JP2018072635A - Developer carrier and developing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developer carrier that improves adhesion between a substrate and a resin layer.SOLUTION: A developer carrier comprises a conductive substrate, and a resin layer in contact with the substrate. The resin layer contains an electronic conductive agent, a resin having at least one partial structure selected from the group consisting of specific structures in a molecule, and an anion.SELECTED DRAWING: None

Description

  The present invention relates to a developer carrier used in an electrophotographic image forming apparatus and a developing device having the developer carrier.

The developer carrier used in the electrophotographic apparatus prevents the developer from adhering to the developer carrier due to the developer charge-up, and friction charging from the surface of the developer carrier to the developer accompanying the developer charge-up. From the viewpoint of preventing improper application, for example, it is used in a low volume resistance region of 1 × 10 ³ Ω · cm or less. Patent Document 1 discloses an electrophotographic member including a conductive shaft core, and a conductive layer formed on the shaft core and including a resin having a specific cation structure and an anion.

Japanese Patent Laying-Open No. 2015-232705

As a result of further studies on the electrophotographic member according to Patent Document 1, the present inventors sometimes have insufficient adhesion between the shaft core and the conductive layer.
Accordingly, one embodiment of the present invention is directed to providing a developer carrying member having improved adhesion between a substrate and a conductive layer.

According to one aspect of the present invention, there is provided a developer carrying body having a conductive substrate and a conductive resin layer in contact with the substrate,
The resin layer includes an electronic conductive agent, a resin having at least one partial structure selected from the group consisting of structures represented by the following formulas (1) to (7) in the molecule, and an anion. A carrier is provided.

In formulas (1) to (7),
R _{101, R 201} and _{R 202, R} 603 from the _{R 301} from _{R 303, R 401 R 404,} R 501 and _{R 502, R 601,} from _{R 701 R 704} each independently represent a hydrogen atom, OH, CH ₂ OH, C ₂ H ₄ OH, COOH,
R ₁₀₂ , R ₂₀₃ and R ₂₀₄ , R ₃₀₄ to R ₃₀₆ , R ₄₀₅ to R ₄₀₈ , R ₅₀₃ to R ₅₀₅ , R ₆₀₄ to R ₆₀₇ , and R ₇₀₅ to R ₇₁₀ are each independently C _m H _2m (m is , An integer of 2 to 16) or (C ₂ H ₄ O) ₁ C ₂ H ₄ (l is an integer of 1 to 8),
R ₃₀₇ represents an alkyl group having 1 to 18 carbon atoms,
X ₅₀₁ , X ₇₀₁ and X ₇₀₂ each independently represent a nitrogen atom or a methine group,
X ₆₀₁ represents a nitrogen cation or a carbon atom,
A ₁₀₁ , A ₅₀₁ and A ₆₀₁ each independently represent any of the following structural formulas (a) to (d), and E ₂₀₁ and E ₇₀₁ each independently represent the following structural formula (e) or (f). Show

In formulas (a) to (f), R _{1 to} R ₉ each independently represents an alkyl group having 1 to 18 carbon atoms, n1 and n2 each independently represent 1 or 2, Y ₁ and Y ₂ represents a methylene group or an oxygen atom.

  According to another aspect of the present invention, there is provided a developer carrying member having a conductive substrate and a resin layer in contact with the substrate, the resin layer comprising an electronic conductive agent and a compound represented by the following formula ( At least one ion conductive agent having one cationic structure and an anion selected from the group consisting of the structures represented by I1) to (I7), and a functional group capable of reacting with the primary or secondary amino group of the ion conductive agent Provided is a developer carrier containing a resin comprising a reaction product with a compound having a group.

In formulas (I1) to (I7),
R _{101, R 201} and _{R 202, R} 603 from the _{R 301} from _{R 303, R 401 R 404,} R 501 and _{R 502, R 601,} from _{R 701 R 704} each independently represent a hydrogen atom, OH, CH ₂ OH, C ₂ H ₄ OH, COOH,
R ₁₀₂ , R ₂₀₃ and R ₂₀₄ , R ₃₀₄ to R ₃₀₆ , R ₄₀₅ to R ₄₀₈ , R ₅₀₃ to R ₅₀₅ , R ₆₀₄ to R ₆₀₇ , and R ₇₀₅ to R ₇₁₀ are each independently C _m H _2m (m is , An integer of 2 to 16) or (C ₂ H ₄ O) ₁ C ₂ H ₄ (l is an integer of 1 to 8),
R ₃₀₇ represents an alkyl group having 1 to 18 carbon atoms,
X ₅₀₁ , X ₇₀₁ , and X ₇₀₂ each independently represent a nitrogen atom or a methine group,
X ₆₀₁ represents a nitrogen cation or a carbon atom,
A ₁₀₁ , A ₅₀₁ and A ₆₀₁ each independently represent any of the following structural formulas (a) to (d),
E ₂₀₁ and E ₇₀₁ each independently represent the following structural formula (e) or (f).

In formulas (a) to (f), R _{1 to} R ₉ each independently represents an alkyl group having 1 to 18 carbon atoms, n1 and n2 each independently represent 1 or 2, Y ₁ and Y ₂ represents a methylene group or an oxygen atom.

  According to still another aspect of the present invention, a developer, a container for containing the developer, and a developer carrier for carrying and transporting the developer contained in the container are provided. A developing device is provided, wherein the developer carrying member is the developer carrying member described above.

According to one embodiment of the present invention, a developer carrier having excellent adhesion between a substrate and a resin layer can be obtained.
Further, according to one embodiment of the present invention, a developing device capable of stably forming a high-quality electrophotographic image can be obtained.

It is a schematic sectional drawing which shows an example of the developer carrier which concerns on this invention. FIG. 2 is a schematic diagram illustrating an example of a developing device using the developer carrying member of the present invention. It is the schematic diagram which showed another example of the developing device using the developing agent carrier of this invention.

When using a resin having a quaternary ammonium salt structure as a resin contained in the conductive resin layer, the present inventors introduce a specific functional group into a nitrogen atom in the quaternary ammonium salt structure to thereby provide a conductive material. It has been found that the adhesion between the conductive resin layer and the substrate can be improved.
The inventors presume the reason as follows. That is, surface functional groups such as OH and H are present on the surface of a substrate that is not surface-treated such as an aluminum base tube. Since a hydrogen bond is formed between the surface functional group and a specific functional group in the resin layer, it is considered that the adhesion is improved. In order to strengthen this hydrogen bond and further enhance the adhesion between the resin layer and the substrate, it is necessary to form a hydrogen bond between an element having high electronegativity and hydrogen.
Resin in which the element bonded to amino nitrogen having high electronegativity is a hydrogen atom, and each resin in which the functional group bonded to amino nitrogen is —OH, —CH ₂ OH, —CH ₂ CH ₂ OH, —COOH The adhesion of the resin layer containing each of the above to the aluminum tube was examined. As a result, the adhesiveness of the resin layer containing a resin in which hydrogen atoms are bonded to amino nitrogen was relatively low, and the adhesiveness of the other resin layers was almost the same.
That is, as compared with a resin layer containing a resin in which all elements bonded to amino nitrogen are H, at least one of functional groups bonded to amino nitrogen is —OH, —CH ₂ OH, —CH ₂ CH ₂ OH, and — The resin layer containing a resin selected from the group consisting of COOH has improved adhesion to the substrate. And as the number of any functional group selected from the above group that binds to the amino nitrogen increases, the adhesion is further improved. That is, when the functional groups bonded to the amino nitrogen are all functional groups selected from the above group, the adhesion to the substrate is particularly excellent.

Hereinafter, the present invention will be described in detail.
FIG. 1 is a schematic sectional view showing an example of the developer carrying member of the present invention. As shown in FIG. 1, the developer carrier 1 according to the present invention can include a conductive substrate 3 and a resin layer 2 provided on the outer periphery thereof. The resin layer 2 is a resin layer containing the resin according to the present invention. The resin layer may have a multilayer structure in which two or more layers are arranged. In this case, if the layer in contact with the substrate is a layer containing the resin according to the present invention, a resin layer having conductivity other than the present invention may be used for the other layers.

<Conductive substrate>
As the conductive substrate, a substrate known in the field of the developer carrying member can be used, and the shape thereof can be appropriately selected from a hollow cylindrical shape, a solid columnar shape, a belt shape, and the like. In the present invention, the adhesion is improved by the interaction of the functional group of the substrate and the resin layer. Therefore, a material containing a metal is preferable as the substrate, and aluminum, iron, etc., which easily form an oxide film (passive) on the surface. Metal base tubes and metal bars are more preferable.

<Resin layer>
The resin constituting the resin layer according to the present invention will be described. The resin according to the present invention has at least one partial structure selected from the group consisting of structures represented by the following formulas (1) to (7) in the molecule.

(Formula 1)
The structure of the formula (1) contained in the resin according to the present invention is shown below.

In formula (1), R ₁₀₁ represents a hydrogen atom, OH, CH ₂ OH, C ₂ H ₄ OH, COOH,
R ₁₀₂ represents C _m H _2m (m is an integer of 2 to 16) or (C ₂ H ₄ O) ₁ C ₂ H ₄ (l is an integer of 1 to 8), and A ₁₀₁ has the following structure One of formulas (a) to (d) is shown.

Here, R < ₁ > -R < ₇ > shows a C1-C18 alkyl group each independently,
n1 represents 1 or 2, and Y ₁ represents a methylene group or an oxygen atom.

In order to obtain a resin having a partial structure represented by the formula (1), a binder resin as a raw material is reacted with an ionic conductive agent having a partial structure represented by the formula (1) to form a quaternary ammonium salt structure. It is important to obtain the introduced resin. Here, the reactive site in the ionic conductive agent as a raw material to be reacted with the binder resin is a nitrogen atom. Therefore, R ₁₀₁ suppresses steric hindrance, does not hinder the reactivity between the ionic conductive agent and the binder resin as a raw material, and improves the adhesion to the substrate, so that hydrogen atoms, OH, CH ₂ OH, C ₂ Selected from H ₄ OH, COOH. Furthermore, OH, CH ₂ OH, C ₂ H ₄ OH, and COOH are preferable because the interaction with the surface functional group of the substrate becomes strong. R ₁₀₂ also has an alkylene chain of 2 to 16 carbon atoms [C _m H _2m (m is an integer of 2 to 16)] from the viewpoints of reactivity and conductivity between the binder resin as a raw material and the ionic conductive agent. Alternatively, it is selected from ethylene oxide chains [(C ₂ H ₄ O) ₁ C ₂ H ₄ (l is an integer of 1 to 8)] having a repeating unit of 1 to 8. If it is this range, it will be sufficient also regarding electroconductivity, without inhibiting the reactivity of the ionic conductive agent to the binder resin as a raw material.
The quaternary ammonium cation structure represented by A ₁₀₁ is any one of formulas (a) to (d), and R _{1 to} R ₇ are each independently an alkyl group having 1 to 18 carbon atoms, n1 When ₁ is 2 or Y ₁ is a methylene group or an oxygen atom, the reaction with the binder resin is not hindered, and high conductivity and compatibility with the binder resin can be obtained. The quaternary ammonium cation structure represented by A ₁₀₁ may be the same or different when the resin has a plurality of partial structures represented by Formula (1).

(Formula 2)
The structure of the formula (2) contained in the resin according to the present invention is shown below.

In Formula (2), R ₂₀₁ and R ₂₀₂ each independently represent a hydrogen atom, OH, CH ₂ OH, C ₂ H ₄ OH, or COOH, and R ₂₀₃ and R ₂₀₄ each independently represent C _m H _2m (where m is , An integer of 2 to 16) or (C ₂ H ₄ O) ₁ C ₂ H ₄ (l is an integer of 1 to 8), and E ₂₀₁ represents the following structural formula (e) or (f).

Here, R < ₈ > and R < ₉ > show a C1-C18 alkyl group each independently.
n2 represents 1 or 2, _{Y 2} represents a methylene group or an oxygen atom.

In order to obtain a resin having a partial structure represented by the formula (2), a binder resin as a raw material is reacted with an ionic conductive agent having a partial structure represented by the formula (2) to form a quaternary ammonium salt structure. It is important to obtain the introduced resin. Here, the reactive site in the ionic conductive agent as a raw material to be reacted with the binder resin is a nitrogen atom as in the formula (1). Therefore, R ₂₀₁ and R ₂₀₂ suppress steric hindrance, do not hinder the reactivity between the ionic conductive agent and the binder resin as a raw material, and improve the adhesion to the substrate, so that hydrogen atoms, OH, CH ₂ OH , C ₂ H ₄ OH, COOH. Furthermore, OH, CH ₂ OH, C ₂ H ₄ OH, and COOH are more preferable because the interaction with the surface functional group of the substrate becomes strong. Further, regarding R ₂₀₃ and R ₂₀₄ , from the viewpoint of reactivity and conductivity between the binder resin as a raw material and the ionic conductive agent, an alkylene chain having 2 to 16 carbon atoms or an ethylene oxide chain having 1 to 8 repeating units. Selected from. If it is this range, it will be sufficient also regarding electroconductivity, without inhibiting the reactivity of the ionic conductive agent to the binder resin as a raw material.
The quaternary ammonium cation structure represented by E ₂₀₁ is a structure of the formula (e) or (f), R ₈ and R ₉ are each independently an alkyl group having 1 to 18 carbon atoms, and n2 is 1 or When Y ₂ is a methylene group or an oxygen atom, the reaction with the binder resin is not hindered, and high conductivity and compatibility with the binder resin can be obtained. The quaternary ammonium cation structure represented by E ₂₀₁ may be the same or different when the resin has a plurality of partial structures represented by Formula (2).

(Formula 3)
The structure of the formula (3) contained in the resin according to the present invention is shown below.

In formula (3), R ₃₀₁ to R ₃₀₃ each independently represent a hydrogen atom, OH, CH ₂ OH, C ₂ H ₄ OH, or COOH, and R ₃₀₄ to R ₃₀₆ each independently represent C _m H _2m (m is , An integer of 2 to 16) or (C ₂ H ₄ O) ₁ C ₂ H ₄ (l is an integer of 1 to 8), R ₃₀₇ represents an alkyl group having 1 to 18 carbon atoms.

In order to obtain a resin having a partial structure represented by the formula (3), a binder resin as a raw material is reacted with an ionic conductive agent having a partial structure represented by the formula (3) to form a quaternary ammonium salt structure. It is important to obtain the introduced resin. Here, the reactive site in the ionic conductive agent as a raw material to be reacted with the binder resin is a nitrogen atom as in the formula (1). Therefore, R ₃₀₁ to R ₃₀₃ suppress steric hindrance, do not hinder the reactivity between the ionic conductive agent and the binder resin as a raw material, and improve the adhesion to the substrate, so that hydrogen atoms, OH, CH ₂ OH , C ₂ H ₄ OH, COOH. Furthermore, OH, CH ₂ OH, C ₂ H ₄ OH, and COOH are preferable because the interaction with the surface functional group of the substrate becomes strong. Also, regarding R ₃₀₄ to R ₃₀₆ , from the viewpoint of the reactivity and conductivity between the binder resin as a raw material and the ionic conductive agent, an alkylene chain having 2 to 16 carbon atoms or an ethylene oxide chain having 1 to 8 repeating units. Selected from. If it is this range, it will be sufficient also regarding electroconductivity, without inhibiting the reactivity of the ionic conductive agent to the binder resin as a raw material. R ₃₀₇ is selected from alkyl groups having 1 to 18 carbon atoms from the viewpoints of reactivity between the binder resin and the ionic conductive agent and conductivity.

(Formula 4)
The structure of the formula (4) contained in the resin according to the present invention is shown below.

In Formula (4), R ₄₀₁ to R ₄₀₄ each independently represent a hydrogen atom, OH, CH ₂ OH, C ₂ H ₄ OH, or COOH, and R ₄₀₅ to R ₄₀₈ each independently represent C _m H _2m (m is , An integer of 2 to 16) or (C ₂ H ₄ O) ₁ C ₂ H ₄ (l is an integer of 1 to 8).

In order to obtain a resin having a partial structure represented by formula (4), a binder resin as a raw material is reacted with an ionic conductive agent having a partial structure represented by formula (4) to form a quaternary ammonium salt structure. It is important to obtain the introduced resin. Here, the reactive site in the ionic conductive agent as a raw material to be reacted with the binder resin is a nitrogen atom as in the formula (1). Therefore, R ₄₀₁ to R ₄₀₄ suppress steric hindrance, do not hinder the reactivity between the ionic conductive agent and the binder resin as a raw material, and improve the adhesion to the substrate, so that hydrogen atoms, OH, CH ₂ OH , C ₂ H ₄ OH, COOH. Furthermore, OH, CH ₂ OH, C ₂ H ₄ OH, and COOH are preferable because the interaction with the surface functional group of the substrate becomes strong. R ₄₀₅ to R ₄₀₈ also have an alkylene chain having 2 to 16 carbon atoms or an ethylene oxide chain having 1 to 8 repeating units from the viewpoint of reactivity and conductivity between the binder resin as a raw material and an ionic conductive agent. Selected from. If it is this range, it will be sufficient also regarding electroconductivity, without inhibiting the reactivity of the ionic conductive agent to the binder resin as a raw material.

(Formula 5)
The structure of the formula (5) contained in the resin according to the present invention is shown below.

In Formula (5), R ₅₀₁ and R ₅₀₂ each independently represent a hydrogen atom, OH, CH ₂ OH, C ₂ H ₄ OH, or COOH, and R ₅₀₃ to R ₅₀₅ are each independently C _m H _2m (m Represents an integer of 2 to 16) or (C ₂ H ₄ O) ₁ C ₂ H ₄ (l is an integer of 1 to 8), X ₅₀₁ represents a nitrogen atom or a methine group, and A ₅₀₁ represents the above One of structural formulas (a) to (d) is shown.

In order to obtain a resin having a partial structure represented by formula (5), a binder resin as a raw material is reacted with a partial structure ionic conductive agent represented by formula (5) to introduce a quaternary ammonium salt structure. It is important to obtain a suitable resin. Here, the reactive site in the ionic conductive agent as a raw material to be reacted with the binder resin is a nitrogen atom as in the formula (1). Therefore, R ₅₀₁ and R ₅₀₂ suppress steric hindrance, do not hinder the reactivity between the ionic conductive agent and the binder resin as a raw material, and improve the adhesion to the substrate, so that hydrogen atoms, OH, CH ₂ OH , C ₂ H ₄ OH, COOH. Furthermore, OH, CH ₂ OH, C ₂ H ₄ OH, and COOH are preferable because the interaction with the surface functional group of the substrate becomes strong. Further, regarding R ₅₀₃ to R ₅₀₅ , from the viewpoint of the reactivity and conductivity between the binder resin as a raw material and the ionic conductive agent, an alkylene chain having 2 to 16 carbon atoms or an ethylene oxide chain having 1 to 8 repeating units. Selected from. If it is this range, it will be sufficient also regarding electroconductivity, without inhibiting the reactivity of the ionic conductive agent to the binder resin as a raw material. X ₅₀₁ is a nitrogen atom or a methine group and can be easily synthesized.
In addition, since the quaternary ammonium cation structure represented by A ₅₀₁ is any one of the structural formulas (a) to (d), the reaction with the binder resin is not hindered, the conductivity is high, and the binder resin The compatibility of is obtained.

(Formula 6)
The structure of the formula (6) contained in the resin according to the present invention is shown below.

In the formula (6), R ₆₀₁ to R ₆₀₃ independently represent a hydrogen atom, OH, CH ₂ OH, C ₂ H ₄ OH, COOH, and R ₆₀₄ to R ₆₀₇ each independently represent C _m H _2m (m Represents an integer of 1 to 16) or (C ₂ H ₄ O) ₁ C ₂ H ₄ (l is an integer of 1 to 8), X ₆₀₁ represents a nitrogen cation or a carbon atom, and A ₆₀₁ represents the structure described above. One of formulas (a) to (d) is shown.

In order to obtain a resin having a partial structure represented by formula (6), a binder resin as a raw material is reacted with an ionic conductive agent having a partial structure represented by formula (6) to form a quaternary ammonium salt structure. It is important to obtain the introduced binder resin. Here, the reactive site in the ionic conductive agent as a raw material to be reacted with the binder resin is a nitrogen atom as in the formula (1). Therefore, R ₆₀₁ to R ₆₀₃ suppress steric hindrance, do not hinder the reactivity between the ionic conductive agent and the binder resin as a raw material, and improve the adhesion to the substrate, so that hydrogen atoms, OH, CH ₂ OH , C ₂ H ₄ OH, COOH. Furthermore, OH, CH ₂ OH, C ₂ H ₄ OH, and COOH are preferable because the interaction with the surface functional group of the substrate becomes strong. R ₆₀₄ to R ₆₀₇ also have an alkylene chain having 2 to 16 carbon atoms or an ethylene oxide chain having 1 to 8 repeating units from the viewpoint of reactivity and conductivity between the binder resin as a raw material and an ionic conductive agent. Selected from. If it is this range, it will be sufficient also regarding electroconductivity, without inhibiting the reactivity of the ionic conductive agent to the binder resin as a raw material. X ₆₀₁ can be easily synthesized by being a nitrogen cation or a carbon atom.
Since quaternary ammonium cation structure represented by A ₆₀₁ is either of the structural formulas (a) ~ (d), without inhibiting the reaction between the binder resin, high conductivity, and a binder resin The compatibility of is obtained.

(Formula 7)
The structure of the formula (7) contained in the resin according to the present invention is shown below.

In formula (7), R ₇₀₁ to R ₇₀₄ independently represent a hydrogen atom, OH, CH ₂ OH, C ₂ H ₄ OH, COOH, and R ₇₀₅ to R ₇₁₀ each independently represent C _m H _2m (m Represents an integer of 2 to 16) or (C ₂ H ₄ O) ₁ C ₂ H ₄ (l is an integer of 1 to 8), X ₇₀₁ and X ₇₀₂ each represent a nitrogen atom or a methine group, E ₇₀₁ represents the structural formula (e) or (f).

In order to obtain a resin having a partial structure represented by formula (7), a binder resin as a raw material is reacted with an ionic conductive agent having a partial structure represented by formula (7) to form a quaternary ammonium salt structure. It is important to obtain the introduced resin. Here, the reactive site in the ionic conductive agent as a raw material to be reacted with the binder resin is a nitrogen atom as in the formula (1). Therefore, R ₇₀₁ to R ₇₀₄ suppress steric hindrance, do not hinder the reactivity between the ionic conductive agent and the binder resin as a raw material, and improve the adhesion to the substrate, so that hydrogen atoms, OH, CH ₂ OH , C ₂ H ₄ OH, COOH. Furthermore, OH, CH ₂ OH, C ₂ H ₄ OH, and COOH are preferable because the interaction with the surface functional group of the substrate becomes strong. R ₇₀₅ to R ₇₁₀ also have an alkylene chain having 2 to 16 carbon atoms or an ethylene oxide chain having 1 to 8 repeating units from the viewpoint of reactivity and conductivity between the binder resin as a raw material and an ionic conductive agent. Selected from. If it is this range, it will be sufficient also regarding electroconductivity, without inhibiting the reactivity of the ionic conductive agent to the binder resin as a raw material. Since X ₇₀₁ and X ₇₀₂ are a nitrogen atom or a methine group, the synthesis is easy.
As quaternary ammonium cation structure represented by E _701, the structural formula (e) or (f) may not inhibit the reaction of the binder resin, high conductivity, and compatibility with a binder resin to give It is done. When the resin has a plurality of partial structures represented by the formula (7), the quaternary ammonium cation structure represented by E ₇₀₁ may be the same or different.

  Below, the binder resin raw material and ionic conductive agent as the raw material of the resin used in the present invention will be described.

<Binder resin raw material>
The resin according to the present invention includes at least one ion conductive agent comprising one partial structure selected from the group consisting of the structures represented by the above formulas (1) to (7) and an anion, and 1 of the ion conductive agent. It consists of a reaction product with a compound (binder resin material) having a functional group capable of reacting with a secondary or secondary amino group.
Examples of the compound having a functional group capable of reacting with an amino group include a monomer compound having the functional group or a prepolymer having the functional group at the terminal. Such a compound is generally selected from those having a known functional group that is reactive with an amino group. Specific examples include, but are not limited to, isocyanate compounds, epoxy compounds, carboxylic acid compounds, acid halides, acid anhydride compounds, aldehyde compounds, ketone compounds, halides, α, β unsaturated carbonyl compounds, and the like. Absent. Examples of the ammonia-catalyzed resol type phenol resin include a resin that forms a covalent bond with an amino group by a Strecker reaction, a Mannich reaction, a Betti reaction or the like in a three-component reaction of an amine compound, an aldehyde, and a nucleophile.
Preferable materials for the binder resin include isocyanate compounds, epoxy compounds, carboxylic acid compounds, acid halides, halides and their prepolymers, and ammonia-catalyzed resol type phenol resins. More preferable are an isocyanate group-terminated prepolymer, an epoxy group-terminated prepolymer, and an ammonia-catalyzed resol type phenol resin. This is because the resin obtained by reacting these binder resin raw materials with an ionic conductive agent having a primary or secondary amino group is easily and chemically stable to be mixed with the electronic conductive agent.
Below, the structure of the coupling | bond part which reacted with the ion conductive agent which has a primary or secondary amino group, and each binder resin raw material is shown. That is, the resin according to the present invention in which a quaternary ammonium cation structure derived from an ionic conductive agent is introduced is represented by the above formulas (1) to (10) through any structure represented by the following formulas (8) to (10). Any partial structure of (7) and the resin molecular chain are bonded.

Here, in formulas (8) to (10), * represents a binding site of any structure of formulas (1) to (7), and ** represents a binding site to the resin molecular chain. The methylene linking chain in formula (10) is bonded to the ortho or para position of the benzene ring with respect to the hydroxy group. In addition, Formula (8) is the structure which the amino group which the ionic conductive agent mentioned later has, and the NCO group which an isocyanate compound has reacted, Formula (9) has the amino group and epoxy compound which the ionic conductive agent mentioned later has. A structure formed by ring-opening addition of an epoxy ring, Formula (10), is a structure in which an amino group of an ionic conductive agent described later reacts with an ammonia-catalyzed resol type phenol resin.

<Ionic conductive agent>
(Cation)
The ionic conductive agent as a raw material of the present invention is an ionic conductive agent having a primary or secondary amino group that reacts with a binder resin and a quaternary ammonium group. Typical cation structures of this ionic conductive agent are shown in the following I1 to I7, but the present invention is not limited only to the resin produced using the ionic conductive agent having the exemplified cation structure.

In the formulas (I1) to (I7), each group has the same meaning as the groups described in the formulas (1) to (7).

(Anion)
The anion of the ionic conductive agent used in the present invention, that is, the anion contained in the resin layer according to the present invention includes halogen ions such as fluorine, chlorine, bromine and iodine, perchlorate ions, sulfonate compound ions, and phosphoric acid. Compound ions, boric acid compound ions, perfluorosulfonylimide ions and the like can be mentioned.
Among the above ionic species, perfluorosulfonylimide ions are preferred. Since perfluorosulfonylimide ions have high hydrophobicity, the affinity with the binder resin raw material according to the present invention tends to be higher than that of general highly hydrophilic ions. As a result, it is easy to disperse and react uniformly with the binder resin raw material and is easy to be immobilized, which is preferable in terms of reducing dispersion unevenness.
Specific examples of perfluorosulfonylimide ions include bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide, bis (pentafluoroethanesulfonyl) imide, bis (nonafluorobutanesulfonyl) imide, and cyclo-hexafluoropropane. Examples include, but are not limited to, -1,3-bis (sulfonyl) imide.
Such an ionic conductive agent comprising a combination of a cation and an anion can be used alone or in combination of two or more. When combining 2 or more types, it is preferable to combine those having the same anion. From the viewpoint of adhesion, at least one ion conductive agent having a secondary amino group is preferably used, and an ion conductive agent having no primary amino group is more preferably used.

(Addition amount)
The addition amount of the ionic conductive agent can be appropriately set, and the ionic conductive agent is preferably blended at a ratio of 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin raw material as a raw material. . When the blending amount is 0.5 parts by mass or more, the conductivity imparting effect due to the addition of the ionic conductive agent can be easily obtained. In the case of 20 parts by mass or less, the environmental dependency of electrical resistance can be reduced.

(Analysis method)
Whether the partial structure of any one of formulas (1) to (7) according to the present invention is introduced into the resin can be confirmed by the following method. By cutting out a part of the resin layer and performing IR (infrared spectroscopy) analysis, it can be confirmed whether or not the partial structure is connected. Moreover, a partial structure can be confirmed by implementing solid ¹³ C-NMR (nuclear magnetic resonance) measurement and TOF-MS (time-of-flight mass spectrometry) measurement on the resin layer. In addition, Soxhlet extraction work was performed for 1 week using a hydrophilic solvent such as ethanol, and the obtained extraction residue was subjected to solid-state ¹³ C-NMR (nuclear magnetic resonance) measurement and TOF-MS (time-of-flight mass spectrometry). ) The anion species can be confirmed by carrying out the measurement.

<Electronic conductive agent>
Examples of the electronic conductive agent contained in the resin layer according to the present invention include metals such as aluminum, copper, nickel, and silver, metal oxides such as antimony oxide, indium oxide, tin oxide, titanium oxide, zinc oxide, and molybdenum oxide, and crystallinity. Examples thereof include conductive particles such as graphite, various carbon fibers, furnace black, lamp black, thermal black, acetylene black, and channel black, and fibers of the above metals. In particular, carbon black and graphite are preferable because they are excellent in dispersibility and conductivity.

<Other materials>
In the present invention, irregularity imparting particles may be added for the purpose of controlling and maintaining the roughness of the resin layer surface at an appropriate value. Examples of the irregularity-imparting particles include the following. Resin particles such as vinyl polymers and copolymers such as polymethyl methacrylate, polyethyl acrylate, polybutadiene, polyethylene, polypropylene, polystyrene, benzoguanamine resin, phenol resin, polyamide resin, fluororesin, silicone resin, epoxy resin, polyester resin Particles formed from oxide particles such as alumina, zinc oxide, silicone, titanium oxide and tin oxide, carbon particles, conductive particles such as resin particles subjected to conductive treatment, and organic compounds such as imidazole compounds. In addition, an inorganic fine powder adhered or fixed to the surface of the resin particle used as the unevenness imparting particle may be used.

<Formation method>
Examples of the method for forming the resin layer include a method in which each component is dispersed and mixed in a solvent to form a paint, which is coated on the substrate and dried. For the dispersion mixing of each component, a known dispersion apparatus using beads such as a sand mill, a paint shaker, a dyno mill, a pearl mill, or a medialess dispersion not using them can be suitably used. Moreover, as a coating method, well-known methods, such as a dipping method, a spray method, and a roll coat method, are applicable.
The thickness of the resin layer is not particularly limited, but is preferably 3 μm or more and 25 μm or less, and more preferably 4 μm or more and 20 μm or less in order to obtain a uniform film thickness without desorption of the electron conductive agent.

[Development equipment]
Next, the developing device according to the present invention will be described. FIG. 2 is a schematic cross-sectional view showing an example of a developing device provided with the developer carrying member according to the present invention. In FIG. 2, an electrostatic latent image holding body that holds an electrostatic latent image, for example, the photosensitive drum 5 rotates in the arrow B direction. The developer carrier 1 according to the present invention carries and conveys a one-component developer which is a magnetic developer supplied by a container (developing container 6) for containing the developer. As the developer carrying member 1 rotates in the direction of arrow A, the developer is transported to the developing region C where the developer carrying member 1 and the photosensitive drum 5 face each other. As shown in FIG. 2, a magnet is inscribed in the hollow cylindrical base of the developer carrier 1 in order to magnetically attract and hold the developer on the developer carrier 1. A roller 7 is arranged.

  In the developing container 6, a stirring blade 8 for stirring the developer is provided. The developer obtains a triboelectric charge capable of developing the electrostatic latent image on the photosensitive drum 5 by friction between the developers and the resin layer 2 of the developer carrier 1. In the example of FIG. 2, in order to regulate the layer thickness of the developer conveyed to the development area C, a magnetic regulation blade 9 made of a ferromagnetic metal as a developer layer thickness regulating member is provided on the surface of the developer carrier 1. To 50 μm to 500 μm so as to face the developer carrier 1. A magnetic force line from the magnetic pole N <b> 1 of the magnet roller 7 concentrates on the magnetic regulation blade 9, whereby a thin layer of developer is formed on the developer carrier 1. A nonmagnetic blade can be used instead of the magnetic regulating blade 9.

  In this manner, the thickness of the thin developer layer formed on the developer carrier 1 is thinner than the minimum gap between the developer carrier 1 and the photosensitive drum 5 in the development region C. It is preferable. As described above, it is particularly effective to incorporate the developer carrying member according to the present invention in a non-contact type developing apparatus. In the developing region C, the developer carrier of the present invention is also applied to a developing device in which the thickness of the developer layer is equal to or greater than the minimum gap between the developer carrier 1 and the photosensitive drum 5, that is, a contact type developing device. Can be applied. In order to avoid complicated description, the following description will be made with the non-contact type developing apparatus as described above as an example.

  In order to fly a one-component developer having a magnetic developer carried on the developer carrying member 1, a developing bias voltage is applied to the developer carrying member 1 by a developing bias power source 10 as a bias means. . When a DC voltage is used as the developing bias voltage, a voltage having a value between the potential of the image portion of the electrostatic latent image (the region visualized as the developer adheres) and the potential of the background portion is carried by the developer. Application to the body 1 is preferred.

FIG. 3 is a schematic cross-sectional view showing another embodiment of the developing device using the developer carrying member of the present invention. In the developing device shown in FIG. 3, as a developer layer thickness regulating member for regulating the developer layer thickness on the developer carrier 1, a material having rubber elasticity such as urethane rubber, silicone rubber, phosphor bronze, stainless steel, or the like is used. An elastic regulating blade 11 made of an elastic plate made of a material having metal elasticity such as steel is used. The elastic regulating blade 11 is pressed in the direction opposite to the rotation direction of the developer carrier 1. In this developing device, a developer layer thickness regulating member is elastically pressed against the developer carrier 1 through the developer layer, thereby forming a thin layer of developer on the developer carrier. Thus, a thin developer layer can be formed on the developer carrier 1. 3 is the same as that of the developing apparatus shown in FIG. 2, and the same reference numerals denote the same members.
The developing device according to the present invention can be used as a process cartridge configured to be detachable from the electrophotographic image forming apparatus main body, or directly incorporated in the main body of the electrophotographic image forming apparatus.

  Examples of the present invention will be described below. In the following synthesis examples and preparation examples, “part” and “%” are based on mass unless otherwise specified.

<1. Synthesis of ionic conductive agent>
(Synthesis of an ionic conductive agent having a cation structure of the formula (I1))
(Ionic conductive agent 1)
10 mmol of N- (4-bromobutyl) phthalimide as a quaternizing agent was dissolved in 10 ml of acetone, and 15 mmol of a 28% aqueous solution of trimethylamine was added as a tertiary amine at room temperature, followed by heating under reflux for 72 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. After repeating this operation three times, the residue was dissolved in 10 ml of ethanol, 15 mmol of hydrazine monohydrate (purity 79%) was added and the mixture was heated and stirred at 40 ° C. for 4 hours, then cooled to room temperature and filtered. The solvent in the filtrate was distilled off under reduced pressure. The resulting anion of the residue is a bromide ion.
In order to perform anion exchange, the obtained residue was dissolved in 5 ml of dichloromethane, and then an aqueous solution in which 10 mmol of lithium bis (trifluoromethanesulfonyl) imide was dissolved as an anion exchange salt was added and stirred for 24 hours. The obtained solution was separated to obtain an organic layer. This organic layer was washed twice with water and separated, and then dichloromethane was distilled off under reduced pressure to obtain ionic conductive agent 1 whose anion was bis (trifluoromethanesulfonyl) imide ion (TFSI). Table 2 shows the structure of the synthesized ionic conductive agent 1.

(Ionic conductive agent 2)
15 mmol of 1,2-dibromoethane, which is a quaternizing agent, was dissolved in 10 ml of acetonitrile, 10 mmol of trimethylamine was added as a tertiary amine at room temperature, and then heated to reflux for 72 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. After this operation was repeated three times, the residue was dissolved in 10 ml of ethanol, 30 mmol of aminomethanol 40% aqueous solution (the amine added here is referred to as the second amine hereinafter) and then heated to reflux for 72 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times. The resulting anion of the residue is a bromide ion.
In order to perform anion exchange, the obtained residue was dissolved in 5 ml of dichloromethane, and then an aqueous solution in which 10 mmol of bis (trifluoromethanesulfonyl) imide lithium salt was dissolved as an anion exchange salt was added and stirred for 24 hours. The obtained solution was separated to obtain an organic layer. This organic layer was washed twice with water and separated, and then dichloromethane was distilled off under reduced pressure to obtain an ionic conductive agent 2 whose anion was TFSI. Table 2 shows the structure of the synthesized ionic conductive agent 2.

(Ionic conductive agent 3-15)
Ionic conductive agents 3 to 15 were synthesized in the same manner as the ionic conductive agent 2 except that the quaternizing agent, tertiary amine, and second amine were changed to those shown in Table 1. In addition, the ion conductive agent 4 did not perform anion exchange, and the ion conductive agent 5 changed the anion exchange salt to cyclohexafluoropropane-1,3-bis (sulfonyl) imide potassium salt (CHFSI K). The ionic conductive agent 15 was subjected to acid hydrolysis before anion exchange. Table 2 shows the structures of the synthesized ionic conductive agents 3 to 15.

(Synthesis of an ionic conductive agent having a cation structure of the formula (I2))
(Ion conductive agent 16)
Fluorenylmethyl chloroformate (Fmoc-Cl) 40 mmol and pyridine were added to 30 mmol of aminomethanol 40% aqueous solution and heated to reflux for 24 hours. Piperidine 20% DMF solution was added, and the mixture was further heated to reflux for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times. The obtained residue was dissolved in 10 ml of ethanol, bis (2-chloroethyl) amine hydrochloride was added, and the mixture was heated to reflux for 72 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times, and the resulting concentrate was dissolved in 10 ml of acetonitrile, and then 20 mmol of iodomethane was added and stirred at room temperature for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. After repeating this operation three times, the residue was dissolved in 10 ml of ethanol, palladium / carbon was added, and the mixture was stirred at room temperature in a hydrogen gas atmosphere. After filtering the reaction solution, the solvent was distilled off under reduced pressure. The anion of the resulting residue is iodine ion.
In order to perform anion exchange, the obtained residue was dissolved in 5 ml of dichloromethane, and then an aqueous solution in which 10 mmol of lithium bis (trifluoromethanesulfonyl) imide was dissolved as an anion exchange salt was added and stirred for 24 hours. The obtained solution was separated to obtain an organic layer. This organic layer was washed twice with water and separated, and then dichloromethane was distilled off under reduced pressure to obtain ionic conductive agent 16 whose anion was bis (trifluoromethanesulfonyl) imide ion (TFSI). Table 3 shows the structure of the synthesized ionic conductive agent 16.

(Ion conductive agent 17)
To 20 mmol of thionyl chloride solution dissolved in 10 ml of benzene, 10 mmol of 8-amino-1-octanol was added and heated to reflux for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times. The obtained residue was dissolved in 10 ml of ethanol, 10 mmol of 8-chloro-1-n-octanol was added, and the mixture was heated to reflux for 72 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times. The obtained residue was dissolved in 10 ml of benzene, 10 mmol of thionyl chloride was added, and the mixture was heated to reflux for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times. After the obtained concentrate was dissolved in 10 ml of acetonitrile, 20 mmol of iodomethane was added and stirred at room temperature for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. After repeating this operation three times, the residue was dissolved in 10 ml of ethanol, palladium / carbon was added, and the mixture was stirred at room temperature in a hydrogen gas atmosphere. After filtering the reaction solution, the solvent was distilled off under reduced pressure. The anion of the resulting residue is iodine ion.
In order to perform anion exchange, the obtained residue was dissolved in 5 ml of dichloromethane, and then an aqueous solution in which 10 mmol of lithium bis (trifluoromethanesulfonyl) imide was dissolved as an anion exchange salt was added and stirred for 24 hours. The obtained solution was separated to obtain an organic layer. This organic layer was washed twice with water and separated, and then dichloromethane was distilled off under reduced pressure to obtain ionic conductive agent 16 whose anion was bis (trifluoromethanesulfonyl) imide ion (TFSI). Table 3 shows the structure of the synthesized ionic conductive agent 17.

(Ion conductive agent 18)
An ionic conductive agent 18 was synthesized in the same manner as the ionic conductive agent 16 except that the iodomethane of the ionic conductive agent 16 was changed to 1-chlorooctadecane. Table 3 shows the structure of the synthesized ionic conductive agent 18.

(Ion conductive agent 19)
After dissolving 10 mmol of morpholine as an amine in 10 ml of acetone, potassium carbonate was added. Thereafter, 20 mmol of N- (4-bromobutyl) phthalimide was added as a quaternizing agent, and the mixture was heated to reflux for 24 hours. Dichloromethane was added to the reaction solution cooled to room temperature, and the solvent of the organic layer obtained by liquid separation was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. After repeating this operation three times, the residue was dissolved in 10 ml of ethanol, added with 15 mmol of hydrazine monohydrate (purity 79%), heated and stirred at 40 ° C. for 4 hours, cooled to room temperature and filtered. The solvent in the filtrate was distilled off under reduced pressure. To the residue was added 40 mmol of fluorenylmethyl chloroformate (Fmoc-Cl) and pyridine to 30 mmol of 40% aqueous solution of aminomethanol, and the mixture was heated under reflux for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times.
In order to perform anion exchange, the obtained residue was dissolved in 5 ml of dichloromethane, and then an aqueous solution in which 10 mmol of lithium bis (trifluoromethanesulfonyl) imide was dissolved as an anion exchange salt was added and stirred for 24 hours. The obtained solution was separated to obtain an organic layer. This organic layer was washed twice with water and separated, and then dichloromethane was distilled off under reduced pressure to obtain ionic conductive agent 19 whose anion was bis (trifluoromethanesulfonyl) imide ion (TFSI). Table 3 shows the structure of the synthesized ionic conductive agent 19.

(Synthesis of an ionic conductive agent having a cation structure of the formula (I3))
(Ion conductive agent 20)
10 mmol of tris (3-aminoethyl) amine and pyridine were dissolved in 10 ml of diethyl ether, and 30 mmol of phenyl chloroformate dissolved in 5 ml of diethyl ether was added dropwise and reacted at room temperature. An aqueous sodium hydroxide solution was added to the reaction solution to make it basic, and then the organic layer solvent obtained by liquid separation was distilled off under reduced pressure. The obtained concentrate was dissolved in 10 ml of acetonitrile, 10 mmol of iodomethane was added, and the mixture was stirred at room temperature for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. After repeating this operation three times, the residue was dissolved in 10 ml of ethanol, palladium / carbon was added, and the mixture was stirred at room temperature in a hydrogen gas atmosphere. After filtering the reaction solution, the solvent was distilled off under reduced pressure. To the residue, 30 mmol of 40% aqueous solution of aminomethanol, 40 mmol of fluorenylmethyl chloroformate (Fmoc-Cl) and pyridine were added, and the mixture was refluxed for 24 hours. A 20% DMF solution was added, and the mixture was heated to reflux for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times.
In order to perform anion exchange, the obtained residue was dissolved in 5 ml of dichloromethane, and then an aqueous solution in which 10 mmol of lithium bis (trifluoromethanesulfonyl) imide was dissolved as an anion exchange salt was added and stirred for 24 hours. The obtained solution was separated to obtain an organic layer. This organic layer was washed twice with water and separated, and then dichloromethane was distilled off under reduced pressure to obtain an ionic conductive agent 20 whose anion was bis (trifluoromethanesulfonyl) imide ion (TFSI). Table 4 shows the structure of the synthesized ionic conductive agent 20.

(Ion conductive agent 21)
After dissolving 30 mmol of potassium phthalimide in 20 ml of dimethylformamide, 30 mmol of 1,2-bis (2-chloroethoxy) ethane was added and heated to reflux. To the solution cooled to room temperature, ion-exchanged water and ethyl acetate were added and separated. The solvent in the obtained organic layer was distilled off under reduced pressure to obtain a quaternizing agent. This quaternizing agent was dissolved in 20 ml of acetone, 10 mmol of stearylamine and potassium carbonate were added, and the mixture was heated to reflux for 24 hours. The obtained reaction solution was filtered, and the solvent in the filtrate was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times. To the residue, 30 mmol of 40% aqueous solution of aminomethanol, 40 mmol of fluorenylmethyl chloroformate (Fmoc-Cl) and pyridine were added, and the mixture was refluxed for 24 hours. A 20% DMF solution was added, and the mixture was heated to reflux for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times.
In order to perform anion exchange, the obtained residue was dissolved in 5 ml of dichloromethane, and then an aqueous solution in which 10 mmol of lithium bis (trifluoromethanesulfonyl) imide was dissolved as an anion exchange salt was added and stirred for 24 hours. The obtained solution was separated to obtain an organic layer. This organic layer was washed twice with water and separated, and then dichloromethane was distilled off under reduced pressure to obtain an ionic conductive agent 21 whose anion is bis (trifluoromethanesulfonyl) imide ion (TFSI). Table 4 shows the structure of the synthesized ionic conductive agent 21.

(Synthesis of an ion conductive agent having a cation structure of the formula (I4))
(Ion conductive agent 22)
10 mmol of tris (3-aminoethyl) amine and pyridine were dissolved in 20 ml of diethyl ether, and 30 mmol of phenyl chloroformate was added dropwise and reacted at room temperature. An aqueous sodium hydroxide solution was added to the reaction solution to make it basic, and then the organic layer solvent obtained by liquid separation was distilled off under reduced pressure. The concentrate obtained in 20 ml of acetone and 10 mmol of N- (16-bromohexadecane) phthalimide synthesized separately separately were dissolved and heated to reflux for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. After repeating this operation three times, the residue was dissolved in 10 ml of ethanol, added with 15 mmol of hydrazine monohydrate (purity 79%), heated and stirred at 40 ° C. for 4 hours, cooled to room temperature and filtered. The organic solvent in the obtained filtrate was distilled off under reduced pressure. The obtained residue was dissolved in 10 ml of ethanol, palladium / carbon was added, and the mixture was stirred at room temperature in a hydrogen gas atmosphere. After filtering the reaction solution, the solvent was distilled off under reduced pressure. To the residue, 30 mmol of 40% aqueous solution of aminomethanol, 40 mmol of fluorenylmethyl chloroformate (Fmoc-Cl) and pyridine were added, and the mixture was refluxed for 24 hours. A 20% DMF solution was added, and the mixture was heated to reflux for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times.
In order to perform anion exchange, the obtained residue was dissolved in 5 ml of dichloromethane, and then an aqueous solution in which 10 mmol of lithium bis (trifluoromethanesulfonyl) imide was dissolved as an anion exchange salt was added and stirred for 24 hours. The obtained solution was separated to obtain an organic layer. This organic layer was washed twice with water and separated, and then dichloromethane was distilled off under reduced pressure to obtain an ionic conductive agent 22 whose anion was bis (trifluoromethanesulfonyl) imide ion (TFSI). Table 5 shows the structure of the synthesized ionic conductive agent 22.

(Ionic conductive agent 23)
10 mmol of 1,2-bis (2-aminoethoxy) ethane and pyridine were dissolved in 10 ml of diethyl ether, and 10 mmol of phenyl chloroformate was added dropwise and reacted at room temperature. An aqueous sodium hydroxide solution was added to the reaction solution to make it basic, and then the organic layer solvent obtained by liquid separation was distilled off under reduced pressure to obtain a raw material amine.
After dissolving 30 mmol of potassium phthalimide in 30 ml of dimethylformamide, 30 mmol of 1,2-bis (2-chloroethoxy) ethane was added and heated to reflux. To the solution cooled to room temperature, ion-exchanged water and ethyl acetate were added and separated. The solvent in the obtained organic layer was distilled off under reduced pressure to obtain a quaternizing agent.
10 mmol of raw material amine and 30 mmol of quaternizing agent were dissolved in 50 ml of acetone, potassium carbonate was added, and the mixture was heated to reflux for 24 hours. Thereafter, filtration was performed, and the organic solvent was distilled off from the filtrate under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. After repeating this operation three times, the residue was dissolved in 30 ml of ethanol, 45 mmol of hydrazine monohydrate (purity 79%) was added, the mixture was heated and stirred at 40 ° C. for 4 hours, cooled to room temperature, and filtered. The organic solvent in the obtained filtrate was distilled off under reduced pressure. The obtained residue was dissolved in 10 ml of ethanol, palladium / carbon was added, and the mixture was stirred at room temperature in a hydrogen gas atmosphere. After filtering the reaction solution, the solvent was distilled off under reduced pressure. To the residue, 30 mmol of 40% aqueous solution of aminomethanol, 40 mmol of fluorenylmethyl chloroformate (Fmoc-Cl) and pyridine were added, and the mixture was refluxed for 24 hours. A 20% DMF solution was added, and the mixture was heated to reflux for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times.
In order to perform anion exchange, the obtained residue was dissolved in 5 ml of dichloromethane, and then an aqueous solution in which 10 mmol of lithium bis (trifluoromethanesulfonyl) imide was dissolved as an anion exchange salt was added and stirred for 24 hours. The obtained solution was separated to obtain an organic layer. This organic layer was washed twice with water and separated, and then dichloromethane was distilled off under reduced pressure to obtain ionic conductive agent 23 whose anion was bis (trifluoromethanesulfonyl) imide ion (TFSI). Table 5 shows the structure of the synthesized ionic conductive agent 23.

(Synthesis of an ionic conductive agent having a cation structure of the formula (I5))
(Ionic conductive agent 24)
In 20 ml of ethanol, 10 mmol of N- (2-bromoethyl) phthalimide as a quaternizing agent was dissolved, 10 mmol of trimethylamine was added as a tertiary amine, and the mixture was heated to reflux for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. After repeating this operation three times, the residue was dissolved in 10 ml of ethanol, 15 mmol of hydrazine monohydrate (purity 79%) was added and the mixture was heated and stirred at 40 ° C. for 4 hours, then cooled to room temperature and filtered. The solvent in the filtrate was distilled off under reduced pressure to obtain a residue. The residue and 20 mmol of N- (2-bromoethyl) phthalimide as a tertiary agent were dissolved in 30 ml of acetone, potassium carbonate was added, and the mixture was heated to reflux for 72 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. After repeating this operation three times, the residue was dissolved in 30 ml of ethanol, 30 mmol of hydrazine monohydrate (purity 79%) was added and the mixture was heated and stirred at 40 ° C. for 4 hours, then cooled to room temperature and filtered. The solvent in the filtrate was distilled off under reduced pressure to obtain a residue. To the residue, 30 mmol of 40% aqueous solution of aminomethanol, 40 mmol of fluorenylmethyl chloroformate (Fmoc-Cl) and pyridine were added, and the mixture was refluxed for 24 hours. A 20% DMF solution was added, and the mixture was heated to reflux for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times.
In order to perform anion exchange, the obtained residue was dissolved in 5 ml of dichloromethane, and then an aqueous solution in which 10 mmol of lithium bis (trifluoromethanesulfonyl) imide was dissolved as an anion exchange salt was added and stirred for 24 hours. The obtained solution was separated to obtain an organic layer. This organic layer was washed twice with water and separated, and then dichloromethane was distilled off under reduced pressure to obtain an ionic conductive agent 24 whose anion was bis (trifluoromethanesulfonyl) imide ion (TFSI). Table 7 shows the structure of the synthesized ionic conductive agent 24.

(Ion conductive agent 25-33)
Ionic conductive agents 25 to 33 were synthesized in the same manner as the ionic conductive agent 24 except that the quaternizing agent, tertiary amine and tertiaryizing agent were changed to those shown in Table 6. Table 7 shows the structures of the synthesized ionic conductive agents 25-33.

(Synthesis of an ionic conductive agent having a cation structure of the formula (I6))
(Ion conductive agent 34)
10 mmol of tris (3-aminoethyl) amine and pyridine were dissolved in 20 ml of diethyl ether, and 30 mmol of phenyl chloroformate was added dropwise and reacted at room temperature. An aqueous sodium hydroxide solution was added to the reaction solution to make it basic, and then the organic layer solvent obtained by liquid separation was distilled off under reduced pressure. The obtained residue and 10 mmol of chlorocholine chloride were dissolved in 20 ml of ethanol and heated to reflux for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. After repeating this operation three times, the obtained residue was dissolved in 10 ml of ethanol, palladium / carbon was added, and the mixture was stirred at room temperature in a hydrogen gas atmosphere. After filtering the reaction solution, the solvent was distilled off under reduced pressure. To the residue, 30 mmol of 40% aqueous solution of aminomethanol, 40 mmol of fluorenylmethyl chloroformate (Fmoc-Cl) and pyridine were added, and the mixture was refluxed for 24 hours. A 20% DMF solution was added, and the mixture was heated to reflux for 24 hours. Thereafter, the solvent was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times.
In order to perform anion exchange, the obtained residue was dissolved in 5 ml of dichloromethane, and then an aqueous solution in which 10 mmol of lithium bis (trifluoromethanesulfonyl) imide was dissolved as an anion exchange salt was added and stirred for 24 hours. The obtained solution was separated to obtain an organic layer. This organic layer was washed twice with water and separated, and then dichloromethane was distilled off under reduced pressure to obtain an ionic conductive agent 34 whose anion was bis (trifluoromethanesulfonyl) imide ion (TFSI). Table 9 shows the structure of the synthesized ionic conductive agent 34.

(Ion conductive agent 35-43)
The quaternizing agent, the tertiary amine, the tertiary agent whose addition amount was changed to 30 mmol, and the anion exchange salt whose addition amount was changed to 20 mmol were each changed to the materials shown in Table 8, and the same as the ionic conductive agent 24. Ionic conductive agents 35 to 43 were synthesized. Table 9 shows the structures of the synthesized ionic conductive agents 35 to 43.

(Synthesis of an ion conductive agent having a cation structure of the formula (I7))
(Ion conductive agent 44)
10 mmol of ionic conductive agent 16 as an amine was dissolved in 30 ml of ethanol, 40 mmol of N- (2-bromoethyl) phthalimide and potassium carbonate were added as halides, and the mixture was heated to reflux for 24 hours. After filtration, 40 mmol of hydrazine monohydrate (purity 79%) was added to the filtrate, and the mixture was stirred with heating at 40 ° C. for 4 hours, and then cooled to room temperature and filtered. The solvent in the filtrate was distilled off under reduced pressure. The obtained concentrate was washed with diethyl ether, and the supernatant was removed by decantation. This operation was repeated three times and then dried under reduced pressure. The resulting anion of the residue is a TFSI ion. Table 11 shows the structure of the synthesized ionic conductive agent 44.

(Ion conductive agent 45-47)
Ionic conductive agents 45 to 47 were synthesized in the same manner as the ionic conductive agent 44 except that amines and halides were changed to the materials shown in Table 10. Table 11 shows the structures of the synthesized ionic conductive agents 45 to 47.

<2. Preparation of coating solution>
The preparation of the coating solution used in the present invention will be described.

(Coating fluid 1)
The following materials were mixed and dispersed for 1 hour in a sand mill using glass beads having a diameter of 1 mm as media particles to obtain a coating solution 1.

・ Binder resin: 20 parts of resol type phenolic resin (made by DIC, trade name: J-325) ・ Carbon black (made by Tokai Carbon, trade name: Toka Black # 5500) 10 parts ・ 50 parts of 2-propanol (IPA) 1 part of conductive agent

(Coating liquid 2-17)
Coating liquids 2 to 17 were prepared in the same manner as coating liquid 1 except that the type and number of parts of the ionic conductive agent were changed to the contents shown in Table 12.

(Coating fluid 18)
In a reaction vessel under nitrogen atmosphere, 100 parts of polytetramethylene glycol (trade name: PTMG1000, manufactured by Mitsubishi Chemical Corporation) with a molecular weight of 1000 is placed in the reaction vessel with respect to 27 parts of polymeric MDI (trade name: Millionate MR200, manufactured by Tosoh Corporation). While maintaining the temperature at 65 ° C., the solution was gradually added dropwise. After completion of the dropping, the reaction was carried out at a temperature of 65 ° C. for 2 hours. The obtained reaction mixture was cooled to room temperature to obtain an isocyanate group-terminated prepolymer having an isocyanate group content of 3.31%.
Polyether diol obtained by addition polymerization of ethylene oxide to polypropylene glycol having a molecular weight of 3000 with respect to 60.4 parts of isocyanate group-terminated prepolymer (trade name: Adeka Polyether PR-3007, manufactured by ADEKA) 39.6 parts, and ions 1 part of conductive agent 2 was mixed with stirring. Thereafter, 10 parts of carbon black (trade name: Toka Black # 5500, manufactured by Tokai Carbon Co., Ltd.) and 2-butanone (MEK) were added so that the total solid content ratio was 30%, and glass beads with a diameter of 1 mm were used as media particles. It mixed in the sand mill used as a coating liquid 18 was obtained.

(Coating fluid 19)
Polyethylene glycol diglycidyl ether (manufactured by Nagase Chemmutex, trade name: Denacol EX-841) 51.8 parts and polypropylene glycol diglycidyl ether (manufactured by Nagase Chemmutex, trade name: Denacol EX-931) 37.1 Parts, 11.1 parts of ethylene glycol bis (aminoethyl) ether (manufactured by Sigma-Aldrich) and 1 part of ionic conductive agent 2 were mixed with stirring. Thereafter, 10 parts of carbon black (product name: Toka Black # 5500, manufactured by Tokai Carbon Co., Ltd.) and 2-propanol (IPA) were added so that the total solid content ratio was 30%, and glass beads having a diameter of 1 mm were used as media particles. The coating liquid 19 was obtained by mixing with the used sand mill.

(Coating liquid 20-51)
Coating liquids 20 to 51 were prepared in the same manner as the coating liquid 1 except that the type and number of parts of the ionic conductive agent were changed to those shown in Table 13.

[Example 1]
(Preparation of developer carrier 1)
A cylindrical aluminum tube having an outer diameter of 16.0 mm and an arithmetic average roughness Ra of 0.2 μm, with the upper and lower ends masked, was prepared as a substrate. The substrate was set up vertically and rotated at a constant speed, and a spray gun set to discharge the coating liquid 1 was applied while being lowered at a constant speed. Subsequently, the coating liquid 1 was cured by heating at a temperature of 150 ° C. for 30 minutes in a hot air drying oven to form a resin layer having a thickness of 12 μm on the substrate, and the developer carrier 1 was produced. In addition, it confirmed that the resin layer contained the partial structure which concerns on this invention by IR, NMR, and TOF-SIMS.

(Cross cut evaluation)
The adhesion was evaluated by observing film peeling between the substrate and the resin layer. The developer carrying member was allowed to stand for 30 days in an environment of a temperature of 40 ° C. and a humidity of 95% RH. Then, it was left still for 24 hours in the environment of temperature 23 ° C and humidity 50% RH. After standing, in the same environment, in accordance with JIS K5600-5-6, an adhesion tape was applied to the 1 mm crosscut grid and a peel test was performed, and the adhesion between the substrate and the resin layer was evaluated according to the following criteria. . The evaluation results are shown in Table 14.

Rank 0: The edge of the cut is completely smooth, and there is no peeling in any lattice eye.
Rank 1: Small peeling of the coating film at the intersection of cuts.
It is clearly not more than 5% that the crosscut is affected.
Rank 2: The coating is peeled along the edge of the cut and / or at the intersection. Black
It is clearly more than 5% but more than 15% that is affected in the scut portion
There is no.
Rank 3: The coating film is partially or totally peeled along the edge of the cut, and
And / or various parts of the eye are partially or completely peeled off. cross
The cut is clearly affected by over 15% but over 35%.
Is not.
Rank 4: The paint film is partially or totally peeled along the edge of the cut.
And / or some eyes are partially or completely peeled off. Cross cut part
The impact on is clearly not over 35%.
Rank 5: Any of the degree of peeling that cannot be classified even in rank 4.

(Durability peeling test)
Furthermore, an endurance test (hereinafter referred to as “endurance delamination test”) was carried out in order to confirm whether or not peeling occurred in the actual machine.
Laser beam printer: LaserJet P3015n (device name, manufactured by Hewlett-Packard) and its genuine cartridge were prepared. A magnet and a flange were attached so that the developer carrier 1 could be attached to the cartridge, and the developer carrier 1 was attached to this cartridge. Durability printing of 60,000 sheets was performed while supplying a genuine developer with a character pattern with a printing ratio of 1% in the intermittent mode of 1 sheet / 5 seconds, and it was confirmed whether or not the resin layer had peeled after durability. The discrimination criteria are as follows. This cartridge has an elastic regulating blade as shown in FIG. 3 in the developing device. The evaluation results are shown in Table 14.

Rank A: No peeling at all Rank B: There is very little peeling. The location where peeling occurred does not exceed 5% of the total.
Rank C: There is some peeling. More than 5% of the places where peeling occurred, but 15%
It will not exceed.
Rank D: There is peeling on the entire surface. The location where peeling occurred exceeds 15% of the total.

[Examples 2-51]
Developer carriers 2 to 51 were produced in the same manner as the developer carrier 1 except that the coating liquids 2 to 51 were used.
Table 14 shows the results of the cross-cut evaluation and the durability peeling test of the developer carriers 2 to 51.

[Comparative Example 1]
(Synthesis of Ionic Conductive Agent Comparison 1)
An ionic conductive agent comparison 1 was synthesized in the same manner as the ionic conductive agent 2 except that the quaternizing agent, tertiary amine and secondary amine were changed to 1,8-dibromooctane, trimethylamine and methylamine, respectively. Synthesized ionic conductive agent The structure of Comparative Example 1 is represented by the following formula (11), and the substituent corresponding to R ₁₀₁ of formula (I1) is a methyl group.

(Preparation of coating solution comparison 1)
A coating liquid comparison 1 was prepared in the same manner as the coating liquid 1 except that the ionic conductive agent was changed to the ionic conductive agent comparison 1.

(Production of developer carrier Comparative 1)
A developer carrier comparison 1 was produced in the same manner as the developer carrier 1 except that the coating liquid comparison 1 was used.
Table 14 shows the results of the cross-cut evaluation and the durability test of the developer carrier Comparative Example 1.

[Comparative Example 2]
A coating liquid comparison 2 was prepared in the same manner as the coating liquid 18 except that the ionic conductive agent was changed to the ionic conductive agent comparison 1. Thereafter, a developer carrier comparison 2 was produced in the same manner as the developer carrier 1 except that the coating liquid comparison 2 was used.
Table 14 shows the results of the cross-cut evaluation and the durability test of the developer carrier Comparative Example 2.

[Comparative Example 3]
A coating liquid comparison 3 was prepared in the same manner as the coating liquid 19 except that the ionic conductive agent was changed to the ionic conductive agent comparison 1. Thereafter, a developer carrier comparison 3 was prepared in the same manner as the developer carrier 1 except that the coating liquid comparison 3 was used.
Table 14 shows the results of the cross-cut evaluation and the durability test of the developer carrier Comparative Example 3.

[Comparative Example 4]
(Preparation of coating solution comparison 4)
A coating liquid comparison 4 was prepared in the same manner as the coating liquid 1 except that the ionic conductive agent was changed to the formula (12) shown below.

(Production of developer carrier Comparative 4)
A developer carrier comparison 4 was produced in the same manner as the developer carrier 1 except that the coating liquid comparison 4 was used.
Table 14 shows the results of the cross-cut evaluation and the durability test of the developer carrier Comparative Example 4.

  In Examples 1 to 51, good results were obtained in both crosscutting and durability peeling. On the other hand, in Comparative Examples 1 to 3, since the functional group in the resin layer is methyl, the adhesion between the resin layer and the substrate is insufficient, and both the cross-cut and the durability peeling are worse than Examples 1 to 51. became. In Comparative Example 4, since an ionic conductive agent that cannot be immobilized on the resin layer was used, the adhesion between the resin layer and the substrate was insufficient, and both the cross-cut and durability peeling were worse than Examples 1-51.

DESCRIPTION OF SYMBOLS 1 Developer carrier 2 Resin layer 3 Base | substrate 4 Conductive particle 5 Photosensitive drum 6 Developing container 7 Magnet roller 8 Stirring blade 9 Magnetic regulation blade 10 Development bias power supply 11 Elastic regulation blade A Rotation direction of developer carrier B Rotation of photosensitive drum Direction C Development area

Claims (8)

A developer carrier having a conductive substrate and a resin layer in contact with the substrate,
The resin layer is
An electronic conducting agent;
A resin having at least one partial structure selected from the group consisting of structures represented by the following formulas (1) to (7) in the molecule;
And a developer carrier characterized by containing an anion:

[In Formula (1)-(7),
R _{101, R 201} and _{R 202, R} 603 from the _{R 301} from _{R 303, R 401 R 404,} R 501 and _{R 502, R 601,} from _{R 701 R 704} each independently represent a hydrogen atom, OH, CH ₂ OH, C ₂ H ₄ OH, COOH,
R ₁₀₂ , R ₂₀₃ and R ₂₀₄ , R ₃₀₄ to R ₃₀₆ , R ₄₀₅ to R ₄₀₈ , R ₅₀₃ to R ₅₀₅ , R ₆₀₄ to R ₆₀₇ , and R ₇₀₅ to R ₇₁₀ are each independently C _m H _2m (m is , An integer of 2 to 16) or (C ₂ H ₄ O) ₁ C ₂ H ₄ (l is an integer of 1 to 8),
R ₃₀₇ represents an alkyl group having 1 to 18 carbon atoms,
X ₅₀₁ , X ₇₀₁ , and X ₇₀₂ each independently represent a nitrogen atom or a methine group,
X ₆₀₁ represents a nitrogen cation or a carbon atom,
A ₁₀₁ , A ₅₀₁ and A ₆₀₁ each independently represent any of the following structural formulas (a) to (d), and E ₂₀₁ and E ₇₀₁ each independently represent the following structural formula (e) or (f). Show:

(In formulas (a) to (f), R ₁ to R ₉ each independently represents an alkyl group having 1 to 18 carbon atoms, n1 and n2 each independently represent 1 or 2, and Y ₁ and Y ₂ represents a methylene group or an oxygen atom))]. The partial structure represented by any one of the formulas (1) to (7) is bonded to the resin molecular chain via the structure represented by any of the following formulas (8) to (10). Developer carrier:

(In formulas (8) to (10), * represents a binding site of the structure of any one of formulas (1) to (7), and ** represents a binding site to the resin molecular chain).   The developer carrier according to claim 1, wherein the resin layer contains perfluorosulfonylimide ion as the anion. A developer carrier having a conductive substrate and a resin layer in contact with the substrate,
The resin layer is
An electronic conducting agent;
At least one ion conductive agent having one cation structure and an anion selected from the group consisting of the structures represented by the following formulas (I1) to (I7);
A developer carrier comprising a resin comprising a reaction product of a compound having a functional group capable of reacting with a primary or secondary amino group of the ionic conductive agent:

[In the formulas (I1) to (I7),
R _{101, R 201} and _{R 202, R} 603 from the _{R 301} from _{R 303, R 401 R 404,} R 501 and _{R 502, R 601,} from _{R 701 R 704} each independently represent a hydrogen atom, OH, CH ₂ OH, C ₂ H ₄ OH, COOH,
R ₁₀₂ , R ₂₀₃ and R ₂₀₄ , R ₃₀₄ to R ₃₀₆ , R ₄₀₅ to R ₄₀₈ , R ₅₀₃ to R ₅₀₅ , R ₆₀₄ to R ₆₀₇ , and R ₇₀₅ to R ₇₁₀ are each independently C _m H _2m (m is , An integer of 2 to 16) or (C ₂ H ₄ O) ₁ C ₂ H ₄ (l is an integer of 1 to 8),
R ₃₀₇ represents an alkyl group having 1 to 18 carbon atoms,
X ₅₀₁ , X ₇₀₁ , and X ₇₀₂ each independently represent a nitrogen atom or a methine group,
X ₆₀₁ represents a nitrogen cation or a carbon atom,
A ₁₀₁ , A ₅₀₁ and A ₆₀₁ each independently represent any of the following structural formulas (a) to (d),
E ₂₀₁ and E ₇₀₁ each independently represent the following structural formula (e) or (f):

(In formulas (a) to (f), R ₁ to R ₉ each independently represents an alkyl group having 1 to 18 carbon atoms, n1 and n2 each independently represent 1 or 2, and Y ₁ and Y ₂ represents a methylene group or an oxygen atom))].   The developer carrier according to claim 4, wherein the compound capable of reacting with the amino group is at least one compound selected from the group consisting of a resol type phenol resin, an epoxy compound, and an isocyanate compound.   The developer carrying member according to claim 1, wherein the conductive substrate includes a metal on a surface thereof.   A developing device having a developer, a container for containing the developer, and a developer carrier for carrying and transporting the developer contained in the container, wherein the developer carrier is A developing device comprising the developer carrying member according to claim 1.   The developing device according to claim 7, wherein the developer carrier has a hollow cylindrical shape for the conductive substrate, and a magnet is provided in the hollow cylindrical substrate.

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