JP2015127818A - Image forming apparatus and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development that achieves both low-temperature fixability and blocking resistance, provides excellent strength of fixed images, and has excellent production stability to provide stable quality; and an image forming apparatus that stably forms high-quality images by using an electrophotographic photoreceptor containing a charge transport material having a specific structure.SOLUTION: There is provided an image forming apparatus that has a toner for electrostatic charge image development having a specific structure, and an electrophotographic photoreceptor having an elastic deformation rate of an outermost surface layer of 42% or more.

Description

  The present invention provides a toner for developing an electrostatic image having both low-temperature fixability and blocking resistance, excellent fixed image strength, and excellent production stability, and an electrophotographic image having an outermost layer having a high elastic deformation rate. The present invention relates to an electrophotographic image forming apparatus and a process cartridge that stably form a high-quality image free from defects caused by filming and the like by using a photoreceptor.

  In the developing process, the developer used in electrophotography, electrostatic recording, electrostatic printing, etc. is once attached to an image carrier such as a photoreceptor on which an electrostatic charge image is formed, and then After being transferred from the photoreceptor to a transfer medium such as transfer paper in the transfer process, it is fixed on the paper surface in the fixing process. At that time, as a developer for developing the electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer that does not require a carrier (magnetic toner, Non-magnetic toners are known.

  Conventionally, as dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like, toner binders such as styrene resins and polyesters are melt-kneaded together with colorants and finely pulverized. In order to obtain high-quality and high-quality images, improvements have been made by reducing the particle diameter of the toner, but the particle shape is indefinite in the production method using the usual kneading and pulverization methods. Internally, the toner is further pulverized by agitation with the carrier in the developing unit, and when it is used as a one-component developer, contact stress between the developing roller and the toner supply roller, the layer thickness regulating blade, the friction charging blade, etc. Or the phenomenon that the image quality deteriorates because the fluidizing agent is embedded in the toner surface. Further, because of its shape, the fluidity as a powder is poor, a large amount of fluidization is required, and the filling rate into the toner bottle is low, which is an obstacle to downsizing. Therefore, the current situation is that the merit of reducing the particle size is not utilized. Furthermore, the pulverization method has a particle size limit, and cannot cope with further reduction in particle size. Further, due to the poor transferability due to the irregular shape such as the pulverized toner, there are problems such as the transfer of the transferred image and the amount of toner consumed to compensate for it.

  Accordingly, there is an increasing demand for further improving transfer efficiency to reduce toner consumption to obtain a high-quality image without missing images and to reduce running costs. If the transfer efficiency is very good, there is no need for a cleaning unit for removing untransferred toner from the photoreceptor or transfer medium, which has the advantages of reducing the size and cost of the equipment and eliminating waste toner. Because. Various spherical toner manufacturing methods have been devised to compensate for the disadvantages of such irregular shape effects.

However, the spherical toner cannot be removed by a device (for example, a cleaning blade or a cleaning brush) for removing the toner remaining on the photosensitive member or the transfer medium, resulting in poor cleaning. In addition, because the toner surface is spherical, the toner surface is exposed to the outside in all directions, and is easily exposed to contact with a charging member such as a carrier or a charging blade, and is an external additive on the toner surface or a charge control agent present on the outermost surface. However, there is a problem in durability such that the toner is easily embedded in the toner surface and the fluidity of the toner is immediately lowered. These dry toners are developed and transferred onto paper or the like, and then fixed by heating and melting using a hot roll. At that time, if the temperature of the hot roll is too high, a problem that the toner is excessively melted and fused to the hot roll (hot offset) occurs. On the other hand, if the heat roll temperature is too low, there is a problem that the toner is not sufficiently melted and fixing becomes insufficient. From the viewpoint of energy saving and downsizing of the apparatus, a toner having a higher hot offset generation temperature (hot offset resistance) and a lower fixing temperature (low temperature fixing property) is required. In addition, heat storage stability is required so that the toner is not blocked during storage and at ambient temperature in the apparatus.

As a method for solving these problems, Japanese Patent Application Laid-Open No. 2001-222138 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2002-182428 (Patent Document 2) incorporate crystalline polyester as a binder resin to obtain a melting point of the crystalline resin. Proposals have been made to obtain low-temperature fixing by using.
However, in these techniques, since the crystalline resin is not compatible with the main binder resin, if the crystalline resin is blended in an amount capable of obtaining low-temperature fixability, the crystalline resin is partially exposed on the toner surface or outside. There are drawbacks such as loss of heat resistance, filming and image defects.

On the other hand, in JP-A-11-149179 (Patent Document 3), the resin used in the polymer dissolution suspension method has a low molecular weight to lower the viscosity of the dispersed phase, facilitate emulsification, and cause the polymerization reaction in the particles. To improve fixability. However, the transferability and cleaning properties were not improved by adjusting the shape of the particles.
Japanese Patent Application Laid-Open No. 2008-112073 (Patent Document 4) has a structure in which a crystalline polyester resin contained in an amorphous polyester resin is in contact with a release agent by an emulsion aggregation method, so that Discloses a technique for improving the adhesion by suppressing recrystallization of the crystalline polyester resin after fixing in order to reduce the dependency of the fixing property on the fixing speed.

  On the other hand, a method using a low-melting crystalline resin containing a long-chain (meth) acrylic ester has also been proposed (Patent Document 5). These monomers can be easily emulsified and are very suitable for aqueous toner production. However, when such a long-chain (meth) acrylic acid ester polymer is used as a binder resin, brittleness is developed, the fixed image strength is remarkably deteriorated, and image defects are easily caused by bending or scratching ( Patent Document 5). In addition, when a long-chain (meth) acrylic acid ester and a vinyl monomer are copolymerized (Patent Documents 6 and 7), the melting point is lowered and the blocking resistance is deteriorated.

  In addition, a method for producing a latex using a long-chain (meth) acrylic acid ester polymer as a core shell with an amorphous resin and using the long-chain (meth) acrylic acid ester polymer as a release agent has also been proposed (Patent Literature). 8). However, these latexes have a high storage elastic modulus in a state in which the long chain (meth) acrylate polymer is melted, and even if it is made into a toner, the long-chain (meth) acrylate polymer alone has a sufficient releasing effect. However, offset occurs, gloss is low, and the particle size of the latex is large, so that there is a problem that coarse powder is generated when the pigment aggregates.

JP 2001-222138 A JP 2002-182428 A JP-A-11-149179 JP 2008-112073 A Japanese Patent Publication No. 56-13943 JP-A-7-301949 JP-A-8-95294 JP 2005-208653 A

Further, the toner containing the crystalline polyester and the crystalline long-chain (meth) acrylic ester as described above is a film in which the toner component adheres to the surface of the photoreceptor when there is even a slight amount of the crystalline resin exposed on the surface. It has been newly found that there is a problem that the image tends to cause image defects.
An object of the present invention is to provide an apparatus and a process cartridge for forming a stable and high-quality image of a toner containing a crystalline resin excellent in low-temperature fixability and anti-blocking property without obstacles such as filming.

  As a result of intensive studies by the present inventors, the toner is a toner containing at least a first polymer and a second polymer, the first polymer being the sea, and the first polymer By having a sea-island structure in which a second polymer having crystallinity is dispersed, and at the same time, using a photoreceptor having an outermost surface having a high elastic deformation rate, without causing troubles such as filming, The present inventors have found that an image can be stably formed throughout the machine life and have completed the present invention.

That is, the gist of the present invention resides in the following (1) to (10).
(1) In an image forming apparatus having at least an electrostatic charge image developing toner and an electrophotographic photosensitive member, the toner is a toner containing at least a first polymer and a second polymer,
The sea has a sea-island structure in which the first polymer is the sea, and the second polymer having crystallinity is dispersed in the first polymer.
The second polymer is mainly composed of a long chain (meth) acrylic acid ester polymer or a crystalline polyester,
And an elastic deformation rate of the outermost surface layer of the photoconductor is 42% or more and 60% or less.
(2) The toner has an island structure in which the second polymer is in the sea in the second polymer island, and the second polymer is a long-chain (meth) acrylate polymer. The image forming apparatus according to (1), characterized by comprising:
(3) The number of carbon atoms in the ester portion of the crystalline long-chain (meth) acrylate used in the long-chain (meth) acrylate polymer is 10 or more, (1) or (2) The image forming apparatus described in 1.
(4) The presence of the polymer obtained in the first step and the first step in which the toner contains at least a binder resin, a colorant and a wax, and the binder resin polymerizes the long-chain (meth) acrylic acid ester. The image forming apparatus according to any one of (1) to (3), wherein the image forming apparatus is manufactured through a second step of polymerizing a vinyl monomer below.
(5) The toner contains 5 to 40 parts by mass of the crystalline polyester resin and 3 to 20 parts by mass of wax with respect to 100 parts by mass of the polyester resin modified with at least a vinyl resin. The image forming apparatus according to any one of (1) to (4).
(6) The image forming apparatus according to any one of (1) to (5), wherein the universal hardness of the outermost surface layer of the electrophotographic photosensitive member is 180 N / mm ² or more.
(7) The image forming layer according to any one of (1) to (6), wherein the outermost surface layer of the electrophotographic photosensitive member contains a charge transport material having the following CT-3 structure: apparatus.

(8) The image forming apparatus according to any one of (1) to (7), wherein the electrophotographic photosensitive member contains a polyester resin as a binder resin of the outermost layer.
(9) The electrophotographic photosensitive member uses a polycarbonate resin containing 30 mol% or more of a biphenol-based unit as a copolymer component as a binder resin of the outermost layer, (1) to (7) The image forming apparatus according to any one of the above.
(10) At least the electrostatic image developing toner according to any one of (1) to (5) and the electrophotographic photosensitive member according to any one of (1) or (6) to (9). An electrophotographic process cartridge characterized by being used.

  According to the present invention, by using in combination with a toner having a sea-island structure with crystalline resin as an island and a photoreceptor having an outermost surface layer having a high elastic deformation rate, filming and the like can be performed throughout a machine or process cartridge life. It is possible to provide an image forming apparatus and a process cartridge that form a stable, high-quality image.

1 is a schematic diagram illustrating a main configuration of an embodiment of an image forming apparatus of the present invention. It is the graph which showed the load curve with respect to the indentation depth of a photoconductor. FIG. 2 is a schematic diagram illustrating an example of a toner cross section.

First, the toner will be described.
The toner used in the present invention is composed of at least a first polymer and a crystalline second polymer. When viewed from the cross section of the toner, it has a sea-island structure (A) in which the second polymer (island) is dispersed in the first polymer (sea). It is preferable that the second polymer exists only inside the first polymer and does not come out of the first polymer. Specifically, it is preferable that 90% by area of the second polymer is present in the first polymer in the TEM cross-sectional photograph, and more preferably 100% by area. Since the crystalline second polymer has a relatively low melting point and is easily deformed and detached mechanically, when exposed to the toner surface, so-called filming, in which the toner component adheres to the photoreceptor, is likely to occur.

  The sea-island structure (A) further preferably includes a sea-island structure (B) in which the second polymer is the sea and the third polymer is the island. The sea-island structure of the toner used in the present invention refers to a structure in which an island-like phase having a closed interface exists in a continuous phase. An example of the structure of the toner used in the present invention will be described with reference to FIG. FIG. 3 is a schematic diagram of a cross section of the toner. In FIG. 3, X1 represents a first polymer, X2 represents a second polymer, and X3 represents a third polymer. As described above, it is preferable that the second polymer phase X2 (island) is entirely present in the sea of the first polymer X1, and the second polymer phase X2 (sea) More preferably, a polymer phase X3 (island) 3 is present. At this time, there may be X2 in which X3 does not exist.

  The third polymer is preferably different from the second polymer. However, the structure of the third polymer may not be completely the same as that of the second polymer. For example, in the case of a copolymer, the monomer constituting the monomer is a monomer constituting the first and second polymers. And may overlap. The third polymer is not particularly limited, but a styrene polymer, an acrylic polymer, a vinyl polymer such as a styrene acrylic copolymer, a condensation polymer such as a polyester polymer, an epoxy polymer, Examples thereof include an amide polymer, an olefin polymer, or a mixture thereof, a first polymer, and those obtained by graft polymerization of monomers constituting the first and second polymers. The interface between the third polymer and the second polymer is not particularly limited, but other components may be present.

  Whether such a sea-island structure (A) is formed is very important in the balance of compatibility between the first polymer and the second polymer. If the compatibility is too high, the two polymers are completely mixed, and the toner performance such as a decrease in Tg and elastic modulus is significantly affected. On the other hand, if the compatibility is low, the two polymers are completely phase-separated and the advantages of each other's polymer are not utilized. Since the toner used in the present invention has a sea-island structure in which the second polymer (island) is dispersed in the first polymer (sea), the island portion is softened rapidly at the melting point of the toner. Further, since the sea-island structure is further provided on at least one island of the second polymer, the softening of the second polymer is further promoted, and the entire toner can be softened at a low temperature, so that fixing at a low temperature is obtained. It is done. Since the toner used in the present invention has such a structure, the balance between the low-temperature fixability and the caking property is very good.

The structure of the toner used in the present invention can be observed with a transmission electron microscope (TEM). TEM is not particularly limited as long as it is usually used by those skilled in the art.
The method for observing the cross section of the toner is not particularly limited as long as it is a commonly used method. After embedding and fixing the toner sample with an epoxy resin, an ultrathin section was prepared using a cryoultramicrotome. These ultrathin sections can be observed with TEM after ruthenium tetroxide staining treatment or the like.

In the toner used in the present invention, the size and dispersion state of the sea-island structure of the polymer depend on the amount of the polymer contained in the toner and are not particularly limited, but the island structure is more dispersed in the whole toner. Since the softening is promoted and the whole toner can be softened at a low temperature, there is a preferable tendency.
The longest diameter of the second polymer island is usually 5 μm or less, and the longest diameter of the third polymer island is preferably 3 μm or less, which tends to be preferable for low-temperature fixing of the toner.

The first polymer used in the toner used in the present invention is not particularly limited as long as it is a polymer used in conventional toners. Specifically, vinyl polymers such as styrene polymers, acrylic polymers, styrene acrylic copolymer polymers, condensation polymers such as (modified) polyester resins, epoxy polymers, amide polymers, Examples thereof include olefin polymers or mixtures thereof. Of these, when a crystalline long-chain (meth) acrylic acid ester is used as the second polymer, a vinyl polymer is preferred as the first polymer, and crystalline as the second polymer. When a polyester resin is used, it is preferable to use a polyester resin modified with a vinyl resin as the first polymer.

<1> Crystalline Long-Chain (Meth) Acrylate Ester Toner A case where a crystalline long-chain (meth) acrylate is used as the second polymer provided in the toner used in the present invention will be described. .
The long chain (meth) acrylic acid ester, which is a resin having crystallinity, may be linear or branched, and may be unsaturated. Here, the long chain (meth) acrylic acid ester means one having 10 or more carbon atoms in the ester portion. The crystalline resin refers to a resin having a clear endothermic peak instead of a stepwise endothermic amount change in differential scanning calorimetry (DSC).

When a long chain (meth) acrylic acid ester is used alone, the lower limit of the carbon number of the ester moiety is usually 10 or more, preferably 18 or more, so that the toner melting point is in a preferred range. More preferably, it is 20 or more, and particularly preferably 22 or more.
Further, the long chain (meth) acrylic acid ester may be used alone or as a mixture, but the average number of carbon atoms in the ester portion of the long chain (meth) acrylic acid ester when mixed is within the preferable range of the melting point of the toner. Therefore, the lower limit is usually 12 or more, preferably 18 or more, more preferably 19 or more, and particularly preferably 20 or more. On the other hand, the average upper limit of the carbon number of the ester moiety is usually 40 or less, preferably 36 or less, more preferably 32 or less, from the viewpoint of the melting point of the toner.

  Moreover, when mixing the long chain (meth) acrylic acid ester from which an ester part differs, it is preferable that the component whose carbon number of the ester part of a long chain (meth) acrylic acid ester is 22 or more is contained at least. Further, since the component having 22 or more carbon atoms in the ester portion of the long chain (meth) acrylate contained tends to have a preferable toner melting point, it is 1% or more of the long chain (meth) acrylate mixture. Is preferably 5% or more, more preferably 10% or more. Also, it may be 100%.

Furthermore, in the long-chain (meth) acrylic acid ester, the component having 12 or more carbon atoms in the ester portion is 50% or more of the long-chain (meth) acrylic acid ester mixture, which optimizes the toner melting point by crystallization. There is a favorable trend. When the number of carbon atoms in the ester portion is too small, the melting point becomes low and the blocking resistance tends to be poor.
The carbon number of the ester portion of the long chain (meth) acrylic acid ester can be measured by DSC, NMR, MS or the like.

Moreover, it is preferable that long-chain (meth) acrylic acid ester contains at least long-chain acrylic acid ester. If a long-chain acrylate ester is contained, as will be described later, a graft polymer is likely to be formed by extracting tertiary hydrogen, and compatibility with the vinyl copolymer is increased, and a uniform toner tends to be obtained. .
Examples of (meth) acrylic acid esters include, but are not limited to, tetracosyl acrylate, behenyl acrylate, icosyl acrylate, stearyl acrylate, cetyl acrylate, mistyryl acrylate, tetracosyl methacrylate, behenyl methacrylate, icosyl methacrylate, Monomers such as stearyl methacrylate, cetyl methacrylate, and mystyryl methacrylate are preferred for achieving low temperature fixing.

The melting point of the long chain (meth) acrylic acid ester polymer is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and particularly preferably 70 ° C. or lower. The melting point is preferably 40 ° C. or higher, more preferably 50 ° C. or higher. If the melting point is too high, the effect of reducing the fixing temperature will be poor, and if the melting point is too low, problems may occur in the caking property and storage stability.
The binder resin of the long chain (meth) acrylate toner is a first monomer for polymerizing the long chain (meth) acrylate, and a vinyl monomer in the presence of the polymer obtained in the first process. It is manufactured through a second step of polymerizing the sucrose.

In the first step, a monomer (long chain (meth) acrylic acid ester) solution is prepared, and the monomer solution is dispersed in oil droplets in an aqueous medium (for example, an aqueous surfactant solution). A dispersion of resin particles is prepared by polymerizing the resin. Further, if necessary, a monomer solution may be prepared by dissolving a crystalline substance such as wax in the monomer.
In the second step, a monomer (vinyl monomer) is further added to the dispersion of resin particles obtained in the first step, and the monomer is polymerized in the presence of the resin particles. Resin particles are formed.

The lower limit of the amount of the long-chain (meth) acrylate polymer used in the second step for obtaining the binder resin of the long-chain (meth) acrylate-based toner is 1 part by mass or more in 100 parts by mass of the binder resin. It is preferable to charge so as to be, more preferably 2 parts by mass or more, and further preferably 5 parts by mass or more, while the upper limit is charged so that 100 parts by mass of the binder resin is 50 parts by mass or less. More preferably, it is 45 mass parts or less, More preferably, it is 40 mass parts or less. If the content of the long-chain (meth) acrylic acid ester polymer in the binder resin is too small, performance such as low-temperature fixability may not be sufficient, and if it is too much, the fixed image strength deteriorates.
An image defect may occur due to bending or scratching.

The monomers used in the first step and the second step for obtaining a binder resin for a long-chain (meth) acrylate toner may be used alone or in combination.
In the long chain (meth) acrylic acid ester toner, by obtaining the binder resin through the first step and the second step, it is possible to obtain a toner for developing an electrostatic image having excellent low-temperature fixability and blocking resistance. it can.

  Although not clear, it is considered that the effects described above are manifested by the following mechanism. First, by first polymerizing a long-chain (meth) acrylic acid ester, a single crystalline polymer having a sharp melting point can be obtained. After that, in order to polymerize vinyl monomers as the second step, a low-melting point such as a long chain (meth) acrylic acid ester and vinyl monomer copolymer formed by polymerizing them at the same time. Generation of a non-crystalline component having a wide melting point range can be suppressed.

  In the second step, when the vinyl monomer is polymerized, the radical derived from the monomer or initiator is generated in the first step, and the acrylic of a part of the long-chain (meth) acrylate polymer. By extracting tertiary hydrogen at the acid site, a graft polymer is produced. This graft polymer becomes a compatibilizer, stabilizes the interface between the long-chain (meth) acrylate polymer and the vinyl polymer, which are crystalline resins, and the long-chain (meth) acrylate in the vinyl copolymer. By obtaining a toner in which a polymer is dispersed, it is considered that a toner having a sharp melting point and excellent in low-temperature fixability and blocking resistance can be produced.

The polymerization time in the first step for obtaining the binder resin of the long chain (meth) acrylate toner is not particularly limited, but it is preferable to carry out the polymerization until the residual monomer after polymerization is less than 1%. Usually, it is 5 minutes or more and 3 hours or less, and the polymerization is preferably performed at a temperature equal to or higher than the melting point of the monomer used in the first step.
The long-chain (meth) acrylic acid ester used in the first step, which is a process for producing a binder resin for a long-chain (meth) acrylic acid ester toner, is mixed with melt, water, a surfactant and the like as necessary. High pressure mechanical emulsification is preferably performed. Moreover, you may perform a high pressure mechanical emulsification with a wax. By performing high-pressure mechanical emulsification, the diameter of the long-chain (meth) acrylic acid ester or wax dispersion can be reduced. By reducing the diameter of the dispersion before polymerization, the specific surface area of the dispersion increases, and the graft reaction tends to proceed.

The volume average particle size of the long chain (meth) acrylic acid ester and wax dispersion is preferably 0.03 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more. Further, it is preferably 2 μm or less, more preferably 1 μm or less, and particularly preferably 0.5 μm or less.
The apparatus used for the high-pressure mechanical emulsification of the long chain (meth) acrylate toner is not particularly limited, but it is preferable to use an apparatus having a pump pressure of 5 MPa or more, more preferably 10 MPa or more.

The high-pressure mechanical emulsification is preferably carried out at a temperature equal to or higher than the melting point of the long-chain (meth) acrylic acid ester and the wax. If the emulsification temperature is too low, the particle size of the dispersion tends to be difficult to decrease.
As the vinyl monomer used in the second step, which is the production process of the binder resin for the long-chain (meth) acrylate toner, a monomer conventionally used in the binder resin for the toner is appropriately selected. Can be used.

For example, as a monomer, a polymerizable monomer having an acidic group (hereinafter sometimes simply referred to as an acidic monomer), a polymerizable monomer having a basic group (hereinafter simply referred to as a basic monomer) A polymerizable monomer having no acidic group or basic group (hereinafter, also referred to as other monomer) may be used. it can.
Examples of the monomer include polymerizable monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and cinnamic acid, polymerizable monomers having a sulfonic acid group such as sulfonated styrene, Examples thereof include polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide. Examples of the basic monomer include aromatic vinyl compounds having an amino group such as aminostyrene, nitrogen-containing heterocyclic-containing polymerizable monomers such as vinylpyridine and vinylpyrrolidone, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, etc. And (meth) acrylic acid ester having an amino group. These acidic monomers and basic monomers may be used singly or as a mixture of a plurality of types, and may exist as a salt with a counter ion. Among these, it is preferable to use an acidic monomer, more preferably acrylic acid and / or methacrylic acid.

  Also, styrenes such as styrene, methyl styrene, chlorostyrene, dichlorostyrene, p-tert-butyl styrene, pn-butyl styrene, pn-nonyl styrene, methyl acrylate, ethyl acrylate, propyl acrylate, Acrylic esters such as n-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid Methacrylic acid esters such as hydroxyethyl acid, 2-ethylhexyl methacrylate, acrylamide, N-propylacrylamide, N, N-dimethylacrylamide, N, N-dipropylacrylamide, N, N-dibutyla Riruamido and the like, the polymerizable monomer may be used singly, or may be used in combination.

  Further, when the binder resin is a cross-linked resin, a polyfunctional monomer having radical polymerizability is used together with the above-mentioned monomers, for example, divinylbenzene, hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diester. Examples include methacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, and diallyl phthalate. It is also possible to use a polymerizable monomer having a reactive group in a pendant group, such as glycidyl methacrylate, methylol acrylamide, acrolein and the like. Among these, radically polymerizable bifunctional polymerizable monomers are preferable, and divinylbenzene and hexanediol diacrylate are particularly preferable. These polyfunctional polymerizable monomers may be used alone or as a mixture of plural kinds.

  The polymerization time in the second step for obtaining the binder resin of the long chain (meth) acrylate toner can be appropriately adjusted depending on the addition method of monomers and emulsifiers used in the second step, and is not particularly limited. However, it is preferable to carry out the polymerization until the monomer remaining after the polymerization is less than 1%. Moreover, it is preferable to perform superposition | polymerization at the temperature more than melting | fusing point of the polymer obtained at the 1st process.

  In the production of a long chain (meth) acrylic acid ester-based toner, the polymerization initiator used in the step of producing the binder resin is not particularly limited in the first step and the second step, but a known polymerization initiator may be used if necessary. The polymerization initiator can be used alone or in combination of two or more. The polymerization initiator includes a radical polymerization initiator and an ionic polymerization initiator. A radical polymerization initiator is preferable for use in water, and when a radical polymerization initiator is used in the second step of obtaining a binder resin, This is particularly preferable because a graft reaction due to hydrogen abstraction is likely to occur.

The radical polymerization initiator includes an organic polymerization initiator and an inorganic polymerization initiator, and hydrogen peroxide and an organic polymerization initiator are preferably used. Inorganic polymerization initiators such as potassium persulfate, sodium persulfate, and ammonium persulfate may need to be used in a large amount, and since a hydrophilic group is generated at the polymerization terminal, there is a tendency to adversely affect charging characteristics.
In particular, as the hydrogen peroxide and the organic polymerization initiator, in the second step of obtaining the binder resin, a ketone peroxide that easily undergoes a graft reaction by hydrogen abstraction and a hydroperoxide containing hydrogen peroxide are preferable. Furthermore, hydroperoxide containing hydrogen peroxide is most preferable.

These polymerization initiators may be added to the polymerization system before, simultaneously with the addition of the monomer, or after the addition, and these addition methods may be combined as necessary.
In the long chain (meth) acrylic acid ester toner, a known chain transfer agent can be used as required. Specific examples of the chain transfer agent include t-dodecyl mercaptan, 2-mercaptoethanol, diisopropylxanthogen, carbon tetrachloride, trichlorobromomethane and the like. The chain transfer agent may be used alone or in combination of two or more, and is used in an amount of 0 to 5% by mass based on the polymerizable monomer.

  In the long chain (meth) acrylic acid ester toner, a known suspension stabilizer can be used as necessary. Specific examples of the suspension stabilizer include calcium phosphate, magnesium phosphate calcium hydroxide, magnesium hydroxide and the like. These may be used alone or in combination of two or more, and may be used in an amount of 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

Both the polymerization initiator and the suspension stabilizer may be added to the polymerization system at any time before, simultaneously with, or after the addition of the polymerizable monomer. You may combine.
In addition, a pH adjuster, a polymerization degree adjuster, an antifoaming agent, and the like can be appropriately added to the reaction system.

In a long chain (meth) acrylic acid ester toner, when a binder resin is polymerized by emulsion polymerization, known emulsifiers can be used, but cationic surfactants, anionic surfactants, nonionic interfaces can be used. One or two or more emulsifiers selected from the active agents can be used in combination.
Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide, and examples of the anionic surfactant include And fatty acid soap such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate and the like. Nonionic surfactants include, for example, polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl sucrose, etc. Is mentioned.

  In the long chain (meth) acrylic acid ester toner, the amount of the emulsifier is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. In addition, these emulsifiers can be used as protective colloids, for example, one or more of partially or completely saponified polyvinyl alcohols such as polyvinyl alcohol and cellulose derivatives such as hydroxyethyl cellulose.

  In the long-chain (meth) acrylic acid ester toner, the volume average particle diameter of the polymer primary particles after multistage polymerization obtained by emulsion polymerization is usually 0.03 μm or more, preferably 0.05 μm or more, more preferably 0.8. It is 1 μm or more, usually 3 μm or less, preferably 2 μm or less, and more preferably 1 μm or less. If the particle size is too small, it may be difficult to control the aggregation rate in the aggregation process. If the particle size is too large, the particle size of the toner particles obtained by aggregation tends to be large. It may be difficult to obtain toner.

<2> Crystalline Polyester Toner A case where a crystalline polyester is used as the second polymer provided for the toner used in the present invention will be described.
Since the crystalline polyester resin has crystallinity, the crystalline polyester resin exhibits a heat-melting characteristic showing a rapid viscosity decrease near the fixing start temperature. In other words, the toner has good heat-resistant storage stability due to crystallinity until just before the melting start temperature, and suddenly drops in viscosity (sharp melt) at the melting start temperature and fixes, so it has both good heat storage stability and low-temperature fixability. Can be designed. Also, good results are shown for the release width (difference between the minimum fixing temperature and the hot offset occurrence temperature).

The crystalline polyester toner is produced by combining the crystalline polyester resin and at least one of a polyester resin or a modified polyester resin.
(Polyester resin)
The polyester resin is obtained by polycondensing a polyhydric alcohol component and a polyvalent carboxylic acid component such as a carboxylic acid, a carboxylic acid anhydride, or a carboxylic acid ester as a raw material monomer.

As the polyhydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4
-Hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (
4-Hydroxyphenyl) propane and other bisphenol A alkylene (2 to 3 carbon atoms) oxide (average added mole number 1 to 10) adduct, ethylene glycol, propylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane , Hydrogenated bisphenol A, sorbitol, or alkylene thereof (2 carbon atoms)
-3) Oxide (average added mole number 1-10) adduct etc. are mentioned, What contains these 1 or more types is preferable.

The polyvalent carboxylic acid component includes dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, fumaric acid and maleic acid, carbon numbers such as dodecenyl succinic acid and octyl succinic acid.
Succinic acid, trimellitic acid, pyromellitic acid, anhydrides of these acids and alkyl (1 to 3 carbon atoms) esters of these acids substituted with -20 alkyl groups or C2-C20 alkenyl groups The thing containing 1 or more types of these is preferable.

The alcohol component and the carboxylic acid component can be subjected to polycondensation by reacting at a temperature of 120 to 230 ° C. in an inert gas atmosphere using an esterification catalyst, a polymerization inhibitor or the like. Specifically, all monomers are charged at once to increase the strength of the resin, or a divalent monomer is first reacted to reduce low molecular weight components, and then a trivalent or higher monomer. A method of adding and reacting may be used. Further, the reaction may be accelerated by reducing the pressure of the reaction system in the latter half of the polymerization.

The glass transition temperature of the polyester is preferably 40 to 70 ° C. This is because when the temperature is lower than 40 ° C., the heat resistance is poor, and when the temperature is higher than 70 ° C., the low-temperature fixability tends to deteriorate.
The molecular weight of the polyester is preferably 3,000 to 20,000. When it is lower than 3,000, the heat resistance and the offset property tend to be inferior, and when it is higher than 20,000, the low-temperature fixability tends to deteriorate.

(Vinyl resin for modification)
Examples of the vinyl resins for modification include polymers of styrene such as polystyrene, poly p-chlorostyrene and polyvinyltoluene and substituted products thereof; styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, and styrene- Vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, Styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethyl Ketone copolymer, styrene-butadiene copolymer Styrene copolymers such as polymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl (meth) acrylates, polybutyl ( Acrylic polymers such as (meth) acrylate, polystearyl (meth) acrylate, polybehenyl (meth) acrylate, or copolymers thereof, as well as polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, etc. These vinyl resins are obtained by a conventional polymerization reaction such as radical (co) polymerization.

(Polyester resin modified with vinyl resin)
As a method of modifying a polyester resin with a vinyl resin, an acidic component (or alcohol component) capable of radical polymerization is compounded at the time of synthesis of the polyester resin, and the vinyl monomer is radically polymerized in the presence of the polyester resin. Then, a method of modifying the graft mer, a method in which an acid group, an alcohol group, or an ester group is added to the vinyl resin and then modified by an esterification reaction or a transesterification reaction, or in the presence of a polyester resin, There is a method of graft-modifying a part of a polyester resin by polymerizing a vinyl monomer using a radical polymerization initiator having a strong hydrogen abstraction property such as hydrogen oxide or an organic acyl peroxide.

  The glass transition temperature of the polyester modified with the vinyl resin is preferably 40 to 70 ° C. This is because when the temperature is lower than 40 ° C., the heat resistance is poor, and when the temperature is higher than 70 ° C., the low-temperature fixability tends to deteriorate. Even when the surface of the toner is made into a capsule structure with a shell resin component having high heat resistance, if the glass transition temperature of the resin component is lower than 40 ° C., sufficient heat resistance tends not to be obtained.

The molecular weight of the polyester modified with the vinyl resin is preferably 5,000 to 100,000. When it is lower than 5,000, the heat resistance and the offset property tend to be inferior, and when it is 100,000 or more, the low-temperature fixability tends to deteriorate. The above-mentioned tendency also exists when a small amount of gel is included.
Such a gel content is suitable for improving the offset property on the high temperature side. Gel content is GPC
Although it is filtered before measuring the molecular weight, the low-temperature fixability is excellent although it is estimated to be approximately 30% or less than the area of the chromatogram.

(Crystalline polyester resin)
Here, the “crystalline polyester” refers to one having a clear endothermic peak, not a stepwise change in endothermic amount in differential scanning calorimetry (DSC). In the toner used in the present invention, the crystalline polyester has an alcohol component containing 80 mol% or more of an aliphatic diol having 2 to 12 carbon atoms, preferably 4 to 10 carbon atoms, and 2 to 12 carbon atoms, preferably 4 to 4 carbon atoms. A resin obtained by polycondensing a carboxylic acid component containing 10 aliphatic dicarboxylic acid compounds in an amount of 80 mol% or more (hereinafter referred to as aliphatic crystalline polyester) is preferred.

Examples of the aliphatic diol having 2 to 12 carbon atoms include 1,4-butanediol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4 -Butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, etc., especially α, ω-linear Alkyl diols are preferred.

Desirably, the aliphatic diol having 2 to 12 carbon atoms is contained in the alcohol component in an amount of 80 mol% or more, preferably 90 to 100 mol%, more preferably 95 to 100 mol%. It is desirable that the aliphatic diol of the species occupies 70 mol% or more, preferably 80 mol% or more, more preferably 85 to 95 mol% in the alcohol component.
Examples of the divalent alcohol component that may be contained in the alcohol component in addition to the aliphatic diol having 2 to 12 carbon atoms include polyoxypropylene (2.2) -2, 2-bis (4-hydroxyphenyl) propane, Aromatic aromatics such as alkylene oxide adducts of bisphenol A such as polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane; diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, Examples include dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and hydrogenated bisphenol A.

Examples of trihydric or higher polyhydric alcohol components include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; sorbitol,, 2,3,6-hexanetetrol, pentaerythritol, dipentaerythritol, tripentaerythritol , 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane and the like Aliphatic alcohols; and alicyclic alcohols such as 1,4-sorbitan.

  Examples of the aliphatic dicarboxylic acid compound having 2 to 12 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid And anhydrides and alkyl esters of these acids. As described above, the aliphatic dicarboxylic compound refers to an aliphatic dicarboxylic acid, an anhydride thereof and an alkyl ester thereof. Among these, an aliphatic dicarboxylic acid is preferable.

Desirably, the aliphatic dicarboxylic acid compound having 2 to 12 carbon atoms is contained in the carboxylic acid component in an amount of 80 mol% or more, preferably 90 to 100 mol%, more preferably 95 to 100 mol%. It is desirable that one of the aliphatic dicarboxylic acid compounds in the occupy 80 mol% or more, preferably 90 to 100 mol% or more of the carboxylic acid component.
Examples of the divalent carboxylic acid component that may be contained in the carboxylic acid component other than the aliphatic dicarboxylic acid compound having 2 to 12 carbon atoms include aromatic carboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; n-dodecyl And aliphatic carboxylic acids such as succinic acid and n-dodecenyl succinic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid; and anhydrides and alkyl esters of these acids.

Trivalent or higher polyvalent carboxylic acid components include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid Aromatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2
-Aliphatic carboxylic acids such as methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, and alicyclic carboxylic acids such as 1,2,4-cyclohexanetricarboxylic acid; and these Derivatives such as acid anhydrides, alkyl esters and the like.

Crystalline polyester can also be produced in the same manner as amorphous polyester.
The melting point of the crystalline polyester is preferably 40 to 110 ° C, more preferably 50 to 90 ° C, and most preferably 55 to 70 ° C. If it is lower than 40 ° C, it tends to be inferior in heat resistance, 110 ° C
If it is higher, the low-temperature fixability tends to be inferior.
The molecular weight of the crystalline polyester is preferably 2,000 to 10,000. If it is lower than 2,000, the heat resistance and filming properties tend to be inferior, and if it exceeds 20,000, the low-temperature fixability tends to deteriorate.

The blending amount of the crystalline polyester in the binder resin is 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, when the polymer 1 such as polyester resin modified with a vinyl resin is 100 parts by mass. Preferably it is 10-25 mass parts. If it is 5 parts by mass or less, the low-temperature fixability is inferior, and if it is 40 parts by mass or more, the filming property tends to be inferior.
(Production method)
There is no particular limitation on the method for producing the crystalline polyester toner relating to the toner used in the present invention. That is, the toner can be produced by a pulverization method or a polymerization method. When a toner is manufactured by a pulverization method, fine particles are generally easily generated, so that a classification step is necessary. The toner used in the present invention is preferably formed with particles in an aqueous medium from the viewpoint of hardly generating fine powder.

  As a production method for obtaining a toner in an aqueous medium, a method in which radical polymerization is carried out in an aqueous medium such as a suspension polymerization method or an emulsion polymerization aggregation method (hereinafter abbreviated as “polymerization method”), the obtained toner is “polymerized”. (Abbreviated as “toner”), a chemical pulverization method represented by a dissolution suspension method, and the like can be preferably used. There is no particular limitation on the method for making the toner particle size within a specific range. For example, in the production process of the polymerized toner, in the case of the suspension polymerization method, a method in which a high shearing force is applied in the process in which polymerizable monomer droplets are generated, or a dispersion stabilizer or the like is increased.

Among the methods for forming particles in an aqueous medium, the method of producing particles by polymerization in an aqueous medium is preferable from the viewpoint of hardly generating fine powder, and further a step of modifying the polyester with a vinyl resin. In order to efficiently carry out the above, a method for producing particles by the dissolution suspension method is preferred.
Hereinafter, the toner production method used in the present invention will be described with the dissolution suspension method as a representative example.

A solution suspension method applied as a method for producing a crystalline polyester toner used for the toner used in the present invention may be a method generally used for toner production. Generally, toner particle granulation methods include a method of adjusting the particle size of droplets using shear force and a method of adjusting the particle size of droplets by phase inversion emulsification.
The phase inversion emulsification method is preferable because it is superior in particle size control, but this method is produced according to the production method disclosed in, for example, JP-A-2007-72488.

Specifically, a polyester resin modified with a vinyl-based resin, a crystalline polyester resin, a colorant, wax fine particles, and a mixture containing an organic solvent as essential components, and if necessary, the resin is self-dispersible. In the presence of a neutralizing agent in a sufficient amount, phase-inversion emulsification is performed in addition to the aqueous medium or phase-inversion emulsification is performed by adding the aqueous medium to the mixture. After the resin particles modified with the vinyl resin encapsulating the agent and the wax fine particles are produced, the particles are separated and dried to obtain toner base particles.

  As the organic solvent, various organic solvents can be used as long as they dissolve a polyester resin modified with a vinyl resin. For example, various hydrocarbons such as toluene, xylene, benzene, n-hexane, cyclohexane and n-heptane; alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol and t-butanol Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoisopropyl ether, propylene glycol mono n-butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, etc. Ether alcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone Various ketones; various esters such as ethyl acetate, butyl acetate and isobutyl acetate; various ether esters such as propylene glycol monoethyl ether acetate and ethylene glycol monoethyl ether acetate; various cyclic ethers such as tetrahydrofuran; methylene chloride And various halogenated hydrocarbons.

  Modification of the polyester with a vinyl resin is preferably performed in this organic solvent. Although the modification method has been described above, for example, a fumaric acid capable of radical polymerization is mixed with a part of the aliphatic dicarboxylic acid which is a constituent component of the polyester, for example, a vinyl monomer such as styrene. Can be subjected to radical polymerization to obtain a modified polyester using styrene as a grafter.

  The method for blending the crystalline polyester, wax and pigment into the modified polyester solution is to mix and disperse the mixture with a media mill or the like, and to form a single dispersion of each of the crystalline polyester, wax and pigment and mix them. There is a way. For crystalline polyesters and waxes, a media mill or the like often cannot obtain a sufficiently small particle size, and therefore, a method of preparing a dispersion in advance and mixing it is preferable.

  As a method for producing a dispersion of crystalline polyester and wax, it is preferable to carry out high-pressure mechanical emulsification after hot-melting if necessary and mixing with water and a surfactant. Further, the high-pressure mechanical emulsification may be performed individually or in combination with the crystalline polyester and the wax. By performing high-pressure mechanical emulsification, the diameter of the dispersion of crystalline polyester and wax can be reduced. By reducing the diameter of the dispersion, it is possible to obtain a toner that easily exhibits low-temperature fixability and hardly causes filming.

In the toner used in the present invention, the volume average particle size of the dispersion of crystalline polyester and wax is preferably 0.03 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more. Further, it is preferably 2 μm or less, more preferably 1 μm or less, and particularly preferably 0.5 μm or less.
As said surfactant, 1 type, or 2 or more types of emulsifiers chosen from a cationic surfactant, an anionic surfactant, and a nonionic surfactant can be used together.

Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide, and examples of the anionic surfactant include And fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, and amine salts thereof. Nonionic surfactants include, for example, polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl sucrose, etc. Is mentioned.

Next, the phase inversion emulsification process will be described. The mixture obtained in the above step is phase-inverted and emulsified in an aqueous medium. As a method for phase inversion emulsification, the following method is suitable.
1) A method of phase inversion emulsification by adding the mixture into an aqueous medium.
2) A method of phase inversion emulsification by adding an aqueous medium to the mixture.
The above aqueous medium may contain a surfactant, and the kind and amount thereof are adjusted according to the desired particle diameter. Further, as the shear force when phase-inverting and emulsifying in an aqueous medium to produce toner particles, a particularly high shear force is not required, and the mixture containing the aqueous medium may be stirred uniformly. Good.

Next, the liquid medium is separated from the aqueous medium dispersion of the toner particles after phase inversion emulsification. At this time, water and the organic solvent may be separated at the same time. However, it is preferable to obtain the toner particles by performing desolvation after removing the solvent mainly using only the organic solvent or the organic solvent.
Solvent removal is performed by distilling off part or all of the organic solvent under reduced pressure. If necessary, the organic solvent alone or the mixture containing only the organic solvent as the main solvent and containing only water as the liquid medium or mainly containing water can be washed or neutralized with an aqueous solution of an acidic compound, for example, with a base. In the case of a self-water dispersible resin having a carboxyl group, an operation of returning the neutralized carboxyl group to the original carboxyl group is performed.

After the liquid medium is separated from the toner particle liquid medium dispersion, drying is performed to obtain toner particle powder. This drying may be performed by a known method. For example, warm air drying, spray drying, freeze drying, and the like can be employed.
The wax, colorant, charge control agent, and external additive that can be commonly used for the long-chain (meth) acrylate toner and the crystalline polyester toner related to the toner used in the present invention will be described below.

(wax)
The toner used in the present invention preferably contains a wax in order to impart releasability. Any wax can be used as long as it has releasability.
Specifically, for example, olefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene and copolymer polyethylene; paraffin wax; ester waxes having a long-chain aliphatic group such as behenyl behenate, montanate ester, stearyl stearate Plant-based waxes such as hydrogenated castor oil and carnauba wax; ketones having long-chain alkyl groups such as distearyl ketone; silicones having alkyl groups; higher fatty acids such as stearic acid; long-chain fatty alcohols such as eicosanol; glycerin; Carboxylic acid ester or partial ester of polyhydric alcohol obtained from polyhydric alcohol such as pentaerythritol and long chain fatty acid; higher fatty acid amide such as oleic acid amide and stearic acid amide; low molecular weight polyester and the like. Among the box, in order to improve the fixing property, the melting point is preferably 30 ° C. or more waxes, and more preferably at least 40 ° C., particularly preferably at least 50 ° C.. Moreover, 100 degrees C or less is preferable, 90 degrees C or less is more preferable, and 80 degrees C or less is especially preferable. If the melting point is too low, the wax may be exposed on the surface after fixing, and stickiness may occur. On the other hand, if the melting point is too high, the fixability at low temperatures may be poor.

Further, as the wax compound type, it is preferable to use at least one of higher fatty acid ester wax, olefin wax such as copolymer polyethylene, paraffin wax, and silicone wax.
Specific examples of the higher fatty acid ester wax include, for example, behenyl behenate, stearyl stearate, stearate ester of pentaerythritol, glyceride montanate and the like, and fatty acids having 15 to 30 carbon atoms and 1 to 5 valent alcohols. Esters are preferred. Moreover, as an alcohol component which comprises ester, a C10-30 thing is preferable in the case of monohydric alcohol, and a C3-C10 thing is preferable in the case of a polyhydric alcohol.

The above waxes may be used alone or in combination. Further, the melting point of the wax compound can be appropriately selected depending on the fixing temperature for fixing the toner.
In the toner used in the present invention, the wax may be used alone or in combination. Among these waxes, in order to improve fixability, the melting point of the wax is preferably 110 ° C. or lower, more preferably 90 ° C. or lower, and particularly preferably 80 ° C. or lower. As a minimum of melting | fusing point, 40 degreeC or more is preferable, More preferably, it is 50 degreeC or more. If the melting point is too high, the effect of reducing the fixing temperature is poor, and if the melting point is too low, problems may occur in the caking property and storage stability.

  In the long chain (meth) acrylic acid ester toner, the amount of wax is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 5 parts by mass or more in 100 parts by mass of the toner. . Moreover, it is preferable that it is 40 mass parts or less, More preferably, it is 35 mass parts or less, More preferably, it is 30 mass parts or less. If the wax content in the toner is too low, performance such as high temperature offset property may not be sufficient, and if the content is too high, the blocking resistance may not be sufficient, or the wax may leak from the toner. It may become contaminated.

The content of the wax in the crystalline polyester toner is usually 3 to 20 parts by mass, preferably 5 to 15 parts by mass when the polymer 1 such as polyester resin modified with a vinyl resin is 100 parts by mass. More preferably, it is 5 to 10 parts by mass.
(Coloring agent)
The colorant used in the toner used in the present invention is not particularly limited, and various known colorants suitable for the toner can be used. For example, carbon blacks such as furnace black and lamp black; benzidine yellow, benzidine orange, quinoline yellow, acid green, alkali blue, rhodamine, magenta, macalite green, hydroxyanthraquinone, phthalocyanine dye, pigment, quinacridone dye, dioxane Synthetic dyes such as dyes, aniline black, azo dyes, naphthoquinone dyes, indigo dyes, nigrosine dyes, phthalocyanine dyes, polymethine dyes, di- and triarylmethane dyes These can be used in combination.

  When the toner used in the present invention is used as a full-color toner, an azo pigment (insoluble monoazo, insoluble disazo, condensed azo, etc.) for yellow, a polycyclic pigment (isoindoline, isoindolinone, Azo pigments (azo lake, insoluble monoazo, insoluble disazo, condensed azo, etc.), polycyclic pigments (quinacridone pigment, perylene pigment, etc.), etc. Examples of cyan pigments include phthalocyanine pigments and selenium pigments.

The combination of the colorants may be appropriately selected in consideration of the hue and the like. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. At least one selected from CI Pigment Yellow 155 is C.I. I. Pigment red 238, C.I. I. Pigment red 269, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 48: 2, C.I. I. At least one selected from CI Pigment Red 122 is C.I. I. Pigment blue 15, C.I. I. At least one selected from CI Pigment Blue 15: 3 is preferable as furnace black carbon as the black colorant. It is preferable to use a colorant that contains as little volatile impurities as possible.

The content ratio of the colorant may be an amount sufficient for the obtained toner to form a visible image by development, and is preferably 1 to 20% by mass in the toner base particles, for example, 2 to 15 It is more preferable that it is mass%, and it is especially preferable that it is 3-10 mass% especially. When two or more colorants are used in combination, the total amount is preferably within the above range.
The toner used in the present invention is effective when used as a toner for developing an electrostatic charge image, such as a monochromatic toner, a full-color toner, a one-component developer, and a two-component developer.

(Charge control agent)
In the toner used in the present invention, a charge control agent may be blended in order to impart charge amount and charge stability. Conventionally known compounds are used as the charge control agent. Examples thereof include hydroxycarboxylic acid metal complexes, azo compound metal complexes, naphthol compounds, naphthol compound metal compounds, nigrosine dyes, quaternary ammonium salts, and mixtures thereof.

The blending amount of the charge control agent is preferably in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin.
(External)
Silica particle powder, titanium oxide powder, and the like can be externally added to the toner particle powder thus obtained as necessary.
To the toner used in the present invention, externally added fine particles can be added as necessary to improve toner fluidity and charge control properties. Examples of such externally added fine particles include various inorganic or organic fine particles. It can be used by appropriately selecting from among them.

  Inorganic fine particles include silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, and other carbides, boron nitride, titanium nitride. , Various nitrides such as zirconium nitride, various borides such as zirconium boride, various oxides such as titanium oxide, calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, cerium oxide, silica, colloidal silica, titanium Various titanate compounds such as calcium oxide, magnesium titanate and strontium titanate, phosphate compounds such as calcium phosphate, sulfides such as molybdenum disulfide, fluorides such as magnesium fluoride and fluorocarbon, aluminum stearate, stearin Calcium, zinc stearate, can be used various metal soaps such as magnesium stearate, talc, bentonite, various carbon black or conductive carbon black, magnetite, ferrite or the like. As the organic fine particles, fine particles such as styrene resin, acrylic resin, epoxy resin, and melamine resin can be used.

  Among these externally added fine particles, silica, titanium oxide, alumina, zinc oxide, various carbon blacks, conductive carbon blacks, and the like are preferably used. Further, the externally added fine particles are obtained by applying the surface of the inorganic or organic fine particles to a silane coupling agent, a titanate coupling agent, a silicone oil, a modified silicone oil, a silicone varnish, a fluorine silane coupling agent, a fluorine silicone oil, What has been subjected to surface treatment such as hydrophobization with a treating agent such as a coupling agent having an amino group or a quaternary ammonium base can also be used. Two or more kinds of the treatment agents can be used in combination.

The externally added fine particles of the toner used in the present invention preferably have an average particle size of 0.001 μm or more, more preferably 0.005 μm or more. Moreover, 3 micrometers or less are preferable, More preferably, it is 1 micrometer. Also, a plurality of types having different particle sizes can be blended. The average particle diameter of the externally added fine particles can be determined by observation with an electron microscope.
In addition, the externally added fine particles can be used in combination of two or more different types, can be used in combination with those that have been surface-treated and those that have not been surface-treated, or can be used in combination with those that have been surface-treated differently, A positively chargeable one and a negatively chargeable one can be used in appropriate combination.

The content of the externally added fine particles of the toner used in the present invention is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 5 parts by mass with respect to 100 parts by mass of the toner particles. Hereinafter, it is more preferably 3 parts by mass or less.
Examples of the method for adding the externally added fine particles include a method using a high-speed stirrer such as a Henschel mixer, a method using an apparatus capable of applying a compressive shear stress, and the like.

Further, inorganic fine powders such as magnetite, ferrite, cerium oxide, strontium titanate, and conductive titania can be added. The amount of these additives used may be appropriately selected depending on the desired performance, and is preferably 0.05 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the toner.
The electrostatic image developing toner obtained by the above production method may be used in the form of a two-component developer using the toner together with a carrier, or a magnetic or non-magnetic one-component developer not using a carrier. . When used as a two-component developer, the carrier may be a magnetic substance such as iron powder, magnetite powder, ferrite powder or the like, or a known material such as a resin-coated surface or a magnetic carrier. As the coating resin of the resin coating carrier, generally known styrene resin, acrylic resin, styrene acrylic copolymer resin, silicone resin, modified silicone resin, fluororesin, or a mixture thereof can be used.

Next, the electrophotographic photosensitive member used in the present invention will be described.
<Mechanical properties of the outermost surface of the photoreceptor>
From the viewpoint of preventing toner sticking (filming), the lower limit of the elastic deformation rate of the outermost layer of the electrophotographic photosensitive member used in the image forming apparatus of the present invention is preferably 40% or more, more preferably 42. % Or more, more preferably 44% or more. The upper limit of the elastic deformation rate is not particularly limited, but is preferably 70% or less, more preferably 65% or less, and still more preferably 60% or less. If the elastic deformation rate is too high, the amount of wear of the photosensitive layer is too small, and it becomes difficult to remove and refresh the deteriorated portion of the photosensitive layer, so that image characteristics and electrical characteristics may deteriorate over time.

When the toner component having the sea-island structure used in the present invention is filmed on the photosensitive member, even if the deposit is peeled off and observed under a microscope, scratches are often not found on the surface of the photosensitive layer. In such a case, adhesion of the toner component is caused by plastic deformation of the photosensitive layer and a large contact area with the toner, thereby increasing non-electrostatic adhesion force such as van der Waals force, and electrostatic charge due to transfer. It is considered that the residual strength exceeds the non-electrostatic release force by the cleaning blade and the like, and as a result, it remains on the surface of the photoreceptor and causes image defects continuously. The toner having the sea-island structure used in the present invention has a high storage elastic modulus, and accordingly, if the photoreceptor does not have a sufficient elastic deformation rate, it is considered that the above-mentioned filming is likely to occur due to plastic deformation during repeated fatigue. . In particular, when the elastic deformation rate of the photoconductor is smaller than 40%, filming may easily occur. In addition, before reaching the filming in which the toner component is continuously adhered to the photoconductor, so-called transfer residual toner that remains on the photoconductor without being transferred after the transfer process may increase (referred to as PC fog). . If such residual toner increases, it is estimated that the possibility of progressing to filming increases. By increasing the elastic deformation rate of the photoconductor, it is considered that there is an effect of reducing non-electrostatic adhesion and reducing such transfer residual toner as in the case described above.

From the viewpoint of preventing scratches caused by toner components, the universal hardness of the outermost surface, the lower limit is usually, 180 N / mm ² or more, 195 N / mm ² or more is preferably, more preferably 210N / mm ² or more . If the surface hardness is less than 180 N / mm ² , the photoreceptor may be easily damaged. Even if there are no scratches that cannot be seen by microscopic observation, for example, if an external additive of the toner sinks into the photoreceptor, there is a possibility of filming, so the surface hardness is high. Is preferred. On the other hand, if the surface hardness is too high, it is difficult to remove and refresh the deteriorated portion of the photosensitive layer, and image characteristics and electrical characteristics may deteriorate over time, or the deterioration of the cleaning blade may be accelerated. is usually at 300N / mm ² or less, preferably 290 N / mm ² or less, and more preferably not more than 280N / mm ^2.

<Resin used for the outermost surface of the photoreceptor>
Examples of the resin for the outermost surface of the photosensitive layer for expressing the high elastic deformation rate include a polycarbonate resin containing 30% by mole or more of a polyester resin and a biphenol-based unit as a copolymerization component. As long as a photosensitive layer containing these resins on the outermost surface is provided, the layer structure is not particularly limited. Among these, a laminated type photoreceptor in which a charge generation layer and a charge transport layer are laminated is preferable.

(A) Polyester resin The polyester resin preferably contains a polyester resin represented by the following general formula [1] (also called a polyarylate resin in the case of a wholly aromatic polyester resin).

In the formula [1], Ar ^{1 to} Ar ⁴ each independently represent an arylene group which may have a substituent, and X represents a single bond, an oxygen atom, a sulfur atom, or a group represented by the following formula [2]. Or a group represented by the following formula [3], wherein R ¹ and R ² in the formula [2] each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R ¹ and R ² And R ³ in the formula [3] may be an alkylene group, an arylene group, or a group represented by the following formula [4], and in the formula [4] R ⁴ and R ⁵ in the formula independently represent an alkylene group, and Ar ⁵ represents an arylene group. k represents an integer of 0 or more.

In the formula [1], Y is a single bond, an oxygen atom, a sulfur atom, or a group represented by the following formula [5]. In the formula [5], R ⁶ and R ⁷ are each independently hydrogen. It represents an atom, an alkyl group, an alkoxy group, or an aryl group, and R ⁶ and R ⁷ may combine to form a ring.

In the above formula [1], Ar ^{1 to} Ar ⁴ each independently represents an arylene group which may have a substituent. As carbon number which an arylene group has, it is 6 or more normally, and the upper limit is 20 or less normally, Preferably it is 10 or less, More preferably, it is 6. If the number of carbon atoms is too large, the production cost increases and the electrical characteristics may deteriorate.
Specific examples of Ar ^{1 to} Ar ⁴ include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, naphthylene group, anthrylene group, phenanthrylene group, and the like. Among these, the arylene group is preferably a 1,4-phenylene group from the viewpoint of electrical characteristics. An arylene group may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.

Specific examples of the substituents for Ar ^{1 to} Ar ⁴ include an alkyl group, an aryl group, a halogen group, and an alkoxy group. Among them, considering the mechanical properties as a binder resin for the photosensitive layer and the solubility in the coating solution for forming the photosensitive layer, the alkyl group is preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group, and is preferably an aryl group. Is preferably a phenyl group or a naphthyl group, a halogen group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and an alkoxy group is preferably a methoxy group, an ethoxy group, a propoxy group or a butoxy group.

In addition, when a substituent is an alkyl group, carbon number of the alkyl group is usually 1 or more, and usually 10 or less, preferably 8 or less, more preferably 2 or less.
More specifically, Ar ³ and Ar ⁴ each independently preferably has a substituent number of 0 or more and 2 or less, more preferably has a substituent from the viewpoint of adhesion, and among these, substitution from the viewpoint of wear resistance. It is particularly preferable that the number of groups is one. Moreover, as a substituent, an alkyl group is preferable and a methyl group is particularly preferable.

From the above viewpoint, at least one of Ar ³ and Ar ⁴ is preferably an arylene group having a substituent.
On the other hand, Ar ¹ and Ar ² each independently preferably have 0 or more and 2 or less substituents, and more preferably have no substituents from the viewpoint of wear resistance.
In the formula [1], X is a single bond, an oxygen atom, a sulfur atom, a group represented by the following formula [2], or a group represented by the following formula [3], R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R ¹ and R ² may be bonded to form a ring such as a cycloalkylidene group. R ^{3 in} [3] is an alkylene group, an arylene group, or a group represented by the following formula [4], and R ⁴ and R ^{5 in} formula [4] are each independently an alkylene group. Ar ⁵ represents an arylene group.

In Formula [1], preferred X includes an oxygen atom, a sulfur atom, a structure represented by Formula [2], or a divalent organic residue having a structure represented by Formula [3].
Examples of the alkyl group of R ¹ and R ² in the formula [2] include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the aryl group include a phenyl group and a naphthyl group. In addition, examples of the cycloalkylidene group formed by combining R ¹ and R ² in the formula [2] include a cyclopentylidene group, a cyclohexylidene group, and a cycloheptylidene group. Furthermore, examples of the alkylene group represented by R ³ in the formula [3] include a methylene group, an ethylene group, and a propylene group. Examples of the arylene group represented by R ³ in the formula [3] include a phenylene group and a terphenylene group. Specific examples of the group represented by the formula [4] include a group represented by the following formula [6].

Among these, X is preferably an oxygen atom. At that time, k is preferably 1.
In the above formula [1], Y is a single bond, an oxygen atom, a sulfur atom, or a group represented by the above formula [5].
R ⁶ and R ⁷ in the formula [5] each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a cycloalkylidene group formed by combining R ⁶ and R ⁷ . Considering the mechanical properties as the binder resin for the photosensitive layer and the solubility in the coating solution for forming the photosensitive layer, R ⁶ and R ⁷ in the formula [5] are preferably phenyl groups and naphthyl groups as aryl groups, As an alkoxy group, a methoxy group, an ethoxy group, and a butoxy group are preferable. Moreover, as an alkyl group, a C1-C10 alkyl group is preferable, More preferably, it is C1-C8, Most preferably, it is C1-2. Considering the simplicity of production of the divalent hydroxyaryl component used for producing the polyester resin, Y is a single bond, —O—, —S—, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — and cyclohexylene are preferable, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — and cyclohexylene are particularly preferable, and —CH ₂ is particularly preferable. _{2 -, - CH (CH 3} ) - is.

In the electrophotographic photoreceptor used in the present invention, the polyester resin [1] is preferably a polyester resin having a repeating structure represented by the following general formula [7] when k = 1. In the following general formula [7], Ar ^{16 to} Ar ¹⁹ each independently represent an arylene group which may have a substituent, and R ⁸ represents a hydrogen atom or an alkyl group.

In the general formula [7], Ar ^{16 to} Ar ¹⁹ respectively correspond to the Ar ^{1 to} Ar ⁴ and particularly preferably a phenylene group which may have a substituent. Moreover, as a preferable substituent, it is a hydrogen atom or an alkyl group, Most preferably, it is a methyl group. Further, in the general formula [7], Ar ¹⁸ and Ar ¹⁹ are phenylene groups having a methyl group, and Ar ¹⁶ and Ar ¹⁷ are particularly preferably phenylene groups having no substituent. R ⁸ represents a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably a methyl group.
-Dicarboxylic acid residue The dicarboxylic acid component which is a dicarboxylic acid residue in the said polyester resin is represented by following General formula [8].

Ar ¹ , Ar ² , X, and k in the general formula [8] are as described above, and the dicarboxylic acid residues contained in the formula [8] are represented by the following general formulas [I] to [VI]. Examples of structures that can be illustrated. Here, k is an integer of 0 or more, but an integer of 0 to 5 is preferable from the viewpoint of electrical characteristics and scratch resistance, and more preferably 0 or 1.

  In the structure represented by the general formula [8], preferably, k is 1 and X is an oxygen atom, which is represented by the following general formula [9].

Specific examples of the preferable dicarboxylic acid residue represented by the general formula [9] include diphenyl ether-2,2′-dicarboxylic acid residue, diphenyl ether-2,3′-dicarboxylic acid residue, diphenyl ether-2,4 ′. -Dicarboxylic acid residue, diphenyl ether-3,3'-dicarboxylic acid residue, diphenyl ether-3,4'-dicarboxylic acid residue, diphenyl ether-4,4'-dicarboxylic acid residue and the like. Among these, considering the simplicity of production of the dicarboxylic acid component, diphenyl ether-2,2′-dicarboxylic acid residue, diphenyl ether-2,4′-dicarboxylic acid residue, diphenyl ether-4,4′-dicarboxylic acid Residues are more preferred, and diphenyl ether-4,4′-dicarboxylic acid residues are particularly preferred.

Specific examples of the dicarboxylic acid residue represented by the general formula [8] and k = 0 include phthalic acid residue, isophthalic acid residue, terephthalic acid residue, toluene-2,5-dicarboxylic acid residue P-xylene-2,5-dicarboxylic acid residue, naphthalene-1,4-dicarboxylic acid residue, naphthalene-2,3-dicarboxylic acid residue, naphthalene-2,6-dicarboxylic acid residue, biphenyl-2 , 2′-dicarboxylic acid residue, biphenyl-4,4′-dicarboxylic acid residue, preferably phthalic acid residue, isophthalic acid residue, terephthalic acid residue, naphthalene-1,4
-Dicarboxylic acid residue, naphthalene-2,6-dicarboxylic acid residue, biphenyl-2,2'-
A dicarboxylic acid residue, a biphenyl-4,4′-dicarboxylic acid residue, particularly preferably
It is an isophthalic acid residue or a terephthalic acid residue, and it is also possible to use a combination of these dicarboxylic acid residues. Specific examples of the preferable polyester resin having a carboxylic acid residue represented by the general formula [8] include those containing a structural unit represented by the following formula [10]. The ratio of isophthalic acid residue to terephthalic acid residue is usually 50:50, but can be arbitrarily changed. In that case, the higher the ratio of terephthalic acid residues, the better from the viewpoint of electrical characteristics.

  The polyester resin may be a resin that contains another dicarboxylic acid component and includes the general formula [8] in a part of the structure. Specific examples of other dicarboxylic acid residues include adipic acid residues, suberic acid residues, sebacic acid residues, pyridine-2,3-dicarboxylic acid residues, pyridine-2,4-dicarboxylic acid residues, pyridine -2,5-dicarboxylic acid residue, pyridine-2,6-dicarboxylic acid residue, pyridine-3,4-dicarboxylic acid residue, pyridine-3,5-dicarboxylic acid residue, preferably, These are adipic acid residues and sebacic acid residues, and a plurality of these dicarboxylic acid residues can be used in combination.

  In addition, when it has dicarboxylic acid residue [8] which comprises the polyester resin used for the electrophotographic photoreceptor used for this invention, and the other dicarboxylic acid residue mentioned above, the electrophotographic photoreceptor used for this invention The dicarboxylic acid residue [8] constituting the polyester resin used in the above is preferably 70% or more, more preferably 80% or more, particularly 90% or more as the number of repeating units. preferable. Most preferably, when having only the dicarboxylic acid residue [8] constituting the polyester resin used in the electrophotographic photoreceptor used in the present invention, that is, the dicarboxylic acid residue [8] constituting the polyester resin is In this case, the number of repeating units is 100%.

(B) Polycarbonate resin As the resin for the outermost surface of the photosensitive layer for expressing the high elastic deformation rate, in addition to the above-mentioned polyester resin, 30 mol% or more of a biphenol-based unit represented by the following general formula [11] The polycarbonate resin contained as a copolymerization component is mentioned.

In the general formula [11], R ^{11 to} R ¹⁸ each independently represents a hydrogen atom or an alkyl group. Those having all hydrogen atoms or having 1 to 4 substituents of methyl, ethyl, and isopropyl groups as substituents are preferred. From the viewpoint of resin production, it is preferred to have alkyl groups symmetrically. Preferred examples of the general formula [11] are listed below. Of these, A-1, A-2, and A-3 are preferable, and A-1 is most preferable.

  The polycarbonate resin used in the electrophotographic photosensitive member used in the present invention is a homopolymer consisting of a single unit represented by the general formula [11], and the structure is too rigid and the solubility in an organic solvent is low. Since the reaction is difficult, it is used in block or random copolymerization with other bisphenol units. Examples of bisphenol units to be copolymerized are shown below. Among these, from the viewpoint of solubility, B-1, B-2, B-3, B-4, B-5, B-7, B-10, B-11, and B-14 are preferable, and the central carbon is used. B-2 and B-5 to which different substituents are bonded are more preferable. From the viewpoint of mechanical properties, B-1, B-2, B-4, B-5, B-7, B-10, and B-14 are more preferable. The copolymerization ratio increases the elastic deformation rate of the photosensitive layer as the number of units represented by the general formula (7) increases. On the other hand, since the production of the resin and the production of the coating solution become difficult, the proportion is 30 mol. % Or more and 50 mol% or less is preferable, more preferably 30 mol% or more and 40 mol% or less, still more preferably 32 mol% or more and 38 mol% or less.

<Molecular weight>
In the above-described polyester resin and polycarbonate resin, the viscosity average molecular weight is arbitrary as long as the effect of the present invention is not significantly impaired, but is preferably 10,000 or more, more preferably 20,000 or more, and the upper limit is Preferably, it is 70,000 or less, more preferably 50,000 or less. If the value of the viscosity average molecular weight is too small, the mechanical strength of the photosensitive layer may be insufficient, and if it is too large, the viscosity of the coating solution for forming the photosensitive layer may be too high and the productivity may decrease. is there. In addition, a viscosity average molecular weight can be measured by the method as described in an Example using an Ubbelohde type capillary viscometer etc., for example.

Next, constituent elements of the photoreceptor will be described.
As the conductive support, the anodic oxide layer, and the undercoat layer, known examples such as those disclosed in Japanese Patent Application Laid-Open No. 2009-186967 can be used.
(Photosensitive layer)
As the type of the photosensitive layer, a charge generation material and a charge transport material are present in the same layer and are dispersed in a binder resin, a charge generation layer in which a charge generation material is dispersed in a binder resin, and a charge. Examples include a functional separation type (laminated type) composed of two layers of a charge transport layer in which a transport material is dispersed in a binder resin. The photosensitive layer of the electrophotographic photosensitive member used in the present invention is of any type. May be.

In addition, as the laminated photosensitive layer, a charge-generating layer and a charge transport layer are laminated in this order from the conductive support side, and conversely, a charge transport layer and a charge generation layer are formed from the conductive support side. There are reverse laminated photosensitive layers provided in order, and any of them can be adopted, but a forward laminated photosensitive layer that can exhibit the most balanced photoconductivity is preferable.
In order to make the surface of the photosensitive layer have a high elastic modulus, the polyester resin represented by the general formula [1] or the biphenol-based unit represented by the general formula [11] is a copolymer component of 30 mol% or more. Is contained in the binder resin in the outermost surface layer of the photoreceptor, preferably 30% by weight or more, more preferably 50% by weight or more, and still more preferably 80 to 100% by weight.

(Laminated photosensitive layer)
-Charge generation layer About a charge generation layer, well-known, for example, the example currently disclosed by Unexamined-Japanese-Patent No. 2009-186967 can be used.
-Charge transport layer The charge transport layer of the multilayer photoconductor contains a charge transport material, a binder resin, and other components used as necessary. Specifically, such a charge transport layer is prepared by dissolving or dispersing a charge transport material or the like and a binder resin in a solvent to prepare a coating solution. In addition, in the case of a reverse lamination type photosensitive layer, it can be obtained by coating and drying on a conductive support (on the undercoat layer when an undercoat layer is provided).

  As the charge transport material, a known carbazole derivative, hydrazone compound, aromatic amine derivative, enamine derivative, butadiene derivative, and a material in which a plurality of these derivatives are bonded are preferable. More specifically, it is described in JP-A-2-230255, JP-A-63-225660, JP-A-58-198043, JP-B-58-32372, and JP-B-7-21646. Compounds are preferably used. Any one of these charge transport materials may be used alone, or a plurality of types may be used in any combination.

The thickness of the charge transport layer is not particularly limited, but is usually 5 μm or more, preferably 10 μm or more, and usually 50 μm or less, preferably 45 μm or less, from the viewpoint of long life, image stability, and high resolution. Is in the range of 30 μm or less.
<Other functional layers>
For the purpose of improving film-forming properties, flexibility, coating properties, stain resistance, gas resistance, light resistance, etc., in both the photosensitive layer and each layer constituting it, both in the multilayer type photosensitive member and the single layer type photosensitive member. Additives such as well-known antioxidants, plasticizers, ultraviolet absorbers, electron-withdrawing compounds, leveling agents, and visible light shielding agents may be included.

  Further, in both the laminated type photoreceptor and the single layer type photoreceptor, the photosensitive layer formed by the above procedure may be the uppermost layer, that is, the surface layer, but another layer may be provided on the photosensitive layer and used as the surface layer. Good. For example, a protective layer may be provided for the purpose of preventing the photosensitive layer from being worn out or preventing or reducing the deterioration of the photosensitive layer due to discharge products generated from a charger or the like. The protective layer can be formed by including the charge transport material used for the charge transport layer or other conductive material in the binder resin of the present application. When the outermost layer is a protective layer, a polyester resin is used in the protective layer.

<Outermost layer and toner adhesion>
The toner particles having a sea-island structure as used in the present invention have a high storage elastic modulus. It becomes easy to do. In addition, since the crystalline resin contained in the toner used in the present invention has a low melting point and is mechanically soft, if it is exposed on the surface of the toner particles, it will be deformed on the surface of the photoreceptor as if it were an adhesive. Therefore, it is not always a good idea to increase the contact pressure of the cleaning blade. It is more effective to increase the elastic deformation rate of the photoconductor and reduce the contact area of the toner. It is.

In order to control the surface physical properties of the photoreceptor, it has been proposed to put an inorganic filler on the outermost surface or to provide a curable protective layer on the outermost surface. However, when an inorganic filler is added, the microscopic uniformity is insufficient, and the grain boundary may cause brittle fracture during fatigue, or the inorganic filler may wear the cleaning blade. In addition, in the case where the surface is made of a curable resin, there is a problem that the surface-modified degradation product due to discharge products or ozone is not cleaned and removed because the curable resin is not easily worn, and is used in the present invention. It is difficult to use the toner with a durable toner. Since the photoreceptor used in the present invention is moderately worn and the surface is constantly refreshed, there are hardly any side effects due to such discharge products or deterioration-modified products. In addition, since the curing reaction such as crosslinking does not proceed 100% in the curable resin, there is always an unreacted residue, so that part is another component in the outermost layer or other member such as a cleaning blade. Chemical reactions with components can lead to image defects.

<Method for forming each layer>
Each layer constituting the above-described photoreceptor is formed by dip coating, spray coating, nozzle coating, bar coating, roll coating, blade coating on a conductive support obtained by dissolving or dispersing a substance to be contained in a solvent. It is formed by repeating a coating / drying step sequentially for each layer by a known method such as coating.

<Image forming apparatus>
Next, an embodiment of an image forming apparatus having the toner and the electrophotographic photosensitive member used in the present invention (an image forming apparatus of the present invention) will be described with reference to FIG. However, the embodiment is not limited to the following description, and can be arbitrarily modified without departing from the gist of the present invention.

As shown in FIG. 1, the image forming apparatus includes an electrophotographic photosensitive member 1, a charging device 2, an exposure device 3, and a developing device 4, and further, a transfer device 5, a cleaning device 6, and a fixing device as necessary. A device 7 is provided.
The electrophotographic photosensitive member 1 is not particularly limited as long as it is the above-described electrophotographic photosensitive member. In FIG. 1, as an example, a drum-shaped photosensitive member in which the above-described photosensitive layer is formed on the surface of a cylindrical conductive support. Showing the body. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5, and a cleaning device 6 are arranged along the outer peripheral surface of the electrophotographic photoreceptor 1.

  The charging device 2 charges the electrophotographic photosensitive member 1 and uniformly charges the surface of the electrophotographic photosensitive member 1 to a predetermined potential. As the charging device, a corona charging device such as a corotron or a scorotron, a direct charging device (contact type charging device) for charging a direct charging member to which a voltage is applied by contacting the photosensitive member surface, and the like are often used. Examples of the direct charging device include a charging roller and a charging brush. In FIG. 1, a roller-type charging device (charging roller) is shown as an example of the charging device 2. As the direct charging means, either charging with air discharge or injection charging without air discharge is possible. Moreover, as a voltage applied at the time of charging, it is possible to use only a direct current voltage or to superimpose an alternating current on a direct current.

  The type of the exposure apparatus 3 is not particularly limited as long as it can expose the electrophotographic photoreceptor 1 to form an electrostatic latent image on the photosensitive surface of the electrophotographic photoreceptor 1. Specific examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He—Ne lasers, LEDs, and the like. Further, exposure may be performed by a photoreceptor internal exposure method. The light used for the exposure is arbitrary. For example, if exposure is performed with monochromatic light with a wavelength of 780 nm, monochromatic light with a wavelength of 600 nm to 700 nm, slightly shorter wavelength, monochromatic light with a wavelength of 380 nm to 500 nm, or the like. Good.

The type of the developing device 4 is not particularly limited, and an arbitrary device such as a dry development method such as cascade development, one-component insulating toner development, one-component conductive toner development, or two-component magnetic brush development, or a wet development method is used. be able to. In FIG. 1, the developing device 4 includes a developing tank 41, an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45, and has a configuration in which toner T is stored inside the developing tank 41. . Further, a replenishing device (not shown) for replenishing the toner T may be attached to the developing device 4 as necessary. This replenishing device is configured to be able to replenish toner T from a container such as a bottle or a process cartridge.

The supply roller 43 is formed from a conductive sponge or the like. The developing roller 44 is made of a metal roll such as iron, stainless steel, aluminum, or nickel, or a resin roll obtained by coating such a metal roll with a silicon resin, a urethane resin, a fluorine resin, or the like. The surface of the developing roller 44 may be smoothed or roughened as necessary.
The developing roller 44 is disposed between the electrophotographic photoreceptor 1 and the supply roller 43 and is in contact with the electrophotographic photoreceptor 1 and the supply roller 43, respectively. The supply roller 43 and the developing roller 44 are rotated by a rotation drive mechanism (not shown). The supply roller 43 carries the stored toner T and supplies it to the developing roller 44. The developing roller 44 carries the toner T supplied by the supply roller 43 and contacts the surface of the electrophotographic photosensitive member 1.

  The regulating member 45 is formed of a resin blade such as silicon resin or urethane resin, a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze, or a blade obtained by coating such a metal blade with a resin. The regulating member 45 contacts the developing roller 44 and is pressed against the developing roller 44 side with a predetermined force by a spring or the like (a general blade linear pressure is 5 to 500 g / cm). If necessary, the regulating member 45 may be provided with a function of imparting charging to the toner T by frictional charging with the toner T.

The agitator 42 is rotated by a rotation driving mechanism, and agitates the toner T and conveys the toner T to the supply roller 43 side. A plurality of agitators 42 may be provided with different blade shapes and sizes.
The type of the transfer device 5 is not particularly limited, and an apparatus using an arbitrary system such as an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method can be used. . Here, it is assumed that the transfer device 5 includes a transfer charger, a transfer roller, a transfer belt, and the like disposed so as to face the electrophotographic photoreceptor 1. The transfer device 5 applies a predetermined voltage value (transfer voltage) having a polarity opposite to the charging potential of the toner T, and transfers the toner image formed on the electrophotographic photosensitive member 1 to a recording paper (paper, medium) P. Is.

  There is no restriction | limiting in particular about the cleaning apparatus 6, Arbitrary cleaning apparatuses, such as a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, can be used. The cleaning device 6 is for scraping off residual toner adhering to the photoreceptor 1 with a cleaning member and collecting the residual toner. However, when there is little or almost no toner remaining on the surface of the photoreceptor, the cleaning device 6 may be omitted.

  The fixing device 7 includes an upper fixing member (fixing roller) 71 and a lower fixing member (fixing roller) 72, and a heating device 73 is provided inside the fixing member 71 or 72. FIG. 1 shows an example in which a heating device 73 is provided inside the upper fixing member 71. The upper and lower fixing members 71 and 72 are known heat fixings such as a fixing roll in which a metal base tube such as stainless steel or aluminum is coated with silicon rubber, a fixing roll in which Teflon (registered trademark) resin is coated, or a fixing sheet. A member can be used. Further, each of the fixing members 71 and 72 may be configured to supply a release agent such as silicon oil in order to improve releasability, or may be configured to forcibly apply pressure to each other by a spring or the like.

When the toner transferred onto the recording paper P passes between the upper fixing member 71 and the lower fixing member 72 heated to a predetermined temperature, the toner is heated to a molten state and cooled after passing through the recording paper. Toner is fixed on P.
The type of the fixing device is not particularly limited, and a fixing device of an arbitrary method such as heat roller fixing, flash fixing, oven fixing, pressure fixing, or the like can be provided.

In the electrophotographic apparatus configured as described above, an image is recorded as follows. That is, first, the surface (photosensitive surface) of the photoreceptor 1 is charged to a predetermined potential (for example, −600 V) by the charging device 2. At this time, charging may be performed by a DC voltage, or charging may be performed by superimposing an AC voltage on the DC voltage.
Subsequently, the photosensitive surface of the charged photoreceptor 1 is exposed by the exposure device 3 according to the image to be recorded, and an electrostatic latent image is formed on the photosensitive surface. The developing device 4 develops the electrostatic latent image formed on the photosensitive surface of the photoreceptor 1.

The developing device 4 thins the toner T supplied by the supply roller 43 with a regulating member (developing blade) 45 and has a predetermined polarity (here, the same polarity as the charging potential of the photosensitive member 1) and the negative polarity. ), And conveyed while being carried on the developing roller 44 to be brought into contact with the surface of the photoreceptor 1.
When the charged toner T carried on the developing roller 44 comes into contact with the surface of the photoreceptor 1, a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the photoreceptor 1. This toner image is transferred onto the recording paper P by the transfer device 5. Thereafter, the toner remaining on the photosensitive surface of the photoreceptor 1 without being transferred is removed by the cleaning device 6.

After the transfer of the toner image onto the recording paper P, the final image is obtained by passing the fixing device 7 and thermally fixing the toner image onto the recording paper P.
In addition to the above-described configuration, the image forming apparatus may be configured to perform, for example, a static elimination process. The neutralization step is a step of neutralizing the electrophotographic photosensitive member by exposing the electrophotographic photosensitive member, and a fluorescent lamp, an LED, or the like is used as the neutralizing device. In addition, the light used in the static elimination process is often light having an exposure energy that is at least three times that of the exposure light.

The image forming apparatus may be further modified. For example, the image forming apparatus may be configured to perform a pre-exposure process, an auxiliary charging process, or the like, or may be configured to perform offset printing. A full-color tandem system configuration using toner may be used.
The electrophotographic photosensitive member 1, the charging device 2, the exposure device 3, the developing device 4, the transfer device 5, the cleaning device 6, and the fixing device 7 are combined with one or two or more for an integrated electrophotography. It may be configured as a process cartridge (hereinafter referred to as “cartridge” as appropriate), and this cartridge may be configured to be detachable from a main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. For example, the electrophotographic photosensitive member 1, the charging device 2, the developing device 4, the transfer device 5, and the integrated cartridge incorporating the cleaning device 6, or the electrophotographic photosensitive member 1, the charging device 2, and the cleaning device 6 are integrated. There is a type in which a cartridge is used and the developing device 4 is a separate cartridge. In these cartridges, for example, when the electrophotographic photosensitive member 1 is deteriorated or the toner in the developing device 4 is consumed and lost, the cartridge is removed from the image forming apparatus main body, and another new cartridge is removed. By attaching to the main body, maintenance and management of the image forming apparatus are facilitated.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the following examples, “part” means “part by mass”.
First, regarding the toner used in the present invention, each particle diameter, circularity, thermal characteristics, weight average molecular weight, and the like were measured as follows.

<Volume average diameter measurement (MV)>
The volume average diameter (MV) of particles with a volume average diameter (MV) of less than 1 micron is from Nikkiso Co., Ltd. Model Microtrac Nanotrac150 (hereinafter abbreviated as Nanotrack) and analysis software Microtrac Particle Analyzer Ver10.1.2-019EE The method described in the instruction manual using the ion-exchanged water having an electric conductivity of 0.5 μS / cm as the solvent, the solvent refractive index: 1.333, the measuring time: 600 seconds, and the number of times of measurement: once. Measured with Other setting conditions were particle refractive index: 1.59, transparency: transmission, shape: true sphere, density: 1.04.

<Volume median diameter measurement (Dv50)>
The volume median diameter (Dv50) of the particles with a volume median diameter (Dv50) of 1 micron or more is measured by using the Beckman Coulter Multisizer III (aperture diameter 100 μm: hereinafter abbreviated as Multisizer). Using II as a dispersion medium, the dispersion was dispersed so that the dispersoid concentration was 0.03%.

<Average circularity>
The “average circularity” in the toner used in the present invention is measured as follows and is defined as follows. That is, the toner base particles are dispersed in a dispersion medium (Isoton II, manufactured by Beckman Coulter, Inc.) so as to be in the range of 5720 to 7140 particles / μL, and a flow particle image analyzer (manufactured by Sysmex Corporation, FPIA 3000) is used. Measured under the following apparatus conditions, the value is defined as “average circularity”. In the toner used in the present invention, the same measurement is performed three times, and an arithmetic average value of three “average circularity” is adopted as the “average circularity”.
・ Mode: HPF
-HPF analysis amount: 0.35 μL
-Number of HPF detected: 8,000-10,000 The following are measured by the above device and automatically calculated and displayed in the above device, but "roundness" is defined by the following formula The

[Circularity] = [Perimeter of a circle with the same area as the projected particle area] / [Perimeter of projected particle image]
Then, the number of HPF detected is 8,000 to 10,000, and the arithmetic average (arithmetic mean) of the circularity of each particle is displayed on the apparatus as “average circularity”.
<Thermal characteristics>
Main peak of the endothermic curve when the temperature is increased from 30 ° C to 120 ° C at a rate of 10 ° C / min using the Seiko Electronics Co., Ltd. thermal analyzer DSC220CU. Measure the melting point, heat of fusion, half-width of melting peak, and then measure the crystallization temperature and half-width of crystallization peak from the exothermic curve when the temperature was lowered from 120 ° C to 30 ° C at a rate of 10 ° C / min. did.

<Weight average molecular weight (Mw)>
The THF-soluble component of the polymer primary particle dispersion was measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC apparatus HLC-8020 manufactured by Tosoh Corporation, column: PL-gel Mixed-B 10 μ manufactured by Polymer Laboratories, solvent: THF, sample concentration: 0.1% by mass, calibration curve: standard polystyrene The toner used in the present invention is It was manufactured as follows.

<1> Crystalline long chain (meth) acrylic acid ester toner <Preparation of emulsion A1>
100 parts behenyl acrylate, 25 parts paraffin wax (Nippon Seiwa Co., Ltd., HNP-9, melting point 82 ° C.), 20% sodium dodecylbenzenesulfonate aqueous solution (Daiichi Kogyo Seiyaku Co., Ltd., Neogen S20D, 20% below) (Abbreviated as DBS aqueous solution) 1.1 parts and 359 parts of demineralized water 9
The mixture was heated to 0 ° C. and stirred for 10 minutes using a homomixer (Mark IIf model manufactured by Tokushu Kika Kogyo Co., Ltd.). Next, under heating at 90 ° C., circulation emulsification is started under a pressure of 20 MPa using a high pressure emulsifier, and the particle diameter is measured with Nanotrac and dispersed until the volume average particle diameter (MV) is 500 nm or less. An emulsion A1 was prepared. The final particle size (MV) was 277 nm.

<Preparation of polymer primary particle dispersion C1>
<First step>
A reactor equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device, 194.8 parts of emulsion A1 and 197 parts of demineralized water (monomer added in the second step) And the temperature was raised to 90 ° C. under a nitrogen stream while stirring.

Thereafter, 4.16 parts of an 8% aqueous hydrogen peroxide solution and an 8% L-(+) ascorbic acid aqueous solution were added while stirring was continued. G '(Tm + 20) of the freeze-dried latex product obtained in the first step
Was 6.8 × 10 ⁻¹ Pa.
<Second step>
The following monomer / emulsifier mixture was added to the liquid of the first step over 5 hours. Simultaneously with the start of dropping of the mixture of monomers and emulsifier solution, dropping of the following aqueous initiator solution 1 was also started. Thereafter, the aqueous initiator solution 2 was further added over 2 hours. Thereafter, the inner temperature was maintained at 90 ° C. for 1 hour under stirring.
[Monomers]
Styrene 76.3 parts Butyl acrylate 23.7 parts Acrylic acid 1.5 parts Hexanediol diacrylate 1.0 part Trichlorobromomethane 1.0 part [Emulsifier aqueous solution]
20% DBS aqueous solution 1.0 part demineralized water 67.3 parts [initiator aqueous solution 1]
8% aqueous hydrogen peroxide solution 17.2 parts 8% L-(+) ascorbic acid aqueous solution 17.2 parts [initiator aqueous solution 2]
8% L-(+) Ascorbic acid aqueous solution 14.2 parts After the completion of the polymerization reaction, the mixture was cooled to obtain a milky white primary polymer particle dispersion C1. The volume average particle diameter (MV) measured using a nanotrack was 245 nm. The weight average molecular weight (Mw) was 75,000.

<Manufacture of toner mother particles E1>
A mixer equipped with a stirrer (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device was charged with 80 parts (solid content) of polymer primary particle dispersion C1 and the internal temperature was set to 26 ° C. Then, 0.05 parts (solid content) of 20% DBS aqueous solution was added and mixed uniformly. Further, a 5% aqueous solution of ferrous sulfate (0.53 parts as FeSO ₄ .7H ₂ O) was added over 5 minutes, and stirring was continued for 5 minutes to mix uniformly. Subsequently, 4.4 parts (solid content) of cyan pigment dispersion (EP750 manufactured by Dainichi Seika Co., Ltd.) was added over 5 minutes and mixed uniformly, and then 100 parts of demineralized water was added dropwise. During this time, the internal temperature was kept at 26 ° C. Thereafter, the temperature was raised to 51 ° C. over 40 minutes, and further raised to 53 ° C. over 30 minutes. Here, the volume median particle size (Dv50) was measured using a multisizer, and it was 4.9 μm. Thereafter, the polymer primary particle dispersion C1 was added over 20 minutes over 20 minutes.
(Solid content) added and held for 30 minutes, then 6 parts of 20% DBS aqueous solution (solid content) added over 10 minutes, then heated to 95 ° C. over 60 minutes and held for 30 minutes did.

  Thereafter, the slurry obtained by cooling to 30 ° C. over 20 minutes was extracted, and suction filtered with an aspirator using 5 types C (No. 5C, manufactured by Toyo Roshi Kaisha, Ltd.). The cake remaining on the filter paper is transferred to a stainless steel container with an internal volume of 10 L equipped with a stirrer (propeller blade), added with 8 kg of ion-exchanged water having an electric conductivity of 1 μS / cm, and uniformly dispersed by stirring at 50 rpm. Thereafter, stirring was continued for 30 minutes.

  After that, using 5 C filter paper again, suction filtration with an aspirator, the solid matter remaining on the filter paper was again equipped with a stirrer (propeller blade), containing 8 kg of ion-exchanged water with an electric conductivity of 1 μS / cm The product was transferred to a stainless steel container having a volume of 10 L and uniformly dispersed by stirring at 50 rpm, and stirring was continued for 30 minutes. When this process was repeated 5 times, the electrical conductivity of the filtrate was 2 μS / cm.

The obtained cake was spread on a stainless steel bat so as to have a height of 20 mm, and dried in a blow dryer set at 40 ° C. for 48 hours to obtain toner mother particles E1.
The volume median particle size (Dv50) of the toner base particles E1 measured using Multisizer III is 5.
The average circularity measured by a flow type particle analyzer was 0.971.
<Manufacture of developing toner F1>
Into Kyoritsu Riko Co., Ltd. sample mill KR-3, 100 parts of toner base particles E1 were introduced.
Subsequently, 2.04 parts of colloidal silica having a volume average primary particle diameter of 80 nm and 0.36 parts of large particle diameter silica having a volume average primary particle diameter of 30 nm were added and stirred and mixed for a total of 5 minutes. Thereafter, 0.30 part of titania particles having a volume average primary particle size of 250 nm treated with alumina and 0.76 part of small particle size silica having a volume average primary particle size of 10 nm are added, stirred and mixed for a total of 6 minutes, and sieved. Thus, developing toner F1 was obtained.

When the cross section of the toner F1 is observed by TEM, the first polymer has a sea-island structure in which a second polymer mainly composed of a long-chain (meth) acrylic acid ester polymer is dispersed, and It was confirmed that at least one island of the second polymer had a sea-island structure with the sea as the third polymer and the island as the third polymer.
<Preparation of emulsion A2>
An emulsion A2 was prepared in the same manner as A1, except that the composition was 100 parts behenyl acrylate, 100 parts stearyl acrylate, 2.2 parts 20% DBS aqueous solution, and 798 parts demineralized water. The final particle size (MV) was 360 nm.

<Preparation of emulsion A3>
The composition is 100 parts paraffin wax (Nippon Seiwa Co., Ltd., HNP-9, melting point 82 ° C.), 6.91 parts stearyl acrylate, 3.3 parts decaglycerin decabehenate (acid value 3.2, hydroxyl value 27). An emulsion A3 was prepared in the same manner as A1, except that 1.415 parts of 20% DBS aqueous solution and 255.9 parts of demineralized water were used. The final particle size (MV) was 225 nm.

<Preparation of polymer primary particle dispersion C2>
Polymer primary particle dispersion C2 was obtained in the same manner as C1, except that 181.6 parts of emulsion A2 and 41.8 parts of emulsion A3 were used instead of emulsion A1, and the amount of water was 199 parts. . The volume average particle diameter (MV) is 230 nm, and the weight average molecular weight (Mw) is 57,000.

<Manufacture of toner mother particles E2>
Using C2 instead of the polymer primary particle dispersion C1, the temperature was raised to 52 ° C. over 40 minutes,
Further, toner mother particles E2 were obtained in the same manner as E1, except that the temperature was raised to 55 ° C. over 60 minutes. The volume median particle size (Dv50) was 5.4 μm, and the average circularity measured by a flow particle analyzer was 0.972.

<Manufacture of developing toner F2>
A developing toner F2 was obtained in the same manner as F1, except that E2 was used instead of the toner base particles E1.
When the cross section of the toner F2 is observed by TEM, it has a sea-island structure in which a second polymer mainly composed of a long-chain (meth) acrylic acid ester polymer is dispersed in the first polymer, and It was confirmed that at least one island of the second polymer had a sea-island structure with the sea as the third polymer and the island as the third polymer.

<Preparation of polymer primary particle dispersion C3>
A polymer primary particle dispersion C3 was obtained in the same manner as in C1, except that the 8% aqueous hydrogen peroxide solution and the 8% L-(+) ascorbic acid aqueous solution in the first step were not added. The volume average particle size (MV) was 234 nm and the weight average molecular weight (Mw) was 40,000.
<Manufacture of toner mother particles E3>
Toner base particles E3 were produced in the same manner as E1 except that C3 was used in place of the polymer primary particle dispersion C1, but they aggregated during drying and were not at a level that could be used as toner base particles. The reason for the agglomeration is that C3 is not polymerized and styrene acrylic is copolymerized in the second step, so that the resulting random copolymer is a low Tm and low Tg polymer. Conceivable. When the cross section of the toner base particle E3 was observed with TEM, a clear sea-island structure was not observed.

<Preparation of polymer primary particle dispersion C4>
A reactor equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device was charged with 100 parts of emulsion A1, and the temperature was raised to 90 ° C. in a nitrogen stream while stirring. . Thereafter, 4.16 parts of an 8% aqueous hydrogen peroxide solution and an 8% L-(+) ascorbic acid aqueous solution were added while stirring was continued to obtain a polymer primary particle dispersion C4.

<Preparation of polymer primary particle dispersion C5>
The emulsion A3 was used in place of the emulsion A1, and the mixture of monomers and emulsifier solution was added over 5 hours without adding the 8% aqueous hydrogen peroxide solution and the 8% L-(+) ascorbic acid aqueous solution. In the same manner as in C1, a polymer primary particle dispersion C5 was obtained. The volume average particle diameter (MV) is 210 nm, and the weight average molecular weight (Mw) is 55,000.

<Manufacture of toner mother particle E4>
Toner mother particles E4 were obtained in the same manner as in E1, except that a mixed liquid of C4 and C5 was used instead of the polymer primary particle dispersion C1. The volume median particle size (Dv50) was 7.2 μm, and the average circularity measured by a flow particle analyzer was 0.924.
<Manufacture of development toner F4>
A developing toner F4 was produced in the same manner as F1 except that E4 was used in place of the toner base particles E1, but the silica fine particles were repelled by the toner base particles and were not at a level usable as a developing toner. . The reason why the silica fine particles were repelled by the toner base particles is that C4 and C5 co-aggregated, so that C4 as the first polymer is considerably present on the surface of E1 (also confirmed by cross-sectional TEM). .

<2> Crystalline polyester toner <Polyester Production Example 1: Polyester A>
Bisphenol A propylene oxide average 2.2 mol adduct (BPA-PO), dimethyl terephthalate (TPM), dimethyl fumarate (FM), tetrabutoxy titanium (CT) in the following amounts,
It put into the pressure reduction reactor with the torque meter, and it heated, stirring up to 180 degreeC under nitrogen sealing so that it might not bump. The reaction was carried out at normal pressure to 10 kPa for 3 hours, and the alcohol produced at this time was extracted out of the system.
Subsequently, it was heated to ~ 220 ° C. The degree of vacuum was gradually raised and reacted at 6 kPa for 2 hours to obtain a polyester resin.
BPO-PO 1.00 mol
TPM 0.95 mol
FM 0.05 mol
CT 0.01 mol The obtained polyester had a molecular weight (Mw) of 14,000 and a Tg of 58 ° C.

<Production Example 2 of Polyester: Polyester B>
The same operation as in Production Example 1 for polyester was performed to obtain a polyester having the following composition. The obtained polyester had Mw of 7,200 and Tg of 65 ° C.
BPO-PO 1.00 mol
TPM 1.10 mol trimellitic anhydride 0.05 mol
CT 0.01 mol <Example of vinyl resin production: Vinyl resin A>
4 parts by mass of benzoyl peroxide was dissolved in a mixed solution of 80 parts by mass of styrene and 20 parts by mass of butyl acrylate, and placed in a polymerization apparatus. Subsequently, 200 parts by mass of deionized water in which 0.2 parts by mass of polyvinylpyrrolidone (manufactured by BASF, Rubiscol K90) was dissolved was added and reacted at 90 ° C. for 6 hours with stirring. Thereafter, dehydration and drying were performed to obtain a styrene / butyl acrylate copolymer resin. The resin had an Mw of 22,000 and a Tg of 62 ° C.

<Production Example 1 of Polyester Modified with Vinyl Resin 1: Modified Polyester A Solution>
100 parts by mass of the polyester A produced above was dissolved in 190 parts by mass of methyl ethyl ketone and put into a polymerization apparatus. Subsequently, 10 parts by mass of styrene and 0.4 part by mass of benzoyl peroxide were added and reacted under reflux (80 ° C.) for 10 hours. The resulting resin had an Mw of 35,000 and this increase in molecular weight indicates that polyester A was copolymerized with styrene as a graftmer. Tg was 62 ° C.

<Production Example 2 of Polyester Modified with Vinyl Resin: Modified Polyester B Solution>
100 parts by mass of the polyester B produced above was put in a vacuum reactor. Subsequently, 20 parts by mass of the vinyl resin A produced above was added, and a transesterification reaction was performed for 2 hours at 200 ° C. and 6 kPa with stirring to obtain a modified polyester resin. Mw of the obtained resin is 65,000, and this increase in molecular weight indicates that polyester resin B was copolymerized by transesterification of vinyl resin A. Tg was 65 ° C.

<Production Example 1 of Crystalline Polyester: Crystalline Polyester A>
A composition having 1 mol of 1,6-hexanediol, 0.95 mol of sebacic acid, and 0.01 mol of CT and having a Mw of 6,800 and a melting point of 60 ° C. by the condensation polymerization reaction in the same procedure as in polyester production example 1. Polyester was obtained.
<Production Example 2 of Crystalline Polyester: Crystalline Polyester B>
Placel H1P (molecular weight 10,000, melting point 60 ° C.) manufactured by Daicel Corporation was used.

<Preparation of emulsion G1>
100 parts by mass of crystalline polyester A, 25 parts by mass of paraffin wax (Nippon Seiwa Co., Ltd., HNP-9, melting point 82 ° C.), 20% sodium dodecylbenzenesulfonate aqueous solution (Daiichi Kogyo Seiyaku Co., Ltd., Neogen S20D, (Hereinafter abbreviated as 20% DBS aqueous solution) 1.1 parts by mass, demineralized water 35
Nine parts were heated to 90 ° C. and stirred for 10 minutes using a homomixer (Mark IIf model, manufactured by Tokushu Kika Kogyo Co., Ltd.). Next, under heating at 90 ° C., circulation emulsification is started under a pressure of 20 MPa using a high pressure emulsifier, and the particle diameter is measured with Nanotrac and dispersed until the volume average particle diameter (MV) is 500 nm or less. Emulsion G1 was prepared. The final particle size (MV) was 265 nm.

<Preparation of emulsion G2>
100 parts by weight of crystalline polyester B, 25 parts by weight of paraffin wax (Nippon Seiwa Co., Ltd., HNP-9, melting point 82 ° C.), 1.1 parts by weight of 20% DBS aqueous solution, 359 parts by weight of demineralized water at 90 ° C. The mixture was heated and stirred for 10 minutes using a homomixer (Mark IIf model manufactured by Tokushu Kika Kogyo Co., Ltd.). Next, under heating at 90 ° C., circulating emulsification is started under a pressure of 35 MPa using a high-pressure emulsifier, and the particle size is measured with Nanotrac and dispersed until the volume average particle size (MV) is 500 nm or less. Emulsion G2 was prepared. The final particle size (MV) was 340 nm.

<Adjustment of developing toner (H1)>
100 parts by mass of the modified polyester A solution, 53 parts by mass of the emulsion G1, and C.I. I. 2.8 parts by mass of Pigment Blue 15 were sufficiently mixed and dispersed using an attritor (manufactured by Mitsui Miike Koki Co., Ltd.) (modified Polyester A mixed solution).
On the other hand, 300 parts by mass of ion-exchanged water and 390 parts by mass of a 0.1 M Na ₃ PO ₄ aqueous solution were put into a four-necked vessel equipped with a high-speed stirring device TK homomixer (manufactured by Special Machine Industries). Warmed to ℃. To this, 60 parts by mass of an aqueous solution of 1.0 M CaCl ₂ was added and stirred at a rotational speed of 10,000 rpm to prepare an aqueous medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

The modified polyester A mixed solution was put into an aqueous medium and kept at 40 ° C. under a nitrogen stream.
Agitation was continued for 4 minutes at 0000 rpm for granulation. Thereafter, the stirring was switched to a paddle type stirring blade, and methyl ethyl ketone was recovered from the granulated liquid under reduced pressure at 40 ° C. for 2 hours.
After completion of distillation under reduced pressure, the contents in the container were cooled to room temperature, hydrochloric acid was added thereto to dissolve the hardly water-soluble dispersion stabilizer, and toner particles (A) were obtained through filtration, washing with water and drying. The volume median particle size (Dv50) of the toner particles (A) measured using Multisizer III was 6.2 μm, and the average circularity measured by a flow particle analyzer was 0.981. The toner particles (A) are obtained by blending 20 parts by mass of crystalline polyester A and 5 parts by mass of wax with 100 parts by mass of modified polyester A.

<External Addition>
To Kyoritsu Riko Co., Ltd. sample mill KR-3, 100 parts of toner particles (A) are charged, followed by 2.04 parts of colloidal silica having a volume average primary particle diameter of 80 nm, and large particle diameter of 30 nm of volume average primary particle diameter. 0.36 part of silica was added and stirred and mixed for a total of 5 minutes. Thereafter, 0.30 part of titania particles having a volume average primary particle size of 250 nm treated with alumina and 0.76 part of small particle size silica having a volume average primary particle size of 10 nm are added, stirred and mixed for a total of 6 minutes, and sieved. Thus, developing toner H1 was obtained.

<Adjustment of developing toner (H2)>
Toner particles (B) were obtained in the same amount and procedure except that the modified polyester A solution was changed to the modified polyester B solution in the adjustment of the developing toner (H1). The volume median particle size (Dv50) of the toner particles (B) measured using Multisizer III was 5.5 μm, and the average circularity measured by a flow particle analyzer was 0.980. The toner particles (B) are obtained by blending 20 parts by mass of crystalline polyester A and 5 parts by mass of wax with 100 parts by mass of modified polyester B. Further, external addition was carried out in the same manner to obtain a developing toner (H2).

<Adjustment of developing toner (H3 to H5)>
As shown in Table 1, toner particles (C, D, E) were produced by adjusting the blending amounts of modified polyester, crystalline polyester, and wax. Further external addition was carried out to develop toner (H3 to H5
) Was manufactured.

<Adjustment of comparative development toner (H6)>
Same as developing toner (H1) except that in Example 1 for producing polyester modified with vinyl resin, a solution in which 100 parts by mass of polyester A was dissolved in 190 parts by mass of methyl ethyl ketone was used without modification. Toner particles (F) and developing toner (H6) were produced by the procedure.

<Adjustment of Comparative Development Toner (H7) (H8)>
Developing toners (H7) and (H8) were produced by using the toner particles (G, H) shown in Table 2 in the same procedure as the developing toner (1).

When the cross sections of the toners H1 to H5 and H7 were observed with a TEM, it was confirmed that the first polymer had a sea-island structure in which the second polymer mainly composed of the crystalline polyester polymer was dispersed. On the other hand, the toners H6 and H8 did not form a good sea-island structure because the crystalline polyester was not sufficiently dispersed or exposed on the toner surface.
Next, regarding the electrophotographic photosensitive member used in the present invention, the elastic deformation rate and the universal hardness were measured as follows.

<Measurement of elastic deformation rate of photoconductor>
The elastic deformation rate of the photoconductor was measured at a temperature of 25 ° C. using a Fischer micro hardness tester FISCHERSCOPE H100C (or HM2000 having the same performance as its successor).
Measured in an environment with a relative humidity of 50%. For the measurement, a Vickers square pyramid diamond indenter having a facing angle of 136 ° is used. The measurement conditions are set as follows, the load applied to the indenter and the indentation depth under the load are continuously read, and profiles as shown in FIG. 2 plotted on the Y axis and the X axis are obtained.
・ Measurement conditions Maximum indentation load 5mN
Load required time 10 seconds Unloading required time 10 seconds The above elastic deformation rate is a value defined by the following formula, and the work performed by the film due to elasticity at the time of unloading with respect to the total work required for indentation. It is a ratio.

Elastic deformation rate (%) = (We / Wt) × 100
In the above formula, the total work Wt (nJ) indicates the area surrounded by A-B-D-A in FIG. 2, and the elastic deformation work We (nJ) is the area surrounded by C-B-D-C. Indicates. As the elastic deformation rate is larger, the deformation with respect to the load is less likely to remain, and when the elastic deformation rate is 100, it means that no deformation remains.

<Measurement of surface hardness of photoreceptor>
The universal hardness of the surface of the photoreceptor was measured using FischerSCOPE H100C manufactured by Fischer in an environment of a temperature of 25 ° C. and a relative humidity of 50%. The universal hardness value is a value obtained when the indentation is pushed down to an indentation load of 5 mN, and is a value defined by the following formula from the indentation depth at that time. In the measurement in this region, the influence of the hardness of the substrate (aluminum tube) can be eliminated.

Universal hardness (N / mm ² ) = Test load (N) / Vickers indenter surface area under test load (mm ² )
Next, the electrophotographic photosensitive member used in the present invention was produced as follows.
<Manufacture of photoconductor P1>
On an aluminum tube (3003 material, for image test I described later) having a diameter of 30 mm and a length of 260.5 mm, and an aluminum tube (3003 material, for image test II described later) having a diameter of 30 mm and a length of 376 mm, The undercoat layer dispersion was applied by dip coating so that the film thickness after drying was 1.25 μm and dried to form an undercoat layer.

The undercoat layer dispersion was prepared by the following method. That is, a rutile type titanium oxide having an average primary particle size of 40 nm (“TTO55N” manufactured by Ishihara Sangyo Co., Ltd.) and 3% by mass of methyldimethoxysilane (“TSL8117” manufactured by Toshiba Silicone Co., Ltd.) with respect to the titanium oxide were flowed at high speed. Disperse the surface-treated titanium oxide obtained by mixing at high speed with a rotary mixing speed of 34.5 m / sec using a ball mill of methanol / 1-propanol. Thus, a dispersion slurry of hydrophobized titanium oxide was obtained. The dispersion slurry, a mixed solvent of methanol / 1-propanol / toluene, and ε-caprolactam [compound represented by the following formula (F)] / bis (4-amino-3-methylcyclohexyl) methane [the following formula ( G)] / hexamethylenediamine [compound represented by the following formula (H)] / decamethylene dicarboxylic acid [compound represented by the following formula (I)] / octadecamethylene dicarboxylic acid [following formula The compound molar ratio of the compound represented by (J) is 60%
/ 15% / 5% / 15% / 5% of the copolymerized polyamide pellets are heated and stirred and mixed to dissolve the polyamide pellets, and then subjected to ultrasonic dispersion treatment to obtain methanol / 1- An undercoat layer dispersion having a solid content concentration of 18.0% and containing a propanol / toluene mass ratio of 7/1/2 and a hydrophobically-treated titanium oxide / copolymerized polyamide at a mass ratio of 3/1.

  Next, 10 parts of oxytitanium phthalocyanine showing a strong diffraction peak with a Bragg angle (2θ ± 0.2) of 27.3 ° in X-ray diffraction using CuKα rays was added to 150 parts of 1,2-dimethoxyethane, and then a sand grind mill was added. The pigment dispersion liquid A was prepared by pulverizing and dispersing with the above. Next, 10 parts of β-type (A-type) oxytitanium phthalocyanine was added to 150 parts of 1,2-dimethoxyethane, and pulverized and dispersed in a sand grind mill to prepare pigment dispersion B. 128 parts of pigment dispersion A thus obtained, 32 parts of pigment dispersion B, and 5% 1,2-dimethoxyethane solution of polyvinyl butyral (trade name # 6000C, manufactured by Denki Kagaku Kogyo Co., Ltd.) 100 And a suitable amount of 1,2-dimethoxyethane were mixed to finally prepare a dispersion for a charge generation layer having a solid content concentration of 4.0%.

This charge generation layer dispersion was dip-coated on the above undercoat layer so that the film thickness after drying was 0.3 μm, and then dried to form a charge generation layer.
Next, 80 parts of a mixture (molar ratio 2: 1) of the following charge transport materials CT-1a and CT-1b, 100 parts of polyester resin PE-1 (viscosity average molecular weight is 43,000) comprising the following structural units: As an antioxidant, 8 parts by weight of IRGANOX 1076, manufactured by Ciba Specialty Chemicals, and 0.1 part of silicone oil as a leveling agent, 640 parts of a mixed solvent of tetrahydrofuran and toluene (80% by weight of tetrahydrofuran, 20% by weight of toluene) And a coating solution for forming a charge transport layer was prepared. This solution is applied onto the above-described charge generation layer using an applicator so that the film thickness after drying is 25 μm, and dried at 125 ° C. for 20 minutes to form a charge transport layer, thereby producing a photoreceptor P1. did.

<Manufacture of photoconductor P2>
A photoconductor P2 is produced in the same manner as the photoconductor P1 except that the following CT-2 is used as the charge transport material of the charge transport layer of the photoconductor P1 instead of the mixture of CT-1a and CT-1b. did.

<Manufacture of photoconductor P3>
The photoconductor P1 (the viscosity average molecular weight is 40,000, isophthalic acid: terephthalic acid = 50: 50) is used in place of the binder resin in the charge transport layer of the photoconductor P1 instead of PE-1. A photoconductor P3 was produced in the same manner as in the production of P1.

<Manufacture of photoconductor P4>
A photoconductor P4 was produced in the same manner as in the production of the photoconductor P3, except that the following CT-3 was used instead of the mixture of CT-1a and CT-1b as the charge transport material of the photoconductor P3.

<Manufacture of photoconductor P5>
As a charge transport material for the charge transport layer of the photoreceptor P1, the following CT-4 is used instead of the mixture of CT-1a and CT-1b, and the binder resin is replaced with PE-1, and the following PE-3 is used. A photoconductor P5 was produced in the same manner as the photoconductor P1, except that the viscosity average molecular weight was 30,000 and isophthalic acid: terephthalic acid = 50: 50 was used.

<Manufacture of photoconductor P6>
As a charge transport material of the charge transport layer of the photoreceptor P1, the following CT-5 is used instead of the mixture of CT-1a and CT-1b, and the binder resin is replaced with PE-1, and the following PC-1 is used. A photoconductor P6 was produced in the same manner as in the production of the photoconductor P1, except that the viscosity average molecular weight was 30,000 and a: b: c = 13: 53: 35 (molar ratio).

<Manufacture of photoconductor P7>
As a charge transport material for the charge transport layer of the photoreceptor P1, the following CT-6 is used instead of the mixture of CT-1a and CT-1b, and the binder resin is replaced with PE-1, and the following PC-2 is used. A photoconductor P7 was produced in the same manner as in the production of the photoconductor P1, except that the viscosity average molecular weight was 30,000 and a: b: c = 17: 53: 30 (molar ratio).

<Manufacture of photoconductor P8>
As the charge transport material of the charge transport layer of the photoreceptor P1, the above CT-3 is used instead of the mixture of CT-1a and CT-1b, and the binder resin is replaced with PE-1, and the following PE-4 is used. (Viscosity average molecular weight is 40,000, m: n = 65: 35 (molar ratio), isophthalic acid: terephthalic acid = 50: 50) did.

<Manufacture of Comparative Photoconductor AP1>
The comparative photoconductor AP1 is the same as the photoconductor P1 except that the following PC-3 (viscosity average molecular weight is 40,000) is used instead of PE-1 as the binder resin in the charge transport layer of the photoconductor P1. Was made.

<Manufacture of Comparative Photoconductor AP2>
The comparative photoconductor AP2 was prepared in the same manner as in the production of the photoconductor P1 except that the binder resin of the charge transport layer of the photoconductor P1 was replaced with PE-1 and the following PC-4 (viscosity average molecular weight was 40,000) was used. Was made.

<Manufacture of Comparative Photoconductor AP3>
Except for using the following PC-5 (viscosity average molecular weight is 50,000, a: b = 85: 15 (molar ratio)) instead of PE-1 as the binder resin of the charge transport layer of the photoreceptor P1, A comparative photoreceptor AP2 was produced in the same manner as in the production of the photoreceptor P1.

<Image test I>
Example 1
The obtained toner F1 and the photoreceptor P1 are mounted on a process cartridge of a tandem full-color printer LaserJet 4650 manufactured by Hewlett-Packard Co., and 8000 sheets are continuously printed at a temperature of 23 ° C. and a relative humidity of 50% at a printing rate of 5%. Then, fogging (background), presence or absence of defective cleaning, remaining amount of toner on the photoconductor after transfer / before cleaning (PC fogging), and occurrence of toner adhesion (filming) on the photoconductor were examined. The results are shown in Table-4.

<Measurement method of fog>
Using an image forming apparatus, the color difference of the white background of each standard paper (OKI Excellent White) before printing and after continuous printing was measured with X-Rite 938 (manufactured by X-Rite), and the magnitude of ΔE Thus, the following criteria were used.
○ (Good): △ E <0.8
Δ (slightly generated): 0.8 ≦ ΔE <1.2
X (Generation): 1.2 ≦ ΔE

<Cleaning evaluation of photoconductor>
The degree of occurrence of stripe unevenness due to poor toner cleaning on the white background of the photoreceptor was evaluated.
○ (No cleaning occurs)
△ (partial occurrence)
× (Overall occurrence)

<PC fogging measurement method>
A tape was affixed and peeled off between the transfer / cleaning blades of the photoreceptor in the image forming apparatus, and the residual toner was sampled. The tape was affixed to a standard paper (OKI Excellent White), the influence of the tape portion was subtracted, and the color difference was measured with X-Rite 938 (manufactured by X-Rite). Since the PC fog represents the amount of toner remaining after transfer, the risk of occurrence of potential cleaning failure and filming can be evaluated.
○ (Good): ΔE <1.2
Δ (decent): 1.2 ≦ ΔE <1.5
× (defect): 1.5 ≦ ΔE

<Evaluation of photoconductor filming>
After continuous printing, the photosensitive member was taken out from the cartridge, and air was strongly applied to blow out the residual toner sufficiently. Then, the toner component remaining on the photosensitive member (strongly fixed component), that is, the degree of filming component was evaluated.
○ (No filming)
△ (partial occurrence)
× (Overall occurrence)

Example 2
Evaluation was performed in the same manner as in Example 1 except that the toner was changed to F2. The results are shown in Table-4.
Example 3
Evaluation was performed in the same manner as in Example 1 except that the photosensitive member was changed to P3. The results are shown in Table-4.
Comparative Example 1
Evaluation was performed in the same manner as in Example 1 except that the photoconductor was changed to AP1. The results are shown in Table-4.
Comparative Example 2
Evaluation was performed in the same manner as in Example 1 except that the photoconductor was changed to AP2. The results are shown in Table-4.

As can be seen from the results in Table 4, the toners F1 and F2 having a good sea-island structure have good PC fogging, cleaning, and filming when used with a toner having a high elastic deformation rate, but AP1 and AP2 having a low elastic deformation rate. When combined with the above, it can be seen that the PC fogging is inferior, the cleaning property and the filming are poor, or the level is just below the level.
<Image test II>
Example 4
Using the developing toner H1 and the photoreceptor P1, the following image evaluation, filming test, and fixing test were performed. The results are shown in Table-5.

The obtained toner H1 and the photoreceptor P1 are equipped with a belt fixing machine using a printing speed of 243 mm / s, a non-magnetic one component, a developing rubber roller, a metal regulating blade, a charging roller (PCR), a belt transfer, and a heat fixing method. Using the full color printer (tandem full color printer MICROLINE9800 manufactured by Oki Data Corporation), continuous printing of 6000 sheets was performed at a printing rate of 5%. At this time, the toner and the photoconductor were mounted on a toner cartridge and a drum cartridge, respectively, and then incorporated into a printer for testing.

<Filming measurement method>
Using an image forming apparatus, the toner filming of the photoconductor after printing and the image background stain due to filming on the printing paper were observed and evaluated.
◎ (Good): No filming on the photoconductor or printing paper ○ (Slightly generated): Slight filming occurs on the photosensitivity, but no smudge on the printing paper × (Generation): Filming Causes smudges on the printed paper

<Fixing test>
Prepare recording paper (OKI Excellent White) carrying an unfixed toner image, change the surface temperature of the heating roller from 100 ° C to 195 ° C in increments of 5 ° C, transport it to the fixing nip, and speed of 243 mm / sec The state of fixation when discharged with the was observed. The temperature range where the toner on the recording paper after fixing does not cause toner offset or paper wrapping at the time of fixing and the toner on the recording paper after fixing is sufficiently adhered to the recording paper is defined as the fixing temperature range. As the fixing machine, a belt fixing machine using a thermal fixing system was used, and evaluation was performed without application of silicone oil.

The obtained image was maintained at 6,000 sheets with high density and no image defects such as background stains. Further, no filming occurred on the photosensitive member, and no image defect due to filming occurred on the image. In the fixing test, a fixing temperature range from 145 ° C. to 195 ° C. was shown, and the fixing temperature range was wide from a low temperature to a high temperature.
Examples 5-9
Evaluation was performed in the same manner as in Example 4 except that the developing toners H2 to H5 and H7 were used in place of the developing toner H1, respectively. The results are shown in Table-5.

Examples 10-16
Evaluation was performed in the same manner as in Example 4 except that the photoreceptors P2 to P8 were used instead of the photoreceptor P1, respectively. The results are shown in Table-5.
Comparative Examples 3 and 4
Evaluation was performed in the same manner as in Example 4 except that comparative developing toners H6 and H8 were used in place of the developing toner H1. The results are shown in Table-5.
Comparative Examples 5-7
Evaluation was performed in the same manner as in Example 4 except that comparative photoconductors AP1 to AP3 were used instead of the photoconductor P1. The results are shown in Table-5.

  The results shown in Table 5 show that when a modified polyester, an appropriate type and amount of crystalline polyester, and a wax are blended and the toner forms a good sea-island structure, an excellent fixing temperature region can be obtained and a high elasticity can be obtained. It can be seen that good image quality and filming resistance can be obtained by using a photoconductor having a deformation rate. On the other hand, as shown in Comparative Example 3, when the modified polyester of the present invention is not used, the fixing temperature region is narrowed, and defects are caused in both image quality and filming. Furthermore, as shown in Comparative Example 4, when the amount of the crystalline polyester used is too large, image defects due to filming occur. It can also be seen that when a low elastic deformation rate photoconductor is used as in Comparative Examples 5 to 7, image defects due to filming occur even when a toner with a good sea-island structure is used.

1 Photoconductor (Electrophotographic photoconductor)
2 Charging device (charging roller; charging unit)
3 Exposure equipment (exposure section)
4 Development device (development unit)
DESCRIPTION OF SYMBOLS 5 Transfer apparatus 6 Cleaning apparatus 7 Fixing apparatus 41 Developing tank 42 Agitator 43 Supply roller 44 Developing roller 45 Control member 71 Upper fixing member (fixing roller)
72 Lower fixing member (fixing roller)
73 Heating device T Toner X1 First polymer X2 Second polymer X3 Third polymer

Claims (10)

In an image forming apparatus having at least an electrostatic charge image developing toner and an electrophotographic photosensitive member, the toner is a toner containing at least a first polymer and a second polymer,
The sea has a sea-island structure in which the first polymer is the sea, and the second polymer having crystallinity is dispersed in the first polymer.
The second polymer is mainly composed of a long-chain (meth) acrylic acid ester polymer or a crystalline polyester,
And an elastic deformation rate of the outermost surface layer of the photoconductor is 42% or more and 60% or less.   The toner has an island structure in which the second polymer is in the sea in the second polymer island, and the second polymer is mainly composed of a long-chain (meth) acrylate polymer. The image forming apparatus according to claim 1, wherein:   3. The image formation according to claim 1, wherein the ester portion of the crystalline long-chain (meth) acrylic acid ester used in the long-chain (meth) acrylic acid ester polymer has 10 or more carbon atoms. apparatus.   The toner contains at least a binder resin, a colorant, and a wax, and the binder resin polymerizes the long-chain (meth) acrylic acid ester in the presence of the polymer obtained in the first step. The image forming apparatus according to any one of claims 1 to 3, wherein the image forming apparatus is manufactured through a second step of polymerizing a monomer.   The toner comprises 5 to 40 parts by mass of the crystalline polyester resin and 3 to 20 parts by mass of a wax with respect to 100 parts by mass of the polyester resin modified with at least a vinyl resin. The image forming apparatus according to any one of 1 to 4. The image forming apparatus according to claim 1, wherein the universal hardness of the outermost surface layer of the electrophotographic photosensitive member is 180 N / mm ² or more. The image forming apparatus according to claim 1, wherein the outermost surface layer of the electrophotographic photosensitive member contains a charge transport material having the following CT-3 structure.
  The image forming apparatus according to claim 1, wherein the electrophotographic photosensitive member contains a polyester resin as a binder resin for the outermost layer.   8. The electrophotographic photosensitive member according to claim 1, wherein a polycarbonate resin containing a biphenol-based unit as a copolymerization component is used in an amount of 30 mol% or more as a binder resin of the outermost layer. The image forming apparatus described. An electrophotographic toner comprising the electrostatic image developing toner according to any one of claims 1 to 5 and the electrophotographic photoreceptor according to any one of claims 1 or 6 to 9. Process cartridge.