JP2020086115A - toner - Google Patents

Abstract

To provide a toner capable of obtaining an image with high definition without fog for a long period of time, even in a toner supply member in a process cartridge or in a system not having means for charging to the toner such as voltage impression to a toner regulation member.SOLUTION: A toner includes: a toner particle containing a binder resin and a colorant; and an external additive. (1) The external additive includes an external additive A with a ferret diameter of 30-300 nm. (2) A fastening index of the external additive A in the toner is 0.00-3.30. (3) In a powder fluidity measurement apparatus, on a surface of a powder layer of the toner prepared in a measurement container while applying a vertical load of 0.88 kPa, a total energy is 100-150 mJ when a propeller-type blade is penetrated in the powder layer while rotating an outermost edge of the propeller-type blade at a peripheral velocity of 10 mm/sec.SELECTED DRAWING: None

Description

The present invention relates to a toner used in a recording method such as electrophotography.

In recent years, an electrophotographic apparatus such as a desktop printer has been changed from an environment in which one person is used by a plurality of persons to one person, and further miniaturization as well as higher image quality is demanded.
Considering the developing method, there are two-component developing method and one-component developing method in the developing method of the printer, but from the viewpoint of downsizing, the one-component developing method which does not use a member such as a carrier is suitable.
Further, from the viewpoint of high image quality, a developing system in which a toner carrier and an electrostatic latent image carrier are arranged in contact with each other (hereinafter referred to as “contact developing system”) is preferable. That is, the one-component contact development system is preferable.
Further, adoption of a cleanerless system can be cited as one of the effective means for downsizing the process cartridge. Most printers use a cleaner system. In the transfer process, the toner remaining on the electrostatic latent image carrier (hereinafter, transfer residual toner) is scraped off from the electrostatic latent image carrier by a cleaning blade. , Collected in the waste toner box. On the other hand, since the cleanerless system does not have the cleaning blade and the waste toner box, it can greatly contribute to downsizing of the main body.
As described above, the one-component contact development type cleaningless system is effective for downsizing. Further, it is also effective for downsizing to reduce the number of toner supply members and the like for supplying toner to the toner carrier.
On the other hand, with the worldwide spread of printers, the types of paper used have been diversified. Among them, when paper having particularly low strength or paper containing a large amount of filler is used, a large amount of so-called “paper dust” tends to be generated during printing.
This paper dust tends to cause various problems in a cleanerless system.
In particular, in the transfer method in which the photoconductor is directly transferred to the paper, the photoconductor and the paper come into direct contact with each other. In that case, the paper dust is likely to adhere to the photoconductor. In the cleaner system, the paper dust adhered on the photoconductor is collected together with the transfer residual toner by the cleaning blade. However, in the cleanerless system, since the transfer residual toner and the paper dust are not collected and the process returns to the charging process and the developing process, various image defects such as defective charging and spot-like image omission are likely to occur.
Particularly, in a system in which a voltage is applied to the toner regulating member in order to improve the charging property of the toner in the developing process, the paper dust tends to be more easily collected at the developing site.
In order to suppress the amount of paper dust collected at the developing portion, it is effective to turn off the voltage to the toner regulating member. However, when the voltage of the toner regulating member is turned off, the chargeability of the toner is likely to deteriorate. Further, in a process cartridge that does not have a toner supply member or the like for downsizing, tribo reduction and charge distribution broadening are more likely to occur. The reduction of tribo and the broadening of charge distribution tend to cause image defects such as fog. The fog is a problem that toner is present in the non-image area, which is an area where toner is not originally developed, and the non-image area is soiled.
In order to improve the fog, it is necessary to give the toner proper charge, and for that purpose, it is important to improve the fluidity of the toner. When the fluidity of the toner is improved, the contact frequency with the charging member such as the toner regulating member and the toner carrier is increased, and the toner is more easily charged. In particular, since the toner in the process cartridge often exists in a compacted state, the ease of loosening from the compacted state is an important characteristic.
Conventionally, proposals have been made for the purpose of improving the fluidity of the toner in the compacted state, and in particular, a case in which the basic fluidity energy amount by a powder rheometer that can evaluate the fluidity in the compacted state is proposed is proposed. Has been done.
For example, Patent Document 1 proposes a toner in which silica particles having a volume average particle diameter of 80 to 300 nm are used as an external additive and a basic fluidity energy amount measured by a powder rheometer is specified.
In addition, Japanese Patent Application Laid-Open No. 2004-242242 proposes a toner in which the fluidity characteristics of the toner in a compacted state are similarly defined by the basic fluidity energy amount of a powder rheometer.

JP, 2007-304331, A JP, 2005-184361, A

However, in Patent Document 1, since the flow characteristics are not consolidated when they are evaluated, the flow characteristics under the consolidated state are not evaluated.
On the other hand, Patent Document 2 defines the flow characteristics when a load of 30 N is applied. However, Patent Document 2 is characterized in that it is easy to aggregate when it is consolidated.
In any case, the fluidity in the consolidated state is not sufficient, and under the use conditions assumed in the present application, image defects such as fog are likely to occur. Further, in both Patent Document 1 and Patent Document 2, under the conditions of the examples, the sticking ratio of the external additive to the toner particles is not sufficient, the flow characteristics are likely to change through durability, and over long-term use, The characteristics of the toner are likely to change, and there is room for improvement in this respect as well.
An object of the present invention is to provide a toner capable of obtaining a high-definition image without fog for a long period of time even in a system having no toner charging member such as voltage application to a toner supply member in a process cartridge or toner regulation member. Is to provide.

The present invention provides a toner containing toner particles containing a binder resin and a colorant, and an external additive, wherein (1) the external additive has a Feret diameter a of 30 nm or more and 300 nm or less. Containing agent A,
(2) The sticking index of the external additive A in the toner is 0.00 or more and 3.30 or less,
(3) In the powder fluidity measuring device, a propeller blade is attached to the surface of the powder layer of the toner produced by applying a vertical load of 0.88 kPa in a measuring container, and the circumference of the outermost edge portion of the propeller blade is measured. The present invention relates to a toner having a total energy of 100 mJ or more and 150 mJ or less when the powder is intruded into the powder layer while rotating at a speed of 10 mm/sec.

It is possible to provide a toner capable of obtaining a high-definition image without fog for a long period of time even in a system having no toner charging member such as voltage application to a toner supply member or toner regulation member in a process cartridge. ..

5 is a schematic diagram showing a method of calculating an embedding index of the external additive A. FIG. FIG. 2 is a schematic diagram showing an example of a mixing processing device that can be used for externally adding and mixing an external additive A. It is a schematic diagram which shows an example of a structure of the stirring member used for a mixing processing apparatus. 1 is a schematic view of a toner processing device that can be used in the present invention. 3 is a schematic view of processing blades 140 in the processing tank 110. FIG. It is a schematic diagram of a stirring blade 120 in the processing tank 110. 3 is a schematic view of processing blades 140 in the processing tank 110. FIG. The ghost evaluation image is shown.

The present inventors have examined the toner characteristics necessary for obtaining proper charging even in a process cartridge having a low charging frequency. As a result, they have found that the above problems can be solved by using the toner characteristics of the present invention.

That is, the present invention is a toner containing toner particles containing a binder resin and a colorant, and an external additive,
(1) The external additive contains an external additive A having a ferret diameter a of 30 nm or more and 300 nm or less,
(2) The sticking index of the external additive A in the toner is 0.00 or more and 3.30 or less,
(3) In the powder fluidity measuring device, a propeller blade is attached to the surface of the powder layer of the toner produced by applying a vertical load of 0.88 kPa in a measuring container, and a propeller blade is provided around the outermost edge portion of the propeller blade. The total energy is 100 mJ or more and 150 mJ or less when the powder layer is penetrated into the powder layer while rotating at a speed of 10 mm/sec.

The toner in the process cartridge often exists in a compacted state due to stirring or the like. In the compacted state, since the contact area of the toner increases, the fluidity of the toner is apt to be deteriorated and the toner tends to be hardly charged. The present inventors considered that it is necessary to highly improve the fluidity of the toner in a compacted state in order to charge the toner with a low charging frequency.

In order to improve the fluidity of the toner in the compacted state, it is effective to reduce the contact area, that is, to make an external additive having a spacer function exist on the surface of the toner particles. That is, the present invention is characterized by having the external additive A as the external additive having a relatively large particle size and having a spacer function.

The particle size of the external additive A is 30 nm or more and 300 nm or less, preferably 60 nm or more and 180 nm or less, and more preferably 80 nm or more and 120 nm or less.

The Feret diameter a (nm) of the external additive A means the maximum diameter of the external additive A in observing the cross section of the toner particles with a transmission electron microscope (TEM). The above-mentioned particle size is suitable as the external additive A as a large particle size external additive that exhibits a spacer function.

However, even if the above-mentioned external additive A is used, if it is not fixed to the surface of the toner particles, the external additive shifts during compaction and the spacer function cannot be obtained. Further, there is a problem that the external additive A is transferred from the surface of the toner particles to other members by stirring or other rubbing in the process cartridge through durability, and it is impossible to maintain high fluidity through durability. there were.

To solve these problems, many proposals have been made to fix an external additive having a large particle size. However, as a method that has been proposed so far, a method of increasing the sticking rate by giving a strong impact force in the external addition step is the mainstream. This method can certainly increase the sticking rate, but at the same time, the external additive is embedded, and the originally expected spacer function tends to be insufficient, resulting in insufficient fluidity in the consolidated state.

Furthermore, since the external additive is fixed by the impact force, the interface between the large particle size external additive and the toner particles is largely deformed, causing distortion. This distortion becomes larger as the external additive is embedded, and cracks and cracks are likely to occur at the interface portion through durability, toner cracking and the like are easily induced, and charging failure is more likely to occur.

As a result of intensive studies, the inventors of the present invention have invented a toner capable of achieving both high adhesion of the external additive A having a spacer function and fluidity in a consolidated state.

That is, the toner of the present invention has a sticking index of the external additive A in the toner of 0.00 or more and 3.30 or less, preferably 0.10 or more and 3.00 or less, and more preferably 0.50 or more. It is 2.50 or less.

In order to ensure the spacer function of the external additive A, the external additive A must be firmly fixed to the toner particles. If the adhesion of the external additive A is weak, the position of the external additive A shifts when the toner particles come into contact with each other, or the external additive A migrates from the surface of the toner particles to other members through repeated use. There is a possibility that it will be lost and the spacer function cannot be fully exerted. When the sticking index of the external additive A is 0.00 or more and 3.30 or less, a sufficient spacer function is exhibited through repeated use.

The sticking index of the external additive A is used as an index of the sticking state of the external additive A to the toner particles.

The method for calculating the sticking index of the external additive A is as follows.

First, the amount of the external additive A transferred to the substrate when the toner is brought into contact with the substrate and pressed with a constant force is calculated using image analysis. The amount of the external additive A transferred to the substrate is expressed by the area ratio [A] of the external additive on the substrate. If the external additive A is strongly adhered to the toner particles, the area ratio [A] of the external additive A becomes a small value because the external additive A does not migrate to the substrate even when the toner is brought into contact with the substrate.

On the other hand, the area ratio [A] of the external additive A depends on the amount of the external additive A present on the surface of the toner particles, and therefore needs to be standardized for indexing. In the present invention, the coverage [B] of the toner particles with the external additive A is obtained in advance by observation, and the following is calculated from the area ratio [A] of the external additive A on the substrate and the coverage [B] of the external additive A. The sticking index of the external additive A was calculated using the formula.
Sticking index of external additive A =area ratio [A] of external additive A on the substrate/coverage ratio of external additive A [B]×100

The smaller the sticking index of the external additive A, the stronger the sticking of the external additive A to the toner particles.

Detailed conditions will be described later.

Further, while obtaining the firmly attached state of the external additive A as described above, in the powder fluidity measuring device, a vertical load of 0.88 kPa was applied in the measuring container to the surface of the powder layer of the toner, Total energy when the propeller blade penetrates into the powder layer while rotating the outer peripheral edge of the propeller blade at a peripheral speed of 10 mm/sec, and the total energy is 100 mJ or more and 150 mJ or less, preferably 100 mJ or more and 135 mJ or less. It is a feature of the present invention that the following high fluidity is achieved at the same time.

The above-mentioned powder fluidity measuring device is a device that can invade a compacted powder layer while rotating a propeller blade and calculate the share applied at that time as Total Energy (mJ). It is suitable for representing the flow state of toner that has received a share of.

In the present invention, as a compaction condition, a vertical load of 0.88 kPa was applied in the measurement container to form a compacted state of the toner. By setting the same conditions, it becomes possible to evaluate the flow characteristics assuming a compacted toner state formed in the process cartridge.

Then, the propeller blade is inserted into the compacted toner layer formed under the same conditions while rotating, and the share applied at that time is calculated as Total Energy (mJ).

In the present invention, considering the external force received from the stirring member in the process cartridge, the total energy was measured while rotating the peripheral speed of the outermost edge of the propeller blade at 10 mm/sec.

The total energy is obtained by converting the rotational torque applied to the propeller and the vertical load into energy and calculating the sum thereof. When the total energy value is small, it means that the toner can be fluidized from the compacted state with a small amount of energy, and the fluidity is good. The higher the value, the opposite.

Even if the total energy is too low, it is necessary to balance the transportability within the cartridge. In the present invention, it is preferable that the total energy is controlled to 100 mJ or more and 150 mJ or less so that the fluidity and the transportability are optimized.

As described above, the greatest feature of the present invention is that the fluidity in the consolidated state is highly improved while achieving the firm adhesion of the external additive A having a relatively large particle size.

In order to obtain the toner characteristics of the present invention, it can be obtained by controlling the fixing state of the external additive A to the toner particles.

In addition, the toner of the present invention is not particularly limited as far as it has the above-mentioned characteristics and other characteristics, but the following characteristics are preferable.

In the toner of the present invention, the external additive A is preferably inorganic fine particles or organic-inorganic composite fine particles. As the external additive A, since it is necessary to exert a spacer function and mechanical strength is required, it is preferable to use endless fine particles or organic-inorganic composite fine particles.

The external additive A used in the present invention is not particularly limited as long as it is an inorganic fine particle or an organic-inorganic composite fine particle. Examples of the inorganic fine particle include silica fine particles, alumina fine particles, titania fine particles, and composite oxides thereof. Examples include fine particles such as fine particles.

For example, as a method for producing silica fine particles, a combustion method obtained by burning a silane compound (that is, a method for producing fumed silica), a deflagration method obtained by explosively burning metallic silicon powder, sodium silicate and a mineral acid. And a sol-gel method (so-called Stoeber method) obtained by hydrolysis of alkoxysilane such as hydrocarbyloxysilane.

The inorganic fine particles are preferably used by controlling the degree of hydrophobicity by a hydrophobic treatment. By controlling the degree of hydrophobicity, the inorganic fine particles are likely to be unevenly distributed at the interface between the droplet and the hydrophobic dispersion medium, and the dispersion stability of the droplet is easily improved. The method of hydrophobizing the inorganic fine particles is not particularly limited, and a known method can be used, but a method of treating the inorganic fine particles with a hydrophobizing agent is preferable.

Examples of the organic-inorganic composite fine particles include organic-inorganic composite fine particles composed of an inorganic material and an organic material. If the organic-inorganic composite fine particles, while maintaining good durability and chargeability as an inorganic material, at the time of fixing, it is difficult to prevent coalescence of toner particles due to the components of the organic material having a low heat capacity, and fixing It is difficult to cause inhibition. Therefore, it is easy to achieve both durability and fixability.

A preferred structure of the organic-inorganic composite fine particles is a composite fine particle composed of inorganic fine particles embedded in the surface of resin fine particles (preferably vinyl-based resin fine particles) as an organic component. More preferably, it has a structure in which the inorganic fine particles are exposed on the surface of the vinyl resin particles. Still more preferably, a structure having convex portions derived from the inorganic fine particles on the surface of the vinyl resin particles is preferable.

Further, the external additive A is preferably subjected to a hydrophobic treatment. Specific examples of the hydrophobizing agent include chlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, t-butyldimethylchlorosilane, and vinyltrichlorosilane;
Tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, n-butyltrimethoxysilane, i-butyltrimethoxysilane Silane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, i-butyltrisilane Ethoxysilane, decyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxy Alkoxysilanes such as silanes;
Hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, hexabutyldisilazane, hexapentyldisilazane, hexahexyldisilazane, hexacyclohexyldisilazane, hexaphenyldisilazane, divinyltetramethyldisilazane, dimethyltetravinyl Silazanes such as disilazane;
Dimethyl silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, alkyl modified silicone oil, chloroalkyl modified silicone oil, chlorophenyl modified silicone oil, fatty acid modified silicone oil, polyether modified silicone oil, alkoxy modified silicone oil, carbinol modified Silicone oils such as silicone oils, amino-modified silicone oils, fluorine-modified silicone oils, and end-reactive silicone oils;
Hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, and other siloxanes;
Fatty acids and metal salts thereof include undecyl acid, lauric acid, tridecyl acid, dodecyl acid, myristic acid, palmitic acid, pentadecyl acid, stearic acid, heptadecyl acid, arachidic acid, montanic acid, oleic acid, linoleic acid, arachidonic acid, etc. Long-chain fatty acids, and salts of the above fatty acids with metals such as zinc, iron, magnesium, aluminum, calcium, sodium and lithium.

Among these, alkoxysilanes, silazanes, and straight silicone oils are preferably used because they are easily subjected to the hydrophobic treatment. These hydrophobizing agents may be used alone or in combination of two or more.

The surface coverage of the toner of the present invention with the external additive A is preferably 28.0 area% or more and 45.0 area% or less, and more preferably 30.0 area% or more and 40.0 area% or less. .. In order to stably control the flow characteristics in the consolidated state within the range of the present application, 28.0 area% or more is required. On the other hand, when it exceeds 45.0 area %, the external additive A is difficult to be uniformly dispersed, so that the adhered state tends to be nonuniform. Therefore, it is preferable to control the amount of the external additive A present on the surface of the toner particles within the above range.

The shape factor SF-2 of the external additive A is preferably 103 or more and 120 or less, more preferably 110 or more and 120 or less.

When SF-2 is in the above range, it means that the external additive A has a structure having a convex portion on the surface. By adopting a structure in which the external additive A has a convex portion, an anchoring effect on the surface of the toner particles can be easily obtained, sticking can be easily controlled, and resistance to external shear increases, so that durability is further improved. Improves stability. Further, since the toner has a convex structure on the surface, the contact between the toners becomes closer to a point contact, and it becomes easier to improve the fluidity under a consolidated state. Furthermore, the adhesion to the charging member such as the toner carrier is lowered, and image defects such as ghosts are less likely to occur, which is preferable.

In a cross-sectional observation of the toner by a transmission electron microscope (TEM), the penetration depth of the external additive A, which is a part of the external additive A invading the inside of the toner particle from the surface of the toner particle, is expressed as b (nm). When the convex height is c (nm), it is preferable that the penetration depth b and the convex height c satisfy the following relational expressions (1) and (2).
30≦b+c≦300 (1)
0.15≦b/(b+c)≦0.30 (2)
(The penetration depth b (nm) of the external additive A means that the external additive A is in contact with the toner particles in the outline of the external additive A in the observation of an image obtained by image-processing the cross section. When the contour line of the part is defined as a contour line X and a line segment obtained by connecting both ends of the contour line X with a straight line is defined as a line segment Z, a perpendicular line drawn from the line segment Z to the contour line X and It means the maximum distance between the intersection with the contour line X and the line segment Z, and the convex height c (nm) of the external additive A is the observation of an image obtained by image-processing the cross section. In, when a contour line of a portion other than the contour line X among the contour lines of the external additive A is defined as a contour line Y, a perpendicular line from the line segment Z to the contour line Y and the contour line Y It means the maximum distance between the intersection and the line segment Z.)

The present invention is characterized in that the strong adhesion of the external additive A and the fluidity in the consolidated state are highly compatible with each other. In order to obtain this characteristic, it is preferable to fix the external additive A without embedding it.
In the present invention, the embedded state of the external additive is defined by observing the cross section of the toner with a transmission electron microscope (TEM), and the preferable range has been found.

Specifically, a transmission electron microscope (TEM) is used to obtain an image obtained by image-processing the cross section of the toner containing the external additive A. FIG. 1 is a schematic diagram showing a method of calculating an index such as the penetration depth of the external additive A.

In the processed image, the penetration depth of the external additive A in which a part of the external additive A penetrates from the surface of the toner particle into the toner particle is defined as b (nm), and the convex height is c (nm). And

The sum b+c (nm) of the penetration depth b (nm) and the convex height c (nm) is a value related to the Feret diameter a (nm) of the external additive A. In the present invention, b+c (nm) is 30 nm or more and 300 nm or less, preferably 60 nm or more and 180 nm or less, and more preferably 80 nm or more and 120 nm or less.

When the ratio of the penetration depth b of the external additive A and the penetration depth b to the sum b+c of the convex heights c is large, the external additive A penetrates deeper into the toner particles. In the present invention, the value of the ratio (b/(b+c)) of the penetration depth b of the external additive A to the sum b+c of the penetration depth b and the convex height c is set to the toner particles of the external additive A. It is used as an index for the invasion of.

That is, the larger the value of b/(b+c), the deeper the external additive A penetrates into the toner particles.

The sum b+c (nm) of the penetration depth b of the external additive A and the convex height c is 30 nm or more and 300 nm or less, and b/(b+c) is 0.30 or less (preferably 0.28 or less, more preferably 0). .26 or less), a sufficient spacer function can be exhibited. However, if the value of b/(b+c) is too small, the external additive A easily migrates to other members through repeated use even if the sticking index is small. Therefore, b/(b+c) is 0.15 or more. Yes, it is preferably 0.18 or more, and more preferably 0.20 or more. The numerical ranges can be arbitrarily combined.

With respect to the degree of penetration of the external additive A from the surface of the toner particles into the inside of the toner particles while maintaining the adhesion of the external additive A to the toner particles in a strong state (fixing index is 0.00 or more and 3.30 or less), .15≦b/(b+c)≦0.30 is controlled. By doing so, it becomes possible to stably maintain the spacer function of the external additive A through repeated use. The value of b/(b+c) can be adjusted by appropriately changing various conditions in the method of fixing the external additive A to the toner particles. Details will be described later.

The standard deviation of b/(b+c), which is an index relating to the penetration of the external additive A into the toner particles, is preferably 0.00 or more and 0.13 or less, and 0.00 or more and 0.12 or less. More preferably.

The convex height c (nm) is preferably 50.0 nm or more and 150.0 nm or less, and more preferably 50.0 nm or more and 120.0 nm or less.

By controlling the standard deviation of b/(b+c) and the standard deviation of the convex height c within the above range, the degree of embedding of the external additive A and the variation of the height of the convex portion are suppressed, and a stable spacer is provided. It is preferable because it can have a function.

Next, a preferable method for producing the toner of the present invention will be described.

The toner of the present invention is not particularly limited in its manufacturing method as long as it has the above-mentioned characteristics, but a method of fixing the external additive A by heat using the mixing processing apparatus shown in FIGS. 2 and 3. Is preferred.

As a means for achieving the solid adhesion of the large particle size external additive, the conventional method has been mainly to improve the impact force and the shearing force between the toner and the stirring blade and the toner and the toner in the external addition mixing processing device. This is due to the fact.

However, as described above, in the fixing method using impact force or shearing force, the external additive is likely to be embedded at the same time, and as a result, the fluidity under a consolidated state is likely to be deteriorated.

Therefore, the present inventors believe that in order to firmly attach the external additive A without embedding it on the surface of the toner particles, an external addition method based on a new idea is required instead of the conventional fixing method using impact force. Focused on the sticking due to.

It was expected that when the toner was heated near the glass transition temperature (Tg) of the toner particles, the surface of the toner particles was partially softened and the external additive A was fixed.

Furthermore, it was considered that if heat can be applied to the toner without applying impact force or shearing force as much as possible, a strong adhesion state can be achieved without embedding an external additive.

However, the impact force and the shearing force by the external addition device also have the function of uniformly dispersing the external additive on the surface of the toner particles. Therefore, if the impact force and the shearing force are not applied as much as possible, the issue is how to uniformly disperse the external additive A on the toner surface.

As a result of intensive studies by the present inventors, by using the mixing processing apparatus shown in FIGS. 2 and 3, the sticking rate and the embedding degree of the external additive A are controlled, and the external additive A on the surface of the toner particles is controlled. It has been found that uniformity can also be ensured.

Hereinafter, the mixing processing apparatus preferably used in the present invention will be described with reference to FIGS.

FIG. 2 is a schematic diagram showing an example of a mixing processing apparatus that can be used in the heating step. On the other hand, FIG. 3 is a schematic view showing an example of the configuration of a stirring member used in the mixing processing apparatus. The mixing processing device includes a rotating body 32 on which at least a plurality of stirring members 33 are installed, a drive unit 38 for rotationally driving the rotating bodies, and a main body casing 31 provided with a gap from the stirring member 33. Have.

In the gap (clearance) between the inner peripheral portion of the main body casing 31 and the stirring member 33, heat is efficiently applied to the toner, and the toner is evenly distributed, so that the external additive is changed from the secondary particles to the primary particles. It can be fixed on the surface of the toner particles while being loosened.

Further, as will be described later, the toner particles and the external additive are likely to circulate in the axial direction of the rotating body, and they are likely to be sufficiently and uniformly mixed before adhering to the fixing.

Further, in this device, the diameter of the inner peripheral portion of the main body casing 31 is not more than twice the diameter of the outer peripheral portion of the rotating body 32. FIG. 2 shows an example in which the diameter of the inner peripheral portion of the main body casing 31 is 1.7 times the diameter of the outer peripheral portion of the rotating body 32 (the diameter of the body portion excluding the stirring member 33 from the rotating body 32). When the diameter of the inner peripheral portion of the main body casing 31 is equal to or less than twice the diameter of the outer peripheral portion of the rotating body 32, the processing space in which the force acts on the toner particles is appropriately limited, so that the secondary particles become secondary particles. It becomes possible to sufficiently disperse the existing external additives.

It is important to adjust the clearance according to the size of the main body casing. It is important to set the diameter of the inner peripheral portion of the main casing 31 to be 1% or more and 5% or less from the viewpoint of efficiently applying heat to the toner. Specifically, when the diameter of the inner peripheral portion of the body casing 31 is about 130 mm, the clearance is set to 2 mm or more and 5 mm or less, and when the diameter of the inner peripheral portion of the body casing 31 is about 800 mm, 10 mm or more and 30 mm or less. It should be about.

As shown in FIG. 3, at least a part of the plurality of stirring members 33 is formed as a feeding stirring member 33a that sends the toner in one axial direction of the rotating body as the rotating body 32 rotates. Further, at least a part of the plurality of stirring members 33 is formed as a returning stirring member 33b that returns the toner to the other direction in the axial direction of the rotating body as the rotating body 32 rotates. Here, when the raw material inlet 35 and the product outlet 36 are provided at both ends of the main body casing 31 as shown in FIG. 2, the direction from the raw material inlet 35 toward the product outlet 36 (in FIG. 2). The right direction) is called the "feed direction".

That is, as shown in FIG. 3, the plate surface of the feeding stirring member 33 a is inclined so as to feed the toner in the feeding direction 43. On the other hand, the plate surface of the stirring member 33b is inclined so as to send the toner in the return direction 42.

As a result, the heating process is performed while repeating the feeding in the “feed direction” 43 and the feeding in the “return direction” 42. The stirring members 33a and 33b are a set of a plurality of members arranged at intervals in the circumferential direction of the rotating body 32. In the example shown in FIG. 3, the stirring members 33a and 33b form a set of two members on the rotating body 32 at intervals of 180 degrees, but three members at intervals of 120 degrees, or at intervals of 90 degrees. A large number of members such as four may be set as one set.

In the example shown in FIG. 3, a total of 12 stirring members 33a and 33b are formed at equal intervals.

Further, in FIG. 3, D indicates the width of the stirring member, and d indicates the interval indicating the overlapping portion of the stirring members. From the viewpoint of efficiently feeding the toner in the feeding direction and the returning direction, it is preferable that D has a width of 20% or more and 30% or less with respect to the length of the rotating body 32 in FIG. In FIG. 3, an example of 23% is shown. Furthermore, it is preferable that the stirring members 33a and 33b have an overlapping portion d of the stirring members 33b and 33a to some extent when an extension line is drawn in the vertical direction from the end position of the stirring member 33a.

Thereby, the external additive on the surface of the toner particles can be efficiently dispersed. It is preferable that d with respect to D is 10% or more and 30% or less in terms of sharing.

Regarding the shape of the blade, in addition to the shape shown in FIG. 3, if the toner particles can be sent in the sending direction and the returning direction and the clearance can be maintained, the shape having a curved surface or the tip blade part The paddle structure may be connected to the rotating body 32 by a rod-shaped arm.

Hereinafter, further details will be described with reference to the schematic views of the apparatus shown in FIGS.

The apparatus shown in FIG. 2 includes a rotating body 32 having at least a plurality of stirring members 33 installed on the surface thereof, a drive unit 38 for rotationally driving the rotating body 32, and a main body casing provided with a gap with the stirring member 33. Has 31. Further, it has a jacket 34 inside the main body casing 31 and adjacent to the side surface 310 of the end portion of the rotating body, through which a cooling/heating medium can flow.

Further, the apparatus shown in FIG. 2 has a raw material inlet 35 formed in the upper part of the main body casing 31 and a product discharge port 36 formed in the lower part of the main body casing 31. The raw material charging port 35 is used for introducing the toner, and the product discharging port 36 is used for discharging the externally added and mixed toner from the main body casing 31.

Further, in the apparatus shown in FIG. 2, the raw material feeding port inner piece 316 is inserted into the raw material feeding port 35, and the product discharging port inner piece 317 is inserted into the product discharging port 36.

First, the raw material input port inner piece 316 is taken out from the raw material input port 35, toner is charged into the processing space 39 from the raw material input port 35, and the raw material input port inner piece 316 is inserted. Next, the rotating body 32 is rotated by the drive unit 38 (41 indicates a rotating direction), and the processed products introduced above are added while being stirred and mixed by the stirring members 33 provided on the surface of the rotating body 32. Perform hot mixing.

By using the above-mentioned mixing treatment device having excellent diffusion ability as described above, the external additive A can be disentangled from the secondary particles to the primary particles with the minimum necessary impact force and shearing force. As a result, the external additive A can be uniformly dispersed on the surface of the toner particles.

Further, in the present invention, heating is performed by passing warm water of a desired temperature through the jacket 34. The temperature is monitored by a thermocouple installed inside the inner piece 316 for raw material inlet.

In order to obtain the toner of the present invention in a stable and required toner performance, when the thermocouple temperature (T1) of the inner piece 316 for the raw material charging port is T2 and the glass transition temperature of the toner particles is T2-10. C. or higher and T2+10.degree. C. or lower are preferable. More preferably, it is T2-10°C or higher and T2+5°C.

When T1 is lower than T2-10°C, the softening of the surface of the toner particles is less likely to occur, the external additive A is less likely to be fixed, and the external additive A is easily transferred to another member due to durability.

On the other hand, when T1 exceeds T2+10° C., the glass transition temperature of the toner is greatly exceeded, so that fusion occurs in the processing device. Furthermore, the embedding of the external additive A into the toner particles becomes remarkable, and it is difficult to sufficiently obtain the initially intended spacer function.

Further, it is preferable that the peripheral speed V of the plurality of stirring blades of the mixing processing apparatus shown in FIGS. 2 and 3 is 0.1 m/sec or more and 7.0 m/sec or less. Further, when the mixing processing energy during the heating and mixing is E(Wh/g), it is preferable that the following formula (3) is satisfied.
1.0×10 ⁻⁴ Wh/g≦E≦1.5×10 ⁻² Wh/g (3)

E in the formula (3) is obtained by multiplying the effective power (W) obtained by subtracting the aerodynamic power (W) operated when the toner is not supplied from the power (W) when the toner is supplied by the time (h), and the toner is supplied. It is a value divided by the amount (g).

As described above, when the stirring blade collides with the toner at a high speed, the external additive particles A are embedded in the surface of the toner particles, which impairs the spacer function and easily causes a non-uniform external addition state. Further, residual stress is accumulated in the interface between the toner particles and the external additive A and the inside of the toner, so that cracking and chipping of the toner may be promoted through durability.

By controlling the peripheral speeds of the plurality of stirring blades, the processing power in the mixing processing device, the processing time, and the processing energy calculated from the processing amount within the above range, while achieving uniformity and firm adhesion, It is preferable because the degree of embedding can be controlled within an appropriate range.

The treatment time depends on the temperature to be heated and is not particularly limited, but is preferably 3 minutes or more and 30 minutes or less, and more preferably 3 minutes or more and 10 minutes or less. By controlling the amount within the above range, it becomes easy to achieve both the toner strength and the fixation. The rotation speed of the stirring member is not particularly limited because it is linked to the power.

As described above, by externally heating and adding by using the mixing processing device shown in FIGS. 2 and 3 which is excellent in diffusibility and circulation, external addition to the surface of the toner particles can be performed with the minimum necessary impact force and shearing force. It is possible to uniformly disperse the agent A and to obtain a strong fixed state in a short period of time. As a result, the fixed state of the external additive A of the present invention is easily achieved, and therefore it is preferably used.

Further, in the toner of the present invention, external heating and heating may be carried out at the same time under the above heating and mixing processing conditions, or the toner particles and the external additive A may be mixed with a known mixer such as a Henschel mixer. The external additive A may be mixed and externally added under such a condition that the external additive A is not embedded therein, the external additive A is sufficiently dispersed on the toner particles, and then the heating and mixing treatment device may be used for heating.

The following are mentioned as a mixer. Mitsui Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.); Super mixer (manufactured by Kawata); Ribocon (manufactured by Okawara Seisakusho); Nauta mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron); Spiral pin mixer (Pacific) Ledige mixer (made by Matsubo).

In the present invention, as a particularly preferable processing method, the toner particles and the external additive A are mixed and externally added by a known mixer such as a Henschel mixer shown in FIG. It is preferable to heat (second step).

As a specific example of the first-stage mixing external addition, a Mitsui Henschel mixer (FM) (Mitsui Miike Kakoki Co., Ltd.) shown in FIG. 4 is used, and a stirring blade 120 shown in FIG. Further, it is preferable to use a mixer in which the processing blade 140 shown in FIG. 5 is attached above the stirring blade 120.

The mixing conditions must be such that the external additive A is not embedded and the particles can be sufficiently dispersed on the toner particles. The peripheral speed of the processing blade is preferably 10 m/sec or more and 40 m/sec, and the mixing time is Is preferably 30 seconds or more and 300 seconds or less.

Further, the toner of the present invention is a differential curve obtained by differentiating the load-displacement curve with the load, in which the abscissa represents the load (mN) and the ordinate represents the displacement amount (μm) in the measurement of the strength of the toner by the nanoindentation method. When obtained, the load F that is the maximum value of the differential curve in the load region of 0.20 mN or more and 2.30 mN or less is preferably 1.0 mN or more and 2.0 mN or less, and more preferably 1.1 mN or more and 1. It is 8 mN or less.

By controlling the external additive A to the fixed state of the present invention and simultaneously increasing the mechanical strength of the toner, it becomes possible to suppress cracking and crushing of the toner due to durability. The cracking or crushing of the toner causes poor charging, which easily causes image results such as fog.

Factors that lower the mechanical strength of the toner are affected by the molecular weight of the binder resin and the like, but are also easily affected by strain and stress accumulated in the toner manufacturing process. In particular, when a strong force is applied to the toner, stress is likely to be accumulated inside.

In the present invention, the nanoindentation method is adopted as an index of toner strength. The nanoindentation method pushes the diamond indenter into the sample placed on the stage, measures the load (pushing strength) and the displacement (pushing depth), and analyzes the mechanical properties from the obtained load-displacement curve. It is an evaluation method.

Conventionally, a micro compression tester has been used as a method for evaluating the mechanical properties of the toner, but since the indenter used for the micro compression test is larger than the size of one toner particle, the macro mechanical properties of the toner are evaluated. Suitable for

However, since the microscopic mechanical properties of the toner particle surface affect the cracking or crushing of the toner particles, which is the focus of the present invention, in particular the cracking, it is required to evaluate the characteristics in a finer area. In the measurement by the nanoindentation method, the indenter has a triangular pyramid shape, and the tip of the indenter is overwhelmingly smaller than the size of one toner particle. Therefore, it is suitable for evaluating the micro mechanical properties of the toner particle surface.

In the measurement of the nanoindentation method, a very small load is continuously applied to the toner, the indenter is pushed into the sample, the displacement at that time is measured, the horizontal axis is the load (mN), and the vertical axis is the displacement amount (μm). Create a load-displacement curve.

In the load-displacement curve, it is considered that the toner particles are largely deformed at the load at which the displacement with respect to the load is maximum, that is, a phenomenon corresponding to cracking occurs. Therefore, in the present invention, the load having the maximum slope on the load-displacement curve is defined as the load at which the toner particles are cracked. That is, the larger the load having the maximum inclination, the larger the load required to break the toner particles, which means that the toner particles are more difficult to break.

In the present invention, as a method of calculating the load having the maximum slope, a load having a maximum differential value is adopted in a differential curve obtained by differentiating the load-displacement curve with the load.

In order to increase the mechanical strength, for example, it is effective to increase the molecular weight of the toner. However, if the molecular weight is excessively increased, the fixability may decrease.

In order to improve the mechanical strength of the toner without raising the molecular weight too much, it is preferable to provide a heating step after the external addition step. This is preferable because it is possible to alleviate the residual stress generated in the manufacturing process of the toner and to promote the fixing of the external additive by heat.

Hereinafter, preferred embodiments of the present invention will be described in more detail.

Examples of the binder resin used in the toner include the following. Vinyl resin, styrene resin, styrene copolymer resin, polyester resin, polyol resin, polyvinyl chloride resin, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, Silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin.

Preferably, it is a styrene-based copolymer resin, a polyester resin, a mixture of a polyester resin and a vinyl resin, or a hybrid resin in which both of them are partially reacted.

The toner may contain a release agent.

As the release agent, waxes containing a fatty acid ester such as carnauba wax and montanic acid ester wax as a main component; deoxidized part or all of the acid component is deoxidized from the fatty acid ester such as carnauba wax Methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and fats; saturated fatty acid monoesters such as stearyl stearate and behenyl behenate; dibehenyl sebacate, distearyl dodecanedioate, dioctadecanedioate Diesters of saturated aliphatic dicarboxylic acids such as stearyl and saturated aliphatic alcohols; Diesters of saturated aliphatic diols and saturated fatty acids such as nonanediol dibehenate and dodecanediol distearate, low molecular weight polyethylene, low molecular weight polypropylene , Microcrystalline wax, paraffin wax, Fischer-Tropsch wax and other aliphatic hydrocarbon waxes; oxides of aliphatic hydrocarbon wax such as oxidized polyethylene wax or block copolymers thereof; aliphatic hydrocarbon wax and styrene Waxes grafted with vinyl monomers such as acrylic acid and acrylic acid; saturated straight-chain fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid and parinaric acid Saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol, and melysyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide Saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, and hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N,N'- Unsaturated fatty acid amides such as dioleyl adipic acid amide and N,N′-dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bisstearic acid amide and N,N′-distearyl isophthalic acid amide; Aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally referred to as metallic soap); long-chain alkyl alcohols having 12 or more carbon atoms or long-chain alkyl carboxylic acids. Acid; and the like.

Among these releasing agents, monofunctional or bifunctional ester waxes such as saturated fatty acid monoesters and diesters, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax are preferable.

The melting point of the release agent, which is determined by the differential scanning calorimeter (DSC) and is defined by the peak temperature of the maximum endothermic peak at the time of temperature increase, is preferably 60°C or higher and 140°C or lower. More preferably, it is 60° C. or higher and 90° C. or lower. When the melting point is 60° C. or higher, the storage stability of the toner is improved. On the other hand, when the melting point is 140° C. or lower, the low temperature fixability tends to be improved.

The content of the releasing agent is preferably 3 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin. When the content of the release agent is 3 parts by mass or more, the fixability is easily improved. On the other hand, when the content of the release agent is 30 parts by mass or less, deterioration of the toner is less likely to occur during long-term use, and image stability is likely to be improved.

The toner of the present invention preferably contains a charge control agent.

As the charge control agent for negative charging, organic metal complex compounds and chelate compounds are effective, and examples thereof include monoazo metal complex compounds; acetylacetone metal complex compounds; metal complex compounds of aromatic hydroxycarboxylic acid or aromatic dicarboxylic acid. To be done.

Specific examples of commercially available products include Spiron Black TRH, T-77, T-95 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark) S-34, S-44, S-54, E-84, E. -88, E-89 (Orient Chemical Industry Co., Ltd.) are mentioned.

These charge control agents can be used alone or in combination of two or more kinds. The amount of these charge control agents used is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, and more preferably 0.1 parts by mass or more and 5 parts by mass, per 100 parts by mass of the binder resin, from the viewpoint of the charging amount of the toner. It is not more than 0.0 parts by mass.

The toner of the present invention can be used as any one of magnetic one-component toner, non-magnetic one-component toner and non-magnetic two-component toner.

When used as a magnetic one-component toner, a magnetic material is preferably used as the colorant. The magnetic substance contained in the magnetic one-component toner includes magnetic iron oxides such as magnetite, maghemite, and ferrite, and magnetic iron oxides containing other metal oxides; metals such as Fe, Co, and Ni, or these metals. Alloys of metals with metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, V, and mixtures thereof. Can be mentioned.

Among these, magnetite is preferably used, and its shape includes polyhedron, octahedron, hexahedron, sphere, needle, scale, etc., but polyhedral, octahedron, hexahedron, spherical and other anisotropic A small amount is preferable for increasing the image density.

The magnetic substance preferably has a volume average particle size of 0.10 μm or more and 0.40 μm or less. When the volume average particle diameter is 0.10 μm or more, the magnetic substance is less likely to aggregate, and the uniform dispersibility of the magnetic substance in the toner is improved. A volume average particle size of 0.40 μm or less is preferable because the coloring power of the toner is improved.

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

The magnetic material used for the toner can be manufactured, for example, by the following method. An aqueous solution containing ferrous hydroxide is prepared by adding an equivalent amount or an equivalent amount or more of an alkali such as sodium hydroxide to the aqueous ferrous salt solution. Air is blown while the pH of the prepared aqueous solution is maintained at pH 7 or higher, and the ferrous hydroxide is oxidized while the aqueous solution is heated to 70° C. or higher to first generate seed crystals that form the core of the magnetic material.

Next, an aqueous solution containing 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 solution at 5 or more and 10 or less, the reaction of ferrous hydroxide is advanced while blowing air, and the magnetic iron oxide powder is grown with the seed crystal as the core. At this time, the shape and magnetic properties of the magnetic substance can be controlled by selecting an arbitrary pH, reaction temperature, and stirring conditions. The pH of the liquid shifts to the acidic side as the oxidation reaction proceeds, but it is preferable that the pH of the liquid is not less than 5. The magnetic iron oxide particles thus obtained are filtered, washed and dried by a conventional method to obtain a magnetic substance.

Further, when the toner is manufactured by the polymerization method, it is preferable that the surface of the magnetic material is made hydrophobic. When the surface treatment is performed by a dry method, the surface of the magnetic material that has been washed, filtered and dried can be treated with a coupling agent. When the surface treatment is carried out by a wet method, after the completion of the oxidation reaction, the dried product is redispersed, or after the completion of the oxidation reaction, the iron oxide obtained by washing and filtration is dried in another aqueous medium. Can be re-dispersed and the coupling treatment can be performed.

Specifically, a coupling treatment is performed by adding a silane coupling agent while sufficiently stirring the redispersion liquid and raising the temperature after hydrolysis, or by adjusting the pH of the dispersion liquid after hydrolysis to an alkaline region. be able to. Among these, from the viewpoint of performing a uniform surface treatment, it is preferable to perform the surface treatment after completion of the oxidation reaction, after filtration and washing, and without drying, to form a reslurry.

To treat the surface of the magnetic material by a wet method, that is, in a water-based medium with a coupling agent, first disperse the magnetic material sufficiently in the water-based medium so as to have a primary particle size, and a stirring blade to prevent sedimentation and aggregation. Stir with. Then, an arbitrary amount of coupling agent is added to the above dispersion liquid, and the surface treatment is performed while hydrolyzing the coupling agent.Also at this time, it is sufficient to prevent agglomeration while using a device such as a pin mill and a line mill while stirring. It is more preferable to perform the surface treatment while dispersing.

Here, the aqueous medium is a medium containing water as a main component. Specific examples thereof include water itself, water to which a small amount of a surfactant has been added, water to which a pH adjusting agent has been added, and water to which an organic solvent has been added. The surfactant is preferably a nonionic surfactant such as polyvinyl alcohol. It is preferable that the surfactant is added in an amount of 0.1% by mass or more and 5.0% by mass or less in the aqueous medium. Examples of the pH adjuster include inorganic acids such as hydrochloric acid. Examples of the organic solvent include alcohols.

Examples of the coupling agent that can be used in the surface treatment of the magnetic material include a silane coupling agent and a titanium coupling agent. A silane coupling agent is more preferably used, which is represented by the general formula (3).
R _m SiY _n (3)
[In the formula, R represents an alkoxy group (preferably having a carbon number of 1 to 3), m is an integer of 1 to 3 and Y is an alkyl group (preferably having a carbon number of 2 to 20) and phenyl. A functional group such as a group, a vinyl group, an epoxy group, an acrylic group, and a methacrylic group is shown, and n is an integer of 1 or more and 3 or less. However, m+n=4. ]

Examples of the silane coupling agent represented by the general formula (3) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, β-(3,4epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, Vinyltriacetoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, n-butyltrimethoxysilane, Isobutyltrimethoxysilane, trimethylmethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, hydroxypropyltrimethoxysilane, n-hexadecyltrimethoxysilane , N-octadecyltrimethoxysilane and the like.

Among these, from the viewpoint of imparting high hydrophobicity to the magnetic material, it is preferable to use an alkyltrialkoxysilane coupling agent represented by the following general formula (4).
_{C p H 2p + 1 -Si- (} OC q H 2q + 1) 3 (4)
[In the formula, p represents an integer of 2 or more and 20 or less, and q represents an integer of 1 or more and 3 or less. ]

When p in the above formula is 2 or more, sufficient hydrophobicity can be imparted to the magnetic material. When p is 20 or less, the hydrophobicity is sufficient and coalescence of magnetic materials can be suppressed. Furthermore, when q is 3 or less, the reactivity of the silane coupling agent is good, and the hydrophobic treatment is likely to be sufficiently performed.

Therefore, in the formula, p represents an integer of 2 or more and 20 or less (more preferably an integer of 3 or more and 15 or less), and q represents an integer of 1 to 3 (more preferably 1 or 2). It is preferable to use a silane coupling agent.

When the above silane coupling agent is used, it can be treated alone or in combination of two or more. When a plurality of them are used in combination, they may be treated individually with each coupling agent or may be treated simultaneously.

The total treatment amount of the coupling agent used 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 material, and depends on the surface area of the magnetic material, the reactivity of the coupling agent, and the like. It is preferable to adjust the amount of the treating agent.

In addition to the magnetic substance, other colorants may be used in combination with the toner.

The following are examples of the colorant when used as the non-magnetic one-component toner and the non-magnetic two-component toner.

As the black pigment, carbon black such as furnace black, channel black, acetylene black, thermal black and lamp black is used, and magnetic powder such as magnetite and ferrite is also used.

A pigment or dye can be used as a colorant suitable for yellow. Examples of the pigment include C.I. I. Pigment Yellow 1,2,3,4,5,6,7,10,11,12,13,14,15,17,23,62,65,73,74,81,83,93,94,95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154, 155, 167, 168, 173, 174, 176, 180, 181, 183, 191, C.I. I. Butt yellow 1, 3, and 20 are mentioned. Examples of the dye include C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162 and the like. These may be used alone or in combination of two or more.

A pigment or dye can be used as a colorant suitable for cyan. Examples of the pigment include C.I. I. Pigment Blue 1, 7, 15, 15; 1, 15; 2, 15; 3, 15; 4, 16, 17, 60, 62, 66, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 may be mentioned. Examples of the dye include C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95 and the like can be mentioned. These may be used alone or in combination of two or more.

As a colorant suitable for magenta color, a pigment or a dye can be used. Examples of the pigment include C.I. I. Pigment Red 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,21,22,23,30,31, 32, 37, 38, 39, 40, 41, 48, 48; 2, 48; 3, 48; 4, 49, 50, 51, 52, 53, 54, 55, 57, 57; 1, 58, 60, 63, 64, 68, 81, 81; 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, etc., C.I. I. Pigment Violet 19; C.I. I. Butred 1,2,10,13,15,23,29,35.

Examples of magenta dyes include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122, C.I. I. Disperse Red 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27 etc., C.I. I. Oil soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic dyes such as basic violet 1,3,7,10,14,15,21,25,26,27,28 and the like can be mentioned. These may be used alone or in combination of two or more.

Hereinafter, the method for producing the toner particles according to the present invention will be exemplified, but the production method is not particularly limited, and it is also possible to produce by a pulverization method, such as a dispersion polymerization method, an association aggregation method, a dissolution suspension method, and a suspension method. The toner particles may be produced in an aqueous medium such as a turbid polymerization method or an emulsion aggregation method. However, a method of producing a toner in an aqueous medium is preferable from the viewpoint of shape control.

As an example, a toner production example of the suspension polymerization method will be described.

In the suspension polymerization method, first, a colorant (and optionally a polymerization initiator, a cross-linking agent, a charge control agent, and other additives) is uniformly dispersed in a polymerizable monomer capable of forming a binder resin. Disperse to obtain a polymerizable monomer composition. After that, the obtained polymerizable monomer composition is dispersed/granulated in a continuous layer (for example, an aqueous phase) containing a dispersion stabilizer by using a suitable stirrer, and polymerization is performed using a polymerization initiator. The reaction is performed to obtain toner particles having a desired particle size.

In the toner obtained by this suspension polymerization method (hereinafter also referred to as “polymerized toner”), since the shape of each individual toner particle is substantially spherical, it is easy to obtain a toner satisfying the physical property requirements suitable for the present invention. It is possible to measure the toner strength by the indentation method with high reproducibility.

The following are mentioned as a polymerizable monomer.

Styrene-based monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene; methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid Isobutyl, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, acrylates such as phenyl acrylate, methyl methacrylate, methacrylic acid Ethyl, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, methacrylic acid. Methacrylic acid esters such as diethylaminoethyl; other monomers such as acrylonitrile, methacrylonitrile and acrylamide. These monomers may be used alone or as a mixture.

Among the above-mentioned monomers, the use of a styrene-based monomer alone or in a mixture with other monomers such as acrylic acid esters and methacrylic acid esters controls the toner structure and develops the toner. It is preferable because the characteristics and durability are easily improved. In particular, it is more preferable to use styrene and alkyl acrylate or styrene and alkyl methacrylate as main components. That is, the binder resin is preferably a styrene-acrylic resin.

The polymerization initiator used in the production of the toner by the polymerization method is preferably one having a half-life in the polymerization reaction of 0.5 hours or more and 30 hours or less. Moreover, it is preferable to use it in an amount of 0.5 to 20 parts by mass based on 100 parts by mass of the polymerizable monomer. By doing so, a polymer having a maximum in the molecular weight range of 5,000 or more and 50,000 or less can be obtained, and the toner can be provided with preferable strength and appropriate melting characteristics.

From the viewpoint of fixability and mechanical strength, the peak molecular weight (Mp(T)) of the toner is preferably 10,000 or more and 35,000 or less, more preferably 15,000 or more and 30,000 or less.

Specific polymerization initiators include 2,2′-azobis-(2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis(cyclohexane-1-carbonitrile). Nitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and other azo or diazo polymerization initiators, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxy. Carbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butylperoxy 2-ethylhexanoate, t-butylperoxypivalate, di(2-ethylhexyl)peroxydicarbonate. , Peroxide polymerization initiators such as di(secondary butyl) peroxydicarbonate.

Among these, t-butyl peroxypivalate is preferable.

When the toner is produced by a polymerization method, a crosslinking agent may be added, and the preferable addition amount 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.

A compound having two or more polymerizable double bonds is mainly used as the cross-linking agent, and examples thereof include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; for example, ethylene glycol diacrylate and ethylene glycol diethylene. Carboxylic acid ester having two double bonds such as methacrylate and 1,3-butanediol dimethacrylate; divinyl compound such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and 3 or more vinyl groups The compound; is used alone or as a mixture of two or more kinds.

It is preferable that the polymerizable monomer composition contains a polar resin. In the suspension polymerization method, since magnetic toner particles are produced in an aqueous medium, a polar resin layer can be formed on the surface of the toner particles by containing a polar resin, and the toner particles having a core/shell structure are formed. Can be obtained.

Having a core/shell structure increases the flexibility of core and shell design. For example, by increasing the glass transition temperature of the shell, it becomes possible to suppress durability deterioration (deterioration during long-term use) such as embedding of an external additive. Further, by imparting a shielding effect to the shell, the composition of the shell can be easily made uniform, so that uniform charging becomes possible.

As the polar resin for the shell layer, for example, polystyrene, a homopolymer of styrene such as polyvinyltoluene and a substitution product thereof; a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, Styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-meth Methyl acrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl Styrene-based copolymers such as ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Polymer: polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, styrene-polyester copolymer, polyacrylate-polyester copolymer, polymethacrylate-polyester copolymer , Polyamide resin, epoxy resin, polyacrylic acid resin, terpene resin, phenol resin and the like.

These may be used alone or in combination of two or more. Further, functional groups such as amino group, carboxyl group, hydroxyl group, sulfonic acid group, glycidyl group, and nitrile group may be introduced into these polymers. Among these resins, polyester resin is preferable.

As the polyester resin, a saturated polyester resin, an unsaturated polyester resin, or both can be appropriately selected and used.

As the polyester resin, a usual one composed of an alcohol component and an acid component can be used, and both components are exemplified below.

Examples of the dihydric alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, butenediol, octenediol, cyclohexenedimethanol, hydrogenated bisphenol A, or a bisphenol derivative represented by the formula (A) A hydrogenated product of the compound represented by the formula (A), a diol represented by the formula (B), or a diol of the hydrogenated product of the compound of the formula (B).

［式中、Ｒはエチレン又はプロピレン基であり、ｘ，ｙはそれぞれ１以上の整数であり、ｘ＋ｙの平均値は２以上１０以下である。］

[In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x+y is 2 or more and 10 or less. ]

As the dihydric alcohol component, the above-mentioned alkylene oxide adduct of bisphenol A, which has excellent charging characteristics and environmental stability and is well balanced in other electrophotographic characteristics, is particularly preferable. In the case of this compound, the average number of moles of alkylene oxide added is preferably 2 or more and 10 or less from the viewpoint of fixing property and toner durability.

Examples of the divalent acid component include benzenedicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride, or an anhydride thereof; alkyldicarboxylic acid such as succinic acid, adipic acid, sebacic acid, azelaic acid or the like. Anhydrides: succinic acid substituted with an alkyl or alkenyl group having 6 to 18 carbon atoms or its anhydride; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid or its anhydride. Be done.

Further, examples of trivalent or higher alcohol components include glycerin, pentaerythritol, sorbit, sorbitan, and oxyalkylene ethers of novolac type phenolic resins. Trivalent or higher acid components include trimellitic acid and pyromellitic acid. Examples thereof include acids, 1,2,3,4-butanetetracarboxylic acid, benzophenonetetracarboxylic acid and anhydrides thereof.

The polyester resin is preferably a polycondensation product of a carboxylic acid component containing 10 to 50 mol% of a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms with respect to the total carboxylic acid component, and an alcohol component. ..

The polyester resin has a carboxylic acid component containing 10 to 50 mol% of a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms with respect to the total carboxylic acid component, thereby increasing the peak molecular weight of the polyester resin. In this state, the softening point of the polyester resin can be easily lowered. Therefore, the toner strength can be increased while maintaining the fixability.

In the polyester resin, it is preferable that 45 mol% or more and 55 mol% or less of the alcohol component is the alcohol component when the total of the alcohol component and the acid component is 100 mol %.

The polyester resin can be produced using any catalyst such as tin-based catalyst, antimony-based catalyst and titanium-based catalyst, but it is preferable to use titanium-based catalyst.

The polar resin for the shell preferably has a number average molecular weight of 2,500 or more and 25,000 or less from the viewpoint of developability, blocking resistance, and durability. The number average molecular weight can be measured by GPC.

The polar resin for the shell preferably has an acid value of 1.0 mgKOH/g or more and 15.0 mgKOH/g or less, and more preferably an acid value of 2.0 mgKOH/g or more and 10.0 mgKOH/g or less. By controlling the acid value within the above range, it is easy to form a uniform shell.

The polar resin for the shell layer is preferably contained in an amount of 2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin from the viewpoint of sufficiently obtaining the effect of the shell layer.

The aqueous medium in which the polymerizable monomer composition is dispersed contains a dispersion stabilizer. As the dispersion stabilizer, known surfactants, organic dispersants and inorganic dispersants can be used. Among them, since the inorganic dispersant has dispersion stability due to its steric hindrance, the stability is not easily deteriorated even when the reaction temperature is changed, the washing is easy, and the toner is not adversely affected, and therefore it is preferably used.

Examples of such inorganic dispersants include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, polyvalent metal phosphates such as hydroxyapatite, carbonates such as calcium carbonate and magnesium carbonate, calcium metasilicate. , Inorganic salts such as calcium sulfate and barium sulfate, and inorganic compounds such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide.

These inorganic dispersants are preferably used in an amount of 0.2 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the polymerizable monomer. The above dispersion stabilizers may be used alone or in combination of two or more. Further, 0.001 part by mass or more and 0.1 part by mass or less of a surfactant may be used in combination. When these inorganic dispersants are used, they may be used as they are, but in order to obtain finer particles, the inorganic dispersant particles may be generated and used in an aqueous medium.

For example, in the case of tricalcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution can be mixed under high-speed stirring to generate water-insoluble calcium phosphate, which enables more uniform and fine dispersion. At this time, a water-soluble sodium chloride salt is by-produced at the same time, but when the water-soluble salt is present in the aqueous medium, dissolution of the polymerizable monomer in water is suppressed, and ultrafine toner particles are generated by emulsion polymerization. This is preferable because it is difficult to do.

Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

In the step of polymerizing the polymerizable monomer, the polymerization temperature is usually set to 40°C or higher, preferably 50°C to 90°C. When the polymerization is carried out within this temperature range, the release agent to be sealed inside is deposited by phase separation and the encapsulation becomes more complete.

After that, there is a cooling step of cooling the reaction temperature from about 50° C. to 90° C. to finish the polymerization reaction step. At that time, it is preferable to gradually cool so that the release agent and the binder resin are kept in a compatible state.

After the polymerization of the polymerizable monomer is completed, the obtained polymer particles are filtered, washed and dried by a known method to obtain toner particles. The toner can be obtained by mixing the toner particles with the external additive as described above and adhering it to the surface of the toner particles. Further, it is possible to cut a coarse powder or a fine powder contained in the toner particles by adding a classification process to the manufacturing process.

The weight average particle diameter (D4) of the toner particles of the present invention is preferably 4.0 μm or more and 15.0 μm or less, and more preferably 5.0 μm or more and 10.0 μm or less.

Further, in the present invention, it is more preferable to use, in addition to the external additive A, another external additive B having a smaller particle size. It is preferable to use inorganic fine particles having different large and small particle diameters because the chargeability and fluidity can be easily controlled. When the external additive is used in combination, it is preferable to use the external additive B having a number average particle diameter (D1) of less than 30 nm.

Regarding the external additive B, fine particles such as silica fine particles, alumina fine particles, titania fine particles, and composite oxide fine particles thereof, or organic-inorganic composite fine particles containing organic fine particles may be used.

In addition to the external additives A and B, lubricants such as fluororesin powder, zinc stearate powder, polyvinylidene fluoride powder; cerium oxide powder, silicon carbide powder, strontium titanate powder, etc. You may use an abrasive etc.

Next, methods for measuring each physical property relating to the present invention will be described.

<Ferre diameter (maximum diameter) (a) of external additive, penetration depth (b) of external additive A, convex height (c) of external additive A, and index relating to penetration (b/(b+c)) ) Measuring method>
(1) Observation of cross section of toner by TEM After dispersing the toner in a visible light curable resin (trade name: Aronix LCR series D-800, manufactured by Toagosei Co., Ltd.), it is cured by irradiation with short wavelength light. Let The obtained cured product is cut out with an ultramicrotome equipped with a diamond knife to prepare a 250 nm thin sample. Then, the cut out sample is magnified at a magnification of 40,000 to 50,000 times using a transmission electron microscope (trade name: electron microscope JEM-2800, manufactured by JEOL Ltd.) (TEM-EDX), Obtain a cross-sectional image of the particles.

The toner to be observed is selected as follows.

First, the cross-sectional area of the toner particles is obtained from the image of the cross-section of the toner particles, and the diameter of a circle having an area equal to the cross-sectional area (circle equivalent diameter) is obtained. Only the image of the cross section of the toner particles whose absolute value of the difference between the equivalent circle diameter and the weight average particle diameter (D4) of the toner is within 1.0 μm is observed.

(2) Feret diameter (maximum diameter) (a) of the external additive, penetration depth (b) of the external additive A, convex height (c) of the external additive A, and index (b/( b+c)) and a method of calculating the length (l) of the line segment Z. From the surface of the external additive A in which the Feret diameter (maximum diameter) (a) of the external additive is 30 nm or more and 300 nm or less, the inner direction of the toner particles A TEM image obtained by cutting out a 400 nm portion is developed, and image processing is performed so that the surface (contour line) of the toner particle becomes a straight line as shown in FIG. It should be noted that there is no intention to make the contour line X described later a straight line.

The Feret diameter (maximum diameter) (a) of the external additive is determined from the developed image, the external additive A having a size of 30 nm or more and 300 nm or less is extracted, and the penetration depth b (nm) and the external depth of the external additive A are extracted. The convex height c (nm) of the additive A is obtained.

From the values of the penetration depth b and the convex height c, the index b/(b+c) relating to the penetration of the external additive A is obtained.

Further, among the contour lines of the external additive A, the contour line of the portion where the external additive A is in contact with the toner particles is defined as the contour line X, and a line segment obtained by connecting both ends of the contour line X with a straight line is obtained. A line segment Z is set, and a length l (nm) of the line segment Z is obtained.

For image processing, image processing software Image J (available from https://imagej.nih.gov/ij/) is used. As for the number of samples to be analyzed, the average value is taken as the value of a, b, c, l of the sample for 100 particles of the external additive A selected at random, and the standard deviation is also obtained. By obtaining the average value of 100 particles of the external additive A randomly selected, it becomes possible to represent the state of the external additive A as a whole.

<Method of measuring sticking index of external additive A>
As a method of indexing the fixed state of the external additive A, the amount of the external additive A transferred when the toner is brought into contact with the substrate is evaluated. In the present invention, as a surface layer material of the substrate, a substrate using a polycarbonate resin as a surface layer material is used as a substrate simulating the surface layer of the photoreceptor. Specifically, first, a bisphenol Z type polycarbonate resin (trade name: Iupilon Z-400, Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight (Mv): 40,000) is added to toluene to a concentration of 10% by mass. To dissolve it into a coating solution.

This coating liquid is applied to an aluminum sheet having a thickness of 50 μm using a No. 50 Meyer bar to form a coating film. Then, by drying this coating film at 100° C. for 10 minutes, a sheet having a polycarbonate resin layer (having a film thickness of 10 μm) on the aluminum sheet is produced. This sheet is held by the substrate holder. The substrate is a square with one side of about 3 mm.

Hereinafter, the measurement process will be described by dividing it into a process of disposing the toner on the substrate, a process of removing the toner from the substrate, and a process of quantifying the adhesion amount of the external additive A supplied to the substrate.

-Step of disposing the toner on the substrate The toner is contained in a porous flexible material (hereinafter referred to as "toner holder"), and the toner holder is brought into contact with the substrate. A sponge (trade name: White Wiper) manufactured by Marusan Sangyo Co., Ltd. is used as the toner holder.

The toner holder is fixed to the tip of a load meter fixed to a stage that moves in the direction perpendicular to the contact surface of the substrate so that the toner holder and the substrate can come into contact with each other while measuring the load. The contact between the toner holding member and the substrate is performed by moving the stage, pressing the toner holding member against the substrate until the load meter shows 10 N, and then separating the toner holding member as one process, and this process is repeated 5 times.

Step of removing toner from the substrate After bringing the toner holder into contact with the substrate, bring the elastomer suction port with an inner diameter of about 5 mm connected to the nozzle tip of the cleaner so as to be perpendicular to the toner placement surface, The toner adhering to the substrate is removed. At this time, the toner is removed while visually confirming the residual amount. The distance between the end of the suction port and the substrate is 1 mm, the suction time is 3 seconds, and the suction pressure is 6 kPa.

Step of quantifying the amount of external additive supplied to the substrate When quantifying the amount and shape of the external additive A remaining on the substrate after removing the toner, observation and image by a scanning electron microscope Use measurement.

First, platinum is sputtered on the substrate from which the toner has been removed under conditions of a current of 20 mA and 60 seconds to obtain a sample for observation.

In the observation with the scanning electron microscope, the observation magnification with which the external additive A can be observed was arbitrarily selected. As a scanning electron microscope, a Hitachi ultra-high resolution field emission scanning electron microscope (trade name: S-4800, Hitachi High-Technologies Corporation) is used, and observation is performed with a backscattered electron image of S-4800 (trade name). .. The observation magnification is 50,000 times, the acceleration voltage is 10 kV, and the working distance is 3 mm. Under this condition, the particle size of the external additive A can be determined and observed.

In the image obtained by the observation, the external additive A has a high brightness and the substrate has a low brightness. Therefore, the amount of the external additive A in the visual field can be quantified by binarization. The binarization conditions are appropriately selected depending on the observation device and sputtering conditions. In the present invention, the image analysis software Image J (available from https://imagej.nih.gov/ij/) is used for binarization. After binarization, only the external additive A having a Feret diameter a (nm) of 30 nm or more and 300 nm or less is extracted.

In Image J, the extraction can be performed by checking Area and Feret's Diameter from Set Measurement and using the function of Analyze Particle. From the results obtained by the function of the Analyse Particle, only the area of the external additive A corresponding to the Ferret diameter a (nm) of 30 nm or more and 300 nm or less is integrated and divided by the area of the entire observation visual field The area ratio of the external additive A is calculated. The above measurement is performed on 100 binarized images, and the average value is defined as the area ratio [A] (unit: area %) of the external additive A on the substrate.

Next, the coverage [B] (unit: area %) of the external additive A on the toner particles is calculated.

The coverage of the external additive A is measured by observation with a scanning electron microscope and image measurement. In the observation with the scanning electron microscope, the observation magnification for observing the external additive A is the same as that for observing the external additive A on the substrate. As the scanning electron microscope, the above Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (trade name) is used.

The image capturing conditions are as follows.

(1) Preparation of sample A sample table (aluminum sample table 15 mm x 6 mm) is thinly coated with a conductive paste, and toner is sprayed on it. Further, air blow is performed to remove excess toner from the sample table and dry it sufficiently. The sample table is set on the sample holder, and the sample table height is adjusted to 36 mm by the sample height gauge.

(2) S-4800 Observation Condition Setting The coverage [B] of the external additive A is calculated using the image obtained by the backscattered electron image observation of S-4800. Since the backscattered electron image has less charge-up than the secondary electron image, the coverage [B] of the external additive A can be accurately measured.

The anti-contamination trap attached to the housing of S-4800 is filled with liquid nitrogen until it overflows and left for 30 minutes. The "PC-SEM" of S-4800 is started and flushing (cleaning of the FE chip which is the electron source) is performed. Click the accelerating voltage display area on the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Execute after confirming that the flushing strength is 2. Confirm that the emission current due to flashing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel and move the sample holder to the observation position.

Click the acceleration voltage display section to open the HV setting dialog, and set the acceleration voltage to [0.8 kV] and the emission current to [20 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select the SE detector [Up (U)] and [+BSE], and select [+BSE] in the selection box to the right. L. A. 100] is selected and the mode is set to observe with a backscattered electron image.

Similarly, in the [Basic] tab of the operation panel, set the probe current of the electron optical system condition block to [Normal], the focus mode to [UHR], and the WD to [3.0 mm]. Press the [ON] button on the acceleration voltage display of the control panel to apply the acceleration voltage.

(3) Focus adjustment Drag inside the magnification display area of the control panel to set the magnification to 5000 (5k) times. The focus knob [COARSE] on the operation panel is rotated to adjust the aperture alignment when the entire field of view is in focus. Click [Align] on the control panel to display the alignment dialog and select [Beam]. Rotate the STIGMA/ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles. Next, select [Aperture] and turn the STIGMA/ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust the movement so as to minimize the movement. Close the aperture dialog and use auto focus to focus. Repeat this operation twice more to focus.

Next, for the target toner, the magnification is set to 10000 (10k) times by dragging in the magnification display section of the control panel with the midpoint of the maximum diameter aligned with the center of the measurement screen. Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is adjusted to some extent. Click [Align] on the control panel to display the alignment dialog and select [Beam]. Rotate the STIGMA/ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles.

Next, select [Aperture] and turn the STIGMA/ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust the movement so as to minimize the movement. Close the aperture dialog and use auto focus to focus. After that, the magnification is set to 50,000 (50k) times, focus adjustment is performed using the focus knob and STIGMA/ALIGNMENT knob in the same manner as above, and focus is adjusted again by autofocus. Repeat this operation again to focus. Here, if the angle of inclination of the observation surface is large, the measurement accuracy of the coverage rate tends to be low, so by selecting one that simultaneously focuses on the entire observation surface when adjusting the focus, select one that has the smallest possible surface inclination. And analyze.

(4) Image storage Brightness adjustment is performed in the ABC mode, and a picture is taken with a size of 640×480 pixels and stored. The following analysis is performed using this image file. One photograph is taken for each toner, and an image is obtained for at least 30 particles of toner.

The observed image is binarized using the image analysis software Image J (available from https://imagej.nih.gov/ij/). After binarization, only the external additive A having a Feret diameter a (nm) of 30 nm or more and 300 nm or less is extracted, and the coverage (unit: area %) of the external additive A on the toner particles is obtained.

The above measurement is performed on 100 binarized images, and the average value of the coverage (unit: area %) of the external additive A is defined as the coverage [B] of the external additive A.

From the area ratio [A] of the external additive A on the substrate and the coverage [B] of the external additive, the sticking index of the external additive A is calculated using the following formula.
Sticking index of external additive A =area ratio [A] of external additive A on the substrate/coverage ratio of external additive A [B]×100

<Measurement Method of Coverage of External Additive A>
For the coverage of the surface of the toner particles with the external additive A, the value of the coverage [B] of the external additive A on the toner particles in the method for measuring the sticking index of the external additive A is used (unit is area %). ..

<Method of measuring number average particle diameter of external additive and shape factor SF-2>
The number average particle diameter and shape factor SF-2 of the external additive A and other external additives are the maximum when the external additive is observed with a transmission electron microscope (trade name: JEM-2800, JEOL Ltd.). In a field of view magnified 200,000 times, the major axis, perimeter and area of 100 randomly selected primary particles of the external additive are calculated using image processing software. The image processing software used is Image-Pro Plus 5.1J (trade name) manufactured by Media Cybernetics.

The number average particle diameter is an average value of the long diameters of 100 randomly selected primary particles of the external additive.

In addition, SF-2 is calculated for each of 100 randomly selected primary particles of the external additive by the following formula, and the average value is calculated.
SF-2=(perimeter of particle) ² /area of particle×100/4π

<Method of measuring toner fluidity (Total Energy)>
(A) Measurement of Total Energy The total energy and the flow rate index FRI in the present invention are determined by using "powder fluidity analyzer powder rheometer FT4" (manufactured by Freeman Technology, hereinafter sometimes referred to as FT4). taking measurement.

Specifically, the measurement is performed by the following operation.

In all the operations, the propeller blade is a FT4 dedicated 48 mm diameter blade (model number: C210, material: SUS, hereinafter sometimes referred to as blade). This propeller type blade has a rotation axis in the normal direction at the center of a blade plate of 48 mm × 10 mm, and the blade plate has 70° at both outermost edges (24 mm from the rotation axis) and 12 mm from the rotation axis. It is twisted smoothly counterclockwise, such as at 35°.

A cylindrical split container (model number: C203, material: glass, diameter: 50 mm, volume: 160 mL, height from bottom surface to split portion: 82 mm, hereinafter sometimes referred to as a container) exclusively for FT4 is used as a measuring container.

(1) Compression operation (a) Preliminary experiment: A compression test piston is attached to the main body. Approximately 50 mL of toner (weight is measured in advance) is put in the measurement container, and the piston is lowered at 0.5 mm/sec to compress the toner. When the load on the piston reaches 0.88 kPa, the descent is stopped and it is held for 20 seconds. Read the volume of compressed toner from the scale on the container.
(B) Measure 1/4 of the amount of compressed toner volume equivalent to 180 mL calculated from the preliminary experiment (use the unused toner in the preliminary experiment, not use the unused toner) Place in a container and perform the same operation as in the preliminary experiment.
(C) The operation of (b) above is performed three more times (four times in total) (toner is added).
(D) The toner layer compressed at the split portion of the measuring container is scraped off, and the upper portion of the powder layer is removed.

(2) Total energy measurement operation (a) A propeller blade is attached to the main body. The propeller blade is rotated counterclockwise (in the direction in which the powder layer is pushed by the rotation of the blade) with respect to the surface of the powder layer so that the peripheral speed of the outermost edge of the blade is 10 mm/sec. The blade is vertically advanced from the surface of the powder layer to a position 10 mm from the bottom surface of the powder layer at an entry speed at which the angle formed is 5°. After that, the blade is rotated clockwise with respect to the surface of the powder layer so that the peripheral speed of the outermost edge of the blade is 60 mm/sec, and the angle forming the vertical approach speed to the powder layer becomes 2°. It is made to penetrate to the position of 1 mm from the bottom surface of the powder layer at the approach speed.

Further, the blade is moved at a speed of an angle of 5° to a position 100 mm from the bottom surface of the powder layer to extract the powder layer. After the extraction is completed, the blade is rotated clockwise and counterclockwise alternately in small increments to remove the toner adhering to the blade.

(B) The operation of (2)-(a) is repeated 6 times (7 times in total), and is obtained when the blade is advanced from the position of 100 mm to the position of 10 mm from the bottom surface of the powder layer in the final time. The total sum of the rotation torque and the vertical load is referred to as Total Energy.

<Method of measuring toner strength by nanoindentation method>
To measure the toner strength by the nanoindentation method, Picodenter HM500 manufactured by Fisher Instrument Co., Ltd. is used. The software uses WIN-HCU. A Vickers indenter (angle: 130°) is used as the indenter.

The measurement includes a step of pressing the indenter at a predetermined speed until a predetermined load is applied (hereinafter, referred to as "pushing step"). The toner strength is calculated from the load displacement curve and the differential curve differentiated by the load as shown in FIG. 5 obtained by this pushing step.

First, the microscope is focused on the video camera screen displayed on the software. A glass plate (hardness: 3600 N/mm2) for Z-axis alignment, which will be described later, is used as the target for focusing. At this time, the objective lens is sequentially focused from 5 times to 20 times and 50 times. After this, adjustment is performed with a 50× objective lens.

Next, using the glass plate that has been focused as described above, an "approach parameter setting" operation is performed to perform Z axis alignment of the indenter. Then, the glass plate is replaced with an acrylic plate, and the "cleaning of the indenter" operation is performed. The “indenter cleaning” operation is an operation of cleaning the tip of the indenter with ethanol and at the same time matching the indenter position designated on the software with the indenter position on the hardware, that is, performing XY axis alignment of the indenter.

After that, the glass is changed to a slide glass to which toner is attached, and the microscope is focused on the toner to be measured. The method of attaching the toner to the slide glass is as follows.

First, the toner to be measured is attached to the tip of a Johnson swab, and the excess toner is sifted off with the edge of a bottle or the like. After that, while pressing the shaft of the cotton swab against the edge of the slide glass, the toner attached to the cotton swab is knocked off so that the toner becomes one layer on the slide glass.

After that, the slide glass on which the toner is further attached as described above is set in a microscope, the toner is focused by a 50× objective lens, and the tip of the indenter is set on the software so as to come to the center of the toner particle. It should be noted that the toner particles selected are limited to particles of D4 (μm)±1.0 μm of the toner, both long and short diameters.

The measurement is carried out by carrying out the pushing step under the following conditions.

(Pushing process)
・Maximum pushing load = 2.5mN
・Pressing time = 100 seconds

By the above measurement, a load-displacement curve is created with the horizontal axis as the load (mN) and the vertical axis as the displacement amount (μm).

As a method of calculating the “load having the maximum inclination” defined as the toner strength in the present invention, a load having a maximum differential value is adopted in a differential curve obtained by differentiating the load-displacement curve with the load. The load range when obtaining the differential curve is set to 0.20 mN or more and 2.30 mN or less in consideration of the accuracy of the data.

The above measurement is carried out for 30 toner particles, and the arithmetic mean value is adopted.

For the measurement, the "cleaning of the indenter" operation (including the XY axis alignment of the indenter) is always performed for each particle measurement.

<Measurement method of weight average particle diameter (D4)>
The weight average particle diameter (D4) of the toner and the toner particles is a precise particle size distribution measuring apparatus "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with an aperture tube having a diameter of 100 μm. And using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data, the number of effective measurement channels is 25,000. The measurement data was analyzed and calculated.

The electrolytic aqueous solution used for the measurement may be prepared by dissolving special grade sodium chloride in ion-exchanged water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.).

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

In the special software “Change Standard Measurement Method (SOM) screen”, set the total count in control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “Standard particles 10.0 μm” (Beckman Coulter, Inc.). The value obtained by using the product is set. The threshold and noise level are automatically set by pressing the threshold/noise level measurement button. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the flash of the aperture tube after the measurement is checked.

On the "pulse-to-particle size conversion setting screen" of the dedicated software, set the bin interval to the logarithmic particle size, the particle size bin to the 256 particle size bin, and the particle size range from 2 μm to 60 μm.

The specific measuring method is as follows.
(1) Approximately 200 ml of the electrolytic aqueous solution is put into a glass 250 ml round-bottom beaker for exclusive use with ultisizer 3, 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 tube flush" function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution was placed in a glass 100 ml flat-bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder, pH7 precision measurement as a dispersant was added to this). Approximately 0.3 ml of a diluted solution prepared by diluting a 10 mass% aqueous solution of a neutral detergent for cleaning vessels with Wako Pure Chemical Industries, Ltd. with ion-exchanged water to 3 mass times is added.
(3) Two oscillators with an oscillating frequency of 50 kHz are installed with their phases shifted by 180 degrees, and are placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetra 150" (manufactured by Nikkaki Bios) with an electric output of 120 W. A fixed amount of ion-exchanged water is added, and about 2 ml of the above Contaminone N is added to this 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 becomes maximum.
(5) About 10 mg of the toner is added little by little to the electrolytic aqueous solution in a state where the electrolytic aqueous solution in the beaker of the above (4) is irradiated with ultrasonic waves and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted so as to be 10°C or higher and 40°C or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the above (5) electrolytic aqueous solution in which the toner is dispersed is dropped using a pipette, and the concentration is adjusted to be about 5%. Then, the measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the apparatus to calculate the weight average particle diameter (D4). The “arithmetic diameter” on the analysis/volume statistical value (arithmetic mean) screen when the graph/volume% is set by the dedicated software is the weight average particle diameter (D4).

<Measurement of Tg of toner particles>
The Tg of the toner particles is measured using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments) in accordance with ASTM D3418-82. The melting point of indium and zinc is used to correct the temperature of the device detection unit, and the heat of fusion of indium is used to correct the amount of heat.

Specifically, about 2 mg of a sample is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rising rate is 10 at a measurement temperature range of 30 to 200°C. Measurement is performed at °C/min. In the measurement, the temperature is once raised to 200° C., then lowered to 30° C., and then raised again. A change in specific heat is obtained in the temperature range of 40° C. to 100° C. in the second heating process. The intersection point between the line at the midpoint of the baseline and the differential heat curve before and after the change in the specific heat at this time is defined as the glass transition temperature Tg.

<Method of measuring acid value Av of polyester resin>
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 amorphous polyester is measured according to JIS K 0070-1992, and specifically, it is measured according to the following procedure.

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

7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95% by volume) is added to make 1 L. The solution is placed in an alkali-resistant container so that it does not come into contact with carbon dioxide gas, left for 3 days, and filtered to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali resistant container. The factor of the potassium hydroxide solution is that 0.1 mol/l of hydrochloric acid (25 ml) is placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution is added, and titration is performed with the potassium hydroxide solution. Calculated from the amount of potassium solution. As the 0.1 mol/l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 2.0 g of the crushed amorphous polyester sample was precisely weighed in a 200 ml Erlenmeyer flask, 100 ml of a toluene/ethanol (2:1) mixed solution was added, and the mixture was dissolved for 5 hours. To do. Then, a few drops of the phenolphthalein solution are added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of the titration is when the pale red color of the indicator continues for about 30 seconds.

(B) Blank test The same titration as the above operation is performed except that the sample is not used (that is, only the mixed solution of toluene/ethanol (2:1) is used).

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

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

Hereinafter, the present invention will be specifically described with reference to examples, but these do not limit the present invention in any way. In addition, the number of parts in the following formulation is based on mass unless otherwise specified.

<Production Example of External Additives A-1 to A-8>
External additives A-1 to A-8, which are organic-inorganic composite fine particles, were produced in accordance with the description in Examples of International Publication No. WO 2013/063291. The physical properties are shown in Table 1.

<Production Example of External Additive A-9>
A mixed gas of silicon tetrachloride, oxygen, and hydrogen was introduced into a burner, burned at a burner temperature of 1100° C., cooled, and collected by a tap filter. The obtained fumed silica fine particles are dispersed in a gas phase, and 6 parts of hexamethyldisilazane as a surface treatment agent is sprayed on 100 parts of the fumed silica fine particles to sufficiently prevent coalescence of the particles. The reaction was carried out with stirring.

After drying the obtained reaction product, it was subjected to a heat treatment at 130° C. for 2 hours, and then adjusted to a desired particle size distribution by classification to obtain an external additive A-9 as silica particles. Table 1 shows the physical properties of the external additive A-9.

<Production Example of External Additive A-10>
After supplying oxygen gas to the burner and igniting the ignition burner, hydrogen gas was supplied to the burner to form a flame, and silicon tetrachloride as a raw material was charged into the gas to gasify it. A flame hydrolysis reaction was carried out with an amount of silicon tetrachloride of 100 kg/h, an amount of oxygen gas of 30 Nm ³ /h, an amount of hydrogen gas of 50 Nm ³ /h, and a residence time of 0.02 sec, and the produced silica powder was recovered.

Then, the obtained silica powder was transferred to an electric furnace, spread in a thin layer, and then heat-treated at 800° C. for sintering and aggregation.

Next, to 100 parts of the obtained silica fine particles, 10 parts of hexamethyldisilazane as a surface treatment agent is added to perform a hydrophobizing treatment, and then a desired particle size distribution is adjusted by classification to obtain silica particles. External additive A-10 was obtained. Table 1 shows the physical properties of the external additive A-10.

<Production Example of External Additives A-11 to 16>
A 3 L glass reactor equipped with a stirrer, a dropping funnel and a thermometer was charged with 687.9 g of methanol, 42.0 g of pure water and 47.1 g of 28 mass% ammonia water and mixed. The obtained solution was adjusted to 35° C., and 1100.0 g (7.23 mol) of tetramethoxysilane and 395.2 g of 5.4 mass% aqueous ammonia were simultaneously added while stirring. Tetramethoxysilane was added dropwise over 5 hours, and aqueous ammonia was added over 4 hours.

After the dropping was completed, the stirring was continued for 0.2 hours to carry out hydrolysis to obtain a methanol-water dispersion liquid of hydrophilic spherical sol-gel silica fine particles. Then, a glass reactor was equipped with an ester adapter and a cooling tube, and the dispersion was heated to 65° C. to distill off methanol. Then, the same amount of pure water as the distilled methanol was added. This dispersion was dried sufficiently at 80° C. under reduced pressure. The obtained silica particles were heated at 400° C. for 10 minutes in a constant temperature bath. The above steps were carried out 20 times, and the obtained silica fine particles were disintegrated with a pulverizer (manufactured by Hosokawa Micron Corp.).

Then, 500 g of silica particles was charged into a polytetrafluoroethylene inner cylindrical stainless autoclave having an inner volume of 1,000 mL. After the inside of the autoclave was replaced with nitrogen gas, 0.5 g of HMDS (hexamethyldisilazane) and 0.1 g of water were atomized with a two-fluid nozzle while rotating the stirring blade attached to the autoclave at 400 rpm. The silica powder was sprayed uniformly. After stirring for 30 minutes, the autoclave was sealed and heated at 200° C. for 2 hours. Subsequently, the system was depressurized while heating and deammonification was carried out to obtain an external additive A-11 which was fine silica particles. Table 1 shows the physical properties of the external additive A-11.

Further, external additives A-12 to 16 were obtained in the same manner except that the particle size of the untreated silica used was changed and the crushing treatment strength was appropriately adjusted. The physical properties of the external additives A-12 to 16 are shown in Table 1.

<External additive A-17 production example>
As the external additive A-17, Eposter S (primary particle diameter 200 nm) manufactured by Nippon Shokubai Co., Ltd. was used. Table 1 shows the physical properties of the external additive A-17.

<Production Example of External Additive B-1>
A silica raw material (fumed silica having a number average particle size of primary particles=12 nm) was put into an autoclave equipped with a stirrer, and heated to 200° C. in a fluidized state by stirring.

The inside of the reactor was replaced with nitrogen gas, and the reactor was sealed. 25 parts of hexamethyldisilazane was sprayed on the inside of 100 parts of the silica raw material, and the silane compound was treated in a fluidized state of silica. After continuing this reaction for 60 minutes, the reaction was terminated. After completion of the reaction, the autoclave was depressurized and washed with a nitrogen gas stream to remove excess hexamethyldisilazane and by-products from the hydrophobic silica.

Furthermore, while stirring the hydrophobic silica in the reaction tank, 10 parts of dimethyl silicone oil (viscosity=100 mm ² /sec) was sprayed on 100 parts of the silica raw material, and stirring was continued for 30 minutes. Then, it heated up to 300 degreeC, stirring, and also stirred for 2 hours. Then, it was taken out and disintegrated to obtain an external additive B-1 which was fine silica particles.

<Synthesis of polyester resin>
The following components were placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, and the reaction was carried out at 230° C. for 10 hours while distilling off water produced under a nitrogen stream.
-Bisphenol A EO 2 mol adduct 350 parts-Bisphenol A PO 2 mol adduct 326 parts-Terephthalic acid 250 parts-Titanium-based catalyst (titanium dihydroxybis(triethanolaminate)) 2 parts Then under reduced pressure of 5 to 20 mmHg. After the reaction, when the acid value was 0.1 mgKOH/g or less, the mixture was cooled to 180° C., 80 parts of trimellitic anhydride was added, the reaction was carried out for 2 hours under a sealed atmosphere and taken out, cooled to room temperature, and pulverized. A polyester resin was obtained. The acid value of the obtained resin was 8 mgKOH/g.

<Production Example of Treated Magnetic Material>
In an aqueous solution of ferrous sulfate, 1.00 to 1.10 equivalents of sodium hydroxide solution with respect to iron element, P ₂ O ₅ with an amount of 0.15 mass% in terms of phosphorus element with respect to iron element, iron SiO ₂ was mixed with the element in an amount of 0.50% by mass in terms of silicon element to prepare an aqueous solution containing ferrous hydroxide. The pH of the aqueous solution was adjusted to 8.0 and an oxidation reaction was carried out at 85° C. while blowing air to prepare a slurry liquid having seed crystals.

Next, an aqueous ferrous sulfate solution was added to this slurry liquid so as to be 0.90 to 1.20 equivalents to the initial amount of alkali (sodium component of sodium hydroxide), and then the slurry liquid was maintained at pH 7.6. Then, the oxidation reaction was promoted while blowing air to obtain a slurry liquid containing magnetic iron oxide.

The obtained slurry liquid was filtered and washed, and then the water-containing slurry was once taken out. At this time, a small amount of the water-containing slurry was sampled and the water content was measured.

Next, this water-containing slurry was put into another aqueous medium without being dried, stirred and re-dispersed with a pin mill while circulating the slurry, and the pH of the re-dispersion liquid was adjusted to about 4.8.

Then, 1.6 parts of the n-hexyltrimethoxysilane coupling agent was added to 100 parts of the magnetic iron oxide while stirring (the amount of the magnetic iron oxide was calculated as a value obtained by subtracting the water content from the water-containing slurry), and the water was added. It was disassembled. After that, sufficient stirring was performed to adjust the pH of the dispersion liquid to 8.6, and surface treatment was performed. The produced hydrophobic magnetic material is filtered with a filter press, washed with a large amount of water, dried at 100° C. for 15 minutes and 90° C. for 30 minutes, and the obtained particles are crushed to obtain a volume average particle size of A treated magnetic material of 0.21 μm was obtained.

<Production Example of Toner Particles T-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 dispersant was obtained.
-Styrene 75.0 parts-n-butyl acrylate 25.0 parts-Polyester resin 10.0 parts-Divinylbenzene 0.6 parts-Monoazo dye iron complex (T-77: Hodogaya Chemical Co., Ltd.) 1.5 parts -Processed magnetic material 65.0 parts The above formulation was uniformly dispersed and mixed using an attritor (Mitsui Miike Kakoki Co., Ltd.) to obtain a monomer composition. This monomer composition was heated to 63° C., and 15.0 parts of paraffin wax (melting point 78° C.) was added and mixed therein, and dissolved. Then, 7.0 parts of a polymerization initiator tert-butyl peroxypivalate was dissolved.

The above monomer composition was put into the above aqueous medium, and the mixture was stirred at 60° C. under a nitrogen atmosphere with a TK homomixer (Tokushu Kika Kogyo Co., Ltd.) at 12000 rpm for 10 minutes to granulate.

Then, the mixture was reacted at 70° C. for 4 hours while stirring with a paddle stirring blade. After the reaction was completed, it was confirmed that the colored resin particles were dispersed in the aqueous medium obtained here, and that calcium phosphate as an inorganic dispersant was attached to the surfaces of the colored resin particles.

Then, the aqueous medium in which the colored resin particles were dispersed was heated to 100° C. and held for 120 minutes. Then, it was cooled to room temperature at 3° C. per minute, hydrochloric acid was added to dissolve the dispersant, and the particles were filtered, washed with water and dried to obtain toner particles T-1 having a weight average particle diameter (D4) of 8.0 μm. Table 2 shows the physical properties of the obtained toner particles T-1.

<Production Example of Toner Particles T-2 and T-3>
In the production of the toner particles 1, as described in Table 2, the toner particles T-2 and T-3 were produced in the same manner as in the production example of the toner particles T-1 except that the addition amount of the polymerization initiator was changed. It was manufactured. Table 2 shows the physical properties of T-2 and T-3 of the obtained toner particles.

<Production Example of Toner 1>
The toner particles T-1: 100 parts, the external additive A-1: 2.7 parts, and the external additive B-1: 0.3 part are mixed with the Mitsui Henschel mixer (FM) (Mitsui Miike Kakoki ( Was used for 100 seconds at a peripheral speed of the processing blade 140 of 35 m/sec (first time).

The Mitsui Henschel mixer (FM) (Mitsui Miike Kakoki Co., Ltd.) shown in FIG. 4 was equipped with a stirring blade 120 shown in FIG. As the stirring blade 120, a blade having an S-shape and a tip end looking up was used.

Further, above the stirring blade 120, the processing blade 140 shown in FIG. 5 was attached to the same drive shaft 111 as a rotating body.

Then, the apparatus shown in FIG. 2 was used for the heating treatment (second time).

The apparatus shown in FIG. 2 has a main casing 31 having an inner peripheral diameter of 130 mm, and the apparatus configuration conditions shown in Table 3 are used. Hot water was passed through the jacket so that the temperature (T1) inside the raw material inlet inner piece 316 was 55°C.

After charging the externally added toner into the apparatus shown in FIG. ) Was adjusted, and heat treatment was performed for 10 minutes.

After completion of the heat treatment, a toner having a mesh size of 75 μm was sieved to obtain Toner 1. Table 3 shows the physical properties of Toner 1.

<Production Example of Toners 2 to 15>
Toners 2 to 15 were obtained in the same manner as in the toner 1 production example except that the formulation and the production conditions shown in Table 3 were used. Table 3 shows the physical properties of Toners 2 to 15.

<Production Example of Toners 16, 19 and 20>
In the production example of Toner 1, the formulation is changed to that shown in Table 3 and the Mitsui Henschel mixer (FM) (Mitsui Miike Kakoki Co., Ltd.) shown in FIG. 4 is used and the peripheral speed of the processing blade 140 is 20 m/sec. After mixing for a minute, toners 16, 19 and 20 were obtained. Table 3 shows the physical properties of Toners 16, 19, and 20.

The blades used were the same as those used in the toner 1 production example.

<Production Example of Toner 17>
In the manufacturing example of Toner 1, the formulation shown in Table 3 was changed, and the peripheral speed of the processing blade 140 was set to 30 m/sec by using the Mitsui Henschel Mixer (FM) (Mitsui Miike Kakoki Co., Ltd.) shown in FIG. After mixing for a minute, Toner 17 was obtained. Table 3 shows the physical properties of Toner 17.
The blades used were the same as those used in the toner 1 production example.

<Production Example of Toner 18>
In the production example of Toner 1, the prescription shown in Table 3 was changed, and the peripheral speed of the processing blade 140 was set to 50 m/sec using a Mitsui Henschel mixer (FM) (Mitsui Miike Kako Co., Ltd.) shown in FIG. After operating for 20 minutes, Toner 18 was obtained. Table 3 shows the physical properties of the obtained toner 18.

The Mitsui Henschel mixer (FM) (Mitsui Miike Kakoki Co., Ltd.) shown in FIG. 4 was equipped with a stirring blade 120 shown in FIG. As the stirring blade 120, a blade having an S-shape and a tip end looking up was used.

Further, above the stirring blade 120, the processing blade 140 shown in FIG. 7 was attached to the same drive shaft 111 as a rotating body.

<Production Example of Toner 21>
In the production example of Toner 1, the formulation is changed to that shown in Table 3, a hybridization system NHS-1 (manufactured by Nara Machinery Co., Ltd.) is used as an external addition device, the peripheral speed is set to 80 m/sec, and the operation is performed for 15 minutes. Toner 21 was obtained. Table 3 shows the physical properties of the obtained toner 21.

[Example 1]
An HP printer (LaserJet Pro m203dw) cartridge (CF230X) adopting a cleanerless system was modified and used for image evaluation. As a modification point, the voltage application to the toner regulating member (blade) was turned off under the condition that the paper dust collection at the developing site was suppressed. The modified cartridge was filled with 150 g of Toner 1, and the following evaluation was performed.

<fog>
The evaluation of fog was carried out using the above-mentioned evaluation machine under the environment of a normal temperature and normal humidity environment (23.0° C., 50.0% RH) and a low temperature low humidity environment (15.0° C., 10.0% RH).

The measurement of fog is performed using REFLECTMETER MODEL TC-6DS manufactured by Tokyo Denshoku Co., Ltd. A green filter is used as the filter. For fogging, the white image immediately after outputting a solid black image is taped on the photoconductor (drum) with Mylar tape, and the reflectance of the Mylar tape pasted on the paper is calculated from the Macbeth density of the Mylar tape pasted directly on the paper. It was calculated by subtracting it and evaluated according to the following criteria.
Fog (%) = reflectance of tape directly attached to paper (%)-reflectance of tape taped on the drum (%)

The evaluation was performed after passing 3,500 sheets and 5,000 sheets under the same conditions as in the evaluation method for the first sheet and the black after-drum.

The criteria for judgment are as follows. C or more is judged to be good. The results are shown in Table 4.
A: less than 10% B: 10% or more and less than 15% C: 15% or more and less than 20% D: 20% or more

<Ghost>
As shown in FIG. 8, there was a block-shaped solid black image for one round of the developing sleeve, and an image in which a halftone full surface solid was followed was printed underneath. Then, how much the image history of the first sleeve of the developing sleeve appears in the halftone after the second sleeve of the developing sleeve was visually evaluated.

The evaluation timing was carried out after passing 3,500 sheets in a low temperature and low humidity environment (15.0° C., 10.0% RH).

The criteria for judgment are as follows. C or more is judged to be good. The results are shown in Table 4.
A: No shade difference is seen.
B: A slight shade difference is seen.
C: A light and shade difference is noticeable.
D: A difference in shade is also seen after the third lap of the sleeve.

[Examples 2 to 15, Comparative Examples 1 to 6]
The toners shown in Table 4 were evaluated in the same manner as in Example 1. The results are shown in Table 4.

31: Main body casing, 32: Rotating body, 33, 33a, 33b: Stirring member, 34: Jacket, 35: Raw material inlet, 36: Product outlet, 37: Central shaft, 38: Drive part, 39: Processing space, 310: side surface of end of rotating body, 41: rotation direction, 42: return direction, 43: feed direction, 316: inner piece for raw material charging port, 317: inner piece for product discharging port, d: overlapping portion of stirring member Interval, D: Width of stirring member, 100: toner processing device, 110: processing tank, 111: drive shaft, 120: stirring blade, 130: deflector, 140: processing blade, 141: processing blade body, 142: processing Part, 150: drive motor, 160: control part, 330: processing blade

Claims (6)

A toner containing toner particles containing a binder resin and a colorant, and an external additive,
(1) The external additive contains an external additive A having a ferret diameter a of 30 nm or more and 300 nm or less,
(2) The sticking index of the external additive A in the toner is 0.00 or more and 3.30 or less,
(3) In the powder fluidity measuring device, a propeller blade is attached to the surface of the powder layer of the toner produced by applying a vertical load of 0.88 kPa in a measuring container, and a propeller blade is provided around the outermost edge portion of the propeller blade. A toner having a total energy of 100 mJ or more and 150 mJ or less when the powder is intruded into the powder layer while rotating at a speed of 10 mm/sec. The toner according to claim 1, wherein the external additive A is inorganic fine particles or organic-inorganic composite fine particles. The toner according to claim 1, wherein the coverage of the toner particles with the external additive A is 28.0 area% or more and 45.0 area% or less. The toner according to claim 1, wherein the external additive A has a shape factor SF-2 of 103 or more and 120 or less. In observing an image obtained by image-processing a cross section of the toner by a transmission electron microscope (TEM), the external additive A in which a part of the external additive A penetrates into the inside of the toner particle from the surface of the toner particle The penetration depth b and the convex height c satisfy the following relational expressions (1) and (2), where b (nm) is the penetration depth and c (nm) is the convex height. The toner according to any one of 1 to 4.
30≦b+c≦300 (1)
0.15≦b/(b+c)≦0.30 (2)
(The penetration depth b (nm) of the external additive A means that the external additive A is in contact with the toner particles in the outline of the external additive A in the observation of an image obtained by image-processing the cross section. When the contour line of the part is defined as a contour line X and a line segment obtained by connecting both ends of the contour line X with a straight line is defined as a line segment Z, a perpendicular line drawn from the line segment Z to the contour line X and It means the maximum distance between the intersection with the contour line X and the line segment Z, and the convex height c (nm) of the external additive A is the observation of an image obtained by image-processing the cross section. In, when a contour line of a portion other than the contour line X among the contour lines of the external additive A is defined as a contour line Y, a perpendicular line from the line segment Z to the contour line Y and the contour line Y It means the maximum distance between the intersection and the line segment Z.) The toner according to any one of claims 1 to 5, wherein a sticking index of the external additive A in the toner is 0.50 or more and 2.50 or less.

Images