JP2021113853A - Developing device, process cartridge, and electrophotographic image forming apparatus - Google Patents

Abstract

To provide a developing device for electrophotography that reduces an increase in fogging even in a long-time operation.SOLUTION: A developing device 10 for electrophotography is used in which a toner supply roller 1 has a conductive layer 3 including a cross-linked urethane resin formed of a reactant of an ion conductive agent having a reactive functional group reacting with an isocyanate group, polyol, and a compound having an isocyanate group, and the toner supply roller 1 has projections formed of an organic silicon polymer having a structure of R-SiO3/2, and is combined with a toner 11 in which the projections are present at a specific ratio in observation of toner by a scanning type electron microscope (STEM).SELECTED DRAWING: Figure 1

Description

The present disclosure relates to an electrophotographic developing apparatus, a process cartridge, and an electrophotographic image forming apparatus used in an electrophotographic image forming apparatus.

In the electrophotographic image forming apparatus, a toner supply roller for stably charging the toner and supplying the toner to the toner carrier roller is used. Patent Document 1 discloses a toner supply roller in which an ionic conductive agent is chemically bonded to a urethane foam layer via a reactive functional group.

JP-A-2017-134252

The electrophotographic image forming apparatus is required to be able to stably form an excellent electrophotographic image even in a harsh environment. According to the study by the present inventors, the developing apparatus using the toner supply roller according to Patent Document 1 may cause fog on the electrophotographic image as a result of long-term use.

One aspect of the present disclosure is to provide an electrophotographic developing apparatus that does not easily cause fog on an electrophotographic image even after long-term use. Another aspect of the present disclosure is to provide a process cartridge that contributes to the stable output of high-quality electrophotographic images. Furthermore, another aspect of the present disclosure is aimed at providing an electrophotographic image forming apparatus capable of stably outputting a high-quality electrophotographic image.

According to the first aspect of the present disclosure.
A developing device that has toner and toner supply rollers.
The toner supply roller
It has a shaft body and a conductive layer containing a crosslinked urethane resin on the outer periphery of the shaft body.
The crosslinked urethane resin is a reaction product of an ionic conductive agent having a reactive functional group that reacts with an isocyanate group, a polyol, and a compound having an isocyanate group.
The toner has a number average particle diameter of 4.0 μm or more and 10.0 μm or less, and contains toner mother particles and toner particles having an organosilicon polymer on the surface of the toner mother particles.
The organosilicon polymer has a structure represented by the following formula (1) and has a structure represented by the following formula (1).
R-SiO _3/2 (1)
(R indicates an alkyl group having 1 or more and 6 or less carbon atoms, or a phenyl group.)
The organosilicon polymer forms a convex portion on the outer surface of the toner particles, and forms a convex portion.
The adhesion rate of the organosilicon polymer to the toner matrix particles is 80% or more.
With respect to the cross-sectional image of the toner particles obtained by a scanning electron microscope (STEM), when the contour line of the toner mother particles is developed into a straight line to obtain a developed image of the cross-sectional image, the developed image shows the straight line. When the length is L and the length of the line segment forming the boundary between the convex portion and the toner mother particle on the straight line is the width w, the sum of the width w with respect to the L is Σw. The ratio (Σw / L) is 0.30 or more and 0.95 or less.
An electrophotographic developing device is provided.
Further, according to another aspect of the present invention, there is provided a process cartridge that is detachably configured on the main body of the electrophotographic image forming apparatus and includes the above-mentioned electrophotographic developing apparatus.
In addition, according to yet another aspect of the present invention, there is provided an electrophotographic image forming apparatus including the above-mentioned electrophotographic developing apparatus.

According to one aspect of the present disclosure, there is provided an electrophotographic developing apparatus that does not easily cause fog on an electrophotographic image even after long-term use.
According to another aspect of the present disclosure, there is provided a process cartridge that contributes to the stable output of high quality electrophotographic images.
According to still another aspect of the present disclosure, there is provided an electrophotographic image forming apparatus capable of stably outputting a high-quality electrophotographic image.

It is a schematic cross-sectional view (a), a schematic perspective view (b) of a toner supply roller, and a schematic cross-sectional view (c) of an electrophotographic developing apparatus. It is a schematic block diagram which shows the process cartridge. It is a schematic cross-sectional view of an electrophotographic image forming apparatus. It is a schematic diagram of the cross-sectional observation by STEM of the toner. It is a schematic diagram which showed the method of measuring a convex shape. It is a schematic diagram which showed the method of measuring a convex shape. It is a schematic diagram which showed the method of measuring a convex shape. It is a schematic cross-sectional view which shows an example of the forming apparatus and manufacturing process of a toner supply roller. FIG. ) Indicates the time when the crosslinked urethane resin is cured (when the molding of the conductive layer is completed).

The present inventors have found that fog on an image can be improved by an electrophotographic developer that combines a specific toner and a toner supply roller.
The present inventors infer the reason as follows. In Patent Document 1, a toner supply roller in which an ionic conductive agent is chemically bonded to a urethane foam layer via a reactive functional group is used in an image forming apparatus. However, as described above, when the conventional toner is used in a long-life cartridge, the external additive is buried and the fluidity is lowered. As a result, it is considered that the amount of charge of the toner becomes non-uniform and fog occurs in the electrophotographic image.

On the other hand, the present inventors have found that the toner particles having an organic silicon polymer on the surface of the toner matrix particles are less likely to be embedded in the toner matrix particles even when they are used for forming an electrophotographic image for a long period of time. It has been found that changes in fluidity over time are suppressed, and as a result, changes in the amount of charge of the toner over time can be suppressed.
Further, by having the convex portion made of the organosilicon polymer on the outer surface of the toner particles, the convex portion of the toner particles bites into the surface of the toner supply roller, and the toner is transferred without slipping on the surface of the toner supply roller. Move. As a result, the surface of the toner particles evenly contacts the surface of the toner supply roller, the contact opportunity with the toner supply roller at each position on the surface of the toner particles becomes uniform, and the amount of charge on the surface of the toner particles reaches equilibrium and becomes uniform. It becomes charged. It has been found that when the charge amount of each toner particle reaches equilibrium and becomes uniform, the charge amount of all the developed toners becomes uniform and fog is suppressed.
Further, the present inventors supply a toner having a conductive layer containing a crosslinked urethane resin which is a reaction product of an ionic conductive agent having a reactive functional group that reacts with an isocyanate group, a polyol, and a compound having an isocyanate group. It has been found that by combining the rollers with the above-mentioned toner, the charge amount of the toner can be maintained uniformly for a longer period of time.
This is because the above-mentioned toner supply roller does not easily change the conductivity of the conductive layer of the toner supply roller even when an electric field due to a high voltage is applied directly to the toner supply roller or through the toner carrier roller, and is used for a long period of time. It is considered that this is because the toner can be stably charged.
Further, since the toner particles having a convex portion made of the organosilicon polymer have a specific organosilicon polymer on the outermost surface, the charge amount tends to be smaller than that of the toner particles having only hydrocarbons on the outermost surface. was there. However, surprisingly, even the toner particles having a convex portion made of the organosilicon polymer are unexpectedly good by using a toner supply roller having a conductive layer containing the crosslinked urethane resin in combination. It was found that the material was charged. The reason for this is not clear, but it is thought that the triboelectric property between the organosilicon polymer and the nitrogen-cationic center of the ionic conductive agent fixed to the urethane resin has an optimum relationship for charging. When the ionic group having the cation center of nitrogen is not fixed to the crosslinked urethane resin, the amount of the ionic group on the outermost surface of the toner supply roller decreases due to friction or energization, and the amount of charge of the toner is reduced. Is expected to decrease. On the other hand, in the toner supply roller used in the developing apparatus of the present invention, since the cationic group is fixed to the crosslinked urethane resin, the amount of charge of the toner does not easily decrease even after long-term use, and fog is suppressed. I'm guessing that it can be done.

[Developer for electrophotographic]
The developing apparatus has a toner 11 and a toner supply roller 1. FIG. 1 shows a schematic cross-sectional view (c) of the developing apparatus 10, a schematic view (a) and a perspective view (b) showing a cross section of the toner supply roller 1 perpendicular to the axial body direction. The developing apparatus 10 includes a toner carrier roller 12 and a developing blade 13 which are developing means. The developing device 10 further includes a toner container 14, and the toner container 14 is filled with the toner 11 according to the present invention. The toner 11 in the toner container 14 is supplied to the surface of the toner carrier roller 12 by the toner supply roller 1, and a layer of toner 11 having a predetermined thickness is formed on the surface of the toner carrier roller 12 by the developing blade 13. ..

<Toner supply roller>
The toner supply roller has a conductive shaft body and a conductive layer containing a crosslinked urethane resin on the shaft body.
The toner supply roller 1 shown in FIGS. 1A and 1B includes a conductive shaft body 2 and a conductive layer 3 containing a crosslinked urethane resin provided on the outer periphery thereof.
The layer structure of the toner supply roller 1 is not limited to the one in which the conductive layer 3 exists on the outermost surface of the toner supply roller 1. Examples of the toner supply roller 1 include those having a surface layer on the shaft body 2 and the conductive layer 3 provided on the outer periphery thereof, and those having an elastic layer further between the shaft body 2 and the conductive layer 3. Be done.

Hereinafter, the configuration of the toner supply roller according to one aspect of the present disclosure will be described in detail.
<Axis body>
The shaft body 2 functions as a support member for the toner supply roller and an electrode. The shaft body 2 is composed of a metal or alloy such as aluminum, copper alloy, or stainless steel; iron plated with chromium or nickel; and a conductive material such as a conductive synthetic resin. The shaft body 2 has a solid cylindrical shape or a hollow cylindrical shape.

<Conductive layer>
The conductive layer 3 contains a crosslinked urethane resin described later. The conductive layer 3 preferably has voids in which the toner particles can be stored in the layer in order to uniformly supply the toner particles to the surface of the toner carrier roller as the toner supply roller.
Examples of voids include a large number of penetrating and non-penetrating holes. Further, as another example of the void, it may be porous in a bubble (continuous bubble) state in which they are connected to each other. The conductive layer containing the crosslinked urethane resin is preferably in a continuous foam state with large voids.
Characteristics such as the average cell diameter, the number of cells, the air volume, and the density of the entire layer on the surface of the conductive layer (also referred to as a foam layer) having such voids are important. The physical property value of the conductive layer 3 (foamed layer) is not particularly limited, but for example, it is preferable to have a value within the following numerical range.
Average cell diameter on the surface: 100 μm or more and 500 μm or less;
Number of cells: 50 / inch or more and 300 / inch or less;
Air volume: 0.5 L / min or more and 3.0 L / min or less;
Density: 0.05 g / cm ³ or more 0.20 g / cm ³ or less.

<Cross-linked urethane resin>
The crosslinked urethane resin is a reaction product of an ionic conductive agent having a reactive functional group that reacts with an isocyanate group, a polyol, and a compound having an isocyanate group.
As the ionic conductive agent having a reactive functional group that reacts with an isocyanate group, an ionic compound having a cation containing at least one group derived from a hydroxyl group, an amino group or a glycidyl group as the reactive functional group is preferable. In this case, the obtained crosslinked urethane resin has a cationic structure. The proportion of the cationic structure in the crosslinked urethane resin is such that the amount of the ionic conductive agent having a reactive functional group is 0.1 to 30% by mass, preferably 0.2, based on the total amount of the raw material charged in the crosslinked urethane resin. The amount is 10% by mass.
Further, the crosslinked urethane resin contains polyurethane obtained by the above reaction and an anion derived from the ionic compound. Therefore, the crosslinked urethane resin can be obtained by reacting a polyol, an isocyanate, and an ionic compound.

<Cation structure>
The cationic structure of the polyurethane in the molecule is preferably at least one cationic structure selected from the group consisting of the structures represented by the structural formulas (1) to (6). Hereinafter, each cation structure represented by the structural formulas (1) to (6) will be described.

In the structural formula (1), R1 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. As the hydrocarbon group, an alkyl group or an alkenyl group is preferable. Z1 to Z3 represent any structure or hydrocarbon group having 1 to 12 carbon atoms independently selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103), and at least Z1 to Z3. One is any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103). As the hydrocarbon group, an alkyl group is preferable.
The structure represented by the structural formula (1) is an ammonium cation having at least one group derived from a hydroxyl group, an amino group, or a glycidyl group. When the structure represented by the structural formula (1) is an ammonium cation having at least one hydroxyl group-derived group, it is represented by at least the structural formula (Z101) by reacting the ionic compound corresponding to the cation with an isocyanate group. A structure having one structure is obtained. When the structure represented by the structural formula (1) is an ammonium cation having at least one amino group-derived group, the ionic compound corresponding to the cation is reacted with an isocyanate group to obtain at least the structural formula (Z102). A structure having one of the structures shown is obtained. When the structure represented by the structural formula (1) is an ammonium cation having at least one group derived from a glycidyl group, it is represented by at least the structural formula (Z103) by reacting the ionic compound corresponding to the cation with a hydroxyl group. A structure having one structure is obtained.

Examples of the ammonium cation of the ionic compound capable of providing the structure represented by the structural formula (1) include an ammonium cation having a hydroxyl group.
2-Hydroxyethyltrimethylammonium cation, 2-hydroxyethyltriethylammonium cation, 4-hydroxybutyltrimethylammonium cation, 4-hydroxybutyl-tri-n-butylammonium cation, 8-hydroxyoctyltrimethylammonium cation, 8-hydroxyoctyl- Tri-n-butylammonium cation;
Bis (hydroxymethyl) dimethylammonary cation, bis (2-hydroxyethyl) dimethylammonium cation, bis (3-hydroxypropyl) dimethylammonary cation, bis (4-hydroxybutyl) dimethylammonary cation, bis (8-hydrochioctyl) dimethyl Ammonium cation, bis (8-hydrochioctyl) -di-n-butylammonium cation;
Tris (hydroxymethyl) methylammonium cation, tris (2-hydroxyethyl) methylammonium cation, tris (3-hydroxypropyl) methylammonium cation, tris (4-hydroxybutyl) methylammonium cation, tris (8-hydroxyoctyl) methyl Ammonium cations; and derivatives of these.
Examples of the ammonium cation having at least one amino group and glycidyl group include cations having a structure in which some or all of the hydroxyl groups of the ammonium cation are replaced with amino groups and glycidyl groups (or epoxy groups).

In structural formula (2), R2 and R3 represent hydrocarbon groups or single bonds required to form a nitrogen-containing complex aromatic 5-membered ring with the nitrogen atoms to which they are bonded. Specifically, one of R2 and R3 is a carbon number 1 and the other is a divalent hydrocarbon group having a carbon number of 2, or one of R2 and R3 is a single bond and the other is a carbon number. It is a divalent hydrocarbon group of 3 in No. 3, and π electrons are delocalized so as to exhibit aromaticity. Z4 and Z5 each independently contain any structure, hydrogen atom, or monovalent hydrocarbon group having 1 to 12 carbon atoms selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103). show. The hydrocarbon group is preferably an alkyl group. Z6 represents any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103), or a hydrocarbon group having 1 to 4 carbon atoms. As the hydrocarbon group, an alkyl group is preferable. d1 represents an integer of 0 or 1, and at least one of Z4 to Z6 is any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103).

The structure represented by the structural formula (2) is a nitrogen-containing heteroaromatic 5-membered ring cation containing two nitrogen atoms having at least one group derived from a hydroxyl group, an amino group, or a glycidyl group. When the structure represented by the structural formula (2) is a nitrogen-containing heteroaromatic 5-membered ring cation having at least one hydroxyl group-derived group, at least by reacting the ionic compound corresponding to the cation with the isocyanate group. A structure having one structure represented by the structural formula (Z101) can be obtained. When the structure represented by the structural formula (2) is a nitrogen-containing heteroaromatic 5-membered ring cation having at least one amino group-derived group, the ionic compound corresponding to the cation is reacted with an isocyanate group. A structure having at least one structure represented by the structural formula (Z102) can be obtained. When the structure represented by the structural formula (2) is a nitrogen-containing heteroaromatic 5-membered ring cation having at least one group derived from a glycidyl group, the ionic compound corresponding to the cation is reacted with the hydroxyl group to cause a reaction. A structure having at least one structure represented by the structural formula (Z103) can be obtained.
As the nitrogen-containing complex aromatic 5-membered ring in the structural formula (2), a structure having an imidazoline ring represented by the structural formula (10) is preferable. In the structural formula (10), Z4, Z5, Z6, and d1 have the same meanings as the structural formula (2).

Examples of cations of ionic compounds that can provide the structure represented by the structural formula (2) include cations having an imidazoline ring structure and having a hydroxyl group.
1-Methyl-3-hydroxymethylimidazolium cation, 1-methyl-3- (2-hydroxyethyl) imidazolium cation, 1-methyl-3- (3-hydroxypropyl) imidazolium cation, 1-methyl-3-3 (4-Hydroxybutyl) imidazolium cation, 1-methyl-3- (6-hydroxyhexyl) imidazolium cation, 1-methyl-3- (8-hydroxyoctyl) imidazolium cation, 1-ethyl-3- (2) -Hydroxyethyl) imidazolium cation, 1-n-butyl-3- (2-hydroxyethyl) imidazolium cation, 1,3-dimethyl-2- (2-hydroxyethyl) imidazolium cation, 1,3-dimethyl- 2- (4-Hydroxybutyl) imidazolium cation, 1,3-dimethyl-4- (2-hydroxyethyl) imidazolium cation;
1,3-bishydroxymethylimidazolium cation, 1,3-bis (2-hydroxyethyl) imidazolium cation, 2-methyl-1,3-bishydroxymethylimidazolium cation, 2-methyl-1,3-bis (2-Hydroxyethyl) imidazolium cation, 4-methyl-1,3-bis (2-hydroxyethyl) imidazolium cation, 2-ethyl-1,3-bis (2-hydroxyethyl) imidazolium cation, 4- Ethyl-1,3-bis (2-hydroxyethyl) imidazolium cation, 2-n-butyl-1,3-bis (2-hydroxyethyl) imidazolium cation, 4-n-butyl-1,3-bis ( 2-Hydroxyethyl) imidazolium cation, 1,3-bis (3-hydroxypropyl) imidazolium cation, 1,3-bis (4-hydroxybutyl) imidazolium cation, 1,3-bis (6-hydroxyhexyl) Imidazolium cation, 1,3-bis (8-hydroxyoctyl) imidazolium cation, 1-methyl-2,3-bis (2-hydroxyethyl) imidazolium cation, 1-methyl-3,4-bis (2-) Hydroxyethyl) imidazolium cation, 1-methyl-3,5-bis (2-hydroxyethyl) imidazolium cation;
1,2,3-Trishydroxymethylimidazolium cation, 1,2,3-tris (2-hydroxyethyl) imidazolium cation, 1,2,3-tris (3-hydroxypropyl) imidazolium cation, 1,2 , 3-Tris (4-hydroxybutyl) imidazolium cation, 1,2,3-tris (6-hydroxyhexyl) imidazolium cation, 1,2,3-tris (8-hydroxyoctyl) imidazolium cation, 1, 3,4-Tris (2-hydroxyethyl) imidazolium cation, 1,3,4-tris (3-hydroxypropyl) imidazolium cation, 1,3,4-tris (4-hydroxybutyl) imidazolium cation, 1, , 3,4-Tris (6-hydroxyhexyl) imidazolium cation, 1,3,4-tris (8-hydroxyoctyl) imidazolium cation; and derivatives thereof.
Examples of the cation having at least one amino group and glycidyl group include cations having a structure in which a part or all of the hydroxyl groups of the above cation is replaced with an amino group or a glycidyl group (or an epoxy group).

In structural formula (3), R4 and R5 represent the hydrocarbon groups or single bonds required to form a nitrogen-containing complex aromatic 6-membered ring with the nitrogen atoms to which they are bonded. Specifically, R4 and R5 are independently selected from divalent hydrocarbon groups having 1 to 3 carbon atoms, and the total carbon number of R4 and R5 is 4. Alternatively, one of R4 and R5 is a single bond and the other is a divalent hydrocarbon group having 4 carbon atoms. Π electrons are delocalized to show aromaticity. Z7 represents any structure, hydrogen atom, or hydrocarbon group having 1 to 4 carbon atoms selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103). As the hydrocarbon group, an alkyl group is preferable. Z8 represents any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103), or a hydrocarbon group having 1 to 4 carbon atoms. As the hydrocarbon group, an alkyl group is preferable. d2 represents an integer of 0 to 2, and at least one of Z7 and Z8 is any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103). When d2 is 2, Z8 may be the same or different.
The structure represented by the structural formula (3) represents a nitrogen-containing heteroaromatic 6-membered ring cation containing two nitrogen atoms having at least one group derived from a hydroxyl group, an amino group, or a glycidyl group. When the structure represented by the structural formula (3) is a nitrogen-containing heteroaromatic 6-membered ring cation having at least one hydroxyl group-derived group, at least by reacting the ionic compound corresponding to the cation with the isocyanate group. A structure having one structure represented by the structural formula (Z101) can be obtained. When the structure represented by the structural formula (3) is a nitrogen-containing heteroaromatic 6-membered ring cation having at least one amino group-derived group, the ionic compound corresponding to the cation is reacted with an isocyanate group. A structure having at least one structure represented by the structural formula (Z102) can be obtained. When the structure represented by the structural formula (3) is a nitrogen-containing heteroaromatic 6-membered ring cation having at least one group derived from a glycidyl group, at least by reacting the ionic compound corresponding to the cation with a hydroxyl group, at least A structure having one structure represented by the structural formula (Z103) can be obtained.
Examples of the nitrogen-containing complex aromatic 6-membered ring in the structural formula (3) include a pyrimidine ring and a pyrazine ring.

Examples of cations of ionic compounds that can provide the structure represented by the structural formula (3) include cations having a pyrimidine ring structure and having a hydroxyl group.
1,4-bis (2-hydroxyethyl) pyrimidinium cation, 1,5-bis (3-hydroxypropyl) pyrimidinium cation, 1- (4-hydroxybutyl) -4- (2-hydroxyethyl) pyri Midinium cations, 1,4-bis (2-hydroxyethyl) -2-methylpyrimidinium cations; and derivatives thereof.
Examples of the cation having at least one amino group and glycidyl group include cations having a structure in which a part or all of the hydroxyl groups of the above cation is replaced with an amino group or a glycidyl group (or epoxy group).

In structural formula (4), R6 and R7 represent a hydrocarbon group or a single bond required to form a nitrogen-containing heteroalicyclic group together with a nitrogen atom to which each is bonded. Specifically, it is preferable that R6 and R7 are independently selected from divalent hydrocarbon groups having 1 to 5 carbon atoms, and the total carbon number is 3 to 6. Z9 to Z11 represent any structure, hydrogen atom, or hydrocarbon group having 1 to 4 carbon atoms, which are independently selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103). As the hydrocarbon group, an alkyl group is preferable. Z12 represents any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103), or a hydrocarbon group having 1 to 4 carbon atoms. As the hydrocarbon group, an alkyl group is preferable. d3 represents an integer of 0 to 2, and at least one of Z9 to Z12 is any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103). When d3 is 2, Z12 may be the same or different.

The structure represented by the structural formula (4) represents a nitrogen-containing heteroalicyclic cation containing two nitrogen atoms having at least one group derived from a hydroxyl group, an amino group, or a glycidyl group. When the structure represented by the structural formula (4) is a nitrogen-containing heteroalicyclic cation having at least one hydroxyl group-derived group, at least the structure is obtained by reacting an ionic compound corresponding to the cation with an isocyanate group. A structure having one structure represented by the formula (Z101) can be obtained. When the structure represented by the structural formula (4) is a nitrogen-containing heteroalicyclic cation having at least one amino group-derived group, at least the structure is obtained by reacting the ionic compound corresponding to the cation with an isocyanate group. A structure having one structure represented by the formula (Z102) can be obtained. When the structure represented by the structural formula (4) is a nitrogen-containing heteroalicyclic cation having at least one group derived from a glycidyl group, at least the structural formula is obtained by reacting the ionic compound corresponding to the cation with a hydroxyl group. A structure having one (Z103) is obtained.
Examples of the nitrogen-containing heterolipocyclic group in the structural formula (4) include a piperazine group, an imidazoline group, an imidazolidine group, a 1,3-diazepan group, and a 1,4-diazepan group. Among them, the piperazine group is preferable, and the structure represented by the structural formula (4) is preferably the structure represented by the structural formula (11). In the structural formula (11), Z9, Z10, Z11, Z12, and d3 are the same as the structural formula (4).

Examples of the cation of the ionic compound capable of providing the structure represented by the structural formula (4) include a cation having a piperazine group and a hydroxyl group.
1,1-bis (2-hydroxyethyl) piperazinium cation, 1,1,4-tris (2-hydroxyethyl) piperadinium cation, 1,4-bis (3-hydroxypropyl) -1-ethylpipe Radinium cations, 1,4-bis (2-hydroxyethyl) -1,3-diethylpiperadinium cations; and derivatives thereof.
Examples of the cation having at least one amino group and glycidyl group include cations having a structure in which a part or all of the hydroxyl groups of the cation is replaced with an amino group or a glycidyl group.

In structural formula (5), R8 represents a hydrocarbon group required to form a nitrogen-containing aromatic ring with the nitrogen atom to be bonded. Specifically, R8 is a divalent hydrocarbon group having 4 to 6 carbon atoms, and π electrons are delocalized so as to exhibit aromaticity. Z13 represents any structure, hydrogen atom, or hydrocarbon group having 1 to 4 carbon atoms selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103). As the hydrocarbon group, an alkyl group is preferable. Z14 represents any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103), or a hydrocarbon group having 1 to 4 carbon atoms. As the hydrocarbon group, an alkyl group is preferable. d4 represents an integer of 0 or 1, and at least one of Z13 and Z14 is any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103).

The structure represented by the structural formula (5) represents a nitrogen-containing aromatic ring cation containing one nitrogen atom having at least one group derived from a hydroxyl group, an amino group or a glycidyl group. When the structure represented by the structural formula (5) is a nitrogen-containing aromatic ring cation having at least one hydroxyl group-derived group, at least the structural formula (Z101) is obtained by reacting the ionic compound corresponding to the cation with an isocyanate group. ), A structure having one structure is obtained. When the structure represented by the structural formula (5) is a nitrogen-containing aromatic ring cation having at least one amino group-derived group, at least the structural formula is obtained by reacting the ionic compound corresponding to the cation with the isocyanate group. A structure having one structure represented by (Z102) can be obtained. When the structure represented by the structural formula (5) is a nitrogen-containing aromatic ring cation having at least one group derived from a glycidyl group, at least the structural formula (5) is obtained by reacting the ionic compound corresponding to the cation with a hydroxyl group. A structure having one structure shown in Z103) can be obtained.
Examples of the nitrogen-containing aromatic ring in the structural formula (5) include a pyrrole ring, a pyridine ring, and an azepine ring. Among them, the pyridine ring is preferable, and the structure represented by the structural formula (5) is preferably the structure represented by the structural formula (12). In the structural formula (12), Z13, Z14, and d4 have the same meanings as the structural formula (5).

Examples of cations of the ionic compound that can provide the structure represented by the structural formula (5) include cations having a pyridine ring structure and a hydroxyl group.
1-Hydroxymethylpyridinium cation, 1- (2-hydroxyethyl) pyridinium cation, 1- (3-hydroxypropyl) pyridinium cation, 1- (4-hydroxybutyl) pyridinium cation, 1- (6-hydroxyhexyl) pyridinium cation , 1- (8-hydroxyoctyl) pyridinium cation, 2-methyl-1- (2-hydroxyethyl) pyridinium cation, 3-methyl-1- (2-hydroxyethyl) pyridinium cation, 4-methyl-1- (2) -Hydroxyethyl) pyridinium cation, 3-ethyl-1- (2-hydroxyethyl) pyridinium cation, 3-n-butyl-1- (2-hydroxyethyl) pyridinium cation, 1-methyl-2-hydroxymethylpyridinium cation, 1-Methyl-3-hydroxymethylpyridinium cation, 1-methyl-4-hydroxymethylpyridinium cation, 1-methyl-2- (2-hydroxyethyl) pyridinium cation, 1-methyl-3- (2-hydroxyethyl) pyridinium Cation, 1-methyl-4- (2-hydroxyethyl) pyridinium cation, 1-ethyl-3- (2-hydroxyethyl) pyridinium cation, 1-n-butyl-3- (2-hydroxyethyl) pyridinium cation, 2 -Methyl-4-n-butyl-1- (2-hydroxyethyl) pyridinium cation;
1,2-bishydroxymethylpyridinium cation, 1,3-bishydroxymethylpyridinium cation, 1,4-bishydroxymethylpyridinium cation, 1,2-bis (2-hydroxyethyl) pyridinium cation, 1,3-bis ( 2-Hydroxyethyl) pyridinium cation, 1,4-bis (2-hydroxyethyl) pyridinium cation, 1,2-bis (3-hydroxypropyl) pyridinium cation, 1,3-bis (3-hydroxypropyl) pyridinium cation, 1,4-bis (3-hydroxypropyl) pyridinium cation, 1,2-bis (4-hydroxybutyl) pyridinium cation, 1,3-bis (4-hydroxybutyl) pyridinium cation, 1,4-bis (4-hydroxybutyl) pyridinium cation Hydroxybutyl) pyridinium cation, 1,2-bis (6-hydroxyhexyl) pyridinium cation, 1,3-bis (6-hydroxyhexyl) pyridinium cation, 1,4-bis (6-hydroxyhexyl) pyridinium cation, 1, 2-bis (8-hydroxyoctyl) pyridinium cation, 1,3-bis (8-hydroxyoctyl) pyridinium cation, 1,4-bis (8-hydroxyoctyl) pyridinium cation, 2-methyl-1,3-bis (2-methyl-1,3-bis (8-hydroxyoctyl) pyridinium cation 2-Hydroxyethyl) pyridinium cation, 2-ethyl-1,3-bis (2-hydroxyethyl) pyridinium cation, 5-methyl-1,3-bis (2-hydroxyethyl) pyridinium cation, 5-ethyl-1,5-ethyl-1, 3-Bis (2-hydroxyethyl) pyridinium cation;
1,2,4-Trishydroxymethylpyridinium cation, 1,2,4-tris (2-hydroxyethyl) pyridinium cation, 1,2,4-tris (3-hydroxypropyl) pyridinium cation, 1,2,4- Tris (4-hydroxybutyl) pyridinium cation, 1,2,4-tris (6-hydroxyhexyl) pyridinium cation, 1,2,4-tris (8-hydroxyoctyl) pyridinium cation, 1,3,5-trishydroxy Methylpyridinium cation, 1,3,5-tris (2-hydroxyethyl) pyridinium cation, 1,3,5-tris (3-hydroxypropyl) pyridinium cation, 1,3,5-tris (4-hydroxybutyl) pyridinium Cations, 1,3,5-tris (6-hydroxyhexyl) pyridinium cations, 1,3,5-tris (8-hydroxyoctyl) pyridinium cations; and derivatives thereof.
Examples of the cation having at least one amino group and glycidyl group include cations having a structure in which a part or all of the hydroxyl groups of the above cation is replaced with an amino group or a glycidyl group (or epoxy group).

In structural formula (6), R9 represents a hydrocarbon group required to form a nitrogen-containing alicyclic group together with a nitrogen atom to be bonded. Specifically, R9 is a divalent hydrocarbon group having 4 to 7 carbon atoms. As the hydrocarbon group, an alkylene group is preferable. Z15 and Z16 each represent any structure, hydrogen atom, or hydrocarbon group having 1 to 4 carbon atoms independently selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103). As the hydrocarbon group, an alkyl group is preferable. Z17 represents any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103), or a hydrocarbon group having 1 to 4 carbon atoms. As the hydrocarbon group, an alkyl group is preferable. d5 represents an integer of 0 or 1, and at least one of Z15 to Z17 is any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103).

The structure represented by the structural formula (6) represents a nitrogen-containing alicyclic cation having at least one group derived from a hydroxyl group, an amino group, and a glycidyl group. When the structure represented by the structural formula (6) is a nitrogen-containing alicyclic cation having at least one hydroxyl group-derived group, at least the structural formula (6) is obtained by reacting the ionic compound corresponding to the cation with the isocyanate group. A structure having one structure shown in Z101) can be obtained. When the structure represented by the structural formula (6) is a nitrogen-containing alicyclic cation having at least one amino group-derived group, at least the structural formula is obtained by reacting the ionic compound corresponding to the cation with an isocyanate group. A structure having one structure represented by (Z102) can be obtained. When the structure represented by the structural formula (6) is a nitrogen-containing alicyclic cation having at least one group derived from a glycidyl group, at least the structural formula (6) is obtained by reacting the ionic compound corresponding to the cation with a hydroxyl group. A structure having one structure represented by Z103) can be obtained.
Examples of the nitrogen-containing alicyclic group in the structural formula (6) include a pyrrolidine group, a pyrroline group, a piperidine group, an azepane group, and an azocane group. Among them, the pyrrolidine group is preferable, and the structure represented by the structural formula (6) is preferably the structure represented by the structural formula (13). In the structural formula (13), Z15, Z16, Z17, and d5 are the same as the structural formula (6).

Examples of the structure represented by the structural formula (6) include cations having a pyrrolidine group and a hydroxyl group.
1-Methyl-1,2-bis (2-hydroxyethyl) pyrrolidinium cation, 1-ethyl-1,2-bis (2-hydroxyethyl) pyrrolidinium cation, 1-butyl-1,2-bis (2-hydroxyethyl) 2-Hydroxyethyl) pyrrolidinium cation, 1-methyl-1,2-bis (4-hydroxybutyl) pyrrolidinium cation; and derivatives thereof.
Examples of the cation having at least one amino group and glycidyl group include cations having a structure in which these hydroxyl groups are substituted with an amino group and a glycidyl group.

In the structural formulas (Z101) to (Z103), R101, R102 and R103 represent divalent hydrocarbon groups having linear or branched independently. The divalent hydrocarbon group is preferably a linear or branched alkylene group having 1 to 8 carbon atoms.
Further, in the structural formulas (Z101) to (Z103), the symbol "*" is a bond with a nitrogen atom in the structural formula (1) or a nitrogen-containing heterocycle in the structural formulas (2) to (6). Represents a bond with a nitrogen atom or a carbon atom in a nitrogen-containing heterocycle. Further, the symbol "**" represents a bond portion with a carbon atom in the polymer chain constituting the resin.

The structure represented by the structural formula (Z101) is a residue (urethane bond) formed by reacting a hydroxyl group having a structure represented by the structural formula (Z111) of a cation with an isocyanate group.
Structural formula (Z111)
-R101-OH
The structure represented by the structural formula (Z102) is a residue (urea bond) formed by reacting an amino group having a structure represented by the structural formula (Z112) of a cation with an isocyanate group.
Structural formula (Z112)
-R102-NH ₂
The isocyanate group that reacts with the hydroxyl group and the amino group is preferably the isocyanate group contained in the oligomer or prepolymer that forms the crosslinked urethane resin.
The structure represented by the structural formula (Z103) is a residue formed by reacting a glycidyl group having a structure represented by the structural formula (Z113) of a cation with a hydroxyl group such as a polyol forming a crosslinked urethane resin. ..

The hydroxyl group that reacts with the glycidyl group is preferably the hydroxyl group of the oligomer or prepolymer that forms the crosslinked urethane resin.
Among the structures represented by the structural formulas (1) to (6), when a resin having the structure represented by the structural formula (2) is contained, the mobility of ion carriers is increased even at a low temperature due to the chemical structure of the cation. The ratio of dissociation between the cation and the anion (ionization rate) is high, and the resistance value in a low temperature environment of about 15 ° C. is less likely to increase, which is preferable.

<Polyol>
Examples of the polyol forming the crosslinked urethane resin of the toner supply roller of the present invention include polyester polyol, polyether polyol, acrylic polyol, polycarbonate polyol, polycaprolactone polyol, and the like. Of these, the polyether polyol is preferable because the crosslinked urethane resin has flexibility.
Examples of the polyether polyol include the following. Polyethylene glycol, polypropylene glycol, poly 1,4-butanediol, poly 1,5-pentanediol, polyneopentyl glycol, poly 3-methyl-1,5-pentanediol, poly 1,6-hexanediol, poly 1, 8-octanediol, poly1,9-nonanediol. Among these, from the viewpoint of suppressing the increase in hardness, polypropylene glycol, poly1,4-butanediol, poly1,5-pentanediol, polyneopentyl glycol, poly3-methyl-1,5-pentanediol, poly1, 6-Hexanediol is preferred.
In addition, examples of the polyester polyol include the following. Ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1 Obtained by condensation reaction of a diol component such as 9-nonanediol or a triol component such as trimethylolpropane with a dicarboxylic acid such as adipic acid, suberic acid, sebacic acid, phthalic anhydride, terephthalic acid and hexahydroxyphthalic acid. Polyester polyol to be. Among these, from the viewpoint of suppressing the increase in hardness, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol A polyester polyol obtained by a condensation reaction between such a diol component and a dicarboxylic acid such as adipic acid, suberic acid, and sebacic acid is preferable.
Examples of the polycaprolactone polyol include the following. Poly ε-caprolactone, poly γ-caprolactone.
In addition, examples of the polycarbonate polyol include the following. Ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1 , A polycarbonate polyol obtained by a condensation reaction with a diol component such as 9-nonanediol, a dialkyl carbonate such as phosgen and dimethyl carbonate, or a cyclic carbonate such as ethylene carbonate. Among these, from the viewpoint of suppressing the increase in hardness, diol components such as neopentyl glycol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,8-octanediol , Polycarbonate polyol obtained by condensation reaction with dialkyl carbonate such as dimethyl carbonate is preferable.
If necessary, these polyol components are prepolymers whose chains are extended with isocyanate compounds such as 2,4-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), and isophorone diisocyanate (IPDI). May be good.

<Isocyanate compound>
The isocyanate compound is not particularly limited, but is an aliphatic polyisocyanate such as ethylene diisocyanate and 1,6-hexamethylene diisocyanate (HDI); isophorone diisocyanate (IPDI), cyclohexane-1,3-diisocyanate, cyclohexane-. Alicyclic polyisocyanates such as 1,4-diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), polyether diphenylmethane diisocyanate, xylylene diisocyanate , Aromatic isocyanates such as naphthalenediocyanates; and copolymers thereof, isocyanurates, TMP adducts, biuret, and blocks thereof can be used. Among these, aromatic isocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate are preferable.
The polyol component and the isocyanate compound are mixed so that the ratio (molar ratio) of the isocyanate groups in the isocyanate compound to 1.0 hydroxyl group in the polyol component is in the range of 1.0 or more and 2.0 or less. Is preferable. When the mixing ratio is within the above range, it is possible to suppress the residual unreacted components.

<Anion>
The anion contained in the crosslinked urethane resin of the present invention may be any anion that can form an ion pair with the cationic structure of the urethane resin and impart conductivity to the toner supply roller of the present invention. Among them, fluoroalkylsulfonylimide anion, fluorosulfonylimide anion, fluoroalkylsulfonate anion, fluorosulfonate anion, fluoroalkylcarboxylic acid anion, fluoroalkylmethide anion, fluoroborate anion, fluorophosphate anion, disianamide anion ((NC)). It is preferably at least one selected from the group consisting of ₂ N ⁻ ) and thiocyanate anions (NCS ^−). The reason is that the anion is chemically very stable and has a high ionization rate as compared with the halogen anion, the sulfate anion, and the nitrate anion due to its chemical structure. Specifically, since the anion has a strong electron-attracting group in the molecule and stabilizes the negative charge of the anion, it exhibits a high ionization rate in a wide temperature range and contributes to the development of high conductivity even at low temperatures. It is thought that this is to be done. As the anion, a chlorine ion or a perchlorate anion can also be used.

Specific examples of the fluoroalkylsulfonylimide anion include bis (trifluoromethanesulfonyl) imide anion, bis (pentafluoroethanesulfonyl) imide anion, bis (heptafluoropropanesulfonyl) imide anion, and bis (nonafluorobutanesulfonyl) imide. Fluoroalkylsulfonylimide anions having fluoroalkyl groups with 1 to 6 carbon atoms, such as anions, bis (dodecafluoropentane sulfonyl) imide anions, and bis (perfluorohexanesulfonyl) imide anions, and N, N-hexafluoro Cyclic fluoroalkylsulfonylimide anions such as propane-1,3-disulfonylimide can be mentioned.
Specific examples of the fluorosulfonylimide anion include bis (fluorosulfonyl) imide anion.
Specific examples of the fluoroalkyl sulfonate anion include trifluoromethanesulfonic acid anion, fluoromethanesulfonic acid anion, perfluoroethanesulfonic acid anion, perfluoropropanesulfonic acid anion, perfluorobutanesulfonic acid anion, and perfluoropentanesulfonic acid. Examples include an anion, a perfluorohexane sulfonic acid anion, and a perfluorooctane sulfonic acid anion.
Specific examples of the fluoroalkylcarboxylic acid anion include trifluoroacetic acid anion, perfluoropropionic acid anion, perfluorobutyrate anion, perfluorovalerate anion, and perfluorocaproate anion.
Specific examples of the fluoroalkylmethide anion include tris (trifluoromethanesulfonyl) methide anion, tris (perfluoroethanesulfonyl) methide anion, tris (perfluoropropanesulfonyl) methide anion, tris (perfluorobutanesulfonyl) methide anion, and tris (perfluorobutanesulfonyl) methide anion. Examples thereof include perfluoropentanesulfonyl) methideanion, tris (perfluorohexanesulfonyl) methideanion, and tris (perfluorooctanesulfonyl) methideanion.
The fluoroborate anion, specifically, tetrafluoroborate anion (BF 4 ^_-) and the like.
Specific examples of the fluorophosphate anion include hexafluorophosphate anion (PF ₆ ⁻ ).
Among these anions, when a fluoroalkylsulfonylimide anion, a fluorosulfonylimide anion, a fluoroborate anion, a disianamide anion, or a thiocyanate anion is used, the decrease in conductivity in a low temperature environment is further suppressed. preferable.

<Crosslinking agent>
It is preferable to include a cross-linking agent as a component constituting the cross-linked urethane resin of the present disclosure. When the crosslinked structure contains a trifunctional or higher functional isocyanate, a trifunctional or higher functional polyol, or a trifunctional or higher functional ionic conductive agent, these can function as a crosslinking agent and form a crosslinked structure. In addition to these, a known cross-linking agent most suitable for urethane resin may be used. Examples thereof include amine-based cross-linking agents such as ethylenediamine and imide-based cross-linking agents such as carbodiimide.

<Other components in the conductive layer>
If necessary, the conductive layer may contain a conductive filler as long as it does not interfere with the effects of the present invention. As the conductive filler, carbon black; a conductive metal such as aluminum or copper can be used. Among these, carbon black is particularly preferably used because it is relatively easily available and has high conductivity-imparting property and reinforcing property.
A catalyst, a foaming agent, a defoaming agent, or other auxiliary agent can be used for the conductive layer, if necessary.

The catalyst is not particularly limited, and can be appropriately selected and used from various conventionally known catalysts. For example, amine-based catalysts (triethylenediamine, bis (dimethylaminoethyl) ether, N, N, N', N'-tetramethylhexanediamine, 1,8-diazabicyclo (5.4.0) undecene-7, 1, 5-diazabicyclo (4.3.0) nonen-5, 1,2-dimethylimidazole, N-ethylmorpholine, N-methylmorpholine, etc.), organic metal catalysts (tin octylate, tin oleate, dibutyltin dilaurate, etc.) Dibutyltin diacetate, tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, etc.), acid catalysts with reduced initial activity of the amine-based catalyst and organic metal-based catalyst ( Carborates, nitrates, octylates, borates, etc.) are used. One type of catalyst may be used, or two or more types may be used in combination.
The foaming agent is not particularly limited, and can be appropriately selected and used from various conventionally known foaming agents. In particular, water is suitably used as a foaming agent because it reacts with polyisocyanate to generate carbon dioxide gas. In addition, the combined use of other foaming agents and water does not impair the gist of the present invention.
The foam stabilizer is not particularly limited, and can be appropriately selected and used from various conventionally known foam stabilizers.
As the other auxiliary agent, if necessary, a cross-linking auxiliary agent, a flame retardant, a colorant, an ultraviolet absorber, an antioxidant and the like may be used as long as the effects of the present invention are not impaired. Further, other ionic conductive agents may be used in combination to the extent that the effects of the present invention are not impaired.

<Manufacturing of toner supply rollers>
The toner supply roller is manufactured by providing a conductive crosslinked urethane resin layer on the outer periphery of the conductive shaft body.

<Method of forming a conductive layer containing crosslinked urethane resin>
The conductive layer containing the crosslinked urethane resin reacts and cures a composition containing a polyol, an isocyanate, and an ionic compound containing at least one selected from the group consisting of a hydroxyl group, an amino group and a glycidyl group in a cationic structure. Obtained by The crosslinked urethane resin layer preferably has voids formed by foaming. There are no particular restrictions on the foaming method. Any method can be used, such as a method using a foaming agent and a method of mixing air bubbles by mechanical stirring. The foaming ratio may be appropriately determined and is not particularly limited, but is 2 to 50 times, more preferably 3 to 30 times. The expansion ratio is obtained by dividing the product of the volume including the voids of the conductive layer containing the crosslinked polyurethane resin and the true specific gravity of the crosslinked polyurethane resin by the mass of the conductive layer.
As a foaming method, for example, the following materials are mixed and reacted while being foamed to obtain a conductive layer containing a crosslinked urethane resin of a toner supply roller.
1. 1. As a material for forming urethane bonds (also called binder resin)
・ Polyether polyol, polyester polyol, etc. ・ Polyisocyanate 2. 2. An ionic compound containing at least one selected from the group consisting of a hydroxyl group, an amino group and a glycidyl group in the cationic structure. Catalyst, cross-linking agent 4. Defoamer 5. Foaming agent The total content of the cation structure represented by at least one selected from the group consisting of the structures represented by the structural formulas (1) to (6) in the conductive layer forming material is as follows. It is preferable that it is within the range of. That is, from the viewpoint of conductivity and suppression of resistance fluctuation due to energization, the crosslinked urethane resin layer is in the range of 0.1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.
There is no particular limitation on the temperature and time for mixing. The mixing temperature is usually in the range of 10 ° C. or higher and 90 ° C. or lower, preferably 20 ° C. or higher and 60 ° C. or lower. The mixing time is usually 1 second or more and 10 minutes or less, preferably 3 seconds or more and 5 minutes or less, although it depends on the structure of the mixing unit used, rotation conditions, and the like.
The state after these reactions can be confirmed by analysis by known means such as thermal decomposition GC / MS, FT-IR, NMR, GPC and the like.

There is no particular limitation on the method of joining the shaft body and the conductive layer. The shaft body is arranged inside the mold in advance, and the raw material mixture as described above is cast-cured, or the raw material mixture is molded into a predetermined shape to be a conductive layer in advance, and then the shaft body and the shaft body are formed. A method of bonding or the like can be used. In either method, an adhesive layer can be provided between the shaft body and the conductive layer, if necessary. As the adhesive layer, a known material such as an adhesive or a hot melt sheet can be used.
In the case of the casting curing method, a mold release agent may be applied in advance to the inner wall of the molding mold. As the release agent, a conventionally known release agent can be used. Examples thereof include a water-based mold release agent containing a wax component and a silicone oil, and a mold release agent in which a fluororesin is dissolved in a fluorine-based solvent.
The method for forming the shape of the conductive layer containing the crosslinked urethane resin as the toner supply roller is not particularly limited. For example, in addition to the above-mentioned method of casting into a mold having a predetermined shape, the following methods and the like can be used. A method of cutting out a block-state polyurethane foam to a predetermined size by cutting, a method of making a predetermined size by polishing, or a method of appropriately combining these methods.
As a method of casting a material in the method of casting and curing, a method of making a hole in a piece on one side of a mold in which a shaft body is set and casting and curing from the hole, or a method in which a mold body is set is used. After casting the material directly, there is a method of closing the mold with a piece on one side and curing it.

The method of directly casting and then closing the mold to cure has the advantage that no material is wasted. Hereinafter, a method of directly casting and then closing the mold to cure the mold will be described with reference to FIG.
As shown in FIG. 8A, the molding die 51 is fitted with the lower piece 52, and the shaft body 53 is installed in the shaft body insertion hole 54 of the lower piece 53. A mold release agent may be applied in advance to the molding surfaces of the molding die 51 and the lower piece 52. As the release agent, a conventionally known release agent can be used. Examples thereof include a water-based mold release agent containing a wax component and a silicone oil, and a mold release agent in which a fluororesin is dissolved in a fluorine-based solvent.
Examples of the mold release agent applied to the molding die and the lower piece include the following.
Product name: Fleet 351, Product name: Fleet 352, Product name: Fleet 640, Product name: Fleet 650, Product name: Fleet 345, Product name: Fleet 430, Product name: Fleet 450, Product Name: FRX-AL9, both manufactured by Neos Co., Ltd.
The mold release agent can also be added to the material and used as an internal mold release agent.
As shown in FIG. 8A, the raw material mixture 55 (foaming material) of the crosslinked urethane resin is injected into the molding space (cavity). There is no particular limitation on the temperature and time when the foam material 55 is mixed. The mixing temperature is usually in the range of 10 ° C. or higher and 90 ° C. or lower, preferably 30 ° C. or higher and 40 ° C. or lower. The mixing time is usually 1 second or more and 10 minutes or less, preferably 3 seconds or more and 5 minutes or less, although it depends on the structure of the mixing unit used, rotation conditions, and the like.
The molding die 51, the lower piece 52, and the shaft body 53 are preheated to a predetermined temperature in advance. The temperature for preheating the molding die 51, the lower piece 52, and the shaft body 53 is a temperature within a range in which a curing reaction does not occur when the foaming material 55 foams up in the molding die 51, and is preferably 40 ° C. or higher and 60 ° C. or lower. The range. The shaft body 53 is slanted at the upper end position by shifting from the center position of the molding die 51 to the side opposite to the injection side. The foam material 55 is injected from a casting machine (not shown) on the upper part of the molding die 51 to a position between the inner surface of the molding die 51 and the inclined shaft body 53, and is injected onto the lower piece 52 which is the bottom surface of the molding die 51. Fall. The foam material 55 is in a state in which the shaft body 53 is returned to the central shaft position of the molding die 51 after the injection of a predetermined amount corresponding to the volume of the cavity of the molding die 51 is completed.

Next, as shown in FIG. 8B, the upper piece 56 is fitted to the molding die 51, and is composed of an inner surface of the molding die 51 and a shaft body 53, and a closed space between the lower piece 52 and the upper piece 56. Cavity is formed. Further, a heating plate 58 in which a heater 57 is installed is arranged on the side surface of the molding die 51, and the foamed material 55 in the cavity is heated to raise the material surface in the upper piece direction. The upper piece 56 is provided with an air vent (not shown) in order to compress the gas and release the generated gas due to the foaming of the foaming material. Further, the upper piece may be subjected to a mold release process in the same manner as the molding die and the lower piece. However, the wax-based release agent may accumulate in the air vent, impeding the passage of gas and affecting the rise of the foam material. Therefore, it is preferable to use a mold release agent that does not contain a wax component or has a low content.
Examples of mold release agents that do not contain a wax component or have a low content include the following.
Product name: Frelease 20A, Product name: Frelease 25, Product name: Frelease 29, Product name: Frelease 11FG, Product name: Frelease 12G, Product name: Frelease 70, Product name: Frelease 75, Product Name: Frelease 310, Product name: Frelease 420, both manufactured by Neos Co., Ltd.

The temperature at which the molding die 51 is heated is the temperature at which the curing reaction of the foam material 55 occurs, and is preferably in the range of 70 ° C. or higher and 80 ° C. or lower. By gradually raising the temperature of the molding die 51 from the preheating temperature range of 40 ° C. or higher and 60 ° C. or lower to the heating temperature of 70 ° C. or higher and 80 ° C. or lower, the foaming material 55 is optimally foamed and cured. Therefore, the uneven hardness due to the uneven filling of the foam material in the conductive layer in the longitudinal direction of the roller after the molding is completed is suppressed.

As shown in FIG. 8C, the curing reaction of the conductive layer 59 is completed in the molding die 51 after a predetermined time has elapsed. After removing the upper piece 56 and the lower piece 52 from the molding die 51, the upper piece 56 and the lower piece 52 are removed from the mold to obtain a toner supply roller. The dimensions of the toner supply roller in the state where the molding die 51, the upper piece 56, and the lower piece 52 are assembled are equal to the final product dimensions, and both end portions of the toner supply roller in the process after molding. It is not necessary to cut and remove the conductive layer 59 such as parting off to finish the product size of the final toner supply roller.

<Toner>
The developing apparatus according to the present invention is characterized in that a specific toner is combined with the toner supply roller manufactured as described above. The toner according to the present invention contains the following toner particles as a main component.

(Toner particles)
The average particle size of the number of toner particles is 4.0 μm or more and 10.0 μm or less. When the number average particle diameter is in this range, the toner can be well rolled on the surface of the toner supply roller and uniformly charged, so that the amount of charge of the toner becomes uniform.
If it is smaller than 4.0 μm, the toner particles and the conductive layer (crosslinked urethane resin) of the toner supply roller come close to each other, and easily adhere to each other, making it difficult to roll, so that rapid charging is difficult to occur. If it is larger than 10.0 μm, it becomes difficult for one particle of the toner to have a uniform charge, and it becomes difficult for the toner to move to the electrophotographic photosensitive member side.
The average particle size of the number of toner particles is preferably 5.0 μm or more and 8.0 μm or less.

The toner particles have an organosilicon polymer on the surface of the toner matrix particles and the toner matrix particles. The organosilicon polymer has a structure represented by the following formula (1).
R-SiO _3/2 (1)
In the formula, R is an alkyl group or a phenyl group having 1 or more and 6 or less carbon atoms.
In the structure represented by the formula (1), R is preferably an alkyl group having 1 or more and 6 or less carbon atoms, and more preferably an alkyl group having 1 or more and 3 or less carbon atoms.
As the alkyl group having 1 or more and 3 or less carbon atoms, a methyl group, an ethyl group and a propyl group can be preferably exemplified. More preferably, R is a methyl group.

The organosilicon polymer has convex portions formed on the outer surface of the toner particles, and is preferably in surface contact with the surface of the toner matrix particles. By surface contact, the movement, desorption, and burial of the convex portion due to the organosilicon polymer can be suppressed. As a result, maintenance of chargeability and fluidity can be achieved at a high level through long-term use. Furthermore, even after the developing device has been used for a long period of time, many protrusions remain on the outer surface of the toner particles, so that the rolling of the toner with respect to the toner supply roller can be sustained, and the toner supply roller and the toner can be used together. Contact opportunity is secured.
When the organosilicon polymer comes into contact with the crosslinked urethane resin of the toner supply roller, the toner is easily charged.

The adhesion rate of the organosilicon polymer to the toner matrix particles is 80% or more. As shown in the measurement method described later, the adhesion rate indicates the difficulty of the organosilicon polymer falling off from the toner matrix particles.
When the adhesion rate is 80% or more, it is possible to prevent the convexity of the organosilicon polymer detached from the surface of the toner mother particles from causing surface contamination of the toner supply roller and reducing the charge applying ability. Further, since the convex portion remains uniformly on the surface of the toner particles after durability, the rolling with respect to the toner supply roller is maintained, the contact opportunity between the toner supply roller and the toner is secured, and the decrease in the charge amount of the toner can be prevented.
The sticking rate is preferably 85% or more, more preferably 90% or more. On the other hand, the upper limit is 100% and may be 99%.

The coverage of the organosilicon polymer with respect to the toner matrix particles is represented by the following Σw / L.
With respect to the cross-sectional image of the toner particles obtained by the scanning transmission electron microscope STEM, when the contour line of the toner mother particles is developed in a straight line to obtain a developed image of the cross-sectional image,
In the developed image,
Let L be the length of the straight line.
When the length of the line segment forming the boundary between the convex portion and the toner mother particle on the straight line is the convex width w, the ratio of the total sum Σw of the convex width w to the L (Σw / L) is required.
That is, Σw / L is a value expressing how much the surface of the toner particles is covered with the organosilicon polymer. When Σw / L is small, the coating with the organosilicon polymer is small, and when Σw / L is large, the coating with the organosilicon polymer is large. This Σw / L needs to be 0.30 or more and 0.95 or less.
When Σw / L is less than 0.30, the amount of the convex portion made of the organosilicon polymer on the surface of the toner particles on the surface of the toner supply roller is insufficient and the rolling property is lowered. Variation is likely to occur. When Σw / L is larger than 0.95, the number of irregularities on the surface of the toner particles is reduced, so that a phenomenon such as slip occurs, the chance of contact of the toner with the toner supply roller is insufficient, and the amount of charge of the toner is reduced. Not stable.
Σw / L is preferably 0.45 or more and 0.80 or less.
These fixation rates and coverage (Σw / L) are used for the method for producing an organosilicon polymer, which will be described later, specifically, the hydrolysis temperature, the number of copies of alkoxysilane used as a raw material, the pH at the time of hydrolysis and polymerization, and the like. Can be controlled by.

Further, the maximum length of the convex portion is defined as the convex diameter D in the normal direction of the convex width w, and the length from the apex of the convex portion to the straight line in the line segment forming the convex diameter D is the convex height H. When
The convex portion includes a "specific height convex portion" having a convex height H of 40 nm or more and 300 nm or less, and among the specific height convex portions, the ratio D / w of the convex diameter D to the convex width w is It is preferable that the number ratio P (D / w) of the specific height convex portion, which is 0.33 or more and 0.80 or less, is 50% by number or more. When the number ratio P is within the above range, the amount of the protrusions of the toner particles biting into the surface of the toner supply roller becomes appropriate, the rolling property of the toner is increased, the contact opportunity between the toner and the toner supply roller is increased, and the toner of the toner is increased. Charging is stable.

In order to show the degree of surface contact between the surface of the toner particles and the organosilicon polymer forming the convex portion, the cross section of the toner is observed by STEM. FIGS. 4 to 7 show a schematic view of the convex portion on the surface of the toner particles.
41 shown in FIG. 4 is a region of the STEM image, which is an image showing about 1/4 of the toner particles. 42 is a toner mother particle, 43 is a toner mother particle surface, and 44 is a convex portion (organosilicon polymer). Further, FIGS. 5 to 7 show the relationship of one convex portion 44 when the contour of the toner mother particle 42 (toner mother particle surface 43) is developed in a straight line, and the width of the convex portion is w and the convex portion. The diameter of is D, and the height of the convex portion is H.
As described above, the cross-sectional image of the toner particles is observed, and the contour lines of the toner mother particles are developed in a straight line to obtain a developed image of the cross-sectional image. In the developed image, the length of the straight line is L. The length of the line segment forming the boundary between the convex portion and the toner mother particle on the straight line is defined as the width w of the convex portion. Further, the maximum length of the convex portion in the normal direction of the width w of the convex portion is defined as the diameter D of the convex portion, and the straight line (toner mother particle surface 43) from the apex of the convex portion in the line segment forming the diameter D of the convex portion. Let the height up to be the height H of the convex portion.
In FIGS. 5 and 7, the diameter D and the height H are the same, and in FIG. 6, the convex portion 44 is a spherical particle partially embedded in the toner mother particle 42, and the diameter D is larger than the height H.
Further, FIG. 7 schematically shows a fixed state of particles similar to bowl-shaped particles in which the central portion of the hemispherical particles is recessed, which is obtained by crushing or breaking the hollow particles. In FIG. 7, the width w is the total length of the organosilicon compounds in contact with the surface of the toner matrix particles. That is, the width w in FIG. 7 is the sum of W1 and W2.

Further, from the viewpoint of improving durability stability and rolling rotation of the toner, a cumulative distribution of the height H is taken in the "specific height convex portion" where the height H is 40 nm or more and 300 nm or less. When the height corresponding to 80% by total from the smaller height H is taken as H80, the H80 is preferably 65 nm or more. It is more preferably 70 nm or more, and further preferably 73 nm or more.
The upper limit of the H80 is not particularly limited, but is preferably 120 nm or less, more preferably 100 nm or less, and further preferably 90 nm or less.
In the observation of the toner by the scanning electron microscope SEM, when the maximum diameter of the convex portion of the organosilicon polymer is the convex diameter R, the number average diameter of the convex diameter R is preferably 20 nm or more and 80 nm or less. More preferably, it is 35 nm or more and 60 nm or less.

The organosilicon polymer is preferably a polycondensation polymer of an organosilicon compound having a structure represented by the following formula (Z).

(In the formula (Z), R ₁₀ represents a hydrocarbon group (preferably an alkyl group) having 1 or more carbon atoms and 6 or less carbon atoms, and R ₁₁ , R ₁₂ and R ₁₃ are independent halogen atoms and hydroxy groups, respectively. , Acetoxy group, or alkoxy group.)
R ₁₀ is preferably an aliphatic hydrocarbon group having 1 or more and 3 or less carbon atoms, and more preferably a methyl group.
R ₁₁ , R ₁₂ and R ₁₃ are independently halogen atoms, hydroxy groups, acetoxy groups, or alkoxy groups (hereinafter, also referred to as reactive groups). These reactive groups are hydrolyzed, addition-polymerized and polycondensed to form a crosslinked structure.
The hydrolyzability is mild at room temperature, and from the viewpoint of the precipitation property of the toner matrix particles on the surface, R ₁₁ , R ₁₂ and R ₁₃ are preferably alkoxy groups having 1 to 3 carbon atoms, and are preferably methoxy groups or ethoxy groups. More preferably it is a group.
Further, _{the hydrolysis, addition polymerization and condensation polymerization of R 11} , R ₁₂ and R ₁₃ can be controlled by the reaction temperature, reaction time, reaction solvent and pH. In order to obtain the organosilicon polymer used in the present invention, an organosilicon compound having three reactive groups (R ₁₁ , R ₁₂ and R _{13 ) in one molecule excluding R 10 in the above formula (Z) is obtained.} (Hereinafter, also referred to as trifunctional silane) may be used alone or in combination of two or more.

Examples of the compound represented by the above formula (Z) include the following.
Methyltrimethoxysilane, Methyltriethoxysilane, Methyldiethoxymethoxysilane, Methylethoxydimethoxysilane, Methyltrichlorosilane, Methylmethoxydichlorosilane, Methylethoxydichlorosilane, Methyldimethoxychlorosilane, Methylmethoxyethoxychlorosilane, Methyldiethoxychlorosilane, Methyl Triacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxy Trifunctional methylsilanes such as hydroxysilane, methylethoxymethoxyhydroxysilane, and methyldiethoxyhydroxysilane.
Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltri Trifunctional such as methoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane Sexual silane.
Trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

Further, an organosilicon polymer obtained by using the following in combination with an organosilicon compound having a structure represented by the formula (Z) may be used to the extent that the effect of the present invention is not impaired. Organosilicon compounds having four reactive groups in one molecule (tetrafunctional silane), organosilicon compounds having two reactive groups in one molecule (bifunctional silane) or organosilicon compounds having one reactive group (bifunctional silane) Monofunctional silane). For example, the following can be mentioned.
Dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriemethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-amino) Ethyl) Aminopropyltriethoxysilane, Vinyltriisocyanasilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyldiethoxymethoxysilane, Vinylethoxydimethoxysilane, Vinylethoxydihydroxysilane, Vinyldimethoxyhydroxysilane, Vinylethoxymethoxyhydroxysilane, A trifunctional vinylsilane, such as vinyldiethoxyhydroxysilane.

Further, the content of the organosilicon polymer in the toner particles is preferably 1.0% by mass or more and 10.0% by mass or less, and more preferably 2.5% by mass or more and 6.0% by mass or less. ..

As a preferable method for forming the above-mentioned specific convex shape on the surface of the toner particles, an organosilicon compound is added to the place where the toner mother particles are dispersed in an aqueous medium to obtain a toner mother particle dispersion liquid to form a convex shape to disperse the toner particles. A method of obtaining a liquid can be mentioned.
The solid content concentration of the toner mother particle dispersion is preferably adjusted to 25% by mass or more and 50% by mass or less. The temperature of the toner mother particle dispersion is preferably adjusted to 35 ° C. or higher. Further, it is preferable to adjust the pH of the toner mother particle dispersion to a pH at which condensation of the organosilicon compound does not easily proceed. Since the pH at which the condensation of the organosilicon polymer is difficult to proceed differs depending on the substance, the pH at which the reaction is most difficult to proceed is preferably within ± 0.5.
On the other hand, it is preferable to use an organosilicon compound that has been hydrolyzed. For example, it is hydrolyzed in a separate container as a pretreatment for the organosilicon compound. When the amount of the organosilicon compound is 100 parts by mass, the concentration of hydrolysis is preferably 40 parts by mass or more and 500 parts by mass or less of deionized water from which ions have been removed by an ion exchange membrane or a reverse osmosis membrane (RO membrane). , 100 parts by mass or more and 400 parts by mass or less is more preferable. The conditions for hydrolysis are preferably pH 2 to 7, temperature 15 to 80 ° C., and time 30 to 600 minutes.

The obtained hydrolyzed solution and the toner mother particle dispersion are mixed to adjust the pH to a pH suitable for condensation (preferably 6 to 12, or 1 to 3, more preferably 8 to 12). By adjusting the amount of the hydrolysis liquid to 5.0 parts by mass or more and 30.0 parts by mass or less of the organosilicon compound with respect to 100 parts by mass of the toner mother particles, it becomes easy to form a convex shape. The temperature and time for forming and condensing the convex shape are preferably maintained at 35 ° C. to 99 ° C. for 60 minutes to 72 hours.
Further, in controlling the convex shape of the surface of the toner particles, it is preferable to adjust the pH in two steps. The convex shape on the surface of the toner particles can be controlled by appropriately adjusting the holding time before adjusting the pH and the holding time before adjusting the pH in the second step to condense the organosilicon compound. For example, it is preferable to hold the mixture at pH 4.0 to 6.0 for 0.5 hours to 1.5 hours and then at pH 8.0 to 11.0 for 3.0 hours to 5.0 hours. The convex shape can also be controlled by adjusting the condensation temperature of the organosilicon compound in the range of 35 ° C. to 80 ° C.

For example, the width w can be controlled by the amount of the organosilicon compound added, the reaction temperature, the reaction pH of the first step, the reaction time, and the like. For example, as the reaction time in the first stage becomes longer, the width w of the convex portion tends to increase.
Further, the diameter D and the height H can be controlled by the temperature at the time of hydrolysis of the organosilicon compound, the amount of the organosilicon polymer added, the reaction temperature, the pH of the second step, and the like. For example, when the hydrolysis temperature is high, the height H tends to be large. Further, when the reaction pH in the second step is high, the diameter D and the height H tend to be large.

Hereinafter, specific methods for producing toner will be described, but the present invention is not limited to these.
It is preferable that the toner mother particles are produced in an aqueous medium to form convex portions containing an organosilicon polymer on the surface of the toner mother particles.
As a method for producing the toner matrix particles, a suspension polymerization method, a dissolution suspension method, and an emulsion aggregation method are preferable, and the suspension polymerization method is more preferable. In the suspension polymerization method, the organosilicon polymer is easily precipitated uniformly on the surface of the toner matrix particles, and the organosilicon polymer has excellent adhesiveness, environmental stability, charge amount reversal component suppressing effect, and durability and durability thereof. Become good. Hereinafter, the suspension polymerization method will be further described.
In the suspension polymerization method, a polymerizable monomer composition capable of producing a binder resin constituting the toner matrix particles and, if necessary, an additive such as a colorant is contained in an aqueous medium. This is a method for obtaining a toner mother particle by granulating with the above and polymerizing the polymerizable monomer contained in the polymerizable monomer composition.
A mold release agent or other resin may be added to the polymerizable monomer composition, if necessary. Further, after the completion of the polymerization step, the produced particles can be recovered by washing and filtration by a known method. The temperature may be raised in the latter half of the polymerization step. Further, in order to remove the unreacted polymerizable monomer or by-product, it is also possible to distill off a part of the dispersion medium from the reaction system in the latter half of the polymerization step or after the completion of the polymerization step.
It is preferable to use the toner mother particles thus obtained to form convex portions of the organosilicon polymer by the above method.
Examples of the release agent include the following.
Paraffin wax, microcrystallin wax, petroleum wax and its derivatives such as petrolatum, Montan wax and its derivatives, hydrocarbon wax and its derivatives by the Fisher Tropsch method, polyolefin wax and its derivatives such as polyethylene and polypropylene, carnauba wax, Natural waxes and derivatives thereof such as candelilla wax, fatty acids such as higher aliphatic alcohols, stearic acid, palmitic acid, or acid amides, esters or ketones thereof, hardened castor oil and derivatives thereof, vegetable waxes, animal products. Wax, silicone resin.
Derivatives include oxides, block copolymers with vinyl-based monomers, and graft-modified products. The release agent may be used alone or in combination of two or more.
The content of the release agent is preferably 2.0 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin or the polymerizable monomer that produces the binder resin.

As other resins, for example, the following resins can be used.
Monopolymers of styrene and its substituents such as polystyrene and polyvinyltoluene; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene-methylacrylate copolymer, styrene -Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-methacrylic acid Ethyl copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Styrene-based copolymers such as coalesced, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethylmethacrylate, polybutylmethacrylate, poly Vinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic type Styrene. These may be used alone or in combination of two or more.

As the polymerizable monomer, the vinyl-based polymerizable monomer shown below can be preferably exemplified.
Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate , Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n -Acrylic polymerizable monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate. , N-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate. Methacrylic polymerizable monomers such as diethyl phosphate ethyl methacrylate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butylate, vinyl acrylate, etc. Vinyl esters; vinyl ethers such as vinyl methyl ethers, vinyl ethyl ethers, vinyl isobutyl ethers; vinyl methyl ketones, vinyl hexyl ketones, vinyl isopropyl ketones.
Among these vinyl monomers, styrene, styrene derivatives, acrylic-based polymerizable monomers and methacrylic-based polymerizable monomers are preferable.

Further, a polymerization initiator may be added when the polymerizable monomer is polymerized. Examples of the polymerization initiator include the following.
2,2'-azobis- (2,4-divaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis Azo-based or diazo-based polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyloxycarbonate, cumene hydroperoxide, 2,4- Peroxide-based polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide.
These polymerization initiators are preferably added in an amount of 0.5 parts by mass to 30.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer, and may be used alone or in combination of two or more.

Further, in order to control the molecular weight of the binder resin constituting the toner matrix particles, a chain transfer agent may be added when the polymerizable monomer is polymerized. The preferable amount of the chain transfer agent added is 0.001 part by mass to 15.000 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

On the other hand, in order to control the molecular weight of the binder resin constituting the toner matrix particles, a cross-linking agent may be added when the polymerizable monomer is polymerized. For example, the following can be mentioned.
Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester diacrylate (MANDA Nipponka), and the above acrylate converted to methacrylate.
Examples of the polyfunctional crosslinkable monomer include the following. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylic phthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl chlorendate.
The preferable amount of these cross-linking agents to be added is 0.001 part by mass to 15.000 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

When the medium used in the suspension polymerization is an aqueous medium, the following can be used as the dispersion stabilizer for the particles of the polymerizable monomer composition.
Tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina ..
In addition, examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch.
It is also possible to use commercially available nonionic, anionic and cationic surfactants. Examples of such a surfactant include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate.

A colorant may be used as the toner, and a known toner may be used without particular limitation.
The content of the colorant is preferably 3.0 parts by mass to 15.0 parts by mass with respect to 100 parts by mass of the binder resin or the polymerizable monomer.
A charge control agent can be used during toner production, and known ones can be used. The amount of these charge control agents added is preferably 0.01 parts by mass to 10.00 parts by mass with respect to 100 parts by mass of the binder resin or the polymerizable monomer.

The toner particles may be used as they are as toner, or various organic or inorganic fine powders may be externally added to the toner particles, if necessary. The organic or inorganic fine powder preferably has a particle size of 1/10 or less of the weight average particle size of the toner particles from the viewpoint of durability when added to the toner particles.

As the organic or inorganic fine powder, for example, the following is used.
(1) Fluidity imparting agent: silica, alumina, titanium oxide, carbon black and carbon fluoride.
(2) Abrasive: Metal oxide (for example, strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitride (for example, silicon nitride), carbide (for example, silicon carbide), metal salt (for example, calcium sulfate, sulfuric acid) Barium, calcium carbonate).
(3) Lubricating agent: Fluorine-based resin powder (for example, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (for example, zinc stearate, calcium stearate).
(4) Charge control particles: metal oxides (for example, tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.

Surface treatment of organic or inorganic fine powder may be performed in order to improve the fluidity of the toner and make the charge uniform. Examples of the treatment agent for hydrophobizing organic or inorganic fine powders include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, and other organosilicon compounds. Includes organotitanium compounds. These treatment agents may be used alone or in combination of two or more.

A method for measuring various physical properties of toner will be described below.
<Method of observing the cross section of toner with a scanning transmission electron microscope (STEM)>
The cross section of the toner observed by the scanning transmission electron microscope (STEM) is prepared as follows.
Hereinafter, the procedure for producing the cross section of the toner will be described.
First, the toner is sprayed on a cover glass (Matsunami Glass Co., Ltd., square cover glass; square No. 1) so as to form a single layer, and an osmium plasma coater (filgen Co., Ltd., OPC80T) is used to apply Os to the toner as a protective film. A film (5 nm) and a naphthalene film (20 nm) are applied.
Next, a PTFE tube (inner diameter Φ1.5 mm × outer diameter Φ3 mm × 3 mm) is filled with a photocurable resin D800 (JEOL Ltd.), and the cover glass is placed on the tube to make the toner a photocurable resin D800. Place it quietly in a contacting orientation. After irradiating light in this state to cure the resin, the cover glass and the tube are removed to form a cylindrical resin in which toner is embedded on the outermost surface.
4 when the radius of the toner (for example, weight average particle size (D4)) from the outermost surface of the cylindrical resin is 8.0 μm at a cutting speed of 0.6 mm / s by an ultrasonic ultramicrotome (Leica, UC7). Cut by a length of .0 μm) to obtain a cross section of the toner center.
Next, cutting is performed so that the film thickness is 100 nm, and a flaky sample of the cross section of the toner is prepared. By cutting by such a method, a cross section of the toner center portion can be obtained.
Images are acquired with a STEM probe size of 1 nm and an image size of 1024 x 1024 pixels. Further, the contrast of the director control panel of the bright field image is adjusted to 1425, the contrast control is adjusted to 3750, the contrast of the image control panel is adjusted to 0.0, the brightness control is adjusted to 0.5, and the Gammma is adjusted to 1.00 to acquire an image. The image magnification is 100,000 times, and the image is acquired so as to fit in about one-fourth to one-half of the circumference of the cross section in one toner particle as shown in FIG.

The obtained image is subjected to image analysis using image processing software (image J (available from https://imagej.nih.gov/ij/)), and the convex portion containing the organosilicon polymer is measured. Image analysis is performed on 30 STEM images.
First, draw a line along the circumference of the toner matrix particle with the line drawing tool (select the segmented line on the Straight tab). The portion where the convex portion of the organosilicon polymer is buried in the toner matrix particles is smoothly connected with the line assuming that the convex portion is not buried.
Convert the line to a straight line (select Selection on the Edit tab, change the line width to 500pixel in Properties, then select Selection on the Edit tab and perform Straightener).
As a result, a developed image in which the contour lines of the toner mother particles are developed in a straight line can be obtained. In the developed image, the width w, the diameter D, and the height H of each of the convex portions containing the organosilicon polymer are measured.
In the developed image, the length of the straight line is L. L corresponds to the length of the surface of the toner matrix particles in the STEM image. The length of the line segment forming the boundary between the convex portion and the toner mother particle on the straight line is defined as the convex width w. Further, the maximum length of the convex portion in the normal direction of the width w is defined as the diameter D, and the length from the apex of the convex portion to the straight line in the line segment forming the diameter D is defined as the height H.
Let Σw be the total value of the width w of the "specific height convex portion" in which the height H existing in the developed image used for the image analysis is 40 nm or more and 300 nm or less. Σw / L is calculated from one image, and the arithmetic mean value of 30 STEM images is adopted.

Further, P (D / w) is calculated from the result of measuring 30 STEM images. H80 is calculated by taking the cumulative distribution of the convex height H.
The detailed measurement of the convex portion is as described above and FIGS. 5 to 7.
The measurement is performed after overlaying the scale on the image with Image J on the Straight Line of the Straight tab and setting the length of the scale on the image with the Set Scale of the Analyze tab. A line segment corresponding to the width w or the height H can be drawn with the Straight Line of the Straight tab and measured with the Measure of the Analyze tab.

<Calculation method of average particle size (convex diameter R) of convex parts in scanning electron microscope (SEM)>
The method of SEM observation is as follows. This is performed using images taken by the Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation). The image capturing conditions of S-4800 are as follows.

(1) Sample preparation A conductive paste (TED PELLA, Inc, Product No. 16053, PELCO Colloid Graphite, Isopropanol base) is thinly applied to a sample table (aluminum sample table 15 mm × 6 mm), and toner is sprayed on the conductive paste. Further air blow is performed to remove excess toner from the sample table, and then platinum is vapor-deposited at 15 mA for 15 seconds. Set the sample table in the sample holder and adjust the sample table height to 30 mm with the sample height gauge.

(2) Setting of observation conditions for S-4800 Inject liquid nitrogen into the anti-contamination trap attached to the housing of S-4800 until it overflows, and leave it for 30 minutes. Start up "PC-SEM" of S-4800 and perform flushing (cleaning of FE chip which is an electron source). Click the acceleration voltage display part of the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Confirm that the flushing intensity is 2, and execute. Confirm that the emission current due to flushing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position.
Click the acceleration voltage display to open the HV setting dialog, and set the acceleration voltage to [2.0 kV] and the emission current to [10 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE] and select [Bottom (L)] for the SE detector to set the mode for observing the reflected electron image. Similarly, in the [Basic] tab of the operation panel, set the probe current of the electro-optical system condition block to [Normal], the focus mode to [UHR], and the WD to [8.0 mm]. Press the [ON] button on the acceleration voltage display of the control panel to apply the acceleration voltage.

(3) Focus adjustment Drag the inside of the magnification display section of the control panel to set the magnification to 5000 (5k) times. Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is reached to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles.
Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and focus with autofocus. This operation is repeated twice more to focus. With the midpoint of the maximum diameter of the observed particles aligned with the center of the measurement screen, drag the inside of the magnification display section of the control panel to set the magnification to 10000 (10k) times. Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is reached to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles.
Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and focus with autofocus. After that, the magnification is set to 50,000 (50k) times, the focus is adjusted using the focus knob and the STIGMA / ALIGNMENT knob in the same manner as above, and the focus is adjusted again by autofocus. Repeat this operation again to focus.

(4) Image saving Perform brightness adjustment in ABC mode, take a picture with a size of 640 x 480 pixels, and save it.
From the obtained SEM image, the number average diameter (D1) of the 500 convex portions having a diameter of 20 nm or more existing on the surface of the toner particles is calculated by the image processing software (image J). The measurement method is as follows.
-Measurement of the number average diameter of the convex parts of the organosilicon polymer The convex parts and the toner mother particles in the image are color-coded by binarization by particle analysis. Next, the maximum length of the selected shape is selected from the measurement commands, and the convex diameter R (maximum diameter) of one convex portion is measured. By performing this operation a plurality of times and obtaining the arithmetic mean value at 500 points, the number average diameter of the convex diameter R is calculated.

<Measurement method of fixation rate of organosilicon polymer>
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved in a water bath to prepare a sucrose concentrate. 31 g of the above sucrose concentrate in a centrifuge tube (capacity 50 ml), and 10 of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of Contaminone N (nonionic surfactant, anionic surfactant, and organic builder). Add 6 mL of a mass% aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a dispersion. 1.0 g of toner is added to this dispersion, and the toner lumps are loosened with a spatula or the like.
The centrifuge tube is shaken on a shaker at 350 spm (strokes per min) for 20 minutes. After shaking, the solution is replaced with a glass tube for a swing rotor (capacity: 50 mL), and the solution is separated by a centrifuge (manufactured by Kokusan Co., Ltd., H-9R) at 3500 rpm for 30 minutes. Visually confirm that the toner and the aqueous solution are sufficiently separated, and collect the separated toner in the uppermost layer with a spatula or the like. After filtering the aqueous solution containing the collected toner with a vacuum filter, it is dried in a dryer for 1 hour or more. The dried product is crushed with a spatula and the amount of silicon is measured by fluorescent X-ray. The adhesion rate (%) is calculated from the ratio of the amount of elements to be measured between the toner after washing with water and the initial toner.

The measurement of fluorescent X-rays of each element conforms to JIS K 0119-1969, but the specifics are as follows.
The measuring devices include the wavelength dispersive fluorescent X-ray analyzer "Axios" (manufactured by PANalytical) and the attached dedicated software "SuperQ ver. 4.0F" (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data. ) Is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 10 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).
As a measurement sample, put about 1 g of toner after washing with water or initial toner in a special press aluminum ring with a diameter of 10 mm and flatten it, and then flatten it with a tablet molding compressor "BRE-32" (manufactured by Maekawa Testing Machine Co., Ltd.). ), Pressurize at 20 MPa for 60 seconds, and use pellets molded to a thickness of about 2 mm.
The measurement is performed under the above conditions, the element is identified based on the obtained peak position of X-rays, and the concentration is calculated from the counting rate (unit: cps) which is the number of X-ray photons per unit time.
As a method for quantifying the toner, for example, the amount of silicon is determined as follows. _{For example, silica (SiO 2} ) fine powder is added to 100 parts by mass of toner particles so as to be 0.5 parts by mass, and the mixture is sufficiently mixed using a coffee mill. Similarly, the silica fine powder is mixed with the toner particles so as to be 2.0 parts by mass and 5.0 parts by mass, respectively, and these are used as a sample for the calibration curve.
For each sample, pellets of the sample for the calibration curve were prepared as described above using a tablet molding compressor, and when PET was used for the spectroscopic crystal, the diffraction angle (2θ) = 109.08 ° was observed. The counting rate (unit: cps) of Si-Kα rays is measured. At this time, the acceleration voltage and current value of the X-ray generator are set to 24 kV and 100 mA, respectively. A calibration curve having a linear function is obtained with the obtained X-ray count rate on the vertical axis and the _{amount of SiO 2 added in each calibration curve sample on the horizontal axis.}
Next, the toner to be analyzed is pelletized as described above using a tablet molding compressor, and the count rate of Si—Kα rays is measured. Then, the content of the organosilicon polymer in the toner is determined from the above calibration curve. The ratio of the amount of silicon in the toner after washing with water to the amount of silicon in the initial toner calculated by the above method is calculated and used as the fixing rate (%).

<Measuring method of weight average particle size (D4) and number average particle size (D1) of toner>
The weight average particle size (D4) and the number average particle size (D1) of the toner are the precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, Beckman.) By the pore electric resistance method equipped with an aperture tube of 100 μm. Using Coulter) and the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (Beckman Coulter) for setting measurement conditions and analyzing measurement data, the number of effective measurement channels is 25,000. The measurement was performed on the channel, and the measurement data was analyzed and calculated.
As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.

Before performing measurement and analysis, set the dedicated software as follows.
In the dedicated software "Change standard measurement method (SOM) screen", set the total count number in the control mode to 50,000 particles, measure once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). The value obtained using (manufactured by) is set. By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flush of the aperture tube after measurement.
On the "pulse to particle size conversion setting screen" of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Approximately 200 ml of the electrolytic aqueous solution is placed in a 250 ml round bottom beaker made of glass dedicated to Multisizer 3 and set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "flash of the aperture tube" function of the dedicated software.
(2) Approximately 30 ml of the electrolytic aqueous solution is placed in a 100 ml flat-bottomed beaker made of glass, and "Contaminone N" (nonionic surfactant, anionic surfactant, and organic builder) as a dispersant is used as a dispersant for precise measurement of pH 7. Add about 0.3 ml of a diluted solution obtained by diluting a 10% by mass aqueous solution of a neutral detergent for cleaning a vessel, manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water 3 times by mass.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and are installed in the water tank of the ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is added, and about 2 ml of the Contaminone N is added into the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) With the electrolytic aqueous solution in the beaker of (4) being irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the electrolytic aqueous solution of (5) in which toner is dispersed is dropped onto the round bottom beaker of (1) installed in the sample stand, and the measured concentration is adjusted to about 5%. .. Then, the measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) and the number average particle size (D1) are calculated. In addition, when the graph / number% and graph / volume% are set by the dedicated software, the "arithmetic diameter" on the analysis / number statistical value (arithmetic mean) and analysis / volume statistics (arithmetic mean) screens is the number average. The particle size (D1) and the weight average particle size (D4).

<Other components of the developing device>
The developing apparatus according to the present invention is not particularly limited as long as it is a combination of the specific toner supply roller and toner, and other components such as the toner carrier roller 12 shown in FIG. Conventionally known blades 13, toner containers 14, and the like can be used.

<Process cartridge>
The process cartridge according to another aspect of the present invention includes a developing device 10 having the toner supply roller 1 and the toner 11.
FIG. 2 is a schematic cross-sectional view showing an example of a process cartridge according to another aspect of the present invention. The process cartridge 20 is configured to be removable from the main body of the electrophotographic image forming apparatus. The process cartridge 20 is a combination of a developing device 10, an electrophotographic photosensitive member 21, a cleaning blade 24 as a cleaning means, a waste toner container 23, and a charging roller 22 as a charging means. Here, the developing apparatus 10 is shown in FIG. 1 (c), and although detailed description thereof will be omitted, it has a combination of a toner supply roller and a toner according to the present invention.

<Electrophotograph image forming apparatus>
The electrophotographic image forming apparatus according to another aspect of the present invention includes a developing apparatus 10 having the toner supply roller 1 and the toner 11.
FIG. 3 is a schematic cross-sectional view showing an example of an electrophotographic image forming apparatus mounted on a contact-type developing apparatus using a one-component toner. Here, the process cartridge 20 shown in FIG. 2 is prepared in each color of black (Bk), cyan (C), magenta (M), and yellow (Y), and each developing apparatus 10 is filled with toner 11 of each color. It enables color printing.

Hereinafter, the printing operation of the electrophotographic image forming apparatus will be described. The electrophotographic photosensitive member 21 rotates in the direction of the arrow and is uniformly charged by the charging roller 22 for charging the electrophotographic photosensitive member 21. Next, an electrostatic latent image is formed on the surface of the electrophotographic photosensitive member 21 by the laser light 25 which is an exposure means. The electrostatic latent image is visualized as a toner image (development) by applying the toner 11 from the toner carrier roller 12 which is contact-arranged with respect to the electrophotographic photosensitive member 21 by the developing device 10. Development is so-called reverse development in which a toner image is formed on an exposed portion. The toner image formed on the electrophotographic photosensitive member 21 is transferred to the paper 34, which is a recording medium, by the transfer roller 29, which is a transfer member. The paper 34 is fed into the apparatus via the paper feed roller 35 and the suction roller 36, and is conveyed between the electrophotographic photosensitive member 21 and the transfer roller 29 by the endless belt-shaped transfer transfer belt 32. The transfer transfer belt 32 is operated by a driven roller 33, a drive roller 28, and a tension roller 31. A voltage is applied from the bias power supply 30 to the toner carrier roller 12, the developing blade 13, the toner supply roller 1, and the suction roller 36. The paper 34 on which the toner image is transferred is fixed by the fixing device 27 and then discharged to the outside of the device to complete the printing operation. On the other hand, the transfer residual toner that remains on the electrophotographic photosensitive member 18 without being transferred is scraped off by a cleaning blade 26 that is a cleaning member for cleaning the surface of the photoconductor, and is stored in the waste toner storage container 25. The cleaned electrophotographic photosensitive member 18 repeats the above printing operation.

<Synthesis of ionic compounds>
<Ionic compound I-1>
15.0 g of bis (2-hydroxyethyl) dimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 40.0 g of ion-exchanged water. Next, 37.7 g of an anion-exchange reagent (hereinafter referred to as "anion raw material"): lithium bis (pentafluoroethanesulfonyl) imide (manufactured by Kishida Chemical Co., Ltd.) dissolved in 60 g of ion-exchanged water was added dropwise over 30 minutes. , Stirred at 30 ° C. for 2 hours. The obtained reaction solution was extracted twice with 100.0 g of ethyl acetate. Subsequently, the separated ethyl acetate layer was washed 3 times with 60 g of ion-exchanged water. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain an ionic compound I-1 in which the anion was a bis (pentafluoroethanesulfonyl) imide anion. The ionic compound I-1 is a compound represented by the following formula.

<Ionic compounds I-2 to I-6>
Ionic compounds I-2 to I-6 were obtained in the same manner as in the synthesis of ionic compound I-1, except that the anionic raw material and the blending amount thereof were changed as shown in Table 1.

<Ionic compound I-7>
30.0 g of a 50% aqueous solution of tris (2-hydroxyethyl) methylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 50.0 g of ion-exchanged water. Next, 30.8 g of an anion raw material: potassium nonafluorobutanesulfonate (trade name: KFBS; manufactured by Mitsubishi Materials Denshi Kasei Co., Ltd.) dissolved in 30 g of ion-exchanged water was added dropwise over 30 minutes, and the mixture was stirred at 30 ° C. for 6 hours. .. The obtained reaction solution was extracted twice with 100.0 g of ethyl acetate. Subsequently, the separated ethyl acetate layer was washed 3 times with 80 g of ion-exchanged water. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain ionic compound I-7. The ionic compound I-7 is a compound represented by the following formula.

＜イオン化合物Ｉ−８〜Ｉ−１１＞
アニオン原料およびその配合量を表２に記載の通りに変更した以外は、イオン化合物Ｉ−７の合成と同様にして、イオン化合物Ｉ−８〜Ｉ−１１を得た。

<Ionic compounds I-8 to I-11>
Ionic compounds I-8 to I-11 were obtained in the same manner as in the synthesis of ionic compound I-7, except that the anionic raw material and the blending amount thereof were changed as shown in Table 2.

<Ionic compound I-12>
15.0 g of diethylenetriamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 35.0 g of tetrahydrofuran. Next, the reaction system was placed in a nitrogen atmosphere and ice-cooled. Subsequently, 45.5 g of methyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 80.0 g of tetrahydrofuran was added dropwise over 30 minutes. After heating and refluxing the reaction solution for 12 hours, 100 ml of water was added, and the solvent was distilled off under reduced pressure. 100 ml of ethanol was added to the residue, and the mixture was stirred at room temperature to remove insoluble matter by filtration through Celite, and then the solvent was distilled off again under reduced pressure. The obtained product was dissolved in 160 ml of pure water, 37.7 g of sodium heptafluorobutyrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added as an anion raw material, and the mixture was stirred at room temperature for 1 hour. The obtained reaction solution was extracted twice with 100.0 g of ethyl acetate. Next, the separated ethyl acetate layer was washed 3 times with 60 g of ion-exchanged water. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain ionic compound I-12. The ionic compound I-12 is a compound represented by the following formula.

<Ionic compound I-13>
Ionic compound I-13 was obtained in the same manner as in the synthesis of ionic compound I-12, except that the anionic raw material was changed to 19.5 g of sodium perchlorate (anhydrous, manufactured by Kanto Chemical Co., Inc.).

<Ionic compound I-14>
2- (2-Methyl-1H-imidazol-1-yl) ethanol (manufactured by Sigma-Aldrich) 15.0 g, sodium hydride 60% liquid paraffin dispersion (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.2 g, tetrahydrofuran 80.0 g Was dissolved in. 14.5 g of ethyl bromide (manufactured by Showa Kagaku Co., Ltd.) dissolved in 80.0 g of tetrahydrofuran was added dropwise thereto over 30 minutes at room temperature, and the mixture was heated and refluxed at 85 ° C. for 12 hours. Next, 100 ml of water was added to the reaction solution, and the solvent was distilled off under reduced pressure. 200 ml of ethanol was added to the residue, and the mixture was stirred at room temperature to remove insoluble matter by filtration through Celite, and then the solvent was distilled off again under reduced pressure. The obtained product is dissolved in 100 ml of pure water, and 38.2 g of lithium N, N-bis (trifluoromethanesulfonyl) imide (trade name: EF-N115, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.) is added as an anion raw material. , Stirred for 1 hour at room temperature. 100 ml of ethyl acetate was added to the reaction solution, and the organic layer was washed 3 times with 80 g of ion-exchanged water. Next, ethyl acetate was distilled off under reduced pressure to obtain ionic compound I-14. The ionic compound I-14 is a compound represented by the following formula.

<Ionic compound I-15>
Under a nitrogen atmosphere, 15.0 g of imidazole (manufactured by Nippon Synthetic Chemical Co., Ltd.) and 9.2 g of sodium hydride 60% liquid paraffin dispersion (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 60.0 g of tetrahydrofuran. 60.7 g of 2-bromoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 80.0 g of tetrahydrofuran was added dropwise thereto at room temperature over 30 minutes, and then the mixture was heated under reflux at 85 ° C. for 12 hours. Then, 100 ml of water was added to the reaction solution, and the solvent was distilled off under reduced pressure. 200 ml of ethanol was added to the residue, and the mixture was stirred at room temperature to remove insoluble matter by filtration through Celite, and then the solvent was distilled off again under reduced pressure. The obtained product was dissolved in 200 ml of pure water, and 69.6 g of lithium N, N-bis (trifluoromethanesulfonyl) imide (trade name: EF-N115, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.) was added as an anion raw material. It was stirred at room temperature for 1 hour. 200 ml of ethyl acetate was added to the reaction solution, and the organic layer was washed 3 times with 120 g of ion-exchanged water. Next, ethyl acetate was distilled off under reduced pressure to obtain ionic compound I-15. The ionic compound I-15 is a compound represented by the following formula.

<Ionic compounds I-16 to I-19, I-27, I-28>
Ionic compounds I-16 to I-19, I-27 and I-28 were obtained in the same manner as in the synthesis of the ionic compound I-15, except that the anionic raw material and the blending amount thereof were changed as shown in Table 3. rice field.

<Ionic compound I-20>
Under a nitrogen atmosphere, 15.0 g of (1H-Imidazole-2-yl) ethanol (manufactured by Sigma-Aldrich) and 9.2 g of sodium hydride 60% liquid paraffin dispersion (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 60.0 g of tetrahydrofuran. I let you. To there, 42.1 g of 2-bromoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 80.0 g of tetrahydrofuran was added dropwise at room temperature over 30 minutes, and the mixture was heated under reflux at 85 ° C. for 12 hours. Then, 100 ml of water was added to the reaction solution, and the solvent was distilled off under reduced pressure. 200 ml of ethanol was added to the residue, and the mixture was stirred at room temperature to remove insoluble matter by filtration through Celite, and then the solvent was distilled off again under reduced pressure. The obtained product was dissolved in 200 ml of pure water, and 48.3 g of lithium N, N-bis (trifluoromethanesulfonyl) imide (trade name: EF-N115, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.) was added as an anion raw material. The mixture was stirred at room temperature for 1 hour. 200 ml of ethyl acetate was added to the reaction solution, and the organic layer was washed 3 times with 120 g of ion-exchanged water. Next, ethyl acetate was distilled off under reduced pressure to obtain ionic compound I-20. The ionic compound I-20 is a compound represented by the following formula.

<Ionic compound I-21>
As a cation raw material, 15.0 g of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 50.0 g of dichloromethane, and 44.9 g of epichlorohydrin (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 50.0 g of dichloromethane was 30 at room temperature. The mixture was added dropwise over a minute, and the mixture was heated under reflux for 6 hours. Next, the reaction solution was cooled to room temperature, 200 ml of a 5 mass% sodium carbonate aqueous solution was added, and the mixture was stirred for 30 minutes, then separated, and the dichloromethane layer was washed twice with 120 g of ion-exchanged water. Next, dichloromethane was distilled off under reduced pressure to obtain a residue.
Further, the obtained residue was dissolved in 50.0 g of acetone and then dissolved in 150.0 g of ion-exchanged water. Anion raw materials: Lithium N, N-bis (trifluoromethanesulfonyl) imide (trade name: EF-N115) , Mitsubishi Materials Denshi Kasei Co., Ltd.) 69.6 g was added dropwise over 30 minutes, and the mixture was stirred at 30 ° C. for 2 hours. The obtained solution was separated and the organic layer was washed 3 times with 50.0 g of ion-exchanged water. Subsequently, acetone was distilled off under reduced pressure to obtain ionic compound I-21. The ionic compound I-21 is a compound represented by the following formula.

<Ionic compound I-22>
(5-methylpyrazin-2-yl) methanol (manufactured by Sigma-Aldrich) 15.0 g and sodium hydride 60% liquid paraffin dispersion (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.2 g were dissolved in tetrahydrofuran (80.0 g). 18.9 g of methyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 80.0 g of tetrahydrofuran was added dropwise thereto over 30 minutes at room temperature, and the mixture was heated under reflux at 85 ° C. for 12 hours. Next, 100 ml of water was added to the reaction solution, and the solvent was distilled off under reduced pressure. 200 ml of ethanol was added to the residue, and the mixture was stirred at room temperature to remove insoluble matter by filtration through Celite, and then the solvent was distilled off again under reduced pressure. The obtained product is dissolved in 100 ml of pure water, 59.8 g of potassium tris (trifluoromethanesulfonyl) methide (trade name: K-TFSM; manufactured by Central Glass Co., Ltd.) is added as an anionic raw material, and the mixture is added at room temperature for 1 hour. Stirred. 100 ml of ethyl acetate was added to the reaction solution, and the organic layer was washed 3 times with 80 g of ion-exchanged water. Next, ethyl acetate was distilled off under reduced pressure to obtain ionic compound I-22. The ionic compound I-22 is a compound represented by the following formula.

<Ion compound I-23>
N, N'-BIS- (2-HYDROXYETHYL) -2,5-DIMETHYLPIPERAZINE (manufactured by Sigma-Aldrich) 15.0 g, sodium hydride 60% liquid paraffin dispersion (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.2 g in tetrahydrofuran80 It was dissolved in 0.0 g. 11.6 g of methyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 80.0 g of tetrahydrofuran was added dropwise thereto over 30 minutes at room temperature, and the mixture was heated under reflux at 85 ° C. for 12 hours. Next, 100 ml of water was added to the reaction solution, and the solvent was distilled off under reduced pressure. 200 ml of ethanol was added to the residue, and the mixture was stirred at room temperature to remove insoluble matter by filtration through Celite, and then the solvent was distilled off again under reduced pressure. The obtained product is dissolved in 100 ml of pure water, and 23.4 g of lithium N, N-bis (trifluoromethanesulfonyl) imide (trade name: EF-N115, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.) is added as an anion raw material. , Stirred for 1 hour at room temperature. 100 ml of ethyl acetate was added to the reaction solution, and the organic layer was washed 3 times with 80 g of ion-exchanged water. Next, ethyl acetate was distilled off under reduced pressure to obtain ionic compound I-23. The ionic compound I-23 is a compound represented by the following formula.

<Ionic compound I-24>
4. Dissolve 15.0 g of 4-Pyridine-4-yl-butan-1-ol (manufactured by Sigma-Aldrich) in 45.0 g of acetonitrile and 4-bromo-1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd.) at room temperature. After dropping 7 g over 30 minutes, the mixture was heated under reflux at 90 ° C. for 12 hours. Next, the reaction solution was cooled to room temperature, and acetonitrile was distilled off under reduced pressure. The obtained concentrate was washed with 30.0 g of diethyl ether, and the supernatant was removed by separation. The washing and liquid separation operation was repeated 3 times to obtain a residue. Further, the obtained residue was dissolved in 110.0 g of dichloromethane and then dissolved in 40.0 g of ion-exchanged water. Anion raw material: Lithium N, N-bis (trifluoromethanesulfonyl) imide (trade name: EF-N115) , Mitsubishi Materials Denshi Kasei Co., Ltd.) 31.4 g was added dropwise over 30 minutes, and the mixture was stirred at 30 ° C. for 12 hours. The obtained solution was separated, and the organic layer was washed 3 times with 80.0 g of ion-exchanged water. Subsequently, dichloromethane was distilled off under reduced pressure to obtain ionic compound I-24. The ionic compound I-24 is a compound represented by the following formula.

<Ionic compound I-25>
2- (2-Hydroxyethyl) -1-methylpyrrolidin (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 15.0 g and sodium hydride 60% liquid paraffin dispersion (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 13.5 g are dissolved in tetrahydrofuran 65.0 g. I let you. Next, the reaction system was placed in a nitrogen atmosphere and ice-cooled. Subsequently, 16.0 g of 2-bromoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 40.0 g of tetrahydrofuran was added dropwise over 30 minutes. After heating and refluxing the reaction solution for 12 hours, 100 ml of water was added, and the solvent was distilled off under reduced pressure. 80 ml of ethanol was added to the residue, and the mixture was stirred at room temperature to remove insoluble matter by filtration through Celite, and then the solvent was distilled off again under reduced pressure. The obtained product is dissolved in 160 ml of pure water, and 36.7 g of lithium N, N-bis (trifluoromethanesulfonyl) imide (trade name: EF-N115, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.) is added as an anion raw material. , Stirred for 1 hour at room temperature. 70 ml of chloroform was added to the reaction solution, 40 ml of a 5% by mass aqueous solution of sodium carbonate was added, and the mixture was stirred for 30 minutes and then separated. The chloroform layer was washed three times with 50 g of ion-exchanged water. Next, chloroform was distilled off under reduced pressure to obtain ionic compound I-25. The ionic compound I-25 is a compound represented by the following formula.

<Ion compound I-26>
Same as the synthesis of ionic compound I-25, except that the anion raw material was changed to 28.0 g of potassium N, N-bis (fluorosulfonyl) imide (trade name "K-FSI"; manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.). The ionic compound I-26 was obtained. The ionic compound I-26 is a compound represented by the following formula.

Table 4 shows the structure of each ionic compound used in the examples and the relationship with R1 to R9 and Z1 to Z17 in each structural formula.

<Ion compound CI-1 for comparative examples>
As the ionic compound CI-1, N, N, N-trimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide (manufactured by Kanto Chemical Co., Inc.) was used as it was.
<Ionic compound CI-2 for comparative examples>
Tetrabutylammonium perchlorate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as it was.

<Manufacturing toner supply rollers>
A toner supply roller was manufactured according to the manufacturing process shown in FIG.
As the shaft body 53, iron (material name: SUM24) having an outer diameter of 5 mm and a length of 272 mm was plated with electroless nickel. As the molding die 51, a cylindrical die having a cavity inner diameter of 13.35 mm and a cavity length of 220 mm was used. A fluorine-based mold release agent (trade name: Frelease 650, manufactured by Neos Co., Ltd.) was used for the mold release treatment of the molding mold 51 and the lower piece 52. A fluorine-based mold release agent (trade name: Frelease 310, manufactured by Neos Co., Ltd.) was used for the mold release treatment of the upper bridge 56. The preheating temperature of the shaft body 53, the molding die 51, and the lower piece 52 was 50 ° C.
After blending the following materials (A), (B), (E) to (H), and (J), adjusting the liquid temperature to 30 ° C., mixing and stirring with a casting machine to obtain a foamed material, A predetermined amount (2.6 g) was injected into a molding die assembled with the lower piece on which the shaft body was installed.
(A): Ion compound I-1: 1.0 part by mass (B): Polyol A (polyethylene propylene ether triol having a number average molecular weight of 3100, trade name: Actol EP-550N; manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd .: 100. 0 parts by mass (E): Polyisocyanate admixture (containing NCO% = 45, MDI = 20%, trade name: Cosmonate TM-20; manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.): 23.9 parts by mass (F): Silicone Foam regulator (trade name: SRX274C, manufactured by Tosoh Dow Corning Co., Ltd.): 1.0 part by mass (G): Tertiary amine catalyst A (mixture of bis (2-dimethylaminoethyl) ether and dipropylene glycol, trade name) : TOYOCAT-ET, manufactured by Tosoh Corporation): 0.3 parts by mass (H): Amine catalyst B (trade name: TOYOCAT-L33, manufactured by Tosoh Corporation): 0.2 parts by mass (J): Foaming agent (water): 1.4 parts by mass

The injection of the foamed material was carried out in a state where the shaft body in the molding die was inclined at the upper end position by 3 mm from the center position of the molding die to the side opposite to the injection side. After injecting the foam material, the upper piece was fitted into the molding die, heated at 75 ° C. for 7 minutes, and then the upper piece and the lower piece were removed to remove the mold.
By the above method, a toner supply roller A provided with an elastic layer containing a crosslinked urethane resin which is a reaction product of an ionic conductive agent having a reactive functional group that reacts with an isocyanate group, a polyol, and a compound having an isocyanate group. -1 was formed.

<Confirmation of components of crosslinked urethane resin>
Whether or not the cationic structure and any of the structures Z101 to Z103 were present in the obtained crosslinked urethane resin of A-1 was ^{confirmed by using solid 13} C-NMR.
Prior to the NMR measurement, the crosslinked urethane resin was washed with methyl ethyl ketone (MEK) to remove small molecule components dissolved in MEK. As a cleaning method with MEK, 2.5 g of crosslinked urethane resin was weighed, soaked in 300 g of MEK at 22 ° C. for 70 hours, then discarded, rinsed with 300 g of MEK, and dried at 90 ° C. for 1 hour. ..
The crosslinked urethane resin of the toner supply roller A-1 washed with MEK was subjected to solid ¹³ C-NMR measurement to examine the structure. Solid ¹³ C-NMR measurement uses a superconducting nuclear magnetic resonance absorber (trade name: AvanceIII400, manufactured by Bruker Biospin), observation nucleus ^13C , integration number 10000 times, pulse sequence DD / MAS, sample rotation speed 8 kHz. Measured under conditions.
The cationic structure of the structural formula (1) and the structure of the structural formula (Z101) were confirmed in the crosslinked urethane resin of the toner supply roller A-1.

<Toner supply rollers A-2 to A-54, comparison toner supply rollers CA-1 to CA-2>
The blending amounts of the materials (A), (B), (E), (F), (G), (H), and (J) were changed as shown in Tables 5 and 6.
The material (C) is polyol B (polyoxy-1,2-alkylene polyol having an average functional group number of 3, number average molecular weight: 6000, average hydroxyl value: 24 mgKOH / g, trade name: Actol EP-950P ;; Mitsui Chemical SKC Polyurethane Co., Ltd.).
The material (D) is a polyisocyanate admixture (containing NCO% = 40, MDI = 50%, trade name: Cosmonate TM-50; manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.).

Toner supply rollers A-2 to A-54 and comparative toner supply rollers CA-1 to CA-2 were manufactured in the same manner as the toner supply rollers A-1 except for the above. In addition, the presence or absence of a cationic structure in the crosslinked urethane resin of each toner supply roller and the presence or absence of any of the structures of Z101 to 103 were confirmed.
A list is shown in Table 7.

[Production example of toner T-1]
(Preparation step of aqueous medium 1)
14.0 parts of sodium phosphate (12-hydrate manufactured by Rasa Industries, Ltd.) was put into 650.0 parts of ion-exchanged water in a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, and while purging with nitrogen. It was kept warm at 65 ° C. for 1.0 hour.
T. K. Using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.), a calcium chloride aqueous solution in which 9.2 parts of calcium chloride (dihydrate) is dissolved in 10.0 parts of ion-exchanged water is batched while stirring at 15,000 rpm. The mixture was charged to prepare an aqueous medium containing a dispersion stabilizer. Further, 10% by mass hydrochloric acid was added to the aqueous medium to adjust the pH to 5.0 to obtain the aqueous medium 1.

(Preparation step of polymerizable monomer composition)
・ Styrene: 60.0 parts ・ C.I. I. Pigment Blue 15: 3: 6.5 parts The material was put into an attritor (manufactured by Mitsui Miike Machinery Co., Ltd.), and further dispersed with zirconia particles having a diameter of 1.7 mm at 220 rpm for 5.0 hours to obtain a pigment. A dispersion was prepared. The following materials were added to the pigment dispersion.
-Styrene: 20.0 parts-n-butyl acrylate: 20.0 parts-Crosslinking agent (divinylbenzene): 0.3 parts-Saturated polyester resin: 5.0 parts (propylene oxide-modified bisphenol A (2 mol adduct) Polycondensate of terephthalic acid (molar ratio 10:12), glass transition temperature Tg = 68 ° C., weight average molecular weight Mw = 10000, molecular weight distribution Mw / Mn = 5.12)
-Fischer-Tropsch wax (melting point 78 ° C): Keeps 7.0 parts or more at 65 ° C, and T.I. K. A polymerizable monomer composition was prepared by uniformly dissolving and dispersing at 500 rpm using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.).

(Granulation process)
The temperature of the aqueous medium 1 was set to 70 ° C., and T.I. K. While maintaining the rotation speed of the homomixer at 15,000 rpm, the polymerizable monomer composition was put into the aqueous medium 1, and 10.0 parts of t-butylperoxypivalate as a polymerization initiator was added. Granulation was carried out for 10 minutes while maintaining 15,000 rpm with the stirring device as it was.

(Polymerization / distillation process)
After the granulation step, the stirrer is replaced with a propeller stirring blade, and while stirring at 150 rpm, polymerization is carried out at 70 ° C. for 5.0 hours, and the temperature is raised to 85 ° C. and heated for 2.0 hours to carry out the polymerization reaction. went.
Then, the reflux tube of the reaction vessel was replaced with a cooling tube, and the slurry was heated to 100 ° C. to carry out distillation for 6 hours to distill off the unreacted polymerizable monomer to obtain a toner mother particle dispersion. ..

(Polymerization of organosilicon compounds)
60.0 parts of ion-exchanged water was weighed in a reaction vessel equipped with a stirrer and a thermometer, and the pH was adjusted to 4.0 with 10% by mass hydrochloric acid. This was heated with stirring to bring the temperature to 40 ° C. Then, 40.0 parts of methyltriethoxysilane, which is an organosilicon compound, was added and stirred for 2 hours or more for hydrolysis. The end point of the hydrolysis was visually confirmed that the oil and water did not separate and became one layer, and the mixture was cooled to obtain a hydrolyzed solution of an organosilicon compound.
After cooling the temperature of the toner mother particle dispersion obtained above to 55 ° C., 25.0 parts of a hydrolyzate of the organosilicon compound was added to start the polymerization of the organosilicon compound. After holding for 15 minutes as it was, the pH was adjusted to 5.5 with a 3.0% aqueous sodium hydrogen carbonate solution. After holding for 60 minutes while continuing stirring at 55 ° C., the pH was adjusted to 9.5 with a 3.0% aqueous sodium hydrogen carbonate solution, and the mixture was further held for 240 minutes to obtain a toner particle dispersion.

(Washing and drying process)
After the polymerization step is completed, the toner particle dispersion is cooled, hydrochloric acid is added to the toner particle dispersion to adjust the pH to 1.5 or less, the mixture is left to stir for 1 hour, and then solid-liquid separated with a pressure filter to separate the toner cake. Got This was reslurried with ion-exchanged water to form a dispersion liquid again, and then solid-liquid separated with the above-mentioned filter to obtain a toner cake.
The obtained toner cake was dried and classified in a constant temperature bath at 40 ° C. for 72 hours to obtain toner particles 1. Table 7 shows the conditions for producing the toner particles 1.

[Manufacturing method of toner particles 2 to 8]
Toner particles 2 to 8 were obtained in the same manner as the toner particles 1 except that the conditions shown in Table 7 were changed.

[Manufacturing method of comparative toner particles (toner particles C1)]
Toner particles C1 which are comparative toner particles were obtained in the same manner as the toner particles 1 except that the polymerization of the organosilicon compound was changed as shown below.
(Polymerization of organosilicon compounds)
A mixed solvent prepared by dissolving 1.0 part of polyvinyl alcohol in 20 parts of a mixed solution of ethanol / water = 1: 1 (mass ratio) was dispersed in a toner mother particle dispersion, and then 3- (methacryloxy) as a silicon compound. Twenty parts of propyltrimethoxysilane was dissolved, and the mixture was further stirred for 5 hours to swell and internalize 3- (methacryloxy) propyltrimethoxysilane in the toner particles.
Then, after the temperature was adjusted to 70 ° C., the pH was adjusted to 9.5 with a 3.0% aqueous sodium hydrogen carbonate solution. By stirring at room temperature for 10 hours, the sol-gel reaction was allowed to proceed on the surface of the toner particles to obtain toner particles C1.

[Manufacturing method of comparative toner particles (toner particles C2)]
Toner particles C2, which are comparative toner particles, were obtained by not polymerizing the organosilicon compound in the production example of the toner particles 1.

The toner particles 1 to 8 and the toner particles C1 were used as they were as toners T-1 to T-8 and CT-1 for evaluation. The toner CT-2 and the toner CT-3 were manufactured as follows using the comparative toner particles C2, and evaluated in the same manner as the toner T-1. Table 7 shows the toner production conditions, and Table 8 shows the physical characteristics of the toner.

-Preparation of toner CT-2 First, organosilicon fine particles A were synthesized as shown below.
500 g of ion-exchanged water was charged into the reaction vessel, and 0.2 g of a 48% sodium hydroxide aqueous solution was added to prepare an aqueous solution. To this aqueous solution, 65 g of methyltrimethoxylane and 50 g of tetraethoxylane were added, a hydrolysis reaction was carried out for 1 hour while keeping the temperature at 13 to 15 ° C., and 2.5 g of a 20% sodium dodecylbenzene sulfonate aqueous solution was further added. The hydrolysis reaction was carried out at the same temperature for 3 hours. A transparent reaction containing a silanol compound was obtained in about 4 hours.
Next, a condensation reaction was carried out for 5 hours while maintaining the temperature of the obtained reaction product at 70 ° C. to obtain an aqueous suspension containing fine particles composed of an organosilicon compound. This aqueous suspension was filtered through a membrane filter, and the passing liquid portion was subjected to a centrifuge to separate white fine particles. The separated white fine particles were washed with water and dried with hot air at 150 ° C. for 5 hours to obtain organosilicon fine particles A.
When the organic silicon fine particles A were observed with a scanning electron microscope, the organic silicon fine particles A were hollow hemispheres, and image analysis was performed to calculate the number average particle diameter (μm) of the major and minor diameters of the hemisphere. The major axis was 180 nm and the minor axis was 80 nm.
3.0 parts of organosilicon fine particles A were added to 100 parts of the toner particles 10 for comparison, mixed with a Henschel mixer at a peripheral speed of 20 m / s of the stirring blade, and then hexamethyldisilazane having an average particle diameter of 12 nm. 1.5 parts of the treated hydrophobic silica was mixed with a Henschel mixer at a peripheral speed of 20 m / s of the stirring blade to prepare a toner CT-2 for comparison.

-Preparation of toner CT-3 In the preparation of toner CT-2 for comparison, hydrophobic sol-gel silica (manufactured by Nippon Aerosil Co., Ltd .: number average diameter 80 nm) was used instead of organic silicon fine particles A, and the circumference of the Henschel mixer stirring blade was used. Toner CT-3 was produced in the same manner as toner CT-2 except that the speed was changed from 20 m / s to 40 m / s.

Table 7 shows the manufacturing conditions of the toner from the toner T-1 to the toner T-8, and the toners from the toner CT-1 to the toner CT-3, and Table 8 shows the physical properties of the toner.

<Example 1>
The toner of a cyan toner process cartridge (trade name: toner cartridge 040H (cyan), manufactured by Canon Inc.) for a laser printer (trade name: LBP712Ci, manufactured by Canon Inc.) was extracted, and the inside was cleaned by air blowing. Next, the toner container from which the toner was removed and cleaned was filled with 140 g of the toner T-1 used in Example 1. Further, the toner supply roller was removed from the process cartridge, and the toner supply roller A-1 of Example 1 was loaded instead to obtain the process cartridge used in Example 1.

[Performance evaluation as a developing device]
As a performance evaluation of the developing apparatus, image fog before and after long-term operation in an environment of a temperature of 30 ° C. and a relative humidity of 80% was evaluated. Due to long-term operation, the ability of the toner supply roller to move with the toner decreases, and the amount of charge in the toner varies. If the amount of charge of the toner varies, the amount of charge of the toner is too low, and the fog on the image increases.
Then, the process cartridge used in the first embodiment is incorporated into the laser printer, left to stand in an environment of a temperature of 32 ° C. and a relative humidity of 80% for one day to be familiarized, and then one solid image is formed, followed by a solid image. One white evaluation image was output, and the printer was stopped while the solid white image was being output. At this time, the toner adhering to the photoconductor was peeled off with a tape (trade name: CT18, manufactured by Nichiban Co., Ltd.), and the reflectance was removed with a reflection densitometer (trade name: TC-6DS / A, manufactured by Tokyo Denshoku Co., Ltd.). Was measured. The amount of decrease in reflectance (%) when the reflectance of the tape was used as a reference was measured, and this was used as the fog value.
Next, 80,000 images in cyan color with a printing rate of 0.5% were continuously output as a durable printing test. After that, one solid image was output again, and then one solid white evaluation image was output, and the printer was stopped while the solid white image was being output again. Then, the fog value on the photoconductor was measured again and used as the fog value after durability.

<Examples 2-54, Comparative Examples 1 and 2>
The same operations as in Example 1 were performed except that the toner supply rollers shown in Tables 9 and 10 were used, and Examples 2 to 54 and Comparative Examples 1 and 2 were evaluated as developing devices. The results are shown in Tables 9 and 10.

<Examples 55 to 68, Comparative Examples 3 to 8>
The same as in Example 1 except that the toner supply rollers A-15 and the toner supply rollers A-9 are used and the toners T-2 to T-8 and CT-1 to CT-3 are used as shown in Table 11. Then, Examples 55 to 68 and Comparative Examples 3 to 8 were evaluated.
The results are shown in Table 11.

From Tables 9 and 10, it was found that by using the toner particles having an organosilicon polymer on the surface of the toner mother particles, the fog on the image can be improved even in the long-life cartridge.
Tables 9 and 10 show the increase in fog due to durability when a toner supply roller with fixed ions of each structure is used. However, when the ions are fixed, deterioration of energization is suppressed and fog due to durability is suppressed. It was found that the increase was suppressed.

Table 11 shows the increase in fog due to durability when various toners and a toner supply roller having a conductive layer of a crosslinked urethane resin on which a cationic group is fixed are used. It was found that when a predetermined convex portion was present in the toner having a number average particle diameter of 4.0 μm or more and 10.0 μm or less, the increase in fog due to durability was suppressed. That is, the fixation rate of the organosilicon polymer to be the convex portion is 80% or more, and the ratio (Σw / L) of the total width w of the convex portion to L is 0.30 or more and 0.95 or less. It was found that the use of a toner having a convex portion suppresses the increase in fog due to durability.

1 Toner supply roller 2 Shaft 3 Cross-linked urethane resin layer 10 Developer 11 Toner 12 Toner carrier roller 13 Develop blade 14 Toner container 20 Process cartridge 21 Photoreceptor (electrophotographic photosensitive member)
42 Toner mother particle 43 Toner mother particle surface 44 Convex part w Convex part width D Convex part diameter H Convex part height

Claims (10)

A developing device that has toner and toner supply rollers.
The toner supply roller
It has a shaft body and a conductive layer containing a crosslinked urethane resin on the outer periphery of the shaft body.
The crosslinked urethane resin is a reaction product of an ionic conductive agent having a reactive functional group that reacts with an isocyanate group, a polyol, and a compound having an isocyanate group.
The toner has a number average particle diameter of 4.0 μm or more and 10.0 μm or less, and contains toner mother particles and toner particles having an organosilicon polymer on the surface of the toner mother particles.
The organosilicon polymer has a structure represented by the following formula (1) and has a structure represented by the following formula (1).
R-SiO _3/2 (1)
(R indicates an alkyl group having 1 or more and 6 or less carbon atoms, or a phenyl group.)
The organosilicon polymer forms a convex portion on the outer surface of the toner particles, and forms a convex portion.
The adhesion rate of the organosilicon polymer to the toner matrix particles is 80% or more.
With respect to the cross-sectional image of the toner particles obtained by a scanning electron microscope (STEM), when the contour line of the toner mother particles is developed into a straight line to obtain a developed image of the cross-sectional image, the developed image shows the straight line. When the length is L and the length of the line segment forming the boundary between the convex portion and the toner mother particle on the straight line is the width w, the sum of the width w with respect to the L is Σw. The ratio (Σw / L) is 0.30 or more and 0.95 or less.
An electrophotographic developing device characterized by this. The crosslinked urethane resin contains a polyurethane of the reaction product and an anion.
The polyurethane is a resin having at least one cationic structure selected from the following structural formulas (1) to (6) in the molecule.

[In the structural formula (1), R1 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Z1 to Z3 represent any structure or hydrocarbon group having 1 to 4 carbon atoms independently selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103), and at least Z1 to Z3. One is any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103). ];

[In structural formula (2), R2 and R3 are each independently a hydrocarbon group or a single bond required to form a nitrogen-containing heteroaromatic 5-membered ring with two nitrogen atoms in structural formula (2). Represents Z4 and Z5, respectively, which represent any structure, hydrogen atom or hydrocarbon group having 1 to 4 carbon atoms, which is independently selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103). , Z6 represent any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103), or a hydrocarbon group having 1 to 4 carbon atoms, and at least one of Z4 to Z6 is. , Which structure is selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103), and d1 represents an integer of 0 or 1. ];

[In Structural Formula (3), R4 and R5 are each independently a hydrocarbon group or single bond required to form a nitrogen-containing heteroaromatic 6-membered ring with the two nitrogen atoms in Structural Formula (3). Represents Z7, any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103), a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and Z8 represents. Represents any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103), or a hydrocarbon group having 1 to 4 carbon atoms, and at least one of Z7 and Z8 is the structural formula (Z7). It is any structure selected from the group consisting of the structures represented by Z101) to (Z103), d2 represents an integer of 0 to 2, and when d2 is 2, Z8 is different even if they are the same. May be];

[In structural formula (4), R6 and R7 each independently represent a hydrocarbon group or a single bond required to form a nitrogen-containing heterolipocyclic group with two nitrogen atoms in structural formula (4). , Z9 to Z11 each independently have any structure, hydrogen atom or hydrocarbon group having 1 to 4 carbon atoms selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103). Represented, Z12 represents any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103), or a hydrocarbon group having 1 to 4 carbon atoms, and at least one of Z9 to Z12. Is any structure selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103), d3 represents an integer of 0 to 2, and when d3 is 2, Z12 is the same. It may be different. ];

[In the structural formula (5), R8 represents a hydrocarbon group required to form a nitrogen-containing aromatic ring together with the bonding nitrogen atom, and Z13 is a structure represented by the structural formulas (Z101) to (Z103). Represents any structure selected from the group consisting of hydrogen atoms or hydrocarbon groups having 1 to 4 carbon atoms, and Z14 is selected from the group consisting of the structures represented by the structural formulas (Z101) to (Z103). Any structure, or any one selected from the group consisting of structures represented by structural formulas (Z101) to (Z103), representing a hydrocarbon group having 1 to 4 carbon atoms and at least one of Z13 and Z14. It is a structure, and d4 represents an integer of 0 or 1. ];

[In structural formula (6), R9 represents a hydrocarbon group required to form a nitrogen-containing alicyclic group together with a bonding nitrogen atom, and Z15 and Z16 are structural formulas (Z101) to (Z101) to (Z101) to (Z10). Represents any structure selected from the group consisting of the structures represented by Z103), a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and Z17 is derived from the structures represented by the structural formulas (Z101) to (Z103). Represents any structure selected from the group, or a hydrocarbon group having 1 to 4 carbon atoms, and at least one of Z15 to Z17 is from the group consisting of the structures represented by the structural formulas (Z101) to (Z103). Any structure of choice, where d5 represents an integer of 0 or 1. ];

[R101, R102, and R103 represent divalent hydrocarbon groups each independently having a straight chain or a branch. The symbol "*" is a bond with a nitrogen atom in the structural formula (1) or a nitrogen atom in the nitrogen-containing heterocycle in the structural formulas (2) to (6) or a carbon atom in the nitrogen-containing heterocycle. The symbol "**" represents a bonding portion, and the symbol "**" represents a bonding portion with a carbon atom in the polymer chain constituting the resin having the cationic structure. ] The anions include fluoroalkylsulfonylimide anion, fluorosulfonylimide anion, fluoroalkylsulfonate anion, fluorosulfonate anion, fluoroalkylcarboxylic acid anion, fluoroalkylmethide anion, fluoroborate anion, fluorophosphate anion, disianamide anion and thiocyanate. The electrophotographic developer according to claim 2, which is at least one selected from the group consisting of anions. The electrophotographic developer according to claim 2 or 3, wherein the cationic structure is a structure represented by the following structural formula (10).

[In the structural formula (10), Z4, Z5, Z6, and d1 have the same meanings as the structural formula (2)]. The electrophotographic developer according to claim 2 or 3, wherein the cationic structure is a structure represented by the following structural formula (11).

[In the structural formula (11), Z9, Z10, Z11, Z12, and d3 have the same meanings as the structural formula (4). ]. The electrophotographic developer according to claim 2 or 3, wherein the cationic structure is a structure represented by the following structural formula (12).

[In the structural formula (12), Z13, Z14, and d4 have the same meanings as the structural formula (5). ]. The electrophotographic developer according to claim 2 or 3, wherein the cationic structure is a structure represented by the following structural formula (13).

[In the structural formula (13), Z15, Z16, Z17, and d5 have the same meanings as the structural formula (6). ]. In the developed image, the maximum length of the convex portion in the normal direction of the width w of the convex portion is defined as the diameter D of the convex portion, and the length from the apex of the convex portion to the straight line in the line segment forming the diameter D. When the height of the convex part is H,
The convex portion includes a "specific height convex portion" having a height H of 40 nm or more and 300 nm or less.
Among the specific height convex portions, the ratio (D / w) of the number ratio P (D / w) of the specific height convex portions in which the ratio (D / w) of the diameter D to the width w is 0.33 or more and 0.80 or less is The electrophotographic developing apparatus according to any one of claims 1 to 7, wherein the number is 50% or more. A process cartridge that is detachably configured on the main body of the electrophotographic image forming apparatus and includes the electrophotographic developing apparatus according to any one of claims 1 to 8. An electrophotographic image forming apparatus comprising the electrophotographic developing apparatus according to any one of claims 1 to 8.

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