JP2014178626A - Toner for electrostatic charge image development, electrostatic charge image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development which substantially prevents image defects.SOLUTION: The toner for electrostatic charge image development comprises a binder resin comprising a non-crystalline polyester resin and a crystalline polyester resin, and a release agent. The proportion of repeating units derived from an ethylene oxide adduct of bisphenol A included in the non-crystalline polyester resin is more than 50 mol% and 100 mol% or less; the proportion of the total amount of repeating units derived from at least one compound selected from the group consisting of 1,4-butanediol and 1,6-hexanediol included in the crystalline polyester resin is 95 mol% or more; the proportion of repeating units derived from terephthalic acid included in the crystalline polyester resin is 3 mol% or more and 20 mol% or less; and the proportion of the total amount of repeating units derived from at least one compound selected from the group consisting of 1,10-decane dicarboxylic acid and 1,8-octane dicarboxylic acid is 80 mol% or more and 97 mol% or less.

Description

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

  In recent years, electrophotographic methods have begun to be used in the printing field. There is a method of using film printing as a three-dimensional expression method that expresses a sense of transparency and overlays it with paper printing such as the cover and mouth painting of the base, and is used for book covers, magazine advertisements, appendices, etc. Has been.

  Here, in order to provide an electrophotographic toner excellent in low-temperature fixability and pressure storage stability, an aqueous dispersion containing a crystalline polyester and an aqueous dispersion containing an amorphous polyester are aggregated and combined. A toner containing the obtained polyester as a binder resin, wherein the crystalline polyester contains an alcohol component containing 70 to at least 70 mol% of an aliphatic diol having 2 to 8 carbon atoms and a carboxylic acid component containing at least 50 mol% of terephthalic acid; An electrophotographic toner obtained by polycondensation is disclosed (for example, see Patent Document 1).

  Further, in order to provide a crystalline polyester which is suitably compatible with an amorphous resin, particularly an amorphous polyester having a bisphenol A skeleton, and can be suitably used as a binder resin for toner, etc. A crystalline polyester having a softening point of 85 to 150 ° C. obtained by condensation polymerization of a monomer containing 0.1 to 10 mol% is disclosed (for example, see Patent Document 2).

  In addition, in order to provide an electrophotographic toner that has stable thermal characteristics and can maintain good image fixability even if it contains a crystalline polyester and an amorphous polyester, An electrophotographic toner comprising an amorphous polyester as a binder resin, wherein the amorphous polyester has a content of an alkylene oxide adduct of bisphenol A of 80 mol% or more, It contains a resin obtained by polycondensing an alcohol component having an alkylene oxide adduct content of 15% by weight or less of a bisphenol A adduct of 3 mol or more of alkylene oxide in an alkylene oxide adduct and a carboxylic acid component. An electrophotographic toner is disclosed (for example, see Patent Document 3).

  In addition, a polymer is formed in order to provide a toner using a crystalline polyester resin having a new composition, which can achieve low temperature fixing, has high chargeability under high temperature and high humidity, and can be applied with an aggregation coalescence method. As the acid-derived constituent component, two or more kinds of dicarboxylic acid-derived constituent components are included, and among the total acid-derived constituent components, the aromatic dicarboxylic acid-derived constituent component content is 0.5 to When the dicarboxylic acid-derived constituent component having a sulfonic acid group is included, the content of the dicarboxylic acid-derived constituent component having the sulfonic acid group among the total acid-derived constituent components is 30 mol%. An electrophotographic toner is disclosed that contains a crystalline polyester resin having 5 mol% or less as a main component of a binder resin (see, for example, Patent Document 4).

JP 2010-079277 A JP 2002-284866 A JP 2006-337872 A JP 2004-168827 A

  SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic image that hardly causes image loss even when a fixing device having a low fixing pressure is used.

Specific means for achieving the above object are as follows.
That is, the invention according to claim 1
A binder resin containing an amorphous polyester resin and a crystalline polyester resin, and at least a first release agent,
The proportion of the repeating unit derived from the ethylene oxide adduct of bisphenol A in the repeating unit derived from the alcohol component contained in the amorphous polyester resin is more than 50 mol% and not more than 100 mol%,
The proportion of the total amount of repeating units derived from at least one selected from the group consisting of 1,4-butanediol and 1,6-hexanediol in the repeating units derived from the alcohol component contained in the crystalline polyester resin is 95 mol. % Or more,
The proportion of the repeating unit derived from terephthalic acid in the repeating unit derived from the carboxylic acid component contained in the crystalline polyester resin is 3 mol% or more and 20 mol% or less, and 1,10-decanedicarboxylic acid and 1,8-octanedicarboxylic acid. The electrostatic charge image developing toner has a total amount of at least one repeating unit selected from the group consisting of acids of 80 mol% or more and 97 mol% or less.

The invention according to claim 2
2. The electrostatic image developing toner according to claim 1, wherein an endothermic peak temperature Tmc derived from the crystalline polyester resin is 50 ° C. or higher and 73 ° C. or lower as measured by a DSC method.

The invention according to claim 3
The difference (Tmc−Tmw) between the endothermic peak temperature Tmc derived from the crystalline polyester resin and the endothermic peak temperature Tmw derived from the first release agent measured by DSC method is −5 ° C. or more and 10 ° C. or less. The toner for developing an electrostatic charge image according to claim 1 or 2.

The invention according to claim 4
A second release agent having an endothermic peak in a range of 100 ° C. or higher and 110 ° C. or lower as measured by DSC method, wherein the endothermic peak is higher than the endothermic peak temperature Tmw derived from the first release agent. The toner for developing an electrostatic charge image according to claim 3, which is contained.

The invention according to claim 5
The repeating unit having a side chain having 5 to 20 carbon atoms is included as at least a part of the repeating unit derived from the alcohol component and the repeating unit derived from the carboxylic acid component contained in the amorphous polyester resin. The toner for developing an electrostatic image according to claim 4.

The invention according to claim 6
A combination of a repeating unit derived from a carboxylic acid component and a repeating unit derived from an alcohol component in the crystalline polyester resin is a combination of a repeating unit derived from 1,10-decanedicarboxylic acid and a repeating unit derived from 1,4-butanediol, A combination of a repeating unit derived from 1,8-octanedicarboxylic acid and a repeating unit derived from 1,6-hexanediol, or a repeating unit derived from 1,8-octanedicarboxylic acid and a repeating unit derived from 1,4-butanediol The toner for developing an electrostatic charge image according to any one of claims 1 to 5, which is a combination.

The invention according to claim 7 provides:
An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1.

The invention according to claim 8 provides:
Containing the toner for developing an electrostatic charge image according to any one of claims 1 to 6,
The toner cartridge is detachable from the image forming apparatus.

The invention according to claim 9 is:
A developing means for containing the electrostatic charge image developer according to claim 7 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer,
It is a process cartridge that can be attached to and detached from the image forming apparatus.

The invention according to claim 10 is:
An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Development means for containing the electrostatic image developer according to claim 7 and developing the electrostatic image formed on the surface of the image carrier as a toner image by the electrostatic image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus.

The invention according to claim 11 is:
The image forming apparatus according to claim 10, wherein a fixing pressure by the fixing unit is 0.5 kgf / cm ² or more and 2.0 kgf / cm ² or less.

The invention according to claim 12
A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with the electrostatic charge image developer according to claim 7;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
Is an image forming method.

The invention according to claim 13 is:
The image forming method according to claim 12, wherein a fixing pressure in the fixing step is 0.5 kgf / cm ² or more and 2.0 kgf / cm ² or less.

According to the first to sixth aspects of the invention, compared to the case where a specific polyester resin is not used as the binder resin, the electrostatic charge image development is less likely to cause image loss even when a fixing device having a low fixing pressure is used. Toner is provided.
According to the seventh aspect of the present invention, there is provided an electrostatic charge image developer that is less likely to cause image defects even when a fixing device having a low fixing pressure is used as compared with a case where a specific polyester resin is not used as a binder resin. The
According to the eighth aspect of the present invention, the toner for developing an electrostatic charge image, which is less likely to cause image loss even when a fixing device having a low fixing pressure is used, is stored as compared with a case where a specific polyester resin is not used as a binder resin. A toner cartridge is provided.
According to the ninth aspect of the present invention, an electrostatic charge image developer that does not easily cause image defects even when a fixing device having a low fixing pressure is used as compared with a case where a specific polyester resin is not used as a binder resin is accommodated. A process cartridge is provided.
According to the tenth to eleventh aspects of the present invention, electrostatic charge image development is less likely to cause image defects even when a fixing device having a low fixing pressure is used as compared with a case where a specific polyester resin is not used as a binder resin. An image forming apparatus using the agent is provided.
According to the inventions according to claims 12 to 13, the electrostatic charge image development is less likely to cause image defects even when a fixing device having a low fixing pressure is used as compared with a case where a specific polyester resin is not used as the binder resin. An image forming method using an agent is provided.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows an example of the process cartridge of this embodiment.

  Hereinafter, embodiments of an electrostatic charge image developing toner, an electrostatic charge image developer, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method according to the present invention will be described in detail.

<Toner for electrostatic image development>
The toner for developing an electrostatic charge image according to this embodiment (hereinafter sometimes referred to as toner according to this embodiment) includes a binder resin containing an amorphous polyester resin and a crystalline polyester resin, and a first resin. And a ratio of the repeating unit derived from the ethylene oxide adduct of bisphenol A in the repeating unit derived from the alcohol component contained in the amorphous polyester resin is more than 50 mol% and not more than 100 mol%. The ratio of the total amount of repeating units derived from at least one selected from the group consisting of 1,4-butanediol and 1,6-hexanediol in the repeating units derived from the alcohol component contained in the crystalline polyester resin. 95 mol% or more, and the recycle derived from the carboxylic acid component contained in the crystalline polyester resin. The proportion of repeating units derived from terephthalic acid in the unit is 3 mol% or more and 20 mol% or less, and is a repetition derived from at least one selected from the group consisting of 1,10-decanedicarboxylic acid and 1,8-octanedicarboxylic acid The ratio of the total amount of units is 80 mol% or more and 97 mol% or less.

Conventionally, films used for film printing include polyethylene terephthalate (PET) films. PET is also an OHP film substrate and has excellent adhesion to conventional toners. However, recent toners contain a large amount of release agent in order to have oilless fixing suitability, and this release agent may reduce the adhesive force with the film.
Furthermore, the fixing pressure tends to be low due to the long life of the fixing member in the fixing means (fixing device). When the fixing pressure is low, the force for crushing the toner at the time of fixing becomes weak, and the adhesive force between the toner and a substrate such as paper tends to decrease. In particular, in film printing with high surface hydrophobicity and high smoothness, image defects may easily occur due to stress such as rubbing.
Therefore, there has been a demand for a toner that does not easily cause image loss even when a fixing device having a low fixing pressure is used.

As a result of intensive studies by the present inventors in order to satisfy such a requirement, the following has been clarified.
A toner used in a low-pressure fixing device is required to have a reduced melt viscosity without depending on pressure deformation. Therefore, it is desirable to use the crystalline polyester resin together with the amorphous polyester resin as the binder resin and use the sharp melt property of the crystalline polyester resin.
Moreover, it is necessary to control the compatibility of the amorphous polyester resin and the crystalline polyester resin more precisely than before. In the present inventors, the carboxylic acid component of the linear monomer constituting the crystalline polyester resin is selected from 1,10-decanedicarboxylic acid and 1,8-octanedicarboxylic acid, and the diol component is 1,4-butanediol. And 1,6-hexanediol, the number of moles of the bisphenol A ethylene oxide adduct (BPA-EO) of the amorphous polyester resin strongly affects the compatibility with the crystalline polyester resin. I found out. The amorphous polyester resin and the crystalline polyester resin are not completely compatible with each other, but are incompatible with each other to the extent that nano-scale fine crystalline polyester resin domains exist. Even when the crystalline polyester resin is not sufficiently melted, it can be fixed by melting the crystalline polyester resin. Such a state appears when the number of moles of BPA-EO exceeds 50 mol%.
Furthermore, by copolymerizing terephthalic acid with a crystalline polyester resin mainly composed of linear monomers, the degree of crystallinity of the crystalline polyester resin is moderately reduced, resulting from internal strain of the crystalline polyester resin itself. By suppressing the volume change, the adhesive force is improved.
From the above viewpoint, the present inventors have completed the toner according to this embodiment.

  Hereinafter, each component constituting the toner of the exemplary embodiment will be described.

-Binder resin-
In the present embodiment, a binder resin including an amorphous polyester resin and a crystalline polyester resin is used.

(Crystalline polyester resin)
The crystalline polyester resin according to this embodiment (hereinafter sometimes referred to as a specific crystalline polyester resin) is composed of 1,4-butanediol and 1,6-hexanediol, which occupy a repeating unit derived from an alcohol component. The ratio of the total amount of the repeating units derived from at least one selected from the group is 95 mol% or more, and the ratio of the repeating units derived from terephthalic acid in the repeating units derived from the carboxylic acid component is 3 mol% or more and 20 mol% or less. The ratio of the total amount of repeating units derived from at least one selected from the group consisting of 1,10-decanedicarboxylic acid and 1,8-octanedicarboxylic acid is 80 mol% or more and 97 mol% or less.

In the specific crystalline polyester resin, the proportion of the total amount of repeating units derived from at least one selected from the group consisting of 1,4-butanediol and 1,6-hexanediol in the repeating units derived from the alcohol component is 95 mol. If it is less than%, the crystallinity may decrease and the blocking property may deteriorate.
The ratio of the total amount of repeating units derived from at least one selected from the group consisting of 1,4-butanediol and 1,6-hexanediol in the repeating units derived from the alcohol component in the specific crystalline polyester resin is as follows: It is preferably 97 mol% or more, and more preferably 100 mol%.

In the specific crystalline polyester resin, when the ratio of the repeating unit derived from terephthalic acid to the repeating unit derived from the carboxylic acid component is less than 3 mol%, the adhesive strength with the film may be reduced and image defects may occur. Moreover, when it exceeds 20 mol%, crystallinity may fall and it may cause blocking.
In the specific crystalline polyester resin, the total amount of repeating units derived from at least one selected from the group consisting of 1,10-decanedicarboxylic acid and 1,8-octanedicarboxylic acid in the repeating units derived from the carboxylic acid component If the ratio is less than 80 mol%, the melting temperature of the crystals may be lowered and the powder characteristics of the toner may be deteriorated. On the other hand, if it exceeds 97 mol%, the adhesive strength with the film is lowered and image defects may occur.

  The specific crystalline polyester resin is preferably composed of a repeating unit derived from terephthalic acid, a repeating unit derived from 1,10-decanedicarboxylic acid, and a repeating unit derived from 1,8-octanedicarboxylic acid. That is, for example, when the proportion of the repeating unit derived from terephthalic acid in the repeating unit derived from the carboxylic acid component is 3 mol%, it is selected from the group consisting of 1,10-decanedicarboxylic acid and 1,8-octanedicarboxylic acid. The total proportion of the repeating units derived from at least one kind is desirably 97 mol%, and when the proportion of the repeating units derived from terephthalic acid in the repeating units derived from the carboxylic acid component is 20 mol%, 1,10- The ratio of the total amount of repeating units derived from at least one selected from the group consisting of decanedicarboxylic acid and 1,8-octanedicarboxylic acid is desirably 80 mol%.

  “Crystalline polyester resin” according to the present embodiment refers to a distinct endothermic peak, not a stepwise endothermic amount change in differential scanning calorimetry (hereinafter sometimes abbreviated as “DSC”). The thing which has.

When fixing the toner according to the present embodiment, the endothermic peak temperature derived from the crystalline polyester resin contained in the toner is lowered in order to melt the toner not by the fixing pressure by the fixing device but by the heat from the fixing device. It is desirable that Therefore, the endothermic peak temperature Tmc derived from the specific crystalline polyester resin, measured by the DSC method, is preferably 50 ° C. or higher and 73 ° C. or lower, more preferably 55 ° C. or higher and 70 ° C. or lower, and 60 ° C. It is particularly desirable that the temperature is 68 ° C. or lower.
The endothermic peak temperature Tmc measured by the DSC method means the melting temperature of the crystalline polyester resin.

  The specific crystalline polyester resin used in this embodiment is synthesized from a polyvalent carboxylic acid component and a polyhydric alcohol component. In the present embodiment, a commercially available product may be used as the crystalline polyester resin, or a synthesized product may be used.

  As the polyvalent carboxylic acid component, terephthalic acid and at least one of 1,10-decanedicarboxylic acid and 1,8-octanedicarboxylic acid are used. If necessary, other polyvalent carboxylic acids may be used in combination. Examples of other polyvalent carboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1, Aliphatic dicarboxylic acids such as 14-tetradecanedicarboxylic acid and 1,18-octadecanedicarboxylic acid; aromatic dicarboxylic acids such as dibasic acids such as phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, and mesaconic acid Acid; and the like, and these anhydrides and lower alkyl esters thereof are also included, but not limited thereto.

  Examples of the trivalent or higher carboxylic acid include specific aromatic carboxylic acids such as 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like. These anhydrides and their lower alkyl esters are exemplified. These may be used individually by 1 type and may use 2 or more types together.

  Moreover, as an acid component, the carboxylic acid component which has a sulfonic acid group other than the said aliphatic dicarboxylic acid and aromatic dicarboxylic acid may be contained.

  As the polyhydric alcohol component, at least one selected from the group consisting of 1,4-butanediol and 1,6-hexanediol is used. If necessary, other polyhydric alcohol components may be used in combination.

  Examples of other polyhydric alcohol components include 1,3-propanediol, 1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- Examples include decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, and the like. However, it is not limited to these.

  Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used individually by 1 type and may use 2 or more types together.

As a combination of a repeating unit derived from a carboxylic acid component and a repeating unit derived from an alcohol component in a specific crystalline polyester resin, a repeating unit derived from 1,10-decanedicarboxylic acid and a repeating unit derived from 1,4-butanediol A combination, a combination of a repeating unit derived from 1,8-octanedicarboxylic acid and a repeating unit derived from 1,6-hexanediol, or a repeating unit derived from 1,8-octanedicarboxylic acid and a repeating unit derived from 1,4-butanediol The combination with is desirable.
When the total number of carbon atoms of the carboxylic acid component and the diol component of the specific crystalline polyester resin is 10 or more and 14 or less, the image strength is improved and image defects are less likely to occur. Here, the carbon number in “the carbon number of the carboxylic acid component” refers to the number of carbon atoms excluding the carbon atom contained in the carboxyl group.

The production of the crystalline polyester resin can be carried out at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower. If necessary, the reaction system is reduced in pressure and reacted while removing water and alcohol generated during condensation. .
When the polymerizable 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 aid is distilled off. If there is a polymerizable monomer having poor compatibility in the copolymerization reaction, the polymerizable monomer having poor compatibility and the polymerizable monomer and the acid or alcohol to be polycondensed are condensed in advance. And then polycondensation with the main component.

  The acid value of the specific crystalline polyester resin (the number of mg of KOH required to neutralize 1 g of resin) is desirably in the range of 3.0 mgKOH / g to 30.0 mgKOH / g, and 6.0 mgKOH / G to 20.0 mgKOH / g, more preferably in the range of 8.0 mgKOH / g to 15.0 mgKOH / g. In the present embodiment, the acid value is measured according to JIS K-0070-1992.

  When the acid value is higher than 3.0 mgKOH / g, the dispersibility in water is improved, and thus the emulsified particles can be easily produced by the wet process. Further, since the stability as emulsified particles during aggregation is improved, efficient toner production is facilitated. On the other hand, if the acid value is 30.0 mgKOH / g or less, the hygroscopicity as a toner does not increase, and it becomes difficult to be affected by the environment as a toner.

  The weight average molecular weight (Mw) of the specific crystalline polyester resin is desirably 6,000 or more and 35,000 or less. When the molecular weight (Mw) is 6,000 or more, the toner does not soak into the surface of a recording medium such as paper at the time of fixing to cause uneven fixing, and the strength against bending resistance of the fixed image does not decrease. In addition, when the weight average molecular weight (Mw) is 35,000 or less, the viscosity at the time of melting does not become excessively high, so that the temperature for reaching a viscosity suitable for fixing does not increase, and as a result, low temperature fixability is achieved. can get.

  The weight average molecular weight is measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC was carried out with a THF (tetrahydrofuran) solvent using a Tosoh GPC / HLC-8120 as a measuring device and a Tosoh column / TSKgel SuperHM-M (15 cm). The weight average molecular weight is calculated from the measurement result using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.

  In the present embodiment, a crystalline resin such as a polyalkylene resin or a long-chain alkyl (meth) acrylate resin may be used in combination with a specific crystalline polyester resin. In this case, the proportion of the specific crystalline polyester resin in the total crystalline resin contained in the toner according to the exemplary embodiment is preferably 85% by mass or more, more preferably 95% by mass or more, and 100% by mass. Particularly preferred.

(Amorphous polyester resin)
The amorphous polyester resin according to the present embodiment (hereinafter sometimes referred to as a specific amorphous polyester resin) is a ratio of the repeating unit derived from the ethylene oxide adduct of bisphenol A to the repeating unit derived from the alcohol component. More than 50 mol% and 100 mol% or less.

In a specific amorphous polyester resin, if the proportion of the repeating unit derived from the ethylene oxide adduct of bisphenol A in the repeating unit derived from the alcohol component is 50 mol% or less, the compatibility with the crystalline resin is increased and the fixing property is increased. May worsen and cause image defects.
The ratio of the repeating unit derived from the ethylene oxide adduct of bisphenol A in the repeating unit derived from the alcohol component in the specific amorphous polyester resin is preferably 53 mol% to 85 mol%, and more preferably 55 mol% to 75 mol%. .

  The “amorphous polyester resin” according to the present embodiment is a resin in which a stepwise endothermic change is recognized instead of a clear endothermic peak in differential scanning calorimetry (DSC).

  In the present embodiment, since the compatibility with the crystalline polyester resin is improved by using the amorphous polyester resin, the amorphous polyester resin is also reduced as the viscosity at the melting temperature of the crystalline polyester resin is reduced. Viscosity and sharp melt properties (sensitive melting characteristics) as a toner are obtained, which is advantageous for low-temperature fixability. In addition, since the wettability with the crystalline polyester resin is good, the dispersibility of the crystalline polyester resin inside the toner is improved, and the exposure of the crystalline polyester resin to the toner surface is suppressed. Is suppressed. For this reason, it is also desirable from the viewpoint of improving the strength of toner and the strength of a fixed image.

  The specific amorphous polyester resin used in this embodiment is synthesized from a polyvalent carboxylic acid component and a polyhydric alcohol component. In the present embodiment, a commercially available product may be used as the amorphous polyester resin, or a synthesized product may be used.

  Examples of the polyvalent carboxylic acid component include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, and naphthalenedicarboxylic acid; maleic anhydride, fumaric acid, succinic acid, Aliphatic carboxylic acids such as alkenyl succinic anhydride and adipic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, and the like. These polyvalent carboxylic acids may be used alone or in combination. Among these polyvalent carboxylic acids, it is desirable to use an aromatic carboxylic acid, and it is desirable to have a crosslinked structure or a branched structure in order to ensure good fixability. It is desirable to use an acid (such as trimellitic acid or its acid anhydride) in combination.

As the polyhydric alcohol component, an ethylene oxide adduct of bisphenol A is used. If necessary, other polyhydric alcohol components may be used in combination.
Examples of other polyhydric alcohol components include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentylglycol, and glycerin; cyclohexanediol, cyclohexanedimethanol, water And alicyclic diols such as bisphenol A; aromatic diols such as propylene oxide adducts of bisphenol A.

  In order to secure better fixing properties, the specific amorphous polyester resin may contain a crosslinked structure or a branched structure. For this reason, a trihydric or higher polyhydric alcohol (glycerin, trimethylolpropane, Pentaerythritol) may be used in combination.

It is desirable that the repeating unit derived from the alcohol component and the repeating unit derived from the carboxylic acid component contained in the specific amorphous polyester resin include a repeating unit having a side chain having 5 to 20 carbon atoms. . The ratio of the repeating unit having a side chain having 5 to 20 carbon atoms in the total of the repeating unit derived from the alcohol component and the repeating unit derived from the carboxylic acid component is preferably 6 to 18 mol%, and 8 mol%. More preferably, it is 16 mol% or less. In addition, the repeating unit having a side chain having 5 to 20 carbon atoms may be a repeating unit derived from an alcohol component, a repeating unit derived from a carboxylic acid component, or both. Good.
As at least part of the repeating unit derived from the alcohol component and the repeating unit derived from the carboxylic acid component contained in the specific amorphous polyester resin, a repeating unit having a side chain having 5 to 20 carbon atoms is included. The intermolecular distance of a specific amorphous polyester resin is moderately widened, so that a specific crystalline polyester resin can easily penetrate between molecules of a specific amorphous polyester resin, resulting in a specific amorphous property during fixing. The compatibility between the polyester resin and the specific crystalline polyester resin is improved.

The carboxylic acid component that is the base of the repeating unit having a side chain having 5 or more and 20 or less carbon atoms preferably contains alkenyl succinic acid or its anhydride. By using an amorphous polyester resin containing alkenyl succinic acid or an anhydride thereof as a constituent component, compatibility with the crystalline resin is improved and good low-temperature fixability is obtained. Examples of alkenyl succinic acid include n-butyl succinic acid, n-butenyl succinic acid, isobutyl succinic acid, isobutenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl Succinic acid, isododecenyl succinic acid and the like are used.
Examples of the alcohol component serving as a base of the repeating unit having a side chain having 5 to 20 carbon atoms include 1,2-octanediol and 1,2-dodecanediol.
In this embodiment, dodecenyl succinic acid is preferred.

The glass transition temperature (Tg) of the specific amorphous polyester resin is desirably in the range of 50 ° C to 80 ° C. When Tg is 50 ° C. or higher, the storage stability of the toner and the storage stability of the fixed image are improved. On the other hand, if it is 80 ° C. or lower, fixing is performed at a lower temperature than in the prior art.
As for Tg of specific amorphous polyester resin, it is more desirable that they are 50 degreeC or more and 65 degrees C or less.

  In addition, you may perform manufacture of a specific amorphous polyester resin according to the case of a specific crystalline polyester resin.

The weight average molecular weight (Mw) of the specific amorphous polyester resin is preferably 30,000 or more and 80,000 or less. When the molecular weight (Mw) is 30,000 or more and 80,000 or less, control of the low-temperature fixability of the toner becomes easy, and furthermore, high-temperature offset resistance can be obtained.
The weight average molecular weight (Mw) of the specific amorphous polyester resin is more preferably from 35,000 to 80,000, particularly preferably from 40,000 to 80,000.

  In this embodiment, a known amorphous resin such as a styrene / acrylic resin, an epoxy resin, a polyurethane resin, a polyamide resin, a cellulose resin, a polyether resin, and a polyolefin resin is used as an amorphous resin together with a specific amorphous polyester resin. Materials may be used in combination.

  In the toner according to the exemplary embodiment, the content ratio (by mass) of the specific amorphous polyester resin and the specific crystalline polyester resin is a specific crystalline polyester with respect to 100 parts by mass of the specific amorphous polyester resin. The resin is preferably 3 parts by mass or more and 30 parts by mass or less, more preferably 5 parts by mass or more and 20 parts by mass or less, and particularly preferably 7 parts by mass or more and 15 parts by mass or less.

(Coloring agent)
As a colorant, yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hansa Yellow, Hansa Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Slen Yellow, Quinoline Yellow, Permanent Yellow. NCG etc. can be mentioned. I. Pigment Yellow 17, 74, 93, 97, 154, 155, 180, 185, etc., among which Pigment Yellow 74 is preferred.

  Magenta pigments include Bengala, Cadmium Red, Red Plum, Mercury Sulfide, Watch Young Red, Permanent Red 4R, Risor Red, Brilliantamine 3B, Brilliantamine 6B, Daypon Oil Red, Pyrazolone Red, Rhodamine B Lake, Lake Red C Pigment Red 31, 146, 147, 150, 176, 238, 269, and the like as Rose Bengal, Eoxin Red, Alizarin Lake, and Naphthol pigments. Pigments include quinacridone pigments. Examples include Red 122, 202, and 209. Among these, Pigment Red 185, 238, 269, and 122 are particularly preferable.

  As cyan pigments, bitumen, cobalt blue, alkali blue lake, Victoria blue lake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, chalcoil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare Rate, and the like. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 or the like is preferably used.

  Examples of orange pigments include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK, pigment orange 16, 34, 36, and 38. , 43, 61, 64, 68, 71, 73, etc., particularly CI Pigment Orange 36, 38, 64, and 71 are preferred.

  Examples of purple pigments include manganese purple, fast violet B, methyl violet lake, pigment violet 19, 23, 32, 37, and 44. Pigment violet 23 and 37 are particularly preferable.

Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like, and particularly, pigment green 7 and 36 are preferable.
These colorants may be mixed and further used in a solid solution state.

  Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white. Also, acridine, xanthene, azo, benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenyl Various dyes such as methane, diphenylmethane, thiazine, thiazole, and xanthene are also used.
These colorants are used alone or in combination.

  Examples of the black pigment used for the black toner include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon and the like, and carbon black is particularly preferably used. Since carbon black has relatively good dispersibility, it does not require any special dispersion, but it is desirable that it be produced by a production method according to the colorant.

  The colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the toner. The colorant is preferably added in the range of 1% by mass to 15% by mass with respect to the total toner mass.

In addition to carbon black, iron, ferrite, magnetite, titanium, solid solution of iron and titanium, and the like can be used as the black colorant. Since these have a large specific gravity, the addition amount differs from other colorants. It can be added in an amount of not less than mass% and not more than 80 mass%.

When the toner is obtained in the aqueous phase, the colorant is dispersed using a dispersant or a surfactant. The surface of the colorant can be modified in advance, for example, a hydrophobic treatment can be performed.

(Release agent)
Examples of mold release agents include hydrocarbon waxes; natural waxes such as carnauba wax, rice wax, and candelilla wax; synthetic or mineral / petroleum waxes such as montan wax; ester types such as fatty acid esters and montanic acid esters Wax; and the like. The release agent is not limited to this.

The endothermic peak temperature Tmw derived from the release agent (first release agent) measured by the DSC method is related to the endothermic peak temperature Tmc derived from the specific crystalline polyester resin measured by the DSC method. The difference in peak temperature (Tmc−Tmw) is preferably −5 ° C. or more and 10 ° C. or less, and particularly preferably −5 ° C. or more and 5 ° C. or less.
If the difference in endothermic peak temperature between the specific crystalline polyester resin and the release agent (first release agent) is within the above range, both of them melt at the time of toner fixing, so that the release agent The specific crystalline polyester resin is also diffused by the diffusion and reaches the toner surface, so that an adhesive force by the specific crystalline polyester resin is developed.

The toner according to the exemplary embodiment has an endothermic peak in a range of 100 ° C. or higher and 110 ° C. or lower as measured by a DSC method, and the endothermic peak is higher than the endothermic peak temperature Tmw derived from the first release agent. You may contain a 2nd mold release agent further.
In this embodiment, the endothermic peak is measured by DSC in accordance with ASTM D3418-8, using a differential scanning calorimeter (manufactured by Mac Science: DSC3110, thermal analysis system 001), and from room temperature (25 ° C.) to 150 ° C. Up to 10 ° C./min.
The endothermic peak temperature derived from the release agent measured by the DSC method means the melting temperature of the release agent.
In combination with the second release agent having a higher melting temperature than the first release agent, the strength of the release agent layer may be improved, and the adhesive force between the fixed image and the film may be improved.

The content of the release agent is, for example, preferably 1% by mass to 20% by mass and more preferably 5% by mass to 15% by mass with respect to the entire toner particles.
When the first mold release agent and the second mold release agent are used in combination, the content of the second mold release agent is 10 parts by mass or more and 70 parts by mass with respect to 100 parts by mass of the first mold release agent. Part or less, preferably 20 parts by weight or more and 50 parts by weight or less.

-Other additives-
Examples of other additives include known additives such as a magnetic material, a charge control agent, and inorganic powder. These additives are contained in the toner particles as internal additives.

-Toner particle characteristics-
The toner particles may be toner particles having a single layer structure, or toner particles having a so-called core / shell structure composed of a core (core particle) and a coating layer (shell layer) covering the core. May be.
Here, the core-shell structure toner particles include, for example, a core portion including a binder resin, a release agent, and, if necessary, other additives such as a colorant, and a binder resin. It is good to be comprised with the comprised coating layer.

  The volume average particle diameter (D50v) of the toner particles is preferably 2 μm or more and 10 μm or less, and more preferably 4 μm or more and 8 μm or less.

The various average particle diameters and various particle size distribution indexes of the toner particles are measured using Coulter Multisizer II (manufactured by Beckman-Coulter), and the electrolyte is measured using ISOTON-II (manufactured by Beckman-Coulter). The
In the measurement, 0.5 mg to 50 mg of a measurement sample is added as a dispersant to 2 ml of a 5% aqueous solution of a surfactant (preferably sodium alkylbenzenesulfonate). This is added to 100 ml or more and 150 ml or less of the electrolytic solution.
The electrolyte in which the sample is suspended is dispersed 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 60 μm is measured using a 100 μm aperture with a Coulter Multisizer II. taking measurement. The number of particles to be sampled is 50,000.
The particle size range divided on the basis of the measured particle size distribution (number of divisions: 1.26 to 50.8 μm is divided into 16 channels so as to be 0.1 intervals on the log scale. Specifically, The channel 1 is 1.26 μm or more and less than 1.59 μm, the channel 2 is 1.59 μm or more and less than 2.00 μm, the channel 3 is 2.00 μm or more and less than 2.52 μm, and the lower limit log value on the left side is ( Log 1.26 =) 0.1, (log 1.59 =) 0.2, (log 2.00 =) 0.3,..., 1.6) The cumulative distribution is drawn from the small diameter side, the particle diameter that becomes 16% cumulative is the volume particle diameter D16v, the number particle diameter D16p, the particle diameter that is 50% cumulative is the volume average particle diameter D50v, the cumulative number average particle diameter D50p, The particle size is 84% cumulative Diameter D84v, defined as the few grains diameter D84p.
Using these, the volume average particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D84p / D16p) ^1/2 .

  The shape factor SF1 of the toner particles is preferably 110 or more and 150 or less, and more preferably 120 or more and 140 or less.

The shape factor SF1 is obtained by the following formula.
Formula: SF1 = (ML ² / A) × (π / 4) × 100
In the above formula, ML represents the absolute maximum length of the toner, and A represents the projected area of the toner.
Specifically, the shape factor SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and is calculated as follows. That is, by capturing an optical microscope image of particles dispersed on the surface of a slide glass into a Luzex image analyzer using a video camera, obtaining the maximum length and projected area of 100 particles, calculating by the above formula, and obtaining the average value can get.

(External additive)
Examples of the external additive include inorganic particles. As the inorganic particles, SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, CaO, K ₂ O, Na ₂ O, ZrO ₂ , CaO. _{SiO 2, K 2 O · (} TiO 2) n, Al 2 O 3 · 2SiO 2, CaCO 3, MgCO 3, BaSO 4, MgSO 4 , and the like.

The surface of the inorganic particles as an external additive is preferably subjected to a hydrophobic treatment. The hydrophobic treatment is performed, for example, by immersing inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents and the like. These may be used individually by 1 type and may use 2 or more types together.
The amount of the hydrophobizing agent is usually, for example, 1 part by mass or more and 10 parts by mass with respect to 100 parts by mass of the inorganic particles.

  Examples of external additives include resin particles (resin particles such as polystyrene, PMMA, and melamine resin), cleaning activators (for example, metal salts of higher fatty acids typified by zinc stearate, particles of a fluorine-based high molecular weight substance), and the like. Can be mentioned.

  The external addition amount of the external additive is, for example, preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.01% by mass or more and 2.0% by mass or less with respect to the toner particles.

(Toner production method)
Next, a toner manufacturing method according to this embodiment will be described.
The toner according to the exemplary embodiment can be obtained by externally adding an external additive to the toner particles after the toner particles are manufactured.

The toner particles may be produced by any of a dry production method (for example, a kneading and pulverizing method) and a wet production method (for example, an aggregation coalescence method, a suspension polymerization method, a dissolution suspension method, etc.). The production method of the toner particles is not particularly limited, and a known production method is adopted.
Among these, it is preferable to obtain toner particles by an aggregation and coalescence method.

  Specifically, for example, when toner particles are produced by an aggregation and coalescence method, a step of preparing a resin particle dispersion in which resin particles serving as a binder resin are dispersed (resin particle dispersion preparation step), and resin particles Step of agglomerating resin particles (other particles as required) to form aggregated particles in the dispersion (if necessary after mixing with other particle dispersions) (aggregated particle formation) Step) and heating the agglomerated particle dispersion in which the agglomerated particles are dispersed, and fusing and coalescing the agglomerated particles to form toner particles (fusing and coalescing step). Manufacturing.

Details of each step will be described below.
In the following description, a method for obtaining toner particles containing a colorant and a release agent will be described. The colorant is used as necessary. Of course, you may use other additives other than a coloring agent and a mold release agent.

-Preparation step of resin particle dispersion-
First, together with a resin particle dispersion in which resin particles to be a binder resin are dispersed, for example, a colorant particle dispersion in which colorant particles are dispersed and a release agent dispersion in which release agent particles are dispersed are prepared. .

  Here, the resin particle dispersion is prepared, for example, by dispersing resin particles in a dispersion medium using a surfactant.

Examples of the dispersion medium used for the resin particle dispersion include an aqueous medium.
Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together.

Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an anionic surfactant and a cationic surfactant are particularly mentioned. The nonionic surfactant may be used in combination with an anionic surfactant or a cationic surfactant.
Surfactant may be used individually by 1 type and may use 2 or more types together.

Examples of the method for dispersing the resin particles in the dispersion medium in the resin particle dispersion include a general dispersion method such as a rotary shear homogenizer, a ball mill having media, a sand mill, and a dyno mill. Depending on the type of resin particles, the resin particles may be dispersed in the resin particle dispersion using, for example, a phase inversion emulsification method.
The phase inversion emulsification method is a method in which a resin to be dispersed is dissolved in a hydrophobic organic solvent in which the resin is soluble, and a base is added to the organic continuous phase (O phase) to neutralize the aqueous medium. (W phase) is added to convert the resin from W / O to O / W (so-called phase inversion) to form a discontinuous phase and disperse the resin in an aqueous medium in the form of particles. It is.

The volume average particle size of the resin particles dispersed in the resin particle dispersion is, for example, preferably 0.01 μm or more and 1 μm or less, more preferably 0.08 μm or more and 0.8 μm or less, and further preferably 0.1 μm or more and 0.6 μm or less. .
The volume average particle size of the resin particles is divided into particle size ranges (channels) using a particle size distribution obtained by measurement with a laser diffraction particle size distribution measuring apparatus (for example, LA-700 manufactured by Horiba, Ltd.). On the other hand, the cumulative distribution is drawn from the small particle diameter side with respect to the volume, and the particle diameter that becomes 50% cumulative with respect to all the particles is measured as the volume average particle diameter D50p. The volume average particle size of particles in other dispersions is also measured in the same manner.

  As content of the resin particle contained in a resin particle dispersion liquid, 5 mass% or more and 50 mass% or less are preferable, for example, and 20 mass% or more and 45 mass% or less are more preferable.

  In addition, similarly to resin particle dispersion, for example, a colorant dispersion and a release agent dispersion are also prepared. In other words, regarding the volume average particle size of the particles in the resin particle dispersion, the dispersion medium, the dispersion method, and the content of the particles, the colorant particles dispersed in the colorant dispersion and the release agent dispersed in the release agent dispersion are used. The same applies to the mold agent particles.

-Aggregated particle formation process-
Next, the colorant particle dispersion and the release agent dispersion are mixed together with the resin particle dispersion.
Then, in the mixed dispersion, resin particles, colorant particles, and release agent particles are hetero-aggregated to have resin particles, colorant particles, and release agent particles having a diameter close to the diameter of the target toner particles. Aggregated particles are formed.

Specifically, for example, the flocculant is added to the mixed dispersion, and the pH of the mixed dispersion is adjusted to acidic (for example, the pH is 2 or more and 5 or less), and a dispersion stabilizer is added as necessary. The resin particles are heated to a glass transition temperature (specifically, for example, the glass transition temperature of the resin particles −30 ° C. or more and the glass transition temperature −10 ° C. or less), and the particles dispersed in the mixed dispersion liquid are aggregated. , Forming aggregated particles.
In the agglomerated particle forming step, for example, the aggregating agent is added at room temperature (for example, 25 ° C.) while stirring the mixed dispersion with a rotary shearing homogenizer, and the pH of the mixed dispersion is acidic (for example, the pH is 2 or more and 5 or less). ), And after adding a dispersion stabilizer as necessary, the heating may be performed.

Examples of the flocculant include surfactants having a polarity opposite to that of the surfactant used as the dispersant added to the mixed dispersion, for example, inorganic metal salts and divalent or higher-valent metal complexes. In particular, when a metal complex is used as the flocculant, the amount of the surfactant used is reduced, and the charging characteristics are improved.
If necessary, an additive that forms a complex or a similar bond with the metal ion of the flocculant may be used. As this additive, a chelating agent is preferably used.

Examples of inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic substances such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include metal salt polymers.
A water-soluble chelating agent may be used as the chelating agent. Examples of the chelating agent include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, iminodiacid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), and the like.
As addition amount of a chelating agent, 0.01 mass part or more and 5.0 mass part or less are preferable with respect to 100 mass parts of resin particles, for example, and 0.1 mass part or more and less than 3.0 mass parts are more preferable.

-Fusion / unification process-
Next, the aggregated particle dispersion in which the aggregated particles are dispersed is heated to, for example, a glass transition temperature or higher of the resin particles (for example, a temperature of 10 to 30 ° C. higher than the glass transition temperature of the resin particles). Are fused and united to form toner particles.

Through the above steps, toner particles are obtained.
In addition, after obtaining the aggregated particle dispersion liquid in which the aggregated particles are dispersed, the aggregated particle dispersion liquid and the resin particle dispersion liquid in which the resin particles are dispersed are further mixed, and the resin particles are further added to the surface of the aggregated particles. A process of aggregating to adhere to form second aggregated particles, and heating the second aggregated particle dispersion in which the second aggregated particles are dispersed to fuse and coalesce the second aggregated particles. The toner particles may be manufactured through a step of forming toner particles having a core / shell structure.

Here, after completion of the fusion / unification process, toner particles formed in the solution are dried through a known washing process, solid-liquid separation process, and drying process to obtain toner particles.
In the washing step, it is preferable to sufficiently carry out substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, etc. are preferably performed from the viewpoint of productivity. Also, the drying process is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, or the like is preferably performed.

  The toner according to the exemplary embodiment is manufactured, for example, by adding an external additive to the obtained dry toner particles and mixing them. Mixing may be performed, for example, with a V blender, a Henschel mixer, a Ladyge mixer, or the like. Furthermore, if necessary, coarse toner particles may be removed using a vibration classifier, a wind classifier, or the like.

<Electrostatic image developer>
The electrostatic charge image developer according to the exemplary embodiment includes at least the toner according to the exemplary embodiment.
The electrostatic image developer according to this embodiment may be a one-component developer including only the toner according to this embodiment, or may be a two-component developer mixed with the toner and a carrier.

There is no restriction | limiting in particular as a carrier, A well-known carrier is mentioned. As a carrier, for example, a coated carrier in which the surface of a core made of magnetic powder is coated with a coating resin; a magnetic powder dispersion type carrier in which magnetic powder is dispersed and mixed in a matrix resin; a porous magnetic powder is impregnated with a resin And a resin-dispersed carrier in which conductive particles are dispersed and blended in a matrix resin.
The magnetic powder dispersion type carrier, the resin impregnated type carrier, and the conductive particle dispersion type carrier may be a carrier in which the constituent particles of the carrier are used as a core material and coated with a coating resin.

  Examples of the magnetic powder include magnetic metals such as iron oxide, nickel, and cobalt, and magnetic oxides such as ferrite and magnetite.

  Examples of the conductive particles include particles of metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.

Examples of the coating resin and matrix resin include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid copolymer. Examples thereof include a polymer, a straight silicone resin containing an organosiloxane bond or a modified product thereof, a fluororesin, a polyester, a polycarbonate, a phenol resin, and an epoxy resin.
Note that the coating resin and the matrix resin may contain other additives such as a conductive material.

Here, in order to coat the surface of the core material with the coating resin, a method of coating with a coating layer forming solution obtained by dissolving the coating resin and, if necessary, various additives in an appropriate solvent may be mentioned. The solvent is not particularly limited, and may be selected in consideration of the coating resin to be used, coating suitability, and the like.
Specific resin coating methods include a dipping method in which the core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed on the surface of the core material, and a state in which the core material is suspended by flowing air. Examples thereof include a fluidized bed method in which a coating layer forming solution is sprayed, a kneader coater method in which a carrier core material and a coating layer forming solution are mixed in a kneader coater, and the solvent is removed.

  The mixing ratio (mass ratio) of the toner and the carrier in the two-component developer is preferably toner: carrier = 1: 100 to 30: 100, and more preferably 3: 100 to 20: 100.

<Image Forming Apparatus / Image Forming Method>
The image forming apparatus / image forming method according to the present embodiment will be described.
The image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the surface of the image carrier, an electrostatic image forming unit that forms an electrostatic image on the surface of the charged image carrier, and an electrostatic charge. Development means for containing an image developer and developing the electrostatic image formed on the surface of the image carrier as a toner image with the electrostatic image developer, and the toner image formed on the surface of the image carrier as a recording medium Transfer means for transferring to the surface of the recording medium, and fixing means for fixing the toner image transferred to the surface of the recording medium. The electrostatic charge image developer according to this embodiment is applied as the electrostatic charge image developer.

  In the image forming apparatus according to this embodiment, a charging process for charging the surface of the image carrier, an electrostatic charge image forming process for forming an electrostatic image on the surface of the charged image carrier, and an electrostatic charge according to this embodiment. A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with an image developer; a transfer step of transferring the toner image formed on the surface of the image carrier to the surface of the recording medium; An image forming method (an image forming method according to the present embodiment) including a fixing step of fixing the toner image transferred onto the surface of the recording medium is performed.

The image forming apparatus according to the present embodiment is a direct transfer type apparatus that directly transfers a toner image formed on the surface of an image carrier to a recording medium; the toner image formed on the surface of the image carrier is transferred to an intermediate transfer member An intermediate transfer type apparatus that primarily transfers the toner image transferred to the surface of the intermediate transfer body and then secondary transfer the toner image to the surface of the recording medium; after the toner image is transferred, the surface of the image carrier before charging is cleaned. An apparatus provided with a cleaning unit; a known image forming apparatus such as an apparatus provided with a charge removing unit that discharges the surface of an image holding member by irradiating a discharge light after charging a toner image and before charging is applied.
In the case of an intermediate transfer type apparatus, the transfer means includes, for example, an intermediate transfer body on which a toner image is transferred to the surface, and a primary transfer that primarily transfers the toner image formed on the surface of the image holding body to the surface of the intermediate transfer body. And a secondary transfer unit that secondarily transfers the toner image transferred onto the surface of the intermediate transfer member onto the surface of the recording medium.

  In the image forming apparatus according to the present embodiment, for example, the part including the developing unit may have a cartridge structure (process cartridge) that is detachable from the image forming apparatus. As the process cartridge, for example, a process cartridge that accommodates the electrostatic charge image developer according to this embodiment and includes a developing unit is preferably used.

  Hereinafter, an example of the image forming apparatus according to the present embodiment will be described, but the present invention is not limited thereto. The main parts shown in the figure will be described, and the description of the other parts will be omitted.

FIG. 1 is a schematic configuration diagram illustrating an image forming apparatus according to the present embodiment.
The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter sometimes simply referred to as “units”) 10Y, 10M, 10C, and 10K are arranged in parallel at a predetermined distance from each other in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the image forming apparatus.

Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a drive roll 22 and a support roll 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other in the left to right direction in the drawing. The vehicle travels in the direction toward the unit 10K. The support roll 24 is applied with a force in a direction away from the drive roll 22 by a spring or the like (not shown), and tension is applied to the intermediate transfer belt 20 wound around the support roll 24. An intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the drive roll 22.
Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of the units 10Y, 10M, 10C, and 10K has yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The toner including the four color toners is supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K have the same configuration, here, the first unit that forms a yellow image disposed on the upstream side in the intermediate transfer belt traveling direction. 10Y will be described as a representative. It should be noted that reference numerals with magenta (M), cyan (C), and black (K) are attached to the same parts as those of the first unit 10Y instead of yellow (Y). Description of the units 10M, 10C, and 10K will be omitted.

The first unit 10Y includes a photoreceptor 1Y that functions as an image holding member. Around the photoreceptor 1Y, a charging roll (an example of a charging unit) 2Y for charging the surface of the photoreceptor 1Y to a predetermined potential, and the charged surface is exposed by a laser beam 3Y based on a color-separated image signal. Then, an exposure device (an example of an electrostatic image forming unit) 3 that forms an electrostatic image, and a developing device (an example of a developing unit) 4Y that develops the electrostatic image by supplying toner charged to the electrostatic image, developed A primary transfer roll 5Y (an example of a primary transfer unit) that transfers a toner image onto the intermediate transfer belt 20, and a photoconductor cleaning device (an example of a cleaning unit) 6Y that removes toner remaining on the surface of the photoconductor 1Y after the primary transfer. Are arranged in order.
The primary transfer roll 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rolls 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roll under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described.
First, prior to operation, the surface of the photoreceptor 1Y is charged to a potential of −600V to −800V by the charging roll 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate (for example, volume resistivity at 20 ° C .: 1 × 10 ⁻⁶ Ωcm or less). This photosensitive layer usually has a high resistance (general resin resistance), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, a laser beam 3Y is output to the surface of the charged photoreceptor 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic charge image having a yellow image pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic charge image is an image formed on the surface of the photoreceptor 1Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam 3Y, and the charged charge on the surface of the photoreceptor 1Y flows. On the other hand, this is a so-called negative latent image formed by the charge remaining in the portion not irradiated with the laser beam 3Y.
The electrostatic charge image formed on the photoreceptor 1Y is rotated to a predetermined development position as the photoreceptor 1Y travels. At this development position, the electrostatic charge image on the photoreceptor 1Y is visualized (developed image) as a toner image by the developing device 4Y.

  In the developing device 4Y, for example, an electrostatic charge image developer containing at least yellow toner and a carrier is accommodated. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged electric charge on the photoreceptor 1Y, and has a developer roll (a developer holding member). Example) is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image is developed with the yellow toner. . The photoreceptor 1Y on which the yellow toner image is formed continues to run at a predetermined speed, and the toner image developed on the photoreceptor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoreceptor 1Y is conveyed to the primary transfer, a primary transfer bias is applied to the primary transfer roll 5Y, and an electrostatic force from the photoreceptor 1Y toward the primary transfer roll 5Y is applied to the toner image, so that the photoreceptor is exposed. The toner image on 1Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time has a (+) polarity opposite to the polarity (−) of the toner, and is controlled to +10 μA by the control unit (not shown) in the first unit 10Y, for example.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the photoreceptor cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rolls 5M, 5C, and 5K after the second unit 10M is also controlled in accordance with the first unit.
Thus, the intermediate transfer belt 20 onto which the yellow toner image has been transferred by the first unit 10Y is sequentially conveyed through the second to fourth units 10M, 10C, and 10K, and the toner images of the respective colors are superimposed and transferred in a multiple manner. The

  The intermediate transfer belt 20 on which the four color toner images are transferred in multiple ways through the first to fourth units is disposed on the image transfer surface side of the intermediate transfer belt 20, the support roll 24 in contact with the inner surface of the intermediate transfer belt 20. The secondary transfer roll (an example of a secondary transfer unit) 26 is formed to a secondary transfer portion configured. On the other hand, recording paper (an example of a recording medium) P is fed at a predetermined timing into a gap where the secondary transfer roll 26 and the intermediate transfer belt 20 are in contact with each other via a supply mechanism, and the secondary transfer bias is supplied to the support roll. 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording paper P is applied to the toner image, so The toner image is transferred onto the recording paper P. The secondary transfer bias at this time is determined according to the resistance detected by a resistance detection means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

  Thereafter, the recording paper P is fed into the pressure contact portions (nip portions) of a pair of fixing rolls in a fixing device (an example of a fixing unit) 28, and the toner image is fixed on the recording paper P to form a fixed image.

In the present embodiment, the fixing pressure of the fixing device 28 may be not less than 0.5 kgf / cm ^{2 and not} more than 2.0 kgf / cm ² . By using the toner according to the present exemplary embodiment, the image defect of the fixed image hardly occurs even under a low fixing pressure where the fixing pressure is 0.5 kgf / cm ² or more and 2.0 kgf / cm ² or less.

Examples of the recording paper P to which the toner image is transferred include plain paper used in electrophotographic copying machines, printers, and the like. In addition to the recording paper P, the recording medium may be an OHP sheet.
In order to further improve the smoothness of the image surface after fixing, the surface of the recording paper P is also preferably smooth. For example, coated paper with the surface of plain paper coated with resin, art paper for printing, etc. are preferably used. Is done.

  The recording paper P on which the color image has been fixed is carried out toward the discharge unit, and a series of color image forming operations is completed.

<Process cartridge / toner cartridge>
The process cartridge according to this embodiment will be described.
The process cartridge according to the present embodiment accommodates the electrostatic image developer according to the present embodiment, and develops the electrostatic image formed on the surface of the image carrier as a toner image by the electrostatic image developer. And a process cartridge that can be attached to and detached from the image forming apparatus.

  Note that the process cartridge according to the present embodiment is not limited to the above-described configuration, and other means such as a developing device and other units such as an image carrier, a charging unit, an electrostatic charge image forming unit, and a transfer unit, if necessary. And at least one selected from the above.

  Hereinafter, an example of the process cartridge according to the present embodiment will be shown, but the present invention is not limited to this. The main parts shown in the figure will be described, and the description of the other parts will be omitted.

FIG. 2 is a schematic configuration diagram showing a process cartridge according to the present embodiment.
The process cartridge 200 shown in FIG. 2 is provided around the photoconductor 107 and the photoconductor 107 by, for example, a housing 117 provided with an attachment rail 116 and an opening 118 for exposure. A charging roller 108 (an example of a charging unit), a developing device 111 (an example of a developing unit), and a photoconductor cleaning device 113 (an example of a cleaning unit) are integrally combined and held to form a cartridge. Yes.
In FIG. 2, 109 is an exposure device (an example of an electrostatic charge image forming unit), 112 is a transfer device (an example of a transfer unit), 115 is a fixing device (an example of a fixing unit), and 300 is a recording paper (a recording medium). An example).

Next, the toner cartridge according to this embodiment will be described.
The toner cartridge according to the present exemplary embodiment is a toner cartridge that accommodates the toner according to the present exemplary embodiment and is detachable from the image forming apparatus. The toner cartridge contains toner for replenishment to be supplied to the developing means provided in the image forming apparatus.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which toner cartridges 8Y, 8M, 8C, and 8K are attached and detached, and the developing devices 4Y, 4M, 4C, and 4K are each developing devices (colors). And a toner supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge becomes low, the toner cartridge is replaced.

  Hereinafter, although an Example and a comparative example are given and this embodiment is described in detail more concretely, this embodiment is not limited to these Examples at all. Further, “parts” and “%” indicate “parts by mass” and “% by mass” unless otherwise specified.

(Shape factor SF1)
The shape factor SF1 is obtained by the following equation.
Formula: SF1 = (ML ² / A) × (π / 4) × 100
In the above formula, ML represents the absolute maximum length of the toner, and A represents the projected area of the toner.
Specifically, the shape factor SF1 was quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and was calculated as follows. That is, by capturing an optical microscope image of particles dispersed on the surface of a slide glass into a Luzex image analyzer using a video camera, obtaining the maximum length and projected area of 100 particles, calculating by the above formula, and obtaining the average value Obtained.

(Weight average molecular weight, number average molecular weight and peak top molecular weight)
The molecular weight of the binder resin or the like is determined 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, the experiment was conducted 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 RI 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 ”.

(1/2 drop temperature)
Using a flow tester (manufactured by Shimadzu Corp .: CFT-500C), sample amount: 1.05 g, sample diameter: 1 mm, preheating: 300 ° C. at 65 ° C., load: 10 kg, die size: diameter 1.0 mm, heating rate: The temperature at which half of the sample flows out when the plunger drop amount is plotted measured under the condition of 7.0 ° C./min is defined as the ½ drop temperature.

(Glass transition temperature and melting temperature)
The glass transition temperature and melting temperature were measured by differential scanning calorimetry based on ASTM D3418-8. This measurement was performed as follows.
That is, first, a substance to be measured is set in a differential scanning calorimeter (device name: DSC-50 type) manufactured by Shimadzu Corporation equipped with an automatic tangential processing system, liquid nitrogen is set as a cooling medium, and 10 ° C. / Heat from 0 ° C. to 150 ° C. at the rate of temperature rise for 1 minute (first temperature rise process) to obtain the relationship between the temperature (° C.) and the amount of heat (mW), and then at the rate of temperature drop of −10 ° C./minute The mixture was cooled to 0 ° C., and again heated to 150 ° C. at a temperature increase rate of 10 ° C./min (second temperature increase process), and data was collected. In addition, it hold | maintained for 10 minutes each at 0 degreeC and 150 degreeC.
The melting temperature of the mixture of indium and zinc was used for temperature correction of the detection part of the measuring device, and the heat of fusion of indium was used for correction of the amount of heat. The sample was placed in an aluminum pan, and an aluminum pan containing the sample and an empty aluminum pan for control were set.
The glass transition temperature of the toner was defined as the temperature at the intersection of the extension line of the base line and the rising line in the endothermic part of the DSC curve obtained in the first temperature raising process.
The glass transition temperature of the amorphous resin was defined as the glass transition temperature at the intersection of the extension line of the base line and the rising line in the endothermic part of the DSC curve obtained in the second temperature raising process.
Regarding the melting temperature of the crystalline resin and the release agent, the maximum peak temperature among the peaks having an endotherm of 25 J / g or more in the DSC curve obtained in the second temperature raising process was taken as the melting temperature.

(Acid value)
The acid value (AV) was measured as follows. The basic operation conforms to JIS K-0070-1992.
The sample was used after removing the THF-insoluble component of the resin in advance, or a soluble component extracted with a THF solvent by a Soxhlet extractor was used as the sample. 1.5 g of the pulverized sample was precisely weighed, and the sample was placed in a 300 ml beaker, and 100 ml of a toluene / ethanol (4/1) mixture was added and dissolved. Potentiometric titration was performed with an ethanol solution of 0.1 mol / l KOH using an automatic titrator GT-100 (manufactured by Dia Instruments). The amount of KOH solution used at this time is A (ml), a blank is measured, and the amount of KOH solution used at this time is B (ml). From these values, the acid value was calculated by the following formula (1). In the formula (1), w is a precisely weighed sample amount, and f is a factor of KOH.
Acid value (mgKOH / g) = {(A−B) × f × 5.61} / w Formula (1)

<Synthesis of Crystalline Polyester Resin (PES-C1)>
・ 1,10-decanedicarboxylic acid: 97 mol%
・ Terephthalic acid: 3mol%
・ 1,6-hexanediol: 100 mol%
The above components were put into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube, and after the inside of the reaction vessel was replaced with dry nitrogen gas, tin dioctanoate was added to 100 parts of the monomer component. .3 parts were added. After stirring and reacting at 170 ° C. for 3 hours under a nitrogen gas stream, the temperature was further raised to 210 ° C. over 1.5 hours, and the reaction vessel was depressurized to 3 kPa and reacted when the desired molecular weight was reached. Ended. The physical properties of the obtained crystalline polyester resin are shown in Table 1.

<Synthesis of Crystalline Polyester Resins (PES-C2) to (PES-C11)>
According to the composition of Table 1, crystalline polyester resins (PES-C2) to (PES-C11) were synthesized by the same operation as the synthesis of the crystalline polyester resin (PES-C1).

<Preparation of crystalline polyester resin dispersion (DA-C1)>
In a reactor with a jacket (Tokyo Rika Kikai Co., Ltd .: BJ-30N) equipped with a condenser, a thermometer, a water dropping device and an anchor blade, 300 parts of the crystalline polyester resin (PES-C1) and methyl ethyl ketone (solvent) ) 160 parts and 100 parts of isopropyl alcohol (solvent) were added, and the resin was dissolved while stirring and mixing at 100 rpm while maintaining the temperature at 70 ° C. in a water circulating thermostat.
Thereafter, the stirring speed was set to 150 rpm, the water circulating thermostat was set to 60 ° C., 15 parts of 10% ammonia aqueous solution was dropped in 5 minutes, mixed for 10 minutes, and then 900 parts of ion-exchanged water kept at 60 ° C. was added. An emulsion was obtained by dripping at a rate of 5 parts per minute to invert the phase.
Immediately, 800 parts of the obtained emulsified liquid and 700 parts of ion-exchanged water were put into an eggplant flask and set in an evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. While rotating the eggplant flask, the mixture was heated in a hot water bath at 60 ° C., and the solvent was removed by reducing the pressure to 7 kPa while paying attention to bumping. When the solvent recovery amount reached 1100 parts, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a dispersion. There was no solvent odor in the obtained dispersion. The volume average particle diameter D _50v of the resin particles in this dispersion was 150 nm. Thereafter, alkyl diphenyl oxide disulfonate sodium salt (Dowfax 2A-1 manufactured by Dow Chemical Co., Ltd.) was added at 2.5% to the resin solids, and the pH was adjusted to 4.5 with nitric acid, and then ion-exchanged water was added. The solid content concentration was adjusted to 20%. This was used as a crystalline polyester resin dispersion (DA-C1).

<Preparation of Crystalline Polyester Resin Dispersions (DA-C2) to (DA-C11)>
In the same operation as the preparation of the crystalline polyester resin dispersion (DA-C1) except that the crystalline polyester resin (PES-C1) was replaced with the crystalline polyester resins (PES-C2) to (PES-C11), Crystalline polyester resin dispersions (DA-C2) to (DA-C11) were prepared.

<Synthesis of Amorphous Polyester Resin (PES-A1)>
Into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube, a polymerizable monomer was charged according to the composition of Table 2, and the reaction vessel was replaced with dry nitrogen gas. 0.3% of the total amount of the polymerizable monomer components was added. After stirring and reacting at 180 ° C. for 6 hours under a nitrogen gas stream, the temperature was further raised to 235 ° C. over 1 hour, reacted for 3 hours, cooled to 220 ° C., and 10.0 mmHg in the reaction vessel. The reaction was terminated when the required molecular weight was reached. Table 2 shows the physical properties (glass transition temperature, weight average molecular weight (Mw), number average molecular weight (Mn), peak top molecular weight (Mp), acid value, 1/2 drop temperature) of the obtained amorphous polyester resin. It was.

<Synthesis of Amorphous Polyester Resin (PES-A2) to (PES-A5)>
According to the composition of Table 2, amorphous polyester resins (PES-A2) to (PES-A5) were synthesized by the same operation as the synthesis of the amorphous polyester resin (PES-A1).

<Preparation of amorphous polyester resin dispersion (DA-A1)>
While maintaining a jacketed reactor equipped with a condenser, thermometer, water dropping device and anchor blade (Tokyo Rika Kikai Co., Ltd .: BJ-30N) at 40 ° C. in a water circulating thermostatic chamber, acetic acid was added to the reactor. A mixed solvent of 180 parts of ethyl and 80 parts of isopropyl alcohol is added, and 300 parts of the above amorphous polyester resin (PES-A1) is added thereto, stirred at 150 rpm using a three-one motor, dissolved, and oiled. Got the phase. A mixture of 1 part of 10% aqueous ammonia solution and 47 parts of 5% aqueous sodium hydroxide solution was added dropwise to the stirred oil phase over 5 minutes, mixed for 10 minutes, and then 900 parts of ion-exchanged water was added every minute. An emulsion was obtained by dropping and inversion at a rate of 5 parts.
Immediately, 800 parts of the obtained emulsified liquid and 700 parts of ion-exchanged water were put into an eggplant flask and set in an evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. While rotating the eggplant flask, the mixture was heated in a hot water bath at 60 ° C., and the solvent was removed by reducing the pressure to 7 kPa while paying attention to bumping. When the solvent recovery amount reached 1,100 parts, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a dispersion. There was no solvent odor in the obtained dispersion. The volume average particle diameter D50v of the resin particles in this dispersion was 130 nm. Thereafter, alkyl diphenyl oxide disulfonate sodium salt (Dowfax 2A-1 manufactured by Dow Chemical Co., Ltd.) was added at 2.5% to the resin solids, and the pH was adjusted to 4.5 with nitric acid, and then ion-exchanged water was added. The solid content concentration was adjusted to 20%. This was designated as an amorphous polyester resin dispersion (DA-A1).

<Preparation of Amorphous Polyester Resin Dispersions (DA-A2) to (DA-A5)>
In the preparation of the amorphous polyester resin dispersion (DA-A1), the amorphous polyester resin (PES-A1) used was changed from an amorphous polyester resin (PES-A2) to an amorphous polyester resin (PES-A5). Amorphous polyester resin dispersions (DA-A2) to (DA-A5) were obtained in the same manner except that the change was made to).

<Preparation of black colorant dispersion (PDK1)>
Carbon black (Cabot Japan Co., Ltd., REALAL 330): 200 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC): 33 parts (active ingredient 60%, 10% to colorant) %)
-Ion exchange water: 750 parts When the above components are all charged, the above components are charged into a stainless steel container whose liquid level is 1/3 of the height of the container, and 280 parts of ion exchange water After adding an anionic surfactant and sufficiently dissolving the surfactant, all the pigments are added, and the mixture is stirred using a stirrer until there are no wet pigments, and the remaining ion exchange water is added. The mixture was sufficiently degassed by stirring.
After defoaming, the mixture was dispersed for 10 minutes at 5,000 rpm using a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then defoamed by stirring for one day with a stirrer. After defoaming, the mixture was dispersed again at 6,000 rpm for 10 minutes using a homogenizer, and then stirred for one day and night with a stirrer to defoam.
After defoaming, dispersion was performed at a pressure of 240 MPa using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006). The dispersion was equivalent to 25 passes in terms of the total charge and the processing capacity of the apparatus.
The obtained dispersion was allowed to stand for 72 hours to remove precipitates, and ion exchange water was added to adjust the solid content concentration to 15% to obtain a black colorant dispersion (PDK1). The volume average particle diameter D50v of the particles in this colorant dispersion was 110 nm.

<Preparation of magenta colorant dispersion (PDM1)>
In the preparation of the black colorant dispersion (PDK1), the magenta colorant was prepared in the same manner except that the colorant was changed from carbon black to magenta pigment (manufactured by Dainichi Seika Co., Ltd., Pigment Red 122, for electrophotography). A dispersion was prepared.

<Preparation of yellow colorant dispersion (PDY1)>
In the preparation of the black colorant dispersion (PDK1), the yellow colorant was prepared in the same manner except that the colorant was changed from carbon black to a yellow pigment (Dainipei Seika Co., Ltd., Pigment Yellow 74, for electrophotography). A dispersion was prepared.

<Preparation of Cyan Colorant Dispersion (PDC1)>
In the preparation of the colorant dispersion (PDK1), the same procedure was followed except that the colorant was changed from carbon black to cyan pigment (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3, for electrophotography). An agent dispersion was prepared.

<Preparation of release agent dispersion (DW1)>
Hydrocarbon wax (manufactured by Nippon Seiki Co., Ltd., trade name: FNP0090, melting temperature Tw = 90.2 ° C.): 270 parts Anionic surfactant (Taika Power BN2060, manufactured by Teika Co., Ltd.) Active ingredient amount: 60%): 13.5 parts (as active ingredient, 3.0% with respect to the release agent)
-Ion-exchanged water: 700 parts The above components were mixed, and the release agent was dissolved at an internal liquid temperature of 120 ° C with a pressure discharge type homogenizer (Gorin homogenizer manufactured by Gorin), and then at a dispersion pressure of 5 MPa for 120 minutes. The dispersion was treated at 40 MPa for 360 minutes and cooled to obtain a release agent dispersion (DW1). The volume average particle diameter D50v of the particles in this release agent dispersion is 220 nm. Thereafter, ion exchange water was added to prepare a solid content concentration of 20.0%.

<Preparation of release agent dispersion (DW2)>
Mold release was performed in the same manner as the preparation of the release agent dispersion (DW1) except that the hydrocarbon wax (manufactured by Nippon Seiki Co., Ltd., trade name: HNP-3, melting temperature Tw = 64 ° C.) was used. An agent dispersion (DW2) was prepared.

<Preparation of release agent dispersion (DW3)>
Mold release in the same manner as the preparation of the release agent dispersion (DW1) except that the hydrocarbon wax (manufactured by Nippon Seiki Co., Ltd., trade name: HNP-9, melting temperature Tw = 74 ° C.) was used. An agent dispersion (DW3) was prepared.

<Preparation of mold release agent dispersion (DW4)>
Dispersing the release agent in the same manner as the preparation of the release agent dispersion (DW1), except that polyethylene wax (Polywax 725, melting temperature Tw = 103 ° C., manufactured by Toyo Adre Co., Ltd.) was used instead of the hydrocarbon wax. A liquid (DW4) was prepared.

[Example 1]
<Preparation of toner particles>
-Crystalline polyester resin dispersion (DA-C1): 100 parts-Amorphous polyester resin dispersion (DA-A1): 610 parts-Black colorant dispersion (PDK1): 110 parts-Release agent dispersion ( DW1): 120 parts Aluminum sulfate aqueous solution: 130 parts (Asada Chemical Industries, Ltd., 1% aqueous solution of aluminum sulfate powder)
-Ion-exchanged water: 450 parts The above components were mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Turrax T50) at 5000 rpm for 10 minutes, and then the contents in the flask were stirred at 40 ° C. The mixture was heated and stirred until the particle size reached 5.0 μm while raising the temperature at 0.05 ° C. per minute, and 300 parts of an amorphous polyester resin dispersion (DA-A1) was added. And held for 60 minutes. When the obtained contents were observed with an optical microscope, it was confirmed that aggregated particles were generated. After adding 9 parts of ethylenediaminetetraacetic acid (EDTA) tetrasodium salt (manufactured by Kirest Co., Ltd., Kirest 40), an aqueous sodium hydroxide solution was added to adjust the pH to 8, and then the temperature was raised to 92 ° C. After that, the pH was lowered by 0.05 with nitric acid every 10 minutes, and when the shape factor SF1 reached 130, it was cooled, filtered, thoroughly washed with ion-exchanged water, and dried to obtain toner particles.

  In the above method, the colorant dispersion (PDK1) used was changed to a magenta colorant dispersion (PDM1), a yellow colorant dispersion (PDY1), and a cyan colorant dispersion (PDC1), respectively. M, Y, and C toner particles were obtained by the above method.

  To 100 parts of the toner particles obtained above, 1.5 parts of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) was added and mixed and blended at 13000 rpm for 30 seconds using a sample mill. Thereafter, each color toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

<Preparation of resin-coated carrier (C)>
Mn-Mg-Sr ferrite particles (average particle size 40 μm): 100 parts Toluene: 14 parts Cyclohexyl methacrylate / dimethylaminoethyl methacrylate copolymer (weight ratio 99: 1, Mw 80000): 2.0 parts Carbon Black (VXC72: manufactured by Cabot): 0.12 parts The above components excluding ferrite particles and glass beads (φ1 mm, equivalent to toluene) were stirred at 1200 rpm for 30 minutes using a sand mill manufactured by Kansai Paint Co., Ltd., and the resin coating layer A forming solution was obtained. Furthermore, this resin coating layer forming solution and ferrite particles were put into a vacuum degassing type kneader, decompressed, distilled off toluene, and dried to prepare a resin-coated carrier (C).

<Production of developer>
36 parts of the obtained toner and 414 parts of the carrier were put into a 2 liter V blender, stirred for 20 minutes, and then sieved at 212 μm to prepare a developer.

<Evaluation method>
In order to obtain an unfixed toner image of the copy, the fixing unit of Apeos Port IV C4470 manufactured by Fuji Xerox Co., Ltd. was removed, and the copy was modified so that it could be discharged without fixing. After cleaning the Apeos Port IV C4470 developer, toner cartridge, and toner supply mechanism area in the main body in an environment room at a temperature of 25 ° C. and a humidity of 60%, the developer of each example is transferred to each color developer. The toner of each color was put in the toner cartridge and set in the original position of the Apeos Port IV C4470 main body. Subsequently, in order to charge the developer, 20 sheets of A3 paper were passed without being developed. Next, using an OHP film (Fuji Xerox Co., Ltd.), the development amount of colored toner on paper was adjusted to 4.0 g / m ² .
Next, five linear images having a line width of 5 mm and a length of 50 mm were produced in parallel with the OHP sheet passing direction in multiple colors at intervals of 30 mm.
Next, remove the fixing unit of PREMAGE 355 manufactured by TOSHIBA TEC, attach an aluminum roll for temperature uniformity outside the pressure roll of this fixing unit so that it contacts the pressure roll, and supply power to the fixing unit. Wiring was done to Further, the coil spring was replaced, and the load for pressing the heating belt and the pressure roll was adjusted to 1.3 kgf / cm ² to obtain a fixing test unit (fixing device). The thermal conductivity of the surface of the aluminum roll (metal roll) was 230 (W / m · K). Further, the heating member in the fixing test unit is configured to include a heat generation layer and a silicon elastic layer in a polyimide base material. The process speed was adjusted so that the heating time during fixing was 100 msec, and the unfixed image was fixed.
Next, the OHP was folded at a half position in the longitudinal direction so that the straight line image was folded, a load of 1000 g was applied to the entire OHP in the folded state, and the load was removed after being left for 10 seconds.
The image portion of the folded OHP was observed and evaluated based on the following criteria. The results obtained are shown in Table 3 together with the toner composition.

-Evaluation criteria for image defects-
No image loss: (A)
There is an image defect but the width is less than 0.5 mm: (B)
There is an image defect, but the width is not less than 0.5 mm and not more than 1.0 mm: (C)
There is an image defect and the width is larger than 1.0 mm: (D)

  The above-mentioned OHP film was changed to plain paper for copying machines (C2 paper manufactured by Fuji Xerox Co., Ltd.), and evaluation was performed with plain paper for copying machines in the same manner except that the heating time at fixing was 35 msec. It was. The obtained results are shown in Table 3.

[Example 2]
The toner and developer were adjusted in the same manner as in Example 1 except that the crystalline polyester resin dispersion (DA-C1) was changed to (DA-C2), and the same evaluation was performed.

[Example 3]
In Example 1, the toner and the developer were adjusted in the same manner except that the crystalline polyester resin dispersion (DA-C1) was changed to (DA-C3), and the same evaluation was performed.

[Example 4]
In Example 1, the same except that the amorphous polyester resin dispersion (DA-A1) was changed to (DA-A2) and the crystalline polyester resin dispersion (DA-C1) was changed to (DA-C3). In this operation, the toner and the developer were adjusted, and the same evaluation was performed.

[Example 5]
In Example 4, the toner and the developer were adjusted in the same manner except that the amorphous polyester resin dispersion (DA-A2) was changed to (DA-A3), and the same evaluation was performed.

[Example 6]
The toner and developer were adjusted in the same manner as in Example 1 except that the crystalline polyester resin dispersion (DA-C1) was changed to (DA-C4), and the same evaluation was performed.

[Example 7]
In Example 1, the toner and developer were adjusted in the same manner except that the crystalline polyester resin dispersion (DA-C1) was changed to (DA-C5), and the same evaluation was performed.

[Example 8]
In Example 1, the toner and developer were adjusted in the same manner except that the crystalline polyester resin dispersion (DA-C1) was changed to (DA-C6), and the same evaluation was performed.

[Example 9]
In Example 1, the toner and developer were adjusted in the same manner except that the crystalline polyester resin dispersion (DA-C1) was changed to (DA-C7), and the same evaluation was performed.

[Example 10]
In Example 1, the toner and developer were adjusted in the same manner except that the crystalline polyester resin dispersion (DA-C1) was changed to (DA-C8), and the same evaluation was performed.

[Example 11]
In Example 6, the toner and the developer were adjusted in the same manner except that the release agent dispersion (DW1) was changed to (DW2), and the same evaluation was performed. The difference between the endothermic peak temperature Tmc derived from the crystalline resin and the endothermic peak temperature Tmw derived from the first release agent was 9.3 ° C.

[Example 12]
In Example 7, the toner and developer were adjusted in the same manner except that the release agent dispersion (DW1) was changed to (DW2), and the same evaluation was performed. The difference between the endothermic peak temperature Tmc derived from the crystalline resin and the endothermic peak temperature Tmw derived from the first release agent was 5.0 ° C.

[Example 13]
In Example 7, the toner and the developer were adjusted in the same manner except that the release agent dispersion (DW1) was changed to (DW3), and the same evaluation was performed. The difference between the endothermic peak temperature Tmc derived from the crystalline resin and the endothermic peak temperature Tmw derived from the first release agent was −5.0 ° C.

[Example 14]
The toner and developer were adjusted in the same manner as in Example 1 except that the amorphous polyester resin dispersion (DA-A1) was changed to (DA-A4), and the same evaluation was performed.

[Example 15]
In Example 1, release agent dispersion (DW1): 120 parts, release agent dispersion (DW1): 100 parts, and release agent dispersion (DW4): 20 parts Then, the toner and the developer were prepared, and the same evaluation was performed.

[Comparative Example 1]
In Example 1, the toner and developer were adjusted in the same manner except that the amorphous polyester resin dispersion (DA-A1) was changed to (DA-A5), and the same evaluation was performed.

[Comparative Example 2]
In Example 1, the toner and developer were adjusted in the same manner except that the crystalline polyester resin dispersion (DA-C1) was changed to (DA-C9), and the same evaluation was performed.

[Comparative Example 3]
In Example 1, the toner and developer were adjusted in the same manner except that the crystalline polyester resin dispersion (DA-C1) was changed to (DA-C10), and the same evaluation was performed.

[Comparative Example 4]
In Example 1, the toner and developer were adjusted in the same manner except that the crystalline polyester resin dispersion (DA-C1) was changed to (DA-C11), and the same evaluation was performed.

1Y, 1M, 1C, 1K, photoconductor (an example of an image carrier)
2Y, 2M, 2C, 2K, charging roll (an example of charging means)
3. Exposure device (an example of electrostatic charge image forming means)
3Y, 3M, 3C, 3K Laser beams 4Y, 4M, 4C, 4K Developing device (an example of developing means)
5Y, 5M, 5C, 5K primary transfer roll (an example of primary transfer means)
6Y, 6M, 6C, 6K Photoconductor cleaning device (an example of cleaning means)
8Y, 8M, 8C, 8K Toner cartridge 10Y, 10M, 10C, 10K Image forming unit 20 Intermediate transfer belt (an example of an intermediate transfer member)
22 Drive roll 24 Support roll 26 Secondary transfer roll (an example of secondary transfer means)
30 Intermediate transfer member cleaning device 107 Photosensitive member (an example of an image holding member)
108 Charging roll (an example of charging means)
109 Exposure apparatus (an example of electrostatic charge image forming means)
111 Developing device (an example of developing means)
112 Transfer device (an example of transfer means)
113 photoconductor cleaning device (an example of cleaning means)
115 Fixing device (an example of fixing means)
116 Attachment rail 118 Opening 117 for exposure 117 Case 200 Process cartridge 300 Recording paper (an example of recording medium)
P Recording paper (an example of a recording medium)

Claims (13)

A binder resin containing an amorphous polyester resin and a crystalline polyester resin, and at least a first release agent,
The proportion of the repeating unit derived from the ethylene oxide adduct of bisphenol A in the repeating unit derived from the alcohol component contained in the amorphous polyester resin is more than 50 mol% and not more than 100 mol%,
The proportion of the total amount of repeating units derived from at least one selected from the group consisting of 1,4-butanediol and 1,6-hexanediol in the repeating units derived from the alcohol component contained in the crystalline polyester resin is 95 mol. % Or more,
The proportion of the repeating unit derived from terephthalic acid in the repeating unit derived from the carboxylic acid component contained in the crystalline polyester resin is 3 mol% or more and 20 mol% or less, and 1,10-decanedicarboxylic acid and 1,8-octanedicarboxylic acid. A toner for developing an electrostatic charge image, wherein the ratio of the total amount of repeating units derived from at least one selected from the group consisting of acids is 80 mol% or more and 97 mol% or less.   2. The electrostatic image developing toner according to claim 1, wherein an endothermic peak temperature Tmc derived from the crystalline polyester resin, measured by a DSC method, is 50 ° C. or higher and 73 ° C. or lower.   The difference (Tmc−Tmw) between the endothermic peak temperature Tmc derived from the crystalline polyester resin and the endothermic peak temperature Tmw derived from the first release agent measured by DSC method is −5 ° C. or more and 10 ° C. or less. The electrostatic image developing toner according to claim 1 or 2.   A second release agent having an endothermic peak in a range of 100 ° C. or higher and 110 ° C. or lower as measured by DSC method, wherein the endothermic peak is higher than the endothermic peak temperature Tmw derived from the first release agent. The electrostatic image developing toner according to claim 3, which is contained.   The repeating unit having a side chain having 5 to 20 carbon atoms is included as at least a part of the repeating unit derived from the alcohol component and the repeating unit derived from the carboxylic acid component contained in the amorphous polyester resin. The electrostatic charge image developing toner according to claim 4.   A combination of a repeating unit derived from a carboxylic acid component and a repeating unit derived from an alcohol component in the crystalline polyester resin is a combination of a repeating unit derived from 1,10-decanedicarboxylic acid and a repeating unit derived from 1,4-butanediol, A combination of a repeating unit derived from 1,8-octanedicarboxylic acid and a repeating unit derived from 1,6-hexanediol, or a repeating unit derived from 1,8-octanedicarboxylic acid and a repeating unit derived from 1,4-butanediol The electrostatic image developing toner according to claim 1, which is a combination.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1. Containing the toner for developing an electrostatic charge image according to any one of claims 1 to 6,
A toner cartridge to be attached to and detached from the image forming apparatus. A developing means for containing the electrostatic charge image developer according to claim 7 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus. An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Development means for containing the electrostatic image developer according to claim 7 and developing the electrostatic image formed on the surface of the image carrier as a toner image by the electrostatic image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising: The image forming apparatus according to claim 10, wherein a fixing pressure by the fixing unit is 0.5 kgf / cm ² or more and 2.0 kgf / cm ² or less. A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with the electrostatic charge image developer according to claim 7;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
An image forming method comprising: The image forming method according to claim 12, wherein a fixing pressure in the fixing step is 0.5 kgf / cm ² or more and 2.0 kgf / cm ² or less.