JP4513621B2 - Toner for developing electrostatic image, method for producing the same, electrostatic image developer, and image forming method - Google Patents

Description

  The present invention relates to an electrostatic charge developing toner used when developing an electrostatic image formed by an electrophotographic method or an electrostatic recording method with a developer, a method for producing the same, an electrostatic image developer, and an image forming method. About.

  A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic charge image is formed on a photoreceptor by charging and exposure processes, and the electrostatic charge image is developed with a developer containing an electrostatic charge image developing toner (hereinafter sometimes referred to simply as “toner”). Then, the electrostatic image is visualized through the transfer and fixing processes.

  As the developer used here, a two-component developer composed of a toner and a carrier, and a one-component developer using a magnetic toner or a non-magnetic toner alone are known. Usually, a kneading and pulverizing method is used in which a thermoplastic resin is melt-kneaded together with a release agent such as a pigment, a charge control agent, and a wax, and after cooling, pulverized and classified. In these toners, if necessary, inorganic and organic fine particles for improving fluidity and cleaning properties may be added to the surface of the toner particles. These methods can produce a very good toner, but due to stress in the developing unit due to the irregular shape of the toner, easy generation of fine powder, and easy exposure of the release agent to the surface. Problems such as poor developability, image quality degradation, and contamination of other members occur.

  In recent years, a method for producing a toner by an emulsion polymerization aggregation method has been proposed as means for intentionally controlling the toner shape and the surface structure of the toner (see, for example, Patent Documents 1 and 2). These are generally prepared by dispersing resin fine particles by emulsion polymerization or the like, while preparing a colorant dispersion in which a colorant is dispersed in a solvent, and then mixing these to form aggregated particles corresponding to the toner particle size, This is a method for producing toner by fusing and coalescing by heating. By this method, the toner shape can be controlled to some extent, and the chargeability and durability can be improved. However, since the internal structure is almost uniform, the elution property of the release agent component may be reduced. Problems remain in the deterioration of oilless peelability from the fixing member and the stabilization of gloss unevenness in high gloss fixed images.

  In order to stabilize the releasability, it is necessary to make it easy to elute a release agent component such as wax at the time of fixing. Conventionally, however, the melting point of the release agent component is lowered or the molecular weight is reduced. It was realized. However, although the elution property can be improved to some extent by the above method, the proportion of the low molecular weight component inevitably increases, and as a result, the binder resin component and the low molecular weight component are compatible, and the toner itself is melted. There was a case where the hot-offset property in a high temperature range deteriorated.

  On the other hand, a release agent using a metallocene catalyst has been proposed as a method for increasing the melting point and lowering the viscosity of the release agent (see, for example, Patent Document 3), but is generally used as a copolymer. Although the acid anhydride itself has a relatively high viscosity, it is certainly preferable for high pressure and low speed fixing systems such as two-roll fixing. However, an energy-saving fixing system does not provide sufficient release agent elution. As a result, a fixed image with good quality cannot be obtained.

  Furthermore, application of an ester release agent having low crystallinity has been proposed to improve transparency (see, for example, Patent Document 4). However, in this case, plasticity due to the compatibility between the binder resin component and the ester release agent occurs, so that the hot offset property in a high temperature range is likely to deteriorate. In order to cope with this, plasticity can be suppressed by a method such as introducing a crosslinked structure into the binder resin, and the transparency problem caused by the release material can be improved to some extent. However, since the melt fluidity of the toner itself at the time of toner fixing is lowered, it is difficult to apply it to high image gloss.

  As described above, in the electrophotographic process, in order to stably maintain the performance of the toner even under various mechanical stresses, it is possible to suppress the exposure of the release agent to the surface and to reduce the surface hardness without impairing the fixing property. It is necessary to increase the mechanical strength of the toner itself as well as to increase both the charging property and the fixing property.

  Further, from the viewpoint of speeding up in recent years and the accompanying low energy consumption, toners with uniform chargeability, durability, toner strength, and narrow particle size distribution are becoming increasingly important. Furthermore, in view of speeding up and energy saving of these machines, further low-temperature fixability is required. From the viewpoint of improving the fixing property, a release agent component is added to the toner. Generally, as the release agent component, a polyolefin wax is internally added for the purpose of preventing a low temperature offset at the time of fixing. At the same time, a small amount of silicone oil is uniformly applied to the fixing roller to improve the high temperature offset property. For this reason, a silicone oil component adheres to the output recording medium, which is not preferable because of uncomfortable feeling such as stickiness when handled.

  In order to avoid the above problems, an oilless fixing toner in which a large amount of a release agent component is included in the toner has been proposed (see, for example, Patent Document 5). However, in this case, the releasability can be improved to some extent by adding a large amount of the release agent. However, the binder resin (binder resin) component and the release agent are compatible, and the release agent is removed. Since the protrusion is not uniform, it is difficult to obtain peeling stability. In addition, since the means for controlling the cohesive force of the binder resin of the toner depends on the weight average molecular weight (Mw) of the resin and the glass transition point (Tg), the spinnability and cohesiveness during toner fixing are directly controlled. It is difficult to do. Furthermore, the free component of the release agent may cause charging inhibition.

  On the other hand, as the demand for energy saving increases, the fixing temperature of the toner is further lowered in order to save power in the fixing process, which accounts for a considerable portion of the power used by the copying machine, and to expand the fixing area. It is necessary to let However, when the fixing temperature of the toner is lowered, the glass transition point of the toner particles is lowered at the same time, and it becomes difficult to achieve both the storage stability of the toner. In order to achieve both low temperature fixing and toner storage stability, it is important to maintain the so-called sharp melt property that rapidly lowers the viscosity of the toner in the high temperature region while maintaining the glass transition temperature of the toner at a higher temperature. However, since the surface temperature of the fixing member is constantly changed by fixing as described above, the fixing performance varies depending on the setting of the temperature at which the sharp melt property is generated. In particular, when using color toners, the glossiness and color mixing properties of the fixed image surface are required. However, variations in the surface temperature of the fixing member have a large effect on the glossiness and color mixing properties, and the initial value during continuous fixing. In the latter stage, the glossiness and color mixing property of the fixed image are remarkably changed, and the reliability of the image quality is remarkably lowered.

  In order to solve the above problems, means for adding a release agent such as wax to the toner and simultaneously processing a highly releasable resin such as a fluorine-containing resin on the surface of the fixing roll is described (for example, (See Patent Documents 6 and 7). According to this method, since the oil supply unit of the fixing device can be removed, it is possible to cope with downsizing. However, in order to develop high glossiness using color toner, as described above. In addition, the toner needs to have a low viscosity, in which case it tends to cause a reduction in peeling performance due to a reduction in cohesion between resin molecules, resulting in a problem that hot offset tends to occur and glossiness is lowered. .

  In order to suppress the reduction in glossiness, there are methods such as increasing the fixing temperature and increasing the contact time between the fixing member and the toner, but the former cannot cope with the low-temperature fixability, and the latter does not support the contact time. As a method of increasing, there are a method of reducing the process speed and a method of reducing the hardness of the fixing member such as a heating roll, but the method of reducing the process speed cannot cope with the increase in speed, and the hardness of the fixing member such as the heating roll. However, the method of reducing the temperature is not preferable because the life of the material of the fixing member tends to be shortened.

In addition, from the toner side, a so-called suspension polymerization method is proposed in which a polymerizable monomer is dispersed and suspended in an aqueous medium together with a colorant, a release agent, and the like, and then polymerized to prepare a toner. A method for producing a toner having a multilayer structure in which a wax as a mold is wrapped with a binder resin has been proposed (see, for example, Patent Documents 8 and 9).
Furthermore, a method has been proposed in which the unevenness of the glossiness at the time of fixing is controlled by defining the rate of change of the glossiness with respect to the temperature to obtain a high-quality image (for example, see Patent Document 10).

  However, these methods need to make a stable dispersion state of the polymerizable monomer in the aqueous medium. For this purpose, there is a method of adding a small amount of a surfactant or an organic / inorganic acid. When a surfactant is added, not only charging control becomes difficult, but also the cleaning process becomes complicated, which is not preferable. Further, when the organic / inorganic acid is added, these acids are likely to remain at the interface even after the polymerization, so that the Tg near the toner surface increases, and as a result, the Tg of the entire toner increases. This is not preferable because the glossiness at the time of fixing decreases.

Further, it has been proposed that a high gloss fixed image can be obtained without uneven gloss by incorporating a crystalline compound into the toner (see, for example, Patent Document 11). However, gloss in this way is not sufficient for the color market.
As described above, although there is an increasing demand for a toner and an image forming method that can achieve a balance between high image quality, high gloss, and high speed, a technology that can sufficiently satisfy this demand has not yet been obtained.
Japanese Patent Laid-Open No. 63-282275 JP-A-6-250439 JP-A-8-248671 JP-A-6-337541 JP-A-5-61239 JP-A-6-67504 Japanese Patent Laid-Open No. 9-106105 JP-A-8-044111 JP-A-8-286416 JP 2000-250258 A JP 2002-278137 A

The present invention provides a toner for developing an electrostatic image that solves the above-described problems in conventional toners, a method for producing the same, an electrostatic image developer using the same, and an image forming method.
That is, an object of the present invention is to provide an electrostatic charge developing toner capable of obtaining a fine image with high glossiness and less gloss unevenness in oilless fixing, a method for producing the same, an electrostatic charge image developer, and an image forming method. Is to provide.

The above-mentioned subject is achieved by the following present invention. That is, the present invention
<1> In an electrostatic charge image developing toner containing at least a binder resin and a colorant,
The binder resin is polymerized using a chain transfer agent containing elemental sulfur, and includes a resin containing a carboxyl group,
An aggregating step of forming aggregated particles in the presence of aluminum ions using a mixed solution comprising a resin fine particle dispersion in which fine particles of the binder resin are dispersed and a colorant dispersion in which the colorant is dispersed; and adjusting the pH to 9 to 10 to stop the growth of the aggregated particles, and then adding ion-exchange resin particles and stirring to contact the aggregated particles. Obtained by
The ratio (A / B) of the aluminum element content (A) and the sulfur element content (B) contained in the vicinity of the surface of the toner measured by X-ray photoelectron spectroscopy is 0.05 to 0.20. And the aluminum element content (A) in the range of 0.01 to 0.5 μm in depth from the surface is in the range of 0.02 to 0.08 atomic%. An electrostatic charge image developing toner characterized by the following.

<2> The volume average particle diameter D50v of the toner is in the range of 3 to 9 μm, the volume particle size distribution index GSDv is 1.15 or more and less than 1.3, and the acid value AV of the toner is divided by the volume average particle diameter D50v. The electrostatic charge image developing toner according to <1>, wherein the measured value (AV / D50v) is in the range of 0.5 to 10.

< 3 > An electrostatic charge image developer containing the electrostatic charge image developing toner according to <1> or <2> .

< 4 > A method for producing a toner for developing an electrostatic charge image according to <1> or <2> ,
A coagulation step in which at least a resin fine particle dispersion in which resin fine particles having a volume average particle size of 1 μm or less are dispersed, a colorant dispersion, and a release agent dispersion are mixed to form aggregated particles in the presence of aluminum ions; A step of adjusting the pH in the system to 9 to 10 to stop the growth of the aggregated particles, adding ion exchange resin particles, stirring and bringing into contact with the aggregated particles; and And a fusing step of fusing and coalescing by heating to a temperature equal to or higher than the melting point of the resin fine particles.

< 5 > A latent image forming step of forming an electrostatic image on the surface of the latent image carrier, a developing step of developing the electrostatic image with a developer containing toner to form a toner image, and the toner image on the surface of the transfer target In an image forming method including a transfer step of transferring to a toner image, and a fixing step of thermally fixing the transferred toner image to the surface of the recording medium
In the image forming method, the toner is the electrostatic image developing toner according to <1> or <2> .

  According to the present invention, as described above, an electrostatic charge developing toner that maintains excellent releasability in oilless fixing and satisfies fine image quality without uneven gloss, a method for producing the same, and an electrostatic image developer An image forming method can be easily obtained.

Hereinafter, the present invention will be described in detail.
<Toner for electrostatic image development>
The toner for developing an electrostatic charge image of the present invention is a toner for developing an electrostatic charge image containing at least a binder resin and a colorant. The content of an aluminum element contained in the vicinity of the surface of the toner measured by X-ray photoelectron spectroscopy ( The ratio (A / B) between A) and the content of sulfur element (B) is in the range of 0.05 to 0.20, and the depth from the surface is 0.01 to 0.5 μm. The aluminum element content (A) in the range is 0.02 to 0.08 atomic%.

  According to the toner for developing an electrostatic charge image of the present invention (hereinafter sometimes simply referred to as “toner”), the present inventors have excellent surface gloss and no uneven gloss in the oilless fixing described above. The inventors have found that a fixed image can be easily obtained, and have completed the present invention.

  That is, in order to obtain a fixed image with high glossiness, it is required to reduce the viscosity of the toner, uniformly melt it, and smooth the surface of the fixed image. However, when the toner viscosity is lowered, the toner melted in the fixing member is pulled by the fixing member, the smoothness of the fixed image is lost, and uneven glossiness occurs. In other words, since the viscosity decreases, the adhesion force between the toner and the fixing member becomes larger than the cohesion force between the toners. Therefore, the toner adheres to the fixing member, and a portion where the smoothness of the surface of the fixed image is lost is formed. Unevenness occurs.

  Further, when the viscosity of the toner is reduced to a range of 100 to 1000 Pa · s (1000 to 10000 P), stringiness occurs, and the toner is pulled to the fixing member at the time of fixing, and the smoothness of the fixed image is lost. Unevenness occurs. In particular, since the surface layer of a normal fixing member is made of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), it has a structure in which toner is difficult to adhere. Since a structure derived from an ester is present, if a highly polar carboxyl group is present on the toner surface, it is likely to be fused.

  The present invention relates to a toner produced by an emulsion polymerization aggregation method (emulsion aggregation method). First, the amount of aluminum element derived from the aggregating agent on the toner surface, which has a large effect on the fixed image characteristics at the time of fixing, is reduced. By reducing the viscosity, high glossiness of the image surface is obtained after fixing, and the amount of aluminum element inside the toner maintains the cohesive force between the toners at the time of fixing as in the past, so that the toner adheres to the fixing member. Reduced.

  Furthermore, by increasing the sulfur element content derived from the chain transfer agent during resin polymerization in the toner, it is possible to reduce the content of carboxyl groups present on the toner surface, and in the PFA on the toner and the fixing member surface. It has been found that the adhesive force with the structure derived from an acrylate ester is reduced, and an excellent fixed image having no gloss unevenness and high gloss can be obtained.

Specifically, the present invention can be achieved by setting the aluminum element and sulfur element contents in the vicinity of the toner surface detected by X-ray photoelectron spectroscopy (XPS) within a certain range and a certain ratio.
That is, in order to obtain the above characteristics, the ratio (A / B) of the aluminum element content (A) and the sulfur element content (B) contained in the toner surface layer measured by X-ray photoelectron spectroscopy. ) Is in the range of 0.05 to 0.20 and the depth (A) of the aluminum element in the range of 0.01 to 0.5 μm from the surface is 0.02 to 0.02 It is necessary to make it the range of 0.08 atomic%.

  In the electrostatic image developing toner of the present invention, first, the ratio (A / B) of the content of aluminum element (A) and the content of sulfur element (B) contained in the vicinity of the surface of the toner measured by XPS. ) Is 0.05-0.20. When the content ratio (A / B) is less than 0.05, the fine particle dispersibility at the time of toner preparation deteriorates, and fine particles with poor colorant dispersibility or fine particles not containing a release agent are generated. In the fixing process, the exudation of the release agent is not uniform, and gloss unevenness is likely to occur. When (A / B) exceeds 0.20, since the amount of sulfur element is small, the polarity of the toner surface is high, and the toner easily adheres to the structure derived from the acrylate ester in the PFA in the fixing member surface layer at the time of fixing. An uneven surface, that is, uneven glossiness occurs on the image surface.

In the above description, the vicinity of the toner surface means a range of 0.01 to 0.5 μm in depth from the toner surface.
The ratio (A / B) of the aluminum element content (A) and the sulfur element content (B) is preferably in the range of 0.07 to 1.8, and preferably 0.9 to 1.4. More preferably, it is the range.

  In the present invention, the aluminum element content existing in the range of 0.01 to 0.5 μm deep from the toner surface needs to be in the range of 0.02 to 0.08 atomic%. When the amount is less than 0.02 atomic%, the viscosity of the toner at the time of fixing decreases, the toner adheres to the fixing roll, and unevenness, that is, uneven glossiness occurs on the surface of the fixed image. When the aluminum element content exceeds 0.08 atomic%, the viscosity of the toner at the time of fixing becomes high and the releasability is good at the time of fixing, but the toner does not spread uniformly on the fixing member, and good glossiness is obtained. I can't.

  The content of aluminum element present in the range of 0.01 to 0.5 μm deep from the toner surface is preferably in the range of 0.02 to 0.08 atomic%, preferably 0.03 to 0.05 atomic%. More preferably, it is the range.

Therefore, in the present invention, in an electrostatic charge developing toner containing at least a binder resin and a colorant, the content of aluminum element (A) and the content of sulfur element (B) contained in the toner surface layer measured by XPS )) (A / B) is in the range of 0.05 to 0.20, and the aluminum element content is in the range of 0.01 to 0.5 μm from the toner surface. By satisfying the condition that (A) is in the range of 0.02 to 0.08 atomic%, it is possible to obtain a high-gloss fixed image without uneven gloss.

The content of aluminum element and the content of sulfur element contained in the vicinity of the toner surface according to the present invention were calculated by performing surface composition analysis by ESCA (X-ray photoelectron spectroscopy).
The ESCA apparatus and measurement conditions in the present invention are as follows.
-Apparatus used: 1600S type X-ray photoelectron spectrometer manufactured by PHI (Physical Electronics Industries, Inc.)-Measurement conditions: X-ray source MgKα (400W)
-Spectral region: 800 μm in diameter

  In the present invention, the surface atomic concentration (atomic%) was calculated from the measured peak intensity of each element using a relative sensitivity factor provided by PHI. Further, the content of the aluminum element having a depth from the toner surface in the range of 0.01 to 0.5 μm can be performed by sputtering the toner surface in the depth direction with an Ar ion beam. The toner surface depth was measured using a transmission electron microscope after sputtering with an Ar ion beam.

Next, the structure and production method of the electrostatic image developing toner of the present invention will be described.
The toner for developing an electrostatic charge image of the present invention contains at least a binder resin (binder resin) and a colorant, and optionally contains other components such as a release agent. The toner of the present invention will be described in detail by dividing it into each component.

(Binder resin)
The binder resin in the present invention is not particularly limited, but is preferably excellent in sharp melt properties at the time of fixing. From the viewpoint of obtaining high glossiness in a fixed image, it is possible to use an amorphous resin and a crystalline resin in combination. preferable.

  In the present invention, the “crystallinity” of the crystalline resin refers to a resin having a clear endothermic peak rather than a stepwise change in endothermic amount in differential thermal analysis (DSC) described later. In the case of a polymer obtained by copolymerizing other components with the crystalline main chain, if the other components are 50% by mass or less, this copolymer is also called a crystalline resin. In addition, the amorphous resin in the present invention refers to a resin having only a stepwise endothermic change, not a clear endothermic peak in the DSC.

In the present invention, it is preferable to use the amorphous resin in the range of 60 to 90% by mass and the crystalline resin in the range of 10 to 40% by mass in the entire binder resin.
If the amorphous resin is less than 60% by mass, the ratio of the crystalline resin is increased, so the viscosity of the toner is decreased, the spinnability of the toner is increased at the time of fixing, the toner adheres to the fixing roll, and uneven gloss tends to occur. There is a case. When the amount of the amorphous resin exceeds 90% by mass, the ratio of the crystalline resin decreases, and the glossiness that is the combined effect of the crystalline resin may not be observed. The ratio of the amorphous resin is more preferably in the range of 70 to 85% by mass.

The amorphous resin that is the main component of the binder resin in the present invention is not particularly limited as long as it is an amorphous resin.
Specific examples of the amorphous resin include homopolymers or copolymers of styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic acid Homopolymers of esters having vinyl groups such as n-butyl, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, or the like Copolymers; Homopolymers or copolymers of vinyl nitriles such as acrylonitrile and methacrylonitrile; Homopolymers or copolymers of vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl methyl ketone, vinyl ethyl ketone , Vinyl isopropeni Homopolymers or copolymers of ketones, ethylene, propylene, butadiene, homopolymers or copolymers of olefins such as isoprene; and the like.

Further, a silicone resin containing methyl silicone, methyl phenyl silicone, or the like, a polyester containing bisphenol, glycol, or the like, an epoxy resin, a polyurethane resin, a polyamide resin, a cellulose resin, a polyether resin, a polycarbonate resin, or the like may be used.
These resins may be used alone or in combination of two or more.

  Among them, styrenes such as styrene, parachlorostyrene, and α-methylstyrene; short-chain alkyl acrylates such as methyl acrylate and methyl methacrylate; and n-propyl acrylate, n-butyl acrylate, It is preferable to use a copolymer obtained by combining lauryl acrylate, 2-ethylhexyl acrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate and the like.

  In the present invention, when a polyester is used as the binder resin, a resin particle dispersion can be prepared by preparing the polyester and dispersing it together with a dispersion stabilizer under high temperature and high pressure conditions. Even in this case, the polar group is moved to the vicinity of the surface by containing the polar group in the polyester resin, so that an amorphous resin having the effects of the present invention can be obtained.

  Specific examples of the crosslinking agent for the amorphous resin used in the present invention include aromatic polyvinyl compounds such as divinylbenzene and divinylnaphthalene; divinyl phthalate, divinyl isophthalate, divinyl terephthalate, divinyl homophthalate, trimesin Polyvinyl esters of aromatic polycarboxylic acids such as divinyl acid / trivinyl, divinyl naphthalenedicarboxylate and divinyl biphenylcarboxylate; divinyl esters of nitrogen-containing aromatic compounds such as divinyl pyridinedicarboxylate; vinyl pyromutate, furan carboxyl Vinyl esters of unsaturated heterocyclic compounds such as vinyl acid, vinyl pyrrole-2-carboxylate and vinyl thiophenecarboxylate; butanediol methacrylate, hexanediol acrylate, octanediol methacrylate, (Meth) acrylic acid esters of linear polyhydric alcohols such as didiol acrylate and dodecane diol methacrylate; Branched, substituted polyhydric alcohols such as neopentyl glycol dimethacrylate and 2-hydroxy-1,3-diacryloxypropane (Meth) acrylic acid esters; polyethylene glycol di (meth) acrylate, polypropylene polyethylene glycol di (meth) acrylates; divinyl succinate, divinyl fumarate, vinyl / divinyl maleate, divinyl diglycolate, vinyl itaconate / Divinyl, acetone dicarboxylate divinyl, divinyl glutarate, divinyl 3,3′-thiodipropionate, trans-aconite divinyl / trivinyl, divinyl adipate, divinyl pimelate, disuberate Alkenyl, azelaic acid, divinyl sebacate, divinyl dodecanedioate divinyl, the polyvinyl esters of polycarboxylic acids such as oxalic acid, divinyl; and the like.

  The crystalline resin is not particularly limited as long as it is a resin having crystallinity, and specifically includes a crystalline polyester resin, a crystalline vinyl resin, and the like. A crystalline polyester resin is preferred from the viewpoint of chargeability and adjustment of the melting point within a preferred range. An aliphatic crystalline polyester resin having an appropriate melting point is more preferable.

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

  On the other hand, the crystalline polyester resin may be referred to as an acid (dicarboxylic acid) component (hereinafter sometimes referred to as “acid-derived constituent component”) and an alcohol (diol) component (hereinafter referred to as “alcohol-derived constituent component”). A). Hereinafter, the acid-derived constituent component and the alcohol-derived constituent component will be described in more detail. In the present invention, a copolymer obtained by copolymerizing other components at a ratio of 50% by mass or less with respect to the crystalline polyester main chain is also a crystalline polyester.

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

  As the acid-derived constituent component, in addition to the above-mentioned aliphatic dicarboxylic acid-derived constituent component, constituent components such as a dicarboxylic acid-derived constituent component having a double bond and a dicarboxylic acid-derived constituent component having a sulfonic acid group are included. It is preferable. The component derived from a dicarboxylic acid having a double bond is derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a double bond, in addition to a component derived from a dicarboxylic acid having a double bond. Components are also included. The dicarboxylic acid-derived component having a sulfonic acid group is derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a sulfonic acid group, in addition to a component derived from a dicarboxylic acid having a sulfonic acid group. Components are also included.

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

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

  The content of acid-derived components other than these aliphatic dicarboxylic acid-derived components (dicarboxylic acid-derived component having a double bond and / or dicarboxylic acid-derived component having a sulfonic acid group) in the acid-derived component Is preferably in the range of 1 to 20 mol%, more preferably in the range of 2 to 10 mol%.

  When the content is less than 1 component mol%, pigment dispersion may not be good, the emulsified particle diameter may be large, and adjustment of the toner diameter by aggregation may be difficult. On the other hand, if it exceeds 20 component mol%, the crystallinity of the polyester resin is lowered, the melting point is lowered, the storage stability of the image is deteriorated, the emulsified particle diameter is too small, and it is dissolved in water, and no latex is produced. Sometimes. In the present invention, “constituent mol%” refers to the percentage when each constituent component (acid-derived constituent component, alcohol-derived constituent component) in the polyester resin is 1 unit (mol).

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

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

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

Examples of the diol having a double bond include 2-butene-1,4-diol, 3-butene-1,6-diol, 4-butene-1,8-diol and the like. On the other hand, as the diol having a sulfonic acid group, 1,4-dihydroxy-2-sulfonic acid benzene sodium salt, 1,3-dihydroxymethyl-5-sulfonic acid benzene sodium salt, 2-sulfo-1,4-butane Examples include diol sodium salt.
Alcohol-derived components in the case of adding alcohol-derived components other than these linear aliphatic diol-derived components (diol-derived component having a double bond and / or diol-derived component having a sulfonic acid group) As content in a component, the range of 1-20 component mol% is preferable, and the range of 2-10 component mol% is more preferable.

  When the content is less than 1 constituent mol%, pigment dispersion may be poor, the emulsified particle diameter may be large, and adjustment of the toner diameter by aggregation may be difficult. On the other hand, if it exceeds 20 component mol%, the crystallinity of the polyester resin is lowered, the melting point is lowered, the storage stability of the image is deteriorated, the emulsified particle diameter is too small, and it is dissolved in water, and no latex is produced. Sometimes.

Further, the crystalline polyester resin is preferably a crystalline polyester resin having an ester concentration M defined by the following formula (1) of 0.01 or more and 0.2 or less.
M = K / α Formula (1)
In the above formula (1), M represents the ester concentration, K represents the number of ester groups in the polymer, and α represents the number of atoms constituting the polymer polymer chain.

  The “ester concentration M” is one index indicating the ester group content in the polymer of the crystalline polyester resin. The “number of ester groups in the polymer” represented by K in the above formula (1) refers to the number of ester bonds contained in the whole polymer.

  The “number of atoms constituting the polymer polymer chain” represented by α in the above formula (1) is the total number of atoms constituting the polymer polymer chain, and includes all the atoms involved in the ester bond. However, it does not include the number of atoms of branched parts in other constituent parts. That is, carbon atoms and oxygen atoms derived from carboxyl groups and alcohol groups involved in ester bonds (two oxygen atoms in one ester bond) and the six carbons constituting the polymer chain, for example, in the aromatic ring, Although included in the calculation of the number of atoms, for example, a hydrogen atom in an aromatic ring or an alkyl group, or an atom or atomic group of a substituent thereof constituting the polymer chain is not included in the calculation of the number of atoms.

  To explain with specific examples, among the total of 10 atoms of 6 carbon atoms and 4 hydrogen atoms in the arylene group constituting the polymer chain, the above-mentioned “number of atoms α constituting the polymer chain of the polymer” Included are only six carbon atoms, and even if the hydrogen is replaced by any substituent, the atoms constituting the substituent are the above-mentioned “number of atoms constituting the polymer polymer chain”. It is not included in “α”.

The crystalline polyester resin has one repeating unit (for example, when the polymer is represented by H— [OCOR ¹ COOR ² O—] _n —H, the one repeating unit is represented in []). In the case of a single polymer consisting of only two ester bonds in one repeating unit (that is, the number of ester groups K ′ = 2 in the repeating unit), the ester concentration M is expressed by the following formula: (1-1).
M = 2 / α ′ (Formula 1-1)
In the above formula (1-1), M represents the ester concentration, and α ′ represents the number of atoms constituting the polymer chain in one repeating unit.

When the crystalline polyester resin is a copolymer composed of a plurality of copolymer units, the number of ester groups K ^X and the number of atoms A ^X constituting the polymer chain are determined for each copolymer unit, It can be obtained by multiplying the polymerization ratios and adding them to the above formula (1). For example, the compound [(Xa) _a (Xb) _b (Xc)] has three copolymerized units of Xa, Xb and Xc, and the copolymerization ratio thereof is a: b: c (where a + b + c = 1). _c ] can be determined by the following formula (1-2).
M = {K ^Xa × a + K ^Xb × b + K ^Xc × c} / {A ^Xa × a + A ^Xb × b + A ^Xc × c} Expression (1-2)

In the above formula (1-2), M represents the ester concentration, K ^Xa represents the copolymer unit Xa, K ^Xb represents the copolymer unit Xb, K ^Xc represents the number of ester groups in the copolymer unit Xc, and A ^Xa represents Copolymer units Xa and A ^Xb represent copolymer units Xb and A ^Xc represent the number of atoms constituting each polymer chain in copolymer unit Xc.

  When a crystalline polyester resin is used as the binder resin, the amount of ester groups present in the polymer has a particularly great influence on the chargeability of the toner. Therefore, keeping the amount of ester groups in the polymer low within a range that does not impair the low-temperature fixability is the key to improving the chargeability. In the present invention, in the crystalline polyester resin used as the binder, the ester concentration M defined by the formula (1) is suppressed to 0.01 or more and 0.2 or less, which is preferable in improving the adhesion to paper. .

  The melting point of the crystalline polyester resin is preferably a maximum endothermic peak temperature determined from differential thermal analysis. The maximum endothermic peak temperature is preferably in the range of 50 to 95 ° C, and more preferably in the range of 60 to 75 ° C. When the melting point is less than 50 ° C., powder aggregation tends to occur or the storability of the fixed image may deteriorate. On the other hand, when the melting point exceeds 95 ° C., the fixing temperature may increase.

  In the present invention, the melting point of the crystalline resin is measured using a differential scanning calorimeter (DSC) using JIS K when measured from room temperature to 150 ° C. at a heating rate of 10 ° C. per minute. It can be obtained as the melting peak temperature of the input compensation differential scanning calorimetry shown in −7121. A crystalline resin may show a plurality of melting peaks, and the maximum peak is regarded as the melting point.

As melting | fusing point of crystalline resin, Preferably it is the range of 50-120 degreeC, More preferably, it is the range of 60-110 degreeC. If the melting point is lower than 50 ° C., the storage stability of the toner and the storage stability of the toner image after fixing may become a problem. On the other hand, when the temperature is higher than 120 ° C., the fixing temperature becomes high, which is not preferable in terms of energy efficiency.

  The method for producing the polyester resin (crystalline or amorphous) is not particularly limited, and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. For example, direct polycondensation, ester Different exchange methods are used depending on the type of monomer. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

  The production of the polyester resin can be carried out at a polymerization temperature of 180 to 230 ° C., and the reaction system is reacted under reduced pressure as necessary to remove water and alcohol generated during condensation. If the monomer is not dissolved or compatible at the reaction temperature, a high boiling point solvent is added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. If there is a monomer with poor compatibility in the copolymerization reaction, it is advisable to condense the monomer with poor compatibility with the monomer and the acid or alcohol to be polycondensed in advance before polycondensing with the main component. .

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

  For example, sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium Tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, naphthene Zirconate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, germanium oxide, triphenyl Phosphite, tris (2,4-di -t- butyl-phenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

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

  In the present invention, a compound having a hydrophilic polar group may be used as long as it is copolymerizable as a binder resin for toner for developing an electrostatic image. As a specific example, when the resin used is a polyester, a dicarboxylic acid compound in which an aromatic ring such as sulfonyl-terephthalic acid sodium salt or 3-sulfonylisophthalic acid sodium salt is directly substituted with a sulfonyl group is used. In the case of a resin, unsaturated aliphatic carboxylic acids such as (meth) acrylic acid and itaconic acid, glycerin mono (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, zinc mono (meth) acrylate, zinc di (meth) acrylate, Esters of (meth) acrylic acid and alcohols such as 2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate, sulfonyl groups at any of the ortho, meta, and para positions Have Derivatives of styrene, sulfonyl group-substituted aromatic vinyl such as sulfonyl group-containing vinyl naphthalene.

(Coloring agent)
Known colorants can be used in the present invention. For example, examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.

  Examples of 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, selenium yellow, quinoline yellow, and permanent yellow NCG. Is mentioned.

  Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK and the like.

  Red pigments include Bengala, cadmium red, red lead, mercury sulfide, watch young red, permanent red 4R, risor red, brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, rhodamine B rake, lake red C , Rose bengal, oxin red, alizarin lake and the like.

  Blue pigments include bitumen, cobalt blue, alkali blue rake, Victoria blue rake, fast sky blue, indanthrene blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Rate and so on.

Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.
Examples of the green pigment include chromium oxide, chrome green, pigment green, malachite green lake, final yellow green G, and the like.

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. Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes, such as nigrosine.

These colorants can be used alone or in combination and further in the form of a solid solution. These colorants are dispersed by a known method, and for example, a rotary shear type homogenizer, a media type dispersing machine such as a ball mill, a sand mill, or an attritor, a high-pressure opposed collision type dispersing machine, or the like is preferably used.
Further, when these colorants are used in the emulsion aggregation method described later, a polar surfactant is used and dispersed in an aqueous system by the homogenizer.

  The colorant in the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the toner. The addition amount of the colorant is preferably in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

Further, when the toner is used as magnetism, magnetic powder may be contained. As such magnetic powder, a substance magnetized in a magnetic field is used, and it is a ferromagnetic powder such as iron, cobalt, or nickel, or a compound such as ferrite or magnetite. In particular, when a toner is obtained in an aqueous layer, it is necessary to pay attention to the water layer's ability to migrate, dissolve, and oxidize, and it is preferable to perform surface modification, for example, hydrophobization treatment. Is preferred.
When a magnetic material is used as the black colorant, it is added in the range of 30 to 100 parts by mass with respect to the binder resin, unlike other colorants.

In the present invention, a release agent can be used as necessary.
Specific examples of releasing agents that can be used include low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene; silicones having a softening point; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, and stearic acid amide. ; Plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc. Mineral / petroleum waxes; ester waxes of higher alcohols with higher fatty acids such as stearyl stearate and behenyl behenate; butyl stearate, propyl oleate, glyceryl monostearate, diste Ester waxes of higher fatty acids such as glyceryl acrylate, pentaerythritol tetrabehenate and unit price or polyhydric lower alcohols; Examples include ester waxes composed of fatty acids and polyhydric alcohol multimers; higher sorbitan fatty acid ester waxes such as sorbitan monostearate; higher cholesterol fatty acid ester waxes such as cholesteryl stearate.
In the present invention, these release agents may be used alone or in combination of two or more.

  As an addition amount of a mold release agent, the range of 5-25 mass parts is preferable with respect to 100 mass parts of binder resin, and it is more preferable that it is the range of 7-20 mass parts.

  In the present invention, when the crystalline resin is included as the binder resin and two types having different melting points are used as the release agent, the maximum endothermic value M1 (crystalline resin) in the differential thermal analysis based on ASTM D3418-8. Is present in the range of 50 to 80 ° C., M2 is present on the lower temperature side, and M3 is present on the higher temperature side (both are based on the release agent). The amount of heat is preferably 40% or less, and the endothermic amount of M3 is preferably in the range of 50 to 120%.

  When the endothermic amount of M2 exceeds 40% with respect to the endothermic amount of M1, it indicates that the amorphous resin in the binder resin exceeds 90% by mass, which is the combined effect of the crystalline resin because there is little crystalline resin. There may be no improvement in glossiness. If the endothermic amount of M3 is less than 50% of the endothermic amount of M1, the amount of toner contained in the release agent is less than necessary, so that the release agent necessary for fixing does not ooze out on the image surface, resulting in poor peeling. Easy to wake up. In addition, if the endothermic amount of M3 exceeds 120% of the endothermic amount of M1, the amount of toner contained in the release agent is too large, so that the release agent exudes excessively during fixing and unevenness of the fixed image surface occurs. , Uneven gloss may occur.

  For the measurement of the endothermic maximum peak of the present invention, for example, a differential scanning calorimeter (manufactured by Mac Science, DSC3110) is used. The temperature correction of the detection part of the apparatus uses the melting points of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. For the sample, an aluminum pan was used, an empty pan was set for control, and the temperature increase rate was 10 ° C./min.

  In the present invention, in addition to the binder resin, the colorant, and the release agent, other components (particles) such as an internal additive, a charge control agent, an organic granule, a lubricant, and an abrasive are used depending on the purpose. ) Can be added.

  Examples of internal additives include metals such as ferrite, magnetite, reduced iron, cobalt, manganese, and nickel, alloys, and magnetic materials such as compounds containing these metals, and inhibit charging properties as toner characteristics. A small amount can be used.

  The charge control agent is not particularly limited, but when a color toner is used, a colorless or light-colored agent can be preferably used. Examples thereof include quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments.

  Examples of the organic particles include all particles usually used as external additives on the toner surface, such as vinyl resins, polyester resins, and silicone resins. These inorganic particles and organic particles can be used as fluidity aids, cleaning aids, and the like.

Examples of the lubricant include fatty acid amides such as ethylene bis stearic acid amide and oleic acid amide, and fatty acid metal salts such as zinc stearate and calcium stearate.
As an abrasive | polishing agent, the above-mentioned silica, alumina, cerium oxide etc. are mentioned, for example.

When the binder resin, the colorant, and the release agent are mixed, the content of the colorant may be 50% by mass or less, and is in the range of about 2 to 40% by mass. Is preferred.
Moreover, as content of the said other component, what is necessary is just a grade which does not inhibit the objective of this invention, generally it is a very small amount, Specifically, it is the range of 0.01-5 mass%, Preferably it is the range of 0.5-2 mass%.

  The toner of the present invention preferably has at least one kind of metal oxide particles on the surface thereof. These metal oxide particles not only improve the fluidity of the toner but also release the metal oxide particles mixed in the release agent layer at the stage where the release agent on the fixed image surface after fixing is recrystallized. It has the effect of hindering the crystallization of the mold and making the fixing roll contact trace less noticeable.

  Specific examples of the metal oxide particles include silica, titania, zinc oxide, strontium oxide, aluminum oxide, calcium oxide, magnesium oxide, cerium oxide, and composite oxides thereof. Of these, silica and titania are preferably used from the viewpoints of particle size, particle size distribution, and manufacturability. Further, metal oxide particles produced by a wet method are preferred. The reason is that these metal oxide particles produced by a wet method have a large surface area and are more likely to inhibit the crystallization.

  These metal oxide particles are preferably subjected to surface modification such as hydrophobization because they can be easily mixed in the release agent layer at the time of fixing and can inhibit crystallization of the release agent. A conventionally known method can be used as the surface modification means. Specific examples include coupling treatments such as silane, titanate, and aluminate.

  The coupling agent used for the coupling treatment is not particularly limited. For example, methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ -Chloropropyltrimethoxysilane, γ-bromopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, fluoroalkyltrimethoxysilane, hexamethyldi Silane coupling agents such as silazane; titanate coupling agents; aluminate coupling agents;

  The average particle diameter of the metal oxide particles is preferably in the range of 1 to 40 nm and more preferably in the range of 5 to 20 nm as the primary particle diameter. Further, it is preferable to add metal oxide particles of 50 to 500 nm because crystallization is more easily inhibited.

These metal oxide particles may be used alone or as a mixture of plural kinds. The amount added to these toners is not particularly limited, but is preferably used in the range of 0.1 to 10% by mass. More specifically, it is in the range of about 0.2 to 8% by mass.
When the addition amount is less than 0.1% by mass, it is difficult to obtain the effect of the metal oxide to be added, and the crystallization of the release agent on the surface of the fixed image may not be inhibited. The required high glossiness may not be obtained.

  The volume average particle size of the toner of the present invention is preferably in the range of 3 to 9 μm, and more preferably in the range of 3 to 8 μm. When the volume average particle diameter of the toner particles exceeds 9 μm, the ratio of coarse particles increases, and the reproducibility and gradation of fine lines and fine dots of the image obtained through the fixing process are lowered. On the other hand, when the volume average particle size of the toner particles is less than 3 μm, the powder fluidity, developability, or transferability of the toner deteriorates, and the cleaning property of the toner remaining on the surface of the image carrier decreases. Various problems occur in other processes due to the deterioration of characteristics.

  Further, as the particle size distribution index of the toner particles used in the present invention, the volume average particle size distribution index GSDv is preferably 1.30 or less, and the ratio GSDv / GSDp to the number average particle size distribution index GSDp is 0.95 or more. It is more preferable that When the volume distribution index GSDv exceeds 1.30, the unevenness of the fixed image described above becomes large, and uneven glossiness may easily occur. Further, when the ratio between the volume average particle size distribution index GSDv and the number average particle size distribution index GSDp is less than 0.95, the amount of small particle size toner increases, and the amount of release agent contained per toner is uneven. May occur, and as a result, peeling failure may occur and a desired glossiness may not be obtained.

The volume average particle size and the particle size distribution index were measured and calculated as follows. First, the volume and number of individual toner particles are accumulated from the smaller diameter side with respect to the divided particle size range (channel) of the toner particle size distribution measured using a Coulter Counter TAII (manufactured by Beckman-Coulter) as a measuring device. Draw a distribution and define the particle size to be 16% cumulative as the volume average particle size D16v and the number average particle size D16p. The particle size to be 50% cumulative is the volume average particle size D50v (this value is the volume average particle size And D50p. Similarly, the particle diameters with an accumulation of 84% are defined as volume average particle diameters D84v and D84p. Using these, the volume average particle size distribution index GSDv is defined as (D84v / D16v) ^1/2 , and the number average particle size distribution index GSDp is defined as (D84p / D16p) ^1/2 .

Further, the toner shape factor SF1 in the present invention is preferably in the range of 120 to 140.
When the shape factor SF1 is less than 120, the blade cleaning property of the transfer residual toner on the photoreceptor is impaired. When the shape factor SF1 exceeds 140, the fluidity of the toner is lowered, and the transfer property may be adversely affected from the beginning.

Here, the shape factor SF1 is obtained by the following equation (2).
SF1 = (ML ² / A) × (π / 4) × 100 (2)
In the above formula (2), ML represents the absolute maximum length of the toner particles, and A represents the projected area of the toner particles.

  The SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and can be calculated as follows, for example. That is, an optical microscope image of the toner spread on the surface of the slide glass is taken into a Luzex image analyzer through a video camera, the maximum length and the projected area of 100 or more toner particles are obtained, calculated by the above equation (2), and the average Obtained by determining the value.

  In the electrostatic image developing toner of the present invention, the value (AV / D50v) obtained by dividing the acid value AV by the volume average particle diameter D50v is an index indicating the height of the acid value per unit area of the toner. Preferably it is in the range of 5-10. When the AV / D50v is less than 0.5, there are few ionic crosslinks between the aluminum ion on the toner surface and the functional group that contributes to the acid value, so that the viscosity at the time of fixing on the toner surface decreases and the peelability deteriorates. There is. On the other hand, if it exceeds 10, there are many ionic crosslinks between the aluminum ions on the toner surface and the functional groups contributing to the acid value, the viscosity at the time of fixing on the toner surface becomes too high, and high glossiness may not be obtained.

  Further, the Z average average molecular weight Mz of the toner for developing an electrostatic charge image of the present invention is preferably in the range of 30000 to 120,000. If the Mz is less than 30000, the amount of ionic crosslinking in the toner is small, so that sufficient toner viscosity cannot be obtained at the time of fixing, and the peelability may deteriorate. If it exceeds 120,000, the toner has many ionic crosslinks, so the viscosity of the toner at the time of fixing becomes high and difficult to dissolve uniformly, and the unevenness of the fixed image becomes prominent, and uneven glossiness is likely to occur. .

Further, it is preferable that the THF-insoluble matter at 40 ° C. is not substantially present in the binder resin constituting the toner.
The presence of THF-insoluble matter in the binder resin component at room temperature and the absence of THF-insoluble matter at 40 ° C. indicate that the molecules in the binder resin are intertwined. When the entangled structure is present in the resin molecule, the resin has rigidity compared to a resin having the same molecular weight that is not entangled, which is advantageous for releasability from the fixing member at the time of fixing. When the THF-insoluble matter at 40 ° C. is substantially present in the binder resin composition, the resin itself is less rigid, so that the toner easily adheres to the fixing member during fixing, and uneven gloss tends to occur.

The surface area of the toner for developing an electrostatic charge image of the present invention is not particularly limited, and any toner can be used as long as it can be used for a normal toner. Specifically, when the BET method is used, a range of 0.5 to 10 m ² / g is preferable, preferably a range of 1.0 to 7 m ² / g, more preferably about 1.2 to ⁵ m ² / g. It is a range. Furthermore, the range of about 1.2-3 m < ² > / g is preferable.

The toner particles in the present invention form agglomerated particles in the presence of aluminum ions, using a mixed solution containing a resin fine particle dispersion in which the binder resin fine particles are dispersed and a colorant dispersion in which the colorant is dispersed. A method comprising: an aggregating step; and a step of adjusting the pH in the system to 9 to 10 to stop the growth of the agglomerated particles, and then adding ion-exchange resin particles and stirring to contact the agglomerated particles. Any production method can be used as long as it is available, but the emulsion polymerization aggregation coalescence method has a sharp particle size distribution, and controllability of the toner shape and toner surface properties (aluminum element and sulfur element content). Therefore, it is preferable as a manufacturing method that satisfies the above requirements.

  The charge amount of the toner for developing an electrostatic image of the present invention is preferably in the range of 20 to 40 μC / g, more preferably in the range of 15 to 35 μC / g in absolute value. If the charge amount is less than 20 μC / g, background stains (fogging) are likely to occur, and if it exceeds 40 μC / g, the image density tends to decrease. The ratio of the charge amount in the summer (high temperature and high humidity) and the charge amount in the winter (low temperature and low humidity) of the toner for developing an electrostatic charge image is preferably in the range of 0.5 to 1.5. A range of 3 is more preferred. When the ratio is outside these ranges, the charging property is highly dependent on the environment, and the charging stability is poor, which is not preferable for practical use.

  By satisfying the characteristics of each toner described above, it is possible to obtain a toner for developing an electrostatic charge image that can form a fixed image with high glossiness and less gloss unevenness in oilless fixing.

<Method for producing toner for developing electrostatic image>
The method for producing the toner for developing an electrostatic charge image of the present invention is not particularly limited. As described above, the characteristics of the toner of the present invention limit the contents of aluminum element and sulfur element in the vicinity of the toner surface. In view of the presence of these elements and the ease of control thereof, a method of production by an emulsion polymerization aggregation method is preferred.
Hereinafter, the production method of the toner for developing an electrostatic charge image of the present invention will be described in detail by an emulsion polymerization aggregation method.

  The method for producing a toner for developing an electrostatic charge image according to the present invention comprises at least mixing a resin fine particle dispersion in which resin fine particles having a volume average particle size of 1 μm or less are dispersed, a colorant dispersion, and a release agent dispersion. An agglomeration step for forming aggregated particles in the presence of aluminum ions, and adjusting the pH in the system to 9 to 10 to stop the growth of the aggregated particles; And a step of bringing the aggregated particles into a temperature equal to or higher than the melting point of the resin fine particles, and a fusion step of fusing and coalescing.

Specifically, at least a resin fine particle dispersion in which resin fine particles having a volume average particle size of 1 μm or less are dispersed, a colorant dispersion, and a dispersion in which a release agent dispersion is further dispersed as necessary are mixed. An aggregating agent is added thereto to form agglomerated particles of the resin fine particles and the colorant or release agent. Next, if necessary, resin fine particles that are the same as or different from the aggregated particles are added, and after surface coating, the pH in the aggregated system is adjusted to a range of 9 to 10 to stop the growth, and then anion and cationic ion exchange are performed. By adding resin particles and bringing them into contact with stirring, the aluminum element content present at a depth of 0.01 to 0.5 μm from the surface is reduced. In addition, the amount of carboxy groups on the surface of the aggregated particles is reduced by using a resin resin in which the amount of chain transfer agent containing sulfur element is increased as the resin fine particles.

  The resin fine particles can be produced by a method such as emulsion polymerization. For example, emulsion polymerization involves adding several kinds of polymerizable monomers that are not soluble in a solvent, such as water, together with a dispersion stabilizer such as a surfactant, into the dispersion medium. Then, micelles are formed, and polymerization is initiated with a water-soluble polymerization initiator to produce resin particles. At this time, the polymerizable monomer in the micelle stabilizes the inside of the micelle by being more hydrophilic or highly polar on the surface of the micelle, in other words, on the contact surface with the solvent.

The polymerization is initiated by the polymerization initiator. At this time, the polymerization tends to start from a polymerizable monomer having low polarity. The reason for this is considered to be that the polymerizability of the polymerizable monomer having high polarity is lowered because π electrons in the polymerizable monomer having polymerizability are attracted by the electron withdrawing property of the polar group.
By using this property, a highly polar polymerizable monomer in the micelle can be provided in the vicinity of the surface of the resin particle, and furthermore, by using this highly polar polymerizable monomer having crosslinkability. Resin particles having a high effect of the present invention can be obtained.

Examples of the polymerization initiator when the resin used in the toner of the present invention is produced by radical polymerization of a polymerizable monomer include the following.
Specifically, hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide Ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, tert-butyl hydroperoxide pertriphenyl acetate, tert-butyl formate, Peroxides such as tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, tert-butyl perN- (3-toluyl) carbamate,
2,2′-azobispropane, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2,2′-azobis (2-amidinopropane) Hydrochloride, 2,2′-azobis (2-amidinopropane) nitrate, 2,2′-azobisisobutane, 2,2′-azobisisobutyramide, 2,2′-azobisisobutyronitrile, 2, Methyl 2′-azobis-2-methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2′-azobis-2-methylbutyronitrile, dimethyl 2,2′-azobisisobutyrate, 1 , 1′-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile, 4,4′-azobis-4-cyanovaleric acid, 3,5-dihydride Roxymethylphenylazo-2-methylmalonodinitrile, 2- (4-bromophenylazo) -2-allylmalonodinitrile, 2,2′-azobis-2-methylvaleronitrile, 4,4′-azobis-4 -Dimethyl cyanovalerate, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'- Azobis-1-chlorophenylethane, 1,1′-azobis-1-cyclohexanecarbonitrile, 1,1′-azobis-1-cycloheptanenitrile, 1,1′-azobis-1-phenylethane, 1,1 ′ -Azobiscumene, 4-nitrophenylazobenzyl cyanoacetate ethyl, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrate Rophenylazotriphenylmethane, 1,1′-azobis-1,2-diphenylethane, poly (bisphenol A-4,4′-azobis-4-cyanopentanoate), poly (tetraethylene glycol-2,2 Azo compounds such as' -azobisisobutyrate), 1,4-bis (pentaethylene) -2-tetrazene, 1,4-dimethoxycarbonyl-1,4-diphenyl-2-tetrazene and the like.
Among these, preferred are water-soluble compounds, specifically hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, peroxide. Examples thereof include dichlorobenzoyl, bromomethylbenzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, and diisopropyl peroxycarbonate.

  In the present invention, a chain transfer agent is used for molecular weight control in the polymerization, but the chain transfer agent to be used is not particularly limited as long as it contains a sulfur element. By using a chain transfer agent containing elemental sulfur and controlling the amount of addition, the probability that the molecular end will be a carboxyl group is reduced, and the sulfur radicals after chain transfer react with other carboxyl groups to cause chain transfer. By this, the probability that a carboxyl group appears on the surface in a sterically hindered manner in the resin after polymerization can be reduced.

As a chain transfer agent used for this invention, what consists of a long-chain alkyl group and a sulfur element is preferable, for example, octanethiol, decanethiol, dodecanethiol, tetradecanethiol, hexadecanethiol etc. are especially preferable.
Further, the addition amount of the chain transfer agent is preferably in the range of 0.3 to 1.0% by mass, more preferably in the range of 0.5 to 0.8% by mass with respect to the resin particles. .

Examples of the dispersion medium in the resin particle dispersion, the colorant dispersion described later, the release agent dispersion, and other components in the present invention include an aqueous medium.
Examples of the aqueous medium include water such as distilled water and ion exchange water, alcohol, and the like. These may be used individually by 1 type and may use 2 or more types together.

A surfactant can be used for the purpose of stabilizing the dispersion of each dispersion.
Examples of the surfactant include anionic surfactants such as sulfate, 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 ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable.

In the toner of the present invention, an anionic surfactant generally has a strong dispersion power and is excellent in dispersion of resin particles and colorants. Therefore, an anionic surfactant is used as a surfactant for dispersing a release agent. It is advantageous to use a surfactant.
The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of anionic surfactants include fatty acid soaps such as potassium laurate, sodium oleate, and castor oil sodium; sulfates such as octyl sulfate, lauryl sulfate, lauryl ether sulfate, and nonyl phenyl ether sulfate; lauryl sulfonate , Sodium alkylnaphthalene sulfonate such as dodecylbenzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate; sulfone such as naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate Acid salts; lauryl phosphate, isopropyl phosphate, nonylphenyl ether Phosphoric acid esters such as Sufeto; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate; sulfosuccinate salts such as sulfosuccinate lauryl disodium; and the like.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyldimethylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleylbispolyoxyethylenemethylammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzene Trimethylammonium chloride, Quaternary ammonium salts such as quilts trimethyl ammonium chloride; and the like.

  Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxy Alkyl phenyl ethers such as ethylene nonyl phenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene Alkylamines such as oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as ethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid Alkanolamides such as diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate And so on.

  The content of the surfactant in each dispersion may be a level that does not inhibit the present invention, generally a small amount, specifically in the range of about 0.01 to 10% by mass, More preferably, it is the range of 0.05-5 mass%, More preferably, it is the range of about 0.1-2 mass%. When the content is less than 0.01% by mass, each dispersion such as a resin particle dispersion, a colorant dispersion, and a release agent dispersion becomes unstable, so that aggregation occurs, and each particle during aggregation There are problems such as the release of specific particles due to the difference in stability between them, and when the amount exceeds 10% by mass, the particle size distribution of the particles becomes wide, and the control of the particle size becomes difficult. It is not preferable for the reason. In general, a suspension polymerization toner dispersion having a large particle size is stable even if the amount of the surfactant used is small.

  Also, a room temperature solid aqueous polymer or the like can be used. Specifically, cellulose compounds such as carboxymethyl cellulose and hydroxypropyl cellulose, polyvinyl alcohol, gelatin, starch, gum arabic and the like can be used.

  In addition, the colorant dispersion is prepared by using colorant particles having a desired color such as blue, red, and yellow by using an ionic surfactant having a polarity opposite to that of the ionic surfactant used in the preparation of the resin fine particle dispersion. Prepare by dispersing in solvent. Furthermore, the release agent dispersion liquid is a homogenizer that disperses the release agent in water together with a polymer electrolyte such as an ionic surfactant, a polymer acid, or a polymer base, and heats above the melting point and applies strong shear. Or by making fine particles with a pressure discharge type disperser.

The resin fine particle diameter of the resin fine particle dispersion in the present invention is 1 μm or less in volume average particle diameter, and is preferably in the range of 100 to 300 nm. When the volume average particle size exceeds 1 μm, the particle size distribution of the toner particles obtained by agglomeration and fusion is widened, or free particles are generated, leading to a decrease in toner performance and reliability. If it is less than 100 nm, it may take time to coagulate and grow the toner, which may not be industrially suitable. If it exceeds 300 nm, the dispersion of the release agent and the colorant becomes non-uniform and control of the toner surface properties. May be difficult.
The particle diameter of the resin fine particle dispersion or the like can be measured, for example, with a laser diffraction particle size distribution measuring device (LA-700, manufactured by Horiba, Ltd.).

  In the aggregation step, the resin fine particle dispersion, the colorant dispersion, and, if necessary, the particles in the release agent dispersion are aggregated to form aggregated particles. The agglomerated particles are formed by heteroaggregation or the like. For the purpose of stabilizing the agglomerated particles and controlling the particle size / particle size distribution, the ionic surfactant having a polarity different from that of the agglomerated particles, or a monovalent or more monovalent metal salt or the like is used. A charged compound is added.

  Further, even if the process is performed by mixing and agglomerating all at once, in the agglomeration step, the initial balance of the amount of the ionic dispersant of each polarity is shifted in advance, and the ionic surfactant is Or a salt having a monovalent or higher charge such as a metal salt, which is ionically neutralized to form a first-stage matrix aggregation below the glass transition point, and then stabilized as a second-stage balance. After adding and coating a resin fine particle dispersion treated with a dispersing agent of polarity and quantity so as to compensate for the deviation, further heat below the glass transition point of the resin contained in the matrix or additional particles as necessary. After stabilization at a higher temperature, the particles added in the second stage of agglomeration by heating above the glass transition point are combined in a state of adhering to the surface of the agglomerated particles (attached particles) But it ’s okay. Furthermore, the stepwise operation of aggregation may be repeated several times.

In the method for producing a toner for developing an electrostatic charge image of the present invention, as described above, particles can be prepared by generating aggregation by pH change in the aggregation step. At the same time, a flocculant is added in order to stably and rapidly aggregate the particles, or to obtain agglomerated particles having a narrower particle size distribution.
The flocculant is not particularly limited, and a metal salt of an inorganic acid is used as the flocculant in consideration of the stability of the flocculent particles, the stability of the flocculant with respect to heat and time, and removal during washing. Specific examples include metal salts of inorganic acids such as magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, and sodium carbonate. In the present invention, final toner particles From the viewpoint of controlling the viscosity at the time of fixing, an aggregating agent containing aluminum (for example, polyaluminum chloride, aluminum sulfate, potassium alum, etc.) is used.

  The amount of the flocculant added varies depending on the valence of the charge, but the amount is small, and in the case of trivalent such as aluminum, it is about 0.5% by mass or less. Since the amount of the flocculant is preferably small, it is preferable to use a compound having a large valence.

  After the aggregated particles (including adhered particles) are formed, the pH in the aggregated system is adjusted to a range of 9 to 10 to stop the growth of the aggregated particles, and then anionic or cationic ion exchange resin particles Contact the agglomerated particles. In this step, the ion-exchange resin particles are brought into contact with the agglomerated particles that are slightly alkaline and slightly swollen to reduce the aluminum ion content on the surface of the particles. Although it is not clear about this mechanism, it is considered that the aluminum ions are removed from the surface portion of the particles by coordinating and desorbing the ion exchange resin particles to the aluminum ions on the particle surface.

  In the present invention, the ion exchange resin particles used are not particularly limited as long as they are anionic and cationic. For example, styrene gel type cationic ion exchange resin, acrylic MR type cationic ion exchange resin, styrene Particles such as a gel-based anionic ion exchange resin and an acrylic gel-type anionic ion exchange resin are preferably used. The volume average particle diameter of these ion exchange resin particles is preferably in the range of 200 to 800 μm. Moreover, it is preferable that the addition amount of an ion exchange resin particle is the range of 0.2-1 mass% with respect to the aggregated particle.

  Next, in the fusion step, the agglomerated particles (including the adhered particles) obtained through the aggregating step are converted into amorphous resin fine particles (including the shell layer constituting resin) contained in the agglomerated particles in a solution. Glass transition temperature (the glass transition temperature of the resin having the highest glass point transition temperature when two or more types of resin are used), and the highest temperature among the melting points of the crystalline resin when a crystalline resin is included. The toner particles are obtained by heating and fusing and coalescing.

  After completion of the aggregation and fusion process, a desired toner is obtained through an arbitrary washing process, solid-liquid separation process, and drying process. In the washing process, replacement washing with ion-exchanged water is sufficiently performed from the viewpoint of chargeability. preferable. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Further, although the drying process is not particularly limited, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

  The toner for developing an electrostatic charge image of the present invention can be produced by preparing toner particles (mother particles) as described above, adding the inorganic fine particles to the toner particles, and mixing with a Henschel mixer or the like. it can.

<Electrostatic image developer>
The electrostatic image developer of the present invention is not particularly limited except that it contains the toner for developing an electrostatic latent image of the present invention, and an appropriate component composition can be taken according to the purpose. The electrostatic image developer of the present invention becomes a one-component electrostatic image developer when the toner for developing an electrostatic image is used alone, and a two-component electrostatic image developer when used in combination with a carrier. It becomes.

  For example, when the carrier is used, the carrier is not particularly limited, and examples thereof include known carriers, such as those described in JP-A Nos. 62-39879 and 56-11461. A known carrier such as a resin-coated carrier can be used.

Specific examples of the carrier include the following resin-coated carriers. Examples of the core particle of the carrier include ordinary iron powder, ferrite, magnetite molding, and the like, and the volume average particle diameter is in the range of about 30 to 200 μm.
Examples of the coating resin for the resin-coated carrier include styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, acrylic acid 2 -Α-methylene fatty acid monocarboxylic acids such as ethylhexyl, methyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; nitrogen-containing acrylics such as dimethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile, etc. Vinyl nitriles; vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl Homopolymers such as vinyl ketones such as ketones; olefins such as ethylene and propylene; vinyl-based fluorine-containing monomers such as vinylidene fluoride, tetrafluoroethylene and hexafluoroethylene; and copolymers composed of two or more types of monomers Furthermore, silicone resins containing methyl silicone, methyl phenyl silicone, etc., polyesters containing bisphenol, glycol, etc., epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, polycarbonate resins and the like can be mentioned. These resins may be used alone or in combination of two or more. The coating amount of the coating resin is preferably in the range of about 0.1 to 10 parts by mass and more preferably in the range of 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the core particles.

For the production of the carrier, a heating kneader, a heating Henschel mixer, a UM mixer, or the like can be used. Depending on the amount of the coating resin, a heating fluidized rolling bed, a heating kiln, or the like can be used. .
The mixing ratio of the electrostatic latent image developing toner of the present invention and the carrier in the electrostatic image developer is not particularly limited and may be appropriately selected according to the purpose.

<Image forming method>
The image forming method of the present invention includes a latent image forming step, a developing step, a transfer step, and a fixing step. Each of the steps is a general step per se, and is described in, for example, Japanese Patent Laid-Open Nos. 56-40868 and 49-91231. The image forming method of the present invention can be carried out using an image forming apparatus such as a copier or a facsimile machine known per se.

  The latent image forming step forms an electrostatic charge image on the surface of the latent image carrier. In the developing step, the electrostatic image is developed by a developer layer on the surface of the developer carrying member to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developer of the present invention containing the electrostatic image developing toner of the present invention. In the transfer step, the toner image is transferred to the surface of the recording medium. In the fixing step, the toner image transferred to the surface of the recording medium is fixed to the recording medium by heating from a fixing member.

  When a full-color image is to be obtained, a toner image developed using toner of at least three colors of cyan, magenta, and yellow and, if necessary, four colors of black is used in the toner image forming step. This is done by laminating and transferring. At this time, using the intermediate transfer member, once transferring these layers onto the surface of the intermediate transfer member (primary transfer) and then transferring them all at once to the transfer member (secondary transfer), there is no positional deviation and color development. This is preferable for obtaining an image having good properties. Although it will not specifically limit if it is a thing, You may have another process as needed.

In the present invention, the fixing roll surface layer of the fixing member used in the fixing step needs to be composed of PFA containing an acrylate ester.
As a result of studies by the present inventors, gloss unevenness is noticeable when an image having a 75-degree specular gloss measured in accordance with JIS Z 8741-1997 is 80 to 120% is formed. I confirmed that there was. On the other hand, the glossiness of the image and the fixing conditions generally vary depending on the fixing member used, the contact time during fixing, and the like, in addition to the binder resin and release agent characteristics of the toner used.

  As described above, various factors are involved in obtaining a high-gloss image. However, when an image is formed using the image forming method of the present invention, the 75-degree specular gloss described above is 80 to 80. Even when an image of 120% is formed, it is possible to obtain a highly glossy fixed image without uneven gloss.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, these do not limit this invention at all.
<Measuring method of various characteristics>
First, the measurement method and evaluation method of the toner and developer used in the following examples and comparative examples will be described.
(Measurement method of acid value)
2 g of the toner was weighed and dissolved in 160 ml of tetrahydrofuran, or if it was insufficiently soluble, dissolved, and then the acid value was measured using this sample by the potentiometric titration method of JIS K0070-1992.

(Method for measuring particle diameter of resin fine particles, colorant particles, and release agent particles)
The particle diameters of the resin fine particles, the colorant particles, and the release agent particles were measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

(Toner particle size, particle size distribution measurement method)
A coulter counter TAII (manufactured by Beckman-Coulter) was used as the volume average particle diameter and particle size distribution index of the agglomerated particles, and an ISOTON-II (manufactured by Beckman-Coulter) was used as the electrolyte. As a measurement method, 0.5 to 50 mg of a measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate, as a dispersant. This is added to 100 to 150 ml of the electrolytic solution. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for 1 minute with an ultrasonic disperser, and the particle size distribution of particles of 1.0 to 30 μm is measured using the Coulter counter TA-II type with an aperture diameter of 50 μm. To obtain volume average distribution and number average distribution.

Draw cumulative distribution from the small diameter side to the divided particle size range (channel) for the measured particle size distribution (channel), define the particle size to be 16% cumulative as D16v and / or D16n, cumulative The particle size at 50% is defined as volume D50v or D50n. Similarly, it is defined as D84v and / or D84v. Using these, the volume average particle size distribution index (GSDv) is obtained from (D84v / D16v) ^1/2 , and the number average particle size index (GSDp) is calculated from (D84p / D16p) ^1/2 .

(Toner shape factor measurement method)
The toner shape factor SF1 is calculated by taking an optical microscope image of toner dispersed on a slide glass into a Luzex image analyzer through a video camera and calculating the square of the maximum length of 50 or more toners / projection area (ML ² / A). The average value is obtained.

(Measurement method of molecular weight and molecular weight distribution of toner and resin particles)
In the electrostatic charge developing toner of the present invention, the specific molecular weight distribution is obtained 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 sample concentration was 0.5%, and the flow rate was 0.6 ml / min. The experiment was conducted using a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and an IR detector. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

<Production of toner>
(Preparation of each dispersion)
-Amorphous resin fine particle dispersion (1)-
Oil layer Styrene (Wako Pure Chemical Industries) 30 parts by weight n-butyl acrylate (Wako Pure Chemical Industries) 10 parts by weight β Carboethyl acrylate (Rhodia Nikka) 1.5 parts by weight Acrylic acid 0.3 parts by weight Dodecanethiol (Wa 0.5 parts by mass

・ Water layer 1
Ion-exchanged water 17.0 parts by weight Anionic surfactant (manufactured by Rhodia) 0.4 parts by weight

・ Water layer 2
Ion-exchanged water 40 parts by weight Anionic surfactant (manufactured by Rhodia) 0.08 parts by weight Potassium persulfate (manufactured by Wako Pure Chemical Industries) 0.30 parts by weight Ammonium persulfate (manufactured by Wako Pure Chemical Industries) 0.10 parts by weight

  The oil layer component and the aqueous layer 1 component were placed in a flask and mixed with stirring to obtain a monomer emulsified dispersion. On the other hand, the components of the aqueous layer 2 were put into a reaction vessel, and the inside of the vessel was sufficiently replaced with nitrogen and stirred, and heated in an oil bath until the temperature in the reaction system reached 75 ° C. Subsequently, the monomer emulsion dispersion was gradually dropped into the reaction vessel over 3 hours to carry out emulsion polymerization. After completion of the dropping, the polymerization was further continued at 75 ° C., and the polymerization was terminated after 3 hours to obtain an amorphous resin fine particle dispersion (1) having a solid content of 42% by mass.

The obtained resin fine particles were 200 nm when the number average particle diameter D _50n of the resin fine particles was measured with a laser diffraction particle size distribution analyzer (manufactured by Horiba, Ltd., LA-700), and a differential scanning calorimeter (manufactured by Shimadzu Corporation). DSC-50) was used to measure the glass transition point of the resin at a heating rate of 10 ° C./min, and it was 51.5 ° C., and a molecular weight measuring device (HLC-8020, manufactured by Tosoh Corporation) was used. It was 30000 when the weight average molecular weight (polystyrene conversion) was measured.

-Amorphous resin fine particle dispersion (2)-
Oil layer Styrene (Wako Pure Chemical Industries) 30 parts by weight n-butyl acrylate (Wako Pure Chemical Industries) 10 parts by weight β Carboethyl acrylate (Rhodia Nikka) 1.5 parts by weight Acrylic acid 0.3 parts by weight Dodecanethiol (Wa 0.2 parts by mass

・ Water layer 1
Ion-exchanged water 17.0 parts by weight Anionic surfactant (manufactured by Rhodia) 0.4 parts by weight

・ Water layer 2
Ion-exchanged water 40 parts by weight Anionic surfactant (manufactured by Rhodia) 0.08 parts by weight Potassium persulfate (manufactured by Wako Pure Chemical Industries) 0.30 parts by weight Ammonium persulfate (manufactured by Wako Pure Chemical Industries) 0.10 parts by weight

  The oil layer component and the aqueous layer 1 component were placed in a flask and mixed with stirring to obtain a monomer emulsified dispersion. On the other hand, the components of the aqueous layer 2 were put into a reaction vessel, and the inside of the vessel was sufficiently replaced with nitrogen and stirred, and then heated in an oil bath until the inside of the reaction system reached 80 ° C. Subsequently, the monomer emulsion dispersion was gradually dropped into the reaction vessel over 3 hours to carry out emulsion polymerization. After completion of the dropping, the polymerization was further continued at 80 ° C., and the polymerization was terminated after 3 hours to obtain an amorphous resin fine particle dispersion (2) having a solid content of 42% by mass.

The obtained resin fine particles were 210 nm when the number average particle diameter D _50n of the resin fine particles was measured with a laser diffraction particle size distribution measuring device (LA-700, manufactured by Horiba, Ltd.), and a differential scanning calorimeter (manufactured by Shimadzu Corporation). DSC-50) was measured for the glass transition point of the resin at a heating rate of 10 ° C./min and found to be 51.8 ° C., and a molecular weight measuring device (HLC-8020, manufactured by Tosoh Corporation) was used to remove THF. As a result, the weight average molecular weight (in terms of polystyrene) was measured to be 30500.

-Amorphous resin fine particle dispersion (3)-
Oil layer Styrene (Wako Pure Chemical Industries) 30 parts by weight n-butyl acrylate (Wako Pure Chemical Industries) 10 parts by weight β Carboethyl acrylate (Rhodia Nikka) 1.5 parts by weight Acrylic acid 0.3 parts by weight Dodecanethiol (Wa 0.9 parts by mass

・ Water layer 1
Ion-exchanged water 17.0 parts by weight Anionic surfactant (manufactured by Rhodia) 0.4 parts by weight

・ Water layer 2
Ion-exchanged water 40 parts by weight Anionic surfactant (manufactured by Rhodia) 0.08 parts by weight Potassium persulfate (manufactured by Wako Pure Chemical Industries) 0.30 parts by weight Ammonium persulfate (manufactured by Wako Pure Chemical Industries) 0.10 parts by weight

  The oil layer component and the aqueous layer 1 component were placed in a flask and mixed with stirring to obtain a monomer emulsified dispersion. On the other hand, the components of the aqueous layer 2 were put into a reaction vessel, and the inside of the vessel was sufficiently replaced with nitrogen and stirred, and then heated in an oil bath until the reaction system reached 70 ° C. Subsequently, the monomer emulsion dispersion was gradually dropped into the reaction vessel over 3 hours to carry out emulsion polymerization. Polymerization was further continued at 70 ° C. after completion of the dropwise addition, and the polymerization was terminated after 3 hours to obtain an amorphous resin fine particle dispersion (3) having a solid content of 42% by mass.

The obtained resin fine particles were 190 nm when the number average particle diameter D _50n of the resin fine particles was measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.), and a differential scanning calorimeter (manufactured by Shimadzu Corporation). DSC-50) was used to measure the glass transition point of the resin at a heating rate of 10 ° C./min and found to be 52.0 ° C., and a molecular weight meter (HLC-8020, manufactured by Tosoh Corporation) was used to remove THF. As a result, the weight average molecular weight (in terms of polystyrene) was measured to be 29000.

-Crystalline polyester resin dispersion (1)-
In a heat-dried three-necked flask, 92.5 mol% dodecanedioic acid, 3 mol% dimethyl-5-sulfonic acid sodium salt, 4.5 mol% 5-t-butylisophthalic acid, and 100 mol% 1,10 decanediol, After adding 0.014 mol% of Ti (OBu) ₄ as a catalyst, the air in the container is decompressed by depressurization, and is further brought into an inert atmosphere with nitrogen gas, and refluxed at 180 ° C. for 6 hours with mechanical stirring. It was. Thereafter, the temperature was gradually raised to 220 ° C. by vacuum distillation and stirred for 2.5 hours. When the mixture became viscous, the molecular weight was confirmed by GPC. When the weight average molecular weight reached 11000, vacuum distillation was performed. Was stopped and air-cooled to obtain a crystalline polyester resin.

  The melting point of the obtained crystalline polyester resin was measured using a thermal analysis apparatus of a differential scanning calorimeter (manufactured by Mac Science: DSC3110, thermal analysis system 001) (hereinafter abbreviated as “DSC”). The measurement was performed from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C. per minute, and the melting point was analyzed by a method based on ASTM D3418-8. When measured by this method, the melting point was 80 ° C. The ester concentration was 0.078.

  Next, 80 parts by mass of this crystalline polyester resin and 587 parts by mass of deionized water were placed in a stainless beaker, placed in a warm bath, and heated to 95 ° C. When the crystalline polyester resin is melted, the mixture is stirred at 8000 rpm using a homogenizer (manufactured by IKA: Ultra Turrax T50). At the same time, dilute aqueous ammonia was added to adjust the pH to 7.0. Subsequently, the emulsion is dispersed while adding 20 parts by mass of an aqueous solution obtained by diluting 0.8 part by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK). Crystallinity having a solid content of 20% by mass. A polyester resin fine particle dispersion (1) was obtained.

The obtained resin fine particles were 210 nm when the number average particle diameter D _50n of the resin fine particles was measured with a laser diffraction particle size distribution analyzer (Horiba, LA-700). The melting point was measured in the same manner as described above. However, it had a clear peak, was 80 ° C., and measured for a weight average molecular weight (polystyrene conversion), it was 28000. The ester concentration was 0.078.

(Colorant dispersion).
-Cyan pigment (copper phthalocyanine B15: 3, manufactured by Dainichi Seika) 45 parts by mass-Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5 parts by mass-Ion-exchanged water 200 parts by mass Mixing and dissolving the above, homogenizer ( The mixture was dispersed for 10 minutes using IKA (Ultra Turrax) to obtain a colorant dispersion having a number average particle size of 170 nm.

(Release agent dispersion)
・ 45 parts by weight of paraffin wax (Nippon Seiwa Co., Ltd., HNP9, melting point: 77 ° C.) 5 parts by weight of cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku) ・ 200 parts by weight of ion-exchanged water The mixture is heated to 90 ° C. and sufficiently dispersed with a homogenizer (IKA, Ultra Turrax T50), and then dispersed with a pressure discharge type gorin homogenizer, the number average particle size is 200 nm, and the solid content is 24.3 mass. % Release agent dispersion.

<Example 1>
(Manufacture of toner).
Amorphous resin fine particle dispersion (1) 70 parts by weight Crystalline polyester resin dispersion (1) 20 parts by weight Colorant dispersion 12 parts by weight Release agent dispersion 16 parts by weight

  The above was placed in a round stainless steel flask, and ion-exchanged water was further added so that the solid content was 15% by mass, and the mixture was sufficiently mixed and dispersed with an Ultra Turrax T50. Next, 0.9 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Thereafter, the flask was heated to 47 ° C. with stirring in an oil bath for heating, and maintained at this temperature for 60 minutes, and then 20 parts by mass of the amorphous resin fine particle dispersion (1) was gradually added thereto.

  Thereafter, the growth was stopped by adjusting the pH in the system to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution. Next, 0.9 part by mass of styrene-based gel-type cationic ion exchange resin (manufactured by Organo Corporation, Amberlite IR120B Na) was added to 100 parts by mass of the aggregated particles, and contacted with stirring. Thereafter, the stainless steel flask was sealed, heated to 96 ° C. while continuing stirring using a magnetic seal, and held for 3 hours.

  After completion of the reaction, the reaction mixture was cooled and subjected to sieving with 20 μm to remove the ion exchange resin particles, and after further washing with filtration and ion exchange water, solid-liquid separation was performed by Nutsche suction filtration. This was further redispersed in 3 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate was 7.01, the electrical conductivity was 9.7 μS / cm, and the surface tension was 71.2 Nm, No. 6 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. This was dried at 40 ° C. and 1000 Pa or less for 12 hours to obtain toner particles.

  The toner particle size at this time was measured with a Coulter counter. The volume average particle size was 8.8 μm, the volume average particle size distribution index GSDv was 1.22, and the number average particle size distribution index GSDp was 1.28. Further, when the content of aluminum element having a depth of 0.3 μm from the surface of the toner was measured by the aforementioned X-ray photoelectron spectroscopic analysis, it was 0.021 atomic% and the content of sulfur element was 0.412 atoms. %, And the ratio (A / B) between the two was 0.051.

  Further, the acid value of the toner was 4.4 mg KOH / g, and the value obtained by dividing the acid value AV of the toner by the volume average particle diameter D50v was 0.5. Further, the Z average molecular weight Mz of the toner was measured by GPC and found to be 115000.

(Preparation of developer)
To 50 parts by mass of the produced toner particles, 1.0 part by mass of hydrophobic silica (TS720, manufactured by Cabot) and 2.0 parts by mass of hydrophobic silica (X24, manufactured by Shin-Etsu Chemical Co., Ltd.) are added, and the sample mill is used. Blended. This is weighed so that the toner concentration becomes 5% by mass with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by mass of polymethacrylate (manufactured by Soken Chemical Co., Ltd.), and stirred and mixed with a ball mill for 5 minutes. (1) was prepared.

(Evaluation of toner)
The developer (1) is loaded in a color copier DocuCentreColor400 (Fuji Xerox Co., Ltd.) remodeled machine, adjusted to have a toner applied amount of 13.0 g / m ^2, and an image is printed. Fixing was performed at a nip width of 6.5 mm, a fixing speed of 180 mm / sec, and a fixing temperature of 120 ° C. using a fixing roll surface (PFA coating, oilless specification).

-Image glossiness-
The image gloss was measured based on JIS Z 8741 using a Gloss Meter GM-26D (Murakami Color Research Laboratory) at an incident angle of 75 °. The surface glossiness of the fixed image obtained from a gloss meter was 102%.
In addition, evaluation of image glossiness was ranked as follows.
A: Gloss is 100% or more B: Gloss is in the range of 90-99% B: Gloss is in the range of 80-89% X: Gloss is in the range of 79% or less

-Uneven gloss-
The fixed image was visually evaluated for uneven gloss according to the following criteria.
A: Image roughness is not observed at all.
○: Image roughness is hardly observed.
Δ: Image roughness is slightly observed.
X: Image roughness is clearly observed.
The above results are summarized in Table 1.

<Example 2>
-Resin fine particle dispersion (1) 60 parts by weight-Crystalline polyester resin dispersion (1) 40 parts by weight-Colorant dispersion 12 parts by weight-Release agent dispersion 16 parts by weight

In the production of the toner of Example 1, toner particles were produced in the same manner as in Example 1 except that the blending was as described above, and 0.6 parts by mass of ion exchange resin particles were added after holding at 47 ° C. for 40 minutes.
The toner particle size at this time was measured with a Coulter counter. As a result, the volume average particle size was 6.0 μm, the volume average particle size distribution index GSDv was 1.25, and the number average particle size distribution index GSDp was 1.28. Further, when the aluminum element content having a depth of 0.2 μm from the surface of the toner was measured by the above-mentioned X-ray photoelectron spectroscopic analysis, it was 0.049 atomic%, and the sulfur element content was 0.407 atoms. %, And the ratio (A / B) between them was 0.12.

  Further, the acid value of the toner was 30.0 mgKOH / g, and the value obtained by dividing the acid value AV of the toner by the volume average particle diameter D50v was 5.0. Further, the Z average molecular weight Mz of the toner was measured by GPC and found to be 50000.

  For the toner particles, a developer was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are summarized in Table 1.

<Example 3>
-Resin fine particle dispersion (1) 60 parts by weight-Crystalline polyester resin dispersion (1) 40 parts by weight-Colorant dispersion 12 parts by weight-Release agent dispersion 16 parts by weight

In the production of the toner of Example 1, toner particles were produced in the same manner as in Example 1 except that the blending was as described above, and 0.3 parts by mass of ion exchange resin particles were added after holding at 47 ° C. for 20 minutes.
The toner particle size at this time was measured with a Coulter counter. As a result, the volume average particle size was 3.2 μm, the volume average particle size distribution index GSDv was 1.23, and the number average particle size distribution index GSDp was 1.25. Further, when the content of aluminum element having a depth of 0.4 μm from the toner surface was measured by the above-mentioned X-ray photoelectron spectroscopic analysis, it was 0.076 atomic%, and the content of sulfur element was 0.40 atom. %, And the ratio (A / B) between them was 0.19.

  The acid value of the toner was 28.8 mgKOH / g, and the value obtained by dividing the acid value AV of the toner by the volume average particle diameter D50v was 9.0. Further, the Z average molecular weight Mz of the toner was measured by GPC and found to be 30500.

  For the toner particles, a developer was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are summarized in Table 1.

<Example 4>
Resin fine particle dispersion (1) 60 parts by weight Crystalline polyester resin dispersion (1) 40 parts by weight Colorant dispersion 12 parts by weight Release agent dispersion 16 parts by weight In the production of the toner of Example 1, Toner particles were produced in the same manner as in Example 1 except that the blending was as described above, and 0.3 parts by mass of ion exchange resin particles were added after holding at 47 ° C. for 60 minutes.

The toner particle size at this time was measured with a Coulter counter. The volume average particle size was 8.8 μm, the volume average particle size distribution index GSDv was 1.25, and the number average particle size distribution index GSDp was 1.25. Further, when the content of aluminum element having a depth of 0.4 μm from the surface of the toner was measured by the aforementioned X-ray photoelectron spectroscopic analysis, it was 0.07 atomic%, and the content of sulfur element was 0.47 atoms. %, And the ratio (A / B) between them was 0.15.
The acid value of the toner was 3.52 mg KOH / g, and the value obtained by dividing the acid value AV of the toner by the volume average particle diameter D50v was 0.4. Further, the Z average molecular weight Mz of the toner was measured by GPC and found to be 122,000.

  For the toner particles, a developer was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are summarized in Table 1.

<Example 5>
Resin fine particle dispersion (1) 75 parts by weight Crystalline polyester resin dispersion (1) 25 parts by weight Colorant dispersion 12 parts by weight Release agent dispersion 16 parts by weight In the production of the toner of Example 1, Toner particles were produced in the same manner as in Example 1 except that the blending was as described above, and 0.8 parts by mass of ion exchange resin particles were added after holding at 47 ° C. for 20 minutes.

The toner particle size at this time was measured with a Coulter counter. As a result, the volume average particle size was 3.1 μm, the volume average particle size distribution index GSDv was 1.24, and the number average particle size distribution index GSDp was 1.24. Further, when the content of aluminum element having a depth of 0.25 μm from the surface of the toner was measured by the above-mentioned X-ray photoelectron spectroscopic analysis, it was 0.022 atomic%, and the content of sulfur element was 0.37 atom. %, And the ratio (A / B) between the two was 0.06.
Further, the acid value of the toner was 37.2 mgKOH / g, and the value obtained by dividing the acid value AV of the toner by the volume average particle diameter D50v was 12. Further, the Z average molecular weight Mz of the toner was measured by GPC and found to be 25000.

  For the toner particles, a developer was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are summarized in Table 1.

<Example 6>
Resin fine particle dispersion (1) 60 parts by weight Crystalline polyester resin dispersion (1) 40 parts by weight Colorant dispersion 12 parts by weight Release agent dispersion 16 parts by weight In the production of the toner of Example 1, Toner particles were produced in the same manner as in Example 1 except that the blending was as described above, and 0.4 parts by mass of ion exchange resin particles were added after holding at 47 ° C. for 20 minutes.

The toner particle size at this time was measured with a Coulter counter. As a result, the volume average particle size was 2.8 μm, the volume average particle size distribution index GSDv was 1.24, and the number average particle size distribution index GSDp was 1.28. Further, when the content of aluminum element having a depth of 0.25 μm from the surface of the toner was measured by the above-mentioned X-ray photoelectron spectroscopic analysis, it was 0.063 atomic%, and the content of sulfur element was 0.42 atom. %, And the ratio (A / B) between them was 0.15.
Further, the acid value of the toner was 14 mg KOH / g, and the value obtained by dividing the acid value AV of the toner by the volume average particle diameter D50v was 5.0. Further, the Z average molecular weight Mz of the toner was measured by GPC and found to be 25000.

  For the toner particles, a developer was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are summarized in Table 1.

<Example 7>
Resin fine particle dispersion (1) 60 parts by weight Crystalline polyester resin dispersion (1) 40 parts by weight Colorant dispersion 12 parts by weight Release agent dispersion 16 parts by weight In the production of the toner of Example 1, Toner particles were produced in the same manner as in Example 1 except that the blending was as described above, and 0.4 parts by mass of ion exchange resin particles were added after holding at 47 ° C. for 60 minutes.

The toner particle size at this time was measured with a Coulter counter. As a result, the volume average particle size was 8.0 μm, the volume average particle size distribution index GSDv was 1.27, and the number average particle size distribution index GSDp was 1.28. Further, when the content of aluminum element having a depth of 0.30 μm from the surface of the toner was measured by the above-mentioned X-ray photoelectron spectroscopic analysis, it was 0.04 atomic%, and the content of sulfur element was 0.4 atom. %, And the ratio (A / B) between them was 0.1.
Further, the acid value of the toner was 40 mgKOH / g, and the value obtained by dividing the acid value AV of the toner by the volume average particle diameter D50v was 5.0. Further, the Z average molecular weight Mz of the toner was measured by GPC and found to be 122,000.

  For the toner particles, a developer was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are summarized in Table 1.

<Comparative Example 1>
Resin fine particle dispersion (1) 60 parts by weight Crystalline polyester resin dispersion (1) 40 parts by weight Colorant dispersion 12 parts by weight Release agent dispersion 16 parts by weight In the production of the toner of Example 1, Toner particles were produced in the same manner as in Example 1, except that the blending was as described above, and 0.1 parts by mass of ion exchange resin particles were added after holding at 47 ° C. for 20 minutes.

The toner particle size at this time was measured with a Coulter counter. As a result, the volume average particle size was 2.9 μm, the volume average particle size distribution index GSDv was 1.32 and the number average particle size distribution index GSDp was 1.34. Further, when the content of aluminum element having a depth of 0.30 μm from the toner surface was measured by the above-mentioned X-ray photoelectron spectroscopy, it was 0.082 atomic% and the content of sulfur element was 0.37 atom. %, And the ratio (A / B) between them was 0.22.
The acid value of the toner was 34.8 mgKOH / g, and the value obtained by dividing the acid value AV of the toner by the volume average particle diameter D50v was 12.0. Further, the Z average molecular weight Mz of the toner was measured by GPC and found to be 122,000.

  For the toner particles, a developer was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are summarized in Table 1.

<Comparative example 2>
Resin fine particle dispersion (1) 60 parts by weight Crystalline polyester resin dispersion (1) 40 parts by weight Colorant dispersion 12 parts by weight Release agent dispersion 16 parts by weight In the production of the toner of Example 1, Toner particles were produced in the same manner as in Example 1 except that the blending was as described above and 1.1 parts by mass of ion exchange resin particles were added after holding at 47 ° C. for 70 minutes.

The toner particle size at this time was measured with a Coulter counter. As a result, the volume average particle size was 9.5 μm, the volume average particle size distribution index GSDv was 1.31, and the number average particle size distribution index GSDp was 1.33. Further, when the content of aluminum element having a depth of 0.40 μm from the toner surface was measured by the above-mentioned X-ray photoelectron spectroscopy, it was 0.019 atomic%, and the content of sulfur element was 0.42 atom. %, And the ratio (A / B) between the two was 0.045.
The acid value of the toner was 2.85 mgKOH / g, and the value obtained by dividing the acid value AV of the toner by the volume average particle diameter D50v was 0.3. Further, the Z average molecular weight Mz of the toner was measured by GPC and found to be 122,000.

  For the toner particles, a developer was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are summarized in Table 1.

<Comparative Example 3>
Resin fine particle dispersion (2) 75 parts by weight Crystalline polyester resin dispersion (1) 25 parts by weight Colorant dispersion 12 parts by weight Release agent dispersion 16 parts by weight In the production of the toner of Example 1, Toner particles were produced in the same manner as in Example 1 except that the blending was as described above, and 1.1 parts by mass of ion exchange resin particles were added after holding at 47 ° C. for 60 minutes.

The toner particle size at this time was measured with a Coulter counter. As a result, the volume average particle size was 8.7 μm, the volume average particle size distribution index GSDv was 1.24, and the number average particle size distribution index GSDp was 1.25. Further, when the content of aluminum element having a depth of 0.40 μm from the surface of the toner was measured by the above-mentioned X-ray photoelectron spectroscopic analysis, it was 0.05 atomic%, and the content of sulfur element was 0.23 atom. %, And the ratio (A / B) between them was 0.22.
The acid value of the toner was 13.1 mg KOH / g, and the value obtained by dividing the acid value AV of the toner by the volume average particle diameter D50v was 1.5. Further, the Z average molecular weight Mz of the toner was measured by GPC and found to be 119000.

  For the toner particles, a developer was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are summarized in Table 1.

<Comparative example 4>
Resin fine particle dispersion (3) 80 parts by weight Crystalline polyester resin dispersion (1) 20 parts by weight Colorant dispersion 12 parts by weight Release agent dispersion 16 parts by weight In the production of the toner of Example 1, Toner particles were produced in the same manner as in Example 1 except that the blending was as described above, and 0.6 parts by mass of ion exchange resin particles were added after holding at 47 ° C. for 20 minutes.

The toner particle size at this time was measured with a Coulter counter. As a result, the volume average particle size was 3.4 μm, the volume average particle size distribution index GSDv was 1.25, and the number average particle size distribution index GSDp was 1.26. Further, when the content of aluminum element having a depth of 0.30 μm from the toner surface was measured by the above-mentioned X-ray photoelectron spectroscopic analysis, it was 0.05 atomic%, and the content of sulfur element was 1.11 atoms. %, And the ratio (A / B) between the two was 0.045.
The acid value of the toner was 30.6 mgKOH / g, and the value obtained by dividing the acid value AV of the toner by the volume average particle diameter D50v was 9.0. Further, the Z average molecular weight Mz of the toner was measured by GPC and found to be 30500.

  For the toner particles, a developer was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are summarized in Table 1.

<Comparative Example 5>
Resin fine particle dispersion (3) 75 parts by weight Crystalline polyester resin dispersion (1) 25 parts by weight Colorant dispersion 12 parts by weight Release agent dispersion 16 parts by weight In the production of the toner of Example 1, Toner particles were produced in the same manner as in Example 1 except that the blending was as described above, and 0.1 parts by mass of ion exchange resin particles were added after holding at 47 ° C. for 70 minutes.

The toner particle size at this time was measured with a Coulter counter. As a result, the volume average particle size was 8.9 μm, the volume average particle size distribution index GSDv was 1.23, and the number average particle size distribution index GSDp was 1.25. Further, when the content of aluminum element having a depth of 0.35 μm from the toner surface was measured by the X-ray photoelectron spectroscopic analysis described above, it was 0.082 atomic% and the content of sulfur element was 0.68 atom. %, And the ratio (A / B) between the two was 0.012.
Further, the acid value of the toner was 14.3 mgKOH / g, and the value obtained by dividing the acid value AV of the toner by the volume average particle diameter D50v was 1.6. Further, the Z average molecular weight Mz of the toner was measured by GPC and found to be 119000.

  For the toner particles, a developer was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are summarized in Table 1.

<Comparative Example 6>
Resin fine particle dispersion (2) 80 parts by weight Crystalline polyester resin dispersion (1) 20 parts by weight Colorant dispersion 12 parts by weight Release agent dispersion 16 parts by weight In the production of the toner of Example 1, Toner particles were produced in the same manner as in Example 1 except that the blending was as described above, and 1.1 parts by mass of ion exchange resin particles were added after holding at 47 ° C. for 20 minutes.

The toner particle size at this time was measured with a Coulter counter. As a result, the volume average particle size was 3.3 μm, the volume average particle size distribution index GSDv was 1.27, and the number average particle size distribution index GSDp was 1.27. Further, when the content of aluminum element having a depth of 0.34 μm from the toner surface was measured by the above-mentioned X-ray photoelectron spectroscopic analysis, it was 0.019 atomic%, and the content of sulfur element was 0.16 atoms. %, And the ratio (A / B) between the two was 0.012.
The acid value of the toner was 28.7 mgKOH / g, and the value obtained by dividing the acid value AV of the toner by the volume average particle diameter D50v was 8.7. Further, the Z average molecular weight Mz of the toner was measured by GPC and found to be 30500.

  For the toner particles, a developer was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are summarized in Table 1.

As shown in Table 1, when the toner of the present invention of the example is used, in addition to low-temperature fixability, even when oilless fixing is performed with a PFA-coated fixing roll, high quality without gloss unevenness is obtained. A good image was obtained.
On the other hand, with the toner of the comparative example, the low-temperature fixability can be maintained to some extent, but a high gloss and non-uniform image could not be obtained.

Claims (5)

In the electrostatic charge image developing toner containing at least a binder resin and a colorant,
The binder resin is polymerized using a chain transfer agent containing elemental sulfur, and includes a resin containing a carboxyl group,
An aggregating step of forming aggregated particles in the presence of aluminum ions using a mixed solution comprising a resin fine particle dispersion in which fine particles of the binder resin are dispersed and a colorant dispersion in which the colorant is dispersed; and adjusting the pH to 9 to 10 to stop the growth of the aggregated particles, and then adding ion-exchange resin particles and stirring to contact the aggregated particles. Obtained by
The ratio (A / B) of the aluminum element content (A) and the sulfur element content (B) contained in the vicinity of the surface of the toner measured by X-ray photoelectron spectroscopy is 0.05 to 0.20. And the aluminum element content (A) in the range of 0.01 to 0.5 μm in depth from the surface is in the range of 0.02 to 0.08 atomic%. A toner for developing an electrostatic charge image.   The volume average particle diameter D50v of the toner is in the range of 3 to 9 μm, the volume particle size distribution index GSDv is 1.15 or more and less than 1.3, and the acid value AV of the toner is divided by the volume average particle diameter D50v ( 2. The electrostatic image developing toner according to claim 1, wherein AV / D50v) is in the range of 0.5 to 10. Electrostatic image developer which comprises a toner according to claim 1 or 2. A method for producing an electrostatic charge image developing toner according to claim 1 or 2 ,
At least a resin fine particle dispersion in which resin fine particles having a volume average particle size of 1 μm or less and a colorant dispersion are mixed, and this is formed into an agglomeration step in the presence of aluminum ions; 10 to 10 to stop the growth of the aggregated particles, add ion exchange resin particles, agitate and contact the aggregated particles, and the aggregated particles at a temperature equal to or higher than the melting point of the resin fine particles. And a fusing step of fusing and fusing to each other, and a method for producing a toner for developing an electrostatic charge image. A latent image forming step of forming an electrostatic image on the surface of the latent image carrier, a developing step of developing the electrostatic image with a developer containing toner to form a toner image, and transferring the toner image to the surface of the transfer target In an image forming method including a transfer step, and a fixing step of thermally fixing the transferred toner image to the surface of the recording medium,
The toner, image forming method, which is a toner according to claim 1 or 2.