JP4696894B2 - Coating agent composition, electrophotographic photoreceptor, image forming apparatus, and process cartridge - Google Patents

Description

  The present invention relates to a coating agent composition used as a constituent material of an electrophotographic photosensitive member, and an electrophotographic photosensitive member, an image forming apparatus, and a process cartridge using the coating agent composition.

  In recent years, in so-called xerographic image forming apparatuses having charging means, exposure means, developing means, transfer means, and fixing means, the speed and lengthening of life have been further improved by the technical progress of each member and system. Yes. As a result, the demand for high-speed compatibility and high reliability of each subsystem is higher than before. In particular, the electrophotographic photosensitive member used for image writing is more susceptible to stress than other members due to sliding with a cleaning member for cleaning the electrophotographic photosensitive member. From the viewpoint, it is desirable to suppress the occurrence of scratches and wear on the photoreceptor that cause image defects.

As a means for extending the life of the electrophotographic photosensitive member, there is a method of coating the surface of the photosensitive layer of the electrophotographic photosensitive member using a material having high mechanical strength, and various coating agents are used as constituent materials of the surface layer. It has been known. For example, the following Patent Document 1 discloses a photofunctional coating liquid obtained by reacting a solution containing a specific photofunctional organosilicon compound with a solid catalyst, followed by reaction, Patent Document 2 listed below discloses silicon-containing coating agents containing specific photofunctional organosilicon compounds, organometallic compounds, and polydentate ligands.
Japanese Patent Laid-Open No. 2001-81401 JP 2001-302975 A

  The electrophotographic photosensitive member provided with the surface layer using the coating agent disclosed in Patent Documents 1 and 2 is excellent in thermal and mechanical strength, and significantly reduces deterioration due to abrasion of the surface layer. It is something that can be done. However, in the case of these electrophotographic photoreceptors, it is difficult to adhere and easily remove contaminants such as discharge products generated in the charging process (hereinafter referred to as difficult to remove and difficult to remove). In general, “contamination resistance” is likely to be insufficient. If the electrophotographic photosensitive member is not so high in mechanical strength, it is removed from the surface along with the wear of the electrophotographic photosensitive member even if the discharge product adheres, but the coating disclosed in Patent Documents 1 and 2 above. In the case of an electrophotographic photosensitive member provided with a surface layer using an agent, since the mechanical strength is high and it is difficult to wear, the discharge product adhering to the surface is difficult to remove, and the image due to moisture absorption of the discharge product, etc. Prone to flow.

  The present invention has been made in view of such circumstances, and when used as a constituent material of an electrophotographic photoreceptor, imparts both mechanical strength and antifouling substance adhesion to the electrophotographic photoreceptor. It is an object of the present invention to provide a coating composition that can be applied. Another object of the present invention is to provide an electrophotographic photosensitive member obtained by using the coating agent composition, and an image forming apparatus and a process cartridge provided with the electrophotographic photosensitive member.

In order to solve the above problems, the present invention provides a coating agent composition used as a constituent material of an electrophotographic photoreceptor, a photofunctional organic compound capable of forming a cured film, sulfonic acid and / or a derivative thereof. And an amine having a boiling point of 250 ° C. or lower.

  According to the present invention, a good cured film can be stably formed by incorporating a sulfonic acid and / or a derivative thereof and an amine having a boiling point of 250 ° C. or less into the coating agent composition. Then, by using the cured film of the coating composition as a surface layer of the electrophotographic photosensitive member, both the mechanical strength and the antifouling substance adhesion property can be sufficiently improved. High reliability and long life can be realized.

  Furthermore, since the coating agent composition of the present invention is excellent in its own stability, it is also effective in extending the pot life in the production process.

  The reason why the above-described effect can be obtained by the coating agent composition of the present invention is not necessarily clear, but the present inventors speculate as follows. That is, the reason why the conventional coating agent composition is insufficient as a constituent material of the electrophotographic photoreceptor is that unreacted hydrolyzable groups (such as hydroxyl groups) derived from the photofunctional organic compound remain in the cured film. It is thought that there is in doing. In contrast, in the case of the coating agent composition of the present invention, the curing reaction is sufficiently achieved by curing the photofunctional organic compound in the presence of sulfonic acid and / or its derivative and an amine having a boiling point of 250 ° C. or lower. It progresses and the residual amount of hydrolyzable groups is sufficiently reduced, so that it is considered that a good cured film can be stably obtained.

  Further, according to the study by the present inventors, the above-described effects of the present invention are exhibited for the first time by the combined use of sulfonic acid and / or a derivative thereof and an amine having a boiling point of 250 ° C. or lower. The sulfonic acid and / or derivative thereof can function as a curing catalyst even when used alone, but in this case, the properties of the resulting cured film are reduced or destabilized, and further, the coating agent Problems such as a decrease in the life of the composition occur.

The photofunctional organic compound contained in the coating agent composition of the present invention is not particularly limited as long as it can form a cured film, but is represented by any one of the following general formulas (I) to (VI). It is preferable to have a structure. By using such a photofunctional organic compound, it is possible to effectively obtain an organic-inorganic hybrid film by forming a strong three-dimensional network of siloxane bonds, and to achieve a higher level of both mechanical strength and contamination resistance adhesion. You will be able to achieve it.
_{^{F [- (X 1) n}} -R 1 -Z 1 H] m (I)
[In the formula (I), F represents an organic group derived from a compound having a hole transport ability, X ¹ represents an oxygen atom or a sulfur atom, R ¹ represents an alkylene group, Z ¹ represents an oxygen atom, a sulfur atom, NH or COO, n represents 0 or 1, and m represents an integer of 1 to 4. ]
_{^{F - [(X 2) n2}} - (R 2) n3 - (Z 2) n4 G] n5 (II)
[In Formula (II), F represents an organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, Z ² represents an alkylene group, O represents an oxygen atom, a sulfur atom, NH or COO, G represents an epoxy group, n2, n3 and n4 each independently represents 0 or 1, and n5 represents an integer of 1 to 4. ]
F [—D—Si (R ³ ) _(3-a) Q _a ] _b (III)
[In Formula (III), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group, and R ³ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group. Q represents a hydrolyzable group, a represents an integer of 1 to 3, and b represents an integer of 1 to 4. ]

[In Formula (IV), F represents an organic group derived from a compound having a hole transporting property, T represents a divalent group, Y represents an oxygen atom or a sulfur atom, R ⁴ , R ⁵ and R ⁶ independently represents a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m 2 represents 0 or 1, n 6 represents an integer of 1 to 4, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

[In Formula (V), F represents an organic group derived from a compound having a hole transporting property, T represents a divalent group, R ⁸ represents a monovalent organic group, and m3 represents 0 or 1 N7 represents an integer of 1 to 4. ]

[In Formula (VI), F represents an organic group derived from a compound having a hole transporting property, L represents an alkylene group, R ⁹ represents a monovalent organic group, and n8 represents an integer of 1 to 4. Indicates. ]
Moreover, it is preferable that the coating agent composition of this invention further contains a phenol resin. By including a phenol resin in the coating agent composition, when the cured film of the coating agent composition is used as a surface layer of an electrophotographic photosensitive member, both mechanical strength and antifouling substance adhesion are further enhanced. You will be able to achieve it. Moreover, when the coating agent composition of this invention contains a phenol resin, it is preferable that a photofunctional organic compound is a charge transport material which has a reactive functional group which can react with a phenol resin.

  The present invention also relates to a method for producing a coating composition comprising a photofunctional organic compound capable of forming a cured film, a sulfonic acid and / or a derivative thereof, and an amine having a boiling point of 250 ° C. or less. A first step of mixing materials other than the amine among the materials constituting the agent composition, and a second step of obtaining the coating agent composition by adding the amine to the mixture obtained in the first step. A method for producing a coating agent composition (hereinafter referred to as “first production method” for convenience) is provided.

  Here, “the material other than the amine among the materials constituting the coating agent composition” in the first production method means a photofunctional organic compound, sulfonic acid and / or a derivative thereof capable of forming a cured product, or It means a resin such as a phenol resin, a solvent, or the like that is added as necessary.

  The present invention also relates to a method for producing a coating composition comprising a photofunctional organic compound capable of forming a cured film, a sulfonic acid and / or a derivative thereof, and an amine having a boiling point of 250 ° C. or less. Among the materials constituting the agent composition, the third step of mixing the sulfonic acid and / or derivative thereof and a material other than the amine, and the mixture obtained in the third step with the sulfonic acid and / or derivative thereof and the above And a fourth step of obtaining the coating agent composition by adding an amine. A method for producing a coating agent composition (hereinafter referred to as “second production method” for convenience) is provided. .

  Here, “the sulfonic acid and / or derivative thereof and the material other than the amine among the materials constituting the coating agent composition” in the second production method means a photofunctional organic compound capable of forming a cured product, or It means a resin such as a phenol resin, a solvent, or the like that is added as necessary.

  The first and second production methods of the present invention are based on the knowledge of the inventors described later.

  That is, when preparing a coating composition, if an amine having a boiling point of 250 ° C. or less is mixed with other constituent materials from the beginning, the amine is decomposed due to thermal decomposition of the amine, loss due to volatilization, separation of the amine from sulfonic acid, etc. The function as a capping agent is impaired, and the curing reaction starts before the reaction temperature rises sufficiently during curing of the coating composition, and various curing reactions occur, resulting in non-uniform portions in the cured product. Many will occur. When the cured product is applied to the functional layer of the electrophotographic photosensitive member, charge trap sites are formed in the functional layer, causing photodegradation.

  Therefore, in the first production method, after the constituent materials other than the amine are first mixed, the amine as the capping agent functions effectively in the coating agent composition by adding the amine to the mixture. The curing reaction can be started after the reaction temperature has sufficiently increased. Therefore, an ideal crosslinking reaction proceeds, and the obtained cured product is uniform in phase and has few trap sites, so that photodegradation can be sufficiently suppressed.

  In the second production method, first, the sulfonic acid and / or derivative thereof and a constituent material other than the amine are mixed, and then the sulfonic acid and / or derivative and amine are added to the mixture. Thus, the amine as the capping agent functions effectively in the coating agent composition, and the curing reaction can be started after the reaction temperature is sufficiently increased. Therefore, an ideal crosslinking reaction proceeds, and the obtained cured product is uniform in phase and has few trap sites, so that photodegradation can be sufficiently suppressed.

  In the said 1st and 2nd manufacturing method, it is preferable for the reason mentioned above that a coating agent composition further contains a phenol resin.

  The present invention also includes a conductive substrate and a photosensitive layer provided on the conductive substrate. The photosensitive layer is obtained by curing the coating agent composition of the present invention on the side far from the conductive substrate. The electrophotographic photosensitive member is provided with a surface layer.

  Since the electrophotographic photoreceptor of the present invention is provided with the cured film of the coating agent composition of the present invention as a surface layer, it is excellent in both the mechanical strength of the photosensitive layer and the antifouling substance adhesion. Therefore, by forming an image using the electrophotographic photosensitive member of the present invention, it is possible to sufficiently prevent discharge products generated during the charging process and residual toner after the transfer process from sticking, and to stabilize a high-quality image over a long period of time. To be able to get to.

  The present invention also provides an electrophotographic photosensitive member according to the present invention, a charging device that charges the electrophotographic photosensitive member, an exposure device that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image, and an electrostatic device. An image forming apparatus comprising: a developing device that develops a latent image to form a toner image; and a transfer device that transfers the toner image to a transfer target.

  The present invention also provides the electrophotographic photosensitive member of the present invention, a charging device that charges the electrophotographic photosensitive member, a developing device that develops an electrostatic latent image formed by exposure to form a toner image, and electrophotography. There is provided a process cartridge comprising at least one selected from a cleaning device that removes toner remaining on a photoreceptor.

  According to the image forming apparatus and the process cartridge of the present invention, by including the electrophotographic photosensitive member of the present invention having excellent mechanical strength and anti-adhesion properties, discharge products generated during the charging process and residual toner after the transfer process can be obtained. Adhesion to the electrophotographic photoreceptor can be sufficiently prevented, and high quality images can be stably obtained over a long period of time.

  According to the coating agent composition of the present invention, it is possible to sufficiently improve both the mechanical strength and the antifouling substance adhesion of the electrophotographic photosensitive member. Further, according to the electrophotographic photosensitive member of the present invention comprising the coating agent composition as a constituent material, and the image forming apparatus and the process cartridge including the electrophotographic photosensitive member, the discharge product generated during the charging step and the post-transfer step The residual toner is sufficiently prevented from adhering to the electrophotographic photosensitive member, and a high-quality image can be stably obtained over a long period of time.

Hereinafter, preferred embodiments of the present invention will be described in detail.
(Coating agent composition)
The coating agent composition of the present invention contains a photofunctional organic compound capable of forming a cured film, sulfonic acid and / or a derivative thereof, and an amine having a boiling point of 250 ° C. or lower.

The photofunctional organic compound used in the present invention is not particularly limited as long as it can form a cured film. From the viewpoint of mechanical strength and stability, among the following general formulas (I) to (VI) A compound having a structure represented by any of the above is preferred.
_{^{F [- (X 1) n}} -R 1 -Z 1 H] m (I)
[In the formula (I), F represents an organic group derived from a compound having a hole transport ability, X ¹ represents an oxygen atom or a sulfur atom, R ¹ represents an alkylene group, Z ¹ represents an oxygen atom, a sulfur atom, NH or COO, n represents 0 or 1, and m represents an integer of 1 to 4. ]
_{^{F - [(X 2) n2}} - (R 2) n3 - (Z 2) n4 G] n5 (II)
[In Formula (II), F represents an organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, Z ² represents an alkylene group, O represents an oxygen atom, a sulfur atom, NH or COO, G represents an epoxy group, n2, n3 and n4 each independently represents 0 or 1, and n5 represents an integer of 1 to 4. ]
F [—D—Si (R ³ ) _(3-a) Q _a ] _b (III)
[In Formula (III), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group, and R ³ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group. Q represents a hydrolyzable group, a represents an integer of 1 to 3, and b represents an integer of 1 to 4. ]

[In Formula (IV), F represents an organic group derived from a compound having a hole transporting property, T represents a divalent group, Y represents an oxygen atom or a sulfur atom, R ⁴ , R ⁵ and R ⁶ independently represents a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m 2 represents 0 or 1, n 6 represents an integer of 1 to 4, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

[In Formula (V), F represents an organic group derived from a compound having a hole transporting property, T represents a divalent group, R ⁸ represents a monovalent organic group, and m3 represents 0 or 1 N7 represents an integer of 1 to 4. ]

[In Formula (VI), F represents an organic group derived from a compound having a hole transporting property, L represents an alkylene group, R ⁹ represents a monovalent organic group, and n8 represents an integer of 1 to 4. Indicates. ]
In the above general formula (I), the divalent group D plays a role of linking the site of F for imparting photoelectric characteristics with a substituted silicon group that contributes to the construction of a three-dimensional inorganic glassy network. Is a valent group. In addition, the divalent group D represents an organic group structure that imparts moderate flexibility to a portion of the inorganic glassy network that is hard but also brittle, and plays a role of improving mechanical toughness as a film. Specific examples _{D, -C α H 2α -,} - C β H 2β-2 -, - C γ H 2γ-4 - 2 divalent hydrocarbon group (here represented by, alpha is 1 to 15 Represents an integer, β represents an integer of 2 to 15, and γ represents an integer of 3 to 15), —COO—, —S—, —O—, —CH ₂ —C ₆ H ₄ —, —N═. CH—, — (C ₆ H ₄ ) — (C ₆ H ₄ ) —, and a characteristic group having a structure in which these characteristic groups are arbitrarily combined, and further, the constituent atoms of these characteristic groups are substituted with other substituents. And the like. The hydrolyzable group Q is preferably an alkoxy group, more preferably an alkoxy group having 1 to 15 carbon atoms.

  Moreover, as the organic group F in the general formulas (I) to (VI), an organic group having a structure represented by the following general formula (VII) is preferable.

In General Formula (IV), Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group, Ar ⁵ represents a substituted or unsubstituted aryl group or an arylene group, and Ar ^{1 to} Ar ⁵ 2 to 4 have a bond with a monovalent organic group represented by the following general formula (VIII), (IX), (X), (XI) or (XII) in the general formulas (I) to (VI). Have.
_{^{- (X 1) n -R 1}} -Z 1 H (VIII)
[In Formula (VIII), X ¹ represents an oxygen atom or a sulfur atom, R ¹ represents an alkylene group, Z ¹ represents an oxygen atom, a sulfur atom, NH or COO, and n represents 0 or 1. ]
_{^{- (X 2) n1 - (}} R 2) n2 - (Z 2) n3 G (IX)
[In the formula (VIII), X ² represents an oxygen atom or sulfur atom, R ² represents an alkylene group, Z ² represents an oxygen atom, sulfur atom, NH or COO, G represents an epoxy group, and n1, n2 and n3 represent Each independently represents 0 or 1. ]
-D-Si (R ³ ) _(3-a) Q _a (X)
{In Formula (IX), D represents a divalent group having flexibility; R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; and Q represents a hydrolyzable group. , A represents an integer of 1 to 3. }

[In Formula (XI), T is a divalent group, Y is an oxygen atom or a sulfur atom, R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent organic group, and R ⁷ is 1 A valent organic group, m2 represents 0 or 1; However, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

[In the formula (XII), T represents a divalent group, R ⁸ represents a monovalent organic group, and m3 represents 0 or 1. ]

[In Formula (XIII), L represents an alkylene group, R ⁹ represents a monovalent organic group, and n8 represents an integer of 1 to 4. ]
In general formula (VII), the substituted or unsubstituted aryl groups represented by Ar ^{1 to} Ar ⁴ are specifically represented by general formulas (VII-1) to (VII-7) shown in Table 1 below. The aryl group is preferred. In General Formulas (VII-1) to (VII-7), R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, R ^{11 to} R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a substituted phenyl group or an unsubstituted phenyl group, or an aralkyl group having 7 to 10 carbon atoms. An alkoxy group having 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group substituted or unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom; The site | part shown by general formula (VIII)-(XIII) in VI) is shown. M and s each independently represent 0 or 1, and t represents an integer of 1 to 3.

As Ar in the aryl group represented by the general formula (VII-7), an aryl group represented by the following formula (VII-8) or (VII-9) is preferable. In general formulas (VII-8) and (VII-9), R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 carbon atom. -4 alkoxy group, phenyl or unsubstituted phenyl group substituted therewith, aralkyl group having 7 to 10 carbon atoms, or halogen atom, X is a group represented by formula (VIII) in formulas (I) to (VI). ) To (XIII). Moreover, t shows the integer of 1-3.

Moreover, as Z in the aryl group represented by the formula (VII-7), a divalent group represented by the following formulas (VII-10) to (VII-17) is preferable. In general formulas (VII-10) to (VII-17), R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 carbon atom. -4 alkoxy group, a phenyl group substituted by them or an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom. Q and r each independently represent an integer of 1 to 10, and t represents an integer of 1 to 3.

  In general formulas (VII-16) to (VII-17), W represents a divalent group represented by general formulas (VII-18) to (VII-26) in Table 4 below. In general formula (VII-25), u represents an integer of 0 to 3.

The specific structure of Ar ⁵ in the general formula (VII) is as follows. When k = 0, the specific structure of Ar ^{1 to} Ar ⁴ is m = 1, and when k = 1, the Ar 5 is Ar. ^The structure of m = 0 in the specific structure of ^{1 to} Ar ⁴ is given.
Specific examples of the compound represented by the general formula (I) include compounds shown in Tables 5 to 10 below. In Tables 5 to 10 below, Me or a bond is described but a substituent is not described indicates a methyl group.

  Specific examples of the compound represented by the general formula (II) include compounds shown in Tables 11 to 24 below. In Tables 11 to 24 below, Me or a bond is described but a substituent is not described, and Et represents an ethyl group.

Moreover, as a specific example of a compound represented by general formula (III), the compound shown to the following Tables 25-32 can be mentioned. In addition, all the compounds shown in Tables 24 to 31 have a structure represented by the general formula (VII) as the organic group F, and Ar ^{1 to} Ar ⁵ and k in Tables 24 to 31 are general formulas. Ar ^{1 to} Ar ⁵ and k in (VII) are shown. S in Tables 24 to 31 represents-[D-Si (R ³ ) _(3-a) Q _a ] in the general formula (III). In Tables 24-31, Me represents a methyl group, Et represents an ethyl group, and iPr represents an isopropyl group.

Specific examples of the compound represented by the general formula (IV) include compounds shown in Tables 33 to 42 below. In Tables 33 to 42 below, Me or a bond is described but a substituent is not described, a methyl group, and Et represents an ethyl group.

  Specific examples of the compound represented by the general formula (V) include compounds shown in Tables 43 to 51 below. In Tables 43 to 51 below, Me or a bond is described but a substituent is not described indicates a methyl group.

  Specific examples of the compound represented by the general formula (VI) include the compounds shown in Tables 52 to 55 below. In Tables 52 to 55 below, Me or a bond is described but a substituent is not described, which represents a methyl group, and Et represents an ethyl group.

  Moreover, the coating agent composition of this invention contains a sulfonic acid and / or its derivative, and an amine with a boiling point of 250 degrees C or less in addition to said optical functional organic compound. Here, the sulfonic acid and / or its derivative function as a curing catalyst for the photofunctional organic compound, while the amine having a boiling point of 250 ° C. or lower functions as a blocking agent for the sulfonic acid and / or its derivative. The inventors consider.

  Examples of the sulfonic acid include p-toluenesulfonic acid (p-TSA), dinonylnaphthalenesulfonic acid (DNNSA), dinonylnaphthalenedisulfonic acid (DNNDSA), dodecylbenzenesulfonic acid (DDBSA), and the like. DNNSA and DDBSA are preferred because of their high catalytic activity. Examples of sulfonic acid derivatives include neutralized sulfonic acid alkali metal salts or alkaline earth metal salts, polymer compounds in which a sulfonic acid skeleton is introduced into a polymer chain (polyvinylsulfonic acid, etc.), etc. Is mentioned.

  Moreover, the boiling point of the amine used by this invention is 250 degrees C or less as above-mentioned, Preferably it is 30-250 degreeC, More preferably, it is 80-150 degreeC. When the boiling point of the amine exceeds 250 ° C., the amine as a blocking agent is hardly detached from the sulfonic acid and / or its derivative by heating during film formation, and curing is insufficient. If the boiling point of the amine exceeds 250 ° C., it tends to remain in the cured film at the time of film formation, which adversely affects the properties of the cured film. On the other hand, when the boiling point of the amine is less than 30 ° C., the stability during storage of the coating agent composition is lowered, and inconveniences such as an increase in defects during film formation tend to occur.

  The amine used in the present invention may be primary, secondary or tertiary as long as the boiling point is 250 ° C. or less, but it is difficult to form charge traps in the cured film, and the electrical properties of the cured film are A secondary or tertiary amine is preferable from the viewpoint of preventing the decrease. Furthermore, secondary amines are particularly preferred from the viewpoint that both the function of the sulfonic acid and / or derivative thereof as a blocking agent and the electrical properties of the cured film can be achieved at a high level.

  Examples of the secondary amine having a boiling point of 250 ° C. or lower include diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-t-butylamine, dihexylamine, di (2-ethylhexyl) amine, and N-isopropyl. N-isobutylamine, di-2-ethylhexylamine, disecondary butylamine, diallylamine, N-methylhexylamine, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, Morpholine, N-methylbenzylamine and the like are used, and examples of the amine having a tertiary amino group include N-methylmorpholine, triethylamine, tributylamine, N, N-dimethylallylamine, N-methyldiallylamine, triallylamine. N, N, N ′, N′-tetramethyl-1,2-diaminoethane, N, N, N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N ′ -Tetraallyl-1,4-diaminobutane, N-methylpiperidine, pyridine, 4-ethylpyridine, tripropylamine, N-pyrrolidylallylamine, 3-dimethylaminopropanol, 2-ethylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,4-lutidine, 2,5-lutidine, 3,4-lutidine, 3,5-lutidine, 2,4,6-collidine, 2-methyl-4-ethylpyridine, 2- Methyl-5-ethylpyridine, N, N, N ′, N′-tetramethylhexamethylenediamine, N-ethyl-3-hydroxypiperidine, 3-methyl-4-ethylpyridine 3-ethyl-4-methylpyridine, 4- (5-nonyl) pyridine, imidazole. Moreover, N-methyl piperazine etc. are mentioned as a tertiary amine with a boiling point of 250 degrees C or less.

  In the present invention, one type of amine having a boiling point of 250 ° C. or lower may be used alone, or two or more types may be used in combination.

  The ratio of the content of the sulfonic acid and / or derivative thereof to the content of the amine having a boiling point of 250 ° C. or lower in the coating agent composition of the present invention is preferably 1: 0.5 to 1: 2. More preferably, the ratio is 1: 0.8 to 1: 1.5. When the amine is less than 0.5 mol relative to 1 mol of the sulfonic acid and / or derivative thereof, the pot life of the coating agent composition is shortened and the properties of the cured film tend to be unstable. Moreover, when amine exceeds 2 mol with respect to 1 mol of sulfonic acid and / or its derivative (s), it will become easy to remain in a cured film at the time of film-forming, and it exists in the tendency for the characteristic of a cured film to fall.

  The coating agent composition of the present invention may comprise the above-mentioned photofunctional organic compound, sulfonic acid and / or a derivative thereof, and an amine having a boiling point of 250 ° C. or lower, in order to further improve the characteristics. Further, various components shown below can be further contained.

The coating composition of the present invention is represented by the following general formula (V) in order to control various physical properties such as mechanical strength, electrical resistance, frictional force, adhesion, and flexibility of the resulting cured film. It is preferable to further contain a compound.
Si (R ¹⁸ ) _(4-e) Q _e (XIV)
[In General Formula (XIV), R ¹⁸ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, and Q represents a hydrolyzable group. Moreover, e shows the integer of 1-4. ]
Specific examples of the compound represented by the general formula (XIV) include the following silane coupling agents. Tetrafunctional alkoxysilanes such as tetramethoxysilane and tetraethoxysilane (e = 4); methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyltrimethoxyethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Phenyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltri Methoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3, 3,3-trifluoropropyl) trimethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoro Trifunctional alkoxysilanes (e = 3) such as decyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane; bifunctional alkoxy such as dimethyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane Silane (e = 2); monofunctional alkoxysilanes such as trimethylmethoxysilane (c = 1) and the like. Trifunctional and tetrafunctional alkoxysilanes are preferable for improving the strength of the film, and bifunctional and monofunctional alkoxysilanes are preferable for improving the flexibility and film forming property.

  Moreover, the silicone type hard-coating agent produced from the said coupling agent can also be used for the coating agent composition of this invention. Commercially available hard coat agents include KP-85, X-40-9740, X-40-2239 (manufactured by Shin-Etsu Silicone), AY42-440, AY42-441, AY49-208 (manufactured by Toray Dow Corning) Manufactured).

The coating composition of the present invention preferably further contains a compound having two or more silicon atoms such as a compound represented by the following general formula (XV) in order to increase the strength.
B- [Si (R ¹⁹ ) _(3-f) Q _f ] ₂ (XV)
[In General Formula (XV), B represents a divalent organic group, R ¹⁹ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, and Q represents a hydrolyzable group. F represents an integer of 1 to 3. ]
Specific examples of the compound represented by the general formula (XV) include compounds shown in Table 56 below.

  Moreover, it is preferable that the coating agent composition of this invention further contains a phenol resin. In this case, the photofunctional organic compound is preferably compatible with the phenol resin to be used, and more preferably forms a chemical bond with the phenol resin to be used.

  Examples of the phenol resin include resorcin, bisphenol, substituted phenols containing one hydroxyl group such as phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, substituted phenols containing two hydroxyl groups such as catechol, resorcinol, hydroquinone, and bisphenol. A, a compound having a phenol structure, such as bisphenols such as bisphenol Z, biphenols, and the like, and formaldehyde, paraformaldehyde, etc. are reacted in the presence of an acid or alkali catalyst to produce monomethylolphenols, dimethylolphenols, trimethylolphenol Class of monomers, and mixtures thereof, or oligomerized thereof, and mixtures of monomers and oligomers. Among these, a relatively large molecule having about 2 to 20 repeating molecular structural units is an oligomer, and a smaller molecule is a monomer.

  Moreover, the coating agent composition of the present invention may further contain a resin soluble in an alcohol-based or ketone-based solvent in addition to the above-described phenolic resin, for the purpose of controlling film characteristics. Examples of such resins include polyvinyl butyral resins, polyvinyl formal resins, and polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins in which a part of butyral is modified with formal, acetoacetal, or the like (for example, ESREC B, K manufactured by Sekisui Chemical Co., Ltd.). Etc.), polyamide resin, cellulose resin and the like. In particular, polyvinyl acetal resin is preferable in terms of electrical characteristics. Various resins can be added for the purpose of discharge gas resistance, mechanical strength, scratch resistance, particle dispersibility, viscosity control, torque reduction, wear amount control, pot life extension, and the like. Particularly in the case of a siloxane-based resin, it is preferable to add a resin that dissolves in alcohol. Examples of resins that are soluble in alcohol solvents include polyvinyl acetal resins such as polyvinyl butyral resin, polyvinyl formal resin, and partially acetalized polyvinyl acetal resin in which a part of butyral is modified with formal or acetoacetal (for example, manufactured by Sekisui Chemical Co., Ltd.) ESREC B, K, etc.), polyamide resin, cellulose resin, phenol resin and the like. In particular, polyvinyl acetal resin is preferable in terms of electrical characteristics. The viscosity average molecular weight of the resin is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. If the viscosity average molecular weight is less than 2,000, the desired effect tends to be lost. Moreover, when a viscosity average molecular weight exceeds 100,000, solubility will become low and the addition amount will be limited, or it may cause the film formation defect at the time of application | coating. The addition amount is preferably 1 to 40%, more preferably 1 to 30%, and most preferably 5 to 20%. If the amount is less than 1%, it is difficult to obtain a desired effect. If the amount is more than 40%, image blurring under high temperature and high humidity tends to occur. These resins may be used alone or in combination.

  Moreover, the coating agent composition of this invention can contain further the cyclic compound which has a repeating structural unit shown by the following general formula (XVI), or the derivative | guide_body from the compound for control of a film | membrane characteristic.

[In General Formula (XVI), A ¹ and A ² each independently represent a monovalent organic group. ]
Examples of the cyclic compound having the repeating structural unit represented by the general formula (XVI) include commercially available cyclic siloxanes. Specifically, cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,3,5-trimethyl-1,3,5- Triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7 , 9-pentaphenylcyclopentasiloxane and other cyclic methylphenylcyclosiloxanes, hexaphenylcyclotrisiloxane and other cyclic phenylcyclosiloxanes, and 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane and other fluorine Contain cyclosiloxanes and methylhydrosiloxane Things, pentamethylcyclopentasiloxane include a phenyl hydrosilyl group-containing cyclosiloxanes such hydrocyclosiloxane, cyclic siloxanes and vinyl group-containing cyclosiloxanes, such as penta vinyl pentamethylcyclopentasiloxane like. These cyclic siloxane compounds may be used alone or in a combination of two or more.

  The coating agent composition of the present invention can further contain various fine particles in order to further improve the antifouling substance adhesion and lubricity of the cured film. The fine particles may be used alone or in combination of two or more. Examples of the fine particles include silicon-containing fine particles. Silicon-containing fine particles are fine particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone fine particles. The colloidal silica used as the silicon-containing fine particles is a dispersion obtained by dispersing particles having an average particle diameter of 1 to 100 nm, preferably 10 to 30 nm, in acidic or alkaline water, or an organic solvent such as alcohol, ketone, or ester. Those selected and generally commercially available can be used. The solid content of the colloidal silica in the surface layer is not particularly limited, but from the viewpoint of film forming properties, electrical properties, and strength, the entire film obtained by curing the coating agent composition of the present invention. It is used in the range of 0.1 to 50% by mass, preferably in the range of 0.1 to 30% by mass, based on the mass.

  Silicone fine particles used as silicon-containing fine particles are spherical and have an average particle diameter of 1 to 500 nm, preferably 10 to 100 nm, and are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and are generally commercially available. Can be used. Silicone fine particles are small particles that are chemically inert and excellent in dispersibility in resin, and since the content required to obtain sufficient characteristics is low, the electron does not hinder the crosslinking reaction, The surface properties of the photographic photoreceptor can be improved. That is, it can improve the lubricity and water repellency of the surface of the electrophotographic photosensitive member while being uniformly incorporated into a strong cross-linked structure, and maintain good wear resistance and adherence to contaminants over a long period of time. it can. The content of the silicone fine particles is in the range of 0.1 to 30% by mass, preferably 0.5 to 10% by mass, based on the total mass of the film obtained by curing the coating agent composition of the present invention. It is a range.

Other fine particles include fluorinated fine particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and "8th Polymer Material Forum Lecture Proceedings, p89". Fine particles comprising a resin obtained by copolymerizing the fluororesin and a monomer having a hydroxyl group as shown, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO ₂ And semiconductive metal oxides such as ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO. For the same purpose, an oil such as silicone oil can be added. Examples of the silicone oil include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, and mercapto. Examples include reactive silicone oils such as modified polysiloxanes and phenol-modified polysiloxanes.

  Moreover, the coating agent composition of this invention can further contain additives, such as a plasticizer, a surface modifier, antioxidant, and a photodegradation inhibitor.

  Examples of the plasticizer include biphenyl, biphenyl chloride, terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenyl phosphate, methyl naphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, and various fluorohydrocarbons.

  Antioxidants include hindered phenols, hindered amines, thioethers or antioxidants having a phosphite partial structure, which are capable of crosslinking reaction with the material forming the crosslinked film, such as alkoxysilyl groups. You may modify | denature with a substituent. These antioxidants are effective in improving the potential stability and image quality when the environment changes, and among them, hindered phenols and hindered amine antioxidants are preferable.

  Examples of hindered phenol-based antioxidants include “Sumilizer BHT-R”, “Sumilizer MDP-S”, “Sumizer BBM-S”, “Sumizer WX-R”, “Sumizer NW”, “Sumizer BP-76”, “Sumilizer BP-101”, “Sumilizer GA-80”, “Sumilizer GM”, “Sumilizer GS” (manufactured by Sumitomo Chemical Co., Ltd.), “IRGANOX1010”, “IRGANOX1035”, “IRGANOX1076”, “IRGANOX1098”, “IRGANOX1098”, “GAR” , “IRGANOX1141”, “IRGANOX1222”, “IRGANOX1330”, “IRGANOX1425WL”, “IRGAN X1520L "," IRGANOX245 "," IRGANOX259 "," IRGANOX3114 "," IRGANOX3790 "," IRGANOX5057 "," IRGANOX565 "(above, manufactured by Ciba Specialty Chemicals)," ADK STAB AO-20 "," ADK STAB AO-30 ", "ADK STAB AO-40", "ADK STAB AO-50", "ADK STAB AO-60", "ADK STAB AO-70", "ADK STAB AO-80", "ADK STAB AO-330" (manufactured by Asahi Denka) It is done. Further, as a hindered amine-based antioxidant, “Sanol LS2626”, “Sanol LS765”, “Sanol LS770”, “Sanol LS744” or more manufactured by Sankyo Lifetech Co., Ltd., “Tinuvin 144”, “Tinubin 622LD” or more Ciba Specialty Chemicals "Mark LA57", "Mark LA67", "Mark LA62", "Mark LA68", "Mark LA63" or more manufactured by Asahi Denka, "Sumilyzer TPS" or more made by Sumitomo Chemical Co., Ltd., "Sumilyzer TP-D" "Mitsubishi Sumitomo Chemical Co., Ltd.," Mark 2112 "," Mark PEP 8 "," Mark PEP 24G "," Mark PEP 36 "," Mark 329K "," Mark HP 10 "and more Asahi An electrification is mentioned.

  Further, the coating agent composition of the present invention may contain a sulfonic acid and / or a derivative thereof and a catalyst other than an amine having a boiling point of 250 ° C. or lower (hereinafter referred to as “other catalyst” for convenience). Alternatively, a predetermined reaction (for example, exchange of protecting group of hydrolyzable group, deprotection reaction, hydrolysis, condensation reaction, etc.) is performed on a part of the components of the coating agent composition using the other catalyst, and the reaction The liquid may be subjected to preparation of a coating agent composition after separating and removing the catalyst as necessary.

  Other catalysts include inorganic acids such as hydrochloric acid, acetic acid and sulfuric acid, organic acids such as formic acid, propionic acid, oxalic acid, benzoic acid, phthalic acid and maleic acid, potassium hydroxide, sodium hydroxide, calcium hydroxide and ammonia And alkaline catalysts.

  A solid catalyst insoluble in the system can also be used. “Solid catalyst insoluble in the system” means a component of the coating composition of the present invention (photofunctional organic compound, sulfonic acid and / or derivative thereof, amine having a boiling point of 250 ° C. or lower, reaction product, or other The solid catalyst is insoluble in additives and solvents. When a solid catalyst insoluble in the system is used, the stability of the coating agent composition tends to be improved during the preparation of the coating agent composition.

Examples of solid catalysts insoluble in the system include Amberlite 15, Amberlite 200C, Amberlyst 15E (above, manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 ( As described above, manufactured by Dow Chemical Co., Ltd.); Lebatit SPC-108, Lebatit SPC-118 (above, manufactured by Bayer); Diaion RCP-150H (manufactured by Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duo Cation exchange resin such as Light C-433, Duolite-464 (manufactured by Sumitomo Chemical Co., Ltd.); Nafion-H (manufactured by DuPont); Amberlite IRA-400, Amberlite IRA-45 (above, ROHM Anion exchange resin such as And Haas Co .; Zr (O ₃ PCH ₂ CH ₂ SO ₃ H) ₂ , Th (O ₃ PCH ₂ CH ₂ COOH) ₂ and other inorganic solids in which a group containing a protonic acid group is bonded to the surface; heteropolyacids such as cobalt tungstic acid and phosphomolybdic acid; niobium Isopolyacids such as acid, tantalum acid and molybdic acid; single metal oxides such as silica gel, alumina, chromia, zirconia, CaO and MgO; complex metal oxides such as silica-alumina, silica-magnesia, silica-zirconia and zeolites Clay minerals such as acid clay, activated clay, montmorillonite and kaolinite; metal sulfates such as LiSO ₄ and MgSO ₄ ; metal phosphates such as zirconia phosphate and lanthanum phosphate; LiNO ₃ , Mn (NO ₃ ) metal nitrates, such as _2; aminopropyltriethoxysilane on silica gel And poly organosiloxanes containing an amino group such as amino-modified silicone resins; inorganic solids group containing an amino group such as solid obtained by response is bound to the surface.

  The amount of the solid catalyst insoluble in the system is not particularly limited, but is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass in total of the compounds having hydrolyzable groups. Moreover, since these solid catalysts are insoluble in the system as described above, they can be easily removed after the reaction according to a conventional method.

  When performing a predetermined reaction using a solid catalyst insoluble in the system, the reaction temperature and reaction time are appropriately selected according to the type and amount of the raw material compound and solid catalyst. The reaction temperature is usually 0 to 100 ° C., preferably 10 to 70 ° C., more preferably 15 to 50 ° C., and the reaction time is preferably 10 minutes to 100 hours. If the reaction time exceeds the upper limit, gelation tends to occur.

  When a catalyst that is insoluble in the system is used, it is preferable to use a catalyst that is further soluble in the system for the purpose of improving strength, liquid storage stability and the like. Catalysts soluble in the system include aluminum triethylate, aluminum triisopropylate, aluminum tri (sec-butyrate), mono (sec-butoxy) aluminum diisopropylate, diisopropoxyaluminum (ethyl). Acetoacetate), aluminum tris (ethyl acetoacetate), aluminum bis (ethyl acetoacetate) monoacetylacetonate, aluminum tris (acetylacetonate), aluminum diisopropoxy (acetylacetonate), aluminum isopropoxy-bis (acetylacetate) Nate), aluminum tris (trifluoroacetylacetonate), aluminum tris (hexafluoroacetylacetonate) and other organoaluminum compounds It is possible to use.

  Besides organic aluminum compounds, organic compounds such as dibutyltin dilaurate, dibutyltin dioctiate, dibutyltin diacetate; titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium bis Organic titanium compounds such as (isopropoxy) bis (acetylacetonate); zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate), zirconium bis (isopropoxy) bis (acetylacetonate), etc. Zirconium compounds; etc. can also be used, but from the viewpoints of safety, low cost, and pot life length, it is preferable to use an organoaluminum compound, particularly an aluminum chelate compound. It is more preferable. Although the usage-amount in particular of these catalysts is not restrict | limited, 0.1-20 mass parts is preferable with respect to a total of 100 mass parts of the compound which has a hydrolysable group, and 0.3-10 mass parts is especially preferable.

  In the present invention, when an organometallic compound is used as a catalyst, it is preferable to add a polydentate ligand from the viewpoint of pot life and curing efficiency. Examples of such multidentate ligands include those shown below and those derived therefrom, but the present invention is not limited to these.

Specific examples of the multidentate ligand include β-diketones such as acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, and dipivaloylmethylacetone; acetoacetate esters such as methyl acetoacetate and ethyl acetoacetate; Bipyridine and derivatives thereof; Glycine and derivatives thereof; Ethylenediamine and derivatives thereof; 8-Oxyquinoline and derivatives thereof; Salicylaldehyde and derivatives thereof; Catechol and derivatives thereof; Bidentate ligands such as 2-oxyazo compounds; Diethyltriamine and derivatives thereof Derivatives; Tridentate ligands such as nitrilotriacetic acid and its derivatives; Hexadentate ligands such as ethylenediaminetetraacetic acid (EDTA) and its derivatives; In addition to the organic ligands as described above, inorganic ligands such as pyrophosphoric acid and triphosphoric acid can be exemplified. As the multidentate ligand, a bidentate ligand is particularly preferable, and specific examples include a bidentate ligand represented by the following general formula (XVII) in addition to the above. Among the bidentate ligands, a bidentate ligand represented by the following general formula (XVII) is more preferable, and R ²⁰ and R ²¹ in the following general formula (XVII) are the same group. Is particularly preferred. By making R ²⁰ and R ^{21 the} same, the coordination power of the ligand near room temperature becomes strong, and the coating agent can be further stabilized.

[Wherein, R ²⁰ and R ²¹ each independently represent an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. ]
The compounding amount of the polydentate ligand can be arbitrarily set, but is 0.01 mol or more, preferably 0.1 mol or more, more preferably 1 mol or more, with respect to 1 mol of the organometallic compound used. It is preferable to do this.

  The coating agent composition of the present invention can be prepared in the absence of a solvent, but may be prepared using a solvent as necessary. Examples of the solvent used in the coating composition of the present invention include various solvents such as alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran; ethers such as diethyl ether and dioxane; And those having a boiling point of 100 ° C. or lower are preferably used. These solvents can be used alone or in combination of two or more. Although content of the solvent in the coating agent composition of this invention can be set arbitrarily, since it will become easy to precipitate an organic compound when there are too few, it shall be 0.5-30 mass parts with respect to 1 mass part of organic compounds. Of these, 1 to 20 parts by mass is more preferable.

  In preparing the coating composition of the present invention, the sulfonic acid and / or derivative thereof and the amine having a boiling point of 250 ° C. or less may be added separately, and the sulfonic acid and / or derivative thereof is added in advance to the amine. (Blocking curing catalyst) may be added. The blocked curing catalyst can be easily obtained by mixing sulfonic acid and / or a derivative thereof and an amine having a boiling point of 250 ° C. or lower and then stirring for several tens of minutes at room temperature. A commercially available block-curing catalyst may be used.

  Further, the timing of addition of the sulfonic acid and / or derivative thereof and an amine having a boiling point of 250 ° C. or lower in the preparation process of the coating agent composition is not particularly limited. May be mixed with other materials from the beginning, or either sulfonic acid and / or derivatives thereof or amines having a boiling point of 250 ° C. or lower may be added to the other materials, and after aging, the remaining one may be added. Also good. In the former case, it is possible to suppress the polymerization from proceeding in a liquid state, and in the latter case, the polymerization can be advanced to a desired state. Although the reason is not clear, the latter may improve the electrophotographic characteristics such as electrical characteristics.

  Moreover, after mixing all materials other than a sulfonic acid and / or its derivative and an amine having a boiling point of 250 ° C. or lower, the sulfonic acid and / or its derivative and an amine having a boiling point of 250 ° C. or lower may be added to the mixture. Also in this case, the polymerization can proceed to a desired state as described above. Moreover, although the reason is not clarified, electrophotographic characteristics such as electrical characteristics may be improved.

Furthermore, from the viewpoint of suppressing photodegradation (for example, fatigue phenomenon against daylight white light) in the cured product of the coating agent composition, it is preferable to prepare the coating agent composition by the method shown in the following (i) or (ii). .
(I) A material other than an amine having a boiling point of 250 ° C. or less among materials constituting the coating agent composition is mixed, and the amine is added to the obtained mixture to obtain a coating agent composition.
(Ii) A material other than sulfonic acid and / or a derivative thereof and an amine having a boiling point of 250 ° C. or lower among the materials constituting the coating agent composition is mixed, and the resulting mixture is mixed with a sulfonic acid and / or a derivative thereof and a boiling point of 250 ° C. The following amine is added to obtain a coating composition.

  In the method shown in (i) above, the temperature when mixing materials other than amine having a boiling point of 250 ° C. or lower is preferably 0 to 100 ° C. Furthermore, when mixing under temperature higher than room temperature, it is preferable to add the amine with a boiling point of 250 degrees C or less after cooling a mixture to room temperature.

  Moreover, in the method shown in said (ii), it is preferable that the temperature at the time of mixing materials other than a sulfonic acid and / or its derivative (s), and an amine with a boiling point of 250 degrees C or less is 0-100 degreeC. Furthermore, when mixing under temperature higher than room temperature, it is preferable to add a sulfonic acid and / or its derivative, and an amine with a boiling point of 250 degrees C or less after cooling a mixture to room temperature.

The reaction temperature and reaction time for curing the coating agent composition of the present invention are not particularly limited, but the reaction temperature is preferably 60 ° C. or higher from the viewpoint of mechanical strength and chemical stability of the resulting cured film. The reaction time is preferably 80 to 200 ° C., and the reaction time is preferably 10 minutes to 5 hours. Moreover, keeping the cured film obtained in a high humidity state is effective in stabilizing the characteristics of the cured film. Furthermore, the cured film can be hydrophobized by subjecting it to a surface treatment using hexamethyldisilazane, trimethylchlorosilane, or the like depending on the application.
(Electrophotographic photoreceptor)
FIG. 1 is a cross-sectional view of an essential part schematically showing a preferred embodiment of the electrophotographic photosensitive member of the present invention. The electrophotographic photosensitive member 1 shown in FIG. 1 includes a photosensitive layer 3 on a conductive substrate 2, and in the photosensitive layer 3, an undercoat layer 4, a charge generation layer 5, and a charge are sequentially formed from the side closer to the conductive substrate 2. A transport layer 6 and a protective layer 7 are provided. Here, the protective layer 7 provided on the side far from the conductive substrate 2 is a surface layer obtained by curing the coating agent composition of the present invention.

  Hereinafter, each component of the electrophotographic photoreceptor 1 will be described in detail.

  As the conductive substrate 2, for example, metals such as aluminum, nickel, chromium, and stainless steel, and thin films such as aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, and ITO are provided. Examples thereof include a plastic film and the like, or a paper coated with or impregnated with a conductivity imparting agent, and a plastic film. The shape of the conductive substrate 2 may be a drum shape, a sheet shape, or a plate shape.

  When a metal pipe is used as the conductive substrate, the metal pipe may remain as it is. However, when the photosensitive drum is used in a laser printer, interference fringes generated when laser light is irradiated are prevented. Therefore, it is preferable to roughen the surface of the conductive substrate. As the surface roughness after roughening, it is preferable to roughen the surface to 0.04 μm to 0.5 μm in terms of centerline average roughness Ra. When Ra is less than 0.04 μm, the effect of preventing interference tends to be insufficient because it is close to a mirror surface. On the other hand, when Ra exceeds 0.5 μm, the image quality tends to be coarse.

  The surface roughening method is not particularly limited, but wet honing by suspending an abrasive in water and spraying it on the support, or centerless in which the support is pressed against a rotating grindstone and continuously ground. It is preferable to form a layer containing grinding, anodic oxidation, organic or inorganic semiconductive fine particles, and the like.

  The anodizing treatment is to form an oxide film on the aluminum surface by anodizing in an electrolyte solution using aluminum as an anode. Examples of the electrolyte solution include a sulfuric acid solution and an oxalic acid solution. However, the intact porous anodic oxide film is chemically active, easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, the pores in the anodized film are sealed with pressurized water vapor or boiling water (a metal salt such as nickel may be added) by volume expansion due to a hydration reaction, and a sealing process is performed to change to a more stable hydrated oxide. .

  The film thickness of the anodized film is preferably 0.3 to 15 μm. When it is thinner than 0.3 μm, the barrier property against injection is poor and the effect is not sufficient. On the other hand, if it is thicker than 15 μm, the residual potential increases due to repeated use.

  The treatment with an acidic treatment liquid comprising phosphoric acid, chromic acid and hydrofluoric acid is carried out as follows. The mixing ratio of phosphoric acid, chromic acid and hydrofluoric acid in the acidic treatment liquid is such that phosphoric acid is in the range of 10 to 11% by mass, chromic acid is in the range of 3 to 5% by mass, and hydrofluoric acid is in the range of 0.5 to 2% by mass. The concentration of these acids as a whole is preferably in the range of 13.5 to 18% by mass. The processing temperature is 42 to 48 ° C., but by keeping the processing temperature high, a thicker film can be formed faster. About the film thickness of a film, 0.3-15 micrometers is preferable. When it is thinner than 0.3 μm, the barrier property against injection is poor and the effect is not sufficient. On the other hand, if it is thicker than 15 μm, the residual potential increases due to repeated use.

  The boehmite treatment can be performed by immersing in pure water at 90 to 100 ° C. for 5 to 60 minutes or by contacting with heated steam at 90 to 120 ° C. for 5 to 60 minutes. About the film thickness of a film, 0.1-5 micrometers is preferable. This can be further anodized using an electrolyte solution with low film solubility such as adipic acid, boric acid, borate, phosphate, phthalate, maleate, benzoate, tartrate, citrate. Good.

  When non-interfering light is used for the light source, it is not particularly necessary to roughen the interference fringes to prevent the occurrence of defects due to irregularities on the surface of the substrate, which is suitable for extending the life.

  The undercoat layer 4 is a layer provided as necessary for the purpose of preventing interference fringes, preventing electrical leakage, and the like. In particular, when a substrate that has been subjected to acidic solution treatment, boehmite treatment, or the like is used as the conductive substrate 2, it is preferable to provide the undercoat layer 4 because the defect concealing power of the substrate tends to be insufficient.

  Materials used for the undercoat layer 4 include organic zirconium compounds such as zirconium chelate compounds, zirconium alkoxide compounds, and zirconium coupling agents, organic titanium compounds such as titanium chelate compounds, titanium alkoxide compounds, and titanate coupling agents, and aluminum chelate compounds. In addition to organoaluminum compounds such as aluminum coupling agents, antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxide compounds, Aluminum titanium alkoxide compound, aluminum zirconium alkoxide Compounds, organometallic compounds such as, in particular an organic zirconium compound, an organic titanyl compound, since the organic aluminum compound to residual potential indicates a satisfactory electrophotographic properties lower, are preferably used.

  The undercoat layer 4 is composed of vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxy. Silane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3 , 4-epoxycyclohexyltrimethoxysilane and other silane coupling agents.

  Further, the undercoat layer 4 can be configured to include a binder resin. Such binder resins include polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinyl imidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, polyester, phenol. Examples thereof include resins, vinyl chloride-vinyl acetate copolymers, epoxy resins, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, and polyacrylic acid.

  Further, the undercoat layer 4 can be configured to include an electron transporting pigment. Examples of the electron transport pigment include organic pigments such as perylene pigment, bisbenzimidazole perylene pigment, polycyclic quinone pigment, indigo pigment, and quinacridone pigment described in JP-A-47-30330, cyano group, nitro group, Examples thereof include organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as nitroso groups and halogen atoms, and inorganic pigments such as zinc oxide and titanium oxide. Among these pigments, perylene pigments, bisbenzimidazole perylene pigments and polycyclic quinone pigments, zinc oxide, and titanium oxide are preferably used because of their high electron mobility. Further, the surface of these pigments may be surface-treated with the above-mentioned coupling agent or binder for the purpose of controlling dispersibility and charge transport property. If the amount of the electron transport pigment is too large, the strength of the undercoat layer 4 is lowered and a coating film defect is caused.

  The undercoat layer 4 is formed by applying a coating solution obtained by mixing / dispersing the above constituent materials in a predetermined solvent onto the conductive substrate 2 and drying it. As the solvent used in the coating solution, any solvent can be used as long as it dissolves a fixed metal compound or resin and does not cause gelation or aggregation when an electron transporting pigment is mixed / dispersed. Methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, toluene And organic solvents such as These solvents may be used alone or in combination of two or more. As a mixing / dispersing method for preparing the coating solution for the undercoat layer 4, a conventional method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like can be applied. In addition, as a method for applying the coating solution for the undercoat layer 4, conventional methods such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method are used. Can be used. The coating film is dried at a temperature at which the solvent can be evaporated to form a film. The thickness of the undercoat layer 4 is preferably 0.1 to 30 μm, more preferably 0.2 to 25 μm.

  The charge generation layer 5 includes a charge generation material and a binder resin.

  Examples of charge generation materials include azo pigments such as bisazo compounds and trisazo compounds, condensed aromatic pigments such as dibromoanthanthrone, organic pigments such as perylene pigments, pyrrolopyrrole pigments, and phthalocyanine pigments, trigonal selenium, and zinc oxide. Although all known ones such as inorganic pigments can be used, inorganic pigments are preferred particularly when exposure wavelengths of 380 nm to 500 nm are used, and metal and metal-free phthalocyanine pigments are preferred when exposure wavelengths of 700 nm to 800 nm are used. preferable. Of these, hydroxygallium phthalocyanine disclosed in JP-A-5-263007 and JP-A-5-279591, chlorogallium phthalocyanine disclosed in JP-A-5-98181, JP-A-5-140472 and JP-A-5-140473. Particularly preferred are dichlorotin phthalocyanine, disclosed in JP-A-4-189873 and titanyl phthalocyanine disclosed in JP-A-5-43813.

  The binder resin can be selected from a wide range of insulating resins, and can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin. Insulating resin such as polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin can be used, but is not limited thereto. These binder resins can be used alone or in admixture of two or more. The content ratio (mass ratio) of the charge generation material and the binder resin in the charge generation layer 5 is preferably in the range of 10: 1 to 1:10.

  The charge generation layer 5 is formed by applying a coating solution in which a charge generation material and a binder resin are mixed / dispersed in a predetermined solvent on the undercoat layer 4 and drying. Solvents used in the coating solution include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, and methylene. A chloride, chloroform, chlorobenzene, toluene etc. are mentioned, These solvents can be used individually by 1 type or in mixture of 2 or more types. In addition, as a method for dispersing the charge generating material in the coating solution, a usual method such as a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method, or the like can be used. It is preferable to perform the dispersion process under conditions that do not change. Further, at the time of dispersion, it is effective to make the particles have a particle size of 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less. In addition, as a coating method used when the charge generation layer is provided, usual methods such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method are used. Can be used. The film thickness of the charge generation layer 5 is preferably 0.1 to 5 μm, more preferably 0.2 to 2.0 μm.

  The charge transport layer 6 includes a charge transport material and a binder resin, or includes a polymer charge transport material.

  Charge transport materials include quinone compounds such as p-benzoquinone, chloranil, bromanyl, anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds , Electron transport compounds such as cyanovinyl compounds and ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, etc. Examples thereof include, but are not limited to, hole transporting compounds. These charge transport materials can be used singly or in combination of two or more.

  Moreover, as a charge transport material, the compound shown by the following general formula (XVIII-1), (XVIII-2) or (XVIII-3) from a mobility viewpoint is preferable.

Here, in the formula (XVIII-1), R ²² is a hydrogen atom or a methyl group, k is 1 or 2, Ar ⁶ and Ar ⁷ are each independently a substituted or unsubstituted aryl group, —C ₆ H ₄ —C (R ²³ ) ═C (R ²⁴ ) (R ²⁵ ) or —C ₆ H ₄ —CH═CH—CH═C (Ar) ₂ is represented, and the substituent is a halogen atom, having 1 carbon atom. The substituted amino group substituted by the alkyl group of -5, a C1-C5 alkoxy group, or a C1-C3 alkyl group is shown. R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar represents a substituted or unsubstituted aryl group.

Here, in the formula (XVIII-2), R ²⁶ and R ²⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are each independently a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group substituted with an alkyl group having 1 to 2 carbon atoms, substituted aryl ^{_{group, -C 6 H 4 -C (R}} 23) = C (R 24) (R 25), _or, a _{-C 6 H 4 -CH = CH-} CH = C (Ar) 2, p, q, r, and s each independently represent an integer of 0-2. R ¹⁹ , R ²⁰ and R ²¹ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar represents a substituted or unsubstituted aryl group.

Here, in the above formula (XVIII-3), R ³² represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group, or —CH═CH. -CH = C (Ar) ₂ is shown. Ar represents a substituted or unsubstituted aryl group. R ³³ , R ³⁴ , R ³⁵ and R ³⁶ are each independently substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 2 carbon atoms. A substituted amino group or a substituted or unsubstituted aryl group.

  Examples of the binder resin used for the charge transport layer 6 include polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, and chloride. Vinylidene-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, etc. . These binder resins can be used individually by 1 type or in mixture of 2 or more types. The blending ratio (mass ratio) of the charge transport material and the binder resin is preferably 10: 1 to 1: 5.

  As the polymer charge transport material, known materials having charge transport properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, the polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 have a high charge transporting property and are particularly preferable. Although the polymer charge transport material alone can be used as a constituent material of the charge transport layer 6, it may be mixed with the binder resin to form a film.

  The charge transport layer 6 is formed by applying a coating liquid containing the above constituent materials onto the charge generation layer 5 and drying it. Solvents used in the coating solution for the charge transport layer 6 include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halongen such as methylene chloride, chloroform and ethylene chloride. Ordinary organic solvents such as cyclic aliphatic ethers such as fluorinated aliphatic hydrocarbons, tetrahydrofuran and ethyl ether. These can be used individually by 1 type or in mixture of 2 or more types. As a coating method of the coating solution for forming the charge transport layer, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method should be used. Can do. The film thickness of the charge transport layer 6 is preferably 5 to 50 μm, more preferably 10 to 30 μm.

  The protective layer 7 is a surface layer obtained by curing the coating agent composition of the present invention. When the protective layer 7 is formed, the coating composition of the present invention is applied onto the charge transport layer 6 by blade coating method, Mayer bar coating method, spray coating method, dip coating method, bead coating method, air coating method. Usual methods such as a knife coating method and a curtain coating method can be used. In addition, the reaction temperature and reaction time for curing the coating agent composition applied on the charge transport layer 6 can be appropriately selected, but from the viewpoint of mechanical strength and chemical stability of the resulting cured film, The reaction temperature is preferably 60 ° C. or higher, more preferably 80 to 200 ° C., and the reaction time is preferably 10 minutes to 5 hours. Moreover, keeping the cured film (protective layer 7) in a high humidity state is effective in stabilizing the characteristics of the cured film. Furthermore, the cured film can be hydrophobized by subjecting it to a surface treatment using hexamethyldisilazane, trimethylchlorosilane, or the like depending on the application. The thickness of the protective layer 7 is preferably 0.1 to 10 μm, more preferably 1 to 5 μm. In addition, when a required film thickness is not obtained by one application | coating, a required film thickness can be obtained by apply | coating several times. When performing multiple times of repeated application, the heat treatment may be performed every time of application, or after multiple times of repeated application.

Further, in each layer constituting the photosensitive layer 3, for the purpose of preventing deterioration of the electrophotographic photosensitive member due to ozone, oxidizing gas, light, or heat generated in the copying machine, an antioxidant, a light stabilizer, a heat Additives such as stabilizers can be added. For example, examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, and organic phosphorus compounds. Examples of the light stabilizer include derivatives such as benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine. In addition, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use. Examples of the electron acceptor usable in the photoreceptor of the present invention include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o -Dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid, etc., and compounds represented by general formula (I) Can do. Of these, benzene derivatives having electron-withdrawing substituents such as fluorenone-based, quinone-based, and -Cl, -CN, -NO ₂ are particularly preferable.

  The electrophotographic photosensitive member of the present invention is not limited to the above embodiment. For example, the photosensitive layer 3 of the electrophotographic photoreceptor 1 according to the above embodiment has the protective layer 7 as a surface layer provided on the side far from the conductive substrate 2, but the charge transport layer without providing the protective layer. May be a surface layer. In this case, since the cured film of the coating agent composition of the present invention has excellent mechanical strength and sufficient photoelectric properties, the cured film can be used as a charge transport layer as it is. Alternatively, the charge transporting material, the binder resin, the polymer charge transporting material and the like exemplified in the description of the charge transport layer 6 are contained in the coating agent composition of the present invention to form a coating solution, and the coating solution is used to charge A transport layer may be formed.

  Further, although the electrophotographic photoreceptor 1 according to the above embodiment includes the undercoat layer 4, the electrophotographic photoreceptor of the present invention may not include the undercoat layer.

The electrophotographic photosensitive member 1 according to the above embodiment is a function-separated type photosensitive member in which the charge generation layer 5 and the charge transport layer 6 are separately provided. However, the electrophotographic photosensitive member of the present invention is a charge generation material. A single-layer type photoreceptor having a layer containing both a charge transport material (including a polymer charge transport material) may be used. In the layer containing both the charge generation material and the charge transport material, the content of the charge generation material is preferably 10 to 85% by mass, more preferably 20 to 50% by mass. Moreover, it is preferable that content of a charge transport material shall be 5-50 mass%. The film thickness is preferably about 5 to 50 μm, more preferably 10 to 40 μm. When the single-layer type photoreceptor does not have a protective layer, that is, when a layer containing both the charge generation material and the charge transport material is a surface layer, the layer is composed of And a coating solution in which a binder resin is contained in the coating agent composition of the present invention as necessary. When the single-layer type photoreceptor has a protective layer that is a cured film of the coating composition of the present invention on the side far from the substrate, a layer containing both the charge generation material and the charge transport material is formed. In this case, the coating agent composition of the present invention may not be used. The solvent and coating method used for the coating solution are the same as described above.
(Image forming device)
FIG. 2 is a schematic configuration diagram showing a preferred embodiment of the electrophotographic apparatus of the present invention. An electrophotographic apparatus 200 shown in FIG. 2 includes an electrophotographic photosensitive member 1 of the present invention, a charging device 208 that charges the electrophotographic photosensitive member 1 by a contact charging method, a power source 209 connected to the charging device 208, and a charging device. An exposure device 210 that exposes the electrophotographic photosensitive member 207 charged by 208 to form an electrostatic latent image, and a developing device that develops the electrostatic latent image formed by the exposure device 210 with toner to form a toner image 211, a transfer device 212 that transfers a toner image formed by the developing device 211 to a transfer medium, a cleaning device 213, a static eliminator 214, and a fixing device 215. Although not shown in FIG. 2, a toner supply device that supplies toner to the developing device 211 is also provided. Moreover, in an embodiment different from the present embodiment, the static eliminator 214 may not be provided.

  The charging device 208 makes a conductive member (charging roll) contact the surface of the photoconductor 1 to uniformly apply a voltage to the photoconductor to charge the surface of the photoconductor to a predetermined potential. The charging device provided in the image forming apparatus of the present invention may be a non-contact type using corotron or scorotron. However, the electrophotographic photoreceptor of the present invention is excellent in mechanical strength. When contact charging with high stress is used, particularly excellent durability is exhibited as compared with a conventional electrophotographic photosensitive member.

  As the conductive member, a member provided with an elastic layer, a resistance layer, a protective layer and the like on the outer peripheral surface of the core material is preferably used. The shape of the conductive member may be any of a brush shape, a blade shape, a pin electrode shape, a roller shape, and the like.

  As the material of the core material, a conductive material such as iron, copper, brass, stainless steel, aluminum, nickel, or the like is used. Also, a resin molded product in which conductive particles or the like are dispersed can be used.

As the material of the elastic layer, a material having conductivity or semiconductivity, for example, a material in which conductive particles or semiconducting particles are dispersed in a rubber material can be used. As the rubber material, EPDM, polybutadiene, natural rubber, polyisobutylene, SBR, CR, NBR, silicone rubber, urethane rubber, epichlorohydrin rubber, SBS, thermoplastic elastomer, norbornene rubber, fluorosilicone rubber, ethylene oxide rubber and the like are used. Examples of the conductive particles or semiconductive particles include carbon black, zinc, aluminum, copper, iron, nickel, chromium, titanium and other metals, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ — Metal oxides such as SnO ₂ , ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , Sb ₂ O ₃ , In ₂ O ₃ , ZnO, or MgO can be used. These materials can be used individually by 1 type or in mixture of 2 or more types.

  As the material of the resistance layer and the protective layer, conductive particles or semiconductive particles are dispersed in a binder resin, and the resistance is controlled. As binder resin, acrylic resin, cellulose resin, polyamide resin, methoxymethylated nylon, ethoxymethylated nylon, polyurethane resin, polycarbonate resin, polyester resin, polyethylene resin, polyvinyl resin, polyarylate resin, polythiophene resin, PFA, FEP or A polyolefin resin such as PET or a styrene-butadiene resin is used. As the conductive particles or semiconductive particles, carbon black, metal, or metal oxide similar to the elastic layer is used. Further, if necessary, an antioxidant such as hindered phenol and hindered amine, a filler such as clay and kaolin, and a lubricant such as silicone oil can be added. As a means for forming these layers, a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like can be used.

  When the photosensitive member 1 is charged using these conductive members, a voltage is applied to the conductive member. The applied voltage may be a DC voltage or a DC voltage obtained by superimposing an AC voltage. In addition to the charging roll shown in this embodiment, charging by a contact charging method may be performed using a charging brush, a charging film, a charging tube, or the like. Moreover, you may charge by the non-contact system using a corotron or a scorotron.

  As the exposure device 210, an optical system device or the like that can expose a light source such as a semiconductor laser, an LED (light emitting diode), a liquid crystal shutter, or the like on the surface of the electrophotographic photosensitive member 1 in a desired image-like manner. Among these, when an exposure apparatus capable of exposing non-interference light is used, interference fringes between the conductive substrate of the electrophotographic photosensitive member 1 and the photosensitive layer can be prevented.

  As the developing device 211, for example, a general developing device that performs development by bringing a magnetic or non-magnetic one-component developer or a two-component developer into contact or non-contact with each other can be used. Such a developing device is not particularly limited as long as it has the functions described above, and can be appropriately selected according to the purpose. For example, a known developing device having a function of attaching the one-component developer or the two-component developer to the photosensitive member 1 using a brush, a roller, or the like can be used. Since the electrophotographic photosensitive member provided in the image forming apparatus of the present invention is excellent in mechanical strength, the electrophotographic photosensitive member can be used for 200000 cycles or more, further 250,000 cycles, or 300000 cycles or more. Therefore, it is preferable that the developing device has a mechanism capable of supplying only toner or developer alone because the unit price per print can be reduced.

  Hereinafter, the toner used for the developing device 211 will be described.

The toner used in the image forming apparatus of the present embodiment preferably has an average shape factor (ML ² / A) of 100 to 150 from the viewpoint of obtaining high developability and transferability and high image quality, and 105 to 145. More preferably, it is more preferably 110-140. Further, the toner preferably has a volume average particle diameter of 3 to 12 μm, more preferably 3.5 to 10 μm, and still more preferably 4 to 9 μm. By using a toner satisfying such an average shape factor and volume average particle diameter, developability and transferability are improved, and a high-quality image called so-called photographic image quality can be obtained.

  The toner is not particularly limited by the production method as long as it satisfies the above average shape factor and volume average particle diameter. For example, the toner may include a binder resin, a colorant, a release agent, and the like. A kneading and pulverizing method in which a charge control agent is added, kneading, pulverizing, and classifying; a method in which the shape of particles obtained by the kneading and pulverizing method is changed by mechanical impact force or thermal energy; Emulsion polymerization of the body, and the resulting dispersion is mixed with a dispersion of a colorant, a release agent and, if necessary, a charge control agent, and then agglomerated and heat-fused to obtain toner particles. Suspension polymerization method in which a polymerizable monomer for obtaining a binder resin, a colorant, a release agent, and a charge control agent, if necessary, are suspended in an aqueous solvent and polymerized; A water-based solution of a resin, a colorant, a release agent, and a solution such as a charge control agent as necessary. Toner is used which is suspended in and produced by a dissolution suspension method in which granulated.

  Further, a known method such as a production method in which the toner obtained by the above method is used as a core, and agglomerated particles are further adhered and heat-fused to have a core-shell structure can be used. The toner production method is preferably a suspension polymerization method, an emulsion polymerization aggregation method, or a dissolution suspension method in which an aqueous solvent is used from the viewpoint of shape control and particle size distribution control, and an emulsion polymerization aggregation method is particularly preferable.

  The toner base particles are composed of a binder resin, a colorant, and a release agent, and include silica and a charge control agent as necessary.

  Binder resins used for toner base particles include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, etc. Α-methylene aliphatics such as vinyl esters, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Homopolymers and copolymers of monocarboxylic acid esters, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone Polyester resins by copolymerization of dicarboxylic acids and diols.

  Particularly representative binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. A polymer, polyethylene, polypropylene, a polyester resin, etc. can be mentioned. In addition, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like can also be mentioned.

  In addition, as colorants, magnetic powders such as magnetite and ferrite, carbon black, aniline blue, caryl blue, chrome yellow, ultramarine blue, Dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, Lamp Black, Rose Bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 can be exemplified as a representative one.

  Typical examples of the release agent include low molecular weight polyethylene, low molecular weight polypropylene, Fischer tropic wax, montan wax, carnauba wax, rice wax, and candelilla wax.

  As the charge control agent, known ones can be used, and azo metal complex compounds, metal complex compounds of salicylic acid, and resin type charge control agents containing polar groups can be used. When the toner is produced by a wet process, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength and reducing wastewater contamination. The toner may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.

  The toner used in the developing device 211 can be manufactured by mixing the toner base particles and the external additive with a Henschel mixer or a V blender. In addition, when the toner base particles are produced by a wet method, external addition can also be performed by a wet method.

  Lubricating particles may be added to the toner used in the developing device 211. Lubricating particles include solid lubricants such as graphite, molybdenum disulfide, talc, fatty acids and fatty acid metal salts, low molecular weight polyolefins such as polypropylene, polyethylene and polybutene, silicones having a softening point upon heating, oleic amides Aliphatic amides such as erucic acid amide, ricinoleic acid amide, stearic acid amide, etc., plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animals such as beeswax Minerals such as system waxes, montan waxes, ozokerites, ceresins, paraffin waxes, microcrystalline waxes, Fischer-Tropsch waxes, etc., petroleum waxes, and modified products thereof can be used. These can be used individually by 1 type or in combination of 2 or more types. However, the average particle size is preferably in the range of 0.1 to 10 μm, and the particles having the above chemical structure may be pulverized to make the particle sizes uniform. The amount added to the toner is preferably in the range of 0.05 to 2.0 mass%, more preferably 0.1 to 1.5 mass%.

  To the toner used in the developing device 211, inorganic fine particles, organic fine particles, composite fine particles obtained by attaching inorganic fine particles to the organic fine particles, and the like can be added for the purpose of removing the adhered matter and deteriorated matter on the surface of the electrophotographic photoreceptor. .

  Inorganic fine particles include silica, alumina, titania, zirconia, barium titanate, aluminum titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, Various inorganic oxides such as manganese oxide, boron oxide, silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, and boron nitride, nitrides, borides, and the like are preferably used.

  In addition, the inorganic fine particles are mixed with titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, bis (dioctylpyrophosphate) oxyacetate titanate, γ- (2- Aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxy Silane hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxy The treatment may be performed with a silane coupling agent such as silane, decyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, and p-methylphenyltrimethoxysilane. In addition, those hydrophobized with higher fatty acid metal salts such as silicone oil, aluminum stearate, zinc stearate and calcium stearate are also preferably used.

  Examples of the organic fine particles include styrene resin particles, styrene acrylic resin particles, polyester resin particles, and urethane resin particles.

  The particle diameter is preferably a number average particle diameter of 5 to 1000 nm, more preferably 5 to 800 nm, and still more preferably 5 to 700 nm. If the average particle size is less than the lower limit, the polishing ability tends to be lacking. On the other hand, if the average particle size exceeds the upper limit, the surface of the electrophotographic photoreceptor tends to be damaged. Moreover, it is preferable that the sum of the addition amount of the particle | grains mentioned above and lubricity particle | grains is 0.6 mass% or more.

  Other inorganic oxides added to the toner are small-diameter inorganic oxides with a primary particle size of 40 nm or less for powder flowability, charge control, etc. It is preferable to add a larger-diameter inorganic oxide. These inorganic oxide fine particles may be known ones, but it is preferable to use silica and titanium oxide in combination for precise charge control. Further, the surface treatment of the small-diameter inorganic fine particles increases the dispersibility and increases the powder flowability. Furthermore, it is also preferable to add carbonates such as calcium carbonate and magnesium carbonate and inorganic minerals such as hydrotalcite in order to remove the discharge purified product.

  In addition, the color toner for electrophotography is used by mixing with a carrier. As the carrier, iron powder, glass beads, ferrite powder, nickel powder, or those having a resin coating on the surface thereof are used. The mixing ratio with the carrier can be set as appropriate.

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

  The cleaning device 213 is for removing residual toner adhering to the surface of the electrophotographic photosensitive member after the transfer process, and the electrophotographic photosensitive member cleaned by this is repeatedly used for the image forming process described above. . As the cleaning device, methods such as brush cleaning and roll cleaning can be used in addition to those using the illustrated cleaning blade. Among these, the cleaning blade is preferably used. Examples of the material for the cleaning blade include urethane rubber, neoprene rubber, and silicone rubber.

  In addition, the electrophotographic apparatus according to the present embodiment further includes a static eliminator such as a static eliminator (erase light irradiation device) 214 and an image fixing device 215 as shown in FIG. As a result, when the electrophotographic photosensitive member is repeatedly used, the phenomenon that the residual potential of the electrophotographic photosensitive member is brought into the next image forming cycle is prevented, so that the image quality can be further improved.

  FIG. 3 is a schematic configuration diagram showing the basic configuration of another embodiment of the electrophotographic apparatus of the present invention. The electrophotographic apparatus 220 shown in FIG. 3 is an intermediate transfer type electrophotographic apparatus. In the housing 400, four electrophotographic photoreceptors 401a to 401d (for example, the electrophotographic photoreceptor 401a is yellow and the electrophotographic photoreceptor 401b is magenta). The electrophotographic photosensitive member 401c can form an image of cyan and the electrophotographic photosensitive member 401d can form a black color) are arranged in parallel along the intermediate transfer belt 409.

  Here, the electrophotographic photoreceptors 401a to 401d mounted in the electrophotographic apparatus 220 are the electrophotographic photoreceptors of the present invention (for example, the electrophotographic photoreceptor 1), respectively.

  Each of the electrophotographic photosensitive members 401a to 401d can be rotated in a predetermined direction (counterclockwise on the paper surface), and the charging rolls 402a to 402d, the developing devices 404a to 404d, and the primary transfer roll 410a along the rotation direction. To 410d and cleaning blades 415a to 415d are arranged. Each of the developing devices 404a to 404d can be supplied with toner of four colors of black, yellow, magenta and cyan accommodated in the toner cartridges 405a to 405d, and the primary transfer rolls 410a to 410d are respectively intermediate transfer belts. 409 is in contact with the electrophotographic photoreceptors 401a to 401d.

  Further, a laser light source (exposure device) 403 is disposed at a predetermined position in the housing 400, and the surface of the electrophotographic photoreceptors 401a to 401d after charging is irradiated with laser light emitted from the laser light source 403. Is possible. Accordingly, charging, exposure, development, primary transfer, and cleaning are sequentially performed in the rotation process of the electrophotographic photosensitive members 401a to 401d, and the toner images of the respective colors are transferred onto the intermediate transfer belt 409 in an overlapping manner.

  The intermediate transfer belt 409 is supported with a predetermined tension by a drive roll 406, a backup roll 408, and a tension roll 407, and can rotate without causing deflection due to the rotation of these rolls. Further, the secondary transfer roll 413 is disposed so as to contact the backup roll 408 via the intermediate transfer belt 409. The intermediate transfer belt 409 passing between the backup roll 408 and the secondary transfer roll 413 is cleaned by, for example, a cleaning blade 416 disposed in the vicinity of the drive roll 406 and then repeatedly used for the next image forming process. Is done.

  A tray (transfer medium tray) 411 is provided at a predetermined position in the housing 400, and a transfer medium 417 such as paper in the tray 411 is transferred to the intermediate transfer belt 409 and the secondary transfer roll by a transfer roll 412. Then, the paper is sequentially transferred between the two fixing rolls 414 that are in contact with each other and the two fixing rolls 414, and then discharged to the outside of the housing 400.

  In the above description, the case where the intermediate transfer belt 409 is used as the intermediate transfer member has been described. However, the intermediate transfer member may have a belt shape like the intermediate transfer belt 409 or a drum shape. Also good. In the case of a belt shape, a conventionally known resin can be used as the resin material used as the base material of the intermediate transfer member. For example, polyimide resin, polycarbonate resin, polyvinylidene fluoride (PVDF), polyalkylene terephthalate (PAT), ethylenetetrafluoroethylene copolymer (ETFE) / PC, ETFE / PAT, blend material of PC / PAT, polyester, polyether Examples thereof include resin materials such as ether ketone and polyamide, and resin materials containing these as main raw materials. Furthermore, a resin material and an elastic material can be blended and used.

  As an elastic material, polyurethane, chlorinated polyisoprene, NBR, chloropyrene rubber, EPDM, hydrogenated polybutadiene, butyl rubber, silicone rubber, or the like can be used, or a material obtained by blending two or more kinds can be used. If necessary, a conductive agent imparting electronic conductivity or a conductive agent having ionic conductivity is added to the resin material and elastic material used for these base materials in combination of one kind or two or more kinds. Among these, it is preferable to use a polyimide resin in which a conductive agent is dispersed from the viewpoint of excellent mechanical strength. As the conductive agent, a conductive polymer such as carbon black, metal oxide, or polyaniline can be used. When a belt-shaped configuration such as the intermediate transfer belt 409 is employed as the intermediate transfer member, the thickness of the belt is generally preferably 50 to 500 μm and more preferably 60 to 150 μm, but is appropriately selected according to the hardness of the material. be able to.

  For example, a belt made of a polyimide resin in which a conductive agent is dispersed is 5 to 20% by mass as a conductive agent in a polyamic acid solution, which is a polyimide precursor, as described in JP-A-63-311263. After the carbon black is dispersed, the dispersion is cast on a metal drum and dried, and then the film peeled off from the drum is stretched at a high temperature to form a polyimide film. Can be produced.

  The film molding is generally performed by injecting a polyamic acid solution film-forming stock solution in which a conductive agent is dispersed into a cylindrical mold and, for example, heating at 100 to 200 ° C. at a rotational speed of 500 to 2000 rpm. The film was formed into a film by a centrifugal molding method while rotating, and then the obtained film was demolded in a semi-cured state and covered with an iron core. It can be carried out by proceeding a ring-closing reaction) and carrying out main curing. In addition, the stock solution is cast on a metal sheet to a uniform thickness and heated to 100 to 200 ° C. to remove most of the solvent in the same manner as described above, and then gradually raised to a high temperature of 300 ° C. or higher. There is also a method of forming a polyimide film. Further, the intermediate transfer member may have a surface layer.

  When a drum-shaped configuration is adopted as the intermediate transfer member, it is preferable to use a cylindrical substrate formed of aluminum, stainless steel (SUS), copper, or the like as the substrate. If necessary, an elastic layer can be coated on the cylindrical substrate, and a surface layer can be formed on the elastic layer.

  The transfer medium according to the present invention is not particularly limited as long as it is a medium that transfers a toner image formed on an electrophotographic photosensitive member. For example, when transferring directly from an electrophotographic photosensitive member to a transfer medium such as paper, paper or the like is the transfer medium. When an intermediate transfer member is used, the intermediate transfer member is a transfer medium.

  FIG. 4 is a sectional view schematically showing a basic configuration of a preferred embodiment of a process cartridge including the electrophotographic photosensitive member of the present invention. In addition to the electrophotographic photosensitive member 1, the process cartridge 400 is attached to a charging device 208, a developing device 211, a cleaning device (cleaning means) 213, an opening 217 for exposure, and an opening 218 for static elimination exposure. Are combined and integrated with each other. The developing device 211 may be separated from the cartridge including the electrophotographic photosensitive member 1.

  The process cartridge 400 is detachable from the main body of the electrophotographic apparatus including the transfer device 212, the fixing device 215, and other components (not shown). It constitutes.

  In the above-described electrophotographic apparatuses 200 and 220 and the process cartridge 400, the electrophotographic photosensitive member of the present invention is provided so that discharge products generated in the charging process and residual toner after the transfer process adhere to the electrophotographic photosensitive member. It is possible to sufficiently prevent and stably obtain a high-quality image over a long period of time.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.
[Example 1-1]
(Preparation of electrophotographic photoreceptor)
The outer peripheral surface of the cylindrical aluminum substrate was polished by a centerless polishing apparatus, and the surface roughness was Ra = 0.6 μm. As a cleaning step for the aluminum substrate, a degreasing treatment, an etching treatment for 1 minute using a 2 mass% sodium hydroxide solution, a neutralization treatment, and a pure water washing were sequentially performed. Next, an anodizing treatment step is performed using a 10% by mass sulfuric acid solution (current density: 1.0 A / dm ² ). After washing with water, sealing is performed by immersing in a 1% by mass nickel acetate solution at 80 ° C. for 25 minutes. went. Further, pure water washing and drying treatment were performed to form an anodic oxide film having a thickness of 8 μm on the outer peripheral surface of the aluminum substrate.

  Next, 1 of chlorogallium phthalocyanine having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) in the X-ray diffraction spectrum of 7.4 °, 16.6 °, 25.5 °, and 28.3 °. Part by weight is mixed with 1 part by weight of polyvinyl butyral (trade name: ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts by weight of n-butyl acetate, treated with a glass bead for 1 hour and dispersed to generate charges. A layer forming coating solution was obtained. This coating solution was dip-coated on the outer peripheral surface (anodized film) of the aluminum substrate, and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 parts by mass of a benzidine compound represented by the following formula (CT-1) and 3 parts by mass of a polymer compound having a structural unit represented by the following formula (B-1) (viscosity average molecular weight 39,000) were added to chlorobenzene 20 A charge transport layer forming coating solution was obtained by dissolving in mass parts. This coating solution was applied onto the charge generation layer by dip coating, and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

  Next, 2 parts by mass of compound (III-16) in Table 27, 0.5 part by mass of tetramethoxysilane, 0.3 part by mass of colloidal silica, 1 part by mass of compound (XV-3) in Table 56, (hepta) Decafluoro-1,1,2,2-tetrahydrodecyl) methyldimethoxysilane 0.1 parts by mass, hexamethylcyclotrisiloxane 0.5 parts by mass, methanol 6 parts by mass, and ion exchange resin (Amberlyst 15E, ROHM (And Haas Co., Ltd.) 0.7 parts by mass was mixed and stirred at room temperature to carry out a protective group exchange reaction for 5 hours. Thereafter, 10 parts by mass of n-butanol and 0.3 parts by mass of distilled water were added, and hydrolysis was performed at room temperature (about 25 ° C.) for 30 minutes.

  0.4 mass part of 3,5-di-t-butyl-4-hydroxytoluene (BHT) and 0.2 mass part of para-toluenesulfonic acid with respect to the liquid obtained by filtering and separating the ion exchange resin from the reaction mixture after hydrolysis Then, 0.12 parts by mass of di-n-butylamine (boiling point 159 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at room temperature for 30 minutes. Further, 0.5 parts by mass of butyral resin (trade name: BX-L, manufactured by Sekisui Chemical Co., Ltd.) was added and dissolved, and then filtered through a 0.5 μm filter to form a coating composition (hereinafter referred to as “Coating Solution-1”). ").

The obtained coating liquid-1 is applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 140 ° C. for 1 hour to provide a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-1”). When the surface of the protective layer of the obtained photoreceptor 1 was observed with a microscope, no coating film defects were observed.
[Example 1-2]
First, in the same manner as in Example 1-1, a charge generation layer and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

Next, coating liquid-1 was prepared in the same manner as in Example 1-1, and stored at 40 ° C. in a sealed state. A protective layer was formed on the charge transport layer in the same manner as in Example 1-1 using the coating liquid-1 after 20 days from the start of storage to obtain an electrophotographic photoreceptor. When the surface of the protective layer of the obtained electrophotographic photosensitive member was observed with a microscope, coating film defects were slightly observed, but when a print test was performed, no image quality defects were observed, and there was no practical problem. It was.
[Example 2-1]
First, a cylindrical aluminum substrate having an outer peripheral surface subjected to a honing process was prepared.

  Next, 100 parts by mass of a zirconium compound (trade name: Olgatics ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 10 parts by mass of a silane compound (trade name: A1100, manufactured by Nihon Unicar Co., Ltd.), polyvinyl butyral (ESREC BM-S, Sekisui Chemical Co., Ltd.) 3 parts by mass), 400 parts by weight isopropanol, and 200 parts by weight butanol were mixed to obtain a coating solution for forming an undercoat layer. This coating solution was applied on the outer peripheral surface of the aluminum substrate by a dip coating method, and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.15 μm.

  Next, 1 part by mass of titanyl phthalocyanine having a strong diffraction peak at a Bragg angle (2θ ± 0.2 °) in an X-ray diffraction spectrum of 27.2 ° is polyvinyl butyral (trade name: ESREC BM-S, Sekisui Chemical) 1 part by mass and 100 parts by mass of n-butyl acetate were mixed and dispersed together with glass beads by treatment with a paint shaker for 1 hour to obtain a charge generation layer forming coating solution. This coating solution was dip-coated on the undercoat layer and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 mass parts of a charge transporting compound represented by the following formula (CT-2) and a polymer compound having a structural unit represented by the following formula (B-2) (viscosity average molecular weight 58,000) 3 mass A part was dissolved in 30 parts of chlorobenzene to obtain a coating solution for forming a charge transport layer. This coating solution was applied onto the charge generation layer by a dip coating method, followed by heating and drying at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

  Next, 2 parts by mass of compound (III-16) in Table 27, 2 parts by mass of methyltrimethoxysilane, 0.5 part by mass of compound (XV-4) in Table 56, 0.3 mass by mass of hexamethylcyclotrisiloxane Parts, 5 parts by mass of methanol, and 0.5 parts by mass of an ion exchange resin (Amberlyst 15E, manufactured by Rohm and Haas) were mixed and stirred at room temperature for 24 hours to exchange protecting groups. Thereafter, 10 parts by mass of n-butanol and 0.3 parts by mass of distilled water were added, and hydrolysis was performed at room temperature (about 25 ° C.) for 30 minutes.

  0.4 mass part of 3,5-di-t-butyl-4-hydroxytoluene (BHT), dinonylnaphthalenesulfonic acid (DNNSA) 0 with respect to the liquid obtained by filtering and separating the ion exchange resin from the reaction mixture after hydrolysis 2 parts by mass and 0.43 parts by mass of diisopropylamine (boiling point 84 ° C., manufactured by Merck & Co., Inc.) were stirred at room temperature for 30 minutes, and then filtered through a 0.5 μm filter to form a coating composition (hereinafter referred to as “ Coating fluid-2 ") was obtained.

The obtained coating liquid-2 is applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, cured by heating at 130 ° C. for 1 hour, and a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-2”). When the surface of the protective layer of the obtained photoreceptor-2 was observed with a microscope, no coating film defects were observed.
[Example 2-2]
First, in the same manner as in Example 2-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

Next, coating liquid-2 was prepared in the same manner as in Example 2-1, and stored at 40 ° C. in a sealed state. A protective layer was formed on the charge transport layer in the same manner as in Example 2-1 using the coating liquid-2 after 20 days from the start of storage to obtain an electrophotographic photoreceptor. When the surface of the protective layer of the obtained electrophotographic photosensitive member was observed with a microscope, coating film defects were slightly observed, but when a print test was performed, no image quality defects were observed, and there was no practical problem. It was.
[Example 3-1]
First, in the same manner as in Example 1-1, the outer peripheral surface of the cylindrical aluminum substrate was polished by a centerless polishing apparatus, and the surface roughness was Ra = 0.6 μm. As the aluminum substrate cleaning step, an aluminum substrate was prepared by performing a degreasing process, a 1 minute etching process using a 2% by mass sodium hydroxide solution, a neutralization process, and a pure water cleaning process in that order.

100 parts by mass of zinc oxide (trade name: SMZ-017N, manufactured by Teika) is stirred and mixed with 500 parts by mass of toluene, and 2 parts by mass of a silane coupling agent (trade name: A1100, manufactured by Nihon Unicar) is added. Stir for hours. Thereafter, toluene was distilled off under reduced pressure and baked at 120 ° C. for 2 hours. As a result of analyzing the obtained surface-treated zinc oxide by fluorescent X-ray, the Si element strength was 1.8 × 10 ⁻⁴ of the zinc element strength.

  35 parts by mass of zinc oxide subjected to the above surface treatment, 15 parts by mass of a curing agent (blocked isocyanate, trade name: Sumidur 3175, manufactured by Sumitomo Bayern Urethane), butyral resin (trade name: BM-1, Sekisui Chemical Co., Ltd.) 6 parts by mass) and 44 parts by mass of methyl ethyl ketone were mixed and dispersed for 2 hours with a sand mill using 1 mmφ glass beads. To the obtained dispersion, 0.005 parts by mass of dioctyltin dilaurate as a catalyst and 17 parts by mass of silicone resin fine particles (trade name: Tospearl 130, manufactured by GE Toshiba Silicone) are added, and a coating liquid for forming an undercoat layer is prepared. Obtained. This coating solution was applied on the outer peripheral surface of the aluminum substrate by a dip coating method, followed by drying and curing at 160 ° C. for 100 minutes to form an undercoat layer having a thickness of 20 μm. The surface roughness of the undercoat layer was measured at a measurement distance of 2.5 mm and a scanning speed of 0.3 mm / sec using a surface roughness shape measuring device Surfcom 570A manufactured by Tokyo Seimitsu Co., Ltd., and the Rz value was 0.24. .

  Next, the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum is 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 °, 1 part by mass of hydroxygallium phthalocyanine having a strong diffraction peak at 28.3 ° is mixed with 1 part by mass of polyvinyl butyral (trade name: ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts by mass of n-butyl acetate. A coating solution for forming the charge generation layer was obtained by dispersing the particles together with the beads for 1 hour using a paint shaker. This coating solution was dip-coated on the undercoat layer and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 mass parts of a benzidine compound represented by the above formula (CT-1) and a polymer compound having a structural unit represented by the above formula (B-1) (viscosity average molecular weight 59,000) 2.5 mass A part was dissolved in 35 parts of chlorobenzene to obtain a coating solution for forming a charge transport layer. This coating solution was applied onto the charge generation layer by a dip coating method, and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

  Next, 2 parts by mass of compound (III-11) in Table 26, 0.5 part by mass of methyltrimethoxysilane, 0.3 part by mass of colloidal silica, 0.5 part by mass of compound (XV-4) in Table 56 5 parts by mixing 0.5 parts by weight of hexamethylcyclotrisiloxane, 6 parts by weight of methanol, and 0.7 parts by weight of ion exchange resin (Amberlyst 15E, manufactured by Rohm and Haas) and stirring at room temperature. A time protecting group exchange reaction was performed. Thereafter, 10 parts by mass of n-butanol and 0.3 parts by mass of distilled water were added, and hydrolysis was performed at room temperature (about 25 ° C.) for 30 minutes.

  0.4 mass part of 3,5-di-t-butyl-4-hydroxytoluene (BHT), dinonylnaphthalenesulfonic acid (DNNSA) 0 with respect to the liquid obtained by filtering and separating the ion exchange resin from the reaction mixture after hydrolysis .3 parts by weight, 0.015 parts by weight of dihexylamine (boiling point 84 ° C., manufactured by Merck & Co., Inc.), stirred at room temperature for 30 minutes, filtered through a 0.5 μm filter and applied to a coating composition (hereinafter referred to as “ Coating liquid-3 ") was obtained.

The obtained coating liquid-3 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 130 ° C. for 1 hour to provide a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-3”). When the surface of the protective layer of the obtained photoreceptor-3 was observed with a microscope, no coating film defects were observed.
[Example 3-2]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

Next, coating liquid-3 was prepared in the same manner as in Example 3-1, and stored at 40 ° C. in a sealed state. A protective layer was formed on the charge transport layer in the same manner as in Example 3-1 by using Coating Solution-3 after 20 days from the start of storage to obtain an electrophotographic photoreceptor. When the surface of the protective layer of the obtained electrophotographic photosensitive member was observed with a microscope, coating film defects were slightly observed, but when a print test was performed, no image quality defects were observed, and there was no practical problem. It was.
[Example 4-1]
In the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 2 parts by mass of compound (I-1) in Table 5, 0.5 part by mass of tetramethoxysilane, 0.3 part by mass of colloidal silica, 1 part by mass of compound (XV-4) in Table 56, methanol 6 Mass parts and 0.5 parts by mass of ion exchange resin (Amberlyst 15E, manufactured by Rohm and Haas) were mixed and stirred at room temperature to carry out a protective group exchange reaction for 5 hours. Thereafter, 10 parts by mass of n-butanol and 0.3 part of distilled water were added, and hydrolysis was performed at room temperature (about 25 degrees) for 30 minutes.

  0.4 mass part of 3,5-di-t-butyl-4-hydroxytoluene (BHT), dodecylbenzenesulfonic acid (DDBSA) 0. 3 parts by mass and 0.067 parts by mass of diisobutylamine (boiling point: 129 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at room temperature for 30 minutes, and then filtered through a 0.5 μm filter to form a coating agent composition (hereinafter referred to as “ Coating liquid-4 ") was obtained.

The obtained coating liquid-4 is applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 130 ° C. for 1 hour to provide a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-4”). When the surface of the protective layer of the obtained photoreceptor 4 was observed with a microscope, no coating film defects were observed.
[Example 4-2]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

Next, a coating liquid-4 was prepared in the same manner as in Example 4-1, and stored at 40 ° C. in a sealed state. A protective layer was formed on the charge transport layer in the same manner as in Example 4-1 using the coating liquid-4 after 20 days from the start of storage to obtain an electrophotographic photoreceptor. When the surface of the protective layer of the obtained electrophotographic photosensitive member was observed with a microscope, coating film defects were slightly observed, but when a print test was performed, no image quality defects were observed, and there was no practical problem. It was.
[Example 5-1]
In the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 2 parts by mass of compound (III-1) in Table 25, 2 parts by mass of methyltrimethoxysilane, 0.7 part by mass of compound (XV-4) in Table 56, and 0.30 of hexamethylcyclotrisiloxane After dissolving 3 parts by mass in a mixed solution of 10 parts by mass of n-butyl alcohol and 0.3 part by mass of distilled water, 0.5 mass of ion exchange resin (Amberlyst 15E, manufactured by Rohm and Haas) Part was added and hydrolysis was performed at room temperature (about 25 degrees) for 30 minutes.

0.1 parts by mass of aluminum trisacetylacetonate (Al (aqaq) ₃ ), 0.1 parts by mass of acetylacetonate, 3,5-di, and the liquid obtained by filtering and separating the ion exchange resin from the reaction mixture after hydrolysis. -0.4 part by mass of t-butyl-4-hydroxytoluene (BHT), 0.3 part by mass of dodecylbenzenesulfonic acid (DDBSA), 0.05 part of diisopropylamine (boiling point 84 ° C., manufactured by Merck & Co., Inc.) After stirring for 30 minutes, the mixture was filtered through a 0.5 μm filter to obtain a coating agent composition (hereinafter referred to as “coating solution-5”).

The obtained coating liquid-5 is applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 130 ° C. for 1 hour to provide a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-5”). When the surface of the protective layer of the obtained photoreceptor 5 was observed with a microscope, no coating film defects were observed.
[Example 5-2]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

Next, a coating solution-5 was prepared in the same manner as in Example 5-1, and stored at 40 ° C. in a sealed state. A protective layer was formed on the charge transport layer in the same manner as in Example 5-1 using the coating liquid-5 after 20 days from the start of storage to obtain an electrophotographic photoreceptor. When the surface of the protective layer of the obtained electrophotographic photoreceptor was observed with a microscope, no coating film defects were observed.
[Comparative Example 1-1]
In the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate, and the target electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-6”). Got.
[Comparative Example 2-1]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

  Next, in the same manner as in Example 5 except that 0.1 part by mass of diphenylamine (liquid at 250 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 0.05 part by mass of diisopropylamine in coating liquid-5. A composition (hereinafter, “coating liquid-7”) was prepared.

The obtained coating liquid-7 was applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, cured by heating at 140 ° C. for 1 hour, and a protective layer having a thickness of about 3 μm. To obtain an intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-7”). When the surface of the protective layer of the obtained photoreceptor 7 was observed with a microscope, no coating film defects were observed.
[Comparative Example 2-2]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

Next, coating liquid-7 was prepared in the same manner as in Comparative Example 2-1, and stored at 40 ° C. in a sealed state. A protective layer was formed on the charge transport layer in the same manner as in Comparative Example 2-1, using the coating liquid-7 after 20 days had elapsed from the start of storage to obtain an electrophotographic photoreceptor. When the surface of the protective layer of the obtained electrophotographic photosensitive member was observed, it was found that a coating film defect was visually observed, which was a practical problem.
[Comparative Example 3-1]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

  Next, in the same manner as in Example 5 except that 0.1 part by mass of dioctylamine (boiling point 297 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 0.05 part by mass of diisopropylamine in coating liquid-5. A composition (hereinafter, “coating liquid-8”) was prepared.

The obtained coating liquid-8 was applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, cured by heating at 140 ° C. for 1 hour, and a protective layer having a thickness of about 3 μm. To obtain an intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-8”). When the surface of the protective layer of the obtained photoreceptor 8 was observed with a microscope, no coating film defects were observed.
[Comparative Example 3-2]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

Next, a coating liquid-8 was prepared in the same manner as in Comparative Example 3-1, and stored at 40 ° C. in a sealed state. A protective layer was formed on the charge transport layer in the same manner as in Comparative Example 3-1, using the coating liquid-8 after 20 days from the start of storage to obtain an electrophotographic photoreceptor. When the surface of the protective layer of the obtained electrophotographic photosensitive member was observed with a microscope, coating film defects were slightly observed, but it was at a level of no problem in practical use.
[Comparative Example 4-1]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

  Next, a coating agent composition (hereinafter referred to as “coating liquid-9”) was prepared in the same manner as in Example 5 except that 0.3 parts by mass of DDBSA and 0.05 part of diisopropylamine were removed from coating liquid-5. ) Was prepared.

The obtained coating liquid-9 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, cured by heating at 140 ° C. for 1 hour, and a protective layer having a thickness of about 3 μm. To obtain an intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-9”). When the surface of the protective layer of the obtained photoreceptor 9 was observed with a microscope, coating film defects were observed. Further, when a print test was performed, image quality defects were observed.
[Comparative Example 4-2]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

Next, a coating solution-9 was prepared in the same manner as in Comparative Example 4-1, and stored at 40 ° C. in a sealed state. A protective layer was formed on the charge transport layer in the same manner as in Comparative Example 3-1, using the coating liquid-9 after 20 days from the start of storage to obtain an electrophotographic photoreceptor. When the surface of the protective layer of the obtained electrophotographic photosensitive member was observed with a microscope, a coating film defect was observed. Further, when a print test was performed, an image quality defect was observed.
[Comparative Example 5-1]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

  Next, a coating agent composition (hereinafter referred to as “coating liquid-10”) was prepared in the same manner as in Example 5 except that 0.05 part of diisopropylamine in the coating liquid-5 was used.

The obtained coating liquid-10 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, cured by heating at 140 ° C. for 1 hour, and a protective layer having a thickness of about 3 μm. To obtain an intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-10”). When the surface of the protective layer of the obtained photoreceptor 10 was observed with a microscope, it was found that a coating film defect was observed with the naked eye, causing a practical problem.
[Comparative Example 5-2]
A coating liquid-10 was prepared in the same manner as in Comparative Example 5-1, and stored at 40 ° C. in a sealed state. As a result, gelation of the coating liquid- 10 occurred after 20 days from the start of storage.
[Example 6-1]
In the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 2 parts by mass of compound (II-16) in Table 15 and 2.2 parts by mass of phenol resin (PL-4852, manufactured by Gunei Chemical Co., Ltd.) were dissolved in 10 parts by mass of n-butyl alcohol. , 5-di-t-butyl-4-hydroxytoluene (BHT) 0.4 parts by mass, dodecylbenzenedisulfonic acid (DDBSA) 0.3 parts by mass, diisopropylamine 0.05 parts by mass (boiling point 84 ° C., manufactured by Merck & Co., Inc.) ) And stirred at room temperature for 30 minutes, and then filtered through a 0.5 μm filter to obtain a coating agent composition (hereinafter referred to as “coating liquid-11”).

The obtained coating liquid-11 is applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, cured by heat treatment at 150 ° C. for 1 hour, and a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-11”). When the surface of the protective layer of the obtained photoreceptor 11 was observed with a microscope, no coating film defect was observed.
[Example 6-2]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

Next, coating liquid-11 was prepared in the same manner as in Example 6-1, and stored at 40 ° C. in a sealed state. A protective layer was formed on the charge transport layer in the same manner as in Example 6-1 using the coating liquid-11 after 20 days from the start of storage to obtain an electrophotographic photoreceptor. When the surface of the protective layer of the obtained electrophotographic photoreceptor was observed with a microscope, no coating film defects were observed.
[Example 7-1]
In the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 2 parts by mass of Compound (IV-1) in Table 33, 2 parts by mass of methyltrimethoxysilane, 0.7 parts by mass of Compound (XV-4) in Table 56, and 0.3 of hexamethylcyclotrisiloxane After dissolving a mass part in a mixed solution of 10 parts by mass of n-butyl alcohol and 0.3 part by mass of distilled water, 0.5 part by mass of an ion exchange resin (Amberlyst 15E, manufactured by Rohm and Haas) is added. In addition, hydrolysis was performed at room temperature (about 25 ° C.) for 30 minutes.

0.1 parts by mass of aluminum trisacetylacetonate (Al (aqaq) ₃ ), 0.1 parts by mass of acetylacetonate, 3,5-di, and the liquid obtained by filtering and separating the ion exchange resin from the reaction mixture after hydrolysis. -0.4 part by mass of t-butyl-4-hydroxytoluene (BHT), 0.3 part by mass of dodecylbenzenedisulfonic acid (DDBSA), 0.05 part by mass of diisopropylamine (boiling point 84 ° C., manufactured by Merck & Co., Inc.) After stirring at room temperature for 30 minutes, the mixture was filtered through a 0.5 μm filter to obtain a coating agent composition (hereinafter referred to as “coating liquid-12”).

The obtained coating liquid-12 was applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 130 ° C. for 1 hour to provide a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-12”). When the surface of the protective layer of the obtained photoreceptor 12 was observed with a microscope, no coating film defects were observed.
[Example 7-2]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

Next, a coating liquid-12 was prepared in the same manner as in Example 7-1 and stored at 40 ° C. in a sealed state. A protective layer was formed on the charge transport layer in the same manner as in Example 7-1 using the coating liquid-12 after 20 days from the start of storage to obtain an electrophotographic photoreceptor. When the surface of the protective layer of the obtained electrophotographic photoreceptor was observed with a microscope, no coating film defects were observed.
[Example 8-1]
In the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, in the same manner as in Example 6-1 except that the compound (V-6) in Table 43 was used instead of the compound (II-16) in the coating-11, a coating agent composition (hereinafter, “ Coating fluid-13 ") was prepared.

The obtained coating liquid-13 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, cured by heat treatment at 150 ° C. for 1 hour, and a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-13”). When the surface of the protective layer of the obtained photoreceptor 13 was observed with a microscope, no coating film defects were observed.
[Example 8-2]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

Next, coating liquid-13 was prepared in the same manner as in Example 8-1, and stored at 40 ° C. in a sealed state. A protective layer was formed on the charge transport layer in the same manner as in Example 8-1 using the coating liquid-13 after 20 days from the start of storage to obtain an electrophotographic photoreceptor. When the surface of the protective layer of the obtained electrophotographic photoreceptor was observed with a microscope, no coating film defects were observed.
[Example 9-1]
In the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, in the same manner as in Example 6-1 except that the compound (VI-3) in Table 52 was used instead of the compound (II-16) in the coating liquid-11, a coating agent composition (hereinafter referred to as “the coating agent composition”) was used. "Coating solution-14") was prepared.

The obtained coating liquid-14 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, cured by heat treatment at 150 ° C. for 1 hour, and a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-14”). When the surface of the protective layer of the obtained photoreceptor 14 was observed with a microscope, no coating film defect was observed.
[Example 9-2]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

Next, coating liquid-14 was prepared in the same manner as in Example 9-1 and stored at 40 ° C. in a sealed state. A protective layer was formed on the charge transport layer in the same manner as in Example 9-1 using the coating liquid-14 after 20 days from the start of storage to obtain an electrophotographic photosensitive member. When the surface of the protective layer of the obtained electrophotographic photoreceptor was observed with a microscope, no coating film defects were observed.
[Example 10-1]
In the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, in the same manner as in Example 6-1 except that the compound (VI-5) in Table 52 was used instead of the compound (II-16) in the coating liquid-11, a coating agent composition (hereinafter referred to as “the coating agent composition”) was used. "Coating solution-15") was prepared.

The obtained coating liquid-15 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 150 ° C. for 1 hour to provide a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-15”). When the surface of the protective layer of the obtained photoreceptor 15 was observed with a microscope, no coating film defects were observed.
[Example 10-2]
First, in the same manner as in Example 3-1, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of an aluminum substrate.

Next, a coating liquid-15 was prepared in the same manner as in Example 10-1, and stored at 40 ° C. in a sealed state. A protective layer was formed on the charge transport layer in the same manner as in Example 10-1 using the coating liquid-15 after 20 days from the start of storage to obtain an electrophotographic photoreceptor. When the surface of the protective layer of the obtained electrophotographic photoreceptor was observed with a microscope, no coating film defects were observed.
[Examples 11-30, Comparative Examples 6-9]
In Examples 11 to 30 and Comparative Examples 6 to 9, the photoreceptors 1 to 15 and developer 1 (developer for DocuCentre color 500) or developer 2 (developer for DocuCentre color 400CP) are shown in Table 57 or Table. An image forming apparatus was manufactured using the combination shown in 58. The elements other than the electrophotographic photosensitive member and the developer used were the same as those of the Fuji Xerox printer DocuCenter color 500.

  Next, a print test was performed using each of the obtained image forming apparatuses. In this test, 5000 sheets were printed in an environment of high temperature and high humidity (28 ° C., 80% RH) in a no-paper single color mode, and then 5000 under conditions of low temperature and low humidity (10 ° C., 20% RH). Sheets were printed, and the initial and 5000th image quality under each environment, the toner cleaning property under each environment, and the presence or absence of scratches and deposits on the surface of the electrophotographic photoreceptor after the test were evaluated.

  Regarding image quality, images were observed using a magnifying microscope, and the presence or absence of streak-like defects, ghosts, missing images, etc. was evaluated. The obtained results are shown in Table 57 and Table 58.

In addition, regarding the cleanability, the image is visually observed, and the following evaluation criteria:
A: Good B: Image quality defects such as streaks are partially recognized, but there is no problem in practical use C: Evaluation is based on image quality defects in a wide range and problems in image quality. The obtained results are shown in Table 57 and Table 58.

Further, regarding the presence or absence of scratches on the surface of the electrophotographic photosensitive member, the surface of the electrophotographic photosensitive member is visually observed, and the following evaluation criteria:
A: No scratches are observed. B: Partial scratches are observed, but there is no problem in image quality. C: Evaluation is based on the presence of scratches and image quality problems. The obtained results are shown in Table 57 and Table 58.

Further, regarding the presence or absence of deposits on the surface of the electrophotographic photosensitive member, the surface of the electrophotographic photosensitive member is visually observed, and the following evaluation criteria:
A: No deposits were observed B: Some deposits were observed, but there was no problem in image quality. C: Evaluation was based on the presence of deposits and problems in image quality. The obtained results are shown in Table 57 and Table 58.

[Example 31]
First, a cylindrical aluminum substrate having an outer peripheral surface subjected to a honing process was prepared.

  Next, 100 parts by mass of a zirconium compound (trade name: Olgatics ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 10 parts by mass of a silane compound (trade name: A1100, manufactured by Nihon Unicar Co., Ltd.), polyvinyl butyral (ESREC BM-S, Sekisui Chemical Co., Ltd.) 3 parts by mass), 400 parts by weight isopropanol, and 200 parts by weight butanol were mixed to obtain a coating solution for forming an undercoat layer. This coating solution was applied on the outer peripheral surface of the aluminum substrate by a dip coating method, and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.15 μm.

  Next, the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum is 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 °, 1 part by mass of hydroxygallium phthalocyanine having a strong diffraction peak at 28.3 ° is mixed with 1 part by mass of polyvinyl butyral (trade name: ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts by mass of n-butyl acetate. A coating solution for forming the charge generation layer was obtained by dispersing the particles together with the beads for 1 hour using a paint shaker. This coating solution was dip-coated on the undercoat layer and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.18 μm.

  Next, 2 parts by mass of a benzidine compound represented by the above formula (CT-1) and 3 parts by mass of a polymer compound having a structural unit represented by the above formula (B-1) (viscosity average molecular weight 59,000) were added to chlorobenzene 20 A charge transport layer forming coating solution was obtained by dissolving in mass parts. This coating solution was applied onto the charge generation layer by dip coating, and heated at 140 ° C. for 40 minutes to form a charge transport layer having a thickness of 10 μm.

  Next, 2 parts by mass of compound (III-16) in Table 27, 0.5 part by mass of tetramethoxysilane, 0.3 part by mass of colloidal silica, 1 part by mass of compound (XV-3) in Table 56, (hepta) Decafluoro-1,1,2,2-tetrahydrodecyl) methyldimethoxysilane 0.1 parts by mass, hexamethylcyclotrisiloxane 0.5 parts by mass, methanol 6 parts by mass, and ion exchange resin (Amberlyst 15E, ROHM (And Haas Co., Ltd.) 0.7 parts by mass was mixed and stirred at room temperature to carry out a protective group exchange reaction for 5 hours. Thereafter, 10 parts by mass of n-butanol and 0.3 parts by mass of distilled water were added, and hydrolysis was performed at room temperature (about 25 ° C.) for 30 minutes.

  0.4 mass part of 3,5-di-t-butyl-4-hydroxytoluene (BHT) and 0.2 mass part of para-toluenesulfonic acid with respect to the liquid obtained by filtering and separating the ion exchange resin from the reaction mixture after hydrolysis Then, 0.12 parts by mass of di-n-butylamine (boiling point 159 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at room temperature for 30 minutes. Further, 0.5 parts by mass of butyral resin (trade name: BX-L, manufactured by Sekisui Chemical Co., Ltd.) was added and dissolved, and then filtered through a 0.5 μm filter to form a coating composition (hereinafter referred to as “Coating Solution-16”). ").

  The obtained coating liquid-16 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 10 minutes, cured by heat treatment at 145 ° C. for 40 minutes, and a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-16”).

  Next, an image forming apparatus was prepared using the photoreceptor-16, and the same print test as in Examples 11 to 30 was performed. The elements other than the electrophotographic photosensitive member were the same as those of the Fuji Xerox printer DocuCenter color 500. The results obtained are shown in Table 59.

Further, a photodegradation test was performed on the photoreceptor-16 as follows. That is, the photoreceptor 16 was irradiated with light for 10 minutes using a fluorescent lamp (Mitsubishi osram Lupika FL15EX-N-T HL15W three-wavelength daylight fluorescent lamp). At this time, the light intensity of the light irradiation part was set to about 1000 lux. The electrophotographic photoreceptor after the light irradiation was mounted on a printer Doccentre 500 manufactured by Fuji Xerox Co., Ltd., and a 20% halftone image was formed. The image formation after the light irradiation is performed three times after 10 minutes, 30 minutes, and 60 minutes, and the density change of the portion corresponding to the light irradiated portion of the photoreceptor in the obtained image is observed, and the following evaluation criteria:
A: No change in concentration after 10 minutes B: Slight change in concentration after 10 minutes, but not after 30 minutes (no problem in practice)
C: Concentration change is slightly observed after 30 minutes, but not observed after 60 minutes (may cause practical problems)
D: Concentration change is recognized after 60 minutes (problem in actual use)
The degree of light degradation was evaluated based on The results obtained are shown in Table 59.
[Example 32]
In the same manner as in Example 31, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, after dissolving 4.5 parts by mass of the compound (I-25) in Table 10 and 5.5 parts by mass of a resol type phenolic resin (PL-4852, manufactured by Gunei Chemical Co., Ltd.) in 20 parts by mass of butanol, The mixture was stirred and mixed at 45 ° C for 1 hour, 0.2 parts by mass of paratoluenesulfonic acid and 0.12 parts by mass of di-n-butylamine (boiling point 159 ° C, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the coating agent composition (hereinafter, “ Coating liquid-17 ").

  The obtained coating liquid-17 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 10 minutes, cured by heat treatment at 145 ° C. for 40 minutes, and a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-17”).

Next, an image forming apparatus was produced in the same manner as in Example 31 except that the photoconductor-17 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 59.
[Example 33]
In the same manner as in Example 31, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 4.5 parts by mass of the compound (II-16) in Table 15 and 5.5 parts by mass of a resol type phenolic resin (PR-53123, manufactured by Sumitomo Chemical Co., Ltd.) were dissolved in 20 parts by mass of butanol. The mixture was stirred and mixed for 1 hour at 0.2 ° C., 0.2 parts by weight of dodecylbenzenesulfonic acid and 0.15 parts by weight of di-n-butylamine (boiling point 159 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the coating agent composition (hereinafter “coating” Liquid-18 ").

  The obtained coating liquid-18 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 10 minutes, cured by heat treatment at 145 ° C. for 40 minutes, and a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-18”).

Next, an image forming apparatus was produced in the same manner as in Example 31 except that the photoreceptor-18 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 59.
[Example 34]
In the same manner as in Example 31, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 3 parts by mass of the compound (IV-6) in Table 34 and 3 parts by mass of a resol type phenolic resin (Phenolite 5010, manufactured by Dainippon Ink & Chemicals) were dissolved in 20 parts by mass of butanol, and then at 45 ° C. Stir and mix for 1 hour. 0.2 parts by weight of dodecylbenzenesulfonic acid is added, 0.15 parts by weight of di-n-butylamine (boiling point 159 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) is added, and a coating agent composition (hereinafter referred to as “coating liquid-19”) is added. Obtained.

  The obtained coating liquid-19 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 10 minutes, cured by heat treatment at 145 ° C. for 40 minutes, and a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-19”).

Next, an image forming apparatus was produced in the same manner as in Example 31 except that the photoconductor-19 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 59.
[Example 35]
In the same manner as in Example 31, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 3 parts by mass of the compound (V-6) in Table 33 and 3 parts by mass of a resol type phenol resin (PL-2211, manufactured by Gunei Chemical Co., Ltd.) were dissolved in 20 parts by mass of butanol, and then 1 at 45 ° C. After stirring and mixing for a period of time, 0.2 parts by mass of paratoluenesulfonic acid and 0.12 parts by mass of di-n-butylamine (boiling point 159 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) were added to form a coating agent composition (hereinafter referred to as “Coating Solution-20” ").

  The obtained coating liquid-20 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 10 minutes, cured by heat treatment at 145 ° C. for 40 minutes, and a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-20”).

Next, an image forming apparatus was produced in the same manner as in Example 31 except that the photoconductor-20 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 59.
[Example 36]
In the same manner as in Example 31, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 3 parts by mass of the compound (V-11) in Table 34 and 3 parts by mass of a resol type phenolic resin (PL-4852, manufactured by Gunei Chemical Co., Ltd.) were dissolved in 20 parts by mass of butanol, and then 1 at 45 ° C. After stirring and mixing for a period of time, 0.2 parts by mass of dodecylbenzenesulfonic acid and 0.15 parts by mass of di-n-butylamine (boiling point 159 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and a coating agent composition (hereinafter “Coating Solution-21” was added. ").

  The obtained coating liquid-21 is applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 10 minutes, cured by heat treatment at 145 ° C. for 40 minutes, and a film thickness of about 3 μm is protected. A layer was formed to obtain a target electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-21”).

Next, an image forming apparatus was prepared in the same manner as in Example 31 except that the photoconductor-21 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 59.
[Example 37]
In the same manner as in Example 31, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 2 parts by mass of compound (III-16) in Table 27, 0.5 part by mass of tetramethoxysilane, 0.3 part by mass of colloidal silica, 1 part by mass of compound (XV-3) in Table 56, (hepta) Decafluoro-1,1,2,2-tetrahydrodecyl) methyldimethoxysilane 0.1 parts by mass, hexamethylcyclotrisiloxane 0.5 parts by mass, methanol 6 parts by mass, and ion exchange resin (Amberlyst 15E, ROHM (And Haas Co., Ltd.) 0.7 parts by mass was mixed and stirred at room temperature to carry out a protective group exchange reaction for 5 hours. Thereafter, 10 parts by mass of n-butanol and 0.3 parts by mass of distilled water were added, and hydrolysis was performed at room temperature (about 25 ° C.) for 30 minutes.

  0.4 mass part of 3,5-di-t-butyl-4-hydroxytoluene (BHT) and 0.2 mass part of para-toluenesulfonic acid with respect to the liquid obtained by filtering and separating the ion exchange resin from the reaction mixture after hydrolysis , Di-n-butylamine (boiling point 159 ° C, manufactured by Tokyo Chemical Industry Co., Ltd.) 0.12 parts by mass, stirred and mixed at 45 ° C for 1 hour, and butyral resin (trade name: BX-L, manufactured by Sekisui Chemical Co., Ltd.) 0 Then, 5 parts by mass was added and dissolved, and then filtered through a 0.5 μm filter to obtain a coating agent composition (hereinafter referred to as “coating liquid-22”).

  The obtained coating liquid-22 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 10 minutes, then cured by heat treatment at 145 ° C. for 40 minutes, and a film thickness of about 3 μm was protected. A layer was formed to obtain a target electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-22”).

Next, an image forming apparatus was produced in the same manner as in Example 31 except that the photosensitive member-22 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 59.
[Example 38]
In the same manner as in Example 31, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, after dissolving 4.5 parts by mass of the compound (I-25) in Table 10 and 5.5 parts by mass of a resol type phenolic resin (PL-4852, manufactured by Gunei Chemical Co., Ltd.) in 20 parts by mass of butanol, 0.2 parts by mass of paratoluenesulfonic acid and 0.12 parts by mass of di-n-butylamine (boiling point 159 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred and mixed at 45 ° C. for 1 hour. Coating solution-23 ”).

  The obtained coating liquid-23 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 10 minutes, cured by heat treatment at 145 ° C. for 40 minutes, and a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-23”).

Next, an image forming apparatus was produced in the same manner as in Example 31 except that the photoconductor-23 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 59.
[Example 39]
In the same manner as in Example 31, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 3 parts by mass of the compound (V-6) in Table 43 and 3 parts by mass of a resol type phenol resin (PL-2211, manufactured by Gunei Chemical Co., Ltd.) were dissolved in 20 parts by mass of butanol, and then paratoluenesulfonic acid. 0.2 parts by mass and 0.12 parts by mass of di-n-butylamine (boiling point 159 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred and mixed at 45 ° C. for 1 hour to form a coating composition (hereinafter “Coating Solution-24”). I got).

  The obtained coating liquid-24 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 10 minutes, then cured by heat treatment at 145 ° C. for 40 minutes, and a film thickness of about 3 μm was protected. A layer was formed to obtain a target electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-24”).

Next, an image forming apparatus was produced in the same manner as in Example 31 except that the photosensitive member-24 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 59.
[Comparative Example 10]
In the same manner as in Example 31, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, after dissolving 4.5 parts by mass of the compound (II-16) in Table 15 and 5.5 parts by mass of a resol type phenol resin (PR-53123, manufactured by Sumitomo Chemical Co., Ltd.) in 20 parts by mass of butanol, dodecyl is dissolved. 0.2 parts by mass of benzenesulfonic acid and 0.15 parts by mass of dioctylamine (boiling point 297 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred and mixed at 45 ° C. for 1 hour, and a coating agent composition (hereinafter referred to as “Coating Solution-25”). ").

  The obtained coating liquid-25 was applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 10 minutes, cured by heat treatment at 145 ° C. for 40 minutes, and a film thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photosensitive member (hereinafter referred to as “photosensitive member-25”).

Next, an image forming apparatus was produced in the same manner as in Example 31 except that the photoconductor-25 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 59.
[Comparative Example 11]
In the same manner as in Example 31, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, after dissolving 3 parts by mass of the compound (IV-6) in Table 34 and 3 parts by mass of a resol type phenolic resin (Phenolite 5010, manufactured by Dainippon Ink & Chemicals) in 20 parts by mass of butanol, dodecylbenzenesulfone is dissolved. Add 0.2 parts by weight of acid and 0.15 parts by weight of dioctylamine (boiling point 297 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) and stir and mix at 45 ° C. for 1 hour to obtain a coating agent composition (hereinafter referred to as “coating liquid-26”). )

  The obtained coating liquid-26 was applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 10 minutes, cured by heat treatment at 145 ° C. for 40 minutes, and a protective film having a thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-26”).

Next, an image forming apparatus was produced in the same manner as in Example 31 except that the photoreceptor 26 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 59.
[Comparative Example 12]
In the same manner as in Example 31, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 3 parts by mass of the compound (V-11) in Table 44 and 3 parts by mass of a resol type phenol resin (PL-4852, manufactured by Gunei Chemical Co., Ltd.) were dissolved in 20 parts by mass of butanol, and then dodecylbenzenesulfonic acid. 0.2 parts by mass and dioctylamine (boiling point 297 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) 0.15 parts by mass were added and mixed with stirring at 45 ° C. for 1 hour to form a coating agent composition (hereinafter referred to as “coating liquid-27”). Got.

  The obtained coating liquid-27 was applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 10 minutes, and then cured by heat treatment at 145 ° C. for 40 minutes to protect the film with a thickness of about 3 μm. A layer was formed to obtain a target electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-27”).

  Next, an image forming apparatus was produced in the same manner as in Example 31 except that the photoconductor-27 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 59.

[Example 40]
First, a cylindrical aluminum substrate having an outer diameter of 30 mm subjected to a honing process was prepared.

  Next, 20 parts by mass of a zirconium compound (trade name: Organotix ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 2.5 parts by mass of a silane compound (trade name: A1100, manufactured by Nihon Unicar Co., Ltd.), polyvinyl butyral resin (trade name: ESREC BM) -S, Sekisui Chemical Co., Ltd.) 20 parts by mass and butanol 45 parts by mass were mixed to obtain a coating solution for forming an undercoat layer. This coating solution was applied onto the outer peripheral surface of the aluminum substrate by a dip coating method and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of 1.0 μm.

  Next, 15 masses of hydroxygallium phthalocyanine having diffraction peaks at X-ray diffraction spectra of Bragg angles (2θ ± 0.2 °) of 7.3 °, 16.0 °, 24.9 °, and 28.0 °. Parts are mixed with 10 parts by mass of vinyl chloride / vinyl acetate copolymer resin (VMCH, manufactured by Nihon Unicar) as binder resin and 300 parts by mass of n-butyl acetate, and dispersed with glass beads for 0.5 hour in a horizontal sand mill. Thus, a coating solution for forming a charge generation layer was obtained. The obtained coating solution was dip-coated on the undercoat layer and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 parts by mass of a benzidine compound represented by the above formula (CT-1) and 3 parts by mass of a polymer compound (viscosity average molecular weight: 39,000) having a structural unit represented by the formula (B-1) A coating solution for forming a charge transport layer was obtained by dissolving in a mixed solvent of 15 parts by mass of tetrahydrofuran and 5 parts by mass of chlorobenzene. The obtained coating solution was applied onto the charge generation layer by a dip coating method and dried in hot air at 130 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

  Next, 5 parts by mass of the compound (III-16) in Table 27 and 5 parts by mass of a resol type phenol resin (trade name: PL-4852, manufactured by Gunei Chemical Industry Co., Ltd.) are used as a solvent of 27 parts by mass of butyl alcohol. Then, 0.2 parts by mass of paratoluenesulfonic acid was added, and the mixture was stirred and mixed at 24 ° C. for 1 hour. Thereafter, 0.1 parts by mass of di-n-butylamine (boiling point 159 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred and mixed at 24 ° C. for 5 minutes to obtain a coating agent composition (hereinafter referred to as “coating liquid-28”). Obtained.

  The obtained coating liquid-28 was applied on the charge transport layer by a dip coating method in a coating chamber at a temperature of 24 ° C. and dried with hot air at 145 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. An electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-28”) was obtained.

  Next, an image forming apparatus was prepared using the obtained photoreceptor-28, and the same print test as in Examples 11 to 30 was performed. The elements other than the electrophotographic photosensitive member were the same as those of the Fuji Xerox printer DocuCenter color 400CP. The results obtained are shown in Table 60.

In addition, a photodegradation test was performed on the photoreceptor-28 as follows. That is, half of the image forming area of the photoconductor-18 was covered with light-shielding paper, and 1000 Lux white light was irradiated for 5 minutes. Next, the photoconductor 18 after the light irradiation is mounted on the image forming apparatus, and a halftone image is formed in an environment of high temperature and high humidity (28 ° C., 85% RH). Compare the image quality corresponding to each part, and the following evaluation criteria:
A: No decrease in density is observed in the light-irradiated part B: A slight decrease in density is observed in the light-irradiated part, but there is no practical problem C: A decrease in density is observed in the light-irradiated part, and there is a practical problem D: The degree of light degradation was evaluated based on a strong density decrease in the light irradiation part. The results obtained are shown in Table 60.
[Example 41]
In the same manner as in Example 40, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 5 parts by mass of the compound (I-1) in Table 5 and 5 parts by mass of a resol type phenol resin (trade name: PR-53123, manufactured by Sumitomo Bakelite Co., Ltd.) are dissolved in a solvent of 27 parts by mass of butyl alcohol. Further, 0.2 part by mass of dodecylbenzenedisulfonic acid was added, and the mixture was stirred and mixed at 30 ° C. for 1 hour. Thereafter, 0.2 parts by mass of diisopropylamine (boiling point 84 ° C., manufactured by Merck & Co., Inc.) was added, and the mixture was stirred and mixed at 24 ° C. for 5 minutes to obtain a coating agent composition (hereinafter referred to as “coating solution-29”).

  The obtained coating liquid-29 was applied by dip coating on the charge generation layer in a coating chamber at a temperature of 24 ° C., and then dried with hot air at 150 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. An intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-29”) was obtained.

Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photoconductor-29 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.
[Example 42]
In the same manner as in Example 40, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 5 parts by mass of the compound (II-1) in Table 11 and 5 parts by mass of a resol type phenol resin (trade name: Phenolite 5010, manufactured by DIC) were dissolved in a solvent of 27 parts by mass of butyl alcohol, and phenol was further added. 0.3 part by mass of sulfonic acid was added, and the mixture was stirred and mixed at 25 ° C. for 1 hour. Thereafter, 0.2 part by mass of dihexylamine (boiling point 84 ° C., manufactured by Merck & Co., Inc.) was added and stirred and mixed at 24 ° C. for 5 minutes to obtain a coating agent composition (hereinafter referred to as “coating solution-30”).

  The obtained coating solution-30 was applied by dip coating on the charge generation layer in a coating chamber at a temperature of 24 ° C., and then dried with hot air at 140 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. An intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-30”) was obtained.

Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photoreceptor-30 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.
[Example 43]
In the same manner as in Example 40, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 5.5 parts by mass of the compound (II-14) in Table 13 and 5 parts by mass of a resol type phenolic resin (trade name: PL-2211, manufactured by Gunei Chemical Industry Co., Ltd.) were added to 27 parts by mass of butyl alcohol. After dissolving in a solvent, 0.2 parts by mass of paratoluenesulfonic acid was added, and the mixture was stirred and mixed at 30 ° C. for 1 hour. Thereafter, 0.15 parts by mass of diisobutylamine (boiling point: 129 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred and mixed at 30 ° C. for 5 minutes to obtain a coating agent composition (hereinafter referred to as “coating liquid-31”). .

  The obtained coating liquid-31 was applied on the charge generation layer by a dip coating method in a coating chamber at a temperature of 24 ° C., and then dried with hot air at 150 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. An intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-31”) was obtained.

Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photoreceptor 31 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.
[Example 44]
In the same manner as in Example 40, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 5.5 parts by mass of the compound (V-6) in Table 43, 5 parts by mass of a resol type phenol resin (trade name: PL-4852, manufactured by Gunei Chemical Industry Co., Ltd.), 7 parts by mass of cyclohexanone, and butyl It was dissolved in a solvent of 20 parts by mass of alcohol, 0.2 parts by mass of dodecylbenzenedisulfonic acid was added, and the mixture was stirred and mixed at 40 ° C. for 1 hour. After cooling to room temperature, 0.1 parts by mass of diisopropylamine (boiling point 84 ° C., manufactured by Merck & Co., Inc.) was added, and the mixture was stirred and mixed at 25 ° C. for 5 minutes to form a coating composition (hereinafter referred to as “Coating Solution-32”). Got.

  The obtained coating liquid-32 was applied by dip coating on the charge generation layer in a coating chamber at a temperature of 24 ° C., and then dried with hot air at 150 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. An intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-32”) was obtained.

Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photoconductor-32 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.
[Example 45]
In the same manner as in Example 40, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 6 parts by mass of the compound (V-56) in Table 51 and 5 parts by mass of a resol type phenol resin (trade name: PL-4852, manufactured by Gunei Chemical Industry Co., Ltd.) are used as a solvent of 27 parts by mass of butyl alcohol. After dissolution, 0.15 parts by mass of dodecylbenzenedisulfonic acid was added, and the mixture was stirred and mixed at 40 ° C. for 1 hour. After cooling to room temperature, 0.1 parts by mass of diisobutylamine (boiling point: 129 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) is added, and stirred and mixed at 25 ° C. for 5 minutes to form a coating agent composition (hereinafter referred to as “coating solution-33”). )

  The obtained coating liquid-33 was applied on the charge generation layer by a dip coating method in a coating chamber at a temperature of 24 ° C., and then dried with hot air at 150 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. An intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-33”) was obtained.

Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photosensitive member-33 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.
[Example 46]
In the same manner as in Example 40, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 5 parts by mass of the compound (III-16) in Table 27 and 5 parts by mass of a resol type phenol resin (trade name: PL-4852, manufactured by Gunei Chemical Industry Co., Ltd.) are used as a solvent of 27 parts by mass of butyl alcohol. Further, 0.2 parts by mass of para-toluenesulfonic acid and 0.1 parts by mass of di-n-butylamine (boiling point 159 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) are added, and the mixture is stirred and mixed at 24 ° C. for 1 hour. (Hereinafter referred to as “coating liquid-34”).

  The obtained coating liquid-34 was applied on the charge generation layer by a dip coating method in a coating chamber at a temperature of 24 ° C. and dried with hot air at 140 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. An electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-34”) was obtained.

Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photoreceptor -34 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.
[Example 47]
In the same manner as in Example 39, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 5 parts by mass of the compound (I-1) in Table 5 and 5 parts by mass of a resol type phenol resin (trade name: PR-53123, manufactured by Sumitomo Bakelite Co., Ltd.) are dissolved in a solvent of 27 parts by mass of butyl alcohol. Furthermore, 0.2 parts by mass of dinonylnaphthalene sulfonic acid (DNNSA) and 0.15 parts by mass of diisopropylamine (boiling point 84 ° C., manufactured by Merck & Co., Inc.) were added, and the mixture was stirred and mixed at 30 ° C. for 1 hour to form a coating composition ( Hereinafter, “coating solution-35”) was obtained.

  The obtained coating liquid-35 was applied by dip coating on the charge generation layer in a coating chamber at a temperature of 24 ° C., and then dried with hot air at 145 ° C. for 60 minutes to form a protective layer having a thickness of 3 μm. An intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-35”) was obtained.

Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photoreceptor 35 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.
[Example 48]
In the same manner as in Example 40, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 5 parts by mass of the compound (II-5) in Table 12 and 5 parts by mass of a resol type phenol resin (trade name: Phenolite 5010, manufactured by DIC) were dissolved in a solvent of 27 parts by mass of butyl alcohol, Add 0.3 parts by weight of nonylnaphthalenesulfonic acid (DNNSA) and 0.2 parts by weight of dihexylamine (boiling point 84 ° C., manufactured by Merck & Co., Inc.), and stir and mix at 25 ° C. for 1 hour to form a coating agent composition (hereinafter “ Coating solution-36 ") was obtained.

  The obtained coating liquid-36 was applied by dip coating on the charge generation layer in a coating chamber at a temperature of 24 ° C., and then dried with hot air at 150 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. An intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-36”) was obtained.

Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photoreceptor 36 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.
[Example 49]
In the same manner as in Example 40, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 5.5 parts by mass of the compound (II-23) in Table 17 and 5 parts by mass of a resol type phenolic resin (trade name: PL-2211, manufactured by Gunei Chemical Industry Co., Ltd.) were added to 27 parts by mass of butyl alcohol. Dissolve in a solvent, add 0.2 parts by weight of dinonylnaphthalenesulfonic acid (DNNSA) and 0.15 parts by weight of diisobutylamine (boiling point 129 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.), stir and mix at 35 ° C. for 1 hour. A coating agent composition (hereinafter referred to as “coating liquid-37”) was obtained.

  The obtained coating liquid-38 was applied on the charge generation layer by a dip coating method in a coating chamber at a temperature of 24 ° C., and then dried with hot air at 130 ° C. for 60 minutes to form a protective layer having a thickness of 3 μm. An intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-37”) was obtained.

Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photoreceptor 37 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.
[Example 50]
In the same manner as in Example 40, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 5.5 parts by mass of the compound (V-6) in Table 43, 5 parts by mass of a resol type phenol resin (trade name: PL-4852, manufactured by Gunei Chemical Industry Co., Ltd.), 7 parts by mass of cyclohexanone, and butyl Dissolve in 20 parts by weight of alcohol, add 0.2 parts by weight of dodecylbenzenedisulfonic acid and 0.15 parts by weight of diisopropylamine (boiling point 84 ° C., manufactured by Merck & Co.) and stir and mix at 45 ° C. for 1 hour to coat. An agent composition (hereinafter referred to as “coating liquid-38”) was obtained.

  The obtained coating liquid-38 was applied on the charge generation layer by a dip coating method in a coating chamber at a temperature of 24 ° C., and then dried with hot air at 140 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. An intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-38”) was obtained.

Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photoconductor-38 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.
[Example 51]
In the same manner as in Example 39, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 6 parts by mass of the compound (V-56) in Table 51 and 5 parts by mass of a resol type phenol resin (trade name: PL-4852, manufactured by Gunei Chemical Industry Co., Ltd.) are used as a solvent of 27 parts by mass of butyl alcohol. Further, 0.2 parts by mass of dodecylbenzenedisulfonic acid and 0.2 parts by mass of diisobutylamine (boiling point: 129 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) are added, and the mixture is stirred and mixed for 1 hour at 45 ° C. And “Coating Solution-39”).

  The obtained coating liquid-39 was applied on the charge generation layer by a dip coating method in an application chamber at a temperature of 24 ° C., and then dried with hot air at 150 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. An intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-39”) was obtained.

Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photoconductor-39 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.
[Comparative Example 13]
In the same manner as in Example 40, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 5.5 parts by mass of the compound (V-6) in Table 43, 5 parts by mass of a resol type phenolic resin (trade name: PL2211, manufactured by Gunei Chemical Industry Co., Ltd.), 7 parts by mass of cyclohexanone and 20 parts of butyl alcohol The resultant was dissolved in part by mass of a solvent, 0.2 parts by mass of dodecylbenzenesulfonic acid (DDBSA) was further added, and the mixture was stirred and mixed at 40 ° C. for 1 hour. After cooling to room temperature, 0.1 parts by mass of diphenylamine (liquid at 250 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) is added, and the mixture is stirred and mixed at 25 ° C. for 5 minutes to form a coating agent composition (hereinafter referred to as “coating solution-40”). )

  The obtained coating solution-40 was applied on the charge generation layer by a dip coating method in a coating chamber at a temperature of 24 ° C., and then dried with hot air at 145 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. An intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-40”) was obtained.

Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photoreceptor 40 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.
[Comparative Example 14]
In the same manner as in Example 40, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 6 parts by mass of the compound (V-56) in Table 51, 5 parts by mass of a resol type phenol resin (trade name: PR53123, manufactured by Sumitomo Bakelite Co., Ltd.) are dissolved in a solvent of 27 parts by mass of butyl alcohol, and 0.25 parts by mass of dodecylbenzenedisulfonic acid was added, and the mixture was stirred and mixed at 35 ° C. for 1 hr. After cooling to room temperature, 0.1 part by mass of dioctylamine (boiling point 297 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) is added, and the mixture is stirred and mixed at 25 ° C. for 5 minutes. )

  The obtained coating liquid-41 was applied by dip coating on the charge generation layer in a coating chamber at a temperature of 24 ° C., and then dried with hot air at 150 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. An intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-41”) was obtained.

Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photoconductor-41 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.
[Comparative Example 15]
In the same manner as in Example 40, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 5.5 parts by mass of the compound (V-6) in Table 43 and 5 parts by mass of a resol-type phenol resin (trade name: Phenolite 5010, manufactured by DIC) were added to 7 parts by mass of cyclohexanone and 20 parts by mass of butyl alcohol. It was dissolved in a solvent, 0.2 parts by mass of dodecylbenzenesulfonic acid (DDBSA) was further added, and the mixture was stirred and mixed at 40 ° C. for 1 hour. After cooling to room temperature, 0.2 parts by mass of diphenylamine (liquid at 250 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.) is added, and the mixture is stirred and mixed at 25 ° C. for 5 minutes to form a coating agent composition (hereinafter referred to as “Coating Solution-42”). )

  The obtained coating liquid -42 was applied by dip coating on the charge generation layer in a coating chamber at a temperature of 24 ° C., and then dried with hot air at 145 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. An intended electrophotographic photoreceptor (hereinafter referred to as “photoreceptor-42”) was obtained.

Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photoreceptor -42 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.
[Comparative Example 16]
In the same manner as in Example 40, an undercoat layer, a charge generation layer, and a charge transport layer were formed on the outer peripheral surface of the aluminum substrate.

  Next, 6 parts by mass of the compound (V-56) in Table 51, 5 parts by mass of a resol type phenol resin (trade name: PR53123, manufactured by Sumitomo Bakelite Co., Ltd.) are dissolved in a solvent of 27 parts by mass of butyl alcohol, and Add 0.2 parts by weight of dodecylbenzenedisulfonic acid and 0.15 parts by weight of dioctylamine (boiling point 297 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.), and stir and mix at 35 ° C. for 1 hour to form a coating agent composition (hereinafter referred to as “coating solution”). -43 ").

  The obtained coating liquid-43 was applied by dip coating on the charge generation layer in a coating chamber at a temperature of 24 ° C., and then dried with hot air at 140 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. The intended electrophotographic photoreceptor was obtained.

  Next, an image forming apparatus was produced in the same manner as in Example 40 except that the photoconductor-43 was used, and a print test and a light deterioration test were performed. The results obtained are shown in Table 60.

1 is a cross-sectional view of a main part showing a preferred embodiment of an electrophotographic photosensitive member of the present invention. 1 is a schematic configuration diagram illustrating a preferred embodiment of an image forming apparatus of the present invention. It is a schematic block diagram which shows other embodiment of the image forming apparatus of this invention. 1 is a schematic configuration diagram showing a preferred embodiment of a process cartridge of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 401a-401d ... Electrophotographic photoreceptor, 2 ... Conductive substrate, 3 ... Photosensitive layer, 4 ... Undercoat layer, 5 ... Charge generation layer, 6 ... Charge transport layer, 7 ... Protective layer, 200, 220 ... Electron Photographic device 208 ... charging device 209 ... power source 210 ... exposure device 211 ... developing device 212 ... transfer device 213 ... cleaning device 214 ... static discharger 215 ... fixing device 216 ... toner supply device 217 ... Opening for exposure, 218 ... Opening for static elimination exposure, 219 ... Mounting rail, 300 ... Process cartridge, 400 ... Housing, 402a to 402d ... Charging roll, 403 ... Laser light source (exposure device), 404a to 404d ... Developing device, 405a to 405d ... Toner cartridge, 406 ... Drive roll, 407 ... Tension roll, 408 ... Backup low 409 ... intermediate transfer belt, 410a to 410d ... primary transfer roll, 411 ... tray (transfer medium tray), 412 ... transfer roll, 413 ... secondary transfer roll, 414 ... fixing roll, 415a-415d ... cleaning blade, 416 ... Cleaning blade, 417, 500 ... Transfer medium.

Claims (10)

A coating agent composition used as a constituent material of an electrophotographic photoreceptor,
A photofunctional organic compound capable of forming a cured film;
Sulfonic acids and / or derivatives thereof;
A coating agent composition comprising an amine having a boiling point of 250 ° C. or less.   The ratio of the content of the sulfonic acid and / or the derivative thereof to the content of an amine having a boiling point of 250 ° C or lower is 1: 0.5 to 1: 2 in a molar ratio. The coating agent composition described in 1. The coating composition according to claim 1 or 2, wherein the photofunctional organic compound has a structure represented by any one of the following general formulas (I) to (VI).
_{^{F [- (X 1) n}} -R 1 -Z 1 H] m (I)
[In the formula (I), F represents an organic group derived from a compound having a hole transport ability, X ¹ represents an oxygen atom or a sulfur atom, R ¹ represents an alkylene group, Z ¹ represents an oxygen atom, a sulfur atom, NH or COO, n represents 0 or 1, and m represents an integer of 1 to 4. ]
_{^{F - [(X 2) n2}} - (R 2) n3 - (Z 2) n4 G] n5 (II)
[In Formula (II), F represents an organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, Z ² represents an alkylene group, O represents an oxygen atom, a sulfur atom, NH or COO, G represents an epoxy group, n2, n3 and n4 each independently represents 0 or 1, and n5 represents an integer of 1 to 4. ]
F [—D—Si (R ³ ) _(3-a) Q _a ] _b (III)
[In Formula (III), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group, and R ³ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group. Q represents a hydrolyzable group, a represents an integer of 1 to 3, and b represents an integer of 1 to 4. ]

[In Formula (IV), F represents an organic group derived from a compound having a hole transporting property, T represents a divalent group, Y represents an oxygen atom or a sulfur atom, R ⁴ , R ⁵ and R ⁶ independently represents a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m 2 represents 0 or 1, n 6 represents an integer of 1 to 4, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

[In Formula (V), F represents an organic group derived from a compound having a hole transporting property, T represents a divalent group, R ⁸ represents a monovalent organic group, and m3 represents 0 or 1 N7 represents an integer of 1 to 4. ]

[In Formula (VI), F represents an organic group derived from a compound having a hole transporting property, L represents an alkylene group, R ⁹ represents a monovalent organic group, and n8 represents an integer of 1 to 4. Indicates. ]   The coating agent composition according to any one of claims 1 to 3, further comprising a phenol resin. A method for producing a coating composition comprising a photofunctional organic compound capable of forming a cured film, a sulfonic acid and / or a derivative thereof, and an amine having a boiling point of 250 ° C. or less,
A first step of mixing a material other than the amine among the materials constituting the coating agent composition;
And a second step of obtaining the coating agent composition by adding the amine to the mixture obtained in the first step. A method for producing a coating composition comprising a photofunctional organic compound capable of forming a cured film, a sulfonic acid and / or a derivative thereof, and an amine having a boiling point of 250 ° C. or less,
A first step of mixing materials other than the sulfonic acid and / or derivative thereof and the amine among the materials constituting the coating agent composition;
Preparation of a coating composition, characterized in that it comprises a second step of the sulfonic acid and / or by the addition of said amine and its derivatives to the mixture obtained in the first step to obtain the coating composition Method.   The method for producing a coating agent composition according to claim 5 or 6, wherein the coating agent composition further contains a phenol resin. Comprising a conductive substrate and a photosensitive layer provided on the conductive substrate;
The electrophotographic photosensitive film, wherein the photosensitive layer includes a surface layer obtained by curing the coating agent composition according to any one of claims 1 to 4 on a side far from the conductive substrate. body. The electrophotographic photosensitive member according to claim 8,
A charging device for charging the electrophotographic photosensitive member;
An exposure apparatus that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image;
A developing device for developing the electrostatic latent image to form a toner image;
An image forming apparatus comprising: a transfer device that transfers the toner image to a transfer target. The electrophotographic photosensitive member according to claim 8,
Selected from a charging device for charging the electrophotographic photosensitive member, a developing device for developing a latent electrostatic image formed by exposure to form a toner image, and a cleaning device for removing toner remaining on the electrophotographic photosensitive member And a process cartridge.

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