction rate, and sodium methoxide is particularly preferable from the viewpoint of cost and reaction controllability.

  The amount of the base used is a value with respect to 1 mole equivalent of the halogen atom of the halogen compound, usually 0.5 mole equivalent or more, preferably 1.0 mole equivalent or more, and usually 2 mole equivalent or less, preferably 1.5 mole equivalent. Hereinafter, the range is more preferably 1.3 molar equivalents or less. If the amount of the base used is too small, the progress of the reaction will be slow, and the reaction may not be completed. On the other hand, if the amount of the base used is too large, the effect of improving the yield cannot be obtained, which is economically disadvantageous and easily produces by-products, which is not preferable from the viewpoint of electrical characteristics.

<Solvent>
The reaction between the starting amine compound and the halogen compound is usually carried out in the presence of a solvent. The reaction solvent may be an organic solvent that can suitably dissolve or disperse raw materials (raw amine compounds, halogen compounds) and is inactive with these raw materials and reaction components such as metallic copper and tertiary phosphorus compounds. Any organic solvent can be used.

  Among these, from the viewpoint of solubility in the raw material, it is preferable to use an aromatic organic solvent or an ether organic solvent as the reaction solvent, and it is more preferable to use an aromatic organic solvent. Among the aromatic organic solvents, alkyl-substituted benzene compounds such as toluene, xylene and trimethylbenzene, and condensed ring aromatic compounds such as tetralin are preferable. On the other hand, as the ether organic solvent, monoglyme, diglyme, triglyme, dioxane and the like are preferable.

  When the reaction solvent is used, the amount used is not particularly limited, but is usually 30% by weight or more, preferably 50% by weight or more, and usually 1000% by weight with respect to the total raw materials (raw material amine compound and halogen compound). It is in the range of not more than wt%, preferably not more than 500 wt%. If the proportion of the solvent for reaction is too small, it is not preferable because the dispersibility of the raw materials is insufficient and the reaction does not proceed easily. Conversely, if the proportion of the solvent for reaction is too large, the reaction rate becomes slow. Moreover, it is not preferable because the manufacturing cost is high and it is industrially disadvantageous.

<Synthetic reaction>
The procedure for carrying out the reaction is not particularly limited, but usually the reaction is carried out by bringing the raw material amine compound into contact with the halogen compound in a reaction vessel in the presence of metallic copper, a tertiary phosphorus compound and a base used as necessary. Just do it.
The order in which the individual components are added is not particularly limited. For example, a raw material amine compound and a halogen compound are mixed in the presence of a solvent to prepare a reaction system solution, and metal copper, a tertiary phosphorus compound, and a base used as necessary are added to the reaction system solution for reaction. Can be started.

  In addition, when metal alkoxide is used as the base during the synthesis reaction, it is also effective to forcibly discharge the low-boiling components derived from the base generated in the system early out of the system from the viewpoint of efficiently promoting the reaction. It is. Nitrogen flow is effective for discharging. When the synthesis reaction is performed under a nitrogen flow (nitrogen flow), the nitrogen flow rate is usually 0.0001% or more, preferably 0.001% or more, and usually 5% per minute with respect to the volume of the reaction vessel. % Or less, preferably 3% or less. Nitrogen to be used is preferably of high purity, but nitrogen produced from liquid nitrogen may be used for inexpensive production.

  The temperature during the reaction is not particularly limited, but is usually in the range of 100 ° C. or higher, preferably 140 ° C. or higher, and usually 250 ° C. or lower, preferably 200 ° C. or lower. If the temperature at the time of reaction is too low, the reaction rate becomes slow and the raw materials may not react completely, which is not preferable. On the other hand, if the temperature at the time of reaction is too high, by-products are easily generated and the purity is low. It is also not preferable because the purification becomes difficult because of low.

  The reaction time is not particularly limited, but may be performed until the reaction reaches the end point (that is, until almost all the raw materials are reacted and the remaining raw materials are substantially eliminated). Whether or not the reaction has reached the end point can be confirmed by a technique such as high performance liquid chromatography.

After completion of the reaction, it is preferable to separate by a method such as filtration in order to remove excess base and the like from the reaction system solution. Inorganic components can also be removed by solvent fractionation using purified water.
In order to obtain a crude product from the reaction system solution, for example, a method of cooling the reaction system solvent, or a solvent that is miscible with the reaction system solvent but has a low solubility of the crude product is added to solidify the crude product. And the like.

<Amine compound>
The amine compound obtained by the production method of the present invention is usually a secondary or tertiary amine compound, preferably a tertiary amine compound. Although the kind in particular is not restrict | limited, A triarylamine compound is preferable at the point that it is useful as an electronic material and the effect by application of this invention is large.

Examples of the triarylamine compound in which the effects of the present invention are remarkably exhibited include those having a structure represented by the following general formula (1) or general formula (2).

In general formula (1) and general formula (2), the rings represented by A to I each independently represent a benzene ring which may have a substituent. Although the kind of substituent which each benzene ring may have is not particularly limited, examples thereof include various substituents exemplified in the description of the raw material amine compound. Of these, hydrocarbon groups are preferred. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an arylalkyl group, and an alkylaryl group. The carbon number of the hydrocarbon group is usually 1 or more, and usually 20 or less, preferably 10 or less.
These substituents may be further substituted with other organic groups without departing from the spirit of the present invention. Examples of this organic group include various substituents exemplified in the description of the raw material amine compound.
The number of substituents that each benzene ring has is usually from 0 to 4, and preferably from 0 to 2. In the case of having a plurality of substituents, these may be bonded to each other via a linking group or directly to form a ring structure.

  Specific examples of amine compounds produced by the production method of the present invention and used for electronic materials are shown below, but the amine compounds produced by the production method of the present invention are not limited to these examples. .

  Among these, examples in which the effects of the present invention are particularly prominent include those having a diphenylbenzidine structure (the above-described exemplary compounds (T-0) (T-5) and the like) and those having a triphenylamine structure (the above-mentioned) Examples of the compound (T-8) (T-9) and the like).

  In addition, the production method of the present invention may be used to produce intermediates in the synthesis process of the triarylamine compounds exemplified above and other various amine compounds.

The amine compound obtained by the production method of the present invention (hereinafter abbreviated as “the amine compound of the present invention” as appropriate) is excellent in various electrical properties. This is presumably because the content of impurities that affect the electrical properties of the amine compound is low. Therefore, it can be used as various electronic materials without performing complicated separation / purification work as it is or simply by performing a simple purification operation.
Among these, triarylamine compounds typified by those exemplified above (hereinafter, abbreviated as “triarylamine compounds of the present invention” as appropriate) are suitable as a charge transport material for a photosensitive layer of an electrophotographic photoreceptor. Can be used.

  Details of the electrophotographic photoreceptor and the image forming apparatus using the amine compound of the present invention will be described below.

[II. Electrophotographic photoreceptor]
The electrophotographic photoreceptor of the present invention has a photosensitive layer provided on a conductive support, and contains the amine compound of the present invention described above in the photosensitive layer. In particular, the triarylamine compound described above (the triarylamine compound of the present invention) is preferably contained in the photosensitive layer as a charge transport material.

  As the conductive support, for example, a metal material such as aluminum, aluminum alloy, stainless steel, copper, nickel, or a resin material imparted with conductivity by adding conductive powder such as metal, carbon, tin oxide, Mainly used are resin, glass, paper, or the like obtained by depositing or coating a conductive material such as aluminum, nickel, ITO (indium oxide tin oxide alloy) on the surface. As a form, a drum shape, a sheet shape, a belt shape or the like is used. A conductive material having an appropriate resistance value may be coated on a conductive support made of a metal material in order to control conductivity and surface properties or to cover defects.

  When a metal material such as an aluminum alloy is used as the conductive support, it may be used after anodizing. When the anodizing treatment is performed, it is desirable to perform a sealing treatment by a known method.

For example, an anodic oxidation film is formed by anodizing in an acidic bath such as chromic acid, sulfuric acid, oxalic acid, boric acid, sulfamic acid, etc. give. In the case of anodic oxidation in sulfuric acid, the sulfuric acid concentration is 100 to 300 g / l, the dissolved aluminum concentration is 2 to 15 g / l, the liquid temperature is 15 to 30 ° C., the electrolysis voltage is 10 to 20 V, and the current density is 0.5 to Although it is preferable to set within the range of ² A / dm ² , it is not limited to the above conditions.

  It is preferable to perform a sealing treatment on the anodic oxide film thus formed. The sealing treatment may be performed by a known method. For example, the low-temperature sealing treatment is performed by immersing in an aqueous solution containing nickel fluoride as a main component, or the high temperature is immersed in an aqueous solution containing nickel acetate as a main component. It is preferable to perform a sealing treatment.

  The concentration of the nickel fluoride aqueous solution used in the case of the low-temperature sealing treatment can be appropriately selected, but more preferable results can be obtained when it is used in the range of 3 to 6 g / l. In order to smoothly proceed with the sealing treatment, the treatment temperature is usually 25 ° C. or higher, preferably 30 ° C. or higher, and usually 40 ° C. or lower, preferably 35 ° C. or lower, and a nickel fluoride aqueous solution. The pH is usually 4.5 or more, preferably 5.5 or more, and usually 6.5 or less, preferably 6.0 or less. As the pH adjuster, oxalic acid, boric acid, formic acid, acetic acid, sodium hydroxide, sodium acetate, aqueous ammonia and the like can be used. The treatment time is preferably in the range of 1 to 3 minutes per 1 μm of film thickness. In order to further improve the physical properties of the film, cobalt fluoride, cobalt acetate, nickel sulfate, a surfactant or the like may be added to the nickel fluoride aqueous solution. Subsequently, it is washed with water and dried to finish the low temperature sealing treatment. As the sealing agent in the case of the high-temperature sealing treatment, an aqueous solution of a metal salt such as nickel acetate, cobalt acetate, lead acetate, nickel acetate-cobalt, and barium nitrate can be used, and it is particularly preferable to use nickel acetate. . The concentration in the case of using an aqueous nickel acetate solution is preferably 5 to 20 g / l. The treatment temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and usually 100 ° C. or lower, preferably 98 ° C. or lower, and the pH of the nickel acetate aqueous solution is 5.0 to 6.0. Is preferred. Here, ammonia water, sodium acetate, or the like can be used as the pH adjuster. The treatment time is 10 minutes or longer, preferably 15 minutes or longer. In this case as well, sodium acetate, organic carboxylic acid, anionic and nonionic surfactants may be added to the nickel acetate aqueous solution in order to improve the film properties. Furthermore, you may process by the high temperature water and high temperature steam which do not contain salts. Subsequently, it is washed with water and dried to finish the high temperature sealing treatment. When the average film thickness is thick, stronger sealing conditions are required due to the higher concentration of the sealing liquid and high temperature / long-time treatment. Accordingly, productivity is deteriorated and surface defects such as spots, dirt, and dusting are likely to occur on the coating surface. From such a point, it is preferable that the average film thickness of the anodic oxide coating is usually 20 μm or less, particularly 7 μm or less.

  The support surface may be smooth, or may be roughened by using a special cutting method or polishing. Further, it may be roughened by mixing particles having an appropriate particle diameter with the material constituting the support. In order to reduce the cost, it is possible to use the drawing tube as it is without cutting. Especially when using non-cutting aluminum supports such as drawing, impact processing, ironing, etc., the process eliminates dirt, foreign matter, etc. on the surface, small scratches, etc., and a uniform and clean support can be obtained. Therefore, it is preferable.

  An undercoat layer may be provided between the conductive support and the photosensitive layer in order to improve adhesion and blocking properties. As the undercoat layer, a resin, a resin in which particles such as a metal oxide are dispersed, or the like is used.

  Examples of metal oxide particles used for the undercoat layer include metal oxide particles containing one metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, calcium titanate, titanium Examples thereof include metal oxide particles containing a plurality of metal elements such as strontium acid and barium titanate. Only one type of particle may be used, or a plurality of types of particles may be mixed and used. Among these metal oxide particles, titanium oxide and aluminum oxide are preferable, and titanium oxide is particularly preferable. The surface of the titanium oxide particles may be treated with an inorganic substance such as tin oxide, aluminum oxide, antimony oxide, zirconium oxide, or silicon oxide, or an organic substance such as stearic acid, polyol, or silicone. As the crystal form of the titanium oxide particles, any of rutile, anatase, brookite, and amorphous can be used. A thing of a several crystalline state may be contained.

  In addition, various particle diameters of the metal oxide particles can be used. Among these, from the viewpoint of characteristics and liquid stability, the average primary particle diameter is usually 1 nm or more, particularly 10 nm or more, and usually 100 nm or less. The range of 50 nm or less is particularly preferable.

  The undercoat layer is preferably formed in a form in which metal oxide particles are dispersed in a binder resin. Examples of the binder resin used for the undercoat layer include phenoxy, epoxy, polyvinyl pyrrolidone, polyvinyl alcohol, casein, polyacrylic acid, celluloses, gelatin, starch, polyurethane, polyimide, and polyamide. These may be used alone or in combination of two or more. Moreover, you may use with the hardening | curing form with the hardening | curing agent. Among these, alcohol-soluble copolymerized polyamide, modified polyamide, and the like are preferable because they exhibit good dispersibility and coating properties.

  The addition ratio of the inorganic particles to the binder resin used in the undercoat layer may be arbitrarily selected, but it is usually used in the range of 10% by weight or more and 500% by weight or less for the stability of the dispersion and the coating property. It is preferable in terms of

  Although the thickness of the undercoat layer can be arbitrarily selected, it is usually preferably in the range of 0.1 μm or more and 20 μm or less from the viewpoint of improving the photoreceptor characteristics and applicability. Further, a known antioxidant or the like may be added to the undercoat layer.

  The type of the photosensitive layer formed on the conductive support includes a single layer type in which the charge generation material and the charge transport material are present in the same layer and dispersed in the binder resin, and the charge generation material in the binder resin. The charge generation layer and the charge transport layer in which the charge transport material is dispersed in a binder resin may be used. In general, it is known that the charge transport material exhibits the same performance as a charge transfer function regardless of whether it is a single layer type or a multilayer type.

  Examples of charge generation materials include selenium and its alloys, cadmium sulfide, and other inorganic photoconductive materials, phthalocyanine pigments, azo pigments, dithioketopyrrolopyrrole pigments, squalene (squarylium) pigments, quinacridone pigments, indigo pigments, and perylene pigments. Various photoconductive materials such as organic pigments such as polycyclic quinone pigments, anthanthrone pigments, and benzimidazole pigments can be used. Of these, organic pigments are preferred.

  When organic pigments are used as the charge generating material, these fine particles are converted into, for example, polyvinyl acetate, polyacrylic acid ester, polymethacrylic acid ester, polyester, polycarbonate, polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral, phenoxy resin, epoxy resin. , Urethane resin, cellulose ester, cellulose ether, and other binder resins. In the case of a multilayer photoreceptor, the organic pigment is used in a range of usually 30 parts by weight or more and 500 parts by weight or less with respect to 100 parts by weight of the binder resin, and its film thickness is usually 0.1 μm or more, preferably A range of 0.15 μm or more, usually 1 μm or less, preferably 0.6 μm or less is suitable. In the case of a single layer type photoreceptor, the range is usually 0.1 parts by weight or more, preferably 1 part by weight or more, and usually 30 parts by weight or less, preferably 10 parts by weight or less with respect to 100 parts by weight of the binder resin. Used in.

  When an organic pigment is used as the charge generating material, a phthalocyanine pigment or an azo pigment is particularly preferable. The phthalocyanine pigment provides a photosensitive material with high sensitivity to a laser beam having a relatively long wavelength, and the azo pigment has a sufficient sensitivity to white light and a laser beam having a relatively short wavelength. , Each is excellent.

  When a phthalocyanine compound is used as the charge generation material, specifically, a metal such as metal-free phthalocyanine, copper, indium, gallium, tin, titanium, zinc, vanadium, silicon, germanium, or an oxide, halide, hydroxide thereof And various crystal forms of coordinated phthalocyanines such as alkoxides. In particular, titanyl phthalocyanines (also known as oxytitanium) such as X-type, τ-type metal-free phthalocyanine, A-type (also known as β-type), B-type (also known as α-type), and D-type (also known as Y-type), which are highly sensitive crystal types Phthalocyanine), vanadyl phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalocyanine such as type II, hydroxygallium phthalocyanine such as type V, μ-oxo-gallium phthalocyanine dimer such as type G and I, μ-oxo such as type II -Aluminum phthalocyanine dimer is preferred. Among these phthalocyanines, A-type (β-type), B-type (α-type) and D-type (Y-type) titanyl phthalocyanine, II-type chlorogallium phthalocyanine, V-type hydroxygallium phthalocyanine, G-type μ-oxo-gallium A phthalocyanine dimer and the like are particularly preferable.

  Further, among phthalocyanines, oxytitanium phthalocyanine having a main diffraction peak at a Bragg angle (2θ ± 0.2 °) of X-ray diffraction spectrum with respect to CuKα characteristic X-ray of 27.3 ° is 9.3 °, 13. Oxytitanium phthalocyanine showing main diffraction peaks at 2 °, 26.2 ° and 27.1 °, dihydroxysilicon having main diffraction peaks at 9.2, 14.1, 15.3, 19.7, 27.1 ° Phthalocyanine, dichlorotin phthalocyanine showing major diffraction peaks at 8.5 °, 12.2 °, 13.8 °, 16.9 °, 22.4 °, 28.4 ° and 30.1 °, 7.5 ° , 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 °, hydroxy potassium phthalocyanine showing main diffraction peaks, and 7.4 °, 16. °, chlorogallium phthalocyanine preferably exhibits a diffraction peak at 25.5 ° and 28.3 °. Among these, oxytitanium phthalocyanine showing a main diffraction peak at 27.3 ° is particularly preferable, and in this case, oxytitanium phthalocyanine showing main diffraction peaks at 9.5 °, 24.1 ° and 27.3 ° is particularly preferable. .

  As the phthalocyanine compound, only a single compound may be used, or several mixed or mixed crystal states may be used. As the mixed state that can be placed in the phthalocyanine compound or crystal state here, the respective constituent elements may be mixed and used later, or the mixed state in the production / treatment process of the phthalocyanine compound such as synthesis, pigmentation, crystallization, etc. It may be generated. As such treatment, acid paste treatment, grinding treatment, solvent treatment and the like are known. In order to generate a mixed crystal state, as described in JP-A-10-48859, two types of crystals are mixed, mechanically ground and made amorphous, and then converted into a specific crystal state by solvent treatment. The method of doing is mentioned.

When an azo pigment is used as the charge generating substance, specific examples include monoazo, bisazo, trisazo, polyazos, etc. Among them, conventionally known various bisazo pigments and trisazo pigments are preferably used.
Examples of preferred azo pigments are shown below.

  As the charge transport material, the above-described triarylamine compound of the present invention is used. Any one of the triarylamine compounds of the present invention may be used alone, or two or more thereof may be used in any combination and ratio.

  In addition to the triarylamine compound of the present invention, other known charge transport materials may be used in combination. When other charge transport materials are used in combination, the kind thereof is not particularly limited. For example, carbazole derivatives, hydrazone compounds, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, and those obtained by bonding a plurality of these derivatives are preferable. More specifically, compounds described in JP-A-2-230255, JP-A-63-225660, JP-A-58-198043, JP-B-58-32372, and JP-B-7-21646 Are preferably used.

  In forming the photosensitive layer, a binder resin is used to ensure film strength. In this case, the photosensitive layer can be obtained by applying and drying a coating solution obtained by dissolving or dispersing the charge transport material and the binder polymer in a solvent. Examples of the binder resin include polymers and copolymers of vinyl compounds such as butadiene, styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinyl alcohol, and ethyl vinyl ether, polyvinyl butyral, polyvinyl formal, and partially modified polyvinyl. Examples include acetal, polycarbonate, polyester, polyarylate, polyamide, polyurethane, cellulose ether, phenoxy resin, silicon resin, epoxy resin, and poly-N-vinylcarbazole resin. Of these, polycarbonate and polyarylate are particularly preferred. These can also be used after being crosslinked with heat, light or the like using an appropriate curing agent or the like. These binders can also be used by blending two or more.

  The ratio between the binder resin and the charge transporting material is usually 20 parts by weight or more with respect to 100 parts by weight of the binder resin in both the single layer type and the laminated type, and more preferably 30 parts or more from the viewpoint of reducing the residual potential. From the viewpoint of stability and charge mobility, 40 parts or more is more preferable. On the other hand, from the viewpoint of thermal stability of the photosensitive layer, it is usually 150 parts by weight or less, more preferably 110 parts by weight or less from the viewpoint of compatibility between the charge transport material and the binder resin, and 80 weights from the viewpoint of printing durability. Part or less is more preferable, and from the viewpoint of scratch resistance, 70 parts by weight or less is most preferable. The film thickness is usually 5 μm or more and usually 50 μm or less, preferably 10 μm or more and 45 μm or less from the viewpoint of long life and image stability, and from the viewpoint of high resolution, the range is 10 μm or more and 30 μm or less. More preferred.

  The photosensitive layer has well-known antioxidants, plasticizers, ultraviolet absorbers, electron-withdrawing compounds to improve film-forming properties, flexibility, coating properties, stain resistance, gas resistance, light resistance, etc. Further, additives such as a leveling agent may be contained.

  In the case of a single-layer type photoreceptor, the above-described charge generating material is further dispersed in the charge transport medium having the above-described blending ratio. In this case, the particle size of the charge generating material needs to be sufficiently small, and is preferably 1 μm or less, more preferably 0.5 μm or less. When the amount of the charge generating material dispersed in the photosensitive layer is too small, sufficient sensitivity cannot be obtained. On the other hand, when the amount is too large, there are problems such as a decrease in chargeability and a decrease in sensitivity. It is used in the range of not less than wt%, preferably not less than 1 wt%, and usually not more than 50 wt%, preferably not more than 20 wt%. The film thickness of the single-layer type photosensitive layer is usually 5 μm or more, preferably 10 μm or more, and usually 100 μm or less, preferably 50 μm or less.

  A protective layer is provided on the laminated or single-layered photosensitive layer for the purpose of preventing the photosensitive layer from being worn out or preventing or reducing the deterioration of the photosensitive layer due to discharge products generated from a charger or the like. Also good.

  The layer that contacts the surface of the photoreceptor may contain a fluorine resin, a silicone resin, or the like for the purpose of reducing frictional resistance and wear on the surface of the photoreceptor. Moreover, you may contain the particle | grains which consist of these resin, and the particle | grains of an inorganic compound.

  Each layer constituting these photoreceptors is formed by immersing, coating, spraying, nozzle coating, bar coating, roll coating, blade coating, etc., on a support, a coating solution obtained by dissolving or dispersing a substance to be contained in a solvent. Are formed by sequential application by the known method.

  Examples of the solvent or dispersion medium used for preparing the coating liquid include alcohols such as methanol, ethanol, propanol, and 2-methoxyethanol, ethers such as tetrahydrofuran, 1,4-dioxane, and dimethoxyethane, methyl formate, and acetic acid. Esters such as ethyl, ketones such as acetone, methyl ethyl ketone, cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene, dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, 1, Chlorinated hydrocarbons such as 1,1-trichloroethane, tetrachloroethane, 1,2-dichloropropane, trichloroethylene, n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine, triethylene Nitrogen-containing compounds such as amine, acetonitrile, N- methylpyrrolidone, N, N- dimethylformamide, aprotic polar solvents such as dimethyl sulfoxide and the like. These may be used alone or in combination of two or more kinds in any combination.

  In the preparation of the coating liquid or dispersion, in the case of a single layer type photosensitive layer and a charge transport layer of a laminated type photosensitive layer, the solid content concentration is preferably 10% by weight or more, and preferably 40% by weight. Hereinafter, it is more preferably in the range of 35% by weight or less, the viscosity is preferably in the range of 50 cps or more, and preferably in the range of 400 cps or less. In the case of the charge generation layer of the laminated photosensitive layer, the solid content concentration is preferably Is 1% by weight or more, preferably 15% by weight or less, more preferably 10% by weight or less, and the viscosity is preferably 0.1 cps or more, and preferably 10 cps or less.

  In the above description, the case where the triarylamine compound of the present invention is used as a charge transport material has been described. However, the content of the amine compound of the present invention is not limited to this, and photosensitive for various purposes. It can be contained in the layer. For example, the above exemplary compound (T-28) can be used as an antioxidant for the photosensitive layer.

[III. Image forming apparatus]
Next, an embodiment of an image forming apparatus using the electrophotographic photosensitive member of the present invention will be described with reference to FIG. However, the embodiment is not limited to the following description, and can be arbitrarily modified without departing from the gist of the present invention.

  As shown in FIG. 1, the image forming apparatus includes an electrophotographic photosensitive member 1, a charging device 2, an exposure device 3, and a developing device 4, and further, a transfer device 5, a cleaning device 6 and a fixing device as necessary. A device 7 is provided.

  The electrophotographic photoreceptor 1 is not particularly limited as long as it is the above-described electrophotographic photoreceptor of the present invention, but in FIG. 1, as an example, a drum in which the above-described photosensitive layer is formed on the surface of a cylindrical conductive support. The photoconductor is shown. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5, and a cleaning device 6 are disposed along the outer peripheral surface of the electrophotographic photosensitive member 1.

  The charging device 2 charges the electrophotographic photosensitive member 1 and uniformly charges the surface of the electrophotographic photosensitive member 1 to a predetermined potential. In FIG. 1, a roller-type charging device (charging roller) is shown as an example of the charging device 2, but other corona charging devices such as corotron and scorotron, and contact-type charging devices such as charging brushes are often used.

  In many cases, the electrophotographic photosensitive member 1 and the charging device 2 are designed to be removable from the main body of the image forming apparatus as a cartridge including both of them (hereinafter, appropriately referred to as a photosensitive cartridge). For example, when the electrophotographic photoreceptor 1 or the charging device 2 deteriorates, the photoreceptor cartridge can be removed from the image forming apparatus main body, and another new photosensitive cartridge can be mounted on the image forming apparatus main body. ing. Also, the toner described later is often stored in the toner cartridge and designed to be removable from the main body of the image forming apparatus. When the toner in the used toner cartridge runs out, this toner cartridge is removed. It can be removed from the main body of the image forming apparatus and another new toner cartridge can be mounted. Further, a cartridge equipped with all of the electrophotographic photosensitive member 1, the charging device 2, and the toner may be used.

  The type of the exposure apparatus 3 is not particularly limited as long as it can expose the electrophotographic photoreceptor 1 to form an electrostatic latent image on the photosensitive surface of the electrophotographic photoreceptor 1. Specific examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He—Ne lasers, LEDs, and the like. Further, exposure may be performed by a photoreceptor internal exposure method. The light used for the exposure is arbitrary. For example, the exposure may be performed using monochromatic light with a wavelength of 780 nm, monochromatic light with a wavelength slightly shorter than 600 nm to 700 nm, or monochromatic light with a short wavelength of 380 nm to 500 nm. .

  The type of the developing device 4 is not particularly limited, and an arbitrary device such as a dry development method such as cascade development, one-component conductive toner development, two-component magnetic brush development, or a wet development method can be used. In FIG. 1, the developing device 4 includes a developing tank 41, an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45, and has a configuration in which toner T is stored inside the developing tank 41. . Further, a replenishing device (not shown) for replenishing the toner T may be attached to the developing device 4 as necessary. The replenishing device is configured to be able to replenish toner T from a container such as a bottle or a cartridge.

  The supply roller 43 is formed from a conductive sponge or the like. The developing roller 44 is made of a metal roll such as iron, stainless steel, aluminum, or nickel, or a resin roll obtained by coating such a metal roll with a silicone resin, a urethane resin, a fluorine resin, or the like. The surface of the developing roller 44 may be smoothed or roughened as necessary.

  The developing roller 44 is disposed between the electrophotographic photoreceptor 1 and the supply roller 43 and is in contact with the electrophotographic photoreceptor 1 and the supply roller 43, respectively. The supply roller 43 and the developing roller 44 are rotated by a rotation drive mechanism (not shown). The supply roller 43 carries the stored toner T and supplies it to the developing roller 44. The developing roller 44 carries the toner T supplied by the supply roller 43 and contacts the surface of the electrophotographic photosensitive member 1.

  The regulating member 45 is formed of a resin blade such as a silicone resin or a urethane resin, a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze, or a blade obtained by coating such a metal blade with a resin. The regulating member 45 contacts the developing roller 44 and is pressed against the developing roller 44 side with a predetermined force by a spring or the like (a general blade linear pressure is 5 to 500 g / cm). If necessary, the regulating member 45 may be provided with a function of imparting charging to the toner T by frictional charging with the toner T.

  The agitator 42 is rotated by a rotation driving mechanism, and agitates the toner T and conveys the toner T to the supply roller 43 side. A plurality of agitators 42 may be provided with different blade shapes and sizes.

  The type of the toner T is arbitrary, and in addition to the powdery toner, a polymerized toner using a suspension polymerization method, an emulsion polymerization method, or the like can be used. In particular, when a polymerized toner is used, a toner having a small particle diameter of about 4 to 8 μm is preferable, and the toner particles are used in various shapes ranging from a nearly spherical shape to a shape outside the spherical shape on the potato. be able to. The polymerized toner is excellent in charging uniformity and transferability and is suitably used for high image quality.

  The type of the transfer device 5 is not particularly limited, and an apparatus using an arbitrary system such as an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method can be used. . Here, it is assumed that the transfer device 5 includes a transfer charger, a transfer roller, a transfer belt, and the like that are disposed to face the electrophotographic photoreceptor 1. The transfer device 5 applies a predetermined voltage value (transfer voltage) having a polarity opposite to the charging potential of the toner T, and transfers the toner image formed on the electrophotographic photosensitive member 1 to a recording paper (paper, medium) P. Is.

  There is no restriction | limiting in particular about the cleaning apparatus 6, Arbitrary cleaning apparatuses, such as a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, can be used. The cleaning device 6 is for scraping off residual toner adhering to the photoreceptor 1 with a cleaning member and collecting the residual toner. However, when there is little or almost no toner remaining on the surface of the photoreceptor, the cleaning device 6 may be omitted.

  The fixing device 7 includes an upper fixing member (fixing roller) 71 and a lower fixing member (fixing roller) 72, and a heating device 73 is provided inside the fixing member 71 or 72. FIG. 1 shows an example in which a heating device 73 is provided inside the upper fixing member 71. Each of the upper and lower fixing members 71 and 72 includes a fixing roll in which a metal base tube such as stainless steel or aluminum is coated with silicon rubber, a fixing roll in which Teflon (registered trademark) resin is coated, and a fixing sheet. A member can be used. Further, each of the fixing members 71 and 72 may be configured to supply a release agent such as silicone oil in order to improve releasability, or may be configured to forcibly apply pressure to each other by a spring or the like.

When the toner transferred onto the recording paper P passes between the upper fixing member 71 and the lower fixing member 72 heated to a predetermined temperature, the toner is heated to a molten state and cooled after passing through the recording paper. Toner is fixed on P.
The type of the fixing device is not particularly limited, and a fixing device of any type such as heat roller fixing, flash fixing, oven fixing, pressure fixing, etc. can be provided including those used here.

  In the electrophotographic apparatus configured as described above, an image is recorded as follows. That is, first, the surface (photosensitive surface) of the photoreceptor 1 is charged to a predetermined potential (for example, −600 V) by the charging device 2. At this time, charging may be performed by a DC voltage, or charging may be performed by superimposing an AC voltage on the DC voltage.

  Subsequently, the photosensitive surface of the charged photoreceptor 1 is exposed by the exposure device 3 according to the image to be recorded, and an electrostatic latent image is formed on the photosensitive surface. The developing device 4 develops the electrostatic latent image formed on the photosensitive surface of the photoreceptor 1.

  The developing device 4 thins the toner T supplied by the supply roller 43 with a regulating member (developing blade) 45 and has a predetermined polarity (here, the same polarity as the charging potential of the photosensitive member 1) and the negative polarity. ), And conveyed while being carried on the developing roller 44 to be brought into contact with the surface of the photoreceptor 1.

  When the charged toner T carried on the developing roller 44 comes into contact with the surface of the photoreceptor 1, a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the photoreceptor 1. This toner image is transferred onto the recording paper P by the transfer device 5. Thereafter, the toner remaining on the photosensitive surface of the photoreceptor 1 without being transferred is removed by the cleaning device 6.

  After the transfer of the toner image onto the recording paper P, the final image is obtained by passing the fixing device 7 and thermally fixing the toner image onto the recording paper P.

  In addition to the above-described configuration, the image forming apparatus may have a configuration capable of performing, for example, a static elimination process. The neutralization step is a step of neutralizing the electrophotographic photosensitive member by exposing the electrophotographic photosensitive member, and a fluorescent lamp, an LED, or the like is used as the neutralizing device. In addition, the light used in the static elimination process is often light having an exposure energy that is at least three times that of the exposure light.

  The image forming apparatus may be further modified. For example, the image forming apparatus may be configured to perform a pre-exposure process, an auxiliary charging process, or the like, or may be configured to perform offset printing. A full-color tandem system configuration using toner may be used.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the following examples are shown in order to explain the present invention in detail, and the present invention is not limited to the following examples unless departing from the gist thereof. In the present specification, “parts” means “parts by weight” unless otherwise specified.

[Production of amine compound]
<Example 1: Production of exemplary compound (T-5)>
At room temperature, in a 300 ml four-necked flask equipped with a stirrer and a thermometer, 20.7 g (0.105 mol) of p, p′-ditolylamine as a starting amine compound and 4,4′-diiodobiphenyl 20 as a halogen compound .3 g (0.05 mol), copper powder (manufactured by Kishida Chemical Co., Ltd., 2% stearic acid, 325 mesh), 6.4 g, 5.2 g of triphenylphosphine as a tertiary phosphorus compound, 12.0 g (0 of sodium tert-butoxide as a base) 125 mol), 50 ml of deoxygenated tetralin as a solvent were sequentially added, and the system was replaced with nitrogen, followed by stirring for about 10 minutes. Then, it heated at 160 degreeC and analyzed the reaction liquid for every fixed time with the high performance liquid chromatography (Column: Inertsil ODS-3V by GL Sciences Inc., solvent: Tetrahydrofuran / water = 7/3). While the generated tert-butyl alcohol was distilled off, the reaction was continued while heating at that temperature until 4,4′-diiodobiphenyl was no longer detected (about 4 hours). After completion of the reaction, the mixture was cooled to 70 ° C., 100 ml of toluene was added, and the solid content was separated by filtration. After the solvent was distilled under reduced pressure, 10 ml of toluene was added, and further 200 ml of methanol was slowly poured to completely crystallize the product. The precipitated crystals are separated by filtration, separated by flash column chromatography (silica gel 300 g, developing solvent: toluene / hexane = 1/2), further purified by reprecipitation with methanol, and then vacuum dried to obtain the above examples. Compound (T-5) was obtained as white fine crystals (22.1 g, yield 81%, purity 99.0%). The product was confirmed to be the target exemplified compound by ¹ H-NMR analysis. Moreover, the purity of the product was calculated from the simple area ratio value of the chart of high performance liquid chromatography.

<Example 2: Production of exemplary compound (T-5)>
Exemplified compound (T-5) was obtained as white crystals by the same production method (reaction time: 4 hours) as in Example 1 except that tricyclohexylphosphine was used instead of triphenylphosphine as the tertiary phosphorus compound. 21.8 g, yield 80%, purity 99.1%). The confirmation of the product and the calculation of the purity were performed in the same manner as in Example 1.

<Example 3: Production of exemplary compound (T-5)>
Except that tri-n-butylphosphine was used in place of triphenylphosphine as the tertiary phosphorus compound, Exemplified Compound (T-5) was converted into white crystals by the same production method as in Example 1 (reaction time 3 hours). Obtained (22.9 g, yield 84%, purity 99.3%). The confirmation of the product and the calculation of the purity were performed in the same manner as in Example 1.

<Example 4: Production of exemplary compound (T-5)>
Exemplified compound (T-5) was converted into white crystals by the same production method (reaction time 6 hours) as in Example 1 except that tri (o-tolyl) phosphine was used in place of triphenylphosphine as the tertiary phosphorus compound. (21.0 g, yield 77%, purity 97.9%). The confirmation of the product and the calculation of the purity were performed in the same manner as in Example 1.

<Example 5: Production of exemplary compound (T-8)>
As a starting amine compound, 10.7 g (0.1 mol) of p-toluidine is used instead of p, p′-ditolylamine, and 43.6 g of p-iodotoluene is substituted for 4,4′-diiodobiphenyl as a halogen compound. Exemplified Compound (T-8) was prepared in the same manner as in Example 1 (reaction time: 3 hours) except that tricyclohexylphosphine was used instead of triphenylphosphine as the tertiary phosphorus compound. Obtained as crystals (23.0 g, yield 80%, purity 98.8%). The confirmation of the product and the calculation of the purity were performed in the same manner as in Example 1.

<Example 6: Production of exemplary compound (T-4)>
Except that m, p'-ditolylamine was used in place of p, p'-ditolylamine and sodium methylate was used in place of sodium tert-butoxide, the same production method as in Example 1 (reaction time 6 hours) was used. The exemplary compound (T-4) was obtained as white crystals (20.2 g, yield 74%, purity 97.6%). The confirmation of the product and the calculation of the purity were performed in the same manner as in Example 1.

<Example 7: Production of exemplary compound (T-0)>
19.2 g (0.105 mol) of N- (m-tolyl) N- (phenyl) amine is substituted for p, p′-ditolylamine, and 17.3 g (0.125 mol) of potassium carbonate is substituted for sodium tert-butoxide. Exemplified compound (T-0) was obtained as white crystals by the same production method (reaction time 12 hours) as in Example 1 except that the reaction temperature was 170 ° C., respectively (22.9 g, yield). 80%, purity 98.0%). The confirmation of the product and the calculation of the purity were performed in the same manner as in Example 1.

<Example 8: Production of exemplary compound (T-28)>
10.7 g (0.1 mol) of benzylamine instead of N- (m-tolyl) -N- (phenyl) amine, 34.2 g (0.2 mol) of benzyl bromide instead of 4,4′-diiodobiphenyl Example Compound (T-28) was obtained as white crystals (23.6 g, yield 82%, purity 98.8) by the same production method (reaction time 10 hours) as in Example 7 except that each was used. %). The confirmation of the product and the calculation of the purity were performed in the same manner as in Example 1.

<Comparative Example 1: Production of Exemplified Compound (T-5)>
In Example 1, when the reaction was conducted in the same manner except that triphenylphosphine (tertiary phosphorus compound) was not used, the reaction was not completed.

<Comparative Example 2: Production of exemplary compound (T-5)>
In Example 2, when the reaction was conducted in the same manner except that sodium tert-butoxide (base) was not used, the reaction was not completed.

<Comparative Example 3: Production of Exemplified Compound (T-0)>
In Example 7, when the reaction was carried out in the same manner except that triphenylphosphine (tertiary phosphorus compound) was not used and the reaction temperature was 200 ° C., the reaction was completed after 20 hours. By treating like Example 1, exemplary compound (T-0) was obtained as yellowish white solid (18.0g, yield 70%, purity 98.1%). The confirmation of the product and the calculation of the purity were performed in the same manner as in Example 1.

[Electrophotographic photoconductor]
<Examples 9 to 12, Comparative Example 4: Production of electrophotographic photoreceptor>
Using a conductive support in which an aluminum vapor-deposited layer (thickness 70 nm) is formed on the surface of a biaxially stretched polyethylene terephthalate resin film (thickness 75 μm), the following undercoat layer dispersion is formed on the aluminum vapor-deposited layer of the conductive support The liquid was applied by a bar coater so that the film thickness after drying was 1.25 μm and dried to form an undercoat layer.

The undercoat layer dispersion was produced as follows. That is, a rutile type titanium oxide having an average primary particle size of 40 nm (“TTO55N” manufactured by Ishihara Sangyo Co., Ltd.) and 3% by weight of methyldimethoxysilane (“TSL8117” manufactured by Toshiba Silicone Co., Ltd.) with respect to the titanium oxide were flowed at high speed. In a mixed solvent of methanol / 1-propanol in a mixed solvent of methanol / 1-propanol, which was introduced into a mixing kneader (“SMG300” manufactured by Kawata Co., Ltd.) and mixed at a high rotational speed of 34.5 m / sec. Then, a dispersion slurry of hydrophobized titanium oxide was obtained by dispersing with a ball mill. The dispersion slurry, a mixed solvent of methanol / 1-propanol / toluene, and ε-caprolactam [compound represented by the following formula (A)] / bis (4-amino-3-methylcyclohexyl) methane [the following formula (B Compound represented by the following formula (C)] / decamethylene dicarboxylic acid [compound represented by the following formula (D)] / octadecamethylene dicarboxylic acid [in the following formula (E) The compositional molar ratio of the compound represented] is 75% / 9.5% / 3% / 9.5% / 3% of the copolymerized polyamide pellets with heating and stirring and mixing to dissolve the polyamide pellets. After that, by carrying out ultrasonic dispersion treatment, the weight ratio of methanol / 1-propanol / toluene is 7/1/2, and hydrophobically treated titanium oxide. The copolymerized polyamide in a weight ratio of 3/1, and a solid concentration of 18.0% of the undercoat layer dispersion.

  Separately, A-type oxytitanium phthalocyanine (in the X-ray diffraction spectrum for CuKa characteristic X-ray, the diffraction peaks are shown at 9.3 °, 10.6 °, and 26.3 ° at the Bragg angle (2θ ± 0.2 °)). 10 parts by weight was added to 150 parts by weight of 4-methoxy-4-methylpentanone-2 and pulverized and dispersed in a sand grind mill for 1 hour. Thereafter, 100 parts by weight of a 5 wt% 1,2-dimethoxyethane solution of polyvinyl butyral (“Denkabutyral # 6000C” manufactured by Denki Kagaku Kogyo Co., Ltd.) as a binder resin, and phenoxy resin (“PKHH” manufactured by Union Carbide) A coating solution for a charge generation layer was prepared by adding 100 parts by weight of a 5 wt% 1,2-dimethoxyethane solution. The charge generation layer coating solution was applied onto the undercoat layer of the conductive support with a bar coater so that the film thickness after drying was 0.4 μm, and dried to form a charge generation layer. .

  Separately, 50 parts by weight of an amine compound shown in Table 1 below as a charge transport material, 100 parts by weight of a binder resin, and 0.03 part by weight of silicone oil as a leveling agent are mixed in a tetrahydrofuran / toluene (weight ratio 8/2) mixed solvent. A charge transport layer coating solution was prepared by dissolving in 640 parts by weight. In addition, as binder resin, the repeating unit 51 mol% which uses the following 2, 2-bis (4-hydroxy-3-methylphenyl) propane as an aromatic diol component, and 1,1-bis (4-hydroxyphenyl) are shown. ) A polycarbonate resin (viscosity average molecular weight 30000) having a terminal structure derived from p-tert-butylphenol, comprising 49 mol% of a repeating unit having 1-phenylethane as an aromatic diol component.

  The resulting charge transport layer coating solution is applied onto the charge generation layer with a film applicator so that the film thickness after drying is 20 μm, and dried to form a charge transport layer, thereby forming a laminated photosensitive film. Electrophotographic photoreceptors A1 to A4 and P1 having layers were produced.

<Evaluation of electrical characteristics of electrophotographic photoreceptor>
The electrophotographic characteristics of the obtained electrophotographic photoreceptors A1 to A4 and P1 were measured according to the following procedures, respectively, by a static method using a photoreceptor evaluation apparatus (Cynthia 55, manufactured by Gentec Corporation).

First, each of the electrophotographic photoreceptors A1 to A4, P1 is discharged in a dark place with a scorotron charger so that the surface potential is about −700 V, and passes through the electrophotographic photoreceptor at a constant speed (125 mm / sec). The initial charged voltage was obtained by measuring the charged voltage (hereinafter sometimes referred to as “V ₀ ”). Thereafter, a decrease in potential when left for 2.5 seconds was measured (hereinafter sometimes referred to as “DD”). Next, irradiation with 780 nm monochromatic light having an intensity of 1.0 μW / cm ² was performed, and the half-exposure energy (μJ / cm ² ) required until the photoreceptor surface potential was changed from −550 V to −275 V was determined (hereinafter “E”). _1/2 "). Further, the residual potential 10 seconds after irradiation was obtained (hereinafter sometimes referred to as “V _r ”).
The evaluation results of the electrophotographic photoreceptors A1 to A4 and P1 are shown in Table 2 below.

Although all amine compounds were purified by the same method, the amine compound obtained in Example 7 (Exemplary Compound (T-0)) was not colored, whereas in Comparative Example 3, The obtained same amine compound (Exemplary Compound (T-0)) was slightly colored. Further, as is apparent from Table 2, the electrophotographic photosensitive member of Example 12 containing the amine compound obtained in Example 7 is the electron of Comparative Example 4 containing the same amine compound obtained in Comparative Example 3. Compared with the photographic photoreceptor, the values of DD, E _1/2 , and V _r were all small. Therefore, it can be seen that the electrophotographic photosensitive member of Example 12 is superior in electrical characteristics to the electrophotographic photosensitive member of Comparative Example 4.
In addition, the electrophotographic photoconductors of Examples 9 to 12 cannot be simply compared with the electrophotographic photoconductor of Comparative Example 4 because the types of amine compounds are different, but DD, E _1/2 , V _r Since the value is very small, it can be seen that the electrical characteristics are good.

[Image formation test and stability / durability test of photoconductor]
<Example 13>
The coating solution for the charge generation layer and the charge transport layer prepared in the same manner as the electrophotographic photosensitive member A2 is immersed on an aluminum tube having a diameter of 3 cm and a length of 25.4 cm, which is anodized and sealed. The electrophotographic photosensitive drum having a charge generation layer of 0.3 μm and a charge transport layer of 20 μm was prepared by coating and drying sequentially by a coating method. When this electrophotographic photosensitive drum was mounted on a laser printer manufactured by Hewlett-Packard Co., Ltd., a laser jet 4 (LJ4) remodeling machine, and an image formation test was performed, a good image free from image defects and noise was obtained. Next, as a stability / durability test, 10,000 sheets were continuously printed, and the formed image was visually evaluated. As a result, the image was not deteriorated such as ghost, fog, and black spots, and was stable.

<Comparative Example 5>
Instead of using the amine compound produced in Example 1 as a charge transport material, an electrophotographic photosensitive member was prepared in the same manner as in Example 13 except that the amine compound produced in Comparative Example 3 was used as a charge transport material. When an image formation test and a photoreceptor stability / durability test were conducted in the same manner as in Example 1, the image density was low from the beginning, and fogging was observed in repeated image formation.

  According to the present invention, an electronic material such as an electrophotographic material can be produced economically, and thus is suitable for industrial applications in various fields. In particular, since there are few impurities of an electronic material, the application to electrophotographic systems, such as a copying machine, a printer, and a printing machine, is effective.

1 is a schematic diagram illustrating a main configuration of an embodiment of an image forming apparatus of the present invention.

Explanation of symbols

1 Photoconductor (Electrophotographic photoconductor)
2 Charging device (charging roller; charging unit)
3 Exposure equipment (exposure section)
4 Development device (development unit)
5 Transfer device 6 Cleaning device (cleaning part)
7 Fixing Device 41 Developing Tank 42 Agitator 43 Supply Roller 44 Developing Roller 45 Regulating Member 71 Upper Fixing Member (Fixing Roller)
72 Lower fixing member (fixing roller)
73 Heating device T Toner P Recording paper (paper, medium)

Claims (2)

  A method for producing an amine compound, comprising reacting a secondary amine compound and an aryl halide in the presence of metallic copper and a trialkyl phosphorus compound or a triaryl phosphorus compound. The method for producing an amine compound according to claim 1, wherein the reaction is carried out in the presence of a base .

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