JP2008170627A - Toner for electrostatic charge image development, electrostatic charge image developer, toner cartridge, process cartridge and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development which can be fixed in a low-temperature region and can suppress gloss unevenness of an image even when fixed in a medium-to high-temperature region. <P>SOLUTION: The toner for electrostatic charge image development has toner base particles containing a crystalline resin, a release agent and a metal element capable of taking a valence of ≥2, wherein an intensity ratio of the metal element capable of taking a valence of ≥2 to intensity of all elements in the toner base particles is in a range of 5-50% as measured by fluorescent X-ray analysis. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner, an electrostatic charge image developer, a toner cartridge, a process cartridge, and an image forming apparatus used for forming an image by electrophotography.

In order to meet the recent demand for energy saving, copying machines that form images using electrophotography are required to save more power. In order to save power, it is effective to lower the fixing temperature. Therefore, various toners that can be fixed at a lower temperature have been studied.
As a general method for lowering the toner fixing temperature, it is known to use a crystalline resin having a low melting point as a binder resin. For example, it includes a crystalline resin having a crystalline block structure and an amorphous block structure and having a weight average molecular weight of 10,000 to 50,000, and the amorphous resin has a molecular weight of A toner having a molecular weight of 2 times or more (Patent Document 1) and a ratio of a bivalent or higher metal atom (A) and a monovalent alkali metal atom out of all metal atoms on the toner surface including a crystalline resin. A toner having a ratio (B) of 0.23 ≦ A / (A + B) ≦ 0.98 (Patent Document 2), a toner including a crystalline resin and a gloss control agent such as extender (Patent Document 3), and the like. Can be mentioned.
The toner using the crystalline resin as a main component melts at a relatively low temperature as compared with a conventional toner, and is suitable for fixing in a low temperature range.
JP 2005-148554 A JP 2003-162093 A Japanese Patent Laid-Open No. 2005-037545

  The present invention relates to a toner for developing an electrostatic charge image that can be fixed in a low temperature range and can suppress uneven glossiness of an image even when fixed in a middle temperature range to a high temperature range, and an electrostatic charge image developer using the same. It is an object of the present invention to provide a toner cartridge, a process cartridge, and an image forming apparatus.

The above object is achieved by the present invention described below. That is,
The invention according to claim 1
It has toner base particles containing a crystalline resin, a release agent, and a metal element capable of taking a valence of 2 or more, and can take a valence of 2 or more as measured by fluorescent X-ray analysis. A toner for developing an electrostatic charge image, wherein the content of metal elements with respect to the strength of all elements in the toner base particles is in the range of 5% to 50%.

The invention according to claim 2
The electrostatic image developing toner according to claim 1, wherein the following formula (1) is satisfied.
Formula (1) 0.2 ≦ Dw / Up ≦ 0.8
[In Formula (1), Dw is 10 ° C./min from 120 ° C. to 70 ° C. after the electrostatic image developing toner is heated from 70 ° C. to 120 ° C. at 10 ° C./min by differential thermal analysis. In the heating / cooling process for lowering the temperature, it represents the temperature range with respect to the reference line of the peak observed in the process of heating from 70 ° C. to 120 ° C., and Up is the process of cooling from 120 ° C. to 70 ° C. in the heating / cooling process The temperature range with respect to the reference line of the peak observed in FIG. Further, the reference line means a straight line connecting the skirt portions on both sides of the peak. ]

The invention according to claim 3 is:
It has toner base particles containing a crystalline resin, a release agent, and a metal element capable of taking a valence of 2 or more, and can take a valence of 2 or more as measured by fluorescent X-ray analysis. An electrostatic charge image developer comprising a toner in which the content of metal elements with respect to the strength of all elements in the toner base particles is in the range of 5% to 50%.

The invention according to claim 4 is:
It is detachable from an image forming apparatus having at least a toner image forming unit, and stores a developer to be supplied to the toner image forming unit.
The developer has toner base particles containing a crystalline resin, a release agent, and a metal element capable of taking a valence of 2 or more, and having a valence of 2 or more measured by fluorescent X-ray analysis. A toner cartridge comprising a toner in which a content of a metal element capable of taking a valence with respect to the strength of all elements in the toner base particles is in a range of 5% to 50%.

The invention according to claim 5 is:
It is detachable from the image forming apparatus,
An image holding member; and at least a toner image forming unit that contains the developer and supplies the developer to an electrostatic latent image formed on the surface of the image holding member to form a toner image.
The developer has toner mother particles containing a crystalline resin, a release agent, and a metal element capable of taking a valence of 2 or more, and having a valence of 2 or more measured by fluorescent X-ray analysis. A process cartridge comprising a toner in which the content of metal elements capable of taking a valence with respect to the strength of all elements in the toner base particles is in the range of 5% to 50%.

The invention according to claim 6 is:
6. The process cartridge according to claim 5, wherein the layer constituting the outermost surface of the image carrier contains at least one resin selected from a siloxane resin having a crosslinked structure and a phenol resin. .

The invention according to claim 7 is:
Cleaning means for cleaning while collecting the toner remaining on the surface of the image carrier after transferring the toner image;
6. The process cartridge according to claim 5, further comprising a toner recycling unit that reuses the toner collected by the cleaning unit as the toner for the developer.

The invention according to claim 8 is:
An image carrier, a charging unit that charges the surface of the image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the charged surface of the image carrier, and the developer At least a toner image forming unit that forms a toner image by developing, a transfer unit that transfers the toner image to the surface of the recording medium, and a fixing unit that fixes the toner image transferred to the surface of the recording medium,
The developer has toner mother particles containing a crystalline resin, a release agent, and a metal element capable of taking a valence of 2 or more, and having a valence of 2 or more measured by fluorescent X-ray analysis. An image forming apparatus comprising a toner in which a content of a metal element capable of taking a valence with respect to the strength of all elements in the toner base particles is in a range of 5% to 50%.

The invention according to claim 9 is
9. The image forming apparatus according to claim 8, wherein the layer constituting the outermost surface of the image carrier contains at least one resin selected from a siloxane-based resin and a phenol-based resin having a crosslinked structure. is there.

The invention according to claim 10 is:
Cleaning means for cleaning while collecting the toner remaining on the surface of the image carrier after transferring the toner image;
The image forming apparatus according to claim 8, further comprising a toner reuse unit that reuses the toner collected by the cleaning unit as the toner for the developer.

As described above, according to the first aspect of the present invention, it is possible to fix in the low temperature range and fix in the middle temperature range to the high temperature range as compared with the case where the present configuration is not provided. In addition, it is possible to provide a toner for developing an electrostatic image capable of suppressing uneven glossiness of an image.
According to the second aspect of the present invention, it is possible to fix in a low temperature range as compared with the case where the present configuration is not provided, and uneven gloss of an image even when fixing in a middle temperature range to a high temperature range. An electrostatic charge image developing toner that can be suppressed can be provided.
According to the third aspect of the present invention, it is possible to fix in a low temperature range as compared with the case where the present configuration is not provided, and uneven gloss of an image even when fixing in a middle temperature range to a high temperature range. An electrostatic charge image developer that can be suppressed can be provided.
According to the fourth aspect of the present invention, it is possible to fix in the low temperature range as compared with the case where the present configuration is not provided, and uneven gloss of the image even when fixing in the middle temperature range to the high temperature range. A toner cartridge that can be suppressed can be provided.
According to the fifth aspect of the present invention, it is possible to fix in a low temperature range as compared with the case where the present configuration is not provided, and uneven gloss of an image even when fixing in a middle temperature range to a high temperature range. A process cartridge that can be suppressed can be provided.
According to the sixth aspect of the present invention, it is possible to provide a process cartridge capable of suppressing the occurrence of filming even when an image is formed over a long period of time, compared to the case where the present configuration is not provided.
According to the seventh aspect of the present invention, there is provided a process cartridge capable of suppressing the occurrence of filming even when an image is formed over a long period of time while recycling the toner as compared with the case where the present configuration is not provided. can do.
According to the eighth aspect of the present invention, it is possible to fix in the low temperature range as compared with the case where the present configuration is not provided, and uneven gloss of the image even when fixing in the middle temperature range to the high temperature range. An image forming apparatus that can be suppressed can be provided.
According to the ninth aspect of the present invention, it is possible to provide an image forming apparatus capable of suppressing the occurrence of filming even when an image is formed over a long period of time as compared with the case where the present configuration is not provided. .
According to the tenth aspect of the present invention, there is provided an image forming apparatus capable of suppressing the occurrence of filming even when an image is formed over a long period of time while recycling the toner as compared with the case where the present configuration is not provided. Can be provided.

<Toner for electrostatic image development>
The toner for developing an electrostatic charge image of the present embodiment (hereinafter sometimes referred to as “toner”) is a toner base containing a crystalline resin, a release agent, and a metal element capable of taking a valence of 2 or more. The content ratio of the metal element having particles and capable of taking the valence of 2 or more as measured by fluorescent X-ray analysis with respect to the strength of all elements in the toner base particles is in the range of 5% to 50% It is characterized by being. In general, the toner includes an external additive. In the present invention, the “toner base particle” means a toner component other than the external additive, that is, a particle main body constituting the toner. In the following description, when only the particle main body constituting the toner is indicated, it is expressed as toner mother particles.

  Since the toner according to the exemplary embodiment includes a crystalline resin, the toner can be fixed in a low temperature range (a temperature range of 80 ° C. to 120 ° C.). This is because, since the crystalline resin has a melting point, the viscosity is greatly reduced at a specific temperature, and when the toner is heated at the time of fixing, the crystalline resin molecules can be fixed after the thermal activity starts. This is because the temperature difference up to a certain temperature range can be reduced.

On the other hand, when fixing is performed from a medium temperature range to a high temperature range (a temperature range of 125 ° C. or more and 175 ° C. or less) using a conventional toner containing a crystalline resin, the viscosity of the crystalline resin during fixing is significantly reduced. As a result, the image surface is flattened and the gloss of the image portion is increased, and as a result, uneven glossiness of the image forming surface is likely to occur.
Therefore, when a toner image formed on the surface of a recording medium is heated at a higher temperature than in single-sided printing, such as in double-sided printing, gloss unevenness occurs when using conventional toner containing crystalline resin. Resulting in. In addition, when the toner also contains a release agent having a low melting point, phase separation between the crystalline resin and the release agent is liable to occur at the time of fixing, and gloss unevenness becomes more prominent.

However, since the toner according to the exemplary embodiment includes a metal element capable of taking a valence of 2 or more in the toner base particles, even when fixing is performed from an intermediate temperature range to a high temperature range, occurrence of uneven glossiness of the image can be suppressed. .
Although the details of this reason are unknown, it is presumed as follows. That is, a metal element capable of taking a valence of 2 or more exists in a state of being dispersed in a crystalline resin or a release agent in the toner base particles, and forms ionic crosslinks to increase the elasticity of the toner base particles. At the same time, the compatibility between the crystalline resin and the release agent is improved. For this reason, even if fixing is performed from a middle temperature range to a high temperature range, the viscosity of the crystalline resin is not significantly reduced during fixing, and phase separation between the crystalline resin and the release agent is also suppressed. It is thought that generation can be suppressed.

Here, in order to suppress the occurrence of gloss unevenness, the content of the metal element capable of taking a valence of 2 or more contained in the toner base particles with respect to the strength of all elements needs to be 5% or more. It is preferably 10% or more, and more preferably 15% or more. When the content of the metal element that can take a valence of 2 or more is less than 5%, gloss unevenness occurs.
From the viewpoint of suppressing the occurrence of uneven gloss, it is preferable that the content of the metal element that can have a valence of 2 or more contained in the toner base particles is high, but if the content is too high, the toner The apparent melting point of the mother particles becomes high, and fixing at low temperatures becomes impossible. For this reason, the content of the metal element capable of taking a valence of 2 or more contained in the toner base particles needs to be 50% or less, preferably 45% or less, and preferably 40% or less. Is more preferable.

The metal element capable of taking a valence of 2 or more is not particularly limited as long as it can exist in an ionic state in the toner base particles such as a crystalline resin and a release agent. Although the upper limit of the valence is not particularly limited, it is practically 4 or less. Specifically, the following metal elements can be used.
Examples of the metal element that can take a divalent valence include metal elements such as Be, Mg, Ca, Sr, Ba, Zn, Ni, Cu, and Fe, and the emulsion polymerization described later in the toner of the present embodiment. In the case of producing using an agglomeration method, it is preferable to use Ca and Mn.
Examples of the metal element capable of taking a trivalent valence include metal elements such as B, Al, Ga, In, and Ti, and the toner of this embodiment is manufactured using an emulsion polymerization aggregation method described later. In this case, it is preferable to use Al or Ti.
Examples of the metal element capable of taking a tetravalent valence include metal elements such as Ge, Sn, and Pb. When the toner of this embodiment is manufactured using an emulsion polymerization aggregation method described later, , Sn is preferably used.

  The method for adding a metal element capable of taking a valence of 2 or more into the toner base particles is not particularly limited. For example, when a crystalline resin used for toner preparation is polymerized using a polycondensation reaction or the like. For this, an ionic metal-containing catalyst used in the polymerization can be used. Further, when a toner is prepared by an emulsion polymerization aggregation method described later, an ionic metal-containing compound that is used as an aggregating agent can also be used. In addition, when a wet manufacturing method other than the emulsion polymerization aggregation method is used, an ionic metal-containing compound can be added to the raw material liquid for toner preparation at any timing as long as the granulation property is not inhibited. .

Measurement of the content of the metal element capable of taking a valence of 2 or more with respect to the strength of all elements in the toner base particles can be performed by fluorescent X-ray analysis. In order to measure toner mother particles, 1 g of toner was ultrasonically dispersed in ion-exchanged water containing a nonionic surfactant (added 60 W, output of 20 W, frequency of 20 kHz for 30 minutes) and then separated by a hot air dryer. The powder after being kept at 40 ° C. and dried was used. 0.3 g of the powder was pressure-molded into a disk shape having a diameter of 10 mm and subjected to fluorescence X-ray analysis.
The acceleration voltage of fluorescence X-ray measurement was 40 kV and the current value was 70 mA, and the ratio (percentage) of metal elements capable of taking a valence of 2 or more with respect to the total net intensity of all detected elements was determined. In fluorescent X-ray measurement, it is needless to say that beryllium cannot be measured in principle from hydrogen having a small atomic number and is not included in all elements.

Next, constituent materials and various physical properties of the toner according to the exemplary embodiment will be described in detail below.
-Binder resin-
In the toner of this embodiment, a crystalline resin is always used as a binder resin. Moreover, it is particularly preferable to use an amorphous resin in combination as necessary.
In the present invention, “crystalline resin” means a resin having a clear endothermic peak (a peak where the half-value width of the endothermic peak is 10 ° C. or less) in differential scanning calorimetry (DSC). The “resin” means a resin that does not have the above-mentioned clear peak. Moreover, it is especially preferable that the weight average molecular weight of binder resin is 10,000 or more regardless of crystalline resin and non-crystalline resin, and it is preferable that the weight average molecular weight is the range of 15000 or more and 50000 or less normally.
As the crystalline resin, for example, a polyester resin, a crystalline vinyl resin, or the like can be used. As the amorphous resin, for example, a polyester resin, a polyurethane resin, an epoxy resin, a polyol resin, or the like can be used. Hereinafter, the binder resin used in the present invention will be described separately for a crystalline resin and an amorphous resin.

-Crystalline resin-
The content of the crystalline resin contained in the toner base particles is preferably in the range of 2% by mass to 30% by mass, and more preferably in the range of 3% by mass to 15% by mass. If the content of the crystalline resin is less than 2% by weight, fixing in a low temperature region may be difficult. Further, if the content of the crystalline resin exceeds 30% by mass, gloss unevenness is likely to occur or filming is likely to occur particularly when fixing is performed in a middle temperature range or a high temperature range.

As melting | fusing point of crystalline resin, the range of 45 to 110 degreeC is preferable, The range of 50 to 100 degreeC is more preferable, The range of 55 to 90 degreeC is still more preferable.
When the melting point is lower than 45 ° C., it becomes difficult to store the toner, and when it exceeds 110 ° C., fixing in a low temperature range (hereinafter sometimes referred to as “low temperature fixability”) may be difficult. In addition, melting | fusing point of crystalline resin means what was calculated | required by the method based on ASTMD3418-8.

  Further, the number average molecular weight (Mn) of the crystalline resin is preferably 5000 or more, and more preferably 7000 or more. If the number average molecular weight (Mn) is less than 7000, the toner may permeate into the surface of a recording medium such as paper at the time of fixing to cause uneven fixing, or the resistance to bending of the fixed image may be reduced. .

  As described above, a crystalline polyester resin, a crystalline vinyl resin, or the like can be used as the crystalline resin. However, the adhesiveness to the paper and the charging property at the time of fixing, and the melting point satisfying the above range can be easily obtained. From the viewpoint, it is preferable to use a crystalline polyester resin. In particular, an aliphatic crystalline polyester resin is more preferable because a resin having a desired melting point is easily obtained.

  Examples of the crystalline vinyl resin include amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, and (meth) acrylic. Decyl acid, undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) acrylate, (meth) acrylic acid Examples thereof include vinyl resins using long-chain alkyl such as behenyl and alkenyl (meth) acrylic acid esters. In the present specification, the description “(meth) acryl” means that both “acryl” and “methacryl” are included.

On the other hand, the crystalline polyester resin can be synthesized from a carboxylic acid (dicarboxylic acid) component and an alcohol (diol) component.
Hereinafter, the carboxylic acid component and the alcohol component will be described in more detail. In the present specification, the “crystalline polyester resin” also means a copolymer obtained by copolymerizing other components in a proportion of 50% by mass or less with respect to the main chain of the crystalline polyester resin.

  The carboxylic acid component is preferably an aliphatic dicarboxylic acid, and particularly preferably a linear carboxylic acid. For example, succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid Acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc., or lower alkyl esters thereof, Acid anhydrides can be mentioned but are not limited to these.

The carboxylic acid component preferably contains constituent components such as a dicarboxylic acid component having a double bond and a dicarboxylic acid component having a sulfonic acid group in addition to the aliphatic dicarboxylic acid component described above. The dicarboxylic acid component having a double bond includes a component derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a double bond, in addition to a component derived from a dicarboxylic acid having a double bond. Is also included. The dicarboxylic acid component having a sulfonic acid group includes a component derived from a dicarboxylic acid having a sulfonic acid group, a lower alkyl ester of a dicarboxylic acid having a sulfonic acid group, or an acid anhydride. Is also included.

  The dicarboxylic acid having a double bond can be suitably used to prevent hot offset at the time of fixing because the entire resin can be crosslinked using the double bond. Examples of the dicarboxylic acid include, but are not limited to, fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, fumaric acid, maleic acid and the like are preferable in terms of cost.

The dicarboxylic acid having a sulfonic acid group is effective in that it can favorably disperse a coloring material such as a pigment. Further, if the entire resin is emulsified or suspended in water to produce particles, if there is a sulfonic acid group, it can be emulsified or suspended without using a surfactant as described later. Examples of the dicarboxylic acid having a sulfonic acid group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, 5-sulfoisophthalic acid sodium salt is preferable in terms of cost.

The content of the carboxylic acid component other than these aliphatic dicarboxylic acid components (dicarboxylic acid component having a double bond and / or dicarboxylic acid component having a sulfonic acid group) in the carboxylic acid component is 1 component mol% or more and 20 Constituent mol% is preferable, and 2 constituent mol% or more and 10 constituent mol% is more preferable.

When the content is less than 1 mol%, the dispersibility of the pigment in the toner base particles may deteriorate if a pigment is used as the colorant.
Further, when a toner is produced using the emulsion polymerization aggregation method, the emulsion particle diameter in the dispersion becomes large, and it may be difficult to adjust the toner diameter by aggregation. On the other hand, if it exceeds 20 component mol%, the crystallinity of the crystalline polyester resin is lowered, the melting point is lowered, and the storage stability of the image may be deteriorated. Further, when a toner is produced using an emulsion polymerization aggregation method, the emulsion particle size in the dispersion may be too small to dissolve in water, and latex may not be generated. In the present invention, “constituent mol%” refers to a percentage when each constituent component (carboxylic acid component, alcohol component) in the polyester resin is 1 unit (mol).

  On the other hand, the alcohol component is preferably an aliphatic diol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7. -Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14 -Tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like are exemplified, but not limited thereto.

The alcohol component preferably has an aliphatic diol component content of 80 constituent mol% or more, and includes other components as necessary. As the alcohol component, the content of the aliphatic diol component is more preferably 90 constituent mol% or more.

  When the content is less than 80 mol%, the crystallinity of the polyester resin is lowered and the melting point is lowered, so that toner blocking resistance, image storage stability and low-temperature fixability may be deteriorated. On the other hand, examples of other components included as necessary include diol components having a double bond and diol components having a sulfonic acid group.

  Examples of the diol having a double bond include 2-butene-1,4-diol, 3-butene-1,6-diol, 4-butene-1,8-diol, and the like. On the other hand, examples of the diol having a sulfonic acid group include 1,4-dihydroxy-2-sulfonic acid benzene sodium salt, 1,3-dihydroxymethyl-5-sulfonic acid benzene sodium salt, and 2-sulfo-1,4. -Butanediol sodium salt and the like.

In the case of adding an alcohol component other than these linear aliphatic diol components (a diol component having a double bond and / or a diol component having a sulfonic acid group), the content in the alcohol component is one component mole. % Or more and 20 component mol% is preferable, and 2 component mol% or more and 10 component mol% is more preferable. When the content is less than 1 constituent mol%, pigment dispersion may be poor, the emulsified particle diameter may be large, and adjustment of the toner diameter by aggregation may be difficult. On the other hand, if it exceeds 20 component mol%, the crystallinity of the polyester resin is lowered, the melting point is lowered, the image storage stability is deteriorated, or the emulsion particle size is too small to dissolve in water, and no latex is produced. There is a case.

The method for producing the crystalline polyester resin is not particularly limited and can be produced by a general polyester polymerization method in which a carboxylic acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. Produced separately depending on the type of monomer. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

  The crystalline polyester resin can be produced at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower. The reaction system is reduced in pressure as necessary, and the reaction is carried out while removing water and alcohol generated during condensation. When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. If a monomer with poor compatibility is present in the copolymerization reaction, the monomer with poor compatibility and the monomer and the carboxylic acid component or alcohol component to be polycondensed are condensed in advance and then polycondensed together with the main component. Good.

  Examples of catalysts that can be used in the production of the crystalline polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; zinc, manganese, antimony, titanium, tin, zirconium, and germanium. Metal compounds such as: phosphorous acid compounds, phosphoric acid compounds, and amine compounds. Specific examples include the following compounds.

  For example, sodium acetate, sodium carbonate, lithium acetate, calcium acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetra Butoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate , Zirconyl octylate, germanium oxide, triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite Ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

  Among the catalysts containing metal elements capable of taking the valences of 2 or more listed above, calcium acetate is preferred from the viewpoint that it is easier to achieve both low-temperature fixability and gloss unevenness suppressing effect at a high level. It is preferable to use manganese acetate.

In addition to the above polymerizable monomer, a compound having a shorter chain alkyl group, alkenyl group, aromatic ring or the like may be used for the purpose of adjusting the melting point, molecular weight, etc. of the crystalline resin.
Specific examples include, for example, dicarboxylic acids, alkyldicarboxylic acids such as succinic acid, malonic acid, and oxalic acid, and phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, 4,4′-bibenzoic acid, 2, Aromatic dicarboxylic acids such as 6-naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid, and nitrogen-containing aromatic dicarboxylic acids such as dipicolinic acid, dinicotinic acid, quinolinic acid, and 2,3-pyrazinedicarboxylic acid, and diols In the case of short chain alkyl diols such as succinic acid, malonic acid, acetone dicarboxylic acid, diglycolic acid, etc., and in the case of short chain alkyl vinyl polymerizable monomers, methyl (meth) acrylate, ( Short chain alkyl such as ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, alkenyl (Meth) acrylic acid esters, vinyl nitriles such as acrylonitrile and methacrylonitrile, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketones, ethylene, propylene, butadiene And olefins such as isoprene. These polymerizable monomers may be used individually by 1 type, and may use 2 or more types together.

-Amorphous resin-
In the toner of the present embodiment, an amorphous resin can be used in combination with a crystalline resin as a binder resin.
The molecular weight of the amorphous resin that can be used is not particularly limited. However, when the toner is produced using the emulsion polymerization aggregation method described later, an amorphous resin (high molecular weight) having a high weight average molecular weight (Mw) is used. Component) and an amorphous resin (low molecular weight component) having a low weight average molecular weight.

  In this case, Mw of the high molecular weight component is preferably 30000 or more and 300000 or less, more preferably 30000 or more and 200000 or less, and particularly preferably 35000 or more and 150,000 or less. By controlling the Mw of the high molecular weight component within the above range, it can be more efficiently compatible with the crystalline resin, and can be prevented from separating from the crystalline resin once compatible.

On the other hand, the Mw of the low molecular weight component is preferably 8000 or more and 25000 or less, more preferably 8000 or more and 22000 or less, and particularly preferably 9000 or more and 20000 or less.
By controlling the Mw of the high molecular weight component within the above range, the inclusion of the high molecular weight component in the toner base particles is improved when the aggregated particles obtained by aggregating the raw material components by the emulsion polymerization aggregation method are heated and fused. Thus, exposure of the crystalline resin to the surface of the toner base particles can be prevented.

As described above, when the high molecular weight component and the low molecular weight component are mixed and used, the blending ratio of both is preferably in the range of high molecular weight component / low molecular weight component = 35/65 to 95/5, and 40/60 The range of thru | or 90/10 is more preferable, and the range of 50/50 thru | or 85/15 is still more preferable.
The high molecular weight component preferably contains alkenyl succinic acid or its anhydride and trimellitic acid or its anhydride as its constituent monomers. Alkenyl succinic acid or its anhydride can be more easily compatible with the crystalline polyester resin due to the presence of highly hydrophobic alkenyl groups.

  Examples of the alkenyl succinic acid component include n-dodecenyl succinic acid, isododecenyl succinic acid, n-octenyl succinic acid, acid anhydrides, acid chlorides thereof, and lower alkyl esters having 1 to 3 carbon atoms. . By containing a trivalent or higher polyvalent carboxylic acid, the polymer chain can take a crosslinked structure. By taking a cross-linked structure, an effect of fixing the crystalline polyester resin once compatible and making it difficult to separate is obtained. Examples of trivalent or higher polyvalent carboxylic acids include hemimellitic acid, trimellitic acid, trimesic acid, merophanic acid, planitic acid, pyromellitic acid, merit acid, 1,2,3,4-butanetetracarboxylic acid and These acid anhydrides, acid chlorides and lower alkyl esters having 1 to 3 carbon atoms can be mentioned.

  There is no restriction | limiting in particular in the manufacturing method of an amorphous polyester resin, It can manufacture with the above-mentioned general polyester polymerization method. As the carboxylic acid component used for the synthesis of the amorphous polyester resin, various dicarboxylic acids mentioned for the crystalline polyester resin can be used. As the alcohol component, various diols used for the synthesis of the amorphous polyester resin can be used. In addition to the aliphatic diols mentioned for the crystalline polyester resin, for example, bisphenol A, bisphenol A ethylene oxide adduct, Bisphenol A propylene oxide adduct, hydrogenated bisphenol A, bisphenol S, bisphenol S ethylene oxide adduct, bisphenol S propylene oxide adduct, and the like can be used. Furthermore, it is particularly preferable to use bisphenol S derivatives such as bisphenol S, bisphenol S ethylene oxide adduct, and bisphenol S propylene oxide adduct from the viewpoints of toner manufacturability, heat resistance, and transparency. Further, both the carboxylic acid component and the alcohol component may contain a plurality of components, and in particular, bisphenol S has an effect of improving heat resistance.

-Cross-linking treatment of binder resin-
Next, an amorphous resin used as the binder resin, a crosslinking treatment of the crystalline resin used as necessary, a copolymer component that can be used for the synthesis of the binder resin, and the like will be described.
In the synthesis of the binder resin, other components can be copolymerized, and a compound having a hydrophilic polar group can be used. As a specific example, when the binder resin is a polyester resin, for example, a dicarboxylic acid compound in which an aromatic ring such as sulfonyl-terephthalic acid sodium salt or 3-sulfonylisophthalic acid sodium salt is directly substituted is used. When the binder resin is a vinyl resin, for example, unsaturated aliphatic carboxylic acids such as (meth) acrylic acid and itaconic acid, glycerin mono (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, and zinc mono (meth) acrylate , Zinc di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, esters of (meth) acrylic acid and alcohols such as polypropylene glycol (meth) acrylate, ortho, meta, para Examples thereof include styrene derivatives having a sulfonyl group at any position, sulfonyl group-substituted aromatic vinyls such as sulfonyl group-containing vinyl naphthalene, and the like.

In addition, a cross-linking agent can be added to the binder resin as necessary for the purpose of preventing uneven glossiness, uneven color development, hot offset, etc. during fixing in a high temperature region.
Specific examples of the crosslinking agent include aromatic polyvinyl compounds such as divinylbenzene and divinylnaphthalene, divinyl phthalate, divinyl isophthalate, divinyl terephthalate, divinyl homophthalate, divinyl trimesate / trivinyl, and naphthalene dicarboxylic acid. Polyvinyl esters of aromatic polyvalent carboxylic acids such as divinyl and divinyl biphenyl carboxylate, divinyl esters of nitrogen-containing aromatic compounds such as divinyl pyridinedicarboxylate, unsaturated heterocyclic compounds such as pyrrole and thiophene, pyromutic acid Vinyl esters of unsaturated heterocyclic compounds such as vinyl, vinyl furancarboxylate, vinyl pyrrole-2-carboxylate, vinyl thiophenecarboxylate, butanediol methacrylate, hexanediol acrylate, octanedio (Meth) acrylic acid esters of linear polyhydric alcohols such as dimethacrylate, decanediol acrylate and dodecanediol methacrylate, branching and substitution such as neopentyl glycol dimethacrylate, 2-hydroxy, 1,3-diacryloxypropane Polyhydric alcohol (meth) acrylic acid esters, polyethylene glycol di (meth) acrylate, polypropylene polyethylene glycol di (meth) acrylates, divinyl succinate, divinyl fumarate, vinyl / divinyl maleate, divinyl diglycolate, itacon Vinyl / divinyl acetate, divinyl acetone dicarboxylate, divinyl glutarate, divinyl 3,3′-thiodipropionate, divinyl aconite / trivinyl, divinyl adipate, dipimelate Cycloalkenyl, divinyl suberate, azelate, divinyl sebacate, divinyl dodecanedioate divinyl, the polyvinyl esters of polycarboxylic acids such as oxalic acid divinyl and the like.

  In particular, in the crystalline polyester resin, for example, unsaturated polycarboxylic acids such as fumaric acid, maleic acid, itaconic acid, trans-aconitic acid, etc. are copolymerized in the polyester, and then the multiple bond portions in the resin are bonded together, Or you may use the method of bridge | crosslinking using another vinyl type compound. In addition, these crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more types.

  As a method of cross-linking with these cross-linking agents, a method of polymerizing and cross-linking with a cross-linking agent at the time of polymerization of a polymerizable monomer (monomer) may be used. Alternatively, the unsaturated portion may be cross-linked by a cross-linking reaction after toner preparation or after toner preparation.

  When the binder resin is a polyester resin, the polymerizable monomer can be polymerized by condensation polymerization. As the polycondensation catalyst, known ones can be used. Specific examples include titanium tetrabutoxide, dibutyltin oxide, germanium dioxide, antimony trioxide, tin acetate, zinc acetate, tin disulfide and the like. It is done. When the binder resin is a vinyl resin, the polymerizable monomer can be polymerized by radical polymerization.

The initiator for radical polymerization is not particularly limited as long as it can be emulsion polymerized. Specifically, hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide Ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyltetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid-tert-butyl hydroperoxide, tert-butyl formate, Peroxides such as tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, tert-butyl perN- (3-toluyl) carbamate, 2,2 '-Azobispro Bread, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2,2′-azobis (2-amidinopropane) hydrochloride, 2,2 ′ -Azobis (2-amidinopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2- Methyl methylpropionate, 2,2′-dichloro-2,
2′-azobisbutane, 2,2′-azobis-2-methylbutyronitrile, dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 2 -(4-methylphenylazo) -2-methylmalonodinitrile, 4
, 4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-
Methylmalonodinitrile, 2- (4-bromophenylazo) -2-allylmalonodinitrile, 2,2′-azobis-2-methylvaleronitrile, dimethyl 4,4′-azobis-4-cyanovalerate, 2 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobiscyclohexanenitrile, 2,2′-azobis-2-propylbutyronitrile,
, 1′-azobis-1-chlorophenylethane, 1,1′-azobis-1-cyclohexanecarbonitrile, 1,1′-azobis-1-cycloheptanenitrile, 1,1′-azobis-1-phenylethane, 1,1′-azobiscumene, ethyl 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1′-azobis-1,2-diphenylethane, Poly (bisphenol A-4,4′-azobis-4-cyanopentanoate)
Azo compounds such as poly (tetraethylene glycol-2,2′-azobisisobutyrate), 1,4-bis (pentaethylene) -2-tetrazene, 1,4-dimethoxycarbonyl-1,4-diphenyl -2-tetrazene and the like. These polymerization initiators can also be used as initiators for the crosslinking reaction.

As the binder resin, mainly the crystalline polyester resin and the non-crystalline polyester resin have been described above. However, other styrenes such as styrene, parachlorostyrene, α-methylstyrene, etc. Acrylic monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, Methacrylic monomers such as lauryl methacrylate and 2-ethylhexyl methacrylate; ethylenically unsaturated acid monomers such as acrylic acid, methacrylic acid and sodium styrenesulfonate; and vinyl nitriles such as acrylonitrile and methacrylonitrile Vinyl vinyl ether, vinyl Vinyl ethers such as isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; homopolymers of olefin monomers such as ethylene, propylene and butadiene, and two or more of these monomers Copolymers combined or a mixture thereof, and further, non-vinyl condensation resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, or the like and the vinyl resins Mixtures, graft polymers obtained by polymerizing vinyl monomers in the presence of these, and the like can be used.

  As will be described later, when the toner of this embodiment is produced by an emulsion polymerization aggregation method, the binder resin is prepared as a resin particle dispersion. This resin particle dispersion can be easily obtained by an emulsion polymerization method and a similar polymerization method in a heterogeneous dispersion system. In addition, it can be obtained by any method such as a method in which a polymer that has been uniformly polymerized by a solution polymerization method, a cage polymerization method, or the like is added together with a stabilizer to a solvent in which the polymer does not dissolve and mixed mechanically and dispersed. it can.

For example, when a vinyl monomer is used, an ionic surfactant or the like is used, and resin particles are preferably obtained by emulsion polymerization or seed polymerization using an ionic surfactant and a nonionic surfactant in combination. A dispersion can be made.
Examples of the surfactant used herein include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; Nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, alkyl alcohol ethylene oxide adducts, polyhydric alcohols, and various graft polymers can be exemplified, but are particularly limited. It is not a thing.

  When preparing a resin particle dispersion by emulsion polymerization, a small amount of unsaturated acid such as acrylic acid, methacrylic acid, maleic acid, styrene sulfonic acid, etc. is added as a part of the monomer component to the particle surface. A protective colloid layer can be formed, and soap-free polymerization is possible, which is particularly preferable.

The volume average particle size of the resin particles in the resin particle dispersion is desirably 1 μm or less, and more desirably 0.01 μm or more and 1 μm or less. If the average particle diameter of the resin particles exceeds 1 μm, the particle size distribution of the finally obtained toner may be broadened, or free particles may be generated, leading to a decrease in performance and reliability.
On the other hand, when the average particle diameter of the resin particles is within the above range, the above disadvantages are eliminated, uneven distribution among the toners is reduced, dispersion in the toners is improved, and variations in performance and reliability are reduced. It is advantageous. The average particle size of the resin particles can be measured using, for example, a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation, SALD2000A).

-Release agent-
As the release agent, known release agents for toner can be used, for example, low molecular weight polyolefins such as polyethylene, polypropylene, polybutene; silicones, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide. Fatty acid amides such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, etc .; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, fisher Examples thereof include mineral-based waxes such as Tropsch wax, petroleum-based waxes, and modified products thereof.

When a toner is prepared using an emulsion polymerization aggregation method, these release agents are also dispersed in water together with a polymer electrolyte such as an ionic surfactant, a polymer acid or a polymer base, and the melting point is exceeded. While being heated, it can be granulated using a homogenizer or a pressure discharge type dispersing machine capable of imparting a strong shearing force, and used as a release agent dispersion containing release agent particles having an average particle size of 1 μm or less.
These release agent particles may be added to the mixed solvent together with other resin particle components at the time of preparation of the toner, or may be divided and added in multiple stages.

  The content of the release agent in the toner base particles is preferably in the range of 0.5% by mass to 50% by mass, more preferably in the range of 1% by mass to 30% by mass, and more preferably 5% by mass to 15% by mass. The range of is more preferable. If the content is less than 0.5% by mass, oilless fixing may be difficult. If the content exceeds 50% by mass, the exfoliation of the release agent on the image surface tends to be insufficient at the time of fixing. The release agent tends to stay, and the transparency of the image may be deteriorated.

The average dispersion diameter of the release agent dispersed and contained in the toner is preferably in the range of 0.3 μm to 0.8 μm, and preferably in the range of 0.4 μm to 0.8 μm. More preferred.
When the average dispersion diameter of the release agent is less than 0.3 μm, the releasability may be insufficient, and this tendency tends to become more remarkable particularly when the process speed is fast. 0.8μm
In the case of exceeding the above, there is a case where the transparency decreases when the OHP sheet is used and the exposure of the release agent component to the toner surface becomes remarkable.

Further, the standard deviation of the dispersion diameter of the release agent is preferably 0.05 or less, and more preferably 0.04 or less. When the standard deviation of the dispersion diameter of the release agent exceeds 0.05, the release property,
It may adversely affect the transparency when using the OHP sheet and the exposure of the release agent to the toner surface.
In addition, the average dispersion diameter of the release agent dispersed and contained in the toner is obtained by analyzing a TEM (transmission electron microscope) photograph of a cross section of the toner base particle with an image analysis device (Lusex image analysis device manufactured by Nireco). The average value of the dispersion diameter (= (major axis + minor axis) / 2) of the release agent in 100 toner base particles is obtained, and the standard deviation is based on the individual dispersion diameters obtained at this time. Asked.

Further, the exposure rate of the release agent on the surface of the toner base particles is preferably in the range of 5 atom% to 12 atom%, and more preferably in the range of 6 atom% to 11 atom%.
When the exposure rate is less than 5 atom%, the fixability may be deteriorated when fixing in a high temperature range, particularly when high-speed image formation with a process speed of 200 mm / s or more is performed, and when the exposure rate exceeds 12 atom%. In long-term use, the developability and transferability may be deteriorated due to uneven distribution of external additives or embedding in toner base particles.

Here, the exposure rate of the release agent on the surface of the toner base particles was determined by XPS (X-ray photoelectron spectroscopy) measurement.
XPS measurement was performed using JPS-9000MX manufactured by JEOL Ltd. as a measuring device, using an MgKα ray as an X-ray source, setting an acceleration voltage to 10 kV, and an emission current to 30 mA.
Then, the amount of the release agent on the toner surface was quantified by peak-separating components derived from the release agent on the toner surface from the C _1S spectrum obtained under the above conditions. In the peak separation, the measured C _1S spectrum is separated into each component using curve fitting by the least square method. As the component spectrum serving as a base for separation, a C _1S spectrum obtained by independently measuring the release agent, binder resin, and crystalline resin used in the preparation of the toner was used.

-Colorant-
It is particularly preferable that the toner of the exemplary embodiment basically contains a colorant. However, if the toner of this embodiment is used for special purposes, such as when an infrared absorber is added for the printing of encryption information, or when a transparent image is formed, instead of forming a colored image, coloring The agent may not be used.
Examples of the colorant used in the present invention include carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliant amine 3B, Brilliantamine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, etc. Various pigments, acridine, xanthene, azo, benzoquinone, azine, anthraquinone Combine one or more dyes such as thioindico, dioxazine, thiazine, azomethine, indico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, and thiazole together Can be used.

When a toner is produced using an emulsion polymerization aggregation method, these colorants are also dispersed in a solvent and used as a colorant dispersion. In this case, the volume average particle diameter of the colorant particles is 0.8.
It is preferable that it is micrometer or less, and it is more preferable that it is 0.05 micrometer or more and 0.5 micrometer or less.
When the average particle diameter of the colorant particles exceeds 0.8 μm, the particle size distribution of the finally obtained toner for developing an electrostatic image is broadened or free particles are generated, resulting in a decrease in performance and reliability. There is. Further, when the average particle diameter of the colorant particles is smaller than 0.05 μm, not only the colorability in the toner is lowered but also the shape controllability which is one of the characteristics of the emulsion aggregation method is impaired, and There are cases where a toner having a close shape cannot be obtained.

In addition, the proportion of coarse particles having a volume average particle size of 0.8 μm or more in the colorant dispersion is preferably less than 10% by number, and more preferably close to 0% by number. The presence of the coarse particles may impair the stability of the formed aggregated particles in the aggregation process in which aggregated particles are formed in a raw material dispersion containing various toner raw material components such as a colorant dispersion. In addition, coarse colored particles may be liberated or the particle size distribution may be broadened.

Further, the proportion of fine particles having a volume average particle size of 0.05 μm or less in the colorant dispersion is preferably 5% by number or less. The presence of the fine particles may impair the shape controllability of the toner base particles in the fusing step in which the aggregated particles are heated and fused, and the average circularity of 0.940 or less may not be obtained.
On the other hand, when the average particle diameter, coarse particles, and fine particles of the colorant particles are within the above ranges, there is no such defect, uneven distribution between the toners is reduced, and dispersion in the toners is improved. In addition, it is advantageous that the variation in reliability is reduced.
The volume average particle size of the colorant particles is also measured by a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation,
SALD2000A) etc. can be used for measurement. The addition amount of the colorant is preferably set in the range of 1% by mass or more and 20% by mass or less with respect to the whole toner particles.

As a method for dispersing these colorants in a solvent, any method such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, a dyno mill, and the like can be adopted. Absent.

In addition, as the colorant, those subjected to surface modification treatment with rosin, polymer or the like can be used. The surface-modified colorant is stabilized in the colorant dispersion, and after the colorant is dispersed to the desired average particle size in the colorant dispersion, it is mixed with the resin particle dispersion. At this time, it is advantageous in that the colorants are not aggregated even in the aggregation process and the like, and a good dispersion state can be maintained. On the other hand, the colorant that has been subjected to an excessive surface modification treatment may be released without agglomerating with the resin particles in the aggregation process. For this reason, the surface modification treatment is performed under selected optimum conditions.
Examples of the polymer used for the surface treatment of the colorant include acrylonitrile polymer and methyl methacrylate polymer.

The conditions for surface modification are generally a polymerization method in which a monomer is polymerized in the presence of a colorant (pigment), a colorant (pigment) is dispersed in a polymer solution, and the solubility of the polymer is lowered to reduce the colorant (pigment). ) A phase separation method for depositing on the surface can be used.

-Other additive components-
When the toner of this embodiment is used as a magnetic toner, magnetic powder is contained. Examples of the magnetic powder used here include metals such as ferrite, magnetite, reduced iron, cobalt, nickel, and manganese, alloys, or these metals. And the like. Furthermore, various charge control agents that are usually used, such as quaternary ammonium salts, nigrosine compounds and triphenylmethane pigments, may be added as necessary.

  If necessary, inorganic particles can be added to the toner of this embodiment. The inorganic particles having a center particle of 5 nm or more and 30 nm or less and the inorganic particle having a center particle diameter of 30 nm or more and 100 nm or less are contained in a range of 0.5 mass% or more and 10 mass% or less with respect to the toner. More preferable in terms of durability.

  Examples of the inorganic particles include silica, hydrophobized silica, titanium oxide, alumina, calcium carbonate, magnesium carbonate, tricalcium phosphate, colloidal silica, cationic surface-treated colloidal silica, and anion surface-treated colloidal silica. These inorganic particles are dispersed in advance in the presence of an ionic surfactant using an ultrasonic disperser or the like, and it is more preferable to use colloidal silica which does not require this dispersion treatment.

  When the added amount of the inorganic particles is less than 0.5% by mass, not only the addition of the inorganic particles does not provide sufficient toughness at the time of melting the toner, but not only the releasability in oilless fixing can be improved, but also when the toner is melted. The coarse dispersion of the toner particles in the toner increases only the viscosity, and as a result, the spinnability is deteriorated, so that the peelability in oilless fixing may be impaired. On the other hand, if it exceeds 10% by mass, sufficient toughness can be obtained, but the fluidity at the time of melting the toner is greatly reduced, and the gloss of the image may be impaired.

  In addition, a known external additive can be externally added to the toner of the exemplary embodiment. As the external additive, inorganic particles such as silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate can be used. For example, as fluidity aids and cleaning aids, inorganic particles such as silica, alumina, titania and calcium carbonate, and resin particles such as vinyl resin, polyester and silicone can be used. The method for adding the external additive is not particularly limited, but it is also possible to add the external additive to the toner particle surface by applying a shearing force in a dry state.

-Various physical properties of toner-
The toner of the exemplary embodiment preferably satisfies the following formula (1).
Formula (1) 0.2 ≦ Dw / Up ≦ 0.8
In formula (1), Dw is the temperature of the electrostatic charge image developing toner increased from 70 ° C. to 120 ° C. at 10 ° C./min by differential thermal analysis and then decreased from 120 ° C. to 70 ° C. at 10 ° C./min. Represents a temperature range with respect to a reference line of an endothermic peak observed in the process of heating from 70 ° C. to 120 ° C. in the heating / cooling process, and Up represents a process of cooling from 120 ° C. to 70 ° C. in the heating / cooling process Represents the temperature width of the exothermic peak observed with respect to the reference line. In addition, the reference line is a base portion on both sides of the peak (a heat amount change line (so-called base line) with respect to a temperature drawn when a rate of change of heat absorption or heat generation with respect to a temperature change is constant) and a peak apex. On the other hand, it means a straight line connecting the peaks (intersections with the low temperature side or high temperature side lines).
When there are a plurality of exothermic peaks observed in the cooling process, Up means the sum of the temperature widths with respect to the reference line at each peak, and this is the same for Dw. The peak includes not only a peak that forms a clear concave or convex with respect to the reference line, but also a peak that forms a gentle broad or concave with respect to the reference line.

In the formula (1), Dw means a thermal change from a state where the toner is solidified by heating to a state where the toner is melted at the time of fixing.
On the other hand, Up means a thermal change to a state where the toner once heated and melted at the time of fixing is cooled and solidified. Specifically, the toner is cooled and solidified from the heat-melted state. This means the degree of transition from the compatible state of the crystalline resin and the release agent to the phase separation state in the process.
Here, when Dw and Up satisfy the relationship represented by the formula (1), the compatibility state between the crystalline resin and the release agent is higher after fixing than before fixing (that is, the phase separation state is higher). In other words, gloss unevenness due to phase separation between the crystalline resin after fixing and the release agent occurs compared to the case where the formula (1) is not satisfied. It means that it is easier.
Dw / Up is preferably 0.2 to 0.8 as shown in formula (1), but more preferably 0.3 to 0.7.

  For the differential thermal analysis, a known differential thermal analyzer such as DSC60A (with an automatic cooling device manufactured by Shimadzu Corporation) can be used. In addition, the temperature correction of the detection part of the apparatus uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. In addition, an aluminum pan is used as a measurement sample, and an empty pan is set as a control. In this state, after heating from 25 ° C. to 120 ° C. at a heating rate of 10 ° C./min, cooling from 120 ° C. to 25 ° C. at a cooling rate of 10 ° C./min. Measure the endothermic / calorific value change with respect to temperature change when the temperature drops.

Further, the molecular weight distribution Mw / Mn of the toner is preferably in the range of 5 or more and 30 or less, more preferably in the range of 6 or more and 28 or less, and further preferably in the range of 7 or more and 25 or less.
When the molecular weight distribution is less than 5, the fixability (offset) on the high temperature side may deteriorate or the gloss may increase. In addition, since the durability of the toner itself is reduced, in a high-speed machine with a process speed of 200 mm / s or more, and an image forming apparatus that uses recycled toner, transferability is reduced due to deformation or cracking of the toner, and image defects due to filming. Etc. may occur easily. On the other hand, when the molecular weight distribution exceeds 30, the toner itself has a high viscosity, which may impair the low-temperature fixability. Further, when the toner is produced using the emulsion polymerization aggregation method, it may be difficult to control the shape of the toner. The means for adjusting the molecular weight distribution is not particularly limited. For example, one type of binder resin may be used, or two or more types of binder resins may be used in combination.

  Molecular weight distribution was measured using Tosoh Corporation HLC-8120GPC, SC-8020 apparatus, TSK gei, SuperHM-H (6.0 mm ID × 15 cm × 2) as a column, and THF (tetrahydrofuran) as an eluent. did. The measurement conditions were a sample concentration of 0.5% and a flow rate of 0.6 ml / min. Sample injection volume 10 μl, measurement temperature 40 ° C., calibration curve is A-500, F-1, F-10, F-80, F-380, A-2500, F-4, F-40, F-128, Made from 10 samples of F-700. The data collection interval in sample analysis was 300 ms.

  Further, the volume average particle diameter D50v of the toner of the present embodiment is preferably in the range of 3 μm or more and 7 μm or less. If the thickness is less than 3 μm, the chargeability may be insufficient and scattering to the surroundings may occur to cause image fogging. If the thickness exceeds 7 μm, the resolution of the image may be reduced, and it may be difficult to achieve high image quality. The volume average particle diameter D50v is more preferably in the range of 5 μm to 6.5 μm.

Further, the volume average particle size distribution index GSDv of the toner is preferably 1.28 or less. If GSDv exceeds 1.28, the sharpness and resolution of the image may decrease. On the other hand, the number average particle size distribution index GSDp is preferably 1.30 or less. When the GSDp exceeds 1.30, the ratio of the small particle size toner increases, and therefore, in some cases, the initial performance may have a very large influence from the viewpoint of reliability. That is, as conventionally known, since the adhesion of small-diameter toner is large, electrostatic control is likely to be difficult, and when a two-component developer is used, it may be likely to remain on the carrier. In this case, if mechanical force is repeatedly applied, carrier contamination may be caused, and as a result, deterioration of the carrier may be promoted.

  Particularly in the transfer process, among the toners developed on the image carrier, it is difficult to transfer the small diameter component, resulting in poor transfer efficiency, resulting in increased waste toner and poor image quality. . As a result of these problems, there are cases where toners that are not electrostatically controlled and reverse-polar toners increase, which may contaminate the surroundings. In particular, the charging roll accumulates these uncontrolled toners via an image carrier or the like, which may cause charging failure.

In addition, since the toner having a small diameter component tends to be insufficient in the inclusion of the crystalline resin, filming on the image carrier may be caused. On the other hand, toner with a large particle size component may cause toner cracking in the developing machine, deflation from the developing machine, image quality deterioration due to charging failure, and the like.
The volume average particle size distribution index GSDv is more preferably 1.25 or less, and the number average particle size distribution index GSDp is more preferably 1.25 or less.

Here, the volume average particle diameter D50v and various particle size distribution indices can be measured using Multisizer II (manufactured by Beckman-Coulter) and the electrolyte using ISOTON-II (manufactured by Beckman-Coulter). it can.
In the measurement, a measurement sample is added in a range of 0.5 mg to 50 mg in 2 ml of a 5% by weight aqueous solution of a surfactant such as sodium alkylbenzenesulfonate as a dispersant. This is added to 100 ml to 150 ml of electrolyte.
The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for 1 minute with an ultrasonic disperser, and the particle size distribution of particles having a particle size in the range of 2 μm to 50 μm is obtained using the Multisizer II type with an aperture diameter of 100 μm. taking measurement. The number of particles to be sampled is 50,000.

For the particle size range (channel) divided on the basis of the particle size distribution measured in this way, the cumulative distribution is drawn from the smaller diameter side for the volume and number, respectively, and the cumulative particle size average particle size is 16%. Diameter D16v, cumulative number average particle diameter D16p, cumulative volume average particle diameter 50v, cumulative number average particle diameter D50p, cumulative number average particle diameter D84p, cumulative volume average particle diameter D84v, cumulative number average The particle size is defined as D84p.
Here, the volume average particle size distribution index (GSDv) is defined as (D84v / D16v) ^1/2 and the number average particle size distribution index (GSDp) is defined as (D84p / D16p) ^1/2 .

  Further, the average circularity of the toner is preferably in the range of 0.940 to 0.980. If the average circularity is less than the above range, the shape becomes indeterminate, and transferability, durability, fluidity, and the like may decrease. On the other hand, if the above range is exceeded, the ratio of the spherical particles increases and the cleaning property may become difficult. The average circularity is more preferably in the range of 0.950 or more and 0.970 or less.

  In the case of a toner containing a crystalline resin, the average circularity is spherical (when the average circularity is closer to 1), and the spherical toner with a large amount of crystalline resin component may increase. Filming due to accumulation, member deterioration due to torque increase, and filming on the image carrier may occur. On the other hand, when it is on the irregular side (when the average circularity is closer to 0), it may cause toner cracking in the developing machine, and the crystalline resin component may be exposed at the cracked interface, thereby impairing charging properties, etc. There is.

The average circularity of the toner can be measured by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant such as an alkylbenzesulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been previously removed, and a measurement sample is further added. Add about 0.1g to 0.5g.
The suspension in which the measurement sample is dispersed is subjected to dispersion treatment for 1 to 3 minutes with an ultrasonic wave disperser, and the average circularity of the toner is measured with the above apparatus with a dispersion concentration of 3000 to 10,000 / μl.

  The glass transition temperature Tg of the toner of the present embodiment is not particularly limited, but a range of 45 ° C. or more and 60 ° C. is preferably selected. Below the above range, problems such as toner storage stability, fixed image storage stability, and durability in the actual machine may occur. If it is higher than the above range, problems such as an increase in the fixing temperature and an increase in the temperature required for granulation may occur.

  In addition, Tg is measured based on ASTMD3418-8 using a DSC measuring machine (differential thermal analyzer DSC60A, manufactured by Shimadzu Corporation). The temperature correction of the detection part of the apparatus uses the melting points of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. As the sample, an aluminum pan is used, an empty pan is set as a control, and the measurement is performed at a heating rate of 10 ° C./min.

The charge amount of the electrostatic image developing toner of the present embodiment is preferably in the range of 10 μC / g to 40 μC / g, more preferably in the range of 15 μC / g to 35 μC / g in absolute value. When it is less than 10 μC / g, background stains are likely to occur, and when it exceeds 40 μC / g, the image density may be easily lowered.
The ratio of the charge amount in the summer (28 ° C., 85% RH) of the electrostatic image developing toner to the charge amount in the winter (10 ° C., 30% RH) is preferably 0.5 or more and 1.5 or less. 0.7 or more and 1.3 or less are more preferable. When this ratio is out of the above range, the toner is highly dependent on the environment, and the charging property is not stable, which is not preferable in practice.

-Toner production method-
Next, the production of the toner of this embodiment will be described.
The toner according to the exemplary embodiment can be manufactured by a known toner manufacturing method, but a so-called wet manufacturing method, that is, at least a crystalline resin and a release agent in water or an organic solvent or a mixed solvent thereof. It is preferable that the toner base particles are produced through a granulation step for granulating the toner base particles and a cleaning / drying step for cleaning / drying the toner base particles. In the wet manufacturing method, it is easy to add a desired amount of a metal element capable of taking a valence of 2 or more to the toner base particles in the granulation step, so that the toner of this embodiment can be easily obtained. it can.

As this wet manufacturing method, in addition to the mold release agent, the components used as necessary, such as a colorant, are suspended together with a polymerizable monomer that forms a binder resin such as a crystalline resin. Suspension polymerization method for polymerizing the body, a compound having an ionic dissociation group, a binder resin such as a crystalline resin, and a toner constituent material such as a release agent are dissolved in an organic solvent and dispersed in an aqueous solvent in a suspended state. And a suspension method for removing the organic solvent after the formation, a binder resin component such as a crystalline resin is prepared by emulsion polymerization, heteroaggregated with a dispersion such as a release agent, and then fused, and the like. However, it is not limited to these.
Of these, the emulsion polymerization aggregation method is used because it has excellent toner particle size controllability, shape controllability, and dispersion controllability of encapsulated components, and a toner having a narrow particle size distribution or narrow shape distribution can be easily obtained. It is preferable.

When this emulsion polymerization aggregation method is used, the toner according to the exemplary embodiment is, for example, a raw material dispersion obtained by mixing at least a resin particle dispersion in which a crystalline resin is dispersed and a release agent dispersion in which a release agent is dispersed. An agglomeration step for forming aggregated particles in the liquid, and the raw material dispersion in which the aggregated particles are formed are heated to a temperature equal to or higher than the glass transition temperature of the binder resin (or the melting point of the crystalline resin). It can be manufactured through at least a fusion step of fusing.
If necessary, other dispersions such as a colorant dispersion in which a colorant is dispersed, an inorganic particle dispersion, and a resin particle dispersion in which an amorphous resin is dispersed are added to the raw material dispersion. Also good. In particular, when an inorganic particle dispersion having a hydrophobic surface is added, the dispersibility of the release agent and crystalline resin inside the toner can be controlled by the degree of hydrophobicity.

Hereinafter, an emulsion polymerization aggregation method will be described in more detail as an example of the toner production method of the present embodiment.
When the toner according to the exemplary embodiment is manufactured by the emulsion polymerization aggregation method, as described above, the toner is manufactured through at least the aggregation process and the fusion process, but the aggregated particles (core) formed through the aggregation process are used. An adhesion step for forming aggregated particles having a core / shell structure in which resin particles are adhered to the surface of the particles may be provided.

-Aggregation process-
In the aggregating step, in addition to the resin particle dispersion in which the crystalline resin or the like is dispersed or the release agent dispersion in which the release agent is dispersed, other dispersions such as the colorant dispersion in which the colorant is dispersed Agglomerated particles are formed in the raw material dispersion liquid mixed as necessary.
Specifically, the raw material dispersion obtained by mixing various dispersions is heated to form aggregated particles in which the particles in the raw material dispersion are aggregated. Note that the heating is performed in a temperature range lower than the melting point of the crystalline resin (a temperature lower by 20 ° C. to 10 ° C. than the melting point).

Agglomerated particles are formed by adding a flocculant under stirring with a rotary shearing homogenizer, specifically at 20 ° C. to 30 ° C., and acidifying the pH of the raw material dispersion.
The aggregating agent used in the aggregating step is a surfactant having a reverse polarity to the surfactant used as a dispersant added to the raw material dispersion, that is, an inorganic metal salt and a metal element capable of taking a valence of 2 or more. A metal complex containing can be preferably used. In particular, the use of a metal complex is particularly preferable because the amount of the surfactant used can be reduced and the charging characteristics are improved.

  Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, calcium polysulfide, etc. Examples thereof include inorganic metal salt polymers. Of these, aluminum salts and polymers thereof are particularly preferred. In order to obtain a sharper particle size distribution, the valence of the inorganic metal salt is divalent than monovalent, trivalent than bivalent, trivalent than trivalent, and tetravalent than trivalent. The inorganic metal salt polymer is more suitable.

It is preferable to add the inorganic metal salt as an inorganic particle dispersion and simultaneously agglomerate. Thereby, it can act effectively on the molecular chain terminal of the binder resin, and can contribute to the formation of a crosslinked structure.
The inorganic particle dispersion can be prepared by an arbitrary method, for example, using a ball mill, a sand mill, an ultrasonic disperser rotary shearing homogenizer, or the like, and the dispersion average particle diameter of the inorganic particles is in the range of 100 nm to 500 nm. preferable.

  In the agglomeration step, the inorganic particle dispersion can be added stepwise or continuously. These methods are effective in uniformly dispersing the metal ion component in the inorganic particle dispersion from the toner surface to the inside. When adding stepwise, it is particularly preferable to add the dispersion at a slow rate of about 0.1 g / m or less when adding continuously in three steps or more.

  The amount of the inorganic particle dispersion added varies depending on the type of metal required and the degree of formation of the crosslinked structure, but is in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin component. Preferably, the range is 1 part by mass or more and 5 parts by mass or less.

In the aggregation step, by adjusting the type and amount of inorganic metal salt or metal complex containing a metal element capable of taking a valence of 2 or more within a range that does not affect the formation of aggregated particles, It is possible to control the content of a metal element that can take a valence of 2 or more contained in.
In addition, from the viewpoint that it is easier to achieve both a low-temperature fixability and a gloss unevenness suppressing effect at a high level, it is preferable to use aluminum sulfate, polyaluminum chloride, or calcium chloride among the flocculants listed above. It is.

-Adhesion process-
After passing through the aggregating step, an attaching step may be performed if necessary. In the attaching step, the coating layer is formed by attaching resin particles to the surface of the aggregated particles formed through the above-described aggregation step. Thereby, a toner having a so-called core layer and a core / shell structure covering the core layer can be obtained.

  The coating layer can be formed by usually adding a resin particle dispersion containing non-crystalline resin particles to the dispersion in which aggregated particles (core particles) are formed in the aggregation step. When an amorphous resin is used in addition to the crystalline resin in the aggregation process, the amorphous resin used in the adhesion process may be the same as or different from that used in the aggregation process.

In general, the adhesion step is used when a toner having a so-called core / shell structure in which a crystalline resin as a main component is included as a binder resin together with a release agent, and the main purpose thereof is the core layer. The purpose is to suppress the exposure of the release agent and crystalline resin contained in the toner surface, and to supplement the strength of the toner particles, which is insufficient with the core layer alone.

-Fusion process-
The fusion step performed after the aggregation step or the aggregation step and the adhesion step is performed by bringing the pH of the suspension containing the aggregated particles formed through these steps to a desired range,
After stopping the progress of aggregation, the aggregated particles are fused by heating.

The pH is adjusted by adding an acid and / or alkali. Although an acid is not specifically limited, The aqueous solution which contains inorganic acids, such as hydrochloric acid, nitric acid, and a sulfuric acid, in 0.1 to 50 mass% is preferable. The alkali is not particularly limited, but an aqueous solution containing an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide in the range of 0.1% by mass to 50% by mass is preferable.
In the pH adjustment, if a local pH change occurs, local aggregated particles themselves may be destroyed or local excessive aggregation may be caused, and the shape distribution may be deteriorated. In particular, the larger the scale, the greater the amount of acid and / or alkali. In general, there is only one place where the acid and alkali are added, so that if the treatment is performed in the same time, the concentration of acid and alkali at the place where the scale is increased increases.

  After performing the composition control described above, the aggregated particles are heated and fused. In the fusion, the agglomerated particles are fused by heating at a temperature of 10 to 30 ° C. or higher from the melting point of the crystalline resin (the glass transition temperature of the amorphous resin when an amorphous resin is used).

The cross-linking reaction may be performed with other components during the heating at the time of fusion or after the fusion is completed. Further, a crosslinking reaction may be performed simultaneously with the fusion. When the crosslinking reaction is performed, the above-described crosslinking agent and polymerization initiator are used in the production of the toner.
The polymerization initiator may be preliminarily mixed with the dispersion at the stage of preparing the raw material dispersion, or may be incorporated into the aggregated particles in the aggregation process. Further, it may be introduced after the fusion step or after the fusion step. In the case of introduction after the aggregation step, the adhesion step, the fusion step, or the fusion step, a solution in which the polymerization initiator is dissolved or emulsified can be added to the dispersion. These polymerization initiators may be added with known crosslinking agents, chain transfer agents, polymerization inhibitors and the like for the purpose of controlling the degree of polymerization.

-Cleaning, drying process, etc.-
After completing the coalesced particle fusion step, desired toner particles (toner base particles) are obtained through an arbitrary washing step, solid-liquid separation step, and drying step. In consideration of charging properties, the washing step is performed with ion-exchanged water. Replacement cleaning is desirable. Moreover, although there is no restriction | limiting in particular in a solid-liquid separation process, From the point of productivity, suction filtration, pressure filtration, etc. are suitable. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity. In addition, the various external additives described above can be added to the dried toner particles (toner base particles) as necessary.

<Electrostatic image developer>
The electrostatic image developer of the present embodiment (hereinafter sometimes referred to as “developer”) includes the toner of the present embodiment, and other components can be blended depending on the purpose.
Specifically, when the toner of this embodiment is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer. The toner concentration is preferably in the range of 1% by mass to 10% by mass.
Here, the carrier is not particularly limited, and examples thereof include known carriers. For example, the core material described in JP-A-62-39879, JP-A-56-11461 or the like is coated with a resin layer. A known carrier such as a prepared carrier (resin-coated carrier) can be used.

Examples of the core material of the resin-coated carrier include molded products such as iron powder, ferrite, and magnetite, and the average diameter is about 30 μm or more and 200 μm or less.
Examples of the coating resin for forming the coating layer include styrenes such as styrene, parachlorostyrene, and α-methylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, and 2-ethylhexyl acrylate. , Α-methylene fatty acid monocarboxylic acids such as methyl methacrylate, n-propyl methacrylate, lauryl methacrylate and 2-ethylhexyl methacrylate, nitrogen-containing acrylics such as dimethylaminoethyl methacrylate, vinyl nitriles such as acrylonitrile and methacrylonitrile Vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone and other vinyl ethers. Nyl ketones, olefins such as ethylene and propylene, homopolymers such as vinyl fluorine-containing monomers such as vinylidene fluoride, tetrafluoroethylene and hexafluoroethylene, or copolymers composed of two or more monomers, methyl silicone, Examples thereof include silicones such as methylphenyl silicone, polyesters containing bisphenol and glycol, epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, polycarbonate resins and the like. These resins may be used alone or in combination of two or more.

  The amount of the coating resin is preferably in the range of 0.1 to 10 parts by mass and more preferably in the range of 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the core material. For example, a heating type kneader, a heating type Henschel mixer, or a UM mixer can be used for manufacturing the carrier. Depending on the amount of the coating resin, a heating type fluidized rolling bed, a heating type kiln, or the like can be used. . The mixing ratio of the toner and the carrier in the electrostatic image developer is not particularly limited and can be selected according to the purpose.

<Image Forming Method, Image Forming Apparatus, Toner Cartridge, Process Cartridge>
Next, an image forming method using the developer of this embodiment will be described.
As a method of forming an image using the toner of the present embodiment, a known electrophotographic method can be used. Specifically, an electrostatic latent image forming step of forming an electrostatic latent image on the surface of the image carrier, A toner image forming step of developing the electrostatic latent image with a developer containing toner to form a toner image, a transfer step of transferring the toner image to a recording medium, and fixing for fixing the toner image to the recording medium It is preferable that a process is included.
In addition to these steps, known steps used in an electrophotographic image forming method can be combined. For example, cleaning is performed while collecting toner remaining on the surface of the image carrier after the transfer step. And a toner recycling step (toner recycling step) in which the toner collected in the cleaning step is reused (recycled) as toner for the developer.

  Here, the electrostatic latent image forming step is a step of forming an electrostatic latent image by charging the surface of the image carrier with a charging means and then exposing the image carrier with a laser optical system or an LED array. is there. Examples of the charging unit include a non-contact type charger such as corotron and scorotron, and a contact type that charges the image carrier surface by applying a voltage to a conductive member that is in contact with the image carrier surface. Any type of charger may be used. However, a contact charging type charger is preferable from the viewpoint that the amount of ozone generated is small, environmentally friendly, and excellent printing durability. In the contact charging type charger, the shape of the conductive member may be any of a brush shape, a blade shape, a pin electrode shape, a roller shape, and the like, and is not limited. Note that the latent image forming step is not limited to the above-described embodiment.

  In the toner image forming step, a developer holding body on which a developer layer containing at least toner is formed is brought into contact with or brought close to the surface of the image holding body, and the electrostatic latent image on the surface of the image holding body is subjected to toner. In which a toner image is formed on the surface of the image carrier. The development method can be performed using a known method, and examples of the development method when the developer is a two-component developer include a cascade method and a magnetic brush method. The developing method is not limited to the above-described mode.

  The transfer step is a step of transferring a toner image formed on the surface of the image carrier to a recording medium. The transfer process may be a system in which a toner image is directly transferred onto a recording medium such as paper, or a system in which the toner image is transferred onto a recording medium such as paper after being transferred onto a drum-like or belt-like intermediate transfer member. The transfer method is not limited to the above-described mode.

  For example, a corotron can be used as a transfer device that transfers the toner image from the image carrier to paper or the like. The corotron is effective as a means for charging the paper, but in order to give a predetermined charge to the paper as a recording medium, a high voltage of several kV must be applied and a high voltage power source is required. In addition, ozone is generated by corona discharge, which causes deterioration of rubber parts and the image carrier. Therefore, contact transfer that transfers a toner image onto a sheet by pressing a conductive transfer roll having an elastic material against the image carrier. The method is preferred. The transfer device is not limited to the above-described embodiment.

  The cleaning step is a step of removing toner, paper dust, dust, etc. adhering to the surface of the image carrier by bringing a blade, a brush, a roll or the like into direct contact with the surface of the image carrier.

  The most commonly employed method is a blade cleaning method in which a rubber blade such as polyurethane is pressed against the image carrier. On the other hand, a magnetic brush method in which a magnet is fixedly arranged inside, a cylindrical non-magnetic sleeve that can rotate on the outer periphery thereof, a magnetic carrier is held on the sleeve surface, and toner is collected, A method may be used in which semiconductive resin fibers and animal hairs are rotatable in a roll shape, and a toner having a polarity opposite to that of the toner is applied to the roll to remove the toner. In the former magnetic brush system, a cleaning pretreatment corotron may be provided. The cleaning method is not limited to the above-described mode.

  The fixing step is a step of fixing the toner image transferred on the surface of the recording medium with a fixing device. As the fixing device, a heat fixing device using a heat roll is preferably used. The heat fixing device includes a fixing roller having a heater lamp for heating inside a cylindrical metal core, a so-called release layer formed on the outer peripheral surface by a heat resistant resin film layer or a heat resistant rubber film layer, and the fixing roller. The pressure roller or the pressure belt is arranged in pressure contact with the roller and has a layer containing a heat-resistant elastic material formed on the outer peripheral surface of the cylindrical metal core or the surface of the belt-like base material. In the toner image fixing process, a recording medium on which a toner image is formed is passed through a contact portion formed by a fixing roller and a pressure roller or a pressure belt, and heat of binder resin, additives, etc. in the toner is passed. Fix by melting. However, the fixing method is not limited to the above-described mode.

In the case of producing a full-color image, each of the plurality of image holding bodies has a developer holding body for each color, and a latent image forming step using each of the plurality of image holding bodies and the developer holding bodies, and a toner image Through a series of steps including a forming step, a transfer step, and a cleaning step, each color toner image for each step is sequentially stacked on the same recording medium surface, and the stacked full-color toner images are thermally fixed in the fixing step. An image forming method is preferably used.
By using the developer of this embodiment in the image forming method, stable development, transfer, and fixing performance can be obtained even in a tandem system that is suitable for, for example, small size and high-speed color.

  The configuration of the toner recycling means for carrying out the toner recycling process is not particularly limited. For example, the toner collected by the cleaning unit is replenished by a transport conveyor or a transport screw, a toner hopper for replenishment, a developing device, Examples thereof include a method of mixing with a replenishing toner and an intermediate chamber and supplying the toner to a developing device containing a developer. A method of returning directly to the developing device or a method of supplying the replenishment toner and the recycled toner in the intermediate chamber is preferable.

  When the toner is recycled and used, it is necessary that the strength of the toner particles is high, the dispersibility of the release agent in the toner is good, and the toner surface is not exposed much. In this regard, the conventional toner containing a crystalline resin as a binder resin and including a release agent has a high content of the crystalline resin, so the toner particles have low strength, and therefore the toner is recycled. Therefore, if the toner is exposed to mechanical stress many times, the toner is deformed or broken, and filming or the like occurs. For this reason, if an image is formed over a long period of time using an above-described toner capable of oilless fixing or fixing in a low temperature range in an image forming apparatus equipped with a toner recycling mechanism, image quality deterioration due to filming or the like is deteriorated. Will occur.

  However, although the toner of this embodiment has a crystalline resin as a main component as a binder resin and includes a release agent, it has higher elasticity than the above-described conventional toner, so that the toner is recycled. Therefore, the toner is unlikely to be deformed or broken even if it is exposed to mechanical stress many times. Therefore, filming can be suppressed even when an image is formed over a long period of time while recycling toner using an image forming apparatus equipped with a toner recycling mechanism. For this reason, deterioration of image quality over time can be suppressed.

The configuration of the image forming apparatus that performs the above-described image forming method is not particularly limited, but the image carrier, a charging unit that charges the surface of the image carrier, and the charged image. An electrostatic latent image forming means for forming an electrostatic latent image on the surface of the holding body; a toner image forming means for developing the electrostatic latent image with the developer to form a toner image; and the toner image on the surface of the recording medium. The image forming apparatus preferably includes at least a transfer unit that transfers the toner image to the surface of the recording medium and a fixing unit that fixes the toner image transferred to the surface of the recording medium.
In this case, the layer constituting the outermost surface of the image carrier preferably contains at least one resin selected from a siloxane-based resin having a crosslinked structure and a phenol-based resin. Also, a cleaning unit for cleaning while collecting the toner remaining on the surface of the image carrier after the toner image is transferred, and a toner reuse for reusing the toner collected by the cleaning unit as the toner for the developer Preferably further comprising means.

In the image forming apparatus having the above-described configuration, a toner cartridge that is detachable from the image forming apparatus and contains a developer to be supplied to the toner image forming unit may be used. Further, the image forming apparatus is detachable from the image forming apparatus, accommodates the image carrier and the developer, and supplies the developer to the electrostatic latent image formed on the surface of the image carrier to form a toner image. A process cartridge including at least a toner image forming unit may be used.
As described above, the process cartridge is a single unit that is detachable from the apparatus main body including at least the image holding member and the toner image forming unit. In addition, the process cartridge includes a charging unit, an exposure unit, and a cleaning unit. It may be.

  Examples of recording media for transferring toner images include plain paper used in electrophotographic copying machines, printers, OHP sheets, coated paper whose surface is coated with resin, art paper for printing, etc. Can be used.

Next, the image carrier will be described.
As the image carrier, a known photoreceptor in which at least a photosensitive layer is provided on a conductive support can be used, but an organic photoreceptor is preferably used. In this case, the layer constituting the outermost surface of the image carrier, for example, the protective layer, preferably contains a resin having a crosslinked structure. As the resin having a crosslinked structure, for example, a phenol resin, a urethane resin, and a siloxane resin can be used, and a siloxane resin and a phenol resin are most preferable.

The image carrier including a resin having a cross-linked structure as a layer constituting the outermost surface has high strength. Therefore, the durability of the image carrier is high and the life of the image carrier can be extended. However, when a cleaning blade is used as a cleaning means for the image carrier in order to ensure cleaning performance, it is necessary to bring the cleaning blade into contact with the image carrier at a relatively high contact pressure.
In this case, the toner remaining on the surface of the image carrier is easily destroyed at the contact portion between the cleaning blade and the image carrier, so that the toner constituent material is likely to adhere to the surface of the image carrier and the charging fluctuations associated therewith are likely to occur. Become. However, since the toner according to the exemplary embodiment has excellent strength, occurrence of filming can be suppressed. Therefore, it is possible to suppress fluctuations in charging due to filming. Further, even when combined with a method of recycling and reusing toner, image quality is not deteriorated over a long period of time.

  The layer structure of the image carrier is not particularly limited as long as it includes a conductive support and a photosensitive layer provided on the conductive support. Preferably, the photosensitive layer is a charge generation layer. It is preferably a function-separated type image carrier comprising a charge transport layer. Specifically, an undercoat layer, a charge generation layer, a charge transport layer, and a protective layer are laminated in this order on the surface of a conductive substrate. Preferably there is. Details of each layer will be described below.

  Examples of the conductive support include a metal plate, a metal drum, a metal belt, or a conductive material using a metal or an alloy such as aluminum, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, or platinum. Examples thereof include paper, a plastic film, a belt, and the like on which a conductive compound such as a polymer or indium oxide, or a metal or alloy such as aluminum, palladium, or gold is applied, vapor-deposited, or laminated. When the image carrier is used in a laser printer, the laser oscillation wavelength is preferably from 350 nm to 850 nm, and the shorter wavelength is preferable because the resolution is excellent.

In order to prevent interference fringes generated when laser light is irradiated, the surface of the support is preferably roughened to a centerline average roughness Ra of 0.04 μm or more and 0.5 μm or less. As a roughening method, wet honing is performed by suspending an abrasive in water and spraying on the support, or centerless grinding in which the support is pressed against a rotating grindstone and grinding is performed continuously, an anode It is preferable to prepare a layer containing oxidized, organic or inorganic semiconductive particles.
If Ra is smaller than 0.04 μm, it becomes close to a mirror surface, so that the effect of preventing interference cannot be obtained. If Ra is larger than 0.5 μm, even if a film is formed, the image quality may become rough and unsuitable. When non-interfering light is used for the light source, it is not particularly necessary to roughen the interference fringes, and it is possible to prevent the occurrence of defects due to the unevenness of the surface of the base material, which is suitable for longer life.

  The anodizing treatment is to form an oxide film on the aluminum surface by anodizing in an electrolyte solution using aluminum as an anode. Examples of the electrolyte solution include a sulfuric acid solution and an oxalic acid solution. However, the intact porous anodic oxide film is chemically active, easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, the pores in the anodized film are sealed with pressurized water vapor or boiling water (a metal salt such as nickel may be added) by volume expansion due to a hydration reaction, and a sealing process is performed to change to a more stable hydrated oxide. . The thickness of the anodized film is preferably 0.3 μm or more and 15 μm or less. When it is thinner than 0.3 μm, the barrier property against injection is poor and the effect is not sufficient. On the other hand, if it is thicker than 15 μm, the residual potential increases due to repeated use.

The treatment with an acidic treatment liquid composed of phosphoric acid, chromic acid and hydrofluoric acid is carried out as follows, for example. The mixing ratio of phosphoric acid, chromic acid and hydrofluoric acid in the acidic treatment liquid is such that phosphoric acid is in the range of 10 mass% to 11 mass%, chromic acid is in the range of 3 mass% to 5 mass%, and hydrofluoric acid is The concentration of these acids is preferably in the range of 13.5 mass% to 18 mass%.
The treatment temperature is preferably 42 ° C. or higher and 48 ° C. or lower. However, by keeping the treatment temperature high, a thicker film can be formed more quickly. The film thickness is preferably from 0.3 μm to 15 μm. When it is thinner than 0.3 μm, the barrier property against injection is poor and the effect is not sufficient. On the other hand, if it is thicker than 15 μm, the residual potential increases due to repeated use.

  The boehmite treatment can be performed, for example, by immersing in pure water at 90 ° C. or higher and 100 ° C. for 5 minutes to 60 minutes or by contacting with heated steam at 90 ° C. or higher and 120 ° C. or lower for 5 minutes to 60 minutes. The film thickness is preferably 0.1 μm or more and 5 μm or less. This can be further anodized using an electrolyte solution with low film solubility such as adipic acid, boric acid, borate, phosphate, phthalate, maleate, benzoate, tartrate, citrate. Good. Examples of organic or inorganic semiconductive particles include organic pigments such as perylene pigments, bisbenzimidazole perylene pigments, polycyclic quinone pigments, indigo pigments, and quinacridone pigments described in JP-A-47-30330. Organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as nitro groups, nitro groups, nitroso groups and halogen atoms, and inorganic pigments such as zinc oxide, titanium oxide and aluminum oxide. Among these pigments, zinc oxide and titanium oxide are preferable because they have high charge transporting ability and are effective for thickening.

The surface of these pigments may be surface-treated with an organic titanium compound such as a titanate coupling agent, an aluminum chelate compound or an aluminum coupling agent for the purpose of improving dispersibility or adjusting the energy level, in particular vinyltrichlorosilane. , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ -Chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3,4-epoxysilane It is preferable to treat with a silane coupling agent such as cyclohexyl trimethoxysilane.

If the amount of the organic or inorganic semiconductive particles is too large, the strength of the undercoat layer decreases and a coating film defect occurs. Therefore, the content of the semiconductive particles contained in the undercoat layer is preferably 95% by mass or less, 90 mass% or less is more preferable. As a method for mixing / dispersing organic or inorganic semiconductive particles, a method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like is applied. Mixing / dispersing is carried out in an organic solvent, but as an organic solvent, a fixed metal compound or resin is dissolved, and no gelation or aggregation occurs when organic / inorganic semiconductive particles are mixed / dispersed. Anything can be used.
For example, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene Ordinary organic solvents such as toluene can be used alone or in admixture of two or more.

An undercoat layer can be formed between the conductive support and the photosensitive layer as necessary.
Examples of materials used for forming the undercoat layer include organic zirconium compounds such as zirconium chelate compounds, zirconium alkoxide compounds and zirconium coupling agents, organic titanium compounds such as titanium chelate compounds, titanium alkoxide compounds and titanate coupling agents, aluminum In addition to organoaluminum compounds such as chelate compounds and aluminum coupling agents, antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxides Compound, aluminum titanium alkoxide compound, aluminum zirconium alloy Kokishido compounds, organometallic compounds such as, in particular an organic zirconium compound, an organic titanyl compound, an organic aluminum compound residual potential to show the good electrophotographic properties lower, are preferably used.

  Also, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3,4-epoxy It can be used by containing a silane coupling agent such as cyclohexyltrimethoxysilane.

  Furthermore, polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinyl imidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, conventionally used for the undercoat layer Known binder resins such as polyester, phenol resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, and polyacrylic acid can also be used. These mixing ratios can be set as required.

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

  As the mixing / dispersing method, for example, a conventional method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like is applied. Mixing / dispersing is carried out in an organic solvent, as long as the organic solvent dissolves a periodical metal compound or resin and does not cause gelation or aggregation when an electron transporting pigment is mixed / dispersed. Anything can be used. For example, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene Ordinary organic solvents such as toluene can be used alone or in admixture of two or more.

In general, the thickness of the undercoat layer is preferably from 0.1 μm to 30 μm, more preferably from 0.2 μm to 25 μm.
In addition, as a coating method used when providing the undercoat layer, for example, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like. Can be used. The coated layer is dried to obtain an undercoat layer. Usually, the drying is performed at a temperature at which the solvent can be evaporated and a film can be formed. In particular, the base material that has been subjected to the acidic solution treatment and the boehmite treatment is preferably formed with an intermediate layer because the defect concealing power of the base material tends to be insufficient.

Next, the charge generation layer will be described.
Charge generation materials used for forming the charge generation layer include, for example, azo pigments such as bisazo and trisazo, condensed aromatic pigments such as dibromoanthanthrone, organic pigments such as perylene pigments, pyrrolopyrrole pigments, and phthalocyanine pigments, and trigonal crystals. All known ones such as inorganic pigments such as selenium and zinc oxide can be used. In particular, when using an exposure wavelength of 380 nm to 500 nm, an inorganic pigment is preferable. And metal-free phthalocyanine pigments are preferred. Among these, hydroxygallium phthalocyanine disclosed in JP-A-5-263007 and JP-A-5-279591, chlorogallium phthalocyanine disclosed in JP-A-5-98181, JP-A-5-140472 and Of these, dichlorotin phthalocyanine disclosed in JP-A-5-140473, titanyl phthalocyanine disclosed in JP-A-4-189873 and JP-A-5-43813 are particularly preferable.

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

  The blending ratio between the charge generation material and the binder resin (weight ratio) is preferably in the range of 10: 1 to 1:10. In addition, as a method for dispersing these, a usual method such as a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method, or the like can be used. Is done. Further, at the time of dispersion, the particle size is preferably 0.5 μm or less, more preferably 0.3 μm or less, and further preferably 0.15 μm or less.

  Examples of the solvent used for dispersion include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, Ordinary organic solvents such as tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene can be used alone or in admixture of two or more.

  The thickness of the charge generation layer is generally preferably 0.1 μm or more and 5 μm or less, and more preferably 0.2 μm or more and 2.0 μm or less. Further, as a coating method used when providing the charge generation layer, for example, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, etc. Can be used.

Next, the charge transport layer will be described.
As the charge transport layer, a layer formed by a known technique can be used. These charge transport layers are formed containing a charge transport material and a binder resin, or are formed containing a polymer charge transport material.
Examples of charge transport materials include quinone compounds such as p-benzoquinone, chloranil, bromanyl, anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds Compounds, electron transport compounds such as cyanovinyl compounds, ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, etc. Examples thereof include hole transporting compounds. These charge transport materials may be used alone or in combination of two or more, but are not limited thereto. In addition, these charge transport materials can be used alone or in combination of two or more, but those having the following structure are preferable from the viewpoint of mobility.

In the general formula (A), R ¹⁴ represents a hydrogen atom or a methyl group. N means 1 or 2. Ar ₆ and Ar ₇ represent a substituted or unsubstituted aryl group, and the substituent includes a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or A substituted amino group substituted with an alkyl group having 1 to 3 carbon atoms.

In general formula (B), R ¹⁵ and R ^{15 ′} may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. . R ¹⁶ ,
R ^{16 ′} , R ¹⁷ and R ^{17 ′} may be the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 1 to 2 carbon atoms. An amino group substituted with an alkyl group, a substituted or unsubstituted aryl group, —C (R ¹⁸ ) ═C (R ¹⁹ ) (R ²⁰ ), or —CH═CH—CH═C (Ar) ₂ is represented. .
R ¹⁸ , R ¹⁹ and R ^{20 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar represents a substituted or unsubstituted aryl group. M and n are integers of 0 or more and 2 or less.

In general formula (C), R ²¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group, or —CH═CH—CH═. C (Ar) ₂ is represented. Ar represents a substituted or unsubstituted aryl group. R ²² and R ²³ may be the same or different and substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 2 carbon atoms Represents a substituted amino group or a substituted or unsubstituted aryl group.

  Further, the binder resin used for the charge transport layer is, for example, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride. -Acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N -Vinylcarbazole, polysilane, polymer charge transport materials such as polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 can also be used. These binder resins can be used alone or in admixture of two or more. The blending ratio (mass ratio) of the charge transport material and the binder resin is preferably 10: 1 to 1: 5.

  In addition, the charge transport layer can be formed by using a polymer charge transport material alone. As the polymer charge transporting material, known materials having charge transporting properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 have a high charge transporting property and are particularly preferable. The polymer charge transport material alone can be used as the charge transport layer, but it may be formed by mixing with the binder resin.

The thickness of the charge transport layer is generally preferably 5 μm or more and 50 μm or less, and more preferably 10 μm or more and 30 μm or less.
As a coating method, for example, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like can be used. Furthermore, examples of the solvent used when the charge transport layer is provided include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halongen such as methylene chloride, chloroform and ethylene chloride. Ordinary organic solvents such as fluorinated aliphatic hydrocarbons, cyclic ethers such as tetrahydrofuran and ethyl ether, or straight-chain ethers can be used alone or in admixture of two or more.

  In addition, additives such as antioxidants, light stabilizers, and heat stabilizers are added to the photosensitive layer for the purpose of preventing deterioration of the image carrier due to ozone, oxidizing gas, or light or heat generated in the copying machine. Can be added. For example, examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, and organic phosphorus compounds. Examples of the light stabilizer include derivatives such as benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine.

Moreover, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, reducing fatigue during repeated use, and the like. Examples of the electron acceptor that can be used for the image carrier include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, and o-dioxide. Examples thereof include nitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid and the like, and compounds represented by the general formula (I). . Of these, benzene derivatives having electron-withdrawing substituents such as fluorenone, quinone and Cl, CN, NO ₂ are particularly preferred.

Next, the protective layer (the layer constituting the outermost surface) will be described.
A high-strength protective layer can be provided in order to provide resistance to abrasion, scratches, and the like of the protective layer. As this high-strength surface layer, conductive particles are dispersed in a binder resin, lubricant particles such as fluororesin and acrylic resin are dispersed in a normal charge transport layer material, and hard materials such as silicone and acrylic. A coating agent can be used, but from the viewpoint of strength, electrical characteristics, image quality maintenance, etc., those having a crosslinked structure are preferred, and those containing a charge transporting material are more preferred. Various materials can be used for forming the crosslinked structure, but phenolic resins, urethane resins, siloxane resins, and the like are preferable in terms of characteristics, and those made of siloxane resins and phenolic resins are particularly preferable.

  Regarding the siloxane meter resin, those having a structure derived from the compounds represented by the general formulas (I) and (II) are particularly preferable because of excellent strength and stability.

F- [D-Si (R ² ) (3-a) Qa] b (I)
In general formula (I), F is an organic group derived from a compound having a hole transporting ability, D is a flexible subunit, R ² is hydrogen, an alkyl group, a substituted or unsubstituted aryl group, and Q is a hydrolyzed group. Represents a decomposable group, a represents an integer of 1 to 3, and b represents an integer of 1 to 4.
As the flexible subunit represented by D in the general formula _{(I), - (CH 2} ) n
It may be a divalent straight chain group that necessarily contains a — group, and is combined with —COO—, —O—, —CH═CH—, and —CH═N— groups. In the — (CH ₂ ) n — group, n represents an integer of 1 or more and 5 or less. Moreover, as a hydrolysable group represented by Q, -OR group (however, R represents an alkyl group) is represented.

^{F - ((X) nR 1} -ZH) m ··· (II)
In general formula (II), F is an organic group derived from a compound having a hole transporting ability, R ¹ is an alkylene group, Z is —O—, —S—, —NH—, or —COO—, m represents an integer of 1 or more and 4 or less. X represents —O— or —S—, and n represents 0 or 1.
More preferable examples of the compounds represented by the general formulas (I) and (II) include those in which the organic group F is particularly represented by the following general formula (III).

In General Formula (III), Ar _{1 to} Ar ₄ each independently represent a substituted or unsubstituted aryl group, Ar ₅ represents a substituted or unsubstituted aryl group or an arylene group, and Ar _{1 to} Ar two to four of the _5, ^-D-Si (R 2) in the general formula (I) having a bond represented by the (3-a) Qa. D represents a flexible subunit, R ² represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and a represents an integer of 1 to 3. K represents 0 or 1.

Ar _{1 to} Ar ₄ in the general formula (III) each independently represent a substituted or unsubstituted aryl group, and specifically, those shown in the following structural group 1 are preferable.

In addition, Ar shown in the structure group 1 is preferably selected from the following structure group 2, and Z ′
Is preferably selected from the following structural group 3

In Structural Groups 1 to 3, R ⁶ is hydrogen, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, or It is selected from an unsubstituted phenyl group and an aralkyl group having 7 to 10 carbon atoms.
R ^{7 to} R ¹³ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, or an unsubstituted group It is selected from a phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen.
m and s represent 0 or 1, q and r represent an integer of 1 to 10, and t represents an integer of 1 to 3. Here, X is the formula ^{(I) -D-Si (R} 2) shown in a group represented by (3-a) Qa.
Further, W shown in the structure group 3 is preferably that shown in the following structure group 4. In Structural Group 4, s ′ represents an integer of 0 or more and 3 or less.

The specific structure of Ar ₅ in the general formula (III) is as follows. When k = 0, the structure of Ar _{1 to} Ar ₄ shown in the structural group 1 is m = 1, and when k = 1, , the structure of m = 0 of _Ar 1 to Ar ₄ shown in the structure group 1 and the like.

Specific examples of the compound represented by the general formula (III) include the compounds (III-1) to (III-61) shown in the following Tables 1 to 7, but the general formula (III) The compound represented by is not limited to these.
In the structural formulas shown in the columns of “Ar ₁ ” to “Ar ₅ ” in Tables 1 to 7, “—S” group bonded to the benzene ring is represented by “S” in Tables 1 to 7. means a monovalent group shown in the column (general formula ^{(I) -D-Si (R} 2 in) (3-a) group corresponding to the structure represented by Qa).

  Specific examples of the general formula (II) include the compounds shown in the following (II) -1 to (II) -26, but the compound of the general formula (II) is not limited thereto. .

Further, in order to control various physical properties such as strength and film resistance, the following general formula (IV)
A compound represented by can also be added.
Si (R ² ) (4-c) Qc (IV)
In general formula (IV), R ² represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and c represents an integer of 1 to 4.

Specific examples of the compound represented by the general formula (IV) include silane coupling agents exemplified below.
Tetrafunctional alkoxysilane such as tetramethoxysilane and tetraethoxysilane (c = 4); methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyltrimethoxyethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Phenyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltri Methoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3, 3,3-trifluoropropyl) trimethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-par Trifunctional alkoxysilanes (c = 3) such as 1-fluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane; dimethyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane and the like Examples thereof include functional alkoxysilane (c = 2); monofunctional alkoxysilane such as trimethylmethoxysilane (c = 1). Trifunctional and tetrafunctional alkoxysilanes are preferable for improving the strength of the film, and bifunctional and monofunctional alkoxysilanes are preferable for improving the flexibility and film-forming property.

  In addition, silicone-based hard coating agents mainly produced from these coupling agents can also be used. Commercially available hard coat agents include KP-85, X-40-9740, X-40-2239 (manufactured by Shin-Etsu Silicone), and AY42-440, AY42-441, AY49-208 (manufactured by Toray Dow Corning). Etc.) can be used.

In order to increase the strength, it is also preferable to use a compound having two or more silicon atoms represented by the general formula (V).
B- (Si (R ² ) (3-a) Qa) 2 (V)
In general formula (V), B represents a divalent organic group, R ² represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and a represents an integer of 1 to 3. .
Specifically, the materials shown in Table 8 below can be mentioned as preferable ones, but are not limited thereto.

  Further, for example, a resin soluble in an alcohol solvent or a ketone solvent may be added in order to control the film characteristics and extend the life of the liquid. Examples of this resin include polyvinyl butyral resins, polyvinyl formal resins, and polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins in which a part of butyral is modified with formal or acetoacetal (for example, Sekisui Chemical). SLECK B, K, etc. manufactured by the company), polyamide resin, cellulose resin, phenol resin and the like. In particular, polyvinyl acetal resin is preferable in terms of electrical characteristics.

Various resins can be added for the purpose of discharge gas resistance, mechanical strength, scratch resistance, particle dispersibility, viscosity control, torque reduction, wear amount control, pot life extension, and the like. Particularly in the case of a siloxane-based resin, it is preferable to add a resin that dissolves in alcohol.
Examples of resins that are soluble in alcohol solvents include polyvinyl butyral resins, polyvinyl formal resins, and polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins in which a part of butyral is modified with formal or acetoacetal (for example, Sekisui Chemical Co., Ltd. S-LEC B, K, etc.), polyamide resin, cellulose resin, phenol resin and the like. In particular, polyvinyl acetal resin is preferable in terms of electrical characteristics.

  The molecular weight of the resin is preferably from 2,000 to 100,000, and more preferably from 5,000 to 50,000. If the molecular weight is less than 2000, the desired effect cannot be obtained. If the molecular weight is more than 100,000, the solubility becomes low and the addition amount is limited, or the film formation is poor at the time of coating. The addition amount is preferably 1% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and most preferably 5% by mass to 20% by mass. When the amount is less than 1% by mass, it is difficult to obtain a desired effect. When the amount is more than 40% by mass, image blurring under high temperature and high humidity tends to occur. These resins may be used alone or in combination.

  Further, for the purpose of extending the pot life and controlling the film properties, a cyclic compound having a repeating structural unit represented by the following general formula (VI) or a derivative thereof can be contained.

In general formula (VI), A ¹ and A ² each independently represent a monovalent organic group.
Examples of the cyclic compound having the repeating structural unit represented by the general formula (VI) include a commercially available cyclic siloxane. Specifically, for example, cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,3,5-trimethyl-1,3,5 -Triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5, Cyclic methylphenylcyclosiloxanes such as 7,9-pentaphenylcyclopentasiloxane, cyclic phenylcyclosiloxanes such as hexaphenylcyclotrisiloxane, 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane, etc. Fluorine-containing cyclosiloxanes, methylhydrosiloxy Down mixture, pentamethylcyclopentasiloxane, it may be mentioned phenyl hydrosilyl group-containing cyclosiloxanes such hydrocyclosiloxane, cyclic siloxanes and vinyl group-containing cyclosiloxanes, such as penta vinyl pentamethylcyclopentasiloxane like. These cyclic siloxane compounds may be used alone or as a mixture thereof.

Furthermore, various particles can be added in order to improve the antifouling substance adhesion and lubricity on the surface of the image carrier. They can be used alone or in combination. As an example of the particles, for example, silicon-containing particles can be mentioned. Silicon-containing particles are particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone particles. The colloidal silica used as the silicon-containing particles preferably has an average particle diameter of 1 nm to 100 nm, more preferably 10 nm to 30 nm, and is dispersed in an acidic or alkaline aqueous dispersion or an organic solvent such as alcohol, ketone, or ester. A commercially available product selected from those prepared can be used. The solid content of colloidal silica in the outermost surface layer is not particularly limited, but it is 0.1% by mass or more in the total solid content of the outermost surface layer in terms of film forming properties, electrical characteristics, and strength. The range of mass% or less is preferable, and the range of 0.1 mass% or more and 30 mass% or less is more preferable.

Silicone particles used as silicon-containing particles are spherical and preferably have an average particle diameter of 1 nm to 500 nm, more preferably 10 nm to 100 nm, and are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and are generally commercially available. Can be used. Silicone particles are small particles that are chemically inert and have excellent dispersibility in the resin, and because the content required to obtain sufficient properties is low, the image can be obtained without inhibiting the crosslinking reaction. The surface properties of the holder can be improved. In other words, it is possible to improve the lubricity and water repellency of the surface of the image carrier while being uniformly incorporated into a strong cross-linked structure, and maintain good wear resistance and adherence to contaminants over a long period of time. .
The content of the silicone particles in the outermost surface layer in the image carrier is preferably in the range of 0.1% by mass to 30% by mass in the total solid content of the outermost surface layer, and is 0.5% by mass to 10% by mass. The range of is more preferable.

As other particles, for example, fluorine-based particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, etc. As shown, particles made of a resin obtained by copolymerizing the fluororesin and a monomer having a hydroxyl group, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO _2. And semiconductive metal oxides such as ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO.
In addition, oil such as silicone oil can be added for the purpose of lubricating the surface of the image carrier and improving volatility. Examples of the silicone oil include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, and mercapto. Examples thereof include reactive silicone oils such as modified polysiloxanes and phenol-modified polysiloxanes.

  The exposure rate of the particles to the protective layer surface is preferably 40% or less. If the above range is exceeded, the influence of the particles alone becomes large, and image flow or the like due to low resistance tends to occur. A more preferable range within the above range is 30% or less, and the particles exposed on the surface are effectively refreshed by the cleaning member, and over a long period of time, suppression of toner component filming on the surface of the image carrier, removal of discharge products, A reduction in wear of the cleaning member due to a reduction in torque is maintained.

  In addition, additives such as plasticizers, surface modifiers, antioxidants, and photodegradation inhibitors can also be used. Examples of the plasticizer include biphenyl, biphenyl chloride, terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenyl phosphate, methyl naphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, and various fluorohydrocarbons.

  An antioxidant having a hindered phenol, hindered amine, thioether or phosphite partial structure can be added to the protective layer, which is effective in improving the potential stability and image quality when the environment changes. Antioxidants include the compounds exemplified below, for example, “Sumizer BHT-R”, “Sumizer MDP-S”, “Sumizer BBM-S”, “Sumizer WX-R”, “Sumizer NW” as hindered phenols, "Sumilizer BP-76", "Sumilizer BP-101", "Sumilizer GA-80", "Sumilizer GM", "Sumizer GS" or more manufactured by Sumitomo Chemical; "IRGANOX1010", "IRGANOX1035", "IRGANOX10X", "98 ”,“ IRGANOX1135 ”,“ IRGANOX1141 ”,“ IRGANOX1222 ”,“ IRGANOX1330 ”,“ IRGANOX “425WL”, “IRGANOX1520L”, “IRGANOX245”, “IRGANOX259”, “IRGANOX3114”, “IRGANOX3790”, “IRGANOX5057”, “IRGANOX565” or more manufactured by Ciba Specialty Chemicals Co., Ltd .; ”,“ ADK STAB AO-40 ”,“ ADK STAB AO-50 ”,“ ADK STAB AO-60 ”,“ ADK STAB AO-70 ”,“ ADK STAB AO-80 ”,“ ADK STAB AO-330 ”or more manufactured by Asahi Denka; As the amine system, “Sanol LS2626”, “Sanol LS765”, “Sanol LS770”, “Sanol LS744”, “Tinuvin 144”, “Tinuvin 622LD”, “Mark LA57” , “Mark LA67”, “Mark LA62”, “Mark LA68”, “Mark LA63”, “Smilizer-TPS”; “Smilizer-TP-D” as thioether system, “Mark 2112” as “phosphite system”, “Mark PEP” * 8, "Mark PEP.24G", "Mark PEP.36", "Mark 329K", "Mark HP.10"; hindered phenols and hindered amine antioxidants are particularly preferable. Further, they may be modified with a substituent such as an alkoxysilyl group capable of undergoing a crosslinking reaction with the material forming the crosslinked film.

It is preferable to add or use a coating liquid used for forming the protective layer or a catalyst when preparing the coating liquid. Examples of the catalyst used include inorganic acids such as hydrochloric acid, acetic acid, phosphoric acid and sulfuric acid, organic acids such as formic acid, propionic acid, oxalic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid and maleic acid, potassium hydroxide, water Alkali catalysts such as sodium oxide, calcium hydroxide, ammonia, triethylamine, and solid catalysts insoluble in the system shown can also be used.
For example, Amberlite 15, Amberlite 200C, Amberlist 15E (above, manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical Co., Ltd.) ); Levacit SPC-108, Levacit SPC-118 (manufactured by Bayer); Diaion RCP-150H (Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duolite C-433, Duolite -464 (above, manufactured by Sumitomo Chemical Co., Ltd.); cation exchange resin such as Nafion-H (produced by DuPont); Amberlite IRA-400, Amberlite IRA-45 (above, Rome and Hearth) Anion exchange resin such as Zr (O ₃ PCH ₂ CH ₂ SO ₃ H) ₂ , An inorganic solid in which a group containing a protonic acid group such as Th (O ₃ PCH ₂ CH ₂ COOH) ₂ is bonded to the surface; a polyorganosiloxane containing a protonic acid group such as a polyorganosiloxane having a sulfonic acid group; Heteropolyacids such as cobalt tungstic acid and phosphomolybdic acid; isopolyacids such as niobic acid, tantalum acid and molybdic acid; monometallic oxides such as silica gel, alumina, chromia, zirconia, CaO and MgO; silica-alumina, silica- Composite metal oxides such as magnesia, silica-zirconia, and zeolites; clay minerals such as acidic clay, activated clay, montmorillonite, and kaolinite; metal sulfates such as LiSO ₄ and MgSO ₄ ; zirconia phosphate, lanthanum phosphate, etc. Metal phosphate; LiNO ₃ , Mn (NO ₃ ) Metal nitrates such as ₂ ; inorganic solids having amino group-containing groups such as solids obtained by reacting aminopropyltriethoxysilane on silica gel; amino groups such as amino-modified silicone resins And polyorganosiloxane containing.

  Moreover, it is preferable to use a solid catalyst that is insoluble in a photofunctional compound, reaction product, water, solvent, or the like in the preparation of the coating liquid because the stability of the coating liquid tends to be improved. A solid catalyst that is insoluble in the system is particularly suitable if the catalyst component is insoluble in the compounds represented by the general formulas (I), (II), (III), (V), other additives, water, solvents, etc. It is not limited. The amount of these solid catalysts used is not particularly limited, but is preferably 0.1 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass in total of the compounds having hydrolyzable groups. Further, as described above, these solid catalysts are insoluble in raw material compounds, reaction products, solvents and the like, and therefore can be easily removed after the reaction according to a conventional method. The reaction temperature and reaction time are selected according to the type and amount of the raw material compound or solid catalyst, but the reaction temperature is usually preferably 0 ° C. or higher and 100 ° C. or lower, more preferably 10 ° C. or higher and 70 ° C. or lower, The reaction temperature is more preferably 15 ° C. or more and 50 ° C. or less, and the reaction time is preferably 10 minutes to 100 hours. If the reaction time exceeds the upper limit, gelation tends to occur.

  When a catalyst that is insoluble in the system is used in the coating liquid preparation step, it is preferable to use a catalyst that is further dissolved in the system for the purpose of improving strength, liquid storage stability and the like. As the catalyst, for example, aluminum triethylate, aluminum triisopropylate, aluminum tri (sec-butyrate), mono (sec-butoxy) aluminum diisopropylate, diisopropoxyaluminum (ethyl acetoacetate) Aluminum tris (ethyl acetoacetate), aluminum bis (ethyl acetoacetate) monoacetylacetonate, aluminum tris (acetylacetonate), aluminum diisopropoxy (acetylacetonate), aluminum isopropoxy-bis (acetylacetonate), Organo aluminum compounds such as aluminum tris (trifluoroacetylacetonate) and aluminum tris (hexafluoroacetylacetonate) It is possible to use.

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

  When an organometallic compound is used as a catalyst, it is preferable to add a multidentate ligand from the viewpoint of pot life and curing efficiency. Examples of the multidentate ligand include those exemplified below and those derived therefrom, but are not limited thereto.

Specifically, for example, β-diketones such as acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, dipivaloylmethylacetone; acetoacetates such as methyl acetoacetate and ethyl acetoacetate; bipyridine and derivatives thereof; glycine and Derivatives thereof; ethylenediamine and derivatives thereof; 8-oxyquinoline and derivatives thereof; salicylaldehyde and derivatives thereof; catechol and derivatives thereof; bidentate ligands such as 2-oxyazo compounds; diethyltriamine and derivatives thereof; nitrilotriacetic acid and And tridentate ligands such as derivatives thereof; hexadentate ligands such as ethylenediaminetetraacetic acid (EDTA) and derivatives thereof; and the like. In addition to the above organic ligands, inorganic ligands such as pyrophosphoric acid and triphosphoric acid can be used. As the multidentate ligand, a bidentate ligand is particularly preferable, and specific examples include a bidentate ligand represented by the following general formula (VII) in addition to the above. Among them, a bidentate ligand represented by the following general formula (VII) is more preferable, and R ⁵ and R ⁶ in the following general formula (VII) are particularly preferable. By making R ⁵ and R ^{6 the} same, the coordination power of the ligand is increased, and the coating liquid can be further stabilized.

In general formula (VII), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, or an alkoxy group having 1 to 10 carbon atoms.
The compounding amount of the polydentate ligand can be arbitrarily set, but is preferably 0.01 mol or more, more preferably 0.1 mol or more, and more preferably 1 mol or more with respect to 1 mol of the organometallic compound to be used. Further preferred.
The coating solution can be produced in the absence of a solvent, but if necessary, for example, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran; ethers such as diethyl ether and dioxane In addition to the above, various solvents can be used. As this solvent, those having a boiling point of 100 ° C. or less are preferable, and they can be arbitrarily mixed and used. The amount of the solvent can be set arbitrarily, but if the amount is too small, the organosilicon compound is likely to be precipitated. Therefore, the amount is preferably 0.5 parts by mass or more and 30 parts by mass or less with respect to 1 part by mass of the organosilicon compound. The following is more preferable.

  The reaction temperature and reaction time for curing the coating liquid are not particularly limited, but the reaction temperature is preferably 60 ° C. or higher, and 80 ° C. or higher, 200 ° C. from the viewpoint of mechanical strength and chemical stability of the resulting silicon resin. The following is more preferable, and the reaction time is preferably 10 minutes to 5 hours. In addition, maintaining the organic layer obtained by curing the coating liquid in a high humidity state is effective in stabilizing the characteristics of the organic layer. Furthermore, depending on the application, the organic layer can be subjected to surface treatment using hexamethyldisilazane, trimethylchlorosilane, or the like to make it hydrophobic.

  On the other hand, the phenolic resin includes phenol containing at least one charge transporting material (structural unit having charge transporting ability) selected from a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thiol group, and an amino group. More preferably, it is a resin.

Examples of phenol derivatives used for the synthesis of phenolic resins include resorcin, bisphenol, substituted phenols containing one hydroxyl group such as phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, catechol, resorcinol, hydroquinone, etc. Compounds having a phenol structure such as substituted phenols containing two hydroxyl groups of the above, bisphenols such as bisphenol A and bisphenol Z, biphenols, and the like, and those commercially available as raw materials for synthesizing phenol resins can be used.
In addition, as the phenol derivative, for example, those containing a methylol group can be used, for example, monomers of monomethylolphenols, dimethylolphenols or trimethylolphenols, a mixture thereof, those oligomerized, or monomers thereof And a mixture of oligomers.
In the present specification, a relatively large molecule in which the number of repeating molecular structural units is about 2 or more and 20 or less is called an oligomer, and a molecule smaller than that is called a monomer.

  Moreover, as aldehydes used for the synthesis | combination of a phenol-type resin, formaldehyde, paraformaldehyde, etc. can be utilized, for example. In synthesizing a phenolic resin, it can be obtained by reacting these raw materials in the presence of an acid catalyst or an alkali catalyst. However, commercially available phenolic resins can also be used.

Examples of the acid catalyst include sulfuric acid, paratoluenesulfonic acid, phosphoric acid and the like. As the alkali catalyst, for example, hydroxides or amine catalysts of alkali metals and alkaline earth metals such as NaOH, KOH, Ca (OH) ₂ and Ba (OH) ₂ are used.
Examples of the amine catalyst include, but are not limited to, ammonia, hexamethylenetetramine, trimethylamine, triethylamine, triethanolamine, and the like.
When a basic catalyst is used, carriers may be trapped remarkably by the remaining catalyst, and the electrophotographic characteristics may be deteriorated. For this reason, when a basic catalyst is used, after the reaction using the catalyst is completed, it must be neutralized with an acid, or deactivated or removed by contacting with an adsorbent such as silica gel or an ion exchange resin. Is preferred.

The phenolic resin having a crosslinked structure used for the image carrier may be one obtained by further crosslinking the above-mentioned known phenolic resin, and the phenolic resin itself has a crosslinked structure like a novolac type. It may be what you are doing. In the former case, it is more preferable to use a resol type phenol resin.
In particular, since the toner containing a crystalline resin like the toner of the present embodiment has a hygroscopic property, the surface layer is used in combination with a photoreceptor having the surface layer of the siloxane resin that is inferior in water absorption and gas barrier properties. It is more preferably used in that a high image quality can be stably obtained over a long period of time.

  The protective layer having a charge transporting property and having a cross-linked structure described above has excellent mechanical strength and sufficient photoelectric properties, so that it can be used as it is as a charge transport layer of a multilayer image carrier. it can. In that case, for example, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method or the like can be used. However, when a required film thickness cannot be obtained by a single application, the necessary film thickness can be obtained by applying a plurality of times. When performing multiple times of repeated application, the heat treatment may be performed every time of application, or after multiple times of repeated application.

In the case of a single-layer type photosensitive layer, it is formed containing the charge generating material and a binder resin. As the binder resin, the same binder resins as those used for the charge generation layer and the charge transport layer can be used. The content of the charge generating substance in the single-layer type photosensitive layer is preferably about 10% by mass to 85% by mass, and more preferably 20% by mass to 50% by mass.
A charge transport material or a polymer charge transport material may be added to the single-layer type photosensitive layer for the purpose of improving photoelectric characteristics. The addition amount is preferably 5% by mass or more and 50% by mass or less. Moreover, you may add the compound shown by general formula (I). The solvent and coating method used for coating can be the same as described above. The film thickness is preferably about 5 μm to 50 μm, and more preferably 10 μm to 40 μm.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited only to the Example shown below.
In the examples, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.

<Measuring method of various characteristics>
First, methods for measuring physical properties of toners and the like used in Examples and Comparative Examples will be described.
(Molecular weight of resin)
The molecular weight distribution of the resin was performed under the following conditions. GPC uses “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)”, and the column uses two “TSKgel, SuperHM-H (6.0 mm ID × 15 cm, manufactured by Tosoh Corporation)” THF (tetrahydrofuran) was used as an eluent. As experimental conditions, an experiment was performed using a sample concentration of 0.5%, a flow rate of 0.6 ml / min, a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and an IR detector. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

(Volume average particle diameter of resin particles, colorant particles, etc.)
Volume average particle diameters of resin particles, colorant particles, and the like were measured with a laser diffraction particle size measuring instrument (SALD2000A, manufactured by Shimadzu Corporation).

(Melting point of resin, glass transition temperature)
The melting point of the toner, the crystalline polyester resin, and the glass transition temperature of the toner and the amorphous resin were determined from each maximum peak measured in accordance with ASTM D3418-8. The glass transition point was the temperature at the intersection of the extension line of the base line and the rising line in the endothermic part, and the melting point was the temperature at the apex of the endothermic peak.
For the measurement, a differential scanning calorimeter (DSC-60A with automatic cooler, manufactured by Shimadzu Corporation) was used.

<Preparation of developer for developing electrostatic image>
-Preparation of non-crystalline polyester resin (A1) and non-crystalline resin particle dispersion (a1)-
To a heat-dried two-necked flask, 10 mol parts of polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (2,2) -2,2-bis (4 -Hydroxyphenyl) propane 90 mol part, terephthalic acid 10 mol part, fumaric acid 67 mol part, n-dodecenyl succinic acid 3 mol part, trimellitic acid 20 mol part, and these acid components (terephthalic acid, n After adding 0.05 mol part of dibutyltin oxide to the total number of moles of dodecenyl succinic acid, trimellitic acid and fumaric acid), introducing nitrogen gas into the container and maintaining the inert atmosphere to raise the temperature The copolycondensation reaction is carried out at 150 ° C. to 230 ° C. for 12 to 20 hours, and then gradually reduced in pressure at 210 ° C. to 250 ° C. to combine the amorphous polyester resin (A1). It was. This resin had a weight average molecular weight Mw of 130000 and a glass transition temperature Tg of 73 ° C.

  3000 parts of the obtained non-crystalline polyester resin, 10000 parts of ion-exchanged water, and 90 parts of surfactant sodium dodecylbenzenesulfonate were charged into an emulsification tank of a high-temperature and high-pressure emulsifier (Cabitron CD1010, slit: 0.4 mm). Then, after heating and melting at 130 ° C., it was dispersed at 110 ° C. at a flow rate of 3 L / m at 10,000 rpm for 30 minutes, passed through a cooling tank, and then a non-crystalline resin particle dispersion (high temperature / high pressure emulsifier (Cabitron CD1010 slit 0 .4 mm) was recovered to obtain an amorphous resin particle dispersion (A1).

-Preparation of crystalline polyester resin (B1) and crystalline resin particle dispersion (b1)-
In a heat-dried three-necked flask, 44 mole parts of 1,9-nonanediol, 56 mole parts of dodecanedicarboxylic acid and 0.05 mole part of dibutyltin oxide as a catalyst were added, and the air in the container was reduced by depressurization. Was placed in an inert atmosphere with nitrogen gas, and stirred at 180 ° C. for 2 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 5 hours. When it became a viscous state, it was air-cooled, the reaction was stopped, and a crystalline polyester resin (B1) was synthesized. This resin had a weight average molecular weight Mw of 27000 and a melting point Tm of 72 ° C.
Thereafter, a crystalline resin particle dispersion (b1) was obtained using a high-temperature, high-pressure emulsification apparatus (Cabitron CD1010, slit: 0.4 mm) under the same conditions as in the preparation of the amorphous resin dispersion (A1).

-Preparation of colorant dispersion (1)-
・ Carbon black (Cabot R330): 25 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku, Neogen RK): 2 parts ・ Ion exchange water: 125 parts A colorant dispersion was prepared by dispersing the colorant (cyan pigment) by dispersing for 1 hour using a type disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006). The volume average particle size of the colorant (carbon black) in the colorant dispersion was 0.12 μm, and the colorant particle concentration was 24% by mass.

-Preparation of release agent particle dispersion (1)-
-Paraffin wax (Nippon Seiki HNP0190: 100 parts-Anionic surfactant (manufactured by Nippon Oil & Fats Co., Ltd., Newlex R): 2 parts-Ion-exchanged water: 300 parts The above ingredients were heated to 95 ° C and homogenizer (IKA Release agent dispersion obtained by dispersing with a pressure-discharge type gorin homogenizer (Gorin) and dispersing a release agent having a volume average particle size of 200 nm. (1) (Mold release agent concentration: 20% by mass) was prepared.

(Production of toner)
<Preparation of Toner A1>
Amorphous resin particle dispersion (a1): 320 parts Crystalline resin particle dispersion (b1): 80 parts Colorant dispersion: 50 parts Release agent particle dispersion: 60 parts Aluminum sulfate (sum 15 parts · Calcium chloride (manufactured by Wako Pure Chemical Industries): 5 parts · Titania sol (manufactured by Catalytic Chemical: 10 parts · Tin chloride (manufactured by Wako Pure Chemical Industries): 5 parts · aqueous surfactant solution: 10 parts 0.3 M aqueous nitric acid solution: 50 parts Ion exchange water: 500 parts After the above components are housed in a round stainless steel flask and dispersed using a homogenizer (IKA, Ultra Turrax T50), The mixture was heated in a heating oil bath with stirring to 45 ° C. After maintaining at 48 ° C., when it was confirmed that aggregated particles having an average particle size of about 5.2 μm were formed, additional amorphous Resin particle dispersion: 100 parts added , It was held for a further 30 minutes.
Subsequently, 10% by mass of EDTA (ethylenediaminetetraacetic acid) metal salt aqueous solution (Cyrest Mg · 40 manufactured by Kyrest Co., Ltd.): After adding 0.5 part, until 1N sodium hydroxide aqueous solution reaches pH 7.0 After gentle addition, the mixture was heated to a predetermined temperature while stirring was continued and held for a predetermined time. Thereafter, the reaction product was filtered, washed with ion exchange water, and then dried using a vacuum dryer to obtain toner base particles.

-External additive treatment-
Thereafter, 1 part of gas phase method silica (manufactured by Nippon Aerosil Co., Ltd., R972) was mixed with a Henschel mixer and externally added to 100 parts of the obtained toner base particles to obtain toner A1.

<Preparation of Toner A2>
Toner A2 was prepared under the same conditions as in preparation of toner A1, except that 30 parts of aluminum sulfate and 10 parts of tin chloride were used in preparation of toner A1.

<Preparation of Toner A3>
Toner A3 was prepared under the same conditions as in preparation of toner A1, except that 5 parts of aluminum sulfate, 1 part of tin chloride, and 1 part of titania sol were used in preparation of toner A1.

<Preparation of Toner A4>
Toner A4 was prepared under the same conditions as for preparation of toner A1, except that 20 parts of aluminum sulfate and 1 part of tin chloride were used in preparation of toner A1 and no titania sol was used.

<Preparation of Toner A5>
Toner A5 was prepared under the same conditions as in preparation of toner A1, except that 5 parts of aluminum sulfate, 1 part of tin chloride, and 15 parts of calcium chloride were used in preparation of toner A1.

<Preparation of Toner B1>
Toner B1 was prepared under the same conditions as in preparation of toner A1, except that 5 parts of aluminum sulfate, tin chloride, and titania sol were not used and 2 parts of calcium chloride were used in preparation of toner A1.

<Preparation of Toner B2>
Toner B2 was prepared under the same conditions as for toner A1, except that 32 parts of aluminum sulfate, 15 parts of tin chloride, and 7 parts of calcium chloride were used in preparation of toner A1.

  Table 1 shows the results of measuring various properties and physical properties of the toners A1 to A5 and the toners B1 to B2.

(Developer adjustment)
100 parts of ferrite particles (Powder Tech, average particle size: 50 μm) and 2.5 parts of methyl methacrylate resin (Mitsubishi Rayon, weight average molecular weight: 95000) are placed in a pressure kneader together with 500 parts of toluene, and After stirring and mixing at 25 ° C. for 15 minutes, the temperature was raised to 70 ° C. while mixing under reduced pressure. After toluene was distilled off, the mixture was cooled and classified using a sieve having an opening of 105 μm. Coated carrier).
Subsequently, the ferrite carrier was mixed with each of the toners A1 to A5 and the toners B1 and B2, to prepare a two-component developer having a toner concentration of 7% by mass.

<Preparation of image carrier>
(Preparation of image carrier 1)
The cylindrical Al substrate was polished by a centerless polishing apparatus, and the 10-point average surface roughness Rz was 0.6 μm. As a cleaning step, this cylinder was degreased, etched with a 2% by mass sodium hydroxide solution for 1 minute, neutralized, and further washed with pure water. Next, as an anodizing treatment step, an anodized film (current density 1.0 A / dm ² ) was formed on the cylinder surface with a 10 mass% sulfuric acid solution. After washing with water, sealing was performed by dipping in a 1% by mass nickel acetate solution at 80 ° C. for 20 minutes. Further, pure water washing and drying treatment were performed. In this manner, a 7 μm anodic oxide film was formed on the surface of the aluminum cylinder.

One part of titanyl phthalocyanine having a strong diffraction peak at a Bragg angle (2θ ± 0.2 °) of X-ray diffraction spectrum on this aluminum substrate of 27.2 ° is polyvinyl butyral (ESREC BM-S, Sekisui Chemical). After mixing with 1 part and 100 parts of n-butyl acetate and treating with glass beads for 1 hour with a paint shaker to disperse, the resulting coating solution was dip coated on the undercoat layer at 100 ° C. for 10 minutes. A heat generation layer having a thickness of 0.15 μm was formed by heating and drying.
Next, a coating solution prepared by dissolving 2 parts of a benzidine compound (the following compound 1) having the following structure and 2.5 parts of a polymer compound (the following compound 2, viscosity average molecular weight: 39,000) in 20 parts of chlorobenzene is used. An image carrier 1 was obtained by coating the charge generation layer by an immersion coating method and heating at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

(Preparation of image carrier 2)
To the constituent materials shown below, 5 parts of methyl alcohol and 0.5 part of ion exchange resin (Amberlyst 15E) were added, and the protecting group was exchanged for 24 hours by stirring at room temperature (25 ° C.).
-Constituent material-
· The following compounds 3: 2 parts of methyltrimethoxysilane: 2 parts of tetraethoxysilane: 0.5 parts Colloidal silica: 0.4 parts _{· Me (MeO) 2Si- (CH} 2) 4 -SiMe (OMe) 2 : 0.5 part (Heptadecafluoro-1,1,2,2-tetrahydrodecyl) methyldimethoxysilane: 0.1 part Hexamethylcyclotrisiloxane: 0.3 part

Thereafter, 10 parts of n-butanol and 0.3 part of distilled water were added and hydrolysis was carried out for 15 minutes. 0.1 parts of aluminum trisacetylacetonate (Al (aqaq) ₃ ), 0.1 part of acetylacetone, 3,5-di-t-to the liquid obtained by filtering and separating the ion exchange resin from the hydrolyzed product 0.4 part of butyl-4-hydroxytoluene (BHT) and 0.5 part of ESREC BX-L (manufactured by Sekisui Chemical Co., Ltd.) were added to obtain a coating solution for forming a protective layer. This coating solution is applied onto the charge transport layer of the photoreceptor 1 by a ring-type dip coating method, air-dried at room temperature (25 ° C.) for 30 minutes, and then cured by heat treatment at 170 ° C. for 1 hour to form a film. A protective layer having a thickness of 3 μm was formed to obtain an image carrier 2.

(Preparation of image carrier 3)
5 parts of the following compound 4, 7 parts of resol type phenol resin (PL-4852, manufactured by Gunei Chemical Co., Ltd.), 0.03 part of methylphenylpolysiloxane, and 20 parts of isopropanol are mixed and dissolved to form a protective layer. A coating solution was obtained. This coating solution was applied onto the charge transport layer of the photoreceptor 1 by dip coating, and dried at 130 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm, whereby an image carrier 3 was obtained.

<Evaluation>
Fuji Xerox printer DocuCenter Color 400CP remodeling machine (
Table 10 shows a combination of a photosensitive member and a developer (toner), as shown in Table 10, using a cleaning blade provided as a cleaning means for the image carrier and having a recycling system that returns the toner in the collection box to the inside of the developing device. The image formation test of 5000 sheets was performed in an environment of high temperature and high humidity (28 ° C., 85% RH), and then the image formation test of 5000 sheets was performed in an environment of low temperature and low humidity (10 ° C., 15% RH). Fixability, transferability, and image carrier surface condition were evaluated. The results are shown in Table 10.
In addition, only when the image carrier 2 and the image carrier 3 are used, the recycling system is operated for confirmation of the recycling system, and further 100,000 in an environment of high temperature and high humidity (28.5 ° C./humidity 85% RH). A sheet image formation test was performed, and the presence or absence of filming on the image carrier after the test was visually observed using a 50 × magnifier.

The evaluation methods and evaluation criteria for the evaluation items shown in Table 10 are as follows.
-Low temperature fixability-
Low-temperature fixability is achieved by controlling the temperature of the fixing device with an external power supply before the image formation test, fixing the fixing temperature in the range of 100 ° C. to 140 ° C. at intervals of 5 ° C., and obtaining an image with a constant shot density An image is formed so as to be (paper C2 paper, manufactured by Fuji Xerox Co., Ltd., density of 1.5 to 1.8 with an X-Rite 404 densitometer), and image defects due to bending of the image thus obtained are sensory. Evaluation was made based on the following criteria. The process speed was implemented at two levels of 160 mm / s and 250 mm / s.
A: No problem at 110 ° C. or lower at any process speed and image density (not visually recognized image defect)
A: Some image defects are observed at 110 ° C. at a high image density of 250 mm / s (no problem in actual use)
Δ: No problem in practical use, but an image defect is observed at a high image density and a low temperature part (110 ° C. or more and 135 ° C. or less).
×: Many image defects in the low temperature part (110 ° C. or more and 135 ° C. or less), which cannot be practically used in this temperature range (fixed at 135 ° C. or more and no image defects are seen).

-Transferability-
The transfer property is 500 sheets (initial), and thereafter, after 1000 sheets, 2000 sheets, and 1000 sheets, a solid image unfixed sample is used with toner weights of 0.3, 0.6, 0.9, 1.2, and 1.5 g. / m ² and collected at, the toner weight and the toner residual weight on the image carrier to measure sought transfer rate was determined by the following criteria.
A: Good up to 5000 sheets at any weight, no change (transfer rate 85% to 95%)
○: No serious problem in actual use (transfer rate: 80% or more and less than 85%), but lower than the initial value at the time of 5000 sheets Δ: Medium weight to high weight (0.9, 1.2) 1.5 g / m ² ), decrease after 1000 sheets (transfer rate 80% or more and less than 85%)
X: Lower than the entire area in the initial stage (transfer rate less than 80%)

-Filming evaluation during operation of recycling system-
The presence or absence of filming on the image carrier after the test was visually observed using a 50 × magnifier and evaluated according to the following criteria.
A: Not confirmed.
○: Confirmed by loupe, but no effect on image.
(Triangle | delta): Although the influence on an image is seen, there is no problem practically.
X: There is a problem in practical use.

-Image gloss unevenness evaluation-
Prior to the image formation test, the temperature of the fixing device is controlled by an external power source control, fixing is performed at 20 ° C. intervals within a fixing temperature range of 100 ° C. to 180 ° C., and the resulting image has a constant reflection density (paper C2, An image is formed so that the density is from 1.5 to 1.8 with an X-Rite 404 densitometer manufactured by Fuji Xerox Co., Ltd., and a gloss meter (BYK micro trigloss gloss meter (20 + 60 + 85 °), manufactured by Gardner), process The speed was implemented at two levels of 160 mm / s and 250 mm / s.
A: Gross difference (maximum-minimum) is within 5 regardless of temperature and process speed. O +: 160 mm / s. Gross difference is in the range of 5 to 10 only at 180.degree. : The difference in gloss is in the range of 5 to 10 only at 160 mm / s at 160 and 180 ° C. Δ +: The difference in gloss is 5 at 160 mm / s at 160, 180 ° C., 250 mm / s and 180 ° C. △ − in the range of 10 or less: 160 mm / s, 160, 180 ° C., 160 in 250 mm / s, 160 or 180 ° C. Gloss difference is in the range of 5 to 10 ××: Gross gross in 160 mm / s The difference is 10 or more and 250 mm / s, and the gross gloss difference is 5 or more and 10 or less.

Claims (10)

  It has toner base particles containing a crystalline resin, a release agent, and a metal element capable of taking a valence of 2 or more, and can take a valence of 2 or more as measured by fluorescent X-ray analysis. A toner for developing an electrostatic charge image, wherein a content of metal elements with respect to the strength of all elements in the toner base particles is in a range of 5% to 50%. The electrostatic image developing toner according to claim 1, wherein the following formula (1) is satisfied.
Formula (1) 0.2 ≦ Dw / Up ≦ 0.8
[In Formula (1), Dw is 10 ° C./min from 120 ° C. to 70 ° C. after the electrostatic image developing toner is heated from 70 ° C. to 120 ° C. at 10 ° C./min by differential thermal analysis. In the heating / cooling process for lowering the temperature, it represents the temperature range with respect to the reference line of the peak observed in the process of heating from 70 ° C. to 120 ° C., and Up is the process of cooling from 120 ° C. to 70 ° C. in the heating / cooling process The temperature range with respect to the reference line of the peak observed in FIG. Further, the reference line means a straight line connecting the skirt portions on both sides of the peak. ]   It has toner base particles containing a crystalline resin, a release agent, and a metal element capable of taking a valence of 2 or more, and can take a valence of 2 or more as measured by fluorescent X-ray analysis. An electrostatic charge image developer comprising: a toner having a metal element content within a range of 5% to 50% with respect to the strength of all elements in the toner base particles. It is detachable from an image forming apparatus having at least a toner image forming unit, and stores a developer to be supplied to the toner image forming unit.
The developer has toner mother particles containing a crystalline resin, a release agent, and a metal element capable of taking a valence of 2 or more, and having a valence of 2 or more measured by fluorescent X-ray analysis. A toner cartridge comprising a toner in which a content of metal elements capable of taking a valence with respect to the strength of all elements in the toner base particles is in a range of 5% to 50%. It is detachable from the image forming apparatus,
An image holding member; and at least a toner image forming unit that contains the developer and supplies the developer to an electrostatic latent image formed on the surface of the image holding member to form a toner image.
The developer has toner mother particles containing a crystalline resin, a release agent, and a metal element capable of taking a valence of 2 or more, and having a valence of 2 or more measured by fluorescent X-ray analysis. A process cartridge comprising a toner in which the content of metal elements capable of taking a valence with respect to the strength of all elements in the toner base particles is in the range of 5% to 50%.   6. The process cartridge according to claim 5, wherein the layer constituting the outermost surface of the image carrier contains at least one resin selected from a siloxane-based resin and a phenol-based resin having a crosslinked structure. Cleaning means for cleaning while collecting the toner remaining on the surface of the image carrier after transferring the toner image;
6. The process cartridge according to claim 5, further comprising a toner recycling unit that reuses the toner collected by the cleaning unit as the toner for the developer. An image carrier, a charging unit that charges the surface of the image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the charged surface of the image carrier, and the developer At least a toner image forming unit that forms a toner image by developing, a transfer unit that transfers the toner image to the surface of the recording medium, and a fixing unit that fixes the toner image transferred to the surface of the recording medium,
The developer has toner mother particles containing a crystalline resin, a release agent, and a metal element capable of taking a valence of 2 or more, and having a valence of 2 or more measured by fluorescent X-ray analysis. An image forming apparatus comprising a toner in which a content of a metal element capable of taking a valence with respect to the strength of all elements in the toner base particles is in a range of 5% to 50%.   9. The image forming apparatus according to claim 8, wherein the layer constituting the outermost surface of the image carrier contains at least one resin selected from a siloxane-based resin and a phenol-based resin having a crosslinked structure. Cleaning means for cleaning while collecting the toner remaining on the surface of the image carrier after transferring the toner image;
The image forming apparatus according to claim 8, further comprising a toner reuse unit that reuses the toner collected by the cleaning unit as the toner for the developer.