JP6789697B2 - toner - Google Patents

Description

The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, a toner jet recording method, or the like.

In recent years, the usage environment of image forming devices such as copiers and printers has been diversified with the expansion of the market. For this reason, the image quality of toner is not inferior even after use in an environment where the temperature and humidity are not properly maintained and after long-term storage, and the quality can be maintained even after the temperature difference between day and night during sea transportation. , Heat-resistant storage performance is required.
Focusing on the fixing process from the viewpoint of requesting higher image quality, the problem that has become apparent with the diversification of the purpose of use and the environment of use is the offset of the rear end of the high print rate image in a high temperature and high humidity environment. There's a problem.
The reason why the offset is stricter in the high print rate image than in the low print rate image is probably due to the amount of heat given to the toner layer. The higher the print rate, the more heat from the fuser is dispersed in more toner, and the more toner tends to be insufficiently melted. That is, the fixing failure is likely to occur.
Generally, in the fixing step, when the paper on which the unfixed image formed by the toner is formed passes through the fuser (particularly, the passing portion is hereinafter referred to as a fixing nip), heat and pressure are applied to the paper. The toner is fixed to the surface.
Here, since the amount of heat given from the fixing nip portion tends to be smaller toward the rear end of the paper, the fixing property tends to be disadvantageous at the rear end of the image.
Further, by lowering the pressure of the fixing nip, the deformation of the toner becomes insufficient and the offset of the rear end (hereinafter referred to as the rear end offset) is likely to occur.
Further, a technique for preventing wrapping of a transfer material by defining an interfacial adhesion force with polytetrafluoroethylene and an internal cohesive force is disclosed. (Patent Document 3) The toner described in Patent Document 3 is excellent in rear end offset resistance in a normal fixing machine configuration. However, when an image with a high printing rate is output at high speed in addition to further reducing the pressure of the fixing nip, the meltability with a small amount of pressure and heat is poor, and the rear end offset resistance is still insufficient.
In particular, the above offset phenomenon tends to be remarkable in paper left in a high temperature and high humidity environment. This is probably because when the paper that has been left unattended and contains a lot of water passes through the fuser, the toner layer on the paper is generated by receiving heat from the fuser at the fixing nip and generating water vapor from the paper. Is presumed to be due to being pushed toward the fixing film side.
In addition to the above-mentioned problem of rear end offset, further energy saving is always required for copiers and printers, and there is an urgent need to improve the low temperature fixing performance of toner. Therefore, in recent years, a technique related to crystalline polyester, which can instantly melt at the time of fixing to reduce the melt viscosity of the toner, has been developed.
However, crystalline polyester has the property of being easily compatible with the binder resin, and crystals that are compatible with the binder resin when stored in a harsh environment at high temperatures, especially when transporting toner. The property polyester easily exudes to the surface of the toner particles. As a result, the crystalline polyester-containing toner has a problem in storage stability in a harsh environment. Further, since crystalline polyester easily melts when heated, adhesion to the fixing film when the toner is plasticized is also an issue.
When the fixing film is contaminated, the pressure roller is also contaminated, causing stains on the back of the paper during printing.
Patent Document 1 is a precedent example for confirming the adhesive force of toner. Here, the adhesive force between toners is observed with a tacking tester, but it is not carried out in a system containing crystalline polyester. In the system containing crystalline polyester, the viewpoint of adhesive force differs depending on the material of the probe of the tacking tester. It is considered that either the binding force between the toners or the adhesive force between the toners acts predominantly depending on the combination of the probe and the toner. Speaking of the toner handled in Patent Document 1, if the material of the probe is stainless steel, the binding force between the toners becomes dominant and the adhesive force between the toner and the probe cannot be observed.
In the device configuration of the tacking test in Patent Document 2, tacking is performed after heating for a long time, and it is not possible to observe the adhesive force due to instantaneous heating assuming an image forming device.
Similarly, in the device configuration of the tacking test in Patent Document 3, instantaneous heating cannot be performed, and a correlation is observed between the measured adhesive force and the rear end offset property, especially in an evaluation machine having a high process speed. I couldn't.

Japanese Unexamined Patent Publication No. 2010-282146 JP-A-2014-71332 Japanese Unexamined Patent Publication No. 2006-330706

An object of the present invention has been made in view of the above problems, and it is an object of the present invention to provide a toner using a crystalline polyester that maintains developability even when exposed to a harsh environment. Further, it is possible to obtain a high-quality image in which the occurrence of rear end offset of a high print rate image is suppressed even in a high temperature and high humidity environment, and to provide a toner having excellent film contamination resistance.

As a result of diligent studies, the present inventors adjusted the instantaneous melting characteristics of the toner to a certain value or less under the condition of giving an instantaneous amount of heat using a tacking tester. At the same time, the present invention has been completed by finding a means for solving the above problems by adjusting the amount of crystalline polyester to be added and the crystallinity of the crystalline material in the produced toner within a certain range. The crystalline material in the present invention is a crystalline polyester and a wax.
That is, the toner of the present invention is a toner having toner particles containing a binder resin, a colorant, a wax and a crystalline polyester.
In the cross section of the toner, the crystalline polyester forms a plurality of domains, and the number average diameter of the major axis of each domain is 50 nm or more and 300 nm or less.
The number of the domains in the cross section of the toner is 8 or more and 500 or less.
The binding resin is mainly composed of a styrene acrylic resin.
The stress integral value measured using a tacking tester in which the part of the probe that comes into contact with the toner is polytetrafluoroethylene is 5.0 g when the probe temperature is 200 ° C. and the pressing and holding time with the toner is 0.05 s.・ It is less than m / sec and
The crystalline polyester is contained in an amount of 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.
The total crystallinity of the wax and the crystalline polyester is 70% or more.

According to the present invention, it is possible to provide a toner that maintains developability even when exposed to a harsh environment. Further, even in a high temperature and high humidity environment, it is possible to obtain a high-quality image in which the occurrence of rear end offset of a high print rate image is suppressed, and it is possible to provide a toner having excellent film contamination resistance.

It is a figure which shows the shape of a domain. It is a figure which shows the existence state of a domain. It is a schematic cross-sectional view which shows an example of the image forming apparatus which can preferably use the toner of this invention. It is a schematic diagram of the tacking tester for measuring the integral value of stress.

The toner of the present invention is a toner having toner particles containing a binder resin, a colorant, a crystalline polyester, and a wax, and the toner has an amount of crystalline polyester added of 5 parts by mass with respect to 100 parts by mass of the binder resin. 200 parts or more and 30 parts by mass or less, the total degree of crystallization of the wax and the crystalline polyester is 70% or more, and it is measured using a tacking tester using a polytetrafluoroethylene probe. The integrated value of the stress of the toner when the pressing and holding time with the toner at ° C. is 0.05 s is 5.0 g · m / sec or less, more preferably 4.0 g · m / sec or less. And.

The reason why the present invention has solved the above problems has not been clarified yet, but the present inventors consider it as follows.

First, film contamination occurs when toner with strong adhesiveness adheres to the fixing film. When film contamination occurs, the adhered toner moves to the pressure roller side, and finally contaminates the back side of the media, so-called paper back stain. Here, it is presumed that the degree of contamination of the fixing film is dominated by the adhesive force of the plastic toner to the fixing film when the toner receives heat.

Therefore, in order to obtain a toner having excellent film stain resistance, it is conceivable to suppress the thermoplasticity of the toner surface, but this has a trade-off relationship with the low temperature fixability. Therefore, as a method of improving film contamination while maintaining low-temperature fixability, when the toner receives heat momentarily from the fixing film and is melted and deformed, the wax inside the toner quickly exudes from the toner, and between the film and the toner. I presume that it is important to improve the releasability of the film.

Therefore, using a tacking tester, the integrated value of the stress between the polytetrafluoroethylene material probe and the toner was measured, and by controlling this value, film contamination could be suppressed. Polytetrafluoroethylene is used assuming a fluorine-based resin with low adhesive strength used in the fixing film. Generally, as the fixing film, a fluororesin such as a copolymer of polytetrafluoroethylene and perfluoroalkyl ether is used. Here, the polymerization ratio of perfluoroalkyl ether is often smaller than that of polytetrafluoroethylene, and it is presumed that the symmetry of the carbon-fluorine bond predominantly contributes from the viewpoint of low adhesion, which we will focus on this time. ing. Therefore, even polytetrafluoroethylene alone has symmetry of carbon-fluorine bond, so that it can be approximated to the same adhesiveness as a copolymer with perfluoroalkyl ether. Further, even when another fixing member (material having low adhesion to toner) is used for the probe, the value of the relative adhesion force of various toners to the probe does not change. Therefore, by confirming the effect by measurement with a polytetrafluoroethylene probe, it is considered that the same effect will be exhibited in the system changed to other fixing members. In the present invention, by using a probe made of polytetrafluoroethylene material, it was possible to confirm a significant difference that could not be detected when a probe having high adhesion to toner such as stainless steel was used. That is, the adhesive force between the toner and the probe, which has a correlation with the content of crystalline polyester, was found in this case.

The tacking tester used in the present invention is capable of instantaneous heating, and is characterized in that the thermal history when the media passes through the nip in the actual machine can be faithfully reproduced. As a result, a high correlation could be found between the measured stress integral value and the actual machine evaluation result.

The details of the specific measurement conditions of the tacking tester will be described later, but will be described below.
Pressing temperature: 200 ° C
Pressing and holding time: 0.05s
Pressing pressure: 19.7 kg ・ m / sec

That is, it was found that the integrated value of the stress having a strong correlation with the film contamination can be obtained by measuring under the above-mentioned conditions.

The pressing temperature can be considered as the temperature of the fixing film at the fixing nip portion. Further, although the stress integral value measured by the pressing temperature used changes, the relative value of the stress integral value of various toners in each temperature zone does not change. Therefore, even if the temperature condition is changed, it can be evaluated by the measurement under the above condition.

The pressing holding time was set to 0.05 s in accordance with the nip passing time when the process speed was 250 mm / sec and the nip width was 1.25 cm, assuming a speed-increasing machine. Further, although the stress integral value measured by the pressing holding time used changes, the relative value of the stress integral value of various toners at each holding time does not change. Therefore, even if the holding time is changed, it can be evaluated by the measurement under the above conditions.

The pressing pressure was set to 19.7 kg · m / sec, assuming a relatively light pressure configuration within a range in which the fixing can be satisfied after setting the pressing temperature and the pressing holding time. Further, although the stress integral value measured by the pressing pressure used changes, the relative value of the stress integral value of various toners at each pressure does not change. Therefore, even if the pressure is changed, it can be evaluated by the measurement under the above conditions.

It is essential to adjust the crystallinity of the crystalline material of the toner within a certain range in order to improve the storage stability. If the crystallinity is too low, the amount of compatible components of the crystalline material in the binder resin increases, and the exudation of the crystalline material onto the toner surface in a harsh environment is likely to be promoted, resulting in toner aggregation and external addition. There is a concern that the developability may be deteriorated due to the change in the fixed state of the agent.

At this time, crystalline polyester and wax are present as a breakdown of the crystalline material, but these materials are also likely to exude in a harsh environment when they are compatible with the binder resin. In the study by the present inventors, the total amount of exudation correlates with the degree of deterioration of the toner quality, so that the overall crystallinity of the wax contained in the toner and the crystalline polyester is increased, that is, It is important that the crystallinity is 70% or more. It is more preferably 75% or more, still more preferably 80% or more.

The method for controlling the crystallinity of the crystalline material can be controlled by the type and number of copies of the crystalline material and the combination of the crystalline polyester and the wax used in combination. Further, the crystallinity can be controlled by the cooling rate in the cooling process in the toner manufacturing process.

If the number of copies of the crystalline material is large, the number of components that are compatible with the binder resin increases, so that the crystallinity decreases. In addition, although the structural tendency is unknown, there is a significant difference in the crystallinity depending on the type of crystalline polyester. In addition, if the crystalline polyester has a structure similar in molecular structure to the wax used in combination, the wax acts as a nucleating agent to increase the crystallinity of the entire crystalline material including the crystalline polyester. It became.

Further, in the present invention, when the crystallinity of the crystalline material is controlled, the crystallinity can be easily controlled within the preferable range of the present invention by using the method described below.

First, after polymerizing the polymerizable monomer to obtain resin particles, the temperature of the dispersion in which the resin particles are dispersed in an aqueous medium is raised to a temperature exceeding the melting points of the crystalline polyester and wax. However, this operation is not necessary when the polymerization temperature exceeds the melting point.

In the present invention, attention will be paid to a method for producing a toner for the purpose of crystallizing a crystalline substance such as a crystalline polyester or a wax, particularly a crystalline polyester. For example, when toner is produced by a pulverization method, suspension polymerization, or emulsion polymerization, it often includes a step of raising the temperature to a temperature at which the crystalline polyester or wax melts and then cooling it to room temperature.

Considering the cooling process, the crystalline polyester liquefied by raising the temperature slows down the molecular motion as the temperature decreases, and crystallization starts when the temperature reaches near the crystallization temperature. Further cooling promotes crystallization and completely solidifies at room temperature. According to the study by the present inventors, it was found that the crystallinity of the crystalline substance differs depending on the cooling rate.

Specifically, when the crystalline polyester or wax is cooled from a sufficiently high temperature (for example, 100 ° C.) at which it melts to near the crystallinity temperature of the crystalline substance at a high cooling rate, the crystallinity of the contained crystalline substance is increased. It tended to increase. Further, when the cooling rate is sufficiently high, the crystallinity can be easily controlled within the preferable range of the present invention.

On the other hand, if the cooling rate is slow, the crystallinity of the crystalline polyester or wax tends to decrease during the gradual cooling, and the crystallinity tends to be compatible with the binder resin. In this case, the small domains of the crystalline polyester tend to be difficult to form, and the wax tends to be difficult to form the larger large domains. As a result, the binder resin is easily softened, and it becomes difficult to suppress the occurrence of fog after being left in a harsh environment of high temperature, and it is also difficult to suppress the occurrence of the rear end offset.

More specifically, the state in which the cooling rate is sufficiently high is the case where the cooling rate is 50.0 ° C./min or more, and particularly for the purpose of crystallizing the crystalline polyester, 100 is preferable. .0 ° C./min or higher, more preferably 150.0 ° C./min or higher. On the contrary, the state where the cooling rate is sufficiently slow is the case where the cooling is performed at a rate sufficiently slower than 10.0 ° C./min, for example, 0.5 ° C./min or more and 5.0 ° C./min or less. Cooling rate can be mentioned.

Further, it is also preferable to perform the annealing treatment in the vicinity of the crystallinity temperature of the crystalline substance (specifically, in the range of the crystallization temperature ± 5 ° C.) from the viewpoint of increasing the crystallinity of the crystalline substance.

The holding time is preferably 30 minutes or more, more preferably 60 minutes or more, and further preferably 100 minutes or more. The upper limit of the holding time is about 24 hours or less in relation to the production efficiency. It is preferable to hold the substance for a long time because it is easy to increase the crystallinity of the crystalline substance.

Regarding the amount of crystalline polyester added, the amount of crystalline polyester added to the toner is 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin. As a result, in the present invention, the amount of crystalline polyester that is compatible with the binder resin is suppressed, and low-temperature fixability is achieved by improving thermoplasticity without oozing out in a harsh environment or manifesting adhesion to a fixing film.

If the amount of the crystalline polyester added is less than 5 parts by mass with respect to 100 parts by mass of the binder resin, the plasticity of the toner at the time of heat bonding is remarkably lost, and it is considered that the toner is inferior in low temperature fixability. Further, when the amount of crystalline polyester added is more than 30 parts by mass with respect to 100 parts by mass of the binder resin, the low temperature fixability is excellent, but the compatible components in the binder resin increase, and the crystalline polyester in a harsh environment It is presumed that the exudation of plastic will increase significantly. As a result, the composition of the toner surface fluctuates, which affects the chargeability and the like, which may cause image harmful effects such as fog.

For the above reasons, if the above conditions can be satisfied, it is possible to obtain a toner having good low-temperature fixability and excellent film stain resistance while maintaining storage stability in a harsh environment. The heading has completed the present invention.

Hereinafter, the present invention will be described in detail.

In the present invention, the integrated value of the stress of the toner measured using a tacking tester when the probe temperature is 200 ° C. and the pressing and holding time with the toner is 0.05 s is 5.0 g · m / sec or less. It is important that the temperature is 4.0 g · m / sec or less, more preferably 4.0 g · m / sec or less. According to the study by the present inventors, when the integrated stress value is higher than 5.0 g · m / sec, the adhesive force with the fixing film at the time of melting the toner is strong, so that the film contamination tends to occur easily. Here, with the aim of improving low-temperature fixability, conventional toner containing a certain amount or more of crystalline polyester has a stress integral value higher than 5.0 g · m / sec, so there is a concern that film stain resistance is low. ..

Therefore, in the present invention, it has been found that even when a certain amount or more of crystalline polyester is contained, the value of the stress integral value can be controlled to be less than a certain amount by controlling the structure inside the toner. As for the stress integral value, the lower the value, the better the film contamination, so the lower limit is not set.

As a method of controlling the integral value of the stress of the toner, in addition to adjusting the amount and type of the binder resin, the crystalline polyester, and the wax, it is possible to control the domain structure of the crystalline material in the toner. ..

Regarding the adjustment of the amount and type of the binder resin, crystalline polyester, and wax, the stress integral value between the toner and the fixing film is controlled within the scope of the present invention by controlling the crystallinity of the crystalline material described above. is there. That is, the higher the crystallinity, the smaller the amount of crystalline material that is compatible with the binder resin. Since this compatible component is considered to be the main component that promotes adhesion to the film during heating, it is presumed that the adhesion to the film was suppressed by increasing the crystallinity.

In the toner of the present invention, it is preferable that each crystalline material has the following structure.

In the toner of the present invention, it is preferable that the crystalline polyester forms a plurality of domains in the toner cross section observed by a transmission electron microscope (TEM) in which the toner is dyed with ruthenium. Further, it is preferable that the number average diameter of the domains is 50 nm or more and 300 nm or less, and the number of the domains in the toner cross section is 8 or more and 500 or less.

By performing a ruthenium dyeing treatment on the cross section of the toner and observing it with a TEM, it is possible to observe the lamellae of the crystalline polyester. One shape that constitutes this lamella is called a domain. That is, in the present invention, it is preferable that the domains of the crystalline polyester form a plurality of relatively small domains in the toner as in the above-mentioned shape. The state in which the domain exists inside the toner in this way is called "domain is dispersed". When the toner receives the heat of the fuser and exceeds the melting point of the crystalline polyester, the domains dispersed inside the toner are instantly softened, but the dispersed domains soften the entire toner. It becomes easier and the fixability is greatly improved.

In the toner of the present invention, it is preferable that the domain of the crystalline polyester is present in a region at a depth of 25% with respect to the particle size of the toner cross section from the surface of the toner by 60% by number or more.

When the domain is present in a region having a depth of 25% with respect to the particle size of the toner cross section from the surface of the toner by 60% by number or more, as shown in FIG. 2, all domains are present in a region near the toner surface. It means that there are 60% or more of the numbers. Since 60% or more of the domains are present near the toner surface in this way, the amount of the domains of the crystalline polyester effective for low temperature fixability can be secured. In the present invention, the ratio (number%) of the domains of the crystalline polyester existing in the region at a depth of 25% with respect to the particle size of the toner cross section from the surface of the toner is hereinafter referred to as "25% ratio".

Further, in order to further suppress the adhesive force between the toner and the fixing film in the toner of the present invention, the wax forms a domain in the toner cross section. Further, it is preferable that the total area of the wax domain with respect to the area of the toner cross section is 10.0 area% or more and 50.0 area% or less.

By forming the domain of the wax, when the toner is excessively melted and deformed at the time of fixing, the wax is eluted from the toner and the adhesion of the toner to the fixing film can be suppressed. Further, it is presumed that the melt deformation of the toner by wax can further accelerate the melt deformation of the toner by the crystalline polyester and improve the low temperature fixability of the toner.

The material used for the toner of the present invention will be specifically described below.

First, in order to exhibit the effects of the present invention, it is essential that the toner contains a certain amount of crystalline polyester.

A crystalline polyester that can be used in the present invention will be described.

Known crystalline polyesters of the present invention can be used, but saturated polyesters are preferable. Further, it is preferably a condensate of an aliphatic dicarboxylic acid, an aliphatic diol, and further an aliphatic monocarboxylic acid. The aliphatic monocarboxylic acid is a preferable form because the molecular weight and the hydroxyl value can be easily adjusted and the affinity with the wax can be controlled. Further, it is preferable that the crystalline polyester has a moiety derived from an aliphatic monoalcohol having 10 or more and 30 or less carbon atoms and / or an aliphatic monocarboxylic acid having 11 or more and 31 or less carbon atoms.

The following is an example of a monomer that can be used when the crystalline polyester is a condensate of an aliphatic dicarboxylic acid, an aliphatic diol, and an aliphatic monocarboxylic acid, and is a saturated polyester.

Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid and the like.

Specific examples of the aliphatic diol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, trimethylene glycol, neopentyl glycol, and 1, 4-butanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12 -Dodecanediol, 1,16-hexadecanediol, 1,18-octadecanediol and the like can be mentioned.

Examples of the aliphatic monocarboxylic acid include decanoic acid (capric acid), dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), and so on. Examples thereof include docosanoic acid (behenic acid) and tetracosanoic acid (lignoceric acid).

Here, since the monocarboxylic acid has only one carboxylic acid, the structure derived from the monocarboxylic acid is located at the end of the crystalline polyester.

Such a crystalline polyester has an increased affinity for wax. As a result, the crystalline polyester becomes like a wax coating, the domain of the crystalline polyester tends to be thermally stabilized, and properties such as fog deteriorate even after receiving a history of high temperature and harsh environment. Hateful. Further, the crystalline polyester and the wax are melted at the same time to instantly plasticize the surrounding binding resin, so that the rear end offset is likely to be improved synergistically.

Regarding the rear end offset, which tends to be a trade-off, and the resistance in a harsh environment, by using the above-mentioned crystalline polyester, it is easy to achieve both of them, which is preferable as the structure of the crystalline polyester.

In particular, when a crystalline polyester having an alkyl group having 10 or more and 24 or less carbon atoms at the terminal and an ester wax having 2 or more and 6 or less ester groups in one molecule are used in combination, the crystalline polyester with respect to the wax has a high affinity between the two. The coverage is dramatically increased, which is preferable. In the present invention, a crystalline polyester having a structure derived from a stearic acid monomer at the end tends to have a higher affinity with the above-mentioned ester wax and a higher coverage of the crystalline polyester with respect to the wax, which is preferable. ..

The crystalline polyester preferably has a weight average molecular weight (Mw) of 10,000 or more and 50,000 or less, and more preferably 30,000 or more and 40,000 or less. When the weight average molecular weight (Mw) of the crystalline polyester is less than 10,000, the components compatible with the binder resin increase and the crystallinity tends to decrease. Further, when the weight average molecular weight (Mw) of the crystalline polyester is larger than 50,000, the instantaneous plasticity becomes dull and it is difficult to obtain good low temperature fixability.

The weight average molecular weight (Mw) of the crystalline polyester can be controlled by various production conditions of the crystalline polyester. For example, the molecular weight (Mw) can be controlled within the above range by bringing the ratio of the alcohol monomer and the acid monomer as raw materials close to 1: 1.

Further, the acid value of the crystalline polyester is preferably controlled to be low when considering the dispersibility in the toner, and specifically, it is 8.0 or less. It is more preferably 5.0 or less, still more preferably 3.5 or less.

Next, wax will be described.

First, the wax that can be used in the present invention preferably contains an ester wax from the viewpoint of storage stability and prevention of film contamination. To state the idea of the inventors regarding this, by containing the ester wax in the toner, it is easy to assist the crystallization of the crystalline material and increase the crystallinity by using the ester wax as the core material. It is presumed that this reduces the compatible components in the binder resin and suppresses the exuding components, thereby improving the storage stability. In addition, when heat is applied, the wax that is the core material of the crystalline polyester melts at the same time, so it is easy to reduce the adhesive force with the film, and it is presumed that film contamination can be suppressed while maintaining low temperature fixability. To do.

Further, as the ester wax applicable to the present invention, a known ester wax can be used. For example, waxes containing fatty acid esters such as carnauba wax and montanic acid ester wax as main components; and deoxidized fatty acid esters such as carnauba wax with some or all of the acid components deoxidized; vegetable fats and oils. Methyl ester compounds having a hydroxyl group obtained by hydrogenation of the above; saturated fatty acid monoesters such as stearyl stearate and behenyl behenate; saturated fats such as dibehenyl sebacate, distearyl dodecane and distearyl octadecane Diesterates of group dicarboxylic acids and saturated aliphatic alcohols; examples thereof include diesterates of saturated aliphatic diols such as nonanediol dibehenate and dodecanediol distearate and saturated fatty acids.

Among these waxes, it is preferable to contain a bifunctional ester wax having two ester bonds in the molecular structure from the viewpoint of improving the dispersibility of the crystalline material and increasing the crystallinity.

In the present invention, waxes other than ester wax can be used as long as the effects of the present invention are not impaired. As a wax other than the ester wax, a known wax can be used, but an aliphatic hydrocarbon wax such as Fischer-Tropsch wax can be preferably used from the viewpoint of releasability of the fixing roller and the toner.

The ratio of the ester wax (A) to the aliphatic hydrocarbon wax (B) in the toner is preferably 0.25 or more and 4.0 or less in (A) / (B), more preferably 0. It is .40 or more and 2.3 or less.

The wax content is preferably 5.0 parts by mass or more and 30.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

The binder resin used in the toner of the present invention is a monopolymer of styrene such as polystyrene and polyvinyltoluene and its substitution product; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer weight. Combined, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene -Methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinylmethyl ether copolymer, styrene Styrene such as −vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer System copolymers; polymethylmethacrylate, polybutylmethacrylate, polyvinylacetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin can be used, and these can be used alone. Alternatively, a plurality of types can be used in combination. Of these, a styrene-based copolymer typified by styrene-butyl acrylate is particularly preferable in controlling the integrated value of stress within a desired range.

Next, examples of the colorant used in the present invention include the following organic pigments, organic dyes, and inorganic pigments.

Examples of the cyan-based colorant include a copper phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound. Specifically, the following can be mentioned. C. I. Pigment Blue 1, 7, 15, 5: 1, 15: 2, 15: 3, 15: 4, 60, 62, and 66.

Examples of the magenta colorant include the following. Condensed azo compound, diketopyrrolopyrrole compound, anthraquinone, quinacridone compound, basic dye lake compound, naphthol compound, benzimidazolone compound, thioindigo compound, and perylene compound. Specifically, the following can be mentioned. C. I. Pigment Red 2, 3, 5, 6, 7, C.I. I. Pigment Violet 19, C.I. I. Pigment Red 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221 And 254.

Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following can be mentioned. C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185, 191 and 194.

Examples of the black colorant include carbon black and those colored black by using the above-mentioned yellow colorant, magenta colorant, cyan colorant, and magnetic powder.

These colorants can be used alone or in the form of a solid solution. The colorant used in the present invention is selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner particles.

When a magnetic powder is used as the toner of the present invention, the magnetic powder contains magnetic iron oxide such as triiron tetraoxide or γ-iron oxide as the main component, and phosphorus, cobalt, nickel, copper, magnesium, etc. It may contain elements such as manganese, aluminum and silicon. These magnetic powders preferably have a BET specific surface area of ² to 30 m ² / g by the nitrogen adsorption method, and more preferably 3 to 28 m ² / g. Further, those having a Mohs hardness of 5 to 7 are preferable. The shape of the magnetic powder includes a polyhedron, an octahedron, a hexahedron, a sphere, a needle, and a scale, but a polyhedron, an octahedron, a hexahedron, a sphere, and the like having less anisotropy have an image density. It is preferable to enhance it.

The number average particle size of the magnetic powder is preferably 0.10 μm or more and 0.40 μm or less. Generally, the smaller the particle size of the magnetic powder, the higher the coloring power, but the magnetic powder tends to aggregate, and the uniform dispersibility of the magnetic powder in the toner becomes inferior, which is not preferable. Further, when the number average particle size is less than 0.10 μm, the magnetic powder itself becomes reddish black, so that the reddish image becomes conspicuous especially in the halftone image, which is not preferable because it cannot be said to be a high-quality image. .. On the other hand, when the number average particle size is larger than 0.40 μm, the coloring power of the toner is insufficient, and the suspension polymerization method (described later), which is a suitable method for producing the toner of the present invention, is not preferable because uniform dispersion becomes difficult. ..

The number average particle size of the magnetic powder can be measured using a transmission electron microscope. Specifically, after the toner particles to be observed are sufficiently dispersed in the epoxy resin, the cured product is obtained by curing in an atmosphere at a temperature of 40 ° C. for 2 days. The obtained cured product is used as a flaky sample by a microtome, and the diameters of 100 magnetic powder particles in the field of view are measured with a transmission electron microscope (TEM) at a magnification of 10,000 to 40,000 times. Then, the number average particle diameter is calculated based on the equivalent diameter of the circle equal to the projected area of the magnetic powder. It is also possible to measure the particle size with an image analyzer.

The magnetic powder used for the toner of the present invention can be produced, for example, by the following method. An aqueous solution containing ferrous hydroxide is prepared by adding an alkali such as sodium hydroxide to the ferrous salt aqueous solution in an equivalent amount or equal to or more than the iron component. Air is blown while maintaining the pH of the prepared aqueous solution at pH 7 or higher, and the ferrous hydroxide oxidation reaction is carried out while heating the aqueous solution to 70 ° C. or higher to first form seed crystals that form the core of the magnetic iron oxide powder. Generate.

Next, an aqueous solution containing about 1 equivalent of ferrous sulfate is added to the slurry-like liquid containing seed crystals based on the amount of alkali added previously. While maintaining the pH of the liquid at 5 to 10, the reaction of ferrous hydroxide is promoted while blowing air to grow magnetic iron oxide powder around the seed crystal. At this time, it is possible to control the shape and magnetic characteristics of the magnetic powder by selecting an arbitrary pH, reaction temperature, and stirring conditions. As the oxidation reaction progresses, the pH of the liquid shifts to the acidic side, but it is preferable that the pH of the liquid is not less than 5. A magnetic powder can be obtained by filtering, washing and drying the magnetic material thus obtained by a conventional method.

Further, in the case of producing toner in an aqueous medium in the present invention, it is very preferable to hydrophobize the surface of the magnetic powder. When surface treatment is performed by the dry method, the magnetic powder that has been washed, filtered, and dried is treated with a coupling agent. When the surface treatment is performed by a wet method, the dried iron oxide is redispersed after the oxidation reaction is completed, or the iron oxide body obtained by washing and filtering after the oxidation reaction is completed in another aqueous medium without drying. Is redistributed and the coupling process is performed. In the present invention, both the dry method and the wet method can be appropriately selected.

Examples of the coupling agent that can be used in the surface treatment of the magnetic powder in the present invention include a silane coupling agent and a titanium coupling agent. More preferably used is a silane coupling agent, which is represented by the general formula (I).
RmSiYn (I)
[In the formula, R represents an alkoxy group, m represents an integer of 1 to 3, Y represents a functional group such as an alkyl group, a vinyl group, an epoxy group, or a (meth) acrylic group, and n represents a functional group of 1 to 3. Indicates an integer. However, m + n = 4. ]

Examples of the silane coupling agent represented by the general formula (I) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and the like. γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, Vinyl triacetoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, n-propyltrimethoxysilane, Isopropyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, trimethylmethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, hydroxy Examples thereof include propyltrimethoxysilane, n-hexadecyltrimethoxysilane, and n-octadecyltrimethoxysilane. In the present invention, those in which Y of the general formula (I) is an alkyl group can be preferably used. Above all, from the viewpoint of setting the thermal conductivity to a desired value, it is an alkyl group having 3 or more carbon atoms and 6 or less carbon atoms, and is particularly preferably 3 or 4.

When the above silane coupling agent is used, it can be treated alone or in combination of a plurality of types. When a plurality of types are used in combination, they may be treated individually with each coupling agent or may be treated at the same time.

The total amount of the coupling agent to be treated is preferably 0.9 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the magnetic powder, and the surface area of the magnetic powder, the reactivity of the coupling agent, etc. It is important to adjust the amount of treatment agent accordingly.

In the present invention, other colorants may be used in combination with the magnetic powder. Examples of the colorant that can be used in combination include the above-mentioned known dyes and pigments, as well as magnetic or non-magnetic inorganic compounds. Specifically, ferromagnetic metal particles such as cobalt and nickel, or alloys obtained by adding chromium, manganese, copper, zinc, aluminum, rare earth elements, etc. to these. Particles such as hematite, titanium black, niglosin dye / pigment, carbon black, phthalocyanine and the like can be mentioned. These are also preferably used after surface treatment.

The content of the magnetic powder in the toner can be measured by using a thermal analyzer TGA7 manufactured by PerkinElmer. The measurement method is as follows. The toner is heated from room temperature to 900 ° C. at a heating rate of 25 ° C./min in a nitrogen atmosphere. The weight loss mass% between 100 ° C. and 750 ° C. is defined as the amount of binder resin, and the residual mass is approximately defined as the amount of magnetic powder.

Next, the weight average particle size (D4) of the toner produced by the present invention is preferably 4.0 μm or more and 12.0 μm or less, and more preferably 5.0 μm or more and 10.0 μm or less. When the weight average particle size (D4) is 4.0 μm or more and 12.0 μm or less, good fluidity can be obtained and the latent image can be faithfully developed.

The toner of the present invention can be produced by making it thermospherical by a pulverization method, but the toner of the present invention also produces a toner in an aqueous medium for controlling the presence state of crystalline polyester or ester wax. It is preferable to do so. In particular, the suspension polymerization method is preferable because it is easy to control the fine dispersion of the crystalline polyester and the promotion of crystallization.

The suspension polymerization method will be described below.

The suspension polymerization method is a polymerizable monomer in which a polymerizable monomer and a colorant (and, if necessary, a polymerization initiator, a cross-linking agent, a charge control agent, and other additives) are uniformly dissolved or dispersed. Obtain the composition. Then, this polymerizable monomer composition is dispersed in a continuous layer (for example, an aqueous phase) containing a dispersant using an appropriate stirrer and simultaneously subjected to a polymerization reaction to obtain a toner having a desired particle size. It is a thing. Since the toners obtained by this suspension polymerization method (hereinafter, also referred to as "polymerized toners") have almost spherical shapes of individual toner particles, the distribution of the amount of charge is relatively uniform, so that the image quality is improved. You can expect it.

In the production of the polymerizable toner according to the present invention, examples of the polymerizable monomer constituting the polymerizable monomer composition include the following.

As the polymerizable monomer, styrene-based monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene; methyl acrylate, ethyl acrylate, etc. Acrylic acid esters such as n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc. Kind, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, Acrylic esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; other monomers such as acrylonitrile, methacrylonitrile and acrylamide can be mentioned. These monomers can be used alone or in admixture. Among the above-mentioned monomers, it is preferable to use styrene alone or in combination with other monomers from the viewpoint of toner development characteristics and durability.

The polymerization initiator used in the production of the toner by the polymerization method of the present invention preferably has a half-life of 0.5 to 30 hours during the polymerization reaction. Further, when the polymerization reaction is carried out by using an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum molecular weight between 5,000 and 50,000 is obtained. , The toner can be given the desired strength and suitable melting properties.

Specific examples of polymerization initiators include 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, and 1,1'-azobis (cyclohexane-1-). Carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and other azo or diazo polymerization initiators, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropylper Oxycarbonate, cumenehydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butylperoxy2-ethylhexanoate, t-butylperoxypivalate, di (2-ethylhexyl) peroxydi Peroxide-based polymerization initiators such as carbonate and di (secondary butyl) peroxydicarbonate can be mentioned.

When the toner of the present invention is produced by the polymerization method, a cross-linking agent may be added, and the preferable amount of addition is 0.001 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. is there.

As the cross-linking agent used in the present invention, a compound having two or more polymerizable double bonds is mainly used, and for example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene, ethylene glycol diacrylate, and ethylene glycol are used. Dimethacrylate, 1,3-butanediol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, 1,7-heptanediol diacrylate, 1,8-octanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,11-undecanediol diacrylate , 1,18-Octadecanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, and other carboxylic acid esters having two double bonds, divinylaniline, divinyl ether, divinyl sulfide, A divinyl compound such as divinyl sulfone or a compound having three or more vinyl groups is used alone or as a mixture of two or more kinds.

In particular, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,7-heptanediol diacrylate, and 1,8-octanediol diacrylate represented by the following formulas. , 1,9-Nonandiol diacrylate, 1,10-decanediol diacrylate, 1,11-undecanediol diacrylate, and 1,18-octadecanediol diacrylate are preferably used.

［式中、Ｒ₁は水素原子または炭素数１乃至３のアルキル基を示し、Ｒ₂は炭素数４乃至１８の直鎖状アルキレン基を示す。］

[In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₂ represents a linear alkylene group having 4 to 18 carbon atoms. ]

Since the above compounds have flexibility and have a relatively long molecular chain, the distance between the cross-linking points of the binder resin tends to be wide, and a large network structure tends to be formed. As a result, it becomes easy to make it compatible with the rear end offset while controlling the stress integral value of the toner in the present invention. The reason for this is not clear, but having a cross-linked structure makes it easier to control the stress integral value of the toner, and at the same time, because the distance between the cross-linking points is wide, it becomes easier to promote the deformation of the resin during fixing, and the cross-linked structure becomes easier. It is presumed that it is difficult to inhibit the fixability.

When the medium used for the polymerization of the polymerizable monomer is an aqueous medium, the following can be used as the dispersion stabilizer of the particles of the polymerizable monomer composition in the aqueous medium. ..

As an inorganic dispersion stabilizer, tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate , Bentonite, silica, alumina and the like.

Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, and starch.

Furthermore, commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such a surfactant include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate.

In the present invention, when a poorly water-soluble inorganic dispersion stabilizer is used to prepare an aqueous medium, the amount of these dispersion stabilizers added is 0.2 to 2 with respect to 100.0 parts by mass of the polymerizable monomer. It is preferably 9.0 parts by mass. Further, it is preferable to prepare an aqueous medium by using 300 to 3,000 parts by mass of water with respect to 100 parts by mass of the polymerizable monomer composition.

In the present invention, when preparing an aqueous medium in which the above-mentioned poorly water-soluble inorganic dispersant is dispersed, a commercially available dispersion stabilizer may be used as it is. Further, in order to obtain a dispersion stabilizer having a fine and uniform particle size, a poorly water-soluble inorganic dispersant may be produced in a liquid medium such as water under high-speed stirring. Specifically, when tricalcium phosphate is used as a dispersion stabilizer, a preferable dispersion stabilizer is formed by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring to form fine particles of tricalcium phosphate. Can be obtained.

In the present invention, the toner particles may contain a polar resin. As the polar resin, a saturated or unsaturated polyester resin can be preferably exemplified.

As the polyester resin, one obtained by condensation polymerization of the carboxylic acid component and the alcohol component listed below can be used.

Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. Examples of the alcohol component include bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.

Further, the polyester resin may be a polyester resin containing a urea group.

In the present invention, the weight average molecular weight of the polar resin is preferably 4,000 or more and less than 100,000. The content of the polar resin is preferably 3.0 to 70.0% by mass, more preferably 3.0 to 50.0% by mass, based on the binder resin component contained in the toner particles. It is more preferably 5.0 to 30.0% by mass.

In the present invention, the toner particles may contain a charge control agent. As the charge control agent, known ones can be used. In particular, a charge control agent having a high charging speed and capable of stably maintaining a constant charge amount is preferable. Further, when the toner particles are produced by the direct polymerization method, a charge control agent having low polymerization inhibitory property and substantially no solubilized product in an aqueous medium is particularly preferable.

Examples of the charge control agent that controls the toner particles to be charge-electric are as follows. Examples of the organic metal compound and chelate compound include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acid-based metal compounds. Others include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenol, and the like. Further, urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, calixarene and the like can be mentioned.

On the other hand, examples of the charge control agent for controlling the toner particles to be positively charged include the following. Nigrosine modified products such as niglosin and fatty acid metal salts; guanidine compounds; imidazole compounds; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and similar thereof. Onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and their lake pigments (as lake agents, phosphotung acid, phosphomolybdic acid, phosphotungene molybdic acid, tannic acid, lauric acid, Caric acid, ferricyanide, ferrocyanide, etc.); Metal salts of higher fatty acids; Resin-based charge control agents.

These charge control agents can be contained alone or in combination of two or more. Among these charge control agents, metal-containing salicylic acid-based compounds are preferable, and the metal is particularly preferably aluminum or zirconium. The most preferred charge control agent is a 3,5-di-tert-butylsalicylate aluminum compound.

Further, as the resin-based charge control agent, a polymer having a sulfonic acid-based functional group is preferable. The polymer having a sulfonic acid-based functional group is a polymer or a copolymer having a sulfonic acid group, a sulfonic acid base or a sulfonic acid ester group.

Examples of the polymer or copolymer having a sulfonic acid group, a sulfonic acid base or a sulfonic acid ester group include a high molecular weight compound having a sulfonic acid group in the side chain. In particular, styrene and / or styrene (meth) containing a sulfonic acid group-containing (meth) acrylamide-based monomer in a copolymerization ratio of 2% by mass or more, preferably 5% by mass or more, and having a glass transition temperature (Tg) of 40 to 90 ° C. ) A polymer compound which is an acrylic ester copolymer is preferable. Improves charge stability under high humidity.

The above-mentioned sulfonic acid group-containing (meth) acrylamide-based monomer is preferably one represented by the following general formula (X), and specifically, 2-acrylamide-2-methylpropanoic acid or 2-methacrylamide-2-methyl. Propionic acid and the like can be mentioned.

［上記一般式（Ｘ）中、Ｒ₁は水素原子、又はメチル基を示し、Ｒ₂とＲ₃は、それぞれ水素原子、Ｃ１乃至Ｃ１０のアルキル基、アルケニル基、アリール基又はアルコキシ基を示し、ｎは１乃至１０の整数を示す。］

[In the above general formula (X), R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ represent a hydrogen atom, an alkyl group of C1 to C10, an alkenyl group, an aryl group or an alkoxy group, respectively. n represents an integer of 1 to 10. ]

The polymer having a sulfonic acid group contains 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the binder resin in the toner particles to further improve the charged state of the toner particles. Can be done.

The amount of these charge control agents added is preferably 0.01 to 10.00 parts by mass with respect to 100.00 parts by mass of the binder resin or the polymerizable monomer.

In the toner of the present invention, the surface of the toner particles may be treated with the following organic fine powder or inorganic fine powder for the purpose of imparting various characteristics.

(1) Fluidity imparting agent: silica, alumina, titanium oxide, carbon black and carbon fluoride.
(2) Polishing agent: Strontium titanate, cerium oxide, alumina, magnesium oxide, metal oxides such as chromium oxide, nitrides such as silicon nitride, carbides such as silicon carbide, calcium sulfate, barium sulfate, metals such as calcium carbonate. salt.
(3) Lubricants: Fluorine-based resin powders such as vinylidene fluoride and polytetrafluoroethylene, fatty acid metal salts such as zinc stearate and calcium stearate.
(4) Charge controllable particles: Metal oxides such as tin oxide, titanium oxide, zinc oxide, silica and alumina, and carbon black.

These fine powders may be used alone or in combination of two or more.

Since these fine powders can be hydrophobized to adjust the chargeability of the toner and improve the charging characteristics in a high humidity environment, they are preferably hydrophobized. Examples of the treatment agent for the hydrophobization treatment include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. .. These treatment agents may be used alone or in combination.

Among them, inorganic fine powder treated with silicone oil is preferable. More preferably, the inorganic fine powder is treated with silicone oil at the same time as or after being hydrophobized with a coupling agent. Hydrophobicized inorganic fine powder treated with silicone oil is preferable for maintaining a high charge amount of toner even in a high humidity environment and reducing selective developability.

The BET specific surface area of these fine powders is preferably 10 m ² / g or more and 450 m ² / g or less. The BET specific surface area can be determined by a low temperature gas adsorption method based on a dynamic constant pressure method according to the BET method (preferably the BET multipoint method). For example, by adsorbing nitrogen gas on the sample surface using the specific surface area measuring device "Gemini 2375 Ver.5.0" (manufactured by Shimadzu Corporation) and measuring using the BET multipoint method, the BET specific surface area ( m ² / g) can be calculated.

These fine powders may be firmly adhered or adhered to the surface of the toner particles. Examples of the external mixer for firmly adhering or adhering fine powder to the surface of toner particles include Henschel mixer, mechanofusion, cyclomix, turbulizer, flexomix, hybridization, mechanohybrid, and novirta. Further, by increasing the rotation peripheral speed or lengthening the processing time, it is possible to strongly adhere or adhere.

From the viewpoint of facilitating the adjustment of the integrated value of stress to a desired range, the amount of these fine powders added is preferably 0.01 to 10.00 parts by mass with respect to 100.00 parts by mass of the toner particles. It is more preferably 0.02 to 5.00 parts by mass, and further preferably 0.03 to 1.00 parts by mass.

The content of the tetrahydrofuran insoluble matter of the toner of the present invention is preferably less than 50.0% by mass, more preferably 0.0% by mass or more and 45 with respect to the toner components other than the colorant and the inorganic fine powder of the toner. It is less than 0.0% by mass, more preferably 5.0% by mass or more and less than 40.0% by mass. By setting the content of the tetrahydrofuran insoluble content to less than 50.0% by mass, the low temperature fixability can be improved.

The content of the tetrahydrofuran insoluble component of the toner means the mass ratio of the superpolymer polymer component (substantially crosslinked polymer) insoluble in the tetrahydrofuran solvent. The content of the tetrahydrofuran insoluble component of the toner can be adjusted by the degree of polymerization and the degree of cross-linking of the binder resin.

Next, an example of an image forming apparatus capable of preferably using the toner of the present invention will be specifically described with reference to FIG. In FIG. 3, 100 is a photosensitive drum, and a primary charging roller 117, a developing device 140 having a developing sleeve 102, a transfer charging roller 114, a cleaner 116, a register roller 124, and the like are provided around the photosensitive drum. The photosensitive drum 100 is charged to, for example, -600 V by the primary charging roller 117 (the applied voltage is, for example, an AC voltage of 1.85 kVpp and a DC voltage of -620 Vdc). Then, the photoconductor 100 is exposed by irradiating the photoconductor 100 with the laser light 123 by the laser generator 121, and an electrostatic latent image corresponding to the target image is formed. The electrostatic latent image on the photosensitive drum 100 is developed by a developer 140 with a one-component toner to obtain a toner image, and the toner image is transferred onto the transfer material by a transfer roller 114 abutted on the photoconductor via the transfer material. Will be done. The transfer material on which the toner image is placed is carried to the fixing device 126 by a transport belt 125 or the like and fixed on the transfer material. Further, the toner partially left on the photoconductor is cleaned by the cleaner 116.

Although the image forming apparatus for magnetic one-component jumping development is shown here, it may be used for either jumping development or contact development.

Next, a method for measuring each physical property of the toner of the present invention will be described.

<Measurement method of integrated toner stress>
(1) Preparation of toner pellet Toner pellets are formed by placing about 3 g of toner (variable depending on the specific gravity of the sample) in a vinyl chloride ring for measuring an inner diameter of 27 mm, pressing at 200 kN for 60 seconds, and molding the sample. To make. The same stress integral value was measured for the one pressed at 100 kN for 60 seconds and the one pressed at 300 kN for 60 seconds. From this, it is considered that the error in the smoothness of the pellet surface when the pellet is prepared by the above method is small and does not affect the stress integral value measurement.

(2) Measurement of integrated stress value The integrated value of the stress of the toner was measured using "TAC-1000" (manufactured by Reska) according to the operation manual of the device. As for the probe, a fixing film material was assumed, and a polytetrafluoroethylene-coated probe having low adhesion to toner was used. The polytetrafluoroethylene coating was carried out through the following steps.

After degreasing and sandblasting the probe site, masking is performed, then preheating is performed, and polytetrafluoroethylene is applied. After drying, the masking was released, and then firing and cooling were performed to complete the coating.

The surface roughness Ra coated by the above method was 0.5 μm. Further, it was confirmed that the value of the stress integral value measured in the range of Ra of 0.3 to 0.8 μm did not change in the error range.

As a specific measurement method, as shown in FIG. 4, the toner pellet 204 is placed on the sample holding plate 205, and the probe tip 203 is set to 200 ° C. using the probe unit 202.

Next, by adjusting the head portion 200, the probe tip 203 is lowered to the point where the probe tip 203 can pressurize the toner pellet 204. Next, the toner pellet 204 is pressurized under the following conditions, and the stress value when the probe tip 203 is pulled up is detected by the load sensor 201.
・ Pressing speed 5 mm / sec
・ Pressing load 19.7 kg ・ m / sec
・ Pressing and holding time 0.05 sec
・ Pulling speed 15mm / sec

The integrated value of stress is calculated by integrating the stress value detected by the load sensor.

<Measurement of weight average particle size (D4) and number average particle size (D1) of toner (particles)>
The weight average particle size (D4) and the number average particle size (D1) of the toner (particles) are the precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark) by the pore electric resistance method equipped with an aperture tube of 100 μm. , Beckman Coulter) and the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (Beckman Coulter) for setting measurement conditions and analyzing measurement data, the number of effective measurement channels is 2. Measure with 15,000 channels, analyze the measurement data, and calculate.

As the electrolytic aqueous solution used for the measurement, one in which special grade sodium chloride is dissolved in ion-exchanged water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.

Before performing measurement and analysis, the dedicated software is set as follows.

In the "Standard measurement method (SOM) change screen" of the dedicated software, the total count number in the control mode is set to 50,000 particles, the number of measurements is once, and the Kd value is "Standard particle 10.0 μm" (Beckman Coulter). Set the value obtained using (manufactured by the company). By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flush of the aperture tube after measurement.

In the "pulse to particle size conversion setting screen" of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set to 2 μm or more and 60 μm or less.

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

<Method of observing toner cross section with a ruthenium-stained transmission electron microscope (TEM)>
Cross-section observation of toner with a transmission electron microscope (TEM) can be carried out as follows.

The toner of the present invention is observed by ruthenium-staining the cross section of the toner. Since the crystalline resin contained in the toner of the present invention is dyed with ruthenium rather than an amorphous resin such as a binder resin, the contrast becomes clear and observation becomes easy. Since the amount of ruthenium atoms differs depending on the strength of staining, many of these atoms are present in the strongly stained part, the electron beam does not pass through, and the part is blackened on the observation image, and the weakly stained part is The electron beam is easily transmitted and becomes white on the observation image.

First, the toner is sprayed on the cover glass (Matsunami Glass Co., Ltd., Square Cover Glass Square No. 1) so as to form a single layer, and an Osmium plasma coater (filgen Co., Ltd., OPC80T) is used as a protective film on the toner as an Os film. (5 nm) and naphthalene film (20 nm) are applied. Next, a PTFE tube (Φ1.5 mm × Φ3 mm × 3 mm) is filled with a photocurable resin D800 (JEOL Ltd.), and the cover glass is placed on the tube so that the toner comes into contact with the photocurable resin D800. Place gently in the orientation. After irradiating light in this state to cure the resin, the cover glass and the tube are removed to form a cylindrical resin in which toner is embedded on the outermost surface. Ultrasonic ultramicrotome (Leica, UC7) with a cutting speed of 0.6 mm / s and a radius of toner from the outermost surface of the cylindrical resin (4 when the weight average particle size (D4) is 8.0 m). Cut by a length of .0 · m) to obtain a cross section of the toner. Next, a thin section sample having a toner cross section was prepared by cutting to a film thickness of 250 nm. By cutting by such a method, a cross section of the toner center portion can be obtained.

The obtained flaky sample was stained with a vacuum electron staining apparatus (filgen, VSC4R1H) in an atmosphere of RuO4 gas 500 Pa for 15 minutes, and STEM observation was performed using TEM (JEOL, JEM2800).

<Identification of crystalline polyester and wax domains>
Based on the TEM image of the cross section of the toner, the domains of the crystalline polyester and the wax are identified by the following procedure.

When crystalline polyester and wax are available as raw materials, their crystal structures are observed in the same manner as in the above-mentioned method for observing the toner cross section in a transmission electron microscope (TEM) dyed with ruthenium, and the crystals of each raw material are observed. Obtain an image of the lamella structure of. By comparing them with the lamellar structure of the domain in the cross section of the toner, if the layer spacing of the lamella is an error of 10% or less, the raw material forming the domain in the cross section of the toner can be identified.

<Isolation of crystalline polyester and wax>
If raw materials for crystalline polyester and wax are not available, isolation is performed as follows. First, the toner is dispersed in ethanol, which is a poor solvent for the toner, and the temperature is raised to a temperature exceeding the melting points of the crystalline polyester and the wax. At this time, pressurization may be performed if necessary. At this point, the crystalline polyester and wax that have exceeded the melting point are melted. Then, by solid-liquid separation, a mixture of crystalline polyester and wax can be collected from the toner. Crystalline polyesters and waxes can be isolated by seeding this mixture by molecular weight.

<Measurement of the number mean diameter of the major axis of the crystalline polyester domain>
In the present invention, the number mean diameter of the crystalline polyester domain means the number mean diameter obtained from the major axis (FIG. 1) of the crystalline polyester domain based on the TEM image. Based on the TEM image obtained by observing the toner cross section with a ruthenium-stained transmission electron microscope (TEM), the number average diameter of the major axis of the crystalline polyester domain is measured. At that time, observe the cross sections of 100 or more toners. Measure all domains and calculate the mean diameter. The obtained number average diameter is defined as the number average diameter of the major axis of the crystalline polyester domain.

<Measurement of the number of domains of crystalline polyester>
The number of crystalline polyester domains contained per toner cross section is measured in the same manner as the above-mentioned measurement of the number average diameter of the major axis of the crystalline polyester domain. This is done for cross sections of 100 or more toners, and the number of domains per toner cross section is defined as the number of domains of crystalline polyester.

<Measurement of 25% rate of crystalline polyester domain>
In the present invention, the 25% ratio is the ratio (number%) of the crystalline polyester present in the region at a depth of 25% with respect to the particle size of the toner cross section from the surface of the toner.

The method of calculating 25% is as follows.

The contour and center point of the toner are obtained in the same manner as the measurement (center ratio) of the proportion of the wax domain present at the center point of the toner cross section, which will be described later. A line is drawn from the center point with respect to a certain point on the contour of the toner, and a position 25% from the contour on the line is defined as a 25% contour. Then, this operation is performed for one round of the contour of the toner to clearly indicate the depth of 25% from the surface of the toner (FIG. 2). Based on this image, the number of crystalline polyester domains present in the region 25% from the toner surface is measured in the same manner as the above-mentioned measurement of the number of domains. The 25% ratio of the domain of crystalline polyester is calculated by the following formula.
25% rate = "Number of crystalline polyester domains present in the region 25% from the toner surface" / "Number of crystalline polyester domains present in the entire toner" x 100 (%)

<Measurement of the total area of the wax domain>
Based on the image obtained by the above-mentioned TEM observation, the area of wax in the toner cross section is calculated using image processing software. If there are multiple wax domains, the area is accumulated. This is performed for the cross sections of 100 or more toners, and the total area of the wax domain per toner is calculated by the following formula.
Total area of wax domain = "total area of wax domain" / "area of toner cross section" x 100 (area%)

<Measurement of the ratio of wax domains present at the center point of the toner cross section (center ratio)>
Based on the image obtained by the above-mentioned TEM observation, the center point of the toner cross section is obtained based on the following work. Using image processing software, the contour (edge detection) of the toner is clarified from the cross section of the toner. Next, the point guided by the center of gravity from the cross section of the toner is set as the center point of the toner. Then, the number of toner cross sections when the wax domain is present at the center point and the number of toner cross sections when the wax domain is not present are measured for the cross sections of 100 or more toners. Then, the center ratio is calculated using the following formula.
Center ratio = "Number of toner cross sections where wax domain exists at the center point" / "Number of measured toner cross sections" x 100 (number%)

<Measurement of acid value>
The acid value of the crystalline polyester and wax in the present invention can be determined by the following operations. The basic operation is JIS K0070. The acid value of the polar resin was measured by the following method.

The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of the polar resin was measured according to JIS K 0070-1992. Specifically, the measurement was performed according to the following procedure.

(1) Preparation of Reagents 1.0 g of phenolphthalein was dissolved in 90 ml of ethyl alcohol (95 vol%), and ion-exchanged water was added to make 100 ml to obtain a phenolphthalein solution.

7 g of special grade potassium hydroxide was dissolved in 5 ml of water, and ethyl alcohol (95 vol%) was added to make 1 liter. It was placed in an alkali-resistant container so as not to come into contact with carbon dioxide and the like, left for 3 days, and then filtered to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution was stored in an alkali-resistant container. As for the factor of the potassium hydroxide solution, take 25 ml of 0.1 mol / l hydrochloric acid in a triangular flask, add a few drops of the phenolphthaline solution, titrate with the potassium hydroxide solution, and carry out the hydroxylation required for neutralization. Obtained from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 was used.

(2) Operation (A) Main test 2.0 g of a crushed crystalline polyester or wax sample is precisely weighed in a 200 ml Erlenmeyer flask, 100 ml of a mixed solution of toluene: ethanol (2: 1) is added, and it takes 5 hours. Dissolved. Then, several drops of the phenolphthalein solution were added as an indicator, and titration was performed using the potassium hydroxide solution. The end point of the titration was when the light red color of the indicator continued for about 30 seconds.
(B) Blank test Titration was carried out in the same manner as described above except that no sample was used (that is, only a mixed solution of toluene: ethanol (2: 1) was used).

(3) The acid value was calculated by substituting the obtained results into the following formula.
A = [(CB) x f x 5.61] / S

Here, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (ml), C: addition amount of potassium hydroxide solution in this test (ml), f: potassium hydroxide Solution factor, S: sample (g).

<Measurement of melting point>
The melting points of the crystalline polyester and the wax are measured according to ASTM D3418-82 using a differential scanning calorimeter "Q1000" (manufactured by TA Instruments).

The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.

Specifically, 1 mg of crystalline polyester or wax is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the measurement range is set between 20 ° C and 140 ° C as follows. Modulation measurement is performed with.
・ Temperature rise rate 1 ℃ / min
・ Amplitude temperature range ± 0.318 ° C / min

In this temperature raising process, a specific heat change is obtained in the temperature range of 20 ° C. to 140 ° C. The melting point Tm (C) of the crystalline polyester or wax is the maximum endothermic peak temperature in the specific heat change curve.

<Measurement of crystallization temperature derived from crystalline substances in toner>
Since it is possible to determine the crystallization peak even with a simple substance of crystalline polyester or wax, the method will be described first.

The crystallization temperature and the exothermic curve of the crystalline polyester or wax are measured using a differential scanning calorimeter "Q1000" (manufactured by TA Instruments).

The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.

Specifically, 1.00 mg of the sample is weighed, placed in an aluminum pan, and an empty aluminum pan is used as a control, and measurement is performed under the following measurement conditions.
-Measurement mode: Standard
-Rising temperature condition: The temperature is raised from 20 ° C. to 100 ° C. at 10 ° C./min.
-Temperature lowering condition: The temperature is lowered from 100 ° C. to 20 ° C. at 0.5 ° C./min.

Based on the obtained results, a temperature-heat flow graph is created, and a heat generation curve of crystalline polyester or wax is obtained from the results when the temperature is lowered. In the heat generation curve, the peak temperature of the maximum heat generation peak is defined as the crystallization temperature.

In order to obtain the crystallization temperature of the crystalline polyester or wax from the toner, it is preferable to carry out the isolation operation from the toner as described above and analyze the obtained simple substance by the above method.

<Measurement of molecular weight of crystalline polyester>
Crystalline polyester, the molecular weight of the amorphous Po Riesuteru resin and toner, by gel permeation chromatography (GPC), is measured as follows.

First, crystalline polyester or toner is dissolved in tetrahydrofuran (THF) at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Maeshori Disc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. This sample solution is used for measurement under the following conditions.
Equipment: High-speed GPC equipment "HLC-8220GPC" [manufactured by Tosoh Corporation]
Column: LF-604 dual eluent: THF
Flow velocity: 0.6 ml / min
Oven temperature: 40 ° C
Sample injection volume: 0.020 ml

In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name "TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-" 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ”, manufactured by Toso Co., Ltd.) is used.

<Identification of the terminal structure of crystalline polyester>
2 mg of the resin sample is precisely weighed, and 2 ml of chloroform is added and dissolved to prepare a sample solution. A crystalline polyester resin A is used as the resin sample, but a toner containing the resin A can be used as a sample. Next, 20 mg of 2,5-dihydroxybenzoic acid (DHBA) is precisely weighed, and 1 ml of chloroform is added and dissolved to prepare a matrix solution. Further, after 3 mg of sodium trifluoroacetate (NaTFA) is precisely weighed, 1 ml of acetone is added and dissolved to prepare an ionization aid solution.

25 μl of the sample solution, 50 μl of the matrix solution, and 5 μl of the ionization aid solution prepared in this manner are mixed, dropped onto a sample plate for MALDI analysis, and dried to obtain a measurement sample. A mass spectrum is obtained using MALDI-TOFMS (Reflex III manufactured by Bruker Daltonics) as an analytical instrument. In the obtained mass spectrum, each peak in the oligomer region (m / Z is 2000 or less) is assigned, and it is confirmed whether or not there is a peak corresponding to the structure in which the monocarboxylic acid is bound at the molecular terminal.

<Calculation of crystallinity>
First, the calorific value (J / g) of each crystalline material is determined using a differential scanning calorimeter "Q1000" (manufactured by TA Instruments). The product of the obtained calorific value and the mass part of each crystalline material contained in the toner is calculated. By dividing the sum of them by the total mass part of the raw material, the calorific value (J / g) when all the crystalline materials contained are crystallized is calculated, and the value is taken as the theoretical ΔH. Subsequently, the calorific value (J / g) of each sample toner was measured by the same apparatus, and the crystallinity (%) was calculated by dividing by the theory ΔH obtained earlier.

Hereinafter, the present invention will be specifically described with reference to Production Examples and Examples, but this does not limit the present invention in any way. Examples 5, 21 to 26 are reference examples. The number of copies in the following formulations is all parts by mass.

<Manufacturing of magnetic iron oxide 1>
A ferrous salt aqueous solution containing a ferrous hydroxide colloid was mixed and stirred with 50 liters of an iron sulfate aqueous solution containing 2.0 mol / L of Fe ²⁺ and 55 liters of a 4.0 mol / L sodium hydroxide aqueous solution. Got This aqueous solution was kept at 85 ° C. and an oxidation reaction was carried out while blowing air at 20 L / min to obtain a slurry containing core particles.

The obtained slurry was filtered and washed with a filter press, and then the core particles were redispersed in water and reslurryed. To this slurry liquid, sodium silicate having a silicon equivalent of 0.20 mass% per 100 parts of core particles is added, the pH of the slurry liquid is adjusted to 6.0, and the mixture is stirred to have a magnetism having a silicon-rich surface. Iron oxide particles were obtained. The obtained slurry was filtered and washed with a filter press, and further reslurryed with ion-exchanged water. 500 g (10% by mass with respect to magnetic iron oxide) of an ion exchange resin SK110 (manufactured by Mitsubishi Chemical) was added to this reslurry solution (solid content 50 g / L), and the mixture was stirred for 2 hours to perform ion exchange. Then, the ion exchange resin was filtered through a mesh to remove it, filtered and washed with a filter press, dried and crushed to obtain magnetic iron oxide 1 having an average number of primary particles of 190 nm.

<Manufacturing of Silane Compound 1>
30 parts of iso-butyltrimethoxysilane was added dropwise to 70 parts of ion-exchanged water with stirring. Then, this aqueous solution was maintained at pH 5.5 and a temperature of 55 ° C., and hydrolyzed by dispersing at a peripheral speed of 0.46 m / sec for 120 minutes using a disper blade. Then, the pH of the aqueous solution was adjusted to 7.0, and the solution was cooled to 10 ° C. to stop the hydrolysis reaction. In this way, silane compound 1 which is an aqueous solution containing a hydrolyzate was obtained (Table 1).

<Manufacturing of magnetic material 1>
1,100 parts of magnetic iron oxide was placed in a high-speed mixer (LFS-2 type manufactured by Fukae Powtech Co., Ltd.), and 1,8.0 parts of silane compound was added dropwise over 2 minutes while stirring at a rotation speed of 2000 rpm. Then, it was mixed and stirred for 5 minutes. Then, in order to enhance the adhesiveness of the silane compound 1, the mixture was dried at 40 ° C. for 1 hour to reduce the water content, and then the mixture was dried at 110 ° C. for 3 hours to allow the condensation reaction of the silane compound 1 to proceed. Then, it was crushed and passed through a sieve having an opening of 100 μm to obtain a magnetic material 1 (Table 2).

<Wax>
The waxes used in this example and comparative examples are shown in Table 3 below.

<Manufacturing of crystalline polyester 1>
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 100.0 parts of sebacic acid as a carboxylic acid monomer 1, 1.6 parts of stearic acid as a carboxylic acid monomer 2, and 1,9 as an alcohol monomer. − 89.3 parts of nonandiol was charged. The temperature was raised to 140 ° C. with stirring, heated to 140 ° C. under a nitrogen atmosphere, and reacted for 8 hours while distilling off water under normal pressure. Then, 0.57 parts of tin dioctylate was added, and then the reaction was carried out while raising the temperature to 200 ° C. at 10 ° C./hour. Further, after the reaction was carried out for 2 hours after reaching 200 ° C., the pressure inside the reaction vessel was reduced to 5 kPa or less, and the reaction was carried out at 200 ° C. while observing the molecular weight to obtain crystalline polyester 1. Table 4 shows the physical properties of the obtained crystalline polyester 1.

<Manufacturing of crystalline polyesters 2 to 9>
In the production of the crystalline polyester 1, the alcohol monomer and the carboxylic acid monomers 1 and 2 were changed as shown in Table 4, and the reaction time and temperature were adjusted to obtain the desired physical properties. 2 to 9 were obtained. Table 4 shows the physical properties and structure of the obtained crystalline polyester.

<Manufacturing of toner particles 1>
After warming to 60 ° C. was charged with 0.1 mol / L-Na ₃ PO ₄ aqueous solution 450 parts to 720 parts of deionized water, with the addition of 1.0 mol / L-CaCl ₂ aqueous solution 67.7 parts , An aqueous medium containing a dispersion stabilizer was obtained.

・ 78.0 parts of styrene ・ 22.0 parts of n-butyl acrylate ・ 0.65 parts of 1,6-hexanediol diacrylate ・ Iron complex of monoazo dye (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 1.5 parts ・ Magnetic amorphous Po Riesuteru resin obtained by condensation reaction of a body 1 90.0 parts amorphous Po Riesuteru resin 3.0 parts (ethylene oxide and propylene oxide adduct and terephthalic acid of bisphenol a; Mw = 9500, acid Valuation = 2.2 mgKOH / g, glass transition temperature = 68 ° C)
The above formulation was uniformly dispersed and mixed using an attritor (Mitsui Miike Machinery Co., Ltd.) to obtain a monomer composition. The monomer composition was heated to 63 ° C., there 10.0 parts of the crystalline polyester 1 shown in Table 4, sebacic acid di behenyl (melting point: 7 4 ° C.) 10.0 parts, and 10.0 parts of paraffin wax (melting point: 75 ° C.) was added and mixed, and dissolved.

The monomer composition was put into the aqueous medium and stirred at 12000 rpm for 10 minutes with a TK homomixer (Special Machinery Chemical Industry Co., Ltd.) in an N ₂ atmosphere at 60 ° C. to granulate. Then, 9.0 parts of the polymerization initiator t-butylperoxypivalate was added while stirring with a paddle stirring blade, the temperature was raised to 70 ° C., and the reaction was carried out for 4 hours. After completion of the reaction, the suspension was heated to 100 ° C. and held for 2 hours. Then, it was cooled, filtered and dried to obtain toner particles 1. Details of the cooling process are described below. The manufacturing method and formulation are shown in Table 5.

(Cooling process)
As a cooling step, water at room temperature is added to the suspension, the suspension is cooled from 100 ° C. to 50 ° C. at a rate of 100 ° C./min, and then held at 50 ° C. for 120 minutes at room temperature (hereinafter, 30 ° C.). Allowed to cool to room temperature).

<Manufacturing and Comparison of Toner Particles 2 to 26> Manufacturing of Toner Particles 1 to 6>
In the production of the toner 1, the type and number of copies of the crystalline polyester and the wax were changed as shown in Table 5, and the cooling rate of the cooling step described above was also changed as shown in Table 5. Particles 2 to 26 and comparative toner particles 1 to 6 were produced. The manufacturing method and formulation are shown in Table 5.

The condition of "100 ° C./min" is that in the cooling step in the manufacturing process of the toner particles 1, the suspension is cooled at a rate of 100 ° C. to 100 ° C./min to near the crystallization peak temperature of the crystalline polyester, and the temperature thereof. (Preferably, the crystallization peak temperature is ± 3 ° C.), which indicates that the mixture is held for 60 minutes and then allowed to cool to room temperature. The "10 ° C./min" condition is the same except that the cooling rate is different.

The condition of "annealing" is that the temperature is lowered to near the crystallization peak temperature of the crystalline polyester at a rate of 100 ° C. to 0.5 ° C./min in the cooling step, and at that temperature (preferably the crystallization peak temperature ± 3 ° C.). , 12 hours, then allow to cool to room temperature.

<Manufacturing of toner 1>
100 parts of toner particles 1 and 0.8 parts of hydrophobic silica fine particles having a BET value of 300 m ² / g and an average number of primary particles of 8 nm are mixed with a Henshell mixer (Mitsui Miike Machinery Co., Ltd.). To obtain 1 toner.

<Manufacturing of Toners 2 to 26 and Comparison of Toners 1 to 6>
In the production of the toner 1, the toners 2 to 26 and the comparative toners 1 to 6 were produced in the same manner except that the toner particles were changed as shown in Table 6. The physical properties of the toners 2 to 26 and the comparative toners 1 to 6 are also shown in Table 6. When "St-Ac 80%" is described in the item of the binder resin component in Table 6, the remaining 20% of the binder resin component is a polyester resin.

[Example 1]
(Evaluation 1. Fog after harsh storage)
As an image forming apparatus, LBP-224X (manufactured by Canon) was modified and used. As a modification point, the process speed was set to 250 mm / sec, which was faster than the original 220 mm / sec, and the contact pressure between the fixing film and the pressure roller was set to 30% of the normal pressure so as to be a light pressure. This makes it possible to evaluate the rear end offset more severely.

As the fixing film, a film having a surface roughness Ra of 0.5 μm was used.

As the cartridge, a modified cartridge equipped with a sleeve having a diameter of 14 mm to a diameter of 10 mm was used as the developing sleeve.

When a cartridge equipped with a small-diameter developing sleeve is used, the nip between the developing sleeve and the developing blade becomes narrow, which makes the toner chargeability disadvantageous, so that fog can be evaluated severely.

Using this modified cartridge, toner 1 is used, and in a low temperature and low humidity environment (15 ° C / 10% RH), a horizontal line chart with a printing rate of 4% is output, and then two solid white sheets are printed and two sheets are printed. Eye fog was measured by the following method. The fog value at this time was defined as fog before harsh storage.

Next, this cartridge was left in a high temperature environment (50 ° C./55% RH) for 12 hours to give a history of a harsh environment. Using this modified cartridge, toner 1 is used, and in a low temperature and low humidity environment (15 ° C / 10% RH), a horizontal line chart with a printing rate of 4% is output, and then two solid white sheets are printed and two sheets are printed. Eye fog was measured by the following method. The fog value at this time was defined as fog after harsh storage.

First, a method for measuring fog is shown. The reflectance of the solid white image obtained in Evaluation 1 was measured using REFLECTMER MODEL TC-6DS manufactured by Tokyo Denshoku Co., Ltd. On the other hand, the reflectance of the transfer paper (standard paper) before forming a solid white image was measured in the same manner. A green filter was used as the filter. Fog was calculated using the following formula from the reflectance before and after the solid white image output.
Fog (reflectance) (%) = reflectance of standard paper (%) -reflectance of solid white image sample (%)

The criteria for determining fog after harsh storage are as follows.

The difference (fog deterioration degree (%)) between fog (reflectance) (%) after harsh storage and fog (reflectance) (%) before harsh storage is
A: Less than 1.0% B: 1.0% or more and less than 1.5% C: 1.5% or more and less than 2.5% D: 2.5% or more

(Evaluation 2. Rear end offset)
As the image forming apparatus, the modified machine used in the evaluation 1 was used, and the setting of the fuser was changed so as to further lower the temperature control of the fuser by 10 ° C. Similarly, the modified cartridge used in evaluation 1 was used as the cartridge. Furthermore, the setting of the fuser was changed so as to lower the temperature control of the fuser by 10 ° C. Similarly, the modified cartridge used in evaluation 1 was used as the cartridge.

In a high temperature and high humidity environment (32.5 ° C./80% RH), the fuser was removed during the evaluation, and the following evaluation was carried out in a state where the fuser was sufficiently cooled using a fan or the like. By sufficiently cooling the fuser after the evaluation, the temperature of the fixing nip portion that has risen after the image output is cooled, so that the toner fixability can be severely evaluated and the evaluation can be performed with good reproducibility.

In evaluating the rear end offset, Canon A4 size OceRedLabel paper (basis weight 80 g / m ² ) left paper (paper left in the above high temperature and high humidity environment for 48 hours or more) was used as a recording material. By using paper that is relatively heavy and has a large surface roughness and that is left unattended, it is possible to severely evaluate the rear edge offset.

A solid black image was output on the above-mentioned neglected paper using the toner 1 in a state where the fuser was sufficiently cooled. At this time, the amount of toner loaded on the paper was adjusted to 9 g / m ² .

In the evaluation result of Toner 1, a good solid black image without a missing image was obtained.

The criteria for determining the rear end offset are described below.

For the rear end offset, the level of missing spots was visually evaluated for the solid black image output by the above procedure. The criteria for determining the rear end offset are as follows.
A: Very good (no dropouts)
B: Good (If you look closely, you can see some spots missing)
C: Normal (missing spots are seen but not noticeable)
D: Inferior (noticeable dropouts)

(Evaluation 3. Film contamination)
As the image forming apparatus, the modified machine used in evaluation 1 was used. Similarly, the modified cartridge used in evaluation 1 was used as the cartridge. The image forming apparatus and the cartridge were sufficiently left in a low temperature environment (7.5 ° C./30 RH) before evaluation. By keeping the image forming apparatus and the cartridge at a low temperature, the adhesion of the toner to the fixing roller can be promoted, and the film stain resistance can be severely evaluated.

When the fixing film was contaminated, the contamination was transferred to the pressure roller and the back of the paper was contaminated. Therefore, the following evaluation method was carried out.

After printing out five solid images, a solid white image was output and the dirt on the pressure roller and the printed paper back was visually confirmed.
A: No stains on both the pressure roller and the back of the paper B: Minor stains are confirmed on the pressure rollers, but no stains are generated on the back of the paper C: Light stains are confirmed on the pressure rollers and the paper Slight stains on the back D: Dirt was confirmed on the pressure roller, and clear stains were also generated on the back of the paper.

[Examples 2 to 26 and Comparative Examples 1 to 6]
The evaluation was carried out in the same manner except that the toner particles 2 to 26 and the comparative toner particles 1 to 6 were used in Example 1. The evaluation results are shown in Table 7.

1: Wax domain 2: Crystalline polyester domain 3: Region 25% depth from the surface of the toner to the particle size of the toner cross section, 100: Electrostatic latent image carrier (photoreceptor), 102 : Toner carrier, 103: Development blade, 114: Transfer member (transfer charging roller), 116: Cleaner container, 117: Charging member (charging roller), 121: Laser generator (latent image forming means, exposure device), 123 : Laser, 124: Pickup roller, 125: Conveyance belt, 126: Fixer, 140: Developer, 141: Stirring member, 142: Toner control member, 200: Head part, 201: Load center, 202 probe unit, 203: Probe tip, 204: Toner pellet, 205: Sample holding plate

Claims (5)

A toner having toner particles containing a binder resin, a colorant, a wax, and a crystalline polyester.
In the cross section of the toner, the crystalline polyester forms a plurality of domains, and the number average diameter of the major axis of each domain is 50 nm or more and 300 nm or less.
The number of the domains in the cross section of the toner is 8 or more and 500 or less.
The binding resin is mainly composed of a styrene acrylic resin.
The stress integral value measured using a tacking tester in which the part of the probe that comes into contact with the toner is polytetrafluoroethylene is 5.0 g when the probe temperature is 200 ° C. and the pressing and holding time with the toner is 0.05 s.・ It is less than m / sec and
The crystalline polyester is contained in an amount of 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.
A toner characterized in that the total crystallinity of the wax and the crystalline polyester is 70% or more. The toner according to claim 1, wherein the crystalline polyester has a moiety derived from an aliphatic monoalcohol having 10 or more and 30 or less carbon atoms and / or an aliphatic monocarboxylic acid having 11 or more and 31 or less carbon atoms. In the cross section of the toner, the wax has formed a domain to claim 1 or 2 the total area of the domain of the wax to the area of the toner section is 50.0 area% or less 10.0 area% or more The toner described. In the cross section of the toner, the crystalline polyester forms a plurality of domains, and the domains are present in a region at a depth of 25% with respect to the particle size of the toner cross section from the surface of the toner by 60% or more. The toner according to any one of claims 1 to 3 . The toner according to any one of claims 1 to 4, wherein the wax contains an ester wax.

Images