Patent Application
20240036487
This application is based on and claims priority under 35 USC 119 from Japanese Patent Application No. 2022-117236 filed Jul. 22, 2022.
The present invention relates to an electrophotographic photoreceptor, a process cartridge, and an image forming apparatus.
JP2019-164241A describes an electrophotographic photoreceptor formed of a coating solution for a charge transport layer that contains, at a specific ratio, at least one selected from the group consisting of a charge transport material, a polycarbonate resin, and a polyester resin, at least one selected from the group consisting of xylene and toluene, cyclopentanone, and an antioxidant.
Aspects of non-limiting embodiments of the present disclosure relate to an electrophotographic photoreceptor that includes a conductive substrate and a lamination type photosensitive layer or a single layer type photosensitive layer, in which a charge transport layer of the lamination type photosensitive layer or the single layer type photosensitive layer is the outermost layer and contains a charge transport material, a polyester resin having a dicarboxylic acid unit (A), and a compound, and burn-in ghosts are unlikely to occur and adhesion of a toner to the surface of the electrophotographic photoreceptor is suppressed, as compared with a case where the compound has a molecular weight of less than 260, a case where the compound has a phenol skeleton in which a hydrogen atom and a tertiary carbon atom or a quaternary carbon atom are bonded to one ortho position and a tertiary carbon atom or a quaternary carbon atom is bonded to the other ortho position, or a case where the compound has a linear alkylene structure having 4 or more carbon atoms.
Aspects of certain non-limiting embodiments of the present disclosure address the above advantages and/or other advantages not described above. However, aspects of the non-limiting embodiments are not required to address the advantages described above, and aspects of the non-limiting embodiments of the present disclosure may not address advantages described above.
Specific means for achieving the above-described object includes the following aspect.
According to an aspect of the present disclosure, there is provided an electrophotographic photoreceptor including: a conductive substrate, and a lamination type photosensitive layer including a charge generation layer and a charge transport layer or a single layer type photosensitive layer that is a photosensitive layer disposed on the conductive substrate, in which the charge transport layer or the single layer type photosensitive layer is an outermost layer and contains a charge transport material, a polyester resin having a dicarboxylic acid unit (A) represented by Formula (A), and a compound that has a molecular weight of 255 or greater, has a phenol skeleton in which a primary carbon atom or a secondary carbon atom is bonded to one ortho position and a tertiary carbon atom or a quaternary carbon atom is bonded to the other ortho position, and has no linear alkylene structure having 4 or more carbon atoms.
In Formula (A), ArA1 and ArA2 each independently represent an aromatic ring that may have a substituent, LA represents a single bond or a divalent linking group, and nA1 represents 0, 1, or 2.
Exemplary embodiment(s) of the present invention will be described in detail based on the following figures, wherein:
Hereinafter, exemplary embodiments of the present disclosure will be described. The following descriptions and examples merely illustrate the exemplary embodiments, and do not limit the scope of the exemplary embodiments.
In the present disclosure, a numerical range shown using “to” indicates a range including numerical values described before and after “to” as a minimum value and a maximum value.
In a numerical range described in a stepwise manner in the present disclosure, an upper limit value or a lower limit value described in a certain numerical range may be replaced with an upper limit value or a lower limit value in another numerical range described in a stepwise manner. Further, in a numerical range described in the present disclosure, an upper limit value or a lower limit value described in the numerical range may be replaced with a value shown in examples.
In the present disclosure, the meaning of the term “step” includes not only an independent step but also a step whose intended purpose is achieved even in a case where the step is not clearly distinguished from other steps.
In the present disclosure, in a case where an exemplary embodiment is described with reference to drawings, the configuration of the exemplary embodiment is not limited to the configuration shown in the drawings. In addition, the sizes of members in each drawing are conceptual and do not limit the relative relationship between the sizes of the members.
In the present disclosure, each component may include a plurality of kinds of substances corresponding to each component. In the present disclosure, in a case where a plurality of kinds of substances corresponding to each component in a composition are present, the amount of each component in the composition indicates the total amount of the plurality of kinds of substances present in the composition unless otherwise specified.
In the present disclosure, each component may include a plurality of kinds of particles corresponding to each component. In a case where a plurality of kinds of particles corresponding to each component are present in a composition, the particle diameter of each component indicates the value of a mixture of the plurality of kinds of particles present in the composition, unless otherwise specified.
In the present disclosure, an alkyl group is any of linear, branched, or cyclic unless otherwise specified.
In the present disclosure, a hydrogen atom in an organic group, an aromatic ring, a linking group, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, or an aryloxy group may be substituted with a halogen atom.
Electrophotographic Photoreceptor
The present disclosure provides a first exemplary embodiment and a second exemplary embodiment of an electrophotographic photoreceptor (hereinafter, also referred to as a “photoreceptor”).
The photoreceptor according to the first exemplary embodiment includes a conductive substrate, and a lamination type photosensitive layer disposed on the conductive substrate and including a charge generation layer and a charge transport layer. The photoreceptor according to the first exemplary embodiment may further include other layers (for example, an undercoat layer and an interlayer). However, in the photoreceptor according to the first exemplary embodiment, the charge transport layer is the outermost layer.
The photoreceptor according to the second exemplary embodiment includes a conductive substrate, and a single layer type photosensitive layer disposed on the conductive substrate. The photoreceptor according to the second exemplary embodiment may further include other layers (for example, an undercoat layer and an interlayer). However, in the photoreceptor according to the second exemplary embodiment, the single layer type photosensitive layer is the outermost layer. Hereinafter, the lamination type photosensitive layer is also referred to as “lamination type photosensitive layer”, and the single layer type photosensitive layer is also referred to as “single layer type photosensitive layer”.
In the photoreceptor according to the first exemplary embodiment, the charge transport layer is the outermost layer and contains a charge transport material, a polyester resin having a dicarboxylic acid unit (A) represented by Formula (A), and a compound having a molecular weight of 255 or greater, a phenol skeleton in which a primary carbon atom or a secondary carbon atom is bonded to one ortho position and a tertiary carbon atom or a quaternary carbon atom is bonded to the other ortho position, and no linear alkylene structure having 4 or more carbon atoms.
In the photoreceptor according to the second exemplary embodiment, the single layer type photosensitive layer is the outermost layer and contains a charge transport material, a polyester resin having a dicarboxylic acid unit (A) represented by Formula (A), and a compound having a molecular weight of 255 or greater, a phenol skeleton in which a primary carbon atom or a secondary carbon atom is bonded to one ortho position and a tertiary carbon atom or a quaternary carbon atom is bonded to the other ortho position, and no linear alkylene structure having 4 or more carbon atoms.
In Formula (A), ArA1 and ArA2 each independently represent an aromatic ring that may have a substituent, LA represents a single bond or a divalent linking group, and nA1 represents 0, 1, or 2.
Hereinafter, in a case of description common to the first exemplary embodiment and the second exemplary embodiment, both exemplary embodiments are collectively referred to as the present exemplary embodiment. In a case where items common to the charge transport layer and the single layer type photosensitive layer are described, both layers are collectively referred to as a photosensitive layer.
Further, the phenol skeleton which contains a phenolic hydroxyl group and in which a primary carbon atom or a secondary carbon atom is bonded to one ortho position with respect to the bonding position of the phenolic hydroxyl group and a tertiary carbon atom or a quaternary carbon atom is bonded to the other ortho position with respect to the bonding position thereof is also referred to as “hindered phenol-based skeleton”, and the structure having a molecular weight of 255 or greater, the hindered phenol-based skeleton, and no linear alkylene structure having 4 or more carbon atoms is also referred to as “specific hindered phenol structure”.
Since the photoreceptor according to the present exemplary embodiment has the configuration described above, burn-in ghosts are unlikely to occur, and adhesion of a toner to the surface of the photoreceptor is suppressed. The reason for this is assumed as follows.
In the photosensitive layer that contains a polyester resin having a dicarboxylic acid unit (A), molecules attract each other due to the interaction of aromatic rings of the polyester resin, and thus abrasion resistance is likely to be obtained.
Meanwhile, since the structure of the dicarboxylic acid unit (A) in which an aromatic ring and a carbonyl group are directly linked to each other has electron-withdrawing properties and is likely to be negatively charged, a positive charge is likely to be captured by the interaction between the structure and the charge transport material. Further, in the photosensitive layer containing the polyester resin having the dicarboxylic acid unit (A), the captured positive charge is likely to remain as a cation radical, images are repeatedly formed, and thus cation radicals are likely to be accumulated in a region with a particularly large exposure history even in the photosensitive layer. Further, in a case where cation radicals are accumulated in a specific region, since the negative charge during charging in the next cycle is canceled out in the region so that the surface potential is lowered, and burn-in ghosts occur. Here, “burn-in ghosts” are image defects in which the surface potential of a portion of the photoreceptor with a large exposure history decreases and thus the density of a halftone image increases.
Examples of a method of suppressing the occurrence of burn-in ghosts include a method of making the photosensitive layer contain an antioxidant. It is considered that the cation radicals in the photosensitive layer are captured by the antioxidant and disappear, and thus the occurrence of burn-in ghosts caused by the accumulation of cation radicals is suppressed.
However, in a case where the photosensitive layer contains an antioxidant, adhesion of a toner to the surface of the photoreceptor (hereinafter, also referred to as “filming”) may occur. In particular, in an image forming apparatus that cleans the surface of the photoreceptor with a cleaning blade, the toner adhering to the surface of the photoreceptor is crushed by the cleaning blade and thus is likely to adhere to the surface of the photoreceptor in a stretched state, and as a result, filming is more likely to occur.
The filming is likely to occur particularly in a case where an antioxidant having a small molecular weight is used or in a case where an antioxidant having a flexible chemical structure is used. For example, in the case where the molecular weight of the antioxidant is small, it is considered that the filming is likely to occur because the antioxidant bleeds out to the surface of the photosensitive layer with the use of the photoreceptor, the surface of the photosensitive layer is plasticized by the antioxidant that has been bled out to the surface of the photosensitive layer, and adhesion of a toner or the like is likely to occur. Further, for example, in the case where the antioxidant has a flexible chemical structure, it is considered that the filming is likely to occur because the photosensitive layer undergoes micro-phase separation due to the flexible chemical structure to form a highly viscous region and adhesion of a toner or the like to the highly viscous region is likely to occur. Further, in the image forming apparatus that cleans the surface of the photoreceptor with the cleaning blade, it is considered that the filming is more likely to occur due to plasticization of the cleaning blade by the antioxidant that has been bled to the surface of the photoreceptor.
Meanwhile, in the present exemplary embodiment, a compound having a specific hindered phenol structure (also referred to as “specific compound”) is used.
The compound having a specific hindered phenol structure has a molecular weight of 255 or greater and does not have a linear alkylene structure having 4 or more carbon atoms which is a flexible chemical structure. Therefore, in the present exemplary embodiment, the filming is assumed to be suppressed in a case where a compound having a molecular weight of less than 255 is used, as compared with a case where a compound that has a linear alkylene structure having 4 or more carbon atoms is used.
In addition, since the compound having a specific hindered phenol structure has a hindered phenol-based skeleton, the ability to capture cation radicals is not extremely high as compared with a case where the compound has a phenol skeleton in which a hydrogen atom is bonded to one ortho position. In a case where the ability to capture cation radicals is extremely high, the compound is deactivated quickly, the cation radicals in the photosensitive layer are likely to remain, and thus burn-in ghosts are likely to occur. Therefore, in the present exemplary embodiment, the occurrence of burn-in ghosts is considered to be suppressed as compared with a case where a compound having a phenol skeleton in which a hydrogen atom is bonded to one ortho position is used.
In addition, the specific compound having a hindered phenol-based skeleton has a higher ability to capture cation radicals as compared with a compound having a phenol skeleton in which a tertiary carbon atom or a quaternary carbon atom is bonded to both ortho positions. Therefore, in the present exemplary embodiment, the occurrence of burn-in ghosts is considered to be suppressed as compared with a case where a compound having a phenol skeleton in which a tertiary carbon atom or a quaternary carbon atom is bonded to both ortho positions is used.
For the above-described reasons, it is assumed that the burn-in ghosts are unlikely to occur and the filming is suppressed in the photoreceptor according to the present exemplary embodiment.
Hereinafter, the polyester resin having a dicarboxylic acid unit (A), the specific compound, and each layer of the photoreceptor will be described in detail.
Polyester Resin Having Dicarboxylic Acid Unit (A)
The polyester resin having a dicarboxylic acid unit (A) is not particularly limited as long as the polyester resin has a dicarboxylic acid unit (A). Hereinafter, the polyester resin having a dicarboxylic acid unit (A) will also be referred to as “specific polyester resin”.
The specific polyester resin may have only one or two or more kinds of dicarboxylic acid units (A).
As the polyester resin having a dicarboxylic acid unit (A), for example, a polyester resin (1) having at least a dicarboxylic acid unit (A) and a diol unit (B) is preferable. The polyester resin (1) may have other dicarboxylic acid units in addition to the dicarboxylic acid unit (A). The polyester resin (1) may have other diol units in addition to the diol unit (B).
The dicarboxylic acid unit (A) is a constitutional unit represented by Formula (A).
In Formula (A), ArA1 and ArA2 each independently represent an aromatic ring that may have a substituent, LA represents a single bond or a divalent linking group, and nA1 represents 0, 1, or 2.
The aromatic ring as ArA1 may be any of a monocycle or a polycycle. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Among these, for example, a benzene ring and a naphthalene ring are preferable.
The hydrogen atom on the aromatic ring as ArA1 may be substituted with an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or the like. As the substituent in a case where the aromatic ring as ArA1 is substituted, for example, an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, and an alkoxy group having 1 or more and 6 or less carbon atoms are preferable.
The aromatic ring of ArA2 may be any of a monocycle or a polycycle. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Among these, for example, a benzene ring and a naphthalene ring are preferable.
The hydrogen atom on the aromatic ring as ArA2 may be substituted with an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or the like. As the substituent in a case where the aromatic ring as ArA2 is substituted, for example, an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, and an alkoxy group having 1 or more and 6 or less carbon atoms are preferable.
In a case where LA represents a divalent linking group, examples of the divalent linking group include an oxygen atom, a sulfur atom, and —C(Ra1)(Ra2)—. Here, Ra1 and Ra2 each independently represent a hydrogen atom, an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, or an aralkyl group having 7 or more and 20 or less carbon atoms, and Ra1 and Ra2 may be bonded to each other to form a cyclic alkyl group.
The alkyl group having 1 or more and 10 or less carbon atoms as Ra1 and Ra2 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and still more preferably 1 or 2.
The aryl group having 6 or more and 12 or less carbon atoms as Ra1 and Ra2 may be any of a monocycle or a polycycle. The number of carbon atoms of the aryl group is, for example, preferably 6 or more and 10 or less and more preferably 6.
The alkyl group in the aralkyl group having 7 or more and 20 or less carbon atoms as Ra1 and Ra2 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the aralkyl group having 7 or more and 20 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2.
The aryl group in the aralkyl group having 7 or more and 20 or less carbon atoms as Ra1 and Ra2 may be any of a monocycle or a polycycle. The number of carbon atoms of the aryl group is, for example, preferably 6 or more and 10 or less and more preferably 6.
It is preferable that the dicarboxylic acid unit (A) includes, for example, at least one selected from the group consisting of a dicarboxylic acid unit (A1) represented by Formula (A1), a dicarboxylic acid unit (A2) represented by Formula (A2), a dicarboxylic acid unit (A3) represented by Formula (A3), a dicarboxylic acid unit (A4) represented Formula (A4), and a dicarboxylic acid unit (A5) represented Formula (A5).
In Formula (A1), n101 represents an integer of 0 or greater and 4 or less, and n101 number of Ra101's each independently represent an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, or an alkoxy group having 1 or more and 6 or less carbon atoms.
In Formula (A2), n201 and n202 each independently represent an integer of 0 or greater and 4 or less, and n201 number of Ra201's and n202 number of Ra202's each independently represent an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, or an alkoxy group having 1 or more and 6 or less carbon atoms.
In Formula (A3), n301 and n302 each independently represent an integer of 0 or greater and 4 or less, and n301 number of Ra301's and n302 number of Ra302's each independently represent an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, or an alkoxy group having 1 or more and 6 or less carbon atoms.
In Formula (A4), n401 represents an integer of 0 or greater and 6 or less, and n401 number of Ra401's each independently represent an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, or an alkoxy group having 1 or more and 6 or less carbon atoms.
In Formula (A5), n501, n502, and n503 each independently represent an integer of 0 or greater and 4 or less, and n501 number of Ra501's, n502 number of Ra502's, and n503 number of Ra503's each independently represent an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, or an alkoxy group having 1 or more and 6 or less carbon atoms.
The specific forms and the preferable forms of Ra101 in Formula (A1), Ra201 and Ra202 in Formula (A2), Ra301 and Ra302 in Formula (A3), Ra401 in Formula (A4), and Ra501, Ra502, and Ra503 in Formula (A5) are the same as each other, and hereinafter, Ra401, Ra201, Ra202, Ra301, Ra302, Ra401, Ra501, Ra502, and Ra503 will be collectively referred to as “Ra”.
The alkyl group having 1 or more and 10 or less carbon atoms as Ra may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and still more preferably 1 or 2.
Examples of the linear alkyl group having 1 or more and 10 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.
Examples of the branched alkyl group having 3 or more and 10 or less carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an isodecyl group, a sec-decyl group, and a tert-decyl group.
Examples of the cyclic alkyl group having 3 or more and 10 or less carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and polycyclic (for example, bicyclic, tricyclic, or spirocyclic) alkyl groups to which these monocyclic alkyl groups are linked.
The aryl group having 6 or more and 12 or less carbon atoms as Ra may be any of a monocycle or a polycycle. The number of carbon atoms of the aryl group is, for example, preferably 6 or more and 10 or less and more preferably 6.
Examples of the aryl group having 6 or more and 12 or less carbon atoms include a phenyl group, a biphenyl group, a 1-naphthyl group, and a 2-naphthyl group.
The alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms as Ra may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2.
Examples of the linear alkoxy group having 1 or more and 6 or less carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, and an n-hexyloxy group.
Examples of the branched alkoxy group having 3 or more and 6 or less carbon atoms include an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, an isohexyloxy group, a sec-hexyloxy group, and a tert-hexyloxy group.
Examples of the cyclic alkoxy group having 3 or more and 6 or less carbon atoms include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.
Hereinafter, dicarboxylic acid units (A1-1) to (A1-9) are shown as specific examples of the dicarboxylic acid unit (A1). The dicarboxylic acid unit (A1) is not limited thereto.
Hereinafter, dicarboxylic acid units (A2-1) to (A2-5) are shown as specific examples of the dicarboxylic acid unit (A2). The dicarboxylic acid unit (A2) is not limited thereto.
Hereinafter, dicarboxylic acid units (A3-1) and (A3-2) are shown as specific examples of the dicarboxylic acid unit (A3). The dicarboxylic acid unit (A3) is not limited thereto.
Hereinafter, dicarboxylic acid units (A4-1) to (A4-3) are shown as specific examples of the dicarboxylic acid unit (A4). The dicarboxylic acid unit (A4) is not limited thereto.
Hereinafter, dicarboxylic acid units (A5-1) to (A5-4) are shown as specific examples of the dicarboxylic acid unit (A5). The dicarboxylic acid unit (A5) is not limited thereto.
As the dicarboxylic acid unit (A), for example, (A1-1), (A1-7), (A2-3), (A2-4), (A3-2), and (A4-3) in the specific examples shown above are preferable, (A2-3) and (A2-4) are more preferable, and (A2-3) is most preferable.
The total mass proportion of the dicarboxylic acid units (A1) to (A5) in the polyester resin (1) is, for example, preferably 15% by mass or greater and 60% by mass or less.
In a case where the total mass proportion of the dicarboxylic acid units (A1) to (A5) is 15% by mass or greater, the abrasion resistance of the photosensitive layer is enhanced. From this viewpoint, the total mass proportion of the dicarboxylic acid units (A1) to (A5) is, for example, more preferably 20% by mass or greater and still more preferably 25% by mass or greater.
In a case where the total mass proportion of the dicarboxylic acid units (A1) to (A5) is 60% by mass or less, peeling of the photosensitive layer can be suppressed. From this viewpoint, the total mass proportion of the dicarboxylic acid units (A1) to (A5) is, for example, more preferably 55% by mass or less and still more preferably 50% by mass or less.
The dicarboxylic acid units (A1) to (A5) contained in the polyester resin (1) may be used alone or in combination of two or more kinds thereof.
Examples of other dicarboxylic acid units (A) in addition to the dicarboxylic acid units (A1) to (A5) include aliphatic dicarboxylic acid (such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenyl succinic acid, adipic acid, and sebacic acid) units, alicyclic dicarboxylic acid (such as cyclohexanedicarboxylic acid) units, and lower (for example, having 1 or more and 5 or less carbon atoms) alkyl ester units thereof.
These dicarboxylic acid units contained in the polyester resin (1) may be used alone or in combination of two or more kinds thereof.
The dicarboxylic acid unit (A) contained in the polyester resin (1) may be used alone or in combination of two or more kinds thereof.
The diol unit (B) is a constitutional unit represented by Formula (B).
In Formula (B), ArB1 and ArB2 each independently represent an aromatic ring that may have a substituent, LB represents a single bond, an oxygen atom, a sulfur atom, or —C(Rb1)(Rb2)—, and nB1 represents 0, 1, or 2. Rb1 and Rb2 each independently represent a hydrogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, or an aralkyl group having 7 or more and 20 or less carbon atoms, and Rb1 and Rb2 may be bonded to each other to form a cyclic alkyl group.
The aromatic ring as ArB1 may be any of a monocycle or a polycycle. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Among these, for example, a benzene ring and a naphthalene ring are preferable.
The hydrogen atom on the aromatic ring as ArB1 may be substituted with an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or the like. As the substituent in a case where the aromatic ring as ArB1 is substituted, for example, an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, and an alkoxy group having 1 or more and 6 or less carbon atoms are preferable.
The aromatic ring as ArB2 may be any of a monocycle or a polycycle. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Among these, for example, a benzene ring and a naphthalene ring are preferable.
The hydrogen atom on the aromatic ring as ArB2 may be substituted with an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or the like. As the substituent in a case where the aromatic ring as ArB2 is substituted, for example, an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, and an alkoxy group having 1 or more and 6 or less carbon atoms are preferable.
The alkyl group having 1 or more and 20 or less carbon atoms as Rb1 and Rb2 may be linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 18 or less, more preferably 1 or more and 14 or less, and still more preferably 1 or more and 10 or less.
The aryl group having 6 or more and 12 or less carbon atoms as Rb1 and Rb2 may be any of a monocycle or a polycycle. The number of carbon atoms of the aryl group is, for example, preferably 6 or more and 10 or less and more preferably 6.
The alkyl group in the aralkyl group having 7 or more and 20 or less carbon atoms as Rb1 and Rb2 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the aralkyl group having 7 or more and 20 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2.
The aryl group in the aralkyl group having 7 or more and 20 or less carbon atoms as Rb1 and Rb2 may be any of a monocycle or a polycycle. The number of carbon atoms of the aryl group is, for example, preferably 6 or more and 10 or less and more preferably 6.
It is preferable that the diol unit (B) includes, for example, at least one selected from the group consisting of a diol unit (B1) represented by Formula (B1), a diol unit (B2) represented by Formula (B2), a diol unit (B3) represented by Formula (B3), a diol unit (B4) represented by Formula (B4), a diol unit (B5) represented by Formula (B5), a diol unit (B6) represented by Formula (B6), a diol unit (B7) represented by Formula (B7), and a diol unit (B8) represented by Formula (B8).
The diol unit (B) includes, for example, more preferably at least one selected from the group consisting of a diol unit (B1) represented by Formula (B1), a diol unit (B2) represented by Formula (B2), a diol unit (B4) represented by Formula (B4), a diol unit (B5) represented by Formula (B5), and a diol unit (B6) represented by Formula (B6), still more preferably at least one selected from the group consisting of a diol unit (B1) represented by Formula (B1), a diol unit (B2) represented by Formula (B2), a diol unit (B5) represented by Formula (B5), and a diol unit (B6) represented by Formula (B6), even still more preferably at least one selected from the group consisting of a diol unit (B1) represented by Formula (B1), a diol unit (B2) represented by Formula (B2), and a diol unit (B6) represented by Formula (B6), and most preferably at least one selected from the group consisting of a diol unit (B1) represented by Formula (B1) and a diol unit (B2) represented by Formula (B2).
In Formula (B1), Rb101 represents a branched alkyl group having 4 or more and 20 or less carbon atoms, Rb201 represents a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms, and Rb401, Rb501, Rb801, and Rb901 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.
The number of carbon atoms of the branched alkyl group having 4 or more and 20 or less carbon atoms as Rb101 is, for example, preferably 4 or more and 16 or less, more preferably 4 or more and 12 or less, and still more preferably 4 or more and 8 or less. Specific examples of Rb101 include an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an isodecyl group, a sec-decyl group, a tert-decyl group, an isododecyl group, a sec-dodecyl group, a tert-dodecyl group, a tert-tetradecyl group, and a tert-pentadecyl group.
In Formula (B2), Rb102 represents a linear alkyl group having 4 or more and 20 or less carbon atoms, Rb202 represents a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms, and Rb402, Rb502, Rb802, and Rb902 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.
The number of carbon atoms of the linear alkyl group having 4 or more and 20 or less carbon atoms as Rb102 is, for example, preferably 4 or more and 16 or less, more preferably 4 or more and 12 or less, and still more preferably 4 or more and 8 or less. Specific examples of Rb102 include an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, a tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group.
In Formula (B3), Rb113 and Rb213 each independently represent a hydrogen atom, a linear alkyl group having 1 or more and 3 or less carbon atoms, an alkoxy group having 1 or more and 4 or less carbon atoms, or a halogen atom, d represents an integer of 7 or greater and 15 or less, and Rb403, Rb503, Rb803, and Rb903 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.
The number of carbon atoms of the linear alkyl group having 1 or more and 3 or less carbon atoms as Rb113 and Rb213 is, for example, preferably 1 or 2 and more preferably 1. Specific examples of such a group include a methyl group, an ethyl group, and an n-propyl group.
The alkyl group in the alkoxy group having 1 or more and 4 or less carbon atoms as Rb113 and Rb213 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the alkoxy group having 1 or more and 4 or less carbon atoms is, for example, preferably 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 1. Specific examples of such a group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a cyclopropoxy group, and a cyclobutoxy group.
Examples of the halogen atom as Rb113 and Rb213 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In Formula (B4), Rb104 and Rb204 each independently represent a hydrogen atom, an alkyl group having 1 or more and 3 or less carbon atoms, and Rb404, Rb504, Rb804, and Rb904 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.
The alkyl group having 1 or more and 3 or less carbon atoms as Rb104 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or 2 and more preferably 1. Specific examples of Rb104 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a cyclopropyl group.
In Formula (B5), Ar105 represents an aryl group having 6 or more and 12 or less carbon atoms or an aralkyl group having 7 or more and 20 or less carbon atoms, Rb205 represents a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms, and Rb405, Rb505, Rb805, and Rb905 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.
The aryl group having 6 or more and 12 or less carbon atoms as Ar105 may be any of a monocycle or a polycycle. The number of carbon atoms of the aryl group is, for example, preferably 6 or more and 10 or less and more preferably 6.
The alkyl group in the aralkyl group having 7 or more and 20 or less carbon atoms as Ar105 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the aralkyl group having 7 or more and 20 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2. The aryl group in the aralkyl group having 7 or more and 20 or less carbon atoms as Ar105 may be any of a monocycle or a polycycle. The number of carbon atoms of the aryl group is, for example, preferably 6 or more and 10 or less and more preferably 6. Examples of the aralkyl group having 7 or more and 20 or less carbon atoms include a benzyl group, a phenylethyl group, a phenylpropyl group, a 4-phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a phenylheptyl group, a phenyloctyl group, a phenylnonyl group, a naphthylmethyl group, a naphthylethyl group, an anthracenylmethyl group, and a phenyl-cyclopentylmethyl group.
In Formula (B6), Rb116 and Rb216 each independently represent a hydrogen atom, a linear alkyl group having 1 or more and 3 or less carbon atoms, an alkoxy group having 1 or more and 4 or less carbon atoms, or a halogen atom, e represents 5 or 6, and Rb406, Rb506, Rb806, and Rb906 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.
The number of carbon atoms of the linear alkyl group having 1 or more and 3 or less carbon atoms as Rb116 and Rb216 is, for example, preferably 1 or 2 and more preferably 1. Specific examples of such a group include a methyl group, an ethyl group, and an n-propyl group.
The alkyl group in the alkoxy group having 1 or more and 4 or less carbon atoms as Rb116 and Rb216 may be linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the alkoxy group having 1 or more and 4 or less carbon atoms is, for example, preferably 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 1. Specific examples of such a group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a cyclopropoxy group, and a cyclobutoxy group.
Examples of the halogen atom as Rb116 and Rb216 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In Formula (B7), Rb407, Rb507, Rb807, and Rb907 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.
In Formula (B8), Rb408, Rb508, Rb808, and Rb908 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.
The specific forms and the preferable forms of Rb201 in Formula (B1), Rb202 in Formula (B2), Rb204 in Formula (B4), and Rb205 in Formula (B5) are the same as each other, and hereinafter, Rb201, Rb202, Rb204, and Rb205 will be collectively referred to as “Rb200”.
The alkyl group having 1 or more and 3 or less carbon atoms as Rb200 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or 2 and more preferably 1.
The alkyl group having 1 or more and 3 or less carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a cyclopropyl group.
The specific forms and the preferable forms of Rb401 in Formula (B1), Rb402 in Formula (B2), Rb403 in Formula (B3), Rb404 in Formula (B4), Rb405 in Formula (B5), Rb406 in Formula (B6), Rb407 in Formula (B7), and Rb408 in Formula (B8) are the same as each other, and hereinafter, Rb401, Rb402, Rb403, Rb404, Rb405, Rb406, Rb407, and Rb408 will be collectively referred to as “Rb400”.
The alkyl group having 1 or more and 4 or less carbon atoms as Rb400 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 1.
Examples of the linear alkyl group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.
Examples of the branched alkyl group having 3 or 4 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
Examples of the cyclic alkyl group having 3 or 4 carbon atoms include a cyclopropyl group and a cyclobutyl group.
The alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms as Rb400 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2.
Examples of the linear alkoxy group having 1 or more and 6 or less carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, and an n-hexyloxy group.
Examples of the branched alkoxy group having 3 or more and 6 or less carbon atoms include an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, an isohexyloxy group, a sec-hexyloxy group, and a tert-hexyloxy group.
Examples of the cyclic alkoxy group having 3 or more and 6 or less carbon atoms include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.
Examples of the halogen atom as Rb400 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The specific forms and the preferable forms of Rb501 in Formula (B1), Rb502 in Formula (B2), Rb503 in Formula (B3), Rb504 in Formula (B4), Rb505 in Formula (B5), Rb506 in Formula (B6), Rb507 in Formula (B7), and Rb508 in Formula (B8) are the same as each other, and hereinafter, Rb501, Rb502, Rb503, Rb504, Rb505, Rb506, Rb507, and Rb508 will be collectively referred to as “Rb500”.
The alkyl group having 1 or more and 4 or less carbon atoms as Rb500 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 1.
Examples of the linear alkyl group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.
Examples of the branched alkyl group having 3 or 4 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
Examples of the cyclic alkyl group having 3 or 4 carbon atoms include a cyclopropyl group and a cyclobutyl group.
The alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms as Rb500 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2.
Examples of the linear alkoxy group having 1 or more and 6 or less carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, and an n-hexyloxy group.
Examples of the branched alkoxy group having 3 or more and 6 or less carbon atoms include an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, an isohexyloxy group, a sec-hexyloxy group, and a tert-hexyloxy group.
Examples of the cyclic alkoxy group having 3 or more and 6 or less carbon atoms include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.
Examples of the halogen atom as Rb500 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The specific forms and the preferable forms of Rb801 in Formula (B1), Rb802 in Formula (B2), Rb803 in Formula (B3), Rb804 in Formula (B4), Rb805 in Formula (B5), Rb806 in Formula (B6), Rb807 in Formula (B7), and Rb808 in Formula (B8) are the same as each other, and hereinafter, Rb801, Rb802, Rb803, Rb804, Rb805, Rb806, Rb807, and Rb808 will be collectively referred to as “Rb800”.
The alkyl group having 1 or more and 4 or less carbon atoms as Rb800 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 1.
Examples of the linear alkyl group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.
Examples of the branched alkyl group having 3 or 4 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
Examples of the cyclic alkyl group having 3 or 4 carbon atoms include a cyclopropyl group and a cyclobutyl group.
The alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms as Rb800 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2.
Examples of the linear alkoxy group having 1 or more and 6 or less carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, and an n-hexyloxy group.
Examples of the branched alkoxy group having 3 or more and 6 or less carbon atoms include an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, an isohexyloxy group, a sec-hexyloxy group, and a tert-hexyloxy group.
Examples of the cyclic alkoxy group having 3 or more and 6 or less carbon atoms include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.
Examples of the halogen atom as Rb800 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The specific forms and the preferable forms of Rb901 in Formula (B1), Rb902 in Formula (B2), Rb903 in Formula (B3), Rb904 in Formula (B4), Rb905 in Formula (B5), Rb906 in Formula (B6), Rb907 in Formula (B7), and Rb908 in Formula (B8) are the same as each other, and hereinafter, Rb901, Rb902, Rb903, Rb904, Rb905, Rb906, Rb907, and Rb908 will be collectively referred to as “Rb900”.
The alkyl group having 1 or more and 4 or less carbon atoms as Rb900 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 1.
Examples of the linear alkyl group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.
Examples of the branched alkyl group having 3 or 4 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
Examples of the cyclic alkyl group having 3 or 4 carbon atoms include a cyclopropyl group and a cyclobutyl group.
The alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms as Rb900 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2.
Examples of the linear alkoxy group having 1 or more and 6 or less carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, and an n-hexyloxy group.
Examples of the branched alkoxy group having 3 or more and 6 or less carbon atoms include an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, an isohexyloxy group, a sec-hexyloxy group, and a tert-hexyloxy group.
Examples of the cyclic alkoxy group having 3 or more and 6 or less carbon atoms include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.
Examples of the halogen atom as Rb900 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Hereinafter, diol units (B1-1) to (B1-6) are shown as specific examples of the diol unit (B1). The diol unit (B1) is not limited thereto.
Hereinafter, diol units (B2-1) to (B2-11) are shown as specific examples of the diol unit (B2). The diol unit (B2) is not limited thereto.
Hereinafter, diol units (B3-1) to (B3-4) are shown as specific examples of the diol unit (B3). The diol unit (B3) is not limited thereto.
Hereinafter, diol units (B4-1) to (B4-7) are shown as specific examples of the diol unit (B4). The diol unit (B4) is not limited thereto.
Hereinafter, diol units (B5-1) to (B5-6) are shown as specific examples of the diol unit (B5). The diol unit (B5) is not limited thereto.
Hereinafter, diol units (B6-1) to (B6-4) are shown as specific examples of the diol unit (B6). The diol unit (B6) is not limited thereto.
Hereinafter, diol units (B7-1) to (B7-3) are shown as specific examples of the diol unit (B7). The diol unit (B7) is not limited thereto.
Hereinafter, diol units (B8-1) to (B8-3) are shown as specific examples of the diol unit (B8). The diol unit (B8) is not limited thereto.
The diol unit (B) contained in the polyester resin (1) may be used alone or in combination of two or more kinds thereof.
The mass proportion of the diol unit (B) in the polyester resin (1) is, for example, preferably 25% by mass or greater and 80% by mass or less.
In a case where the mass proportion of the diol unit (B) is 25% by mass or greater, peeling of the photosensitive layer can be further suppressed. From this viewpoint, the mass proportion of the diol unit (B) is, for example, more preferably 30% by mass or greater and still more preferably 35% by mass or greater.
In a case where the mass proportion of the diol unit (B) is 80% by mass or less, the solubility in a coating solution for forming the photosensitive layer is maintained, and thus the abrasion resistance can be improved. From this viewpoint, the mass proportion of the diol unit (B) is, for example, more preferably 75% by mass or less and still more preferably 70% by mass or less.
Examples of other diol units in addition to the diol unit (B) include aliphatic diol (such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, and neopentyl glycol) units and alicyclic diol (such as cyclohexanediol, cyclohexane dimethanol, and hydrogenated bisphenol A) units. These diol units contained in the polyester resin (1) may be used alone or in combination of two or more kinds thereof.
A terminal of the polyester resin (1) may be sealed or modified with a terminal-sealing agent, a molecular weight modifier, or the like used in a case of the production. Examples of the terminal-sealing agent or the molecular weight modifier include monohydric phenol, monovalent acid chloride, monohydric alcohol, and monovalent carboxylic acid.
Examples of the monohydric phenol include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-propylphenol, m-propylphenol, p-propylphenol, o-tert-butylphenol, m-tert-butylphenol, p-tert-butylphenol, pentylphenol, hexylphenol, octylphenol, nonylphenol, a 2,6-dimethylphenol derivative, a 2-methylphenol derivative, o-phenylphenol, m-phenylphenol, p-phenylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, 2,3,6-trimethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2-phenyl-2-(4-hydroxyphenyl)propane, 2-phenyl-2-(2-hydroxyphenyl)propane, and 2-phenyl-2-(3-hydroxyphenyl)propane.
Examples of the monovalent acid chloride include monofunctional acid halides such as benzoyl chloride, benzoic acid chloride, methanesulfonyl chloride, phenylchloroformate, acetic acid chloride, butyric acid chloride, octyl acid chloride, benzenesulfonyl chloride, benzenesulfinyl chloride, sulfinyl chloride, benzene phosphonyl chloride, and substituents thereof.
Examples of the monohydric alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, and phenethyl alcohol.
Examples of the monovalent carboxylic acid include acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butylbenzoic acid, and p-methoxyphenylacetic acid.
The weight-average molecular weight of the polyester resin (1) is, for example, preferably 30,000 or greater and 300,000 or less, more preferably 40,000 or greater and 250,000 or less, and still more preferably 50,000 or greater and 200,000 or less.
The molecular weight of the polyester resin (1) is a molecular weight measured by gel permeation chromatography (GPC) in terms of polystyrene. The GPC is carried out by using tetrahydrofuran as an eluent.
Examples of the method of producing the polyester resin (1) include an interfacial polymerization method, a solution polymerization method, and a melt polymerization method.
Compound Having Specific Hindered Phenol Structure
The compound having a specific hindered phenol structure is a compound having a molecular weight of 255 or greater, a hindered phenol-based skeleton, and no linear alkylene structure having 4 or more carbon atoms.
The molecular weight of the specific compound is 255 or greater, for example, preferably 255 or greater and 1,200 or less, more preferably 300 or greater and 980 or less, and still more preferably greater than 350 and 750 or less from the viewpoint of suppressing both filming and burn-in ghosts.
The hindered phenol-based skeleton is a phenol skeleton in which a primary carbon atom or a secondary carbon atom is bonded to one ortho position and a tertiary carbon atom or a quaternary carbon atom is bonded to the other ortho position.
The atom bonded to the meta position of the hindered phenol-based skeleton is not particularly limited, and examples thereof include a hydrogen atom, a primary carbon atom, a secondary carbon atom, a tertiary carbon atom, and a quaternary carbon atom. Among these, for example, a hydrogen atom or a primary carbon atom is preferable, and a hydrogen atom is more preferable. The atoms bonded to the two meta positions may be the same as or different from each other.
The atom bonded to the para position of the hindered phenol-based skeleton is not particularly limited, and examples thereof include a hydrogen atom, a primary carbon atom, a secondary carbon atom, a tertiary carbon atom, and a quaternary carbon atom. Among these, for example, a hydrogen atom, a primary carbon atom, or a secondary carbon atom is preferable, and a primary carbon atom or a secondary carbon atom is more preferable.
Examples of the compound having a hindered phenol-based skeleton include a compound represented by Formula (C).
In Formula (C), Rc001 represents a monovalent organic group in which the atom directly linked to a benzene ring is a primary carbon atom or a secondary carbon atom, Rc002 represents a monovalent organic group in which the atom directly linked to a benzene ring is a tertiary carbon atom or a quaternary carbon atom, Rc003 and Rc004 each independently represent a hydrogen atom or an alkyl group, Rc005 represents a monovalent organic group or a hydrogen atom in which the atom directly linked to a benzene ring is a carbon atom, and none of Rc001 to Rc005 has a linear alkylene structure having 4 or more carbon atoms.
Rc001 may represent a monovalent organic group in which the atom directly linked to a benzene ring is a primary carbon atom or a secondary carbon atom and which does not have a linear alkylene structure having 4 or more carbon atoms, and examples thereof include a group represented by Formula (C001).
In Formula (C001), * represents a bonding position with respect to the ortho position of the benzene ring in Formula (C), Rc011 represents a hydrogen atom or a monovalent organic group, and Rc011 does not have a linear alkylene structure having 3 or more carbon atoms.
The monovalent organic group represented by Rc011 may have a heteroatom. Here, in the monovalent organic group represented by Rc011, for example, it is preferable that the atom directly linked to the carbon atom in Formula (C001) is a carbon atom. Examples of the heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom. As the monovalent organic group represented by Rc011, for example, a group consisting of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a hydrogen atom is preferable, a group consisting of a carbon atom, an oxygen atom, and a hydrogen atom is more preferable, and a group consisting of a carbon atom and a hydrogen atom is still more preferable. Further, the monovalent organic group represented by Rc011 may have an aromatic ring and a hindered phenol-based skeleton.
Examples of Rc011 include a hydrogen atom, an alkyl group which may have a heteroatom between carbon atoms, and a group having a hindered phenol-based skeleton. Among these, a hydrogen atom, a methyl group, an ethyl group, or a group having a hindered phenol-based skeleton is preferable, a hydrogen atom, a methyl group, or a group having a hindered phenol-based skeleton is more preferable, and a hydrogen atom or a group having a group having a hindered phenol-based skeleton is still more preferable.
Rc001 represents, for example, preferably a methyl group, an ethyl group, or a group having a hindered phenol-based skeleton and more preferably a methyl group or a group having a hindered phenol-based skeleton.
Rc002 represents a monovalent organic group in which the atom directly linked to a benzene ring is a tertiary carbon atom or a quaternary carbon atom and may represent a group that does not have a linear alkylene structure having 4 or more carbon atoms, and examples thereof include a group represented by Formula (C002).
In Formula (C002), * represents a bonding position with respect to the ortho position of the benzene ring in Formula (C), Rc012 and Rc022 each independently represent a monovalent organic group, Rc012 and Rc022 may be bonded to each other to form a ring, Rc032 represents a monovalent organic group or a hydrogen atom, and none of Rc012, Rc022, and Rc033 has a linear alkylene structure having 3 or more carbon atoms.
The monovalent organic group represented by Rc012, Rc022, or Rc032 may have a heteroatom. Here, in the monovalent organic group represented by Rc012, Rc022, or Rc032, for example, it is preferable that the atom directly linked to the carbon atom in Formula (C002) is a carbon atom. Examples of the heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom. The monovalent organic group represented by Rc012, Rc022, or Rc032 is, for example, preferably a group consisting of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a hydrogen atom, more preferably a group consisting of a carbon atom, an oxygen atom, and a hydrogen atom, and still more preferably a group consisting of a carbon atom and a hydrogen atom.
In Formula (C005), * represents a bonding position with respect to the para position of the benzene ring in Formula (C), Rc015 and Rc025 each independently represent a hydrogen atom or a monovalent organic group, and both Rc015 and Rc025 do not have a linear alkylene structure having 3 or more carbon atoms.
The monovalent organic group represented by Rc015 or Rc025 may each independently have a heteroatom. Here, in the monovalent organic group represented by Rc015 or Rc025, for example, it is preferable that the atom directly linked to the carbon atom in Formula (C005) is a carbon atom. Examples of the heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom. As the monovalent organic group represented by Rc015 or Rc025, for example, a group consisting of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a hydrogen atom is preferable, a group consisting of a carbon atom, an oxygen atom, and a hydrogen atom is more preferable, and a group consisting of a carbon atom and a hydrogen atom is still more preferable. Further, the monovalent organic groups represented by Rc015 or Rc021 may each independently have an aromatic ring or a hindered phenol-based skeleton.
Rc015 and Rc025 each independently represent, for example, a hydrogen atom, an alkyl group that may have a heteroatom between carbon atoms, a group having a hindered phenol-based skeleton, or the like, preferably a hydrogen atom, a methyl group, an ethyl group, or a group having a hindered phenol-based skeleton, more preferably a hydrogen atom, a methyl group, or a group having a hindered phenol-based skeleton, and still more preferably a hydrogen atom or a group having a hindered phenol-based skeleton.
Rc005 represents, for example, preferably a hydrogen atom, an alkyl group that may have a heteroatom between carbon atoms, or a group having a hindered phenol-based skeleton, more preferably a hydrogen atom, a methyl group, an ethyl group, or a group having a hindered phenol-based skeleton, and still more preferably a methyl group or a group having a hindered phenol-based skeleton.
From the viewpoint of suppressing burn-in ghosts, it is preferable that the specific compound has, for example, two or more hindered phenol-based skeletons in one molecule.
The number of hindered phenol-based skeletons in one molecule of the specific compound is, for example, 2 or more and 4 or less, preferably 2 or more and 3 or less, and more preferably 2.
In a case where the specific compound has two or more hindered phenol-based skeletons in one molecule, any of the ortho position, the meta position, or the para position of one hindered phenol-based skeleton may be bonded to another hindered phenol-based skeleton via a linking group. Among these, for example, it is preferable that the ortho position or the para position of one hindered phenol-based skeleton is bonded to another hindered phenol-based skeleton via a linking group. The bonding positions in the two or more hindered phenol-based skeletons may be the same as or different from each other. That is, in the two or more hindered phenol-based skeletons, the ortho positions may be bonded to each other via a linking group, the para positions may be bonded to each other via a linking group, or the ortho position of one hindered phenol-based skeleton may be bonded to the para position of another hindered phenol-based skeleton via a linking group.
The linking group that links two or more phenol skeletons is not particularly limited as long as the linking group does not have a linear alkylene structure having four or more carbon atoms, and examples thereof include a linear or branched divalent or higher valent and tetravalent or lower valent aliphatic hydrocarbon group, a cyclic divalent or higher valent and tetravalent or lower valent aliphatic hydrocarbon group, an ester bond (—C(═O)O—), an ether bond (—O—), an aromatic ring, an isocyanurate ring, and a combination thereof.
Among these, as the linking group that links two or more phenol skeletons, for example, a linking group consisting of a linear or branched divalent or higher valent and tetravalent or lower valent aliphatic hydrocarbon group, a linking group in which at least one of an ester bond (—C(═O)O—) or an ether bond (—O—) is sandwiched between carbon-carbon bonds of a divalent or higher valent and tetravalent or lower valent aliphatic hydrocarbon group, a combination of a divalent or higher valent and tetravalent or lower valent aliphatic hydrocarbon group and an aromatic ring, and a combination of a divalent or higher valent and tetravalent or lower valent aliphatic hydrocarbon group and an isocyanurate ring are preferable, a linking group consisting of a linear or branched divalent or higher valent and tetravalent or lower valent aliphatic hydrocarbon group and a linking group in which at least one of an ester bond (—C(═O)O—) or an ether bond (—O—) is sandwiched between carbon-carbon bonds of a divalent or higher valent and tetravalent or lower valent aliphatic hydrocarbon group are more preferable.
In a case where the specific compound has two or more hindered phenol-based skeletons in one molecule, it is preferable that the two or more phenol skeletons have, for example, at least one of a structure in which the ortho position of the first phenol skeleton is bonded to the ortho position of the second phenol skeleton via an alkylene group having 1 to 3 carbon atoms or a structure in which the para position of the first phenol skeleton is bonded to the para position of the second phenol skeleton via a divalent linking group.
The specific compound is, for example, more preferably a compound represented by Formula (C1), Formula (C2), or Formula (C3) and still more preferably a compound represented by Formula (C1) or Formula (C2).
In Formulae (C1), (C2), and (C3), Rc201, Rc211, Rc301, Rc311, and Rc321 each independently represent a monovalent organic group in which an atom directly linked to a benzene ring is a primary carbon atom or a secondary carbon atom, Rc102, Rc112, Rc202, Rc212, Rc302, Rc312, and Rc322 each independently represent a monovalent organic group in which an atom directly linked to a benzene ring is a tertiary carbon atom or a quaternary carbon atom, Rc103, Rc104, Rc113, Rc114, Rc203, Rc204, Rc213, Rc214, Rc303, Rc304, Rc313, Rc314, Rc323, and Rc324 each independently represent a hydrogen atom or an alkyl group, Rc105 and Rc115 each independently represent a hydrogen atom or a monovalent organic group in which an atom directly linked to a benzene ring is a carbon atom, nc1 represents an integer of 1 or greater and 3 or less, Lc200 represents a divalent linking group, Lc300 represents a trivalent linking group, and none of Rc102 to Rc105, Rc112 to Rc115, Rc201 to Rc204, Rc211 to Rc214, Rc301 to Rc304, Rc311 to Rc314, Rc321 to Rc324, Lc200, and Lc300 does not have a linear alkylene structure having 4 or more carbon atoms.
Specific examples and preferable groups of Rc201, Rc211, Rc301, Rc311, and Rc321 are the same as the specific examples and the preferable groups of Rc001 described above.
Specific examples and preferable groups of Rc102, Rc112, Rc202, Rc212, Rc302, Rc312, and Rc322 are the same as the specific examples and the preferable groups of Rc002 described above.
Specific examples and preferable groups of Rc103, Rc104, Rc113, Rc114, Rc203, Rc204, Rc213, Rc214, Rc303, Rc304, Rc313, Rc314, Rc323, and Rc324 are the same as the specific examples and the preferable groups of Rc003 and Rc004 described above.
Specific examples and preferable groups of Rc105 and Rc115 are the same as the specific examples and the preferable groups of Rc005 described above.
nc1 represents an integer of 1 or greater and 3 or less, for example, preferably 1 or greater and 2 or less, and more preferably 1.
The divalent linking group represented by Lc200 is not particularly limited as long as the group is a divalent linking group and does not have a linear alkylene structure having 4 or more carbon atoms.
Examples of the divalent linking group represented by Lc200 include a linear or branched divalent aliphatic hydrocarbon group, a cyclic divalent aliphatic hydrocarbon group, an ester bond (—C(═O)O—), an ether bond (—O—), an aromatic ring, an isocyanurate ring, and a combination thereof.
As the divalent linking group represented by Lc200, for example, a linking group consisting of a linear or branched divalent aliphatic hydrocarbon group, a linking group in which at least one of an ester bond (—C(═O)O—) or an ether bond (—O—) is sandwiched between carbon-carbon bonds of a divalent aliphatic hydrocarbon group, and a combination of a divalent aliphatic hydrocarbon group and an aromatic ring are preferable, and a linking group consisting of a linear or branched divalent aliphatic hydrocarbon group and a linking group in which at least one of an ester bond (—C(═O)O—) or an ether bond (—O—) is sandwiched between carbon-carbon bonds of a divalent aliphatic hydrocarbon group are more preferable.
Specific examples of the divalent linking group represented by Lc200 include linking groups represented by Formulae (Lc2-1) to (Lc2-6). In the following formulae, * represents a bonding position with respect to the para position of the benzene ring in Formula (C2), and nc21, nc22, nc23, nc24, nc25, nc26, nc27, nc28, nc29, and nc30 each independently represent an integer of 1 or greater and 3 or less. The divalent linking group represented by Lc200 is not limited thereto.
The trivalent linking group represented by Lc300 is not particularly limited as long as the group is a trivalent linking group and does not have a linear alkylene structure having 4 or more carbon atoms.
Examples of the trivalent linking group represented by Lc300 include a trivalent aliphatic hydrocarbon group, an ester bond (—C(═O)O—), an ether bond (—O—), an aromatic ring, an isocyanurate ring, and a combination thereof.
As the trivalent linking group represented by Lc300, for example, a linking group consisting of a trivalent aliphatic hydrocarbon group, a linking group in which at least one of an ester bond (—C(═O)O—) or an ether bond (—O—) is sandwiched between carbon-carbon bonds of a trivalent aliphatic hydrocarbon group, a combination of a trivalent aliphatic hydrocarbon group and an aromatic ring, and a combination of a trivalent aliphatic hydrocarbon group and an isocyanurate ring are preferable, and a linking group consisting of a trivalent aliphatic hydrocarbon group, a combination of a trivalent aliphatic hydrocarbon group and an aromatic ring, and a combination of a trivalent aliphatic hydrocarbon group and an isocyanurate ring are more preferable.
Specific examples of the trivalent linking group represented by Lc300 include a trivalent alkylene group having 3 or more and 10 or less carbon atoms and a linking group represented by any of Formulae (Lc3-1) and (Lc3-2). In the following formulae, * represents a bonding position with respect to the para position of the benzene ring in Formula (C3), and nc31, nc32, nc33, nc34, nc35, and nc36 each independently represent an integer of 1 or greater and 3 or less. The trivalent linking group represented by Lc300 is not limited thereto.
Hereinafter, specific examples of the specific compound include specific compounds (C1-1) to (C1-12), (C2-1) to (C2-18), (C3-1) to (C3-9), and (C4-1) to (C4-3). The specific compound is not limited thereto.
The content of the compound having a specific hindered phenol structure in the charge transport layer of the photoreceptor according to the first exemplary embodiment is, for example, preferably 0.5% by mass or greater and 10.0% by mass or less, more preferably 1.5% by mass or greater and 7.5% by mass or less, and still more preferably 2.0% by mass or greater and 5.0% by mass or less with respect to the total content of the charge transport layer.
The content of the compound having a specific hindered phenol structure in the single layer type photosensitive layer of the photoreceptor according to the second exemplary embodiment is, for example, preferably 0.5% by mass or greater and 10.0% by mass or less, more preferably 1.5% by mass or greater and 7.5% by mass or less, and still more preferably 2.0% by mass or greater and 5.0% by mass or less with respect to the content of the single layer type photosensitive layer.
In a case where the content of the compound having a specific hindered phenol structure with respect to the total content of the photosensitive layer is in the above-described ranges, burn-in ghosts are suppressed as compared with a case where the content thereof is lower than the above-described ranges, and filming is suppressed as compared with a case where the content thereof is higher than the above-described ranges.
The amount of the phenolic hydroxyl group contained in the compound having a specific hindered phenol structure in the charge transport layer of the photoreceptor according to the first exemplary embodiment is, for example, preferably 5% by mole or greater and 50% by mole or less, more preferably 8% by mole or greater and 40% by mole or less, and still more preferably 10% by mole or greater and 30% by mole or less with respect to the mol number of the charge transport material contained in the charge transport layer.
The amount of the phenolic hydroxyl group contained in the compound having a specific hindered phenol structure in the single layer type photosensitive layer of the photoreceptor according to the second exemplary embodiment is, for example, preferably 5% by mole or greater and 50% by mole or less, more preferably 8% by mole or greater and 40% by mole or less, and still more preferably 10% by mole or greater and 30% by mole or less with respect to the mol number of the charge transport material contained in the single layer type photosensitive layer.
In a case where the amount of the phenolic hydroxyl group contained in the compound having a specific hindered phenol structure with respect to the mol number of the charge transport material is in the above-described ranges, there are advantages that burn-in ghosts are suppressed as compared with a case where the amount thereof is lower than the above-described ranges, and the residual potential during a cycle stress is suppressed as compared with a case where the amount thereof is higher than the above-described ranges.
Hereinafter, each layer of the electrophotographic photoreceptor according to the first exemplary embodiment and the second exemplary embodiment will be described in detail. Further, the reference numerals will not be provided.
Conductive Substrate
Examples of the conductive substrate include metal plates containing metals (such as aluminum, copper, zinc, chromium, nickel, molybdenum, vanadium, indium, gold, and platinum) or alloys (such as stainless steel), metal drums, metal belts, and the like. Further, examples of the conductive substrate include paper, a resin film, a belt, and the like obtained by being coated, vapor-deposited or laminated with a conductive compound (such as a conductive polymer or indium oxide), a metal (such as aluminum, palladium, or gold) or an alloy. Here, the term “conductive” denotes that the volume resistivity is less than 1013 Ωcm.
In a case where the electrophotographic photoreceptor is used in a laser printer, for example, it is preferable that the surface of the conductive substrate is roughened such that a centerline average roughness Ra thereof is 0.04 μm or greater and 0.5 μm or less for the purpose of suppressing interference fringes from occurring in a case of irradiation with laser beams. Further, in a case where incoherent light is used as a light source, roughening of the surface to prevent interference fringes is not particularly necessary, and roughening of the surface to prevent interference fringes is appropriate for longer life because occurrence of defects due to the roughness of the surface of the conductive substrate is suppressed.
Examples of the roughening method include wet honing performed by suspending an abrasive in water and spraying the suspension to the conductive substrate, centerless grinding performed by pressure-welding the conductive substrate against a rotating grindstone and continuously grinding the conductive substrate, and an anodizing treatment.
Examples of the roughening method also include a method of dispersing conductive or semi-conductive powder in a resin without roughening the surface of the conductive substrate to form a layer on the surface of the conductive substrate, and performing roughening using the particles dispersed in the layer.
The roughening treatment performed by anodization is a treatment of forming an oxide film on the surface of the conductive substrate by carrying out anodization in an electrolytic solution using a conductive substrate made of a metal (for example, aluminum) as an anode. Examples of the electrolytic solution include a sulfuric acid solution and an oxalic acid solution. However, a porous anodized film formed by anodization is chemically active in a natural state, is easily contaminated, and has a large resistance fluctuation depending on the environment. Therefore, for example, it is preferable that a sealing treatment is performed on the porous anodized film so that the micropores of the oxide film are closed by volume expansion due to a hydration reaction in pressurized steam or boiling water (a metal salt such as nickel may be added thereto) for a change into a more stable a hydrous oxide.
The film thickness of the anodized film is, for example, preferably 0.3 μm or greater and 15 μm or less. In a case where the film thickness is in the above-described range, the barrier properties against injection tend to be exhibited, and an increase in the residual potential due to repeated use tends to be suppressed.
The conductive substrate may be subjected to a treatment with an acidic treatment liquid or a boehmite treatment.
The treatment with an acidic treatment liquid is carried out, for example, as follows. First, an acidic treatment liquid containing phosphoric acid, chromic acid, and hydrofluoric acid is prepared. In the blending ratio of phosphoric acid, chromic acid, and hydrofluoric acid to the acidic treatment liquid, for example, the concentration of the phosphoric acid is 10% by mass or greater and 11% by mass or less, the concentration of the chromic acid is 3% by mass or greater and 5% by mass or less, and the concentration of the hydrofluoric acid is 0.5% by mass or greater and 2% by mass or less, and the concentration of all these acids may be 13.5% by mass or greater and 18% by mass or less. The treatment temperature is, for example, preferably 42° C. or higher and 48° C. or lower. The film thickness of the coating film is, for example, preferably 0.3 μm or greater and 15 μm or less.
The boehmite treatment is carried out, for example, by immersing the conductive substrate in pure water at 90° C. or higher and 100° C. or lower for 5 minutes to 60 minutes or by bringing the conductive substrate into contact with heated steam at 90° C. or higher and 120° C. or lower for 5 minutes to 60 minutes.
The film thickness of the coating film is, for example, preferably 0.1 μm or greater and 5 μm or less. This coating film may be further subjected to the anodizing treatment using an electrolytic solution having low film solubility, such as adipic acid, boric acid, a borate, a phosphate, a phthalate, a maleate, a benzoate, a tartrate, or a citrate.
Undercoat Layer
The undercoat layer is, for example, a layer containing inorganic particles and a binder resin.
Examples of the inorganic particles include inorganic particles having a powder resistance (volume resistivity) of 102 Ωcm or greater and 1011 Ωcm or less.
Among these, as the inorganic particles having the above-described resistance value, for example, metal oxide particles such as tin oxide particles, titanium oxide particles, zinc oxide particles, and zirconium oxide particles may be used, and zinc oxide particles are particularly preferable.
The specific surface area of the inorganic particles measured by the BET method may be, for example, 10 m2/g or greater.
The volume average particle diameter of the inorganic particles may be, for example, 50 nm or greater and 2,000 nm or less (for example, preferably 60 nm or greater and 1,000 nm or less).
The content of the inorganic particles is, for example, preferably 10% by mass or greater and 80% by mass or less and more preferably 40% by mass or greater and 80% by mass or less with respect to the amount of the binder resin.
The inorganic particles may be subjected to a surface treatment. As the inorganic particles, inorganic particles subjected to different surface treatments or inorganic particles having different particle diameters may be used in the form of a mixture of two or more kinds thereof.
Examples of the surface treatment agent include a silane coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, and a surfactant. In particular, for example, a silane coupling agent is preferable, and a silane coupling agent containing an amino group is more preferable.
Examples of the silane coupling agent containing an amino group include 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and N,N-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, but are not limited thereto.
The silane coupling agent may be used in the form of a mixture of two or more kinds thereof. For example, a silane coupling agent containing an amino group and another silane coupling agent may be used in combination. Examples of other silane coupling agents include vinyltrimethoxysilane, 3-methacryloxypropyl-tris(2-methoxyethoxy)silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N,N-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-chloropropyltrimethoxysilane, but are not limited thereto.
The surface treatment method using a surface treatment agent may be any method as long as the method is a known method, and any of a dry method or a wet method may be used.
The treatment amount of the surface treatment agent is, for example, preferably 0.5% by mass or greater and 10% by mass or less with respect to the amount of the inorganic particles.
Here, the undercoat layer may contain, for example, an electron-accepting compound (acceptor compound) together with the inorganic particles from the viewpoint of enhancing the long-term stability of the electrical properties and the carrier blocking properties.
Examples of the electron-accepting compound include electron-transporting substances, for example, a quinone-based compound such as chloranil or bromanil; a tetracyanoquinodimethane-based compound; a fluorenone compound such as 2,4,7-trinitrofluorenone or 2,4,5,7-tetranitro-9-fluorenone; an oxadiazole-based compound such as 2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole, 2,5-bis(4-naphthyl)-1,3,4-oxadiazole, or 2,5-bis(4-diethylaminophenyl)-1,3,4-oxadiazole; a xanthone-based compound; a thiophene compound; and a diphenoquinone compound such as 3,3′,5,5′-tetra-t-butyldiphenoquinone.
In particular, as the electron-accepting compound, for example, a compound having an anthraquinone structure is preferable. As the compound having an anthraquinone structure, for example, a hydroxyanthraquinone compound, an aminoanthraquinone compound, or an aminohydroxyanthraquinone compound is preferable, and specifically, for example, anthraquinone, alizarin, quinizarin, anthrarufin, or purpurin is preferable.
The electron-accepting compound may be contained in the undercoat layer in a state of being dispersed with inorganic particles or in a state of being attached to the surface of each inorganic particle.
Examples of the method of attaching the electron-accepting compound to the surface of the inorganic particle include a dry method and a wet method.
The dry method is, for example, a method of attaching the electron-accepting compound to the surface of each inorganic particle by adding the electron-accepting compound dropwise to inorganic particles directly or by dissolving the electron-accepting compound in an organic solvent while stirring the inorganic particles with a mixer having a large shearing force and spraying the mixture together with dry air or nitrogen gas. The electron-accepting compound may be added dropwise or sprayed, for example, at a temperature lower than or equal to the boiling point of the solvent. After the dropwise addition or the spraying of the electron-accepting compound, the compound may be further baked at 100° C. or higher. The baking is not particularly limited as long as the temperature and the time are adjusted such that the electrophotographic characteristics can be obtained.
The wet method is, for example, a method of attaching the electron-accepting compound to the surface of each inorganic particle by adding the electron-accepting compound to inorganic particles while dispersing the inorganic particles in a solvent using a stirrer, ultrasonic waves, a sand mill, an attritor, or a ball mill, stirring or dispersing the mixture, and removing the solvent. The solvent removing method is carried out by, for example, filtration or distillation so that the solvent is distilled off. After removal of the solvent, the mixture may be further baked at 100° C. or higher. The baking is not particularly limited as long as the temperature and the time are adjusted such that the electrophotographic characteristics can be obtained. In the wet method, the moisture contained in the inorganic particles may be removed before the electron-accepting compound is added, and examples thereof include a method of removing the moisture while stirring and heating the moisture in a solvent and a method of removing the moisture by azeotropically boiling the moisture with a solvent.
Further, the electron-accepting compound may be attached to the surface before or after the inorganic particles are subjected to a surface treatment with a surface treatment agent or simultaneously with the surface treatment performed on the inorganic particles with a surface treatment agent.
The content of the electron-accepting compound may be, for example, 0.01% by mass or greater and 20% by mass or less and preferably 0.01% by mass or greater and 10% by mass or less with respect to the amount of the inorganic particles.
Examples of the binder resin used for the undercoat layer include known polymer compounds such as an acetal resin (such as polyvinyl butyral), a polyvinyl alcohol resin, a polyvinyl acetal resin, a casein resin, a polyamide resin, a cellulose resin, gelatin, a polyurethane resin, a polyester resin, an unsaturated polyester resin, a methacrylic resin, an acrylic resin, a polyvinyl chloride resin, a polyvinyl acetate resin, a vinyl chloride-vinyl acetate-maleic acid anhydride resin, a silicone resin, a silicone-alkyd resin, a urea resin, a phenol resin, a phenol-formaldehyde resin, a melamine resin, a urethane resin, an alkyd resin, and an epoxy resin, a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound, a titanium alkoxide compound, an organic titanium compound, and known materials such as a silane coupling agent.
Examples of the binder resin used for the undercoat layer include a charge-transporting resin containing a charge-transporting group, and a conductive resin (such as polyaniline).
Among these, as the binder resin used for the undercoat layer, for example, a resin insoluble in a coating solvent of the upper layer is preferable, and a resin obtained by the reaction between a curing agent and at least one resin selected from the group consisting of a thermosetting resin such as a urea resin, a phenol resin, a phenol-formaldehyde resin, a melamine resin, a urethane resin, an unsaturated polyester resin, an alkyd resin, or an epoxy resin; a polyamide resin, a polyester resin, a polyether resin, a methacrylic resin, an acrylic resin, a polyvinyl alcohol resin, and a polyvinyl acetal resin is particularly preferable.
In a case where these binder resins are used in combination of two or more kinds thereof, the mixing ratio thereof is set as necessary.
The undercoat layer may contain various additives for improving the electrical properties, the environmental stability, and the image quality.
Examples of the additives include known materials, for example, an electron-transporting pigment such as a polycyclic condensed pigment or an azo-based pigment, a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound, a titanium alkoxide compound, an organic titanium compound, and a silane coupling agent. The silane coupling agent is used for a surface treatment of the inorganic particles as described above, but may be further added to the undercoat layer as an additive.
Examples of the silane coupling agent serving as an additive include vinyltrimethoxysilane, 3-methacryloxypropyl-tris(2-methoxyethoxy)silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N,N-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-chloropropyltrimethoxysilane.
Examples of the zirconium chelate compound include zirconium butoxide, ethyl zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl zirconium butoxide acetoacetate, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octanoate, zirconium naphthenate, zirconium laurate, zirconium stearate, zirconium isostearate, zirconium butoxide methacrylate, stearate zirconium butoxide, and isostearate zirconium butoxide.
Examples of the titanium chelate compound include tetraisopropyl titanate, tetranormal butyl titanate, a butyl titanate dimer, tetra(2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, titanium lactate, titanium lactate ethyl ester, titanium triethanol aminate, and polyhydroxy titanium stearate.
Examples of the aluminum chelate compound include aluminum isopropylate, monobutoxyaluminum diisopropylate, aluminum butyrate, diethylacetoacetate aluminum diisopropylate, and aluminum tris(ethylacetoacetate).
These additives may be used alone or in the form of a mixture or a polycondensate of a plurality of compounds.
The undercoat layer may have, for example, a Vickers hardness of 35 or greater.
The surface roughness (ten-point average roughness) of the undercoat layer may be adjusted, for example, to ½ from 1/(4n) (n represents a refractive index of an upper layer) of a laser wavelength λ for exposure to be used to suppress moire fringes.
Resin particles or the like may be added to the undercoat layer to adjust the surface roughness. Examples of the resin particles include silicone resin particles and crosslinked polymethyl methacrylate resin particles. Further, the surface of the undercoat layer may be polished to adjust the surface roughness. Examples of the polishing method include buff polishing, a sandblast treatment, wet honing, and a grinding treatment.
The formation of the undercoat layer is not particularly limited, and a known forming method is used. For example, a coating film of a coating solution for forming an undercoat layer in which the above-described components are added to a solvent is formed, and the coating film is dried and, as necessary, heated.
Examples of the solvent for preparing the coating solution for forming an undercoat layer include known organic solvents such as an alcohol-based solvent, an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, a ketone-based solvent, a ketone alcohol-based solvent, an ether-based solvent, and an ester-based solvent.
Specific examples of these solvents include typical organic solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene.
Examples of the method of dispersing the inorganic particles in a case of preparing the coating solution for forming an undercoat layer include known methods such as a roll mill, a ball mill, a vibration ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker.
Examples of the method of coating the conductive substrate with the coating solution for forming an undercoat layer include typical coating 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.
The film thickness of the undercoat layer is set to, for example, preferably 15 μm or greater and more preferably 20 μm or greater and 50 μm or less.
Interlayer
Although not shown in the figures, an interlayer may be further provided between the undercoat layer and the photosensitive layer.
The interlayer is, for example, a layer containing a resin. Examples of the resin used for the interlayer include a polymer compound, for example, an acetal resin (such as polyvinyl butyral), a polyvinyl alcohol resin, a polyvinyl acetal resin, a casein resin, a polyamide resin, a cellulose resin, gelatin, a polyurethane resin, a polyester resin, a methacrylic resin, an acrylic resin, a polyvinyl chloride resin, a polyvinyl acetate resin, a vinyl chloride-vinyl acetate-maleic acid anhydride resin, a silicone resin, a silicone-alkyd resin, a phenol-formaldehyde resin, or a melamine resin.
The interlayer may be a layer containing an organometallic compound. Examples of the organometallic compound used for the interlayer include an organometallic compound containing metal atoms such as zirconium, titanium, aluminum, manganese, and silicon.
The compounds used for the interlayer may be used alone or in the form of a mixture or a polycondensate of a plurality of compounds.
Among these, it is preferable that the interlayer is, for example, a layer containing an organometallic compound having a zirconium atom or a silicon atom.
The formation of the interlayer is not particularly limited, and a known forming method is used. For example, a coating film of a coating solution for forming an interlayer in which the above-described components are added to a solvent is formed, and the coating film is dried and, as necessary, heated.
Examples of the coating method of forming the interlayer include typical coating methods such as a dip coating method, a push-up coating method, a wire bar coating method, a spray coating method, a blade coating method, an air knife coating method, and a curtain coating method.
The film thickness of the interlayer is set to be, for example, preferably in a range of 0.1 μm or greater and 3 μm or less.
Further, the interlayer may be used as the undercoat layer.
Charge Generation Layer
The charge generation layer is, for example, a layer containing a charge generation material and a binder resin. Further, the charge generation layer may be a deposition layer of the charge generation material. The deposition layer of the charge generation material is preferable in a case where an incoherent light source, for example, a light emitting diode (LED) or an organic electroluminescence (EL) image array is used.
Examples of the charge generation material include an azo pigment such as bisazo or trisazo; a fused ring aromatic pigment such as dibromoanthanthrone; a perylene pigment; a pyrrolopyrrole pigment; a phthalocyanine pigment; zinc oxide; and trigonal selenium.
Among these, for example, a metal phthalocyanine pigment or a metal-free phthalocyanine pigment is preferably used as the charge generation material in order to deal with laser exposure in a near infrared region. Specifically, for example, hydroxygallium phthalocyanine, chlorogallium phthalocyanine, dichloro-tin phthalocyanine, and titanyl phthalocyanine are more preferable.
On the other hand, for example, a fused ring aromatic pigment such as dibromoanthanthrone, a thioindigo-based pigment, a porphyrazine compound, zinc oxide, trigonal selenium, or a bisazo pigment is preferable as the charge generation material in order to deal with laser exposure in a near ultraviolet region.
The above-described charge generation material may also be used even in a case where an incoherent light source such as an LED or an organic EL image array having a center wavelength of light emission at 450 nm or greater and 780 nm or less is used, but from the viewpoint of the resolution, the field intensity in the photosensitive layer is increased, and a decrease in charge due to injection of a charge from the substrate, that is, image defects referred to as so-called black spots are likely to occur in a case where a thin film having a thickness of m or less is used as the photosensitive layer. The above-described tendency is evident in a case where a p-type semiconductor such as trigonal selenium or a phthalocyanine pigment is used as the charge generation material that is likely to generate a dark current.
On the other hand, in a case where an n-type semiconductor such as a fused ring aromatic pigment, a perylene pigment, or an azo pigment is used as the charge generation material, a dark current is unlikely to be generated, and image defects referred to as black spots can be suppressed even in a case where a thin film is used as the photosensitive layer.
Further, the n-type is determined by the polarity of the flowing photocurrent using a typically used time-of-flight method, and a material in which electrons more easily flow as carriers than positive holes is determined as the n-type.
The binder resin used for the charge generation layer is selected from a wide range of insulating resins, and the binder resin may be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane.
Examples of the binder resin include a polyvinyl butyral resin, a polyarylate resin (a polycondensate of bisphenols and aromatic divalent carboxylic acid), a polycarbonate resin, a polyester resin, a phenoxy resin, a vinyl chloride-vinyl acetate copolymer, a polyamide resin, an acrylic resin, a polyacrylamide resin, a polyvinylpyridine resin, a cellulose resin, a urethane resin, an epoxy resin, casein, a polyvinyl alcohol resin, and a polyvinylpyrrolidone resin. Here, the term “insulating” denotes that the volume resistivity is 1013 Ωcm or greater.
These binder resins may be used alone or in the form of a mixture of two or more kinds thereof.
Further, the blending ratio between the charge generation material and the binder resin is, for example, preferably in a range of 10:1 to 1:10 in terms of the mass ratio.
The charge generation layer may also contain other known additives.
The formation of the charge generation layer is not particularly limited, and a known forming method is used. For example, a coating film of a coating solution for forming a charge generation layer in which the above-described components are added to a solvent is formed, and the coating film is dried and, as necessary, heated. Further, the charge generation layer may be formed by vapor deposition of the charge generation material. The formation of the charge generation layer by vapor deposition is, for example, particularly appropriate in a case where a fused ring aromatic pigment or a perylene pigment is used as the charge generation material.
Examples of the solvent for preparing the coating solution for forming a charge generation layer 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, methylene chloride, chloroform, chlorobenzene, and toluene. These solvents are used alone or in the form of a mixture of two or more kinds thereof.
As a method of dispersing particles (for example, the charge generation material) in the coating solution for forming a charge generation layer, for example, a media disperser such as a ball mill, a vibration ball mill, an attritor, a sand mill, or a horizontal sand mill, or a medialess disperser such as a stirrer, an ultrasonic disperser, a roll mill, or a high-pressure homogenizer is used. Examples of the high-pressure homogenizer include a collision type homogenizer in which a dispersion liquid is dispersed by a liquid-liquid collision or a liquid-wall collision in a high-pressure state, and a penetration type homogenizer in which a dispersion liquid is dispersed by penetrating the liquid through a micro-flow path in a high-pressure state.
During the dispersion, it is effective to set the average particle diameter of the charge generation material in the coating solution for forming a charge generation layer to 0.5 μm or less, for example, preferably 0.3 μm or less, and more preferably 0.15 μm or less.
Examples of the method of coating the undercoat layer (or the interlayer) with the coating solution for forming a charge generation layer include typical 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.
The film thickness of the charge generation layer is set to be, for example, in a range of preferably 0.1 μm or greater and 5.0 μm or less and more preferably in a range of 0.2 μm or greater and 2.0 μm or less.
Charge Transport Layer
The charge transport layer is, for example, a layer containing a charge transport material and a binder resin. The charge transport layer may be a layer containing a polymer charge transport material.
Examples of the charge transport material include a quinone-based compound such as p-benzoquinone, chloranil, bromanil, or anthraquinone; a tetracyanoquinodimethane-based compound; a fluorenone compound such as 2,4,7-trinitrofluorenone; a xanthone compound; a benzophenone-based compound; a cyanovinyl-based compound; and an electron-transporting compound such as an ethylene-based compound. Examples of the charge transport material include a positive hole-transporting compound such as a triarylamine-based compound, a benzidine-based compound, an arylalkane-based compound, an aryl-substituted ethylene-based compound, a stilbene-based compound, an anthracene-based compound, or a hydrazone-based compound. These charge transport materials may be used alone or in combination of two or more kinds thereof, but are not limited thereto.
As the polymer charge transport material, known materials having charge transport properties, such as poly-N-vinylcarbazole and polysilane, can be used. For example, a polyester-based polymer charge transport material is particularly preferable. Further, the polymer charge transport material may be used alone or in combination of binder resins.
Examples of the charge transport material or the polymer charge transport material include a polycyclic aromatic compound, an aromatic nitro compound, an aromatic amine compound, a heterocyclic compound, a hydrazone compound, a styryl compound, an enamine compound, a benzidine compound, a triarylamine compound (particularly, a triphenylamine compound), a diamine compound, an oxadiazole compound, a carbazole compound, an organic polysilane compound, a pyrazoline compound, an indole compound, an oxazole compound, an isoxazole compound, a thiazole compound, a thiadiazole compound, an imidazole compound, a pyrazole compound, a triazole compound, a cyano compound, a benzofuran compound, an aniline compound, a butadiene compound, and a resin containing a group derived from any of these substances. Specific examples thereof include compounds described in paragraphs 0078 to 0080 of JP2021-117377A, paragraphs 0046 to 0048 of JP2019-035900A, paragraphs 0052 and 0053 of JP2019-012141A, paragraphs 0122 to 0134 of JP2021-071565A, paragraphs 0101 to 0110 of JP2021-015223A, paragraph 0116 of JP2013-097300A, paragraphs 0309 to 0316 of WO2019/070003A, paragraphs 0103 to 0107 of JP2018-159087A, and paragraphs 0102 to 0113 of JP2021-148818A.
From the viewpoint of the charge mobility, it is preferable that the charge transport material contains, for example, at least one selected from the group consisting of a compound (D1) represented by Formula (D1), a compound (D2) represented by Formula (D2), a compound (D3) represented by Formula (D3), and a compound (D4) represented by Formula (D4).
In Formula (D1), ArT1, ArT2, and ArT3 each independently represent an aryl group, —C6H4—C(RT4)═C(RT5)(RT6) or —C6H4—CH═CH—CH═C(RT7)(RT8). RT4, RT5, RT6, RT7, and RT8 each independently represent a hydrogen atom, an alkyl group, or an aryl group. In a case where RT5 and RT6 represent an aryl group, the aryl groups may be linked to each other via at least one divalent group selected from the group consisting of —C(R51)(R52)— and —C(R61)═C(R62)—. R51, R52, R61, and R62 each independently represent a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms.
The group in Formula (D1) may be substituted with a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, or a substituted amino group substituted with an alkyl group having 1 or more and 3 or less carbon atoms.
From the viewpoint of the charge mobility, as the compound (D1), for example, a compound containing at least one of an aryl group or —C6H4—CH═CH—CH═C(RT7)(RT8) is preferable, and a compound (D′1) represented by Formula (D′1) is more preferable.
In Formula (D′1), RT111, RT112, RT121, RT122, RT131, and RT132 each independently represent a hydrogen atom, a halogen atom, an alkyl group (for example, preferably an alkyl group having 1 or more and 3 or less carbon atoms), an alkoxy group (for example, preferably an alkoxy group having 1 or more and 3 or less carbon atoms), a phenyl group, or a phenoxy group. Tj1, Tj2, Tj3, Tk1, Tk2, and Tk3 each independently represent 0, 1, or 2.
In Formula (D2), RT201, RT202, RT211, and RT212 each independently represent a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, an amino group substituted with an alkyl group having 1 or 2 carbon atoms, an aryl group, —C(RT21)═C(RT22)(RT23), or —CH═CH—CH═C(RT24)(RT25). RT21, RT22, RT23, RT24, and RT25 each independently represent a hydrogen atom, an alkyl group, or an aryl group. RT221 and RT222 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, or an alkoxy group having 1 or more and 5 or less carbon atoms. Tm1, Tm2, Tn1, and Tn2 each independently represent 0, 1, or 2.
The group in Formula (D2) may be substituted with a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, or a substituted amino group substituted with an alkyl group having 1 or more and 3 or less carbon atoms.
From the viewpoint of the charge mobility, as the compound (D2), for example, a compound containing at least one of an alkyl group, an aryl group, or —CH═CH—CH═C(RT24)(RT25) is preferable, and a compound containing two of an alkyl group, an aryl group, or —CH═CH—CH═C(RT24)(RT25) is more preferable.
In Formula (D3), RT301, RT302, RT311, and RT312 each independently represent a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, an amino group substituted with an alkyl group having 1 or 2 carbon atoms, an aryl group, —C(RT31)═C(RT32)(RT33), or —CH═CH—CH═C(RT34)(RT35). RT31, RT32, RT33, RT34, and RT35 each independently represent a hydrogen atom, an alkyl group, or an aryl group. RT321, RT322, and RT331 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, or an alkoxy group having 1 or more and 5 or less carbon atoms. To1, To2, Tp1, Tp2, Tq1, Tq2, and Tr1 each independently represent 0, 1, or 2.
The group in Formula (D3) may be substituted with a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, or a substituted amino group substituted with an alkyl group having 1 or more and 3 or less carbon atoms.
In Formula (D4), RT401, RT402, RT411, and RT412 each independently represent a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, an amino group substituted with an alkyl group having 1 or 2 carbon atoms, an aryl group, —C(RT41)═C(RT42)(RT43), or —CH═CH—CH═C(RT44)(RT45). RT41, RT42, RT43, RT44, and RT45 each independently represent a hydrogen atom, an alkyl group, or an aryl group. RT421, RT422, and RT431 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, or an alkoxy group having 1 or more and 5 or less carbon atoms. Ts1, Ts2, Tt1, Tt2, Tu1, Tu2, and Tv1 each independently represent 0, 1, or 2.
The group in Formula (D4) may be substituted with a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, or a substituted amino group substituted with an alkyl group having 1 or more and 3 or less carbon atoms.
The content of the charge transport material contained in the charge transport layer is, for example, preferably 20% by mass or greater and 70% by mass or less with respect to the total mass of the charge transport layer.
The charge transport layer contains a polyester resin having at least a dicarboxylic acid unit (A) as a binder resin. The total proportion of the polyester resin having a dicarboxylic acid unit (A) in the total amount of the binder resin contained in the charge transport layer is, for example, preferably 50% by mass or greater, more preferably 80% by mass or greater, still more preferably 90% by mass or greater, particularly preferably 95% by mass or greater, and most preferably 100% by mass.
The charge transport layer may contain other binder resins in addition to the polyester resin having a dicarboxylic acid unit (A). Examples of other binder resins include a polyester resin other than the polyester resin having a dicarboxylic acid unit (A), a polycarbonate resin, a methacrylic resin, an acrylic resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polystyrene resin, a polyvinyl acetate resin, a styrene-butadiene copolymer, a vinylidene chloride-acrylonitrile copolymer, a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-vinyl acetate-maleic acid anhydride copolymer, a silicone resin, a silicone alkyd resin, a phenol-formaldehyde resin, a styrene-alkyd resin, poly-N-vinylcarbazole, and polysilane. These binder resins may be used alone or in combination of two or more kinds thereof.
The charge transport layer contains at least the specific compound as an antioxidant. The charge transport layer may contain an antioxidant other than the specific compound. From the viewpoint of suppressing both filming and burn-in ghosts, it is preferable that the charge transport layer does not contain, for example, an antioxidant other than the specific compound.
The total proportion of the specific compound in the total amount of the antioxidant contained in the charge transport layer is, for example, preferably 80% by mass or greater, more preferably 90% by mass or greater, still more preferably 95% by mass or greater, and particularly preferably 100% by mass.
The charge transport layer may also contain other known additives. Examples of the additives include a leveling agent, an antifoaming agent, a filler, and a viscosity adjuster.
The formation of the charge transport layer is not particularly limited, and a known forming method is used. For example, a coating film of a coating solution for forming a charge transport layer in which the above-described components are added to a solvent is formed, and the coating film is dried and, as necessary, heated.
Examples of the solvent for preparing the coating solution for forming a charge transport layer include typical organic solvents, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; ketones such as acetone and 2-butanone; halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, and ethylene chloride; and cyclic or linear ethers such as tetrahydrofuran and ethyl ether. These solvents are used alone or in the form of a mixture of two or more kinds thereof.
Examples of the coating method of coating the charge generation layer with the coating solution for forming a charge transport layer include typical 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.
The average thickness of the charge transport layer is, for example, preferably 5 μm or greater and 60 μm or less, more preferably 10 μm or greater and 55 μm or less, and still more preferably 15 μm or greater and 50 μm or less.
Single Layer Type Photosensitive Layer
The single layer type photosensitive layer (charge generation layer/charge transport layer) is a layer containing a charge generation material, a charge transport material, a binder resin, a compound having a specific hindered phenol structure, and, as necessary, other additives. These materials are the same as the materials described in the sections of the charge generation layer and the charge transport layer.
The single layer type photosensitive layer contains at least a polyester resin having a dicarboxylic acid unit (A) as a binder resin. The total proportion of the polyester resin having a dicarboxylic acid unit (A) in the total amount of the binder resin contained in the single layer type photosensitive layer is, for example, preferably 50% by mass or greater, more preferably 80% by mass or greater, still more preferably 90% by mass or greater, particularly preferably 95% by mass or greater, and most preferably 100% by mass.
The content of the charge generation material in the single layer type photosensitive layer may be, for example, 0.1% by mass or greater and 10% by mass or less and preferably 0.8% by mass or greater and 5% by mass or less with respect to the total solid content.
The content of the charge transport material contained in the single layer type photosensitive layer may be, for example, 40% by mass or greater and 60% by mass or less with respect to the total solid content.
The method of forming the single layer type photosensitive layer is the same as the method of forming the charge generation layer or the charge transport layer.
The average thickness of the single layer type photosensitive layer is, for example, preferably 5 μm or greater and 60 μm or less, more preferably 10 μm or greater and 55 μm or less, and still more preferably 15 μm or greater and 50 μm or less.
Image Forming Apparatus and Process Cartridge
An image forming apparatus according to the present exemplary embodiment includes the electrophotographic photoreceptor, a charging device that charges a surface of the electrophotographic photoreceptor, an electrostatic latent image forming device that forms an electrostatic latent image on the charged surface of the electrophotographic photoreceptor, a developing device that develops the electrostatic latent image formed on the surface of the electrophotographic photoreceptor with a developer containing a toner to form a toner image, and a transfer device that transfers the toner image to a surface of a recording medium. Further, the electrophotographic photoreceptor according to the present exemplary embodiment is employed as the electrophotographic photoreceptor.
As the image forming apparatus according to the present exemplary embodiment, a known image forming apparatus such as an apparatus including a fixing device that fixes a toner image transferred to the surface of a recording medium; a direct transfer type apparatus that transfers a toner image formed on the surface of an electrophotographic photoreceptor directly to a recording medium; an intermediate transfer type apparatus that primarily transfers a toner image formed on the surface of an electrophotographic photoreceptor to the surface of an intermediate transfer member and secondarily transfers the toner image transferred to the surface of the intermediate transfer member to the surface of a recording medium; an apparatus including a cleaning device that cleans the surface of an electrophotographic photoreceptor after the transfer of a toner image and before the charging; an apparatus including a destaticizing device that destaticizes the surface of an electrophotographic photoreceptor by irradiating the surface with destaticizing light after the transfer of a toner image and before the charging; or an apparatus including an electrophotographic photoreceptor heating member for increasing the temperature of an electrophotographic photoreceptor and decreasing the relative temperature is employed.
In a case of the intermediate transfer type apparatus, the transfer device is, for example, configured to include an intermediate transfer member having a surface onto which the toner image is transferred, a primary transfer device primarily transferring the toner image formed on the surface of the electrophotographic photoreceptor to the surface of the intermediate transfer member, and a secondary transfer device secondarily transferring the toner image transferred to the surface of the intermediate transfer member to the surface of the recording medium.
The image forming apparatus according to the present exemplary embodiment may be any of a dry development type image forming apparatus or a wet development type (development type using a liquid developer) image forming apparatus.
Further, in the image forming apparatus according to the present exemplary embodiment, for example, the portion including the electrophotographic photoreceptor may have a cartridge structure (process cartridge) that is attachable to and detachable from the image forming apparatus. As the process cartridge, for example, a process cartridge including the electrophotographic photoreceptor according to the present exemplary embodiment is preferably used. Further, the process cartridge may include, for example, at least one selected from the group consisting of a charging device, an electrostatic latent image forming device, a developing device, and a transfer device in addition to the electrophotographic photoreceptor.
Hereinafter, an example of the image forming apparatus according to the present exemplary embodiment will be described, but the present exemplary embodiment is not limited thereto. Further, main parts shown in the figures will be described, but description of other parts will not be provided.
As shown in
The process cartridge 300 in
Further,
Hereinafter, each configuration of the image forming apparatus according to the present exemplary embodiment will be described.
Charging Device
As the charging device 8, for example, a contact-type charger formed of a conductive or semi-conductive charging roller, a charging brush, a charging film, a charging rubber blade, a charging tube, or the like is used. Further, a known charger such as a non-contact type roller charger, or a scorotron charger or a corotron charger using corona discharge is also used.
Exposure Device
Examples of the exposure device 9 include an optical system device that exposes the surface of the electrophotographic photoreceptor 7 to light such as a semiconductor laser beam, LED light, and liquid crystal shutter light in a predetermined image pattern. The wavelength of the light source is within the spectral sensitivity region of the electrophotographic photoreceptor. As the wavelength of a semiconductor laser, near infrared, which has an oscillation wavelength in the vicinity of 780 nm, is mostly used. However, the wavelength is not limited thereto, and a laser having an oscillation wavelength of approximately 600 nm or a laser having an oscillation wavelength of 400 nm or greater and 450 nm or less as a blue laser may also be used. Further, a surface emission type laser light source capable of outputting a multi-beam is also effective for forming a color image.
Developing Device
Examples of the developing device 11 include a typical developing device that performs development in contact or non-contact with the developer. The developing device 11 is not particularly limited as long as the developing device has the above-described functions, and is selected depending on the purpose thereof. Examples of the developing device include known developing machines having a function of attaching a one-component developer or a two-component developer to the electrophotographic photoreceptor 7 using a brush, a roller, or the like.
Among these, for example, a developing device formed of a developing roller having a surface on which a developer is held is preferably used.
The developer used in the developing device 11 may be a one-component developer containing only a toner or a two-component developer containing a toner and a carrier. Further, the developer may be magnetic or non-magnetic. Known developers are employed as these developers.
Cleaning Device
As the cleaning device 13, a cleaning blade type device including the cleaning blade 131 is used.
In addition to the cleaning blade type device, a fur brush cleaning type device or a simultaneous development cleaning type device may be employed.
Transfer Device
Examples of the transfer device 40 include a known transfer charger such as a contact-type transfer charger using a belt, a roller, a film, a rubber blade, or the like, or a scorotron transfer charger or a corotron transfer charger using corona discharge.
Intermediate Transfer Member
As the intermediate transfer member 50, a belt-like intermediate transfer member (intermediate transfer belt) containing semi-conductive polyimide, polyamide-imide, polycarbonate, polyarylate, polyester, rubber, or the like is used. Further, as the form of the intermediate transfer member, a drum-like intermediate transfer member may be used in addition to the belt-like intermediate transfer member.
An image forming apparatus 120 shown in
Hereinafter, exemplary embodiments of the invention will be described in detail based on examples, but the exemplary embodiments of the invention are not limited to the examples.
In the following description, “parts” and “%” are on a mass basis unless otherwise specified.
In the following description, the synthesis, the treatment, the production, and the like are carried out at room temperature (25° C.±3° C.) unless otherwise specified.
Preparation of Polyester Resin
Polyester resins (PE1) to (PE7) are prepared. Table 1 shows units and compositions constituting the polyester resins.
A2-3 and the like listed in Table 1 are specific examples of the dicarboxylic acid unit (A) described above.
B1-4 and the like described in Table 1 are specific examples of the diol unit (B) described above.
Production of Photoreceptor Including Lamination Type Photosensitive Layer
An aluminum cylindrical tube having an outer diameter of 30 mm, a length of 365 mm, and a thickness of 1.6 mm is prepared as a conductive substrate.
100 parts of zinc oxide (average particle diameter of 70 nm, specific surface area of 15 m2/g, manufactured by Tayca Corporation) is stirred and mixed with 500 parts of toluene, 1.3 parts of a silane coupling agent (trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd., N-2-(aminoethyl)-3-aminopropyltrimethoxysilane) is added thereto, and the mixture is stirred for 2 hours. Thereafter, toluene is distilled off under reduced pressure and baked at 120° C. for 3 hours to obtain zinc oxide subjected to a surface treatment with a silane coupling agent.
110 parts of the surface-treated zinc oxide is stirred and mixed with 500 parts of tetrahydrofuran, a solution obtained by dissolving 0.6 part of alizarin in 50 parts of tetrahydrofuran is added thereto, and the mixture is stirred at 50° C. for 5 hours. Thereafter, the solid content is separated by filtration by carrying out filtration under reduced pressure and dried at 60° C. under reduced pressure, thereby obtaining zinc oxide with alizarin.
0 parts of a solution obtained by dissolving 60 parts of the zinc oxide with alizarin, 13.5 parts of a curing agent (blocked isocyanate, trade name: SUMIDUR 3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.), and 15 parts of a butyral resin (trade name: S-LEC BM-1, manufactured by Sekisui Chemical Co., Ltd.) in 68 parts of methyl ethyl ketone is mixed with 5 parts of methyl ethyl ketone, and the solution is dispersed in a sand mill for 2 hours using 1 mmφglass beads, thereby obtaining a dispersion liquid. 0.005 part of dioctyltin dilaurate as a catalyst and 4 parts of silicone resin particles (trade name: TOSPEARL 145, manufactured by Momentive Performance Materials Inc.) are added to the dispersion liquid, thereby obtaining a coating solution for forming an undercoat layer. The outer peripheral surface of the conductive substrate is coated with the coating solution for forming an undercoat layer by a dip coating method, and dried and cured at 170° C. for 40 minutes to form an undercoat layer. The average thickness of the undercoat layer is 25 m.
Formation of Charge Generation Layer
A mixture of 15 parts of hydroxygallium phthalocyanine as a charge generation material (Bragg angle (2θ+0.2°) of the X-ray diffraction spectrum using Cukα characteristic X-ray has diffraction peaks at positions at least of 7.5°, 9.9°, 12.5, 16.3°, 18.6°, 25.1°, and 28.3°), 10 parts of a vinyl chloride-vinyl acetate copolymer resin (trade name: VMCH, Nippon Unicar Company Limited) as a binder resin, and 200 parts of n-butyl acetate is dispersed in a sand mill for 4 hours using glass beads having a diameter of 1 mm. 175 parts of n-butyl acetate and 180 parts of methyl ethyl ketone are added to the dispersion liquid, and the mixture is stirred, thereby obtaining a coating solution for forming a charge generation layer. The undercoat layer is immersed in and coated with the coating solution for forming a charge generation layer, and dried at room temperature (25° C. 3° C.) to form a charge generation layer having an average thickness of 0.18 m.
Formation of Charge Transport Layer
60 parts of a polyester resin of the type listed in Tables 2 to 3 as a binder resin, 40 parts of a charge transport material of the type listed in Tables 2 to 3 as a charge transport material, and a specific compound or an antioxidant other than the specific compound of the type in the addition amount listed in Tables 2 and 3 as an antioxidant are dissolved in 550 parts of tetrahydrofuran and 50 parts of toluene, thereby obtaining a coating solution for forming a charge transport layer. The charge generation layer is immersed in and coated with the coating solution for forming a charge transport layer, and dried at a temperature of 150° C. for 60 minutes to form a charge transport layer having an average thickness of 40 m.
The charge transport materials CTM-1 to CTM-5 listed in Tables 2 and 3 are the following compounds.
C1-1, C2-1, C1-4, C1-3, C1-2, C2-4, and C4-1 listed in Table 2 are specific examples of the specific compound described above.
HP-1 to HP-15 listed in Table 3 are the following compounds.
The amounts of the phenolic hydroxyl group in the specific compounds or the antioxidants other than the specific compounds with respect to the mol number of the charge transport material are collectively listed in Tables 2 and 3 (“amount of hydroxyl group (mol %) in the tables).
Production of Photoreceptor Including Single Layer Type Photosensitive Layer
45.75 parts of the polyester resin of the type listed in Table 4 as a binder resin, 1.25 parts of V-type hydroxygallium phthalocyanine as a charge generation material (Bragg angle (2θ+0.2°) of the X-ray diffraction spectrum using Cukα characteristic X-ray has diffraction peaks at positions of at least 7.3°, 16.0°, 24.9°, and 28.0°), 13 parts of ETM-1 as an electron transport material, 40 parts of a charge transport material of the type listed in Table 4 as a charge transport material, a specific compound or an antioxidant other than the specific compound of the type in the addition amount listed in Table 4 as an antioxidant, and 175 parts of tetrahydrofuran and 75 parts of toluene as solvents are mixed, and the mixture is subjected to a dispersion treatment in a sand mill for 4 hours using glass beads having a diameter of 1 mm, thereby obtaining a coating solution for forming a single layer type photosensitive layer.
An aluminum substrate having an outer diameter of 30 mm, a length of 365 mm, and a thickness of 1.6 mm is coated with the obtained coating solution for forming a photosensitive layer by a dip coating method, and dried at a temperature of 150° C. for 60 minutes to form a single layer type photosensitive layer having an average thickness of 36 m.
The electron transport material ETM-1 described above and the charge transport material CTM-1 listed in Table 4 are the following compounds.
C1-1, C2-1, C1-3, and C2-4 listed in Table 4 are specific examples of the specific compound described above.
HP-1, HP-5, and HP-15 listed in Table 4 are the compounds described above.
The amounts of the phenolic hydroxyl group in the specific compounds or the antioxidants other than the specific compounds with respect to the mol number of the charge transport material are collectively listed in Table 4 (“amount of hydroxyl group (mol %) in the table).
Performance Evaluation of Photoreceptor
Electrical Properties (Burn-in Ghost)
The photoreceptor is mounted on an electrophotographic type image forming apparatus (Apeos C7070, manufactured by FUJIFILM Business Innovation Corporation). Lattice pattern charts are continuously output onto 500 sheets of A3 size plain paper, and a K (black) monochrome 30 halftone image is output onto one sheet of A3 size plain paper in a high-temperature and high-humidity environment of a temperature of 28° C. and a relative humidity of 85%. The output halftone image is observed, and sensory evaluation (grade determination) is visually performed on a difference in the density between the image area and the non-image area of the lattice pattern charts that have been continuously output on 500 sheets of paper. The grade determination is performed from 0 to 5G in an increment of 1G, and the difference in density decreases and occurrence of burn-in ghosts is suppressed as the digit of G decreases. The results of the grade determination are listed in Tables 2 to 4.
Filming
The photoreceptor is mounted on the above-described image forming apparatus. Image quality patterns with an image density of 10% are continuously output onto 50,000 sheets of A3 size paper in a high-temperature and high-humidity environment of a temperature of 28° C. and a relative humidity of 85%, the photoreceptor after the evaluation is performed is taken out, the surface thereof is directly observed with a confocal laser microscope (OLS1100, manufactured by OLYMPUS Corporation), and filming is evaluated based on the following evaluation standards. The results are listed in Tables 2 to 4.
Evaluation of Filming
The present disclosure includes the following aspects.
In Formula (A), ArA1 and ArA2 each independently represent an aromatic ring that may have a substituent, LA represents a single bond or a divalent linking group, and nA1 represents 0, 1, or 2.
In Formula (B), ArB1 and ArB2 each independently represent an aromatic ring that may have a substituent, LB represents a single bond, an oxygen atom, a sulfur atom, or —C(Rb1)(Rb2)—, and nB1 represents 0, 1, or 2. Rb1 and Rb2 each independently represent a hydrogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, or an aralkyl group having 7 or more and 20 or less carbon atoms, and Rb1 and Rb2 may be bonded to each other to form a cyclic alkyl group.
In Formula (D4), RT401, RT402, RT411, and RT412 each independently represent a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, an amino group substituted with an alkyl group having 1 or 2 carbon atoms, an aryl group, —C(RT41)═C(RT42)(RT43), or —CH═CH—CH═C(RT44)(RT45). RT41, RT42, RT43, RT44, and RT45 each independently represent a hydrogen atom, an alkyl group, or an aryl group. RT421, RT422, and RT431 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, or an alkoxy group having 1 or more and 5 or less carbon atoms. Ts1, Ts2, Tt1, Tt2, Tu1, Tu2, and Tv1 each independently represent 0, 1, or 2.
The foregoing description of the exemplary embodiments of the present invention has been provided for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Obviously, many modifications and variations will be apparent to practitioners skilled in the art. The embodiments were chosen and described in order to best explain the principles of the invention and its practical applications, thereby enabling others skilled in the art to understand the invention for various embodiments and with the various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the following claims and their equivalents.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-117236 | Jul 2022 | JP | national |
