阅读说明：本技术 化合物、其制造方法和原料以及电子照相感光体 (Compound, method and raw material for producing the same, and electrophotographic photoreceptor ) 是由 东润 小岛健辅 于 2019-06-17 设计创作，主要内容包括：本发明提供一种化合物、其制造方法和原料以及电子照相感光体。本发明的化合物(双丁二烯衍生物)由通式(1)表示。通式(1)中,R<Sup>a</Sup>、R<Sup>b</Sup>和R<Sup>c</Sup>各自独立,表示C1-C8烷基或者C1-C8烷氧基。l和m各自独立,表示0以上5以下的整数。n表示0以上4以下的整数。若干个R<Sup>a</Sup>彼此可以相同或不同。若干个R<Sup>b</Sup>彼此可以相同或不同。若干个R<Sup>c</Sup>彼此可以相同或不同。若干个l彼此可以相同或不同。若干个m彼此可以相同或不同。若干个n彼此可以相同或不同。【化1】<Image he="314" wi="700" file="DDA0002096341810000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention provides a compound, a method and a raw material for producing the same, and an electrophotographic photoreceptor. The compound (bis-butadiene derivative) of the present invention is represented by general formula (1). In the general formula (1), R a 、R b And R c Independently of one another, represents a C1-C8 alkyl group or a C1-C8 alkoxy group. l and m are each independently 0 or more and 5 or lessThe following integers. n represents an integer of 0 to 4. A plurality of R a May be the same or different from each other. A plurality of R b May be the same or different from each other. A plurality of R c May be the same or different from each other. Several l may be the same or different from each other. Several m may be the same or different from each other. The number n may be the same or different from each other. [ CHEM 1 ])

1. A bis-butadiene derivative is provided, which is a bis-butadiene derivative,

represented by the following general formula (1),

[ CHEM 1 ]

In the general formula (1) described above,

R^a、R^band R^cIndependently of one another, represents C1-C8 alkyl or C1-C8 alkoxy,

l and m are each independently an integer of 0 to 5,

n represents an integer of 0 to 4 inclusive,

a plurality of R^aMay be the same as or different from each other,

a plurality of R^bMay be the same as or different from each other,

a plurality of R^cMay be the same as or different from each other,

several l may be the same or different from each other,

several m may be the same or different from each other,

the number n may be the same or different from each other.

2. The bis-butadiene derivative according to claim 1,

in the general formula (1) described above,

R^band R^cIndependently of one another, represents C1-C3 alkyl or C1-C3 alkoxy,

l and m are each independently an integer of 0 to 2,

n represents 0.

3. The bis-butadiene derivative according to claim 1 or 2,

the bis-butadiene derivative represented by the general formula (1) is represented by the following chemical formula (HTM-1), (HTM-2), (HTM-3), (HTM-4) or (HTM-5),

[ CHEM 2 ]

4. An electrophotographic photoreceptor comprising a conductive substrate and a photosensitive layer provided directly or indirectly on the conductive substrate,

the photosensitive layer contains at least a charge generating agent, a charge transporting agent and a binder resin,

the charge transport agent contains the bis-butadiene derivative according to claim 1 or 2.

5. The electrophotographic photoreceptor according to claim 4,

the binder resin comprises a polyarylate resin having a repeating unit represented by the following general formula (r-1) or a polycarbonate resin having a repeating unit represented by the following general formula (r-2),

[ CHEM 3 ]

In the general formulae (r-1) and (r-2),

R¹、R²、R¹¹and R¹²Each independently represents a hydrogen atom or a C1-C4 alkyl group,

R³、R⁴、R¹³and R¹⁴Each independently represents a hydrogen atom, a C1-C4 alkyl group or a phenyl group,

R³and R⁴May be bonded to each other to represent a divalent group represented by the following general formula (W),

R¹³and R¹⁴May be bonded to each other to represent a divalent group represented by the following general formula (W),

y represents a divalent group represented by the following chemical formula (Y1), (Y2), (Y3), (Y4), (Y5) or (Y6),

[ CHEM 4 ]

In the general formula (W) described above,

t represents an integer of 1 to 3 inclusive,

the symbol indicates a bond of the compound,

[ CHEM 5 ]

In the chemical formulae (Y1) to (Y6), a represents a bond.

6. The electrophotographic photoreceptor according to claim 5,

the binder resin comprises a polyarylate resin represented by the following chemical formula (R-1), (R-2) or (R-3) or a polycarbonate resin represented by the following chemical formula (R-4) or (R-5),

[ CHEM 6 ]

7. The electrophotographic photoreceptor according to claim 4,

the photosensitive layer has a charge generation layer and a charge transport layer,

the charge generation layer contains the charge generation agent,

the charge transport layer contains at least the charge transport agent and the binder resin.

8. The electrophotographic photoreceptor according to claim 7,

the charge transport layer further contains a compound represented by the following chemical formula (ETM-1), a compound represented by the following chemical formula (ETM-2), a compound represented by the following chemical formula (ETM-3), a compound represented by the following chemical formula (ETM-4), or a compound represented by the following chemical formula (ETM-5),

[ CHEM 7 ]

9. A bis-butadiene halide compound having a double bond,

represented by the following general formula (10),

[ CHEM 8 ]

In the general formula (10) described above,

R^arepresents a C1-C8 alkyl group or a C1-C8 alkoxy group,

n represents an integer of 0 to 4 inclusive,

x represents a halogen atom, and X represents a halogen atom,

a plurality of R^aMay be the same as or different from each other,

several n may be the same or different from each other,

several xs may be the same or different from each other.

10. A process for producing a bis-butadiene derivative,

a process for producing the bis-butadiene derivative according to claim 1 or 2, which comprises a step of carrying out a reaction represented by the following reaction formula (P),

[ CHEM 9 ]

In the reaction equation (P), the reaction is carried out,

R^a、R^b、R^cn, m and l are each independently of R in the general formula (1)^a、R^b、R^cN, m and l have the same meaning,

x represents a halogen atom, and X represents a halogen atom,

several xs may be the same or different from each other.

Technical Field

The present invention relates to a compound (specifically, a bis-butadiene derivative), a method and a raw material thereof (specifically, a bis-butadiene halide), and an electrophotographic photoreceptor.

Background

Electrophotographic photoreceptors are used in electrophotographic image forming apparatuses. Examples of the electrophotographic photoreceptor include: a laminated electrophotographic photoreceptor or a single-layer electrophotographic photoreceptor. The photosensitive layer in the laminated electrophotographic photoreceptor includes a charge generation layer having a charge generation function and a charge transport layer having a charge transport function. The photosensitive layer in the single-layer electrophotographic photoreceptor is a single-layer photosensitive layer and has a charge generating function and a charge transporting function.

An example of the electrophotographic photoreceptor includes a photosensitive layer. The photosensitive layer contains a charge transporting substance, for example, a compound having a bisstilbene structure represented by the following chemical formula (h-3) as a charge transporting substance.

[ CHEM 1 ]

Disclosure of Invention

However, with respect to the compounds of the above examples, the present inventors have found through studies that there is room for improvement in improving the sensitivity characteristics of electrophotographic photoreceptors.

The present invention has been made in view of the above problems, and an object thereof is to provide a bis-butadiene derivative capable of improving the sensitivity characteristics of an electrophotographic photoreceptor, and a method for producing the same. Still another object of the present invention is to provide an electrophotographic photoreceptor having excellent sensitivity characteristics. Further, another object of the present invention is to provide a bis-butadiene halide which can be used in the above-mentioned process for producing a bis-butadiene derivative.

The bis-butadiene derivative of the present invention is represented by the following general formula (1).

[ CHEM 2 ]

In the general formula (1), R^a、R^bAnd R^cIndependently of one another, represents a C1-C8 alkyl group or a C1-C8 alkoxy group. l and m are each independently an integer of 0 to 5. n represents an integer of 0 to 4. A plurality of R^aMay be the same or different from each other. A plurality of R^bMay be the same or different from each other. A plurality of R^cMay be the same or different from each other. The several pieces 1 may be the same or different from each other. Several m may be the same or different from each other. The number n may be the same or different from each other.

The method for producing a bis-butadiene derivative of the present invention is used for producing the above bis-butadiene derivative, and comprises a step of performing a reaction represented by the following reaction formula (P).

[ CHEM 3 ]

R in the reaction equation (P)^a、R^b、R^cN, m and l are each independently of R in the general formula (1)^a、R^b、R^cN, m and l have the same meaning. X represents a halogen atom. Several xs may be the same or different from each other.

The electrophotographic photoreceptor of the present invention includes a conductive substrate and a photosensitive layer provided directly or indirectly on the conductive substrate. The photosensitive layer contains at least a charge generating agent, a charge transporting agent, and a binder resin. The charge transport agent contains the above-mentioned bis-butadiene derivative.

The bis-butadiene halide of the present invention is represented by the following general formula (10).

[ CHEM 4 ]

In the general formula (10), R^aRepresents a C1-C8 alkyl group or a C1-C8 alkoxy group. n represents an integer of 0 to 4. X represents a halogen atom. A plurality of R^aCan be connected with each otherEither the same or different. The number n may be the same or different from each other. Several xs may be the same or different from each other.

The bis-butadiene derivative of the present invention can improve the sensitivity characteristics of an electrophotographic photoreceptor. The method for producing a bis-butadiene derivative of the present invention can efficiently produce the bis-butadiene derivative. The electrophotographic photoreceptor of the present invention has excellent sensitivity characteristics. The bis-butadiene halide of the present invention can be used in the above-described process for producing a bis-butadiene derivative.

Drawings

Fig. 1 is a sectional view of an example of an electrophotographic photoreceptor according to a third embodiment of the present invention.

Fig. 2 is a sectional view of another example of an electrophotographic photoreceptor according to a third embodiment of the present invention.

Fig. 3 is a cross-sectional view of another example of the electrophotographic photoreceptor according to the third embodiment of the present invention.

Fig. 4 is a sectional view of another example of the electrophotographic photoreceptor according to the third embodiment of the present invention.

Fig. 5 is a sectional view of another example of the electrophotographic photoreceptor according to the third embodiment of the present invention.

Fig. 6 is a sectional view of another example of the electrophotographic photoreceptor according to the third embodiment of the present invention.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments in any way. The present invention can be implemented with appropriate modifications within the intended scope of the present invention. Note that, although the overlapping description may be omitted as appropriate, the gist of the present invention is not limited thereto.

Hereinafter, the compound and its derivatives may be collectively referred to by adding "class" to the compound name. When a "class" is added to a compound name to indicate a polymer name, the repeating unit indicating the polymer is derived from the compound or a derivative thereof.

Hereinafter, unless otherwise specified, the meanings of the halogen atom, C1-C8 alkyl group, C1-C6 alkyl group, C1-C5 alkyl group, C1-C4 alkyl group, C1-C3 alkyl group, C1-C8 alkoxy group, C1-C6 alkoxy group, C1-C3 alkoxy group, C6-C14 aryl group, C6-C10 aryl group, C7-C15 aralkyl group, C7-C11 aralkyl group and heterocyclic group are as follows, respectively.

Examples of the halogen atom (halo) include: fluorine atom (fluoro group), chlorine atom (chloro group), bromine atom (bromo group), and iodine atom (iodo group).

The C1-C8 alkyl group, C1-C6 alkyl group, C1-C5 alkyl group, C1-C4 alkyl group and C1-C3 alkyl group are all straight-chain or branched-chain and unsubstituted. Examples of the C1-C8 alkyl group include: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1, 2-dimethylpropyl group, straight-chain or branched-chain hexyl group, straight-chain or branched-chain heptyl group, and straight-chain or branched-chain octyl group. Examples of C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl and C1-C3 alkyl are C1-C6, C1-C5, C1-C4 and C1-C3 radicals, respectively, in the case of C1-C8 alkyl.

The C1-C8 alkoxy, C1-C6 alkoxy and C1-C3 alkoxy are all straight-chain or branched-chain and unsubstituted. Examples of the C1-C8 alkoxy group include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, hexoxy, heptoxy and octoxy. Examples of C1-C6 alkoxy and C1-C3 alkoxy are the C1-C6 and C1-C3 groups, respectively, of the examples of C1-C8 alkoxy.

Both the C6-C14 aryl and the C6-C10 aryl are unsubstituted. Examples of the C6-C14 aryl group include: phenyl, naphthyl, indacenyl, biphenylene, acenaphthylene, anthryl and phenanthryl. Examples of the C6-C10 aryl group include: phenyl and naphthyl.

Both the C7-C15 aralkyl and C7-C11 aralkyl groups are unsubstituted. Examples of the C7-C15 aralkyl group include: C1-C6 alkyl with C6-C14 aryl substituents. Examples of the C7-C11 aralkyl group include: C1-C3 alkyl with C6-C10 aryl substituents.

Examples of the heterocyclic group include 5-to 14-membered heterocyclic groups. The heterocyclic group having 5 to 14 members contains carbon atoms and at least 1 hetero atom, and is unsubstituted. The hetero atom is 1 or more atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom. Examples of the heterocyclic group having 5 to 14 members include: a heterocyclic group containing a heterocycle (H) which is a 5-or 6-membered monocyclic heterocyclic ring containing carbon atoms and 1 or more and 3 or less heteroatoms; a heterocyclic group obtained by condensing 2 heterocyclic rings (H); a heterocyclic group obtained by condensing a heterocyclic ring (H) with a 5-or 6-membered monocyclic hydrocarbon ring; a heterocyclic group obtained by condensing 3 heterocyclic rings (H); a heterocyclic group obtained by condensing 2 heterocyclic rings (H) with 1 or 5-or 6-membered monocyclic hydrocarbon ring; or a heterocyclic group obtained by condensing 1 heterocyclic ring (H) with 2 5-or 6-membered monocyclic hydrocarbon rings. Specific examples of the heterocyclic group having 5 to 14 members include: piperidinyl, piperazinyl, (2-or 3-) morpholinyl, thiophenyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, isothiazolyl, isoxazolyl, oxazolyl, thiazolyl, furazanyl, pyranyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, 1H-indazolyl, isoindolyl, benzopyranyl, quinolinyl, isoquinolinyl, purinyl, pteridinyl, triazolyl, tetrazolyl, 4H-quinolizinyl, naphthyridinyl, benzofuranyl, 1, 3-benzodioxolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, carbazolyl, phenanthridinyl, acridinyl, phenazinyl, and phenanthrolinyl.

< first embodiment: bis-butadiene derivative >

The bis-butadiene derivative according to the first embodiment of the present invention is represented by the following general formula (1) (hereinafter, the bis-butadiene derivative represented by the following general formula (1) may be referred to as the bis-butadiene derivative (1)).

[ CHEM 5 ]

In the general formula (1), R^a、R^bAnd R^cIndependently of one another, represents a C1-C8 alkyl group or a C1-C8 alkoxy group. l and m are each independently an integer of 0 to 5. n represents an integer of 0 to 4. A plurality of R^aCan be connected with each otherEither the same or different. A plurality of R^bMay be the same or different from each other. A plurality of R^cMay be the same or different from each other. The several pieces 1 may be the same or different from each other. Several m may be the same or different from each other. The number n may be the same or different from each other.

In a method of forming a photosensitive layer of an electrophotographic photoreceptor (hereinafter, sometimes referred to as a photoreceptor), the bis-butadiene derivative (1) can be used as a charge transporting agent (particularly, a hole transporting agent). The bis-butadiene derivative (1) can improve the sensitivity characteristics of the photoreceptor when used as a charge transporting agent for the photoreceptor. The reason is presumed as follows.

The bis-butadiene derivative (1) has a pi conjugated system with a relatively large spatial range. Therefore, the bis-butadiene derivative (1) tends to have excellent carrier (hole) receptivity. Since the pi conjugated system of the bis-butadiene derivative (1) is relatively large, the distance of movement of carriers (holes) within the molecule is relatively long, while the distance of movement of carriers (holes) between molecules is relatively short. Therefore, the bis-butadiene derivative (1) tends to have excellent carrier (hole) transport properties. Thus, the bis-butadiene derivative (1) tends to have excellent carrier (hole) receptivity and carrier (hole) transportability, and the sensitivity characteristics of the photoreceptor can be improved.

However, the bis-butadiene derivative (1) is difficult to synthesize by the conventional synthesis method. For example, the compound represented by the above chemical formula (h-3) can be obtained by the reaction of tetraethyl ortho-xylene diphosphate and 4- (di-p-tolylamino) benzaldehyde as a conventional charge transport substance. On the other hand, in the above known synthesis method, the bis-butadiene derivative (1) cannot be obtained from the viewpoint of yield and the like. In contrast, the present inventors have found that the bis-butadiene derivative (1) can be efficiently synthesized by a synthesis method including the reaction equation (P) described later, and have completed the present invention.

In the general formula (1), R^a、R^bAnd R^cThe C1-C8 alkyl group is preferably a C1-C6 alkyl group, more preferably a C1-C3 alkyl group, and still more preferably a methyl group.

In the general formula (1), R^a、R^bAnd R^cThe C1-C8 alkoxy group is preferably a C1-C6 alkoxy group, more preferably a C1-C3 alkoxy group, and still more preferably a methoxy group.

In the general formula (1), m and l are each independently an integer of 0 to 2. When one of m and l represents 0, the other preferably represents an integer of 1 to 5, and more preferably the other represents 1 or 2.

In the general formula (1), n preferably represents an integer of 0 to 2, and more preferably 0.

In the general formula (1), R^bAnd R^cPreferably each independently represents a C1-C3 alkyl group or a C1-C3 alkoxy group. L and m preferably each independently represent an integer of 0 to 2. Also, n preferably represents 0.

In the general formula (1), a plurality of R^aPreferably identical to each other. In the general formula (1), a plurality of R^bPreferably identical to each other. In the general formula (1), a plurality of R^cPreferably identical to each other. In the general formula (1), several 1 s are preferably identical to each other. In the general formula (1), several m are preferably the same as each other. In the general formula (1), n is preferably the same as each other.

The bis-butadiene derivative (1) includes, for example, compounds represented by the following general formulae (1-a), (1-b) or (1-c), and among them, compounds represented by the following general formulae (1-a) or (1-b) are preferable.

[ CHEM 6 ]

R in the general formulae (1-a), (1-b) and (1-c)^a、R^b、R^cL, m and n are each independently of R in the formula (1)^a、R^b、R^cL, m and n have the same meaning.

The bis-butadiene derivative (1) is preferably a compound represented by the following chemical formula (HTM-1), (HTM-2), (HTM-3), (HTM-4) or (HTM-5) (hereinafter, sometimes referred to as bis-butadiene derivative (HTM-1), (HTM-2), (HTM-3), (HTM-4) or (HTM-5), respectively).

[ CHEM 7 ]

< second embodiment: process for producing bis-butadiene derivative (1) >

The method for producing a bis-butadiene derivative (1) according to the second embodiment of the present invention includes a step of performing a reaction represented by the following reaction equation (P) (hereinafter, may be referred to as reaction (P)). Hereinafter, the compounds represented by the general formulae (10) and (11) in the reaction equation (P) may be referred to as a bis-butadiene halide (10) and a diphenylamine compound (11), respectively. According to the method for producing the bis-butadiene derivative (1) according to the second embodiment of the present invention, the bis-butadiene derivative (1) can be efficiently obtained by using a synthesis method using the bis-butadiene halide (10) as a starting compound. Specifically, in this synthesis method, the bis-butadiene derivative (1) can be synthesized with a very high yield, and the synthesized bis-butadiene derivative (1) can be easily purified, so that the bis-butadiene derivative (1) can be produced at a low cost.

[ CHEM 8 ]

R in the reaction equation (P)^a、R^b、R^cL, m and n are each independently of R in the formula (1)^a、R^b、R^cL, m and n have the same meaning. X represents a halogen atom. Several xs may be the same or different from each other.

In the reaction (P), 1 molar equivalent of the bis-butadiene halide (10) is reacted with 2 molar equivalents of the diphenylamine compound (11) to obtain 1 molar equivalent of the bis-butadiene derivative (1). In the reaction (P), a palladium compound is preferably used as a catalyst. By using a palladium compound as a catalyst, the activation energy in the reaction (P) tends to be lowered. As a result, it is considered that the yield of the bis-butadiene derivative (1) can be improved.

Examples of the palladium compound include: a tetravalent palladium compound, a divalent palladium compound, or other palladium compound. Examples of the tetravalent palladium compound include: sodium hexachloropalladium (IV) tetrahydrate or potassium hexachloropalladium (IV) tetrahydrate. Examples of the divalent palladium compound include: palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium (II) acetoacetate, bis (cyanophenyl) palladium (II) dichloride, bis (triphenylphosphine) palladium (II) dichloride, tetraamminepalladium (II) chloride or (1, 5-cyclooctadiene) palladium (II) dichloride. Other palladium compounds are, for example: tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium trichloromethane complex (0) or tetrakis (triphenylphosphine) palladium (0). The palladium compound may be used alone or in combination of two or more. The palladium compound is preferably palladium (II) acetate.

When a palladium compound is used as a catalyst in the reaction (P), the amount of the palladium compound added is preferably 0.0005 mol or more and 20 mol or less, and more preferably 0.001 mol or more and 1mol or less, based on 1mol of the bis-butadiene halide (10).

When a palladium compound is used as the catalyst, a ligand may be further added to further improve the reactivity of the reaction (P). Examples of ligands include: tricyclohexylphosphine, triphenylphosphine, diphenylmethylphosphine, trifuranylphosphine, tri (o-tolyl) phosphine, phenyldicyclohexylphosphine, 2-dicyclohexylphosphine-2 ', 4', 6 '-triisopropylbiphenyl, tri (tert-butyl) phosphine, 1' -binaphthyl-2, 2 '-bis (diphenylphosphine) and 2, 2' -bis [ (diphenylphosphino) diphenyl ] ether. One ligand may be used alone, or two or more ligands may be used in combination. The ligand is preferably 2-dicyclohexylphosphine-2 ', 4 ', 6 ' -triisopropylbiphenyl.

When the ligand is added in the reaction (P), the amount of the ligand added is preferably 0.0005 mol or more and 20 mol or less, and more preferably 0.001 mol or more and 1mol or less, based on 1mol of the bis-butadiene halide (10).

The reaction (P) is preferably carried out in the presence of a base. From this, it is considered that hydrogen halide (for example, hydrogen chloride) generated in the reaction system is rapidly neutralized, and the catalytic activity can be improved. As a result, it is considered that the yield of the bis-butadiene derivative (1) can be improved. The base may be an inorganic base or an organic base. The organic base is, for example, an alkali metal alkoxide (more specifically, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, etc.), and among them, sodium tert-butoxide is preferred. Inorganic bases are, for example, tripotassium phosphate and cesium fluoride.

When a palladium compound and a base are used as a catalyst in the reaction (P), the amount of the base to be added may be appropriately adjusted according to the amount of the palladium compound to be added. Specifically, when 0.0005 mol or more and 20 mol or less of the palladium compound is added to 1mol of the bis-butadiene halide (10), the amount of the base added is preferably 1mol or more and 10 mol or less, and more preferably 1mol or more and 5 mol or less, based on 1mol of the bis-butadiene halide (10).

The reaction (P) may also be carried out in a solvent. Examples of the solvent include: xylene (more specifically, mixed xylene, etc.), toluene, tetrahydrofuran, and dimethylformamide. The solvent is preferably xylene, more preferably mixed xylene.

In the reaction (P), the amount of the diphenylamine compound (11) to be added is preferably 0.5 mol to 10 mol, more preferably 1.5 mol to 4 mol, based on 1mol of the bis-butadiene halide (10).

The reaction temperature of the reaction (P) is preferably 120 ℃ to 180 ℃. The reaction time of the reaction (P) is preferably 1 hour to 10 hours.

The bis-butadiene derivative (1) obtained by the reaction (P) may be purified as necessary. The purification method is, for example, a well-known method (for example, filtration, silica gel column chromatography or crystallization).

< third embodiment: electrophotographic photoreceptor

The third embodiment of the present invention relates to a photoreceptor. The photoreceptor according to the third embodiment includes a conductive substrate and a photosensitive layer, and the photosensitive layer is provided directly or indirectly on the conductive substrate. Examples of the photoreceptor include: a single-layer electrophotographic photoreceptor (hereinafter, sometimes referred to as a single-layer photoreceptor) and a laminated electrophotographic photoreceptor (hereinafter, sometimes referred to as a laminated photoreceptor).

[ Single-layer type photoreceptor ]

The structure of the single-layer photoreceptor will be described below with reference to fig. 1 to 3. Fig. 1 to 3 are schematic cross-sectional views of an example of a photoreceptor 1 according to a third embodiment.

In fig. 1, the photoreceptor 1 is a single-layer type photoreceptor. As shown in fig. 1, the single layer type photoreceptor includes, for example, a conductive substrate 2 and a photosensitive layer 3. The photosensitive layer 3 in the single layer type photoreceptor is a single photosensitive layer 3 a. The single photosensitive layer 3a is a single photosensitive layer 3. As shown in fig. 1, the photosensitive layer 3 may be directly disposed on the conductive substrate 2.

As shown in fig. 2, the single layer type photoreceptor may also include a conductive substrate 2, a single photosensitive layer 3a, and an intermediate layer 4 (undercoat layer). The intermediate layer 4 is provided between the conductive substrate 2 and the single photosensitive layer 3 a. As shown in fig. 2, the photosensitive layer 3 may be indirectly disposed on the conductive substrate 2 through the intermediate layer 4. As shown in fig. 3, a protective layer 5 may be provided on a single photosensitive layer 3 a.

The thickness of the single photosensitive layer 3a is not particularly limited as long as the photosensitive layer 3a can sufficiently function. The thickness of the single photosensitive layer 3a is preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm.

[ laminated photoreceptor ]

In the laminated photoreceptor, the photosensitive layer includes a charge generation layer and a charge transport layer. The structure of the laminated photoreceptor will be described below with reference to fig. 4 to 6. Fig. 4 to 6 are schematic cross-sectional views of another example of the photoreceptor 1 according to the third embodiment.

In fig. 4, the photoreceptor 1 is a laminated photoreceptor. As shown in fig. 4, the laminated photoreceptor includes, for example, a conductive substrate 2 and a photosensitive layer 3. The photosensitive layer 3 includes a charge generation layer 3b and a charge transport layer 3 c. In order to improve the abrasion resistance of the laminated photoreceptor, as shown in fig. 4, it is preferable to provide a charge generation layer 3b on the conductive substrate 2 and a charge transport layer 3c on the charge generation layer 3 b. As shown in fig. 5, in the laminated photoreceptor, a charge transport layer 3c may be provided on the conductive substrate 2, and a charge generation layer 3b may be provided on the charge transport layer 3 c.

As shown in fig. 6, the laminated photoreceptor may also include a conductive substrate 2, a photosensitive layer 3, and an intermediate layer 4 (undercoat layer). The intermediate layer 4 is between the conductive substrate 2 and the photosensitive layer 3. The photosensitive layer 3 may be provided with a protective layer 5 (see fig. 3).

The thicknesses of the charge generation layer 3b and the charge transport layer 3c are not particularly limited as long as each layer can sufficiently function. The thickness of the charge generation layer 3b is preferably 0.01 μm to 5 μm, and more preferably 0.1 μm to 3 μm. The thickness of the charge transport layer 3c is preferably 2 μm to 100 μm, and more preferably 5 μm to 50 μm.

The photosensitive layer 3 provided in the photoreceptor 1 according to the third embodiment contains at least a charge generating agent, a charge transporting agent, and a binder resin. The charge transport agent contains the bis-butadiene derivative (1) according to the first embodiment. In the single-layer photoreceptor, the single photosensitive layer 3a contains, for example, a charge generating agent, a charge transporting agent, and a binder resin. In the laminated photoreceptor, the charge generation layer 3b contains, for example, a charge generating agent and a binder resin for the charge generation layer (hereinafter, may be referred to as a matrix resin). The charge transport layer 3c contains, for example, a charge transport agent and a binder resin. The single photosensitive layer 3a, charge generation layer 3b, and charge transport layer 3c may further contain an additive. In the photoreceptor 1 according to the third embodiment, the aforementioned bis-butadiene derivative (1) is contained in the photosensitive layer 3 as a charge transporting agent, and therefore the photoreceptor 1 is excellent in sensitivity characteristics.

[ conductive substrate ]

The conductive substrate 2 may be formed of a material having conductivity (hereinafter, may be referred to as a conductive material) at least on the surface portion thereof. An example of the conductive substrate 2 is: a conductive substrate formed of a conductive material. Another example of the conductive substrate 2 is: a conductive substrate coated with a conductive material. Examples of the conductive material include: aluminum, iron, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, or indium. These conductive materials may be used alone, or two or more of them may be used in combination. Examples of the combination of 2 or more are: an alloy (more specifically, an aluminum alloy, stainless steel, brass, or the like). Among these conductive materials, aluminum or an aluminum alloy is preferable because the movement of charges from the photosensitive layer 3 to the conductive substrate 2 is good. The conductive substrate 2 may have an oxide film of the conductive material on the surface thereof.

The shape of the conductive substrate 2 is appropriately selected according to the structure of the image forming apparatus. Examples of the shape of the conductive substrate 2 include: sheet-like or drum-like. The thickness of the conductive substrate 2 is appropriately selected according to the shape thereof.

(Charge generating agent)

When the photoreceptor 1 is a single-layer photoreceptor, the single photosensitive layer 3a contains a charge generator. When the photoreceptor 1 is a laminated photoreceptor, the charge generation layer 3b contains a charge generating agent.

Examples of the charge generating agent include: phthalocyanine pigments, perylene pigments, disazo pigments, trisazo pigments, dithione-pyrrolopyrrole (dithioketo-pyrrozole) pigments, metal-free naphthalocyanine pigments, metal naphthalocyanine pigments, squaric acid pigments, indigo pigments, azulene pigments, cyanine pigments, powders of inorganic photoconductive materials (more specifically, selenium-tellurium, selenium-arsenic, cadmium sulfide, amorphous silicon, or the like), pyran pigments, anthanthroquinone pigments, triphenylmethane pigments, threne pigments, toluidine pigments, pyrazoline pigments, or quinacridone pigments. One kind of charge generating agent may be used alone, or two or more kinds may be used in combination.

Examples of the phthalocyanine pigments include: a metal phthalocyanine pigment or a metal-free phthalocyanine pigment. Examples of the metal phthalocyanine pigment include: hydroxygallium phthalocyanine pigment, chlorogallium phthalocyanine pigment or oxytitanium phthalocyanine pigment represented by the formula (CGM-A). The metal-free phthalocyanine pigment is represented by the chemical formula (CGM-B). The crystal shape (for example, X-type, α -type, β -type, Y-type, V-type, or II-type) of the phthalocyanine pigment is not particularly limited, and phthalocyanine pigments having various crystal shapes can be used.

[ CHEM 9 ]

Examples of the metal-free phthalocyanine pigment include: an X-type crystal of metal-free phthalocyanine (hereinafter, sometimes referred to as X-type metal-free phthalocyanine). Examples of the crystal of the oxytitanium phthalocyanine pigment include: an α -type, β -type or Y-type crystal of a oxytitanium phthalocyanine pigment (hereinafter, sometimes referred to as an α -type oxytitanium phthalocyanine crystal, a β -type oxytitanium phthalocyanine crystal and a Y-type oxytitanium phthalocyanine crystal, respectively). Examples of the crystals of hydroxygallium phthalocyanine pigment include V-type crystals of hydroxygallium phthalocyanine pigment. Examples of the crystal of chlorogallium phthalocyanine include type II crystals of chlorogallium phthalocyanine pigments.

For example, in a digital optical image forming apparatus, a photoreceptor having sensitivity in a wavelength region of 700nm or more is preferably used. Examples of the digital optical image forming apparatus include: laser printers or facsimile machines using a light source such as a semiconductor laser. The charge generating agent is preferably a phthalocyanine-based pigment, more preferably a oxytitanium phthalocyanine pigment, and still more preferably a Y-type oxytitanium phthalocyanine pigment, from the viewpoint of having a high quantum yield in a wavelength region of 700nm or more.

The Y-type oxytitanium phthalocyanine crystal has a main peak at 27.2 ° of the bragg angle (2 θ ± 0.2 °) in the CuK α characteristic X-ray diffraction spectrum, for example. The main peak in the CuK α characteristic X-ray diffraction spectrum means a peak having a first or second large intensity in a range where the bragg angle (2 θ ± 0.2 °) is 3 ° or more and 40 ° or less.

(method for measuring CuK alpha characteristic X-ray diffraction Spectrum)

An example of a method for measuring CuK α characteristic X-ray diffraction spectrum will be described. A sample (Y-type oxytitanium phthalocyanine pigment) was filled in a sample holder of an X-ray diffraction apparatus ("RINT (Japanese registered trademark) 1100" manufactured by Rigaku Corporation) at X-ray tube Cu, tube voltage 40kV, tube current 30mA and CuK α characteristic X-ray wavelengthThe X-ray diffraction spectrum was measured. The measurement range (2 θ) is 3 ° to 40 ° (start angle 3 ° and stop angle 40 °), and the scanning speed is, for example, 10 °/min.

In the case where the photoreceptor 1 is a laminated photoreceptor, the content of the charge generating agent in the charge generating layer 3b is preferably 5 parts by mass or more and 1000 parts by mass or less, and more preferably 30 parts by mass or more and 500 parts by mass or less, with respect to 100 parts by mass of the matrix resin.

(Charge transport agent)

The photosensitive layer 3 contains a charge transporting agent. Examples of charge transport agents are: an electron transport agent and a hole transport agent. The charge transport agent contains the above-mentioned bis-butadiene derivative (1). The bis-butadiene derivative (1) generally functions as a hole transporting agent in the photosensitive layer 3. In the single-layer type photoreceptor, the bis-butadiene derivative (1) is contained in the photosensitive layer 3a of a single layer. In the laminated photoreceptor, the bis-butadiene derivative (1) is contained in the charge transport layer 3 c.

When the photoreceptor 1 is a laminated photoreceptor, the content of the bis-butadiene derivative (1) in the charge transport layer 3c is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 20 parts by mass or more and 100 parts by mass or less, with respect to 100 parts by mass of the binder resin.

The photosensitive layer 3 may further contain a hole-transporting agent (hereinafter, sometimes referred to as another hole-transporting agent) other than the bis-butadiene derivative (1) in addition to the bis-butadiene derivative (1). Other hole-transporting agents are, for example: triphenylamine derivatives, diamine derivatives (e.g., N ' -tetraphenylbenzidine derivatives, N ' -tetraphenylphenylenediamine derivatives, N ' -tetraphenylnaphthalenediamine derivatives, N ' -tetraphenylphenylenediamine (N, N ' -tetraphenylphenylenediamine) derivatives or bis (aminophenylvinyl) benzene derivatives), oxadiazole compounds (e.g., 2, 5-bis (4-methylaminophenyl) -1, 3, 4-oxadiazole), styrene compounds (e.g., 9- (4-diethylaminostyryl) anthracene), carbazole compounds (e.g., polyvinylcarbazole), organic polysilane compounds, pyrazoline compounds (e.g., 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline), hydrazone compounds, indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds and triazole compounds. The other hole-transporting agent may be used alone or in combination of two or more.

The hole-transporting agent in the photosensitive layer 3 may be only the bis-butadiene derivative (1). The content of the bis-butadiene derivative (1) is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass, based on the total mass of the hole transporting agent.

In the single-layer photoreceptor, the single photosensitive layer 3a may further contain an electron-transporting agent as a charge-transporting agent.

Examples of the electron-transporting agent include: quinone compounds, imide compounds, hydrazone compounds, malononitrile compounds, thiopyran compounds, trinitrothioxanthone compounds, 3,4, 5, 7-tetranitro-9-fluorenone compounds, dinitroanthracene compounds, dinitroacridine compounds, tetracyanoethylene, 2, 4, 8-trinitrothioxanthone, dinitrobenzene, dinitroacridine, succinic anhydride, maleic anhydride or dibromomaleic anhydride. Examples of the quinone compound include: a diphenoquinone compound, an azoquinone compound, an anthraquinone compound, a naphthoquinone compound, a nitroanthraquinone compound or a dinitroanthraquinone compound. These electron transport agents may be used alone or in combination of two or more.

The electron-transporting agent is preferably a compound represented by the following general formulae (E-1) to (E-4).

An electron-transporting agent represented by the following general formula (E-1) will be described.

[ CHEM 10 ]

In the general formula (E-1), R²¹And R²²Independently of one another, represents C1-C6 alkyl, C1-C6 alkoxy, C6-C14 aryl or C7-C20 aralkyl.

In the general formula (E-1), R²¹And R²²Independently of one another, preferably represents a C1-C6 alkyl group. R in the general formula (E-1)²¹And R²²The C1-C6 alkyl group is preferably a C1-C5 alkyl group, more preferably 1, 1-dimethylpropanolAnd (4) a base.

The compound represented by the general formula (E-1) is preferably a compound represented by the following chemical formula (ETM-1) (hereinafter, sometimes referred to as compound (ETM-1)).

[ CHEM 11 ]

A compound represented by the following general formula (E-2) will be described.

[ CHEM 12 ]

In the general formula (E-2), R²³、R²⁴、R²⁵And R²⁶Each independently represents a C1-C6 alkyl group.

In the general formula (E-2), R²³、R²⁴、R²⁵And R²⁶Independently of one another, preferably represents a C1-C4 alkyl group.

The compound represented by the general formula (E-2) is preferably a compound represented by the following chemical formula (ETM-2) or (ETM-3) (hereinafter, sometimes referred to as compound (ETM-2) or (ETM-3)).

[ CHEM 13 ]

A compound represented by the following general formula (E-3) will be described.

[ CHEM 14 ]

In the general formula (E-3), R²⁷And R²⁸Each independently represents a C1-C6 alkyl group. R²⁹Represents a C6-C14 aryl group or a C6-C14 aryl group having a halogen atom substituent.

In the general formula (E-3), R²⁷And R²⁸Independently of one another, preferably represents a C1-C4 alkyl group. In the general formula (E-3), R²⁹Preferably represents a phenyl group having a halogen atom substituent, and more preferably represents a phenyl group having a chlorine atom substituent.

The compound represented by the general formula (E-3) is preferably a compound represented by the following chemical formula (ETM-4) (hereinafter, sometimes referred to as compound (ETM-4)).

[ CHEM 15 ]

A compound represented by the following general formula (E-4) will be described.

[ CHEM 16 ]

In the general formula (E-4), R³⁰And R³¹Independently of one another, represents a C6-C14 aryl group or a C6-C14 aryl group with a C1-C4 alkyl substituent.

In the general formula (E-4), R³⁰And R³¹Each independently preferably represents a phenyl group having a C1-C4 alkyl substituent, more preferably a phenyl group having 2 hydrogen atoms substituted with a C1-C4 alkyl group.

The compound represented by the general formula (E-4) is preferably a compound represented by the following chemical formula (ETM-5) (hereinafter, sometimes referred to as compound (ETM-5)).

[ CHEM 17 ]

The charge transport layer 3c of the laminated photoreceptor may further contain the above-mentioned electron transport agent. In this case, the electron transport agent functions as an electron acceptor compound in the charge transport layer 3 c. The electron acceptor compound is preferably a compound represented by any one of the general formulae (E-1) to (E-4), and more preferably a compound (ETM-1), (ETM-2), (ETM-3), (ETM-4) or (ETM-5).

When the photoreceptor 1 is a laminated photoreceptor, the content of the electron acceptor compound in the charge transport layer 3c is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 3 parts by mass, based on 100 parts by mass of the binder resin.

(Binder resin)

Examples of the binder resin include: thermoplastic resins, thermosetting resins, and photocurable resins. Examples of the thermoplastic resin include: polycarbonate resins, polyarylate resins, styrene-butadiene copolymers, styrene-acrylonitrile copolymers, styrene-maleic acid copolymers, acrylic polymers, styrene-acrylic acid copolymers, polyethylene resins, ethylene-vinyl acetate copolymers, chlorinated polyethylene resins, polyvinyl chloride resins, polypropylene resins, ionomer resins, vinyl chloride-vinyl acetate copolymers, alkyd resins, polyamide resins, polyurethane resins, polysulfone resins, diallyl phthalate resins, ketone resins, polyvinyl butyral resins, polyester resins, and polyether resins. Examples of the thermosetting resin include: silicone resins, epoxy resins, phenolic resins, urea-formaldehyde resins and melamine resins. Examples of the photocurable resin include: acrylic acid adducts of epoxy compounds and acrylic acid adducts of urethane compounds. The photosensitive layer 3 may contain 1 kind of the binder resin alone or 2 or more kinds thereof.

Among these resins, a polyarylate resin or a polycarbonate resin is preferable, and a polyarylate resin having a repeating unit represented by the following general formula (r-1) or a polycarbonate resin having a repeating unit represented by the following general formula (r-2) is more preferable.

[ CHEM 18 ]

In the general formulae (R-1) and (R-2), R¹、R²、R¹¹And R¹²Each independently represents a hydrogen atom or a C1-C4 alkyl group. R³、R⁴、R¹³And R¹⁴Each independently represents a hydrogen atom, a C1-C4 alkyl group or a phenyl group. R³And R⁴May also be represented by bonding to each otherA divalent group represented by the following general formula (W). R¹³And R¹⁴The divalent group represented by the following general formula (W) may be bonded to each other. Y represents a divalent group represented by the following chemical formula (Y1), (Y2), (Y3), (Y4), (Y5) or (Y6).

[ CHEM 19 ]

In the general formula (W), t represents an integer of 1 to 3. Denotes a bond.

[ CHEM 20 ]

In chemical formulae (Y1) to (Y6), a represents a bond.

In the general formulae (R-1) and (R-2), R¹、R²、R¹¹And R¹²Each independently preferably represents a hydrogen atom or a methyl group. Also, R¹And R²Preferably identical to each other. And, R¹¹And R¹²Preferably identical to each other.

In the general formulae (R-1) and (R-2), R³、R⁴、R¹³And R¹⁴Each independently preferably represents a methyl group or an ethyl group. In this case, R³And R⁴More preferably, one represents a methyl group and the other represents an ethyl group. Also, R¹³And R¹⁴More preferably, one represents a methyl group and the other represents an ethyl group. R³And R⁴Also preferred is a divalent group represented by the general formula (W) in which the divalent groups are bonded to each other. Also, R¹³And R¹⁴Also preferred is a divalent group represented by the general formula (W) in which the divalent groups are bonded to each other.

In the general formula (W), t preferably represents 2.

In the general formula (r-1), Y preferably represents a divalent group represented by the formula (Y1), (Y2) or (Y3).

The repeating unit represented by the general formula (r-1) is preferably a repeating unit represented by the following chemical formulae (r-1a) to (r-1e) (hereinafter, may be referred to as repeating units (r-1a) to (r-1 e)).

[ CHEM 21 ]

The polyarylate resin is preferably:

a polyarylate resin having a repeating unit (r-1a) and a repeating unit (r-1b),

A polyarylate resin having a repeating unit (r-1c) and a repeating unit (r-1d) or

A polyarylate resin having a repeating unit (r-1c) and a repeating unit (r-1 e).

The repeating unit represented by the general formula (r-2) is preferably a repeating unit represented by the following chemical formula (r-2a) or (r-2b) (hereinafter, may be referred to as the repeating unit (r-2a) or (r-2 b)).

[ CHEM 22 ]

The binder resin preferably contains a polyarylate resin represented by the following chemical formula (R-1), (R-2) or (R-3) (hereinafter, sometimes referred to as polyarylate resins (R-1) to (R-3)) or a polycarbonate resin represented by the following chemical formula (R-4) or (R-5) (hereinafter, sometimes referred to as polycarbonate resin (R-4) or (R-5)). In the following chemical formulae (R-1) to (R-5), the lower right numerals of the repeating units represent: the percentage of the number of repeating units with numbers in the polyarylate resin or the polycarbonate resin with respect to the number of the total repeating units. The polyarylate resins (R-1) to (R-3) and the polycarbonate resins (R-4) and (R-5) may be any of random copolymers, block copolymers, periodic copolymers and alternating copolymers.

[ CHEM 23 ]

The viscosity average molecular weight of the binder resin is preferably 25,000 or more, more preferably 30,000 or more and 70,000 or less, and further preferably 45,000 or more and 54,000 or less. When the viscosity average molecular weight of the binder resin is 30,000 or more, the abrasion resistance of the photoreceptor 1 is easily improved. When the viscosity average molecular weight of the binder resin is 70,000 or less, the binder resin is easily dissolved in a solvent when forming the photosensitive layer 3, and the viscosity of the coating liquid for the charge transport layer or the coating liquid for the photosensitive layer in a single layer tends to be appropriately lowered. As a result, the charge transport layer 3c or the single photosensitive layer 3a is easily formed.

(matrix resin)

When the photoreceptor 1 is a laminated photoreceptor, the charge generation layer 3b contains a matrix resin. The matrix resin is not particularly limited as long as it is a matrix resin that can be applied to the photoreceptor 1. Examples of the matrix resin include: a thermoplastic resin, a thermosetting resin, or a photocurable resin. Examples of the thermoplastic resin include: styrene-butadiene resin, styrene-acrylonitrile resin, styrene-maleic acid resin, styrene-acrylic acid resin, acrylic resin, polyethylene resin, ethylene-vinyl acetate resin, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, ionomer, chlorinated ethylene-vinyl acetate resin, alkyd resin, polyamide resin, polyurethane resin, polycarbonate resin, polyarylate resin, polysulfone resin, diallyl phthalate resin, ketone resin, polyvinyl acetal resin, polyether resin, or polyester resin. Examples of the thermosetting resin include: silicone resins, epoxy resins, phenolic resins, urea-formaldehyde resins, melamine resins, or other cross-linking thermosetting resins. Examples of the photocurable resin include: an epoxy-acrylic resin (more specifically, an acrylic acid derivative adduct of an epoxy compound, etc.) or a urethane-acrylic resin (more specifically, an acrylic acid derivative adduct of a urethane compound, etc.). The base resin may be used alone in 1 kind, or two or more kinds may be used in combination.

The matrix resin contained in the charge generation layer 3b is preferably different from the binder resin contained in the charge transport layer 3 c. In the production of the laminated photoreceptor, generally, a charge generation layer 3b is formed on a conductive substrate 2, and a charge transport layer 3c is further formed on the charge generation layer 3 b. In the production of such a laminated photoreceptor, the charge generating layer 3b is coated with a coating liquid for the charge transport layer in order to form the charge transport layer 3 c. Therefore, by making the matrix resin contained in the charge generation layer 3b different from the binder resin contained in the charge transport layer 3c, it is possible to suppress dissolution of the charge generation layer 3b in the solvent of the charge transport layer coating liquid when coating the charge generation layer 3b with the coating liquid.

(additives)

Each layer (the charge generation layer 3b, the charge transport layer 3c, or the single photosensitive layer 3a) of the photosensitive layer 3 of the photoreceptor 1 may further contain various additives as necessary. Examples of additives include: a deterioration inhibitor (more specifically, an antioxidant, a radical scavenger, a quencher or an ultraviolet absorber, etc.), a softening agent, a surface modifier, an extender, a thickener, a dispersion stabilizer, a wax, a donor, a surfactant, a plasticizer, a sensitizer or a leveling agent. The charge transport layer 3c preferably further contains an antioxidant as an additive.

When the photoreceptor 1 is a multilayer photoreceptor and the charge transport layer 3c contains an antioxidant, the content of the antioxidant in the charge transport layer 3c is preferably 0.05 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 3 parts by mass or less, with respect to 100 parts by mass of the binder resin.

(combination)

In the photosensitive layer 3, the combination of the hole transport agent and the binder resin is preferably combinations (j-1) to (j-9) in table 1 below. In the photosensitive layer 3, the combination of the hole transporting agent, the binder resin, and the electron transporting agent is preferably combinations (k-1) to (k-13) in the following table 2.

[ TABLE 1 ]

Combination of	Hole transport agent	Adhesive resin
			j-1	HTM-1	R-1
j-2	HTM-2	R-1
			j-3	HTM-3	R-1
j-4	HTM-4	R-1
			j-5	HTM-5	R-1
j-6	HTM-1	R-2
			j-7	HTM-1	R-3
j-8	HTM-1	R-4
			j-9	HTM-1	R-5

[ TABLE 2 ]

Combination of	Hole transport agent	Adhesive resin	Electron transport agent
				k-1	HTM-1	R-1	ETM-1
k-2	HTM-2	R-1	ETM-1
				k-3	HTM-3	R-1	ETM-1
k-4	HTM-4	R-1	ETM-1
				k-5	HTM-5	R-1	ETM-1
k-6	HTM-1	R-1	ETM-2
				k-7	HTM-1	R-1	ETM-3
k-8	HTM-1	R-1	ETM-4
				k-9	HTM-1	R-1	ETM-5
k-10	HTM-1	R-2	ETM-1
				k-11	HTM-1	R-3	ETM-1
k-12	HTM-1	R-4	ETM-1
				k-13	HTM-1	R-5	ETM-1

[ intermediate layer ]

The intermediate layer 4 (undercoat layer) contains, for example, inorganic particles and a resin (intermediate layer resin). It can be considered that: the presence of the intermediate layer 4 makes it possible to smoothly flow a current generated when the photoreceptor 1 is exposed to light and suppress an increase in resistance while maintaining an insulating state to such an extent that the occurrence of electric leakage can be suppressed.

Examples of the inorganic particles include: particles of a metal (more specifically, aluminum, iron, copper, or the like), particles of a metal oxide (more specifically, titanium oxide, aluminum oxide, zirconium oxide, tin oxide, zinc oxide, or the like), or particles of a non-metal oxide (more specifically, silicon dioxide, or the like). These inorganic particles may be used alone or in combination of 2 or more.

The resin for the intermediate layer is not particularly limited as long as it can be used as a resin for forming the intermediate layer 4. The intermediate layer 4 may also contain various additives. The additives are the same as those of the photosensitive layer 3.

[ method for producing photoreceptor ]

For example, the photoreceptor 1, which is a single-layer type photoreceptor, is manufactured by applying a coating liquid for a single-layer photosensitive layer to the conductive substrate 2 to form a coating film and drying the coating film. For example, a coating liquid for a single-layer photosensitive layer is prepared by dissolving or dispersing a charge generating agent, a charge transporting agent containing the bis-butadiene derivative (1), a binder resin, and an additive added as needed in a solvent.

The photoreceptor 1 as a laminated photoreceptor is manufactured by, for example, the following method. First, a coating liquid for a charge generating layer and a coating liquid for a charge transporting layer were prepared. Then, the charge generation layer coating liquid is applied onto the conductive substrate 2 to form a coating film, and the coating film is dried to form the charge generation layer 3 b. Next, a charge transport layer 3c is formed by applying a charge transport layer coating solution to the charge generation layer 3b to form a coating film and drying the coating film. In this way, a laminated photoreceptor was produced.

For example, a charge generating agent, a matrix resin, and an additive added as needed are dissolved or dispersed in a solvent, thereby preparing a coating liquid for a charge generating layer. A charge transport agent containing the bis-butadiene derivative (1), a binder resin, and an additive added as needed are dissolved or dispersed in a solvent, thereby preparing a coating liquid for a charge transport layer.

The solvent contained in the coating liquid for a single-layer photosensitive layer, the coating liquid for a charge generation layer, and the coating liquid for a charge transport layer (hereinafter, these 3 coating liquids may be referred to as coating liquids) is not particularly limited as long as the solvent can dissolve or disperse the respective components contained in the coating liquids and can be removed from the coating film. Examples of the solvent include: alcohols (more specifically, methanol, ethanol, isopropanol, butanol, or the like), aliphatic hydrocarbons (more specifically, n-hexane, octane, cyclohexane, or the like), aromatic hydrocarbons (more specifically, benzene, toluene, xylene, or the like), halogenated hydrocarbons (more specifically, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, or the like), ethers (more specifically, dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, or the like), ketones (more specifically, acetone, methyl ethyl ketone, cyclohexanone, or the like), esters (more specifically, ethyl acetate, methyl acetate, or the like), dimethyl formaldehyde, dimethyl formamide, and dimethyl sulfoxide. These solvents may be used alone or in combination of two or more. In order to improve the workability in manufacturing the photoreceptor 1, it is preferable to use a non-halogenated solvent (a solvent other than halogenated hydrocarbon) as the solvent of the coating liquid.

The coating liquid is prepared by mixing and dispersing the respective components into a solvent. For the mixing or dispersing operation, for example, it is possible to use: bead mills, roller mills, ball mills, attritors, paint shakers or ultrasonic dispersers.

The coating liquid may contain a surfactant, for example, in order to improve dispersibility of each component.

The method for coating with the coating liquid is not particularly limited as long as it can uniformly coat the coating liquid. Examples of the coating method include: dip coating, spray coating, spin coating or bar coating.

The method for drying the coating film is not particularly limited as long as it is a method capable of evaporating the solvent in the coating liquid. Examples of methods for drying the coating film include: a method of performing heat treatment (hot air drying) using a high-temperature dryer or a reduced-pressure dryer. The heat treatment temperature may be, for example, 40 ℃ to 150 ℃. The heat treatment time may be, for example, 3 minutes to 120 minutes.

The method for manufacturing the photoreceptor 1 may further include one or both of the step of forming the intermediate layer 4 and the step of forming the protective layer 5, as necessary. In the step of forming the intermediate layer 4 and the step of forming the protective layer 5, a known method is appropriately selected.

< fourth embodiment: bis-butadiene halide >

The bis-butadiene halide according to the fourth embodiment of the present invention is represented by the following general formula (10) (hereinafter, may be referred to as bis-butadiene halide (10)).

[ CHEM 24 ]

In the general formula (10), R^aRepresents a C1-C8 alkyl group or a C1-C8 alkoxy group. n represents an integer of 0 to 4. X represents a halogen atom. A plurality of R^aMay be the same or different from each other. The number n may be the same or different from each other. Several xs may be the same or different from each other.

The bis-butadiene halide (10) can be used in the method for producing the bis-butadiene derivative (1) according to the second embodiment of the present invention. That is, the bis-butadiene halide (10) can be used as a starting compound of the bis-butadiene derivative (1) according to the first embodiment of the present invention.

General formula (1)0) In, R^aAnd n are the same as R in the general formula (1) described in the first embodiment^aAnd n has the same preferred base and value.

In the general formula (10), X is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

The bis-butadiene halide (10) is, for example, a compound represented by the following general formula (10-a), (10-b) or (10-c), and among them, a compound represented by the following general formula (10-a) or (10-b) is preferable.

[ CHEM 25 ]

R in the general formulae (10-a), (10-b) and (10-c)^aN and X are each independently of R in the formula (10)^aN and X have the same meaning.

The bis-butadiene halide (10) is preferably a compound represented by the following chemical formula (10-1) or (10-2) (hereinafter, may be referred to as bis-butadiene halide (10-1) or (10-2), respectively).

[ CHEM 26 ]

[ Process for producing bis-butadiene halide (10) ]

The bis-butadiene halide (10) can be obtained, for example, by a production method including a step of performing reactions represented by the following reaction equations (Q-1) and (Q-2) (hereinafter, sometimes referred to as reactions (Q-1) and (Q-2), respectively). Hereinafter, the compounds represented by the general formulae (20), (22) and (23) in the following reaction equations (Q-1) and (Q-2) may be referred to as compounds (20), (22) and (23), respectively.

[ CHEM 27 ]

R in the reaction equations (Q-1) and (Q-2)^aX and n are as defined for R in formula (10)^aX and n have the same contentAnd (5) defining. Z is a halogen atom.

[ reaction (Q-1) ]

In the reaction (Q-1), 1 molar equivalent of the compound (20) was reacted with 2 molar equivalents of triethyl phosphite represented by the chemical formula (21) to obtain 1 molar equivalent of the compound (22). In the reaction (Q-1), the molar ratio of the amount of the compound (20) to the amount of triethyl phosphite added (compound (20)/triethyl phosphite) is preferably 1/1.5 or more and 1/2.5 or less. The reaction temperature of the reaction (Q-1) is preferably 160 ℃ to 200 ℃. The reaction time of the reaction (Q-1) is preferably 2 hours or more and 10 hours or less. The reaction (Q-1) is preferably carried out under an inert atmosphere (for example, under a nitrogen atmosphere or the like).

[ reaction (Q-2) ]

In the reaction (Q-2), 1 molar equivalent of the compound (22) is reacted with 2 molar equivalents of the compound (23) to obtain 1 molar equivalent of the bis-butadiene halide (10). In the reaction (Q-2), the compound (23) may be added without purifying the compound (22) obtained in the reaction (Q-1). In this case, the molar ratio of the amount of the compound (20) to be added in the reaction (Q-1) to the amount of the compound (23) to be added in the reaction (Q-2) (compound (20)/compound (23)) is preferably 1/2 or more and 1/6 or less. The reaction temperature of the reaction (Q-2) is preferably 0 ℃ to 50 ℃. The reaction time of the reaction (Q-2) is preferably 2 hours or more and 24 hours or less.

The reaction (Q-2) may be carried out in the presence of a base. Examples of bases are: sodium alkoxide (more specifically, sodium methoxide, sodium ethoxide, sodium butoxide, and the like), metal hydride (more specifically, sodium hydride, potassium hydride, and the like), or metal salt (more specifically, n-butyllithium, and the like). The base is preferably a sodium alkoxide, more preferably sodium butoxide. These bases may be used alone or in combination of two or more. The amount of the base to be added is preferably 0.5 mol or more and 1.5 mol or less relative to 1mol of the compound (23).

The solvent is exemplified as a solvent usable in the above reaction (P), and dimethylformamide is preferable.

The bis-butadiene halide (10) obtained by the reaction (Q-2) may be purified as required. The purification method is, for example, a well-known method (for example, filtration, silica gel column chromatography or crystallization).