JP2018004879A - Toner and developing device including the toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that can prevent white streaks when rough paper having a rough surface is used in a normal-temperature and high-humidity environment and provide good images even when used for a long period in a high-temperature and high-humidity environment.SOLUTION: There is provided a toner including toner particles each containing a binder resin, amorphous polyester, and colorant, and inorganic fine particles, the toner having a softening point of 110°C or higher and 140°C or lower, and satisfying all the following formulas (1) to (3). Formula (1) f≤25.0; formula (2) 2.0≤F≤5.0; and formula (3) F≤5.0. In the formulas (1) to (3), frepresents a force between two particles (nN); frepresents a maximum pulling stress (kN/m) when a load of 78.5 N is applied to the toner left standing for 10 minutes at 55°C to be broken; Frepresents a maximum pulling stress (kN/m) when a load of 1962.5 N is applied to the toner for five minutes at 55°C to be broken.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method, a magnetic recording method, and the like, and a developing device provided with the toner.

Printers and copiers must have excellent reproducibility of latent images and high resolution. At the same time, the printer can be downsized for small offices such as private business owners, and can be used for a long time in any environment. There is a need to provide stable images.
In order to reduce the size of the printer, it is preferable to employ a cleanerless system. The cleanerless system is a method in which the cleaning blade and the cleaner container are eliminated and the transfer residual toner is collected in the developing device.
There are many problems specific to the cleanerless system.
First, in the cleaner-less system, the transfer residual toner is collected again in the developing device, so that the stress between the members is greatly received not only in the developing process but also in the charging process. Therefore, in the cleanerless system, toner deterioration such as embedding of inorganic fine particles (hereinafter also referred to as external additives) added to enhance toner fluidity and charge stabilization, aggregation between toners, and toner cracking occurs. easy. Therefore, a toner having higher durability than that of the conventional toner is demanded.
On the other hand, in order to reduce the size of the printer, not only the components are omitted, but also the size reduction of the components is an effective means. The downsizing of the fixing device is an effective means for downsizing the constituent members. Specifically, film fixing is advantageous for miniaturization from the viewpoint of simplifying the heat source and the device configuration.
However, in general, film fixing requires a small amount of heat to be applied to the toner and is light pressure, so that heat is not sufficiently transferred to the toner, so that it tends to have a strict structure for fixing properties. In recent years, there are many examples where printers are used in various environments, and in particular, in a room temperature and high humidity environment, heat from the fixing film is deprived by moisture, and the fixability tends to decrease.
In recent years, the diversification of printing paper has progressed, and printing on paper called rough paper having low smoothness, that is, paper with many irregularities on the surface of the paper is also increasing. When the toner is placed on the concave portion of the paper, the pressure from the fixing film is not easily received, and the toner is hardly melted because the toner is hardly melted, and the adhesion between the toner and the paper or the adhesion between the toners tends to be weak. It is in. For this reason, as a result of fixing with such a configuration, toner enters the concave portion of the paper, and part of the toner in the solid image is peeled off from the paper, resulting in a small white dropout (hereinafter referred to as “white dropout”). ") Is more likely to occur.
If the melt viscosity of the toner is lowered in order to solve this problem, the external additive is embedded on the toner surface or the toner is cracked as described above, which is not desirable because the toner is liable to deteriorate.
Especially in cleanerless systems where the toner is likely to deteriorate, due to the remarkable occurrence of embedding of external additives on the toner surface, aggregation between toners, or poor charging due to moisture absorption during long-term use in a high-temperature and high-humidity environment. Image defects are likely to occur, and adverse effects such as fogging and ghosting are also likely to occur.
From the above, cleanerless systems and film fixing are effective for downsizing printers, but in order to apply to these systems, toners with better low-temperature fixing properties, charging properties and durability than before are required. is there.
Patent Document 1 proposes a toner having a core-shell structure in which a crystalline polyester resin is dispersed as a domain phase in a matrix phase of an amorphous polyester resin as a shell layer, and has excellent low-temperature fixability. And has achieved durability.
In Patent Document 2, an excellent low-temperature fixability is achieved by promoting the melting of the surface layer by regulating the aluminum content in the surface layer portion and inside of the toner.
In Patent Document 3, in toner particles containing a binder resin containing a non-crystalline resin (A) and an amorphous polyester resin (B) and a colorant, the toner particles contain the non-crystalline resin (A). A toner is described in which an amorphous polyester resin (B) is dispersed as a domain phase in a matrix phase. It is described that the number average domain diameter has a specific range of size in the observed image of the toner particle cross section.

Japanese Patent Laying-Open No. 2015-045719 JP 2010-204243 A Japanese Patent Laying-Open No. 2015-152703

Any of the above-mentioned toners is improving with respect to improving the low-temperature fixability and stabilizing the image quality during long-term use. However, it is still inadequate in terms of suppression of white spots when using rough paper in a room temperature and high humidity environment, and suppression of toner deterioration in a high temperature and high humidity environment, in a configuration that is harsh against toner deterioration such as a cleanerless system. There was room for improvement.
That is, the present invention provides a toner that suppresses white spots when using rough paper having a rough paper surface under a normal temperature and high humidity environment, and can obtain a good image even when used for a long time under a high temperature and high humidity environment. It is. The present invention also provides a developing device including the toner.

The present invention is a toner having toner particles containing a binder resin, an amorphous polyester and a colorant, and inorganic fine particles,
The softening point of the toner is 110 ° C. or higher and 140 ° C. or lower
The toner satisfies all of the following formulas (1) to (3).
Formula (1) f _A ≦ 25.0
Formula (2) 2.0 ≦ F ₁ ≦ 5.0
Formula (3) F ₂ ≦ 5.0
[In the formulas (1) to (3),
f _A is a force between two particles (nN) calculated from the maximum tensile breaking force when a toner compact is formed by applying a load of 78.5 N at 25 ° C. and the toner compact is broken. ).
F ₁ is a maximum tensile stress (kN / m ² ) when a toner compact is formed by applying a load of 78.5 N to the toner left at 55 ° C. for 10 minutes, and the toner compact is broken. Show.
F ₂ represents a maximum tensile stress (kN / m ² ) when a toner compact is formed by applying a load of 1962.5 N at 55 ° C. for 5 minutes and the toner compact is broken. ]
The present invention also provides a toner for developing an electrostatic latent image formed on an electrostatic latent image carrier, and a toner carrier that carries the toner and conveys the toner to the electrostatic latent image carrier. A developing device comprising:
The developing device is characterized in that the toner is the toner.

  According to the present invention, a toner that suppresses white spots when using rough paper having a rough paper surface under a normal temperature and high humidity environment, and can obtain a good image even when used for a long time under a high temperature and high humidity environment, and the toner, A developing device provided with toner can be provided.

Schematic diagram showing an example of a mixing treatment device The schematic diagram which shows an example of a structure of the stirring member used for a mixing processing apparatus Schematic sectional view showing an example of a developing device Schematic sectional view showing an example of an image forming apparatus Schematic sectional view showing another example of the developing device (A) And (b) is a figure which shows the apparatus which measures the force between two particles, (c) is an example of a tensile stress curve Example of measurement data of half-width of inorganic fine particles Schematic diagram of flow curve

In the present invention, the description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit as endpoints unless otherwise specified.
The toner of the present invention is
A toner having toner particles containing a binder resin, amorphous polyester and a colorant, and inorganic fine particles,
The softening point of the toner is 110 ° C. or higher and 140 ° C. or lower
The toner satisfies all of the following formulas (1) to (3).
Formula (1) f _A ≦ 25.0
Formula (2) 2.0 ≦ F ₁ ≦ 5.0
Formula (3) F ₂ ≦ 5.0
[In the formulas (1) to (3),
f _A is a force between two particles (nN) calculated from the maximum tensile breaking force when a toner compact is formed by applying a load of 78.5 N at 25 ° C. and the toner compact is broken. ).
F ₁ is a maximum tensile stress (kN / m ² ) when a toner compact is formed by applying a load of 78.5 N to the toner left at 55 ° C. for 10 minutes, and the toner compact is broken. Show.
F ₂ represents a maximum tensile stress (kN / m ² ) when a toner compact is formed by applying a load of 1962.5 N at 55 ° C. for 5 minutes and the toner compact is broken. ]

A phenomenon (white spots) in which the image area is small during fixing will be described.
White spots indicate that when toner is transferred from a latent electrostatic image bearing member to a medium such as paper, the toner is present in a concave portion of the paper with respect to the pressing direction of a fixing device such as a fixing film. Occurs.
Specifically, the mechanism is as follows.
The toner present in the concave portion of the paper is not easily pressed by the fixing device at the time of fixing, and is close to a non-pressurized state, so that it is difficult to adhere to the paper. Therefore, the toner present in the concave portion of the paper is not fixed on the paper and peeled off. As a result, an image defect such as a white spot in the fixed image occurs.
In order to suppress such white spots at the time of fixing, the toners have a low adhesive force (that is, a low interparticle force) at room temperature, and further, the toners have a high adhesion temperature at which the toner starts to melt. It is important to control the state to have a certain degree of adhesion.

The present inventors consider the mechanism for suppressing white spots during fixing as follows.
First, it is important that the force between two particles is low between toners at normal temperature.
Since the adhesion between toners at normal temperature is low, the toner is uniformly developed on the electrostatic latent image carrier, and further, the toner is less likely to aggregate when transferred to a medium such as paper. As a result, when the solid image is output, the toner transferred around the concave portion of the paper is less likely to fall into the concave portion of the paper, and the toner is uniformly transferred onto the paper even if the solid image portion has concave and convex portions. Is done.
Further, in addition to the low adhesion between the toners at normal temperature, the toner is exposed to a certain high temperature, that is, the temperature at which the toner is exposed before passing through the fixing nip (the area where the paper and the fixing film are in contact). It is important that the adhesion is increased.
By increasing the adhesion between the toners at this high temperature, the toners in the solid image portion adhere to each other or become weakly bonded, so that even if there are paper irregularities, the toners do not break. , White spots where toner is peeled off from the paper can be suppressed.
As a means for realizing a high adhesion force between toners at a high temperature, conventionally, a core-shell type toner structure has been studied in consideration of durability. This core-shell type structure has a structure in which a shell portion has a high softening point material and a core portion has a low softening point material or a plasticizer. However, when used for a long time in an image forming apparatus that easily applies stress to the toner, such as a cleaner-less system, even if the shell portion has a high softening point material, the core portion may be Toner deterioration such as toner aggregation is likely to occur. In particular, image defects such as fogging and ghosting also occur in a high-temperature and high-humidity environment where external additives are embedded and charging defects tend to occur.

Based on the above findings, the present inventors examined in detail and obtained the configuration of the present invention. The present invention will be described in detail below.
In the present invention, the softening point of the toner is 110 ° C. or higher and 140 ° C. or lower, preferably 120 ° C. or higher and 140 ° C. or lower, and more preferably 125 ° C. or higher and 135 ° C. or lower.
In a system such as a cleaner-less system in which toner is easily stressed between members, control of the softening point of the toner is important in order to suppress toner deterioration.
When the softening point of the toner is 110 ° C. or higher, it is possible to suppress toner deterioration such as embedding of an external additive and toner cracking. As a result, fog and ghost in a high temperature and high humidity environment are suppressed. On the other hand, considering the fixability, the softening point of the toner is 140 ° C. or less. When the softening point of the toner is 140 ° C. or less, the toner can be sufficiently fixed on the paper when heat or pressure is applied from the fixing device.
In order to adjust the softening point of the toner within the above range, the molecular weight of the toner, the type and molecular weight of the binder resin constituting the toner, and the type and content of a plasticizer such as wax may be adjusted.

In the present invention, a load of 78.5 N is applied to the toner at 25 ° C. to form a toner compact, and the two-particle force f _A calculated from the maximum tensile breaking force when the toner compact is broken. Is 25.0 nN or less, preferably 23.0 nN or less, more preferably 15.0 nN or less. The lower limit is not particularly limited, but is preferably 0.1 nN or more, more preferably 1.0 nN or more.
The compression condition at 78.5N assumes a load applied when the compacted toner in the process cartridge passes through the regulating portion. In recent years, the size of printers has been reduced, and the outer diameter of a toner carrier is often used having a diameter of about 10 mm to 14 mm. The torque applied to the toner carrier of these outer diameters is about 0.1 N · m to 0.3 N · m on the shaft, and a force of about 20 N to 60 N is applied between the toner carrier surface and the regulating blade. It depends. Furthermore, if the diameter of the toner carrier is further reduced, it is expected that a load exceeding the above will be applied to the restricting portion.
Therefore, the load of 78.5 N is assumed in consideration of a reduction in the diameter of the toner carrier, and a configuration in which the load is about 20% stronger than the conventional load is assumed. Further, deteriorated toner after long-term use enters the regulating portion. It is a value that assumes.

It was found that when f _A is 25.0 nN or less, white spots during fixing are suppressed. About this reason, the present inventors guess as follows.
When f _A is 25.0 nN or less, toner particles adjacent to each other in the restricting portion in the process cartridge can exist in a state close to point contact via the external additive. By obtaining such a state, it is considered that the external additive works effectively as a charging site, and a uniform charge distribution can be obtained. As a result, a good charge amount can be obtained even in a high humidity environment where it is difficult to secure the charge amount. Further, when toner is transferred from the electrostatic latent image carrier to the medium, it is considered that the toner moves to the medium with less unevenness even if unevenness of the paper exists.
In addition, when the toners are in contact with each other in a form close to point contact, the area where the toners are in contact with each other is extremely small, so that heat conduction between the toners is efficiently performed when receiving heat from the fixing film. It becomes easier to communicate. The present inventors believe that this is because the contact area through which heat is transmitted becomes small, and the amount of heat transmitted is concentrated locally, so that the toner is easily melted and plasticized on the surface. As a result, the present inventors consider that low-temperature fixability tends to be improved and it is easy to suppress white spots that are toner peeling from paper.
The f _A can be adjusted by the type of external additive, particle size, particle size distribution, external addition method, and the like.

In the present invention, a 78.5 N load is applied to the toner left at 55 ° C. for 10 minutes to form a toner compact, and the maximum tensile stress F ₁ when the toner compact is broken is 2.0 kN. / ^{m 2} or more 5.0 kN / ^{m 2} or less, it is preferably, 2.5 kN / ^{m 2} or more 3.0 kN / ^{m 2} or less is 2.3KN / ^{m 2} or more 5.0 kN / ^{m 2} or less It is more preferable.
White spots at the time of fixing are likely to occur due to toner entering the concave portions of the paper. When entering the concave portion of the paper, almost no pressure is applied from the fixing film. Therefore, the present inventors consider that it is important to bond the toners after transfer in order to bond the toner present in the concave portion of the paper in the solid image portion to the paper. The present inventors have studied intensively, by controlling the F _1, the front passes through the fixing nip, can adhesive force control between toner present in the recess of the paper was found that the white spots can be suppressed .

First, the meaning of leaving it at 55 ° C. for 10 minutes in the measurement of F ₁ will be described.
The temperature to which the toner on the paper is exposed before passing through the fixing nip is about 55 ° C.
Further, it was found that when the toner was left at 55 ° C. for 10 minutes, the toner softened from the vicinity of the surface layer and the adhesion between the toners increased. It has been found that the maximum tensile stress F ₁ corresponding to the adhesion force correlates with the adhesion state of the toners on the paper before passing through the fixing nip.
Further, the higher the adhesion force between the toners at 55 ° C. in the non-pressurized state, the higher the maximum tensile stress is obtained when compressed at 78.5N. In addition, the adhesive force between the toners exposed to a high temperature of about 55 ° C. increases before the toner passes through the fixing nip, so that the toner hardly moves. Further, since the toner on the paper is difficult to move, the paper is not easily rolled into the concave portion, and the toner is fixed in a state where the toners are connected at the time of fixing. As a result, it is possible to suppress the peeling of the toner in the solid image portion, that is, the white spot.
When the F ₁ is 2.0 kN / m ² or more, the adhesion force between the toners increases, and the toner does not easily fall into the concave portions of the paper, so that white spots during fixing can be suppressed. On the other hand, if F ₁ is too high, the adhesion force between the toners is excessively increased and winding around the fixing film is likely to occur.
Specifically, when F ₁ is 5.0 kN / m ² or less, the adhesion force between the toners is hardly excessive, and the wrapping around the fixing film can be suppressed.

Next, the meaning of 78.5N in the measurement of F ₁ will be described.
The pressure from the fixing film is about 130 N, and the measurement of F ₁ is performed by applying a pressure of about 60% of the fixing pressure. In order to reduce the stress on the toner due to the pressurization at the time of fixing, fixing with a light pressure that is about half of the conventional pressure can be considered in the future, and this pressure is assumed.
The F ₁ can be adjusted by controlling the structure near the toner surface.

In the present invention, a toner compact is formed by applying a load of 1962.5 N at 55 ° C. for 5 minutes, and the maximum tensile stress F ₂ when the toner compact is broken is 5.0 kN / m ² or less. , and the is preferably 3.7kN / ^{m 2} or less, and more preferably 3.3kN / ^{m 2} or less. The lower limit is not particularly limited, but is preferably 2.5 kN / m ² or more, and more preferably 3.0 kN / m ² or more.
First, temperature conditions and compression conditions in the measurement of F ₂ will be described.
Usually, in a high temperature environment, the toner is easily deteriorated due to embedding of external additives or aggregation due to heat, and fog and ghost due to poor charging and fluidity are likely to occur.
In particular, when the toner is softened, for example, by lowering the softening point of the toner in order to improve the low-temperature fixability, this toner deterioration occurs remarkably.
In view of the temperature rise of the main body in the process cartridge, use in a harsh environment, or the state of transportation of the cartridge, it is assumed that the toner is exposed to a temperature up to about 55 ° C. At this temperature, a condition assuming that 20 to 60 N, which is the load that the toner receives at the regulating portion, is received 100 to 300 times is a state in which a load of 1962.5 N is applied for 5 minutes.
By controlling the maximum tensile stress F ₂ that reflects the condition, it is possible to suppress toner deterioration, also it is possible to obtain good images during long-term use.
When the F ₂ is 5.0 kN / m ² or less, toner deterioration is suppressed, and a good image can be obtained even during long-term use. On the other hand, when the F ₂ is larger than 5.0 kN / m ² , the toner deteriorates during long-term use, and fogging and ghosting occur due to toner fluidity and charging failure.
The F ₂ can be adjusted by controlling the state of the toner surface using a toner softening point or an external additive.

The toner binder resin preferably contains a vinyl resin.
When the binder resin contains a vinyl resin, the softening point of the toner can be easily controlled, and toner deterioration during long-term use can be easily suppressed. In order to further improve the control and suppression, the binder resin is more preferably a vinyl resin. The binder resin may contain a known resin used for the toner binder resin to the extent that the effects of the present invention are not impaired.
Further, it is preferable that the toner particles contain both a vinyl resin and an amorphous polyester, since the toner deterioration can be highly suppressed and white spots can be suppressed at the time of fixing.

Examples of the vinyl resin include the following.
Homopolymers of styrene such as polystyrene and polyvinyltoluene and substituted products thereof;
Styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, Styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-methacrylic acid Dimethylaminoethyl acid copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene -Maleic acid copolymerization , Styrene - styrene copolymer and maleic acid ester copolymers;
Polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, and polyacrylic acid resin can be used. These can be used alone or in combination of two or more. Among these, styrenic copolymers are preferable from the viewpoints of development characteristics and fixability. Furthermore, a styrene-butyl acrylate copolymer is more preferable because it can easily reduce the hygroscopicity and can improve the transferability in a high-temperature and high-humidity environment.

The amorphous polyester preferably has a monomer unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms and a monomer unit derived from an alcohol component. In addition, the content ratio of the monomer unit derived from the linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms is 10 mol% or more and 50 mol with respect to all monomer units derived from the carboxylic acid component constituting the amorphous polyester. % Or less is preferable.
Here, the monomer unit refers to a reacted form of the monomer substance in the polymer.
Softening of the amorphous polyester in a state where the peak molecular weight of the amorphous polyester is increased by the content ratio of the monomer unit derived from the straight chain aliphatic dicarboxylic acid having 6 to 12 carbon atoms satisfying the above specific ratio It becomes easy to lower the point. For this reason, it is easy to achieve both suppression of toner deterioration during long-term use and suppression of white spots during fixing.
Since the amorphous polyester contains a monomer unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms as a constituent component, it can be melted instantaneously at the time of fixing. The effect of suppressing white spots is further improved.
It is speculated that this phenomenon is caused by the fact that the linear aliphatic dicarboxylic acid site is folded and the amorphous polyester tends to have a structure like a pseudo-crystalline state.
That is, from the viewpoint of forming a quasicrystalline state, the linear aliphatic dicarboxylic acid preferably has 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms.
When the straight aliphatic dicarboxylic acid has 6 or more carbon atoms, the straight aliphatic dicarboxylic acid portion is easily folded, so that it has a structure like a quasicrystalline state and can be melted instantaneously at the time of fixing. Therefore, it is easy to suppress white spots during fixing.
On the other hand, if the linear aliphatic dicarboxylic acid has 12 or less carbon atoms, it becomes easier to control the softening point and peak molecular weight of the amorphous polyester, so that toner deterioration during long-term use and white spots during fixing are suppressed. It becomes easy to make it compatible.

In addition, the content ratio of the monomer unit derived from the linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms is 10 mol% or more and 50 mol% or less with respect to all the monomer units derived from the carboxylic acid component constituting the amorphous polyester. It is preferable that it is 30 mol% or more and 50 mol% or less.
When the content is 10 mol% or more, the softening point of the amorphous polyester is likely to be lowered. On the other hand, when the content is 50 mol% or less, it is difficult to reduce the peak molecular weight of the amorphous polyester.

Examples of the carboxylic acid component for obtaining the amorphous polyester include linear aliphatic dicarboxylic acids having 6 to 12 carbon atoms and other carboxylic acids.
Examples of the linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms include adipic acid, suberic acid, sebacic acid, and 1,12-dodecanedioic acid.
Examples of the carboxylic acid other than the straight chain aliphatic dicarboxylic acid having 6 to 12 carbon atoms include the following.
Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, glutaric acid, n-dodecenyl succinic acid, and acid anhydrides or lower alkyl esters thereof.
Examples of the trivalent or higher polyvalent carboxylic acid component include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, emporic trimer acid, and acid anhydrides thereof. These lower alkyl esters.
Among these, terephthalic acid is preferably used because it can maintain a high peak molecular weight and easily maintain durability.
In addition to the propylene oxide adduct of bisphenol A, the following are mentioned as an alcohol component for obtaining amorphous polyester.
Examples of the divalent alcohol component include an ethylene oxide adduct of bisphenol A, ethylene glycol, 1,3-propylene glycol, and neopentyl glycol.
Examples of the trivalent or higher alcohol component include sorbitol, pentaerythritol, and dipentaerythritol.
The above divalent alcohol component and trihydric or higher alcohol component can be used alone or in combination of a plurality of compounds.

The amorphous polyester can be produced by an esterification reaction or a transesterification reaction using the above alcohol component and carboxylic acid component. In the case of polycondensation, a known esterification catalyst such as dibutyltin oxide may be appropriately used to promote the reaction.
The molar ratio of the alcohol component and the carboxylic acid component (carboxylic acid component / alcohol component), which is the raw material monomer of the amorphous polyester, is preferably 0.60 or more and 1.00 or less.
The glass transition temperature (Tg) of the amorphous polyester is preferably 45 ° C. or higher and 75 ° C. or lower from the viewpoint of fixability and heat resistant storage stability.
The glass transition temperature (Tg) can be known by measuring a differential scanning calorimeter (DSC).

The peak molecular weight (Mp) of the amorphous polyester is preferably 8000 or more and 13000 or less, and more preferably 9000 or more and 12000 or less.
When the peak molecular weight (Mp) is 8000 or more, it is easy to suppress toner deterioration during long-term use. On the other hand, when the peak molecular weight (Mp) is 13000 or less, it becomes possible to melt instantaneously at the time of fixing, so that white spots at the time of fixing can be easily suppressed.
The softening point of the amorphous polyester is preferably 85 ° C. or higher and 105 ° C. or lower, and more preferably 90 ° C. or higher and 100 ° C. or lower.
When the softening point is 85 ° C. or higher, it is easy to suppress toner deterioration during long-term use. On the other hand, when the softening point is 105 ° C. or lower, it becomes possible to melt instantaneously at the time of fixing, so that white spots at the time of fixing can be easily suppressed.
In order to control the peak molecular weight and softening point of the amorphous polyester within the above range, for example, the amorphous polyester is obtained by adding 10 mol of linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms to the total carboxylic acid component. % Or more and 50 mol% or less of a carboxylic acid component and an alcohol component are preferable.

The content of the amorphous polyester is preferably 5.0 parts by mass or more and 30.0 parts by mass or less, and 7.0 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin. More preferably.
When the content of the amorphous polyester is 5.0 parts by mass or more, since it becomes possible to melt instantaneously at the time of fixing, high adhesiveness is easily developed. On the other hand, when the content of the amorphous polyester is 30.0 parts by mass or less, it becomes easy to suppress toner deterioration during long-term use.

The peak molecular weight (Mp) of the toner is preferably 15000 or more and 30000 or less, and more preferably 20000 or more and 30000 or less.
When the peak molecular weight (Mp) of the toner is 15000 or more, it becomes easy to suppress toner deterioration during long-term use. On the other hand, when the peak molecular weight (Mp) of the toner is 30000 or less, it becomes difficult to inhibit melting during fixing.

When the toner was subjected to time-of-flight secondary ion mass spectrometry (TOF-SIMS),
The peak intensity derived from the vinyl resin is S85,
When the peak intensity derived from amorphous polyester is S211,
The S85 and S211 preferably satisfy the following formula (4), and more preferably satisfy the relationship of the following formula (4) ′.
Formula (4) 0.30 <= S211 / S85 <= 3.00
Formula (4) ′ 1.00 ≦ S211 / S85 ≦ 2.50
In time-of-flight secondary ion mass spectrometry (TOF-SIMS), information of several nanometers can be obtained from the toner surface, so that the constituent material of the outermost layer of the toner can be specified.
The amorphous polyester preferably has a monomer unit derived from bisphenol A as an alcohol component, and S211 is a peak derived from the bisphenol A.
Further, as described above, the vinyl resin is preferably a styrene-butyl acrylate copolymer, and S85 is a peak derived from the butyl acrylate.
When [S211 / S85] is 0.30 or more, the toner has a structure having an amorphous polyester on the toner surface side, so that the toner can be instantaneously melted at the time of fixing, so that white spots at the time of fixing can be easily suppressed. On the other hand, when [S211 / S85] is 3.00 or less, it is easy to suppress toner deterioration during long-term use.
In order to adjust [S211 / S85] to the above range, methods such as adjustment of acid value and hydroxyl value of amorphous polyester and adjustment of toner particle production conditions can be exemplified.

In the cross section of the toner observed with a transmission electron microscope (TEM),
Vinyl resin forms a matrix, amorphous polyester forms a domain,
Amorphous polyester domains are 30 area% or more and 70 areas with respect to the total area of the amorphous polyester domains within 25% of the distance between the outline and the center point of the cross section from the outline of the cross section. % Or less is preferable. More preferably, it is 45 area% or more and 70 area% or less.
The amorphous polyester controls the softening point to be lower in a state where the peak molecular weight (Mp) is larger than that of the conventional amorphous polyester.
However, when amorphous polyester forms a shell portion, the toner tends to deteriorate during long-term use. In addition, since amorphous polyester tends to absorb moisture compared to vinyl resin, in a high-temperature and high-humidity environment, the occurrence of poor regulation and a decrease in transferability are likely to occur due to a decrease in fluidity.
In contrast, in the cross section of the toner observed with a transmission electron microscope (TEM), the vinyl resin forms a matrix, and the amorphous polyester forms a domain.
Amorphous polyester domains are 30 area% or more and 70 areas with respect to the total area of the amorphous polyester domains within 25% of the distance between the outline and the center point of the cross section from the outline of the cross section. % Or less, it is easy to achieve both toner deterioration suppression during long-term use and white spot suppression during fixing.

Since the vinyl resin forms a matrix in the vicinity of the toner surface, it becomes easy to suppress toner deterioration during long-term use. In addition, compared to amorphous polyesters where the terminal of the resin is a carboxylic acid group or a hydroxyl group, vinyl resin is easy to suppress hygroscopicity. It is easy to suppress the occurrence.
In addition, since the amorphous polyester forms a plurality of domains in the vicinity of the toner surface, it can be melted instantaneously at the time of fixing, so that white spots at the time of fixing can be easily suppressed.
From the above, the area ratio of the amorphous polyester domains existing within 25% of the distance between the contour and the center point of the cross section to the total area of the amorphous polyester domains from the outline of the cross section of the toner If it is 30 area% or more (hereinafter also referred to as “25% area ratio”), melting can be instantaneously performed at the time of fixing, so that white spots at the time of fixing can be easily suppressed.
On the other hand, when the 25% area ratio is 70 area% or less, it is easy to maintain fluidity in a high-temperature and high-humidity environment, and to suppress the occurrence of fog and ghost.

Further, the amorphous polyester domains are 80 area% with respect to the total area of the amorphous polyester domains within 50% of the distance between the outline and the center point of the cross section from the outline of the cross section of the toner. Preferably, it is present in an amount of 100 area% or less. More preferably, it is 90 area% or more and 100 area% or less.
From the contour of the cross section of the toner, the area ratio of the amorphous polyester domain existing within 50% of the distance between the contour and the center point of the cross section to the total area of the amorphous polyester domain (hereinafter referred to as “50”). % Area ratio) is 80 area% or more, it can be melted instantaneously at the time of fixing, and it becomes easy to suppress white spots at the time of fixing.
The fact that the 50% area ratio is 80 area% or more means that the amorphous polyester domain is “from the central point of the toner cross section”, “from the outline of the toner cross section, between the outline and the central point of the cross section. In other words, it can be said that 20 area% or less of the total area of the domains of the amorphous polyester exists in the region up to “the boundary line of 50% of the distance”. In this case, the softening point of the toner can be easily controlled to 110 ° C. or more, the fluidity during long-term use can be easily maintained, and the occurrence of fogging and ghosting can be easily suppressed.

Further, from the contour of the cross section of the toner, the area of the domain of the amorphous polyester existing within 25% of the distance between the contour and the center point of the cross section is A,
From the contour of the cross section, when the area of the domain of the amorphous polyester existing in 25% to 50% of the distance between the contour and the center point of the cross section is B,
The A and B preferably satisfy the relationship of the following formula (5).
Formula (5) A / B ≧ 1.05
[A / B] (hereinafter also referred to as domain area ratio) is preferably 3.00 or less.
Further, it is more preferable that A and B satisfy the relationship of the following formula (1) ′.
Formula (5) ′ 3.00 ≧ A / B ≧ 1.20
When A and B satisfy the relationship of the above formula (5), it indicates that the domain of the amorphous polyester is unevenly distributed on the toner surface. Since the amorphous polyester domains are unevenly distributed on the toner surface, the amorphous polyester can be melted instantaneously at the time of fixing, so that white spots at the time of fixing can be easily suppressed.

In the cross section of the toner observed with a transmission electron microscope,
The number average diameter of the domains of the amorphous polyester is preferably 0.3 μm or more and 3.0 μm or less, and more preferably 0.3 μm or more and 2.0 μm or less.
When the number average diameter of the domains of the amorphous polyester is 0.3 μm or more, the F1 can be easily controlled to 2.0 kN / m ² or more, and the adhesion between the toner particles when melted at the time of fixing. It becomes easier to suppress white spots during fixing.
On the other hand, when the number average diameter of the domains of the amorphous polyester is 3.0 μm or less, the presence state of the domains of the amorphous polyester in the toner particles can be easily controlled. In addition, the variation of the amorphous polyester domain between the toner particles can be reduced. Therefore, it becomes easier to suppress white spots during fixing.
As a measure to form amorphous polyester domains near the toner surface and to control the number average diameter of the amorphous polyester domains, adjustment of acid value and hydroxyl value of amorphous polyester, amorphous property Examples include adjustment of softening points of polyester and toner, and adjustment of production conditions of toner particles.

The acid value of the amorphous polyester is preferably 1.0 mgKOH / g or more and 10.0 mgKOH / g or less, and more preferably 4.0 mgKOH / g or more and 8.0 mgKOH / g or less.
When the acid value of the amorphous polyester is adjusted to the above range, the amorphous polyester domain is formed in the vicinity of the toner surface, for example, the 25% area ratio can be easily controlled to 30 area% or more and 70 area% or less. It becomes easy.

In the present invention, the inorganic fine particles (hereinafter also referred to as inorganic fine particles B) contain silica fine particles.
The silica fine particles preferably have a number average particle size of primary particles of 80 nm to 200 nm, and more preferably 80 nm to 120 nm.
Further, the silica fine particles preferably have a maximum peak half-value width of 25.0 nm or less, more preferably 15.0 nm or less, in the particle size distribution of the primary particles.
When the number average particle diameter of primary particles of silica fine particles is 80 nm or more, toner deterioration is easily suppressed. On the other hand, when the number average particle size of the primary particles of the silica fine particles is 200 nm or less, the low-temperature fixability tends to be improved.
On the other hand, when the full width at half maximum of the maximum peak is 25.0 nm or less, uniform dispersion and uniform fixation of the silica fine particles on the toner particles can be achieved at a high level, and the force between the two particles can be easily controlled.

The silica fine particles are preferably silica fine particles produced by a sol-gel method from the viewpoint of easy control of the particle size distribution.
The sol-gel method is a method of removing particles from a silica sol suspension obtained by hydrolyzing and condensing alkoxysilane with a catalyst in an organic solvent in which water is present, and drying to form particles. The silica fine particles obtained by this sol-gel method have an appropriate particle size and a narrow particle size distribution, and are monodispersed and spherical. The force can be reduced.
In addition, sol-gel silica obtained by the sol-gel method exists in a spherical and monodisperse form, but some of them are united. In the particle size distribution of the primary particles, when the full width at half maximum is 25.0 nm or less, the number of such coalesced particles is small, the uniform adhesion of the silica fine particles to the toner particles is increased, and higher fluidity can be obtained. . As a result, the uniform chargeability and riseability of the toner are further improved. This effect becomes more remarkable with toner having an average circularity of 0.960 or more.

Next, a method for producing silica fine particles by the sol-gel method will be described below.
First, a silica sol suspension is obtained by hydrolyzing and condensing alkoxysilane with a catalyst in an organic solvent in which water is present. Then, the solvent is removed from the silica sol suspension and dried to obtain silica fine particles.
The silica fine particles thus obtained are usually hydrophilic and have many surface silanol groups. Therefore, it is preferable to subject the surface of the silica fine particles to a hydrophobic treatment.
The hydrophobic treatment method includes removing the solvent from the silica sol suspension and drying it, followed by treatment with the hydrophobic treatment agent, and adding the hydrophobic treatment agent directly to the silica sol suspension. The method of processing simultaneously with drying is mentioned.
From the viewpoint of controlling the half width and controlling the saturated water adsorption amount, a method of directly adding a hydrophobizing agent to the silica sol suspension is preferable. Hydrophobic treatment in suspension allows the sol-gel silica to remain in a monodispersed state, making it possible to apply the hydrophobization treatment, making it difficult for aggregates to form after drying and enabling even coating. .
Further, the pH of the silica sol suspension is more preferably acidic. By making the suspension acidic, the reactivity with the hydrophobizing agent is increased, and a stronger and more uniform hydrophobizing treatment can be performed.

Examples of the hydrophobizing agent include the following.
γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ -Aminopropyltrimethoxysilane hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, phenyl Trimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, methyltriethoxysilane, butyltriethoxysilane, hexyltriethoxysilane, octyl lithoate Xylsilane, decyltriethoxysilane, dodecyltriethoxysilane, phenyltriethoxysilane, o-methylphenyltriethoxysilane, p-methylphenyltriethoxysilane.
Furthermore, the silica fine particles may be subjected to a pulverization treatment in order to facilitate the monodispersion of the silica fine particles on the toner particle surfaces or to exhibit a stable spacer effect.
The silica fine particles preferably have an apparent density of 150 g / L or more and 300 g / L or less. The apparent density of the fine silica particles is in the above range, which indicates that the fine silica particles are not densely packed and exist with a lot of air between the fine particles, and the apparent density is very low. For this reason, the mixing property of the toner particles and the silica fine particles is improved during the external addition step, and a uniform coating state is easily obtained. This phenomenon is more remarkable when the average circularity of the toner particles is high, and the coverage tends to be higher. As a result, the toners of the externally added toner are not easily clogged with each other, and the adhesion between the toners tends to be reduced.

  As means for controlling the apparent density of the silica fine particles within the above range, the adjustment of the hydrophobization treatment in the silica sol suspension or the strength of the crushing treatment after the hydrophobization treatment, and the hydrophobization treatment amount, etc. Is mentioned. By performing a uniform hydrophobization treatment, relatively large aggregates themselves can be reduced. Alternatively, by adjusting the strength of the crushing treatment, relatively large aggregates contained in the silica fine particles after drying can be loosened into relatively small secondary particles, and the apparent density can be reduced. is there.

  The addition amount of the inorganic fine particles is preferably 0.1 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the toner particles. When the addition amount of the inorganic fine particles is within the above range, the uniform diffusion state of the inorganic fine particles on the toner particle surface can be easily controlled, and the force between the two particles can be easily controlled within a predetermined range.

The weight average particle diameter (D4) of the toner is preferably 5.0 μm or more and 12.0 μm or less, and more preferably 5.5 μm or more and 11.0 μm or less.
The aspect ratio of the toner is preferably 0.920 or more. When the aspect ratio of the toner is 0.920 or more, the toner has a spherical shape or a shape close thereto, and it is easy to obtain uniform triboelectric chargeability with excellent fluidity. In addition, it is easy to suppress poor regulation and to improve transferability.

The glass transition temperature (Tg) of the toner is preferably 40 ° C. or higher and 70 ° C. or lower.
When the glass transition temperature is in the above range, the storage stability and durability of the toner can be improved while maintaining good fixability.
The glass transition temperature (Tg) can be measured using a differential scanning calorimeter (DSC).

If necessary, the toner particles may contain a charge control agent to improve charging characteristics.
Various charge control agents can be used, but a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable.
Examples of the charge control agent include the following.
Metallic compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid and dicarboxylic acid; metal salts or metal complexes of azo dyes or azo pigments; polymer type having sulfonic acid or carboxylic acid groups in the side chain Compound; boron compound; urea compound; silicon compound; calixarene.
The content of the charge control agent is preferably 0.1 parts by weight or more and 10.0 parts by weight or less, more preferably 0.1 parts by weight with respect to 100 parts by weight of the binder resin when added inside the toner particles. Part to 5.0 parts by weight. When added outside the toner particles, the amount is preferably 0.005 parts by mass or more and 1.000 parts by mass or less, more preferably 0.010 parts by mass or more and 0.300 parts by mass or less with respect to 100 parts by mass of the toner particles. It is.

The toner particles may contain a release agent in order to improve fixability.
The content of the release agent in the toner particles is preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 25% by mass or less.
If the content of the release agent is 1% by mass or more, white spots during fixing can be easily suppressed. Moreover, if it is 30 mass% or less, it will become easy to suppress the toner deterioration at the time of long-term use.
The following can be illustrated as a mold release agent.
Petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam and derivatives thereof; montan wax and derivatives thereof; hydrocarbon waxes and derivatives thereof according to the Fischer-Tropsch method; polyolefin waxes and derivatives thereof such as polyethylene; carnauba wax and candelilla wax Natural waxes and their derivatives.
The derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. In addition, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, acid amide waxes, ester waxes, hardened castor oil and derivatives thereof, plant waxes, animal waxes and the like can also be used as mold release agents.
Among these release agents, ester wax and paraffin wax are preferably used from the viewpoint of low-temperature fixability.

The melting point defined by the peak temperature of the maximum endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the release agent is preferably 60 ° C. or higher and 140 ° C. or lower, 65 It is more preferable that the temperature is not lower than 120 ° C and not higher than 120 ° C.
When the melting point is 60 ° C. or higher, it is easy to suppress toner deterioration during long-term use. On the other hand, if the melting point is 140 ° C. or lower, the low-temperature fixability is unlikely to decrease.
As described above, the melting point of the release agent is the peak temperature of the maximum endothermic peak when measured by DSC. Moreover, the peak temperature of the maximum endothermic peak is performed according to ASTM D3417-99.
For these measurements, for example, DSC-7 manufactured by PerkinElmer, DSC2920 manufactured by TA Instruments, and Q1000 manufactured by TA Instruments can be used.
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. An aluminum pan is used as a measurement sample, and an empty aluminum pan is set for measurement and measured.

The toner particles contain a colorant. Examples of the colorant include the following.
Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds.
Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds.
Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.
Examples of the black colorant include carbon black, a magnetic material, and the above-described yellow colorant, magenta colorant, and cyan colorant that are toned to black.
The content of the colorant is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or the binder resin.

The magnetic material is preferably composed mainly of magnetic iron oxide such as triiron tetroxide and γ-iron oxide, and may contain elements such as phosphorus, cobalt, nickel, copper, magnesium, manganese, aluminum, and silicon. .
The shape of the magnetic body includes a polyhedron, an octahedron, a hexahedron, a sphere, a needle, and a scale. Preferred above.
The content of the magnetic substance is preferably 50 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or the binder resin.
The magnetic material preferably has a number average particle diameter of 0.10 μm or more and 0.40 μm or less from the viewpoint of uniform dispersibility and color in the toner.
The magnetic material can be produced, for example, by the following method.
First, an aqueous solution containing ferrous hydroxide is prepared by adding an alkali such as sodium hydroxide in an amount equivalent to or greater than the iron component to the ferrous salt aqueous solution. Air was blown in while maintaining the pH of the prepared aqueous solution at 7.0 or higher, and ferrous hydroxide was oxidized while heating the aqueous solution to 70 ° C. or higher, and seed crystals serving as the core of magnetic iron oxide particles Is generated.
Next, an aqueous solution containing about 1 equivalent of ferrous sulfate is added to the slurry containing seed crystals based on the amount of alkali added previously. And the pH of the obtained liquid mixture is maintained at 5.0-10.0, reaction of ferrous hydroxide is advanced, blowing in air, and a magnetic iron oxide particle is grown centering on a seed crystal. At this time, it is possible to control the shape and magnetic properties of the magnetic iron oxide by selecting an arbitrary pH, reaction temperature, and stirring conditions. As the oxidation reaction proceeds, the pH of the mixed solution shifts to the acidic side, but the pH of the mixed solution is preferably not less than 5.0.
After completion of the oxidation reaction, a silicon source such as sodium silicate is added to adjust the pH of the mixed solution to 5.0 or more and 8.0 or less to form a silicon coating layer on the surface of the magnetic iron oxide particles. The magnetic iron oxide particles (magnetic material) can be obtained by filtering, washing and drying the obtained magnetic iron oxide particles by a conventional method.

Further, when the toner particles are produced in an aqueous medium such as suspension polymerization, it is preferable that the surface of the magnetic material is subjected to a hydrophobic treatment because the magnetic material is easily included in the toner particles.
When the hydrophobizing treatment is performed by a dry method, the hydrophobizing treatment is performed on the washed, filtered, and dried magnetic iron oxide using a coupling agent.
When the hydrophobization treatment is performed in a wet manner, the magnetic iron oxide obtained above is redispersed in an aqueous medium, or the magnetic iron oxide obtained by washing and filtering is not dried and another aqueous system is used. Redispersion in a medium and treatment with a coupling agent are performed.
For example, the coupling treatment is performed by adding a silane coupling agent while sufficiently stirring the re-dispersed liquid and raising the temperature after hydrolysis, or adjusting the pH of the dispersion to an alkaline region after hydrolysis.

In the present invention, the toner particles can be produced by any known method.
First, the case where it manufactures by the grinding | pulverization method is demonstrated.
The binder resin, amorphous polyester and colorant, and if necessary, a release agent and a charge control agent are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. Thereafter, the toner material is melted and kneaded using a heat kneader such as a heating roll, a kneader, or an extruder to disperse or dissolve the toner material, and after cooling and solidification, pulverization, classification, and surface treatment as necessary, the toner Get particles.
Either the classification or the surface treatment may be performed first. In the classification step, it is preferable to use a multi-division classifier from the viewpoint of production efficiency.
The pulverization can be performed by a method using a known pulverizer such as a mechanical impact type or a jet type. Further, in order to obtain a toner (toner particles) having a preferable circularity or aspect ratio, it is preferable to further pulverize by applying heat or to perform an auxiliary mechanical shock treatment. Further, a hot water bath method in which finely pulverized (classified if necessary) toner particles are dispersed in hot water, a method of passing in a hot air stream, or the like may be used.
The mechanical impact force can be applied by using a mechanical impact pulverizer such as a kryptron system manufactured by Kawasaki Heavy Industries, Ltd. or a turbo mill manufactured by Turbo Industry, or a mechano-fusion system manufactured by Hosokawa Micron. For example, a method of applying a mechanical impact force to the toner particles by pressing the toner particles against the inner side of the casing by a centrifugal force with the blades.

The toner particles can be produced by the above pulverization method. However, in order to form amorphous polyester domains in the vicinity of the toner surface and to control the number average diameter of the amorphous polyester domains, a solution suspension is used. The toner particles are preferably produced in an aqueous medium such as a turbid method or a suspension polymerization method. Among these, the suspension polymerization method is more preferable.
In the suspension polymerization method, a polymerizable monomer capable of forming a binder resin, an amorphous polyester, a colorant, and a release agent, a polymerization initiator, a crosslinking agent, a charge control agent, and the like as necessary. Other additives are uniformly dissolved or dispersed by a disperser to obtain a polymerizable monomer composition.
Examples of the disperser include a homogenizer, a ball mill, and an ultrasonic disperser.
Next, the obtained polymerizable monomer composition is suspended in an aqueous medium containing a dispersant to form particles of the polymerizable monomer composition. At this time, the particle size of the obtained toner particles becomes sharper by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to obtain a desired toner particle size all at once. Further, after the formation of the particles of the polymerizable monomer composition, stirring may be performed using a normal stirrer to such an extent that the particle state is maintained and the particles are prevented from floating and settling.
Furthermore, the polymerizable monomer contained in the particles of the polymerizable monomer composition is polymerized to obtain toner particles. Here, the polymerization temperature may be set to 40 ° C. or higher, generally 50 ° C. or higher and 90 ° C. or lower. Moreover, the addition time of a polymerization initiator may be added simultaneously when adding another additive in a polymerizable monomer, or may be mixed immediately before suspending in an aqueous medium. Further, a polymerization initiator can be added before the polymerization reaction is started.
The toner particles obtained by the suspension polymerization method are almost spherical in shape, so that the fluidity at the regulating part is easy to improve and the frictional charge is likely to be easily made. Become. Further, since the toner particles have a relatively uniform charge amount distribution, an improvement in image quality can be expected.

Examples of the polymerizable monomer include the following.
Styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene;
Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, Acrylic ester monomers such as phenyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic acid Methacrylate monomers such as dimethylaminoethyl and diethylaminoethyl methacrylate;
Monomers such as acrylonitrile, methacrylonitrile, acrylamide.
These can be used alone or in combination of two or more.
Among the polymerizable monomers, styrene monomers, acrylate monomers, and methacrylate monomers can be preferably exemplified.
Moreover, it is preferable that content of a styrene-type monomer is 60 to 90 mass% in a polymerizable monomer, and it is more preferable that it is 65 to 85 mass%. On the other hand, the content of the acrylic acid ester monomer or the methacrylic acid ester monomer is preferably 10% by mass or more and 40% by mass or less, and preferably 15% by mass or more and 35% by mass or less. More preferred.
Furthermore, it is more preferable to use a combination of styrene and n-butyl acrylate because the hygroscopicity is easily lowered and the transferability in a high-temperature and high-humidity environment is easily improved.
The polymerizable monomer composition may contain a polar resin.
In the suspension polymerization method, since toner particles are produced in an aqueous medium, the polar resin can be present on the surface of the toner particles by adding the polar resin, and the chargeability is easily improved, and the development ghost is generated. Easy to suppress.
Examples of polar resins include the following.
Homopolymers of styrene such as polystyrene and polyvinyltoluene and substituted products thereof;
Styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, Styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, Styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer Coalescence, styrene-maleic acid Polymer, a styrene - styrene copolymer and maleic acid ester copolymers;
Polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyamide resin, epoxy resin, polyacrylic acid resin, terpene resin, phenol resin and the like.
These can be used alone or in combination of two or more. Moreover, you may introduce | transduce functional groups, such as an amino group, a carboxy group, a hydroxyl group, a sulfonic acid group, a glycidyl group, a nitrile group, in these polymers.

As the polymerization initiator, those having a half-life at the time of the polymerization reaction of 0.5 hours or more and 30.0 hours or less are preferable. Further, when the polymerization reaction is carried out using 100 parts by mass of the polymerizable monomer at an addition amount of 0.5 parts by mass or more and 20.0 parts by mass or less, the toner particles are given desirable strength and appropriate melting characteristics. be able to.
Specific examples include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2 , 2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo- or diazo-based polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydro Examples thereof include peroxide polymerization initiators such as peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butylperoxy 2-ethylhexanoate, and tert-butyl peroxypivalate.

As the cross-linking agent, a compound having two or more polymerizable double bonds is preferably used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinyl Examples include divinyl compounds such as aniline, divinyl ether, divinyl sulfide, and divinyl sulfone. These are used alone or as a mixture of two or more.
The addition amount of the crosslinking agent is preferably 0.01 parts by mass or more and 5.00 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

As the dispersant, a surfactant, an organic dispersant, or an inorganic dispersant can be used.
Examples of inorganic dispersants include polycalcium phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; calcium metasilicate, calcium sulfate, and barium sulfate. Inorganic salts; inorganic compounds such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide are listed.
The addition amount of the dispersant is preferably 0.2 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. Moreover, a dispersing agent may be used independently and may use multiple types together.

In order to form amorphous polyester domains in the vicinity of the toner surface and control the number average diameter of the amorphous polyester domains, the following steps are preferably performed.
After the polymerization of the polymerizable monomer is completed to obtain resin particles, a dispersion in which the resin particles are dispersed in an aqueous medium is used in the vicinity of the softening point of the amorphous polyester (for example, the softening point of the amorphous polyester). To the softening point + 10 ° C.), specifically, the temperature is raised to about 100 ° C., and the temperature is preferably maintained for 30 minutes or more.
The holding time is more preferably 60 minutes or more, and further preferably 120 minutes or more. The upper limit of the holding time is about 24 hours or less from the viewpoint of production efficiency.
Thereafter, the dispersion is preferably cooled at a cooling rate of 5 ° C./min or higher, more preferably at a cooling rate of 20 ° C./min or lower, to a glass transition temperature (Tg) or lower of the resin particles, and a cooling rate of 100 More preferably, the cooling is performed at a temperature of ° C / min or more. The upper limit of the cooling rate is about 500 ° C./min or less from the viewpoint of production efficiency.
Further, after cooling at the cooling rate, it is preferable to hold at that temperature for 30 minutes or more.
The holding time is more preferably 60 minutes or more, and further preferably 120 minutes or more. The upper limit of the holding time is about 24 hours or less from the viewpoint of production efficiency.

Toner particles are obtained by filtering, washing, and drying the resin particles obtained through the above steps. The toner particles are mixed with inorganic fine particles and adhered to the surface of the toner particles to obtain a toner.
It is also possible to insert a classification step in the manufacturing process (before mixing of the inorganic fine particles) to cut coarse powder and fine powder contained in the toner particles.

In the present invention, in addition to the inorganic fine particles B, the number average particle size of primary particles is preferably 4 nm or more and less than 80 nm, more preferably 6 nm or more and 40 nm or less (hereinafter also referred to as inorganic fine particles A). It is preferably added (externally added) to the particles.
The inorganic fine particles A are added to improve the fluidity of the toner and make the charge uniform. It is also a preferred form that the inorganic fine particles A are imparted with functions such as adjustment of the charge amount of the toner and improvement of environmental stability by hydrophobizing.
The number average particle diameter of the primary particles of these inorganic fine particles may be determined by using a photograph of toner magnified by a scanning electron microscope.
As the inorganic fine particles A, fine particles such as silica fine particles, titanium oxide fine particles, and alumina fine particles can be used, but silica fine particles are preferable from the viewpoint of fluidity of the toner and uniform charge.
The silica fine particles are preferably fine particles generated by vapor phase oxidation of silicon halide, that is, what is called dry process silica or fumed silica.
For example, it utilizes a thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen, and the basic reaction formula is as follows.
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl
In this production process, for example, it is possible to obtain composite fine particles of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds, and these are also included. .
The silica fine particles produced by vapor phase oxidation of a silicon halogen compound are more preferably hydrophobized silica fine particles having a hydrophobized surface. The hydrophobized silica fine particles are particularly preferably those obtained by treating the silica fine particles so that the degree of hydrophobicity measured by a methanol titration test is in the range of 30-80.
The addition amount of the inorganic fine particles B is preferably 0.1 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the toner particles. The content of these inorganic fine particles may be quantified using a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

As a method of the above hydrophobization treatment, treatment agents such as silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds, and organic titanium compounds are used. And a chemical treatment method.
Among the treatment agents, those treated with silicone oil are preferable.
The silicone oil preferably has a viscosity below 10 mm ² / s or more 200,000 mm ² / s at 25 ° C., and more preferably the following 3,000 mm ² / s or more 80,000mm ² / s.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil.
Examples of the method of treating inorganic fine particles with silicone oil include a method of directly mixing inorganic fine particles and silicone oil using a mixer such as a Henschel mixer, and a method of spraying silicone oil onto inorganic fine particles. Alternatively, after dissolving or dispersing silicone oil in an appropriate solvent, inorganic fine particles may be added and mixed to remove the solvent. A spraying method is more preferable in that the formation of aggregates of inorganic fine particles is relatively small.
The treatment amount of the silicone oil is preferably 1 part by mass to 40 parts by mass, and more preferably 3 parts by mass to 35 parts by mass with respect to 100 parts by mass of the inorganic fine particles.
Inorganic fine particles A is preferably a specific surface area measured by the BET method by nitrogen adsorption is 350 meters ² / g from ^{20 m} 2 / g, more preferably from ^{25 m} 2 / g is 300m ² / g.

The silica fine particles are preferably treated with silicone oil and then treated with an organosilicon compound such as hexamethyldisilazane.
Since the surface of the untreated silica base material remaining by this treatment can be hydrophobized, silica particles having a high hydrophobicity can be stably obtained.
Further, it is preferable to process in this order because the ease of toner loosening can be improved.
The reason why the ease of unraveling can be improved is estimated as follows. Of the silicone oil molecule ends on the surface of the silica fine particles, only one end has a degree of freedom, which affects the cohesiveness between the silica fine particles. On the other hand, by carrying out the two-stage treatment as described above, the silicone oil molecular terminal is hardly present on the outermost surface of the silica fine particles, so that the cohesiveness of the silica fine particles can be further reduced. As a result, the cohesiveness between the toners when externally added can be greatly reduced, the ease of toner loosening is improved, and the force between the two particles can be easily controlled.

  For the toner particles, other additives such as lubricant particles such as fluororesin particles, zinc stearate particles and polyvinylidene fluoride particles; abrasives such as cerium oxide particles, silicon carbide particles and strontium titanate particles; caking Inhibitors: Reverse polarity organic fine particles and inorganic fine particles can also be used in small amounts as developability improvers. It is also possible to use the surface of these additives after hydrophobizing them.

Hereinafter, specific examples of the method of externally adding and mixing inorganic fine particles into toner particles will be described, but the present invention is not limited to these methods.
As a mixing processing apparatus for externally mixing the inorganic fine particles, a known mixing processing apparatus can be used.
For example, a Henschel mixer is used as a mixing processing device for externally mixing the silica fine particles B, and a mixing processing device for externally mixing silica fine particles A is used to easily control the force between two particles within the scope of the present invention. A device as shown in FIG.
FIG. 1 is a schematic view showing an example of a mixing treatment apparatus that can be used when externally mixing the silica fine particles.
Since the mixing processing apparatus is configured to share the toner particles and the inorganic fine particles in a narrow clearance part, the inorganic fine particles are loosened from the secondary particles to the primary particles, and are applied to the surface of the toner particles. Can be attached.
Further, as will be described later, the toner particles and the inorganic fine particles are likely to circulate in the axial direction of the rotator, and this is preferable because the force between the two particles can be easily controlled from the viewpoint that the toner particles are sufficiently uniformly mixed before the adhesion proceeds.

On the other hand, FIG. 2 is a schematic diagram showing an example of a configuration of a stirring member used in the mixing treatment apparatus.
Hereinafter, one aspect of the external addition mixing process of the inorganic fine particles will be described with reference to FIGS.
A mixing processing apparatus for externally mixing inorganic fine particles is provided with a rotating body 302 having at least a plurality of stirring members 303 installed on a surface thereof, a drive unit 308 for rotationally driving the rotating body, and a stirring member 303 provided with a gap. Main body casing 301.
The clearance (clearance) between the inner peripheral portion of the main body casing 301 and the stirring member 303 gives a uniform share to the toner particles and adheres to the surface of the toner particles while loosening the inorganic fine particles from the secondary particles to the primary particles. To make it easier, keep it constant and minute.
Further, in this apparatus, the diameter of the inner peripheral portion of the main body casing 301 is preferably set to be not more than twice the diameter of the outer peripheral portion of the rotating body 302. FIG. 1 shows an example in which the diameter of the inner peripheral part of the main body casing 301 is 1.7 times the diameter of the outer peripheral part of the rotating body 302 (the diameter of the body part obtained by removing the stirring member 303 from the rotating body 302). If the diameter of the inner peripheral part of the main body casing 301 is not more than twice the diameter of the outer peripheral part of the rotating body 302, the processing space in which the force acts on the toner particles is appropriately limited. A sufficient impact force is applied to the inorganic fine particles.

The clearance may be adjusted according to the size of the main casing. It is appropriate that the diameter of the inner peripheral portion of the main body casing 301 is about 1% or more and 5% or less in that a sufficient share is applied to the inorganic fine particles. Specifically, when the diameter of the inner peripheral part of the main body casing 301 is about 130 mm, the clearance is about 2 mm to 5 mm, and when the diameter of the inner peripheral part of the main body casing 301 is about 800 mm, it is 10 mm to 30 mm. It should be about.
In the external addition mixing step of the inorganic fine particles in the present invention, the rotating body 302 is rotated by the driving unit 308 using a mixing processing device, and the toner particles and the inorganic fine particles charged into the mixing processing device are stirred and mixed. Inorganic fine particles are externally mixed on the surface of the toner particles.
As shown in FIG. 2, at least a part of the plurality of stirring members 303 sends the toner particles and the inorganic fine particles in one axial direction of the rotating body as the rotating body 302 rotates.
03a is formed. Further, at least a part of the plurality of stirring members 303 is formed as a return stirring member 303b that returns the toner particles and the inorganic fine particles to the other direction in the axial direction of the rotating body as the rotating body 302 rotates. . Here, as shown in FIG. 1, when the raw material inlet 305 and the product outlet 306 are provided at both ends of the main body casing 301, the direction from the raw material inlet 305 to the product outlet 306 (in FIG. 1). (Right direction) is called “feed direction”.
That is, as shown in FIG. 2, the plate surface of the feeding stirring member 303a is inclined so as to feed toner particles and inorganic fine particles in the feeding direction (313). On the other hand, the plate surface of the stirring member 303b is inclined so as to send toner particles and inorganic fine particles in the return direction (312).
Thus, the external addition mixing process of the inorganic fine particles is performed on the surface of the toner particles while repeatedly performing the feeding in the “feeding direction” (313) and the feeding in the “returning direction” (312).

The stirring members 303a and 303b are a set of a plurality of members arranged at intervals in the circumferential direction of the rotating body 302. In the example shown in FIG. 2, the stirring members 303a and 303b form a pair of two members on the rotating body 302 at an interval of 180 degrees, but at three intervals of 120 degrees or at intervals of 90 degrees. It is good also as a set of many members, such as four sheets.
In the example shown in FIG. 2, a total of 12 stirring members 303a and 303b are formed at equal intervals.
Further, in FIG. 2, D indicates the width of the stirring member, and d indicates the interval indicating the overlapping portion of the stirring member. From the viewpoint of efficiently feeding the toner particles and the inorganic fine particles in the feeding direction and the returning direction, it is preferable that D has a width of about 20% to 30% with respect to the length of the rotating body 302 in FIG. FIG. 2 shows an example of 23%. Further, the stirring members 303a and 303b preferably have an overlap portion d between the stirring member 303b and the stirring member 303a to some extent when an extension line is drawn vertically from the end position of the stirring member 303a.
Thereby, it is possible to efficiently share the inorganic fine particles which are secondary particles. D is preferably 10% or more and 30% or less in terms of applying a share.
Regarding the shape of the blade, in addition to the shape shown in FIG. 2, if the toner particles can be sent in the feeding direction and the returning direction and the clearance can be maintained, the shape having a curved surface and the tip blade portion are A paddle structure coupled to the rotating body 302 with a rod-shaped arm may be used.

Hereinafter, the present invention will be described in more detail with reference to the schematic views of the apparatus shown in FIGS.
The apparatus shown in FIG. 1 includes a rotating body 302 having at least a plurality of stirring members 303 installed on the surface thereof, a drive unit 308 that rotationally drives the rotating body 302, and a main body casing provided with a gap between the stirring member 303 301. Furthermore, it has the jacket 304 which can flow a cooling-heat medium in the inner side of the main body casing 301, and the rotary body end part side surface 310. FIG.
Further, the apparatus shown in FIG. 1 has a raw material inlet 305 formed in the upper part of the main body casing 301 and a product outlet 306 formed in the lower part of the main body casing 301. The raw material input port 305 is used for introducing toner particles and inorganic fine particles, and the product discharge port 306 is used for discharging toner particles subjected to external addition mixing processing from the main body casing 301 to the outside.
Further, in the apparatus shown in FIG. 1, a raw material charging port inner piece 316 is inserted into the raw material charging port 305, and a product discharging port inner piece 317 is inserted into the product discharge port 306.
In the present invention, first, the raw material inlet inner piece 316 is taken out from the raw material inlet 305, and toner particles are put into the processing space 309 from the raw material inlet 305. Next, the inorganic fine particles are introduced into the processing space 309 from the raw material inlet 305, and the inner piece 316 for raw material inlet is inserted. Next, the rotating body 302 is rotated by the driving unit 308 (311 indicates the direction of rotation), and the processed material introduced above is removed while being stirred and mixed by a plurality of stirring members 303 provided on the surface of the rotating body 302. Add and mix.

The order of charging may be such that the inorganic fine particles are first charged from the raw material inlet 305 and then the toner particles are charged from the raw material inlet 305. Further, after the toner particles and the inorganic fine particles are mixed in advance by a mixer such as a Henschel mixer, the mixture may be supplied from the raw material input port 305 of the apparatus shown in FIG.
In order to control the force between two particles, it is preferable to control the power of the drive unit 308 to be 0.2 W / g or more and 2.0 W / g or less as the external addition mixing treatment condition. Moreover, it is more preferable to control the power of the drive unit 308 to be 0.6 W / g or more and 1.6 W / g or less. When the power of the driving unit 308 is 0.2 W / g or more and 2.0 W / g or less, the inorganic fine particles diffuse on the surface of the toner particles and are easily mixed without being embedded in the toner particles. Easy to control and easy to obtain high fluidity of toner.
Although it does not specifically limit as processing time, Preferably it is 3 to 10 minutes.
When the treatment time is shorter than 3 minutes, the inorganic fine particles hardly diffuse on the surface of the toner particles, and the force between the two particles is difficult to control.
The number of rotations of the stirring member during external addition mixing is not particularly limited. In the apparatus in which the volume of the processing space 309 of the apparatus shown in FIG. 1 is 2.0 × 10 ⁻³ m ³ , the rotation speed of the agitating member when the shape of the agitating member 303 is that shown in FIG. The following is preferable. It becomes easy to control the force between two particles by being 800 rpm or more and 3000 rpm or less.

As described above, it is preferable to perform two-stage mixing in which the toner particles and the inorganic fine particles B are once mixed and then the inorganic fine particles A are added and mixed.
Furthermore, in the present invention, a particularly preferable treatment method is to provide each of the inorganic fine particles A or the inorganic fine particles B with a pre-mixing step before the external addition mixing operation. By including the pre-mixing step, the inorganic fine particles are easily dispersed highly uniformly on the surface of the toner particles. More specifically, as pre-mixing processing conditions, the power of the drive unit 308 is set to 0.06 W / g or more and 0.20 W / g or less, and the processing time is set to 0.5 minutes or more and 1.5 minutes or less. preferable.
If the load power is 0.06 W / g or more as the premixing treatment condition, or if the treatment time is 0.5 minutes or more, sufficient uniform mixing is performed as premixing. On the other hand, when the premixing treatment condition is a load power of 0.20 W / g or less, or a treatment time of 1.5 minutes or less, inorganic fine particles are formed on the surface of the toner particles before sufficient uniform mixing. Will not stick.

Regarding the rotation speed of the stirring member in the pre-mixing process, when the volume of the processing space 309 of the apparatus shown in FIG. 1 is 2.0 × 10 ⁻³ m ³ and the shape of the stirring member 303 is as shown in FIG. The rotation speed of the stirring member is preferably 50 rpm or more and 500 rpm or less. It becomes easy to control the force between two particles by being 50 rpm or more and 500 rpm or less.
After the external addition mixing process, the product discharge port inner piece 317 is taken out from the product discharge port 306, and the rotating body 302 is rotated by the drive unit 308, and the toner is discharged from the product discharge port 306. From the obtained toner, coarse particles and the like are separated by a sieve such as a circular vibratory sieve as needed to obtain a toner.

The developing device of the present invention includes a toner for developing an electrostatic latent image formed on an electrostatic latent image carrier, a toner carrier that carries the toner, and transports the toner to the electrostatic latent image carrier, A developing device comprising:
The toner is the toner of the present invention.
The developing device will be described in detail with reference to the drawings.
FIG. 3 is a schematic cross-sectional view illustrating an example of a developing device. FIG. 4 is a schematic cross-sectional view showing an example of an image forming apparatus in which a developing device is incorporated.
3 or 4, the electrostatic latent image carrier 45 is rotated in the direction of arrow R1. The toner carrier 47 rotates in the direction of the arrow R2 to convey the toner 57 to the development area where the toner carrier 47 and the electrostatic latent image carrier 45 are opposed to each other. Further, a toner supply member 48 is in contact with the toner carrier, and the toner 57 is supplied to the surface of the toner carrier by rotating in the direction of arrow R3. Further, the toner 57 is stirred by the stirring member 58.
Around the electrostatic latent image carrier 45, a charging roller 46, a transfer roller 50, a film fixing device 51, a pickup roller 52, and the like are provided. The film fixing device 51 is mainly composed of a fixing film 61 into which a heat source is introduced and a pressure roller 62. The electrostatic latent image carrier 45 is charged by the charging roller 46. Then, exposure is performed by irradiating the electrostatic latent image carrier 45 with laser light by the laser generator 54, and an electrostatic latent image corresponding to the target image is formed. The electrostatic latent image on the electrostatic latent image carrier 45 is developed with toner in the developing device 49 to obtain a toner image. The toner image is transferred onto a transfer material (paper) 53 by a transfer roller 50 in contact with the electrostatic latent image carrier 45 via the transfer material. The transfer material (paper) 53 on which the toner image is placed is conveyed in the paper feeding direction P and fixed by the film fixing device 51.

In the charging step in the image forming apparatus, the electrostatic latent image carrier and the charging roller form a contact portion to come into contact with each other, and a predetermined charging bias is applied to the charging roller so that the surface of the electrostatic latent image carrier is predetermined. A contact charging device that charges to polarity and potential may be used. By performing contact charging in this manner, stable and uniform charging can be performed, and generation of ozone can be reduced.
In order to maintain uniform contact with the electrostatic latent image carrier and perform uniform charging, a charging roller that rotates in the same direction as the electrostatic latent image carrier may be used.

  In addition, it is preferable to regulate the thickness of the toner layer on the toner carrier by a toner regulating member (reference numeral 55 in FIG. 3) contacting the toner carrier via the toner. By doing so, it is possible to obtain a high image quality without any defective regulation. As a toner regulating member that abuts on the toner carrier, a regulating blade is generally used and can be suitably used in the present invention.

The base which is the upper side of the regulating blade is fixedly held on the developing device side, and the lower side is bent in the forward or reverse direction of the toner carrier against the elastic force of the blade. With an appropriate elastic pressing force.
For example, as shown in FIG. 3, the toner regulating member 55 is fixed to the developing device by sandwiching the free end of one side of the toner regulating member 55 between two fixing members (for example, a metal elastic body, reference numeral 56 in FIG. 3). It is good to fix by fastening.

The developing step is preferably a step of applying a developing bias to the toner carrier and transferring the toner to the electrostatic latent image on the electrostatic latent image carrier to form a toner image. A voltage obtained by superimposing an alternating electric field on a DC voltage may be used.
Further, in the case of using a method of conveying toner by magnetism without using a toner supply member, a magnet may be disposed inside the toner carrier (reference numeral 59 in FIG. 5). In this case, the toner carrier preferably has a fixed magnet having multiple poles inside, and preferably has 3 to 10 magnetic poles.

It describes about the measuring method of each physical property which concerns on this invention.
<Method for Measuring Force between Two Particles (f _A )>
The two-particle force (f _A ) of the toner is measured using an Agrobot manufactured by Hosokawa Micron Corporation according to the instructions of the apparatus.
A specific measurement method is as follows.
(1) In the case of magnetic toner In a 25 ° C./50% environment, 9.2 g of toner is filled in a cylindrical cell divided into two upper and lower parts as shown in FIG. After that, by lowering the compression rod at 0.1 mm / sec, 78.5 N
A toner compact is formed by applying a vertical load of.
Thereafter, as shown in FIG. 6B, the upper cell is lifted by a spring at a speed of 0.4 mm / sec to pull the toner compact, and the maximum tensile fracture obtained when the toner compact is broken. The force between two particles f _A (nN) is measured based on the force.
Here, the “maximum tensile breaking force”, that is, the force applied when breaking the powder is obtained by subtracting the “stress at the time of breaking” from the “maximum tensile stress” in FIG. .
The cylindrical cell has an inner diameter of 25 mm and a height of 37.5 mm.
(2) In the case of non-magnetic toner Except that the filling amount of the toner is changed from 9.2 g to 7.7 g, the measurement is performed in the same manner as the method for measuring the force between two particles (f _A ) of the magnetic toner.

<Measurement method of maximum tensile stress (F ₁ )>
The maximum tensile stress (F ₁ ) of the toner is measured using an Agrobot manufactured by Hosokawa Micron Corporation according to the instructions of the apparatus.
A specific measurement method is as follows.
(1) In the case of magnetic toner In a 55 ° C./50% environment, 9.2 g of toner is filled in a cylindrical cell divided into two upper and lower parts as shown in FIG. Leave for a minute. Thereafter, the compression rod is lowered at 0.1 mm / sec to apply a vertical load of 78.5 N to form a toner compact.
Thereafter, as shown in FIG. 6B, when the upper cell is lifted by a spring at a speed of 0.4 mm / sec and the toner compact is pulled, a tensile stress curve as shown in FIG. 6C is obtained. The “maximum tensile stress” in the tensile stress curve shown in FIG. 6C is F ₁ (kN / m ² ).
The cylindrical cell has an inner diameter of 25 mm and a height of 37.5 mm, and the cell area S is calculated as {(25/2) ² × π} mm ² to obtain the maximum tensile stress.
(2) In the case of non-magnetic toner Except that the filling amount of the toner is changed from 9.2 g to 7.7 g, the measurement is performed in the same manner as the method for measuring the maximum tensile stress (F ₁ ) of the magnetic toner.

<Measurement method of maximum tensile stress (F ₂ )>
The maximum tensile stress (F ₂ ) of the toner is measured using an Agrobot manufactured by Hosokawa Micron Corporation according to the instructions of the apparatus.
A specific measurement method is as follows.
(1) In the case of magnetic toner In a 55 ° C./50% environment, 9.2 g of toner is filled in a vertically divided cylindrical cell shown in FIG. 6A, and immediately after that, compressed at 0.1 mm / sec. By lowering the rod, a toner compact is formed by applying a vertical load of 1962.5 N for 5 minutes.
Thereafter, as shown in FIG. 6B, when the upper cell is lifted by a spring at a speed of 0.4 mm / sec and the toner compact is pulled, a tensile stress curve as shown in FIG. 6C is obtained. The “maximum tensile stress” in the tensile stress curve shown in FIG. 6C is F ₂ (kN / m ² ).
The cylindrical cell has an inner diameter of 25 mm and a height of 37.5 mm, and the cell area S is calculated as {(25/2) ² × π} mm ² to obtain the maximum tensile stress.
(2) In the case of non-magnetic toner Except that the toner filling amount is changed from 9.2 g to 7.7 g, the measurement is performed in the same manner as the method for measuring the maximum tensile stress (F ₂ ) of the magnetic toner.

<Measuring method of softening point of toner and amorphous polyester>
The softening point of the toner and amorphous polyester is measured using a constant load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the apparatus. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.
In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). The temperature of the flow curve when the piston descending amount is the sum of X and Smin in the flow curve is the melting temperature in the ½ method (a schematic diagram of the flow curve is shown in FIG. 8).
The measurement sample was about 1.0 g of toner or amorphous polyester at about 10 MPa using a tablet compression machine (for example, NT-100H, manufactured by NPA System) in an environment of 25 ° C., about 60 A cylinder having a diameter of about 8 mm and compression-molded for 2 seconds is used.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

<Method for Measuring Toner Weight Average Particle Size (D4)>
The weight average particle diameter (D4) of the toner is a precision particle size distribution measuring apparatus “Coulter Counter Multisizer by pore electrical resistance method equipped with an aperture tube of 100 μm.
3 ”(registered trademark, manufactured by Beckman Coulter) and attached dedicated software“ Beckman Coulter Multisizer 3 Version 3.51 ”(manufactured by Beckman Coulter, Inc.) for measurement condition setting and measurement data analysis, Measure with 25,000 effective measurement channels, analyze and calculate the measurement data.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows.
In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
(1) About 200 mL of the electrolytic solution is placed in a glass 250 mL round-bottom beaker dedicated to Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 mL of the electrolytic aqueous solution is put in a glass 100 mL flat-bottom beaker, and “Contaminone N” (nonionic surfactant, anionic surfactant, organic builder consisting of an organic builder) is used as a dispersant. About 0.3 mL of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel, manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water three times as much is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is added, and about 2 mL of the contamination N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the (1) round bottom beaker installed in the sample stand, the (5) electrolytic aqueous solution in which the toner is dispersed is dropped using a pipette, and the measured concentration is adjusted to about 5%. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “arithmetic diameter” on the analysis / volume statistics (arithmetic mean) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Measurement method of number average particle diameter (D1) of primary particles of silica fine particles>
The number average particle size of the primary particles of the silica fine particles is determined by observing the silica fine particles present on the toner particle surfaces with a scanning electron microscope. As the scanning electron microscope, Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (manufactured by Hitachi, Ltd.) is used. The image capturing conditions of S-4800 are as follows. In addition, the elemental analysis by an energy dispersive X-ray analyzer (manufactured by EDAX) is performed in advance, and the measurement is performed after confirming that the particles are silica fine particles.
(1) Sample preparation A conductive paste is thinly applied to a sample table (aluminum sample table 15 mm × 6 mm), and toner is sprayed thereon. Further, air is blown to remove excess toner from the sample stage and sufficiently dry. The sample stage is set on the sample holder, and the height of the sample stage is adjusted to 36 mm by the sample height gauge.
(2) S-4800 observation condition setting The number average particle diameter of the primary particles of the silica fine particles is calculated using an image obtained by the reflected electron image observation of S-4800. Since the reflected electron image has less charge-up of the silica fine particles than the secondary electron image, the particle size of the silica fine particles can be accurately measured.
Liquid nitrogen is poured into the anti-contamination trap attached to the S-4800 housing until it overflows, and is placed for 30 minutes. S-4800 “PCSTEM” is activated and flushing (cleaning of the FE chip as an electron source) is performed. Click the acceleration voltage display part of the control panel on the screen and press the [Flushing] button to open the flushing execution dialog.
Confirm that the flushing intensity is 2 and execute. Confirm that the emission current by flashing is 20-40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to 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 [Up (U)] and [+ BSE] for the SE detector, and select [+ BSE] in the selection box on the right. L. A. 100] to select a mode in which observation is performed with a reflected electron image.
Similarly, in the [Basic] tab of the operation panel, the probe current of the electron optical system condition block is set to [Normal], the focus mode is set to [UHR], and the WD is set to [3.0 mm]. Press the [ON] button in the acceleration voltage display section of the control panel to apply the acceleration voltage.
(3) Calculation of number average particle diameter (D1) of silica fine particles Drag within the magnification display section of the control panel to set the magnification to 100000 (100k). The focus knob [COARSE] on the operation panel is rotated, and the aperture alignment is adjusted when the focus is achieved to some extent. Click [Align] on the control panel to display the alignment dialog and select [Beam]. The STIGMA / ALIGNMENT knob (X, Y) on the operation panel is rotated to move the displayed beam to the center of the concentric circle.
Next, select [Aperture], and turn the STIGMA / ALIGNMENT knob (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and focus with auto focus. Repeat this operation two more times to focus.
Thereafter, the particle size is measured for at least 300 silica fine particles on the surface of the toner particles to obtain an average particle size. Here, since silica fine particles may exist as agglomerates depending on the external addition method, the maximum diameter of what can be confirmed as primary particles is obtained, and by arithmetically averaging the obtained maximum diameter, A number average particle diameter (D1) is obtained.

<Measurement method of half-width of maximum peak in primary particle size distribution of silica fine particles>
The full width at half maximum of the maximum peak in the particle size distribution of primary particles of silica fine particles is CPS Instruments Inc. This is measured using a disk centrifugal particle size distribution measuring device “DC24000”. The measuring method is shown below.
(A) In the case of magnetic toner First, 0.5 mg of Triton-X100 (manufactured by Kishida Chemical Co., Ltd.) is added to 100 g of ion-exchanged water to prepare a dispersion medium. 1 g of toner is added to 9 g of this dispersion medium, and dispersed for 5 minutes by an ultrasonic disperser. Thereafter, the toner particles are constrained using a neodymium magnet to produce a supernatant.
Next, a syringe dedicated to a measuring device manufactured by CPS is attached to the tip of an all plastic disposable syringe (Tokyo Glass Instrument Co., Ltd.) equipped with a syringe filter (diameter: 13 mm / pore diameter 0.45 μm) (manufactured by Advantech Toyo Co., Ltd.). Attach a needle and collect 0.1 mL of supernatant.
The supernatant collected with a syringe is injected into a disk centrifugal particle size distribution measuring apparatus DC24000, and the half-value width of the maximum peak in the particle size distribution of primary particles of silica fine particles is measured.
Details of the measurement method are as follows.
First, the disk is rotated at 24000 rpm with Motor Control on CPS software. Then, the following conditions are set from Procedure Definitions.
(1) Sample parameter
・ Maximum Diameter: 0.5μm
・ Minimum Diameter: 0.05μm
・ Particle Density: 2.0-2.2 g / mL (adjust as appropriate depending on the sample)
-Particle Refractive Index: 1.43
・ Particle Absorption: 0K
・ Non-Sphericity Factor: 1.1
(2) Calibration Standard Parameters
・ Peak Diameter: 0.226μm
・ Half Height Peak Width: 0.1 μm
・ Particle Density: 1.389 g / mL
・ Fluid Density: 1.059g / mL
-Fluid Refractive Index: 1.369
Fluid Fluidity: 1.1 cps
After setting the above conditions, CPS Instruments Inc. Using an auto gradient maker AG300, a density gradient solution of 8 mass% sucrose aqueous solution and 24 mass% sucrose aqueous solution is prepared, and 15 mL is injected into the measurement container.
After injection, in order to prevent evaporation of the density gradient solution, 1.0 mL of dodecane (manufactured by Kishida Chemical Co., Ltd.) is injected to form an oil film, and wait for 30 minutes or more to stabilize the apparatus.
After waiting, calibration standard particles (weight-based center particle size: 0.226 μm) are injected into the measuring apparatus with a 0.1 mL syringe, and calibration is performed. Thereafter, the collected supernatant is poured into the apparatus, the particle size distribution based on weight is measured, and the half width is measured from the obtained distribution data.
An example of data obtained when actually measured is shown in FIG.
As shown in FIG. 7, the distribution data is obtained as a graph in which the horizontal axis is “particle diameter” and the vertical axis is “value obtained by dividing mass by particle diameter”. In this graph, the distribution data is obtained from 80 nm to 200 nm. The full width at half maximum of the maximum peak is the value of the full width at half maximum of the maximum peak in the particle size distribution of the primary particles of silica fine particles.

(B) In case of non-magnetic toner First, 0.5 mg of Triton-X100 (manufactured by Kishida Chemical Co., Ltd.) is added to 100 g of ion-exchanged water to prepare a dispersion medium. To 9.4 g of this dispersion medium, 0.6 g of toner is added and dispersed with an ultrasonic disperser for 5 minutes. Then, a syringe needle dedicated to the measuring device manufactured by CPS is attached to the tip of an all plastic disposable syringe (Tokyo Glass Instrument Co., Ltd.) equipped with a syringe filter (diameter: 13 mm / pore diameter 0.45 μm) (manufactured by Advantech Toyo Corporation). And 0.1 mL of the supernatant is collected. The supernatant collected with a syringe is injected into a disk centrifugal particle size distribution analyzer DC24000, and the half-width of the maximum peak in the particle size distribution of the primary particles of silica fine particles is measured in the same manner as in the case of (A) magnetic toner. To do.

<Aspect ratio measurement method>
The aspect ratio of the toner is measured using a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.
A specific measurement method is as follows.
First, about 20 mL of ion-exchanged water from which impure solids and the like are previously removed is placed in a glass container.
In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 mL of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
Further, about 0.02 g of a measurement sample is added, and a dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC.
As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is put, and about 2 mL of the above-mentioned Contaminone N is added to this water tank.
For the measurement, the above-mentioned flow type particle image analyzer equipped with “LUCPLFLN” (magnification 20 ×, numerical aperture 0.40) as an objective lens is used, and particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. Is used. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and the HPF measurement mode is 20 in the total count mode.
00 toners are measured. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to a circle equivalent diameter of 1.977 μm or more and less than 39.54 μm, and the toner aspect ratio is obtained.
In the measurement, automatic focus adjustment is performed using standard latex particles (eg, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5100A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

<Method of Measuring Toner Peak Molecular Weight Mp (T) and Amorphous Polyester Peak Molecular Weight Mp (P)>
The molecular weight distribution of the toner and the amorphous polyester is measured by gel permeation chromatography (GPC) as follows.
First, a sample is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample, standard polystyrene resin (trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Measurement Method of 25% Area Ratio, 50% Area Ratio, and Domain Area Ratio (above [A / B])>
The toner is sufficiently dispersed in a visible light curable resin (trade name, Aronix LCR series D-800; manufactured by Toagosei Co., Ltd.), and then cured by irradiation with short wavelength light. The obtained cured product is cut out with an ultramicrotome equipped with a diamond knife to produce a 250-nm flaky sample. Next, the cut out sample was enlarged at a magnification of 40000 to 50000 times using a transmission electron microscope (Electron Microscope JEM-2800 manufactured by JEOL Ltd.) (TEM-EDX), and the cross section of the toner was observed and the element using EDX Perform mapping.
The cross section of the toner to be observed is selected as follows. First, the cross-sectional area of the toner is obtained from the cross-sectional image of the toner, and the diameter (equivalent circle diameter) of a circle having an area equal to the cross-sectional area is obtained. Only a toner cross-sectional image in which the 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.
The mapping conditions are a storage rate of 9000 to 13000 and an integration count of 120.
Among the domains derived from the resin confirmed from the observed image, the spectrum intensity derived from the C element and the spectrum intensity derived from the O element are measured. It is a domain of amorphous polyester. After identifying the amorphous polyester domain, the binarization process is performed to determine the distance between the contour and the center point of the cross section from the contour of the cross section of the toner to the total area of the amorphous polyester domains existing in the cross section of the toner. The area ratio (area%) of the amorphous polyester domain existing within 25% of the above is calculated. For the binarization process, Image Pro PLUS (manufactured by Nippon Roper Co., Ltd.) is used.
The calculation method is as follows. In the TEM image, the contour and center point of the toner cross section are obtained. The outline of the toner cross section is assumed to be along the surface of the toner observed in the TEM image. The center point of the toner cross section is the center of gravity of the toner cross section.
A line is drawn from the obtained center point to a point on the contour of the toner cross section. On the line, the position of 25% of the distance between the outline and the center point of the cross section is specified from the outline.
Then, this operation is performed once for the contour of the toner cross section, and a boundary line of 25% of the distance between the contour and the center point of the cross section is clearly shown from the contour of the toner cross section.
Based on the TEM image in which the 25% boundary line is clearly defined, the area of the amorphous polyester domain existing in the region surrounded by the outline of the toner cross section and the 25% boundary line is measured. . Then, the total area of the amorphous polyester domains present in the toner cross section is measured, and the area% based on the total area is calculated.
(50% area ratio)
Similarly to the measurement of the 25% area ratio described above, a boundary line of 50% of the distance between the contour and the center point of the cross section is clearly shown from the contour of the toner cross section. The area of the amorphous polyester domain existing in the region surrounded by the outline of the cross section of the toner and the boundary line of 50% is measured, and area% based on the total domain area is calculated.
(Area ratio of domain)
Further, from the outline of the cross section of the toner, from the area of the amorphous polyester domain existing within 25% of the distance between the outline and the center point of the cross section (that is, [A] above), and from the outline of the cross section of the toner The ratio (area ratio of the domain: [A / B]) to the area of the amorphous polyester domain existing in 25% to 50% of the distance between the contour and the center point of the cross section (that is, the above [B]) ) Is obtained by the following formula using the calculated value obtained above.
Domain area ratio (ie, [A / B]) =
(25% area ratio (area%)) / [(50% area ratio (area%)) − (25% area ratio (area%))]

<Measuring method of number average diameter of domains of amorphous polyester>
Elemental mapping is performed using EDX in the same manner as described above, and the domain of the amorphous polyester is specified.
The number average diameter of the domains of the amorphous polyester is obtained by determining the equivalent circle diameter from the area of the domains. The number of measurements is 100, and the arithmetic average value of the equivalent circle diameters of the 100 domains is the number average diameter of the amorphous polyester domains. The toner for calculating the number average diameter is determined as follows.
First, the cross-sectional area of the toner is obtained from the cross-sectional image of the toner, and the diameter (equivalent circle diameter) of a circle having an area equal to the cross-sectional area is obtained. The number average diameter is calculated only for the toner cross-sectional image whose absolute value of the difference between the equivalent circle diameter and the weight average particle diameter (D4) of the toner is 1.0 μm or less.

<Method for measuring acid value of amorphous polyester>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the amorphous polyester is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), and ion exchanged water is added to make 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. In order to avoid contact with carbon dioxide, etc., it is placed in an alkali-resistant container and allowed to stand for 3 days, followed by filtration to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. As the factor of the potassium hydroxide solution, take 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, add a few drops of the phenolphthalein solution, titrate with the potassium hydroxide solution, and the hydroxylation required for neutralization. Determined 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 A 2.0 g sample of pulverized amorphous polyester is precisely weighed in a 200 mL Erlenmeyer flask, and 100 mL of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. To do. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a 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 = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (mL) of potassium hydroxide solution in blank test, C: addition amount (mL) of potassium hydroxide solution in final test, f: potassium hydroxide Solution factor, S: sample (g).

<Measurement of intensity ratio (S211 / S85) of peak intensity (S85) derived from vinyl resin and peak intensity (S211) derived from amorphous polyester using time-of-flight secondary ion mass spectrometry (TOF-SIMS) Method>
The measurement of the intensity ratio (S211 / S85) of the peak intensity derived from vinyl resin using TOF-SIMS (S85) and the peak intensity derived from amorphous polyester (S211 / S85) was made by ULVAC-PHI, TRIFT-IV. Is used.
The analysis conditions are as follows.
Sample preparation: Sample pretreatment for adhering toner particles to an indium sheet: None Primary ion: Au ion Acceleration voltage: 30 kV
Charge neutralization mode: On
Measurement mode: Negative
Raster: 100 μm
Calculation of peak intensity derived from vinyl resin (S85): The total number of masses of 84.5 to 85.5 is defined as peak intensity (S85) in accordance with ULVAC-PHI standard software (Win CAD).
Calculation of peak intensity derived from amorphous polyester (S211): In accordance with ULVAC-PHI standard software (Win CAD), the total count number of mass numbers 210.5 to 211.5 is defined as peak intensity (S211).
Calculation of intensity ratio (S211 / S85): Using the calculated S85 and S211, the intensity ratio (S211 / S85) is calculated.

<Measurement method of true specific gravity of toner>
The true specific gravity of the toner is measured by a dry automatic densimeter Accupic II 1340 series (manufactured by Shimadzu Corporation). The measurement is performed with a cell size of 10 cc and a toner mass of 5.0 g.
<Measurement method of carbon oil-based immobilization ratio (oil immobilization ratio [%]) of silica fine particles>
(Extraction of free silicone oil)
(1) Put 0.50 g of silica fine particles and 40 mL of chloroform in a beaker and stir for 2 hours.
(2) Stop stirring and let stand for 12 hours.
(3) The sample is filtered and washed 3 times with 40 mL of chloroform.
(Measurement of carbon content)
The sample is burned at 1100 ° C. in an oxygen stream, and the amount of generated CO and CO ₂ is measured by IR absorbance to measure the amount of carbon in the sample. The carbon amount before and after extraction of the silicone oil is compared, and the immobilization rate based on the carbon amount of the silicone oil is calculated as follows.
(1) Place 0.40 g of sample in a cylindrical mold and press.
(2) 0.15 g of the pressed sample is precisely weighed, placed on a combustion board, and measured with Horiba EMA-110.
(3) [Carbon amount after silicone oil extraction] / [Carbon amount before silicone oil extraction] × 100 is defined as the immobilization rate based on the carbon amount of silicone oil.
In the case of silica fine particles that have been surface treated with silicone oil after hydrophobic treatment with alkoxysilane or silazane, the amount of carbon in the sample is measured after hydrophobic treatment with alkoxysilane or silazane. The carbon amount before and after extraction is compared, and the immobilization rate based on the amount of carbon derived from silicone oil is calculated as follows.
(4) [Carbon amount after silicone oil extraction-carbon amount of sample after hydrophobic treatment with alkoxysilane or silazane] / [Carbon amount before silicone oil extraction-carbon amount of sample after hydrophobic treatment with alkoxysilane or silazane] X100 is defined as the carbon oil-based immobilization rate of silicone oil.
On the other hand, in the case of silica fine particles that have been subjected to a hydrophobic treatment with alkoxysilane or silazane after the surface treatment with silicone oil, using the sample after the hydrophobic treatment with silicone oil, the immobilization rate based on the amount of carbon derived from silicone oil is determined. Calculate as follows.
(5) [Carbon amount after silicone oil extraction of sample after surface treatment with silicone oil] / [Carbon amount before silicone oil extraction of sample after surface treatment with silicone oil] × 100, based on carbon amount of silicone oil The immobilization rate.
<Method for measuring apparent density of silica fine particles>
The apparent density of the silica fine particles is measured by slowly adding a measurement sample placed on a paper to a 100 mL graduated cylinder to 100 mL, and obtaining the mass difference between the graduated cylinder before and after adding the sample by the following formula: calculate. When adding the sample to the graduated cylinder, be careful not to strike the paper.
Apparent density (g / L) = (mass (g) when 100 mL was added) /0.1
<Method for measuring BET specific surface area of silica fine particles>
The measurement of the specific surface area by nitrogen adsorption measured by the BET method is performed according to JIS Z8830 (2001). As a measuring device, an “automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)” which employs a gas adsorption method by a constant volume method as a measuring method is used.
<Measurement method of true specific gravity of silica fine particles>
The true specific gravity of the silica fine particles is measured by a dry automatic densimeter autopycnometer (manufactured by Yuasa Ionics). The conditions are as follows.
Cell: SM cell (10 mL)
Sample amount: 0.05g
This measurement method measures the true specific gravity of a solid / liquid based on a gas phase substitution method. Similar to the liquid phase replacement method, it is based on Archimedes' principle, but uses a gas (argon gas) as a replacement medium, and therefore has high accuracy for micropores.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these at all. All parts and percentages in the examples are based on mass unless otherwise specified.

<Example of production of toner carrier 1>
(Preparation of substrate)
A substrate (trade name, DY35-051; manufactured by Toray Dow Corning Co., Ltd.) was applied to a 6 mm diameter cored bar made of SUS304 as a substrate and baked.
(Production of elastic roller)
The substrate was placed in a mold, and an addition type silicone rubber composition in which the following materials were mixed was injected into a cavity formed in the mold.
-Liquid silicone rubber material 100 parts (trade name, SE6724A / B; manufactured by Toray Dow Corning)
・ 15 parts of carbon black (trade name, Toka Black # 4300; manufactured by Tokai Carbon Co., Ltd.)
-0.2 part of silica particles as heat resistance imparting agent-0.1 part of platinum catalyst Subsequently, the mold was heated to vulcanize and cure the silicone rubber at a temperature of 150 ° C for 15 minutes. The substrate on which the cured silicone rubber layer was formed on the peripheral surface was removed from the mold, and then the substrate was further heated at a temperature of 180 ° C. for 1 hour to complete the curing reaction of the silicone rubber layer. In this way, an elastic roller having a silicone rubber elastic layer having a diameter of 12 mm so as to cover the outer peripheral surface of the substrate was produced.
(Preparation of surface layer)
(Synthesis of isocyanate group-terminated prepolymer)
Polypropylene glycol polyol (trade name: Exenol 4030; manufactured by Asahi Glass Co., Ltd.) 100 with respect to 17.7 parts of tolylene diisocyanate (TDI) (trade name: Cosmonate T80; manufactured by Mitsui Chemicals) in a reaction vessel under a nitrogen atmosphere 0.0 part was gradually added dropwise while maintaining the temperature in the reaction vessel at 65 ° C. After completion of the dropping, the reaction was carried out at a temperature of 65 ° C. for 2 hours. The resulting reaction mixture was cooled to room temperature to obtain an isocyanate group-terminated prepolymer having an isocyanate group content of 3.8% by mass.
(Synthesis of amino compounds)
100.0 parts (1.67 mol) of ethylenediamine and 100 parts of pure water were heated to 40 ° C. while stirring in a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device, and a temperature controller. Next, while maintaining the reaction temperature at 40 ° C. or lower, 425.3 parts (7.35 mol) of propylene oxide was gradually added dropwise over 30 minutes. The reaction was further stirred for 1 hour to obtain a reaction mixture. The obtained reaction mixture was heated under reduced pressure to distill off water, thereby obtaining 426 g of an amino compound.
(Preparation of toner carrier 1)
-Isocyanate group-terminated prepolymer 617.9 parts-Amino compound 34.2 parts-Carbon black 117.4 parts (trade name, MA230; manufactured by Mitsubishi Chemical Corporation)
-Urethane resin fine particles 130.4 parts (trade name, Art Pearl C-400; manufactured by Negami Kogyo Co., Ltd.)
Were stirred and mixed.
Next, methyl ethyl ketone (hereinafter also referred to as “MEK”) was added so that the total solid content was 30% by mass, and then mixed in a sand mill. Subsequently, the viscosity was further adjusted to 10 cps or more and 13 cps or less with MEK to prepare a coating material for forming a surface layer.
The previously produced elastic roller was immersed in the surface layer forming paint to form a paint film of the paint on the surface of the elastic layer of the elastic roller and dried. Further, a heat treatment was performed at a temperature of 150 ° C. for 1 hour to provide a surface layer having a film thickness of 15 μm on the outer periphery of the elastic layer, whereby the toner carrier 1 was obtained.

<Example of production of amorphous polyester (APES1)>
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple,
The carboxylic acid component and the alcohol component were adjusted as shown in Table 1, and after addition, 1.5 parts of dibutyltin was added as a catalyst to 100 parts of the total amount of monomers.
Next, the temperature was quickly raised to 180 ° C. under normal pressure in a nitrogen atmosphere, and then water was distilled off while heating from 180 ° C. to 210 ° C. at a rate of 10 ° C./hour to perform polycondensation.
After reaching 210 ° C., the pressure in the reaction vessel was reduced to 5 kPa or less, and polycondensation was performed under the conditions of 210 ° C. and 5 kPa or less to obtain amorphous polyester (APES1).
The polymerization time was adjusted so that the peak molecular weight of the amorphous polyester (APES1) was the value shown in Table 1. Table 1 shows the physical properties of the amorphous polyester (APES1).

<Production Example of Amorphous Polyester (APES2) to (APES15)>
Amorphous polyesters (APES2) to (APES15) were obtained in the same manner as the amorphous polyester (APES1) except that the raw material monomers and the amounts used were changed as described in Table 1. Table 1 shows the physical properties of these amorphous polyesters.

表１中、ビスフェノールＡにおいて、「ＰＯ」はプロピレンオキサイドを、「ＥＯ」はエチレンオキサイドを意味する。

In Table 1, in bisphenol A, “PO” means propylene oxide, and “EO” means ethylene oxide.

<Example of production of amorphous polyester (APES16)>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 100 g of bisphenol A ethylene oxide 2 mol adduct, 189 g of bisphenol A propylene oxide 2 mol adduct, 51 g of terephthalic acid, 61 g of fumaric acid, adipine An acid 25 g and an esterification catalyst (tin octylate) 2 g were added, and a condensation polymerization reaction was performed at 230 ° C. for 8 hours.
Furthermore, after reacting at 8 kPa for 1 hour and cooling to 160 ° C., a mixture of 6 g of acrylic acid, 70 g of styrene, 31 g of n-butyl acrylate and 20 g of a polymerization initiator (di-t-butyl peroxide) was added for 1 hour with a dropping funnel. The addition polymerization reaction was continued for 1 hour while maintaining the temperature at 160 ° C.
Thereafter, the temperature is raised to 200 ° C. and held at 10 kPa for 1 hour, and then the unreacted acrylic acid, styrene and n-butyl acrylate are removed to bond the vinyl polymer portion and the polyester portion. Amorphous polyester (APES16) was obtained.

<Production example of treated magnetic material>
In a ferrous sulfate aqueous solution, 1.00 to 1.10 equivalent of sodium hydroxide solution with respect to iron element, P ₂ O _{5 in} an amount of 0.15% by mass in terms of phosphorus element with respect to iron element, iron An aqueous solution containing ferrous hydroxide was prepared by mixing SiO ₂ in an amount of 0.50% by mass in terms of silicon with respect to the element. The aqueous solution was adjusted to pH 8.0 and subjected to an oxidation reaction at 85 ° C. while blowing air to prepare a slurry liquid having seed crystals.
Subsequently, after adding ferrous sulfate aqueous solution to this slurry liquid so that it may become 0.90 to 1.20 equivalent with respect to the original alkali amount (sodium component of sodium hydroxide), the slurry liquid is maintained at pH 7.6. Then, an oxidation reaction was promoted while blowing air, and a slurry liquid containing magnetic iron oxide was obtained.
The obtained slurry was filtered and washed, and the water-containing slurry was once taken out. At this time, a small amount of the water-containing slurry was collected and the water content was measured.
Next, this water-containing slurry was put into another aqueous medium without being dried, stirred and redispersed with a pin mill while circulating the slurry, and the pH of the redispersed liquid was adjusted to about 4.8.
Then, 1.6 parts of n-hexyltrimethoxysilane coupling agent was added to 100 parts of magnetic iron oxide with stirring (the amount of magnetic iron oxide was calculated as a value obtained by subtracting the water content from the water-containing slurry). Decomposition was performed. Thereafter, the mixture was sufficiently stirred, and the dispersion was subjected to surface treatment at a pH of 8.6. 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 then at 90 ° C. for 30 minutes. A treated magnetic body of 0.21 μm was obtained.

<Production Example of Toner Particle 1>
(Preparation of the first aqueous medium)
3.1 parts of sodium phosphate dodecahydrate was added to 342.8 parts of ion-exchanged water. K. Using a homomixer (made by Tokushu Kika Kogyo Co., Ltd.), the mixture was heated to 60 ° C. with stirring.
Thereafter, an aqueous calcium chloride solution in which 1.8 parts of calcium chloride dihydrate was added to 12.7 parts of ion-exchanged water, and 2.3 parts of sodium chloride in 14.5 parts of ion-exchanged water were added to the aqueous solution. A sodium aqueous solution was added and stirring was continued to obtain a first aqueous medium containing a dispersant. (Preparation of polymerizable monomer composition)
-Styrene 75.0 parts-N-butyl acrylate 25.0 parts-Amorphous polyester APES1 10.0 parts-Divinylbenzene 0.6 parts-Iron complex of monoazo dye (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 5 parts, treated magnetic material 65.0 parts The above materials were uniformly dispersed and mixed using an attritor (Mitsui Miike Chemical Co., Ltd.), then heated to 60 ° C and paraffin wax (melting point 80 ° C). 15.0 parts was added, mixed and dissolved to obtain a polymerizable monomer composition.
(Preparation of second aqueous medium)
0.9 parts of sodium phosphate dodecahydrate was added to 164.7 parts of ion-exchanged water, heated to 60 ° C. with stirring using a paddle stirring blade, and then 3.8 parts of ion-exchanged water was chlorinated. An aqueous calcium chloride solution to which 0.5 part of calcium dihydrate was added was added and stirring was continued to obtain a second aqueous medium containing a dispersant.
(Granulation)
In the first aqueous medium, the polymerizable monomer composition and 6.0 parts of t-butyl peroxypivalate as a polymerization initiator were added, and T. butyl peroxygen was added at 60 ° C. in a nitrogen atmosphere. K. The mixture was granulated while stirring at 12000 rpm for 10 minutes with a homomixer to obtain a granulated liquid containing particles of the polymerizable monomer composition.
(Polymerization / distillation / drying)
The whole amount of the granulation liquid was put into the second aqueous medium and reacted at 74 ° C. for 3 hours while stirring with a paddle stirring blade. After completion of the reaction, it was confirmed that the colored particles were dispersed in the aqueous medium obtained here, and calcium phosphate was adhered to the surface of the colored particles as an inorganic dispersant.
At this point, hydrochloric acid was added to the aqueous medium to wash away calcium phosphate, followed by filtration and drying to analyze the colored particles. As a result, the glass transition temperature (Tg) of the colored particles was 55 ° C.
Subsequently, the aqueous medium in which the colored particles were dispersed was heated to 100 ° C. and held for 120 minutes. Then, 5 degreeC water was thrown into the aqueous medium, and it cooled from 100 degreeC to 50 degreeC with the cooling rate of 100 degreeC / min. Subsequently, the aqueous medium was held at 50 ° C. for 120 minutes.
Thereafter, hydrochloric acid was added to the aqueous medium to wash away calcium phosphate, followed by filtration and drying to obtain toner particles 1. The production conditions of the toner particles 1 are shown in Table 2.

<Production Example of Toner Particles 2 to 28 and Production Example of Comparative Toner Particles 2 to 5>
In the production of the toner particles 1, the toner particles are similarly produced except that the addition amount of the polymerization initiator, the types and addition amounts of the amorphous polyester and the colorant, and the production conditions are changed as shown in Table 2. 2 to 28 and comparative toner particles 2 to 5 were obtained. Each condition is shown in Table 2.

<Production Example of Comparative Toner Particle 1>
<Example of production of hybrid resin 1>
-Bisphenol A ethylene oxide 2 mol adduct 100.0 mol part-Terephthalic acid 60.0 mol part-Trimellitic anhydride 20.0 mol part-Acrylic acid 10.0 mol part The above monomer mixture for polyester 60 parts is charged into a 4-neck flask, A decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device were attached and stirred at 160 ° C. in a nitrogen atmosphere. A mixture of 40 parts of styrene and 1.9 parts of benzoyl peroxide as a polymerization initiator was added dropwise from the dropping funnel over 4 hours.
Then, after reacting at 160 degreeC for 5 hours, it heated up at 230 degreeC and 0.2 mass% of dibutyltin oxide was added. After completion of the reaction, the resin was taken out from the container, cooled and pulverized to obtain a hybrid resin 1. The hybrid resin 1 had a glass transition temperature (Tg) of 61 ° C. and a softening point of 130 ° C.
・ Amorphous polyester APES1 45.0 parts ・ Hybrid resin 1 55.0 parts ・ Iron complex of monoazo dye (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 1.5 parts ・ Processed magnetic material 90.0 parts ・ Polyethylene wax 4 0.0 part (PW2000: manufactured by Toyo Petrolite Co., Ltd., melting point 120 ° C.)
Charge control agent (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 2.0 parts The above materials were premixed with a Henschel mixer, then melt kneaded with a biaxial extruder heated to 110 ° C, and the cooled kneaded product was hammered A coarsely pulverized resin particle was obtained by coarsely pulverizing with a mill.
The obtained coarsely pulverized product was coated with a mechanical pulverizer turbo mill (manufactured by Turbo Kogyo Co., Ltd .; coated with chromium alloy plating containing chromium carbide on the rotor and stator surfaces (plating thickness 150 μm, surface hardness HV1050)). And pulverized.
The finely pulverized product obtained was classified and removed simultaneously with a multi-division classifier (Elbow Jet Classifier manufactured by Nittetsu Mining Co., Ltd.) using the Coanda effect. After classification, surface treatment of the resin particles was performed using a surface modification apparatus Faculty F-600 (manufactured by Hosokawa Micron Corporation) to obtain comparative toner particles 1.

<Production Example of Comparative Toner Particle 6>
(Preparation of each dispersion)
[Resin particle dispersion (1)]
Styrene (Wako Pure Chemical Industries): 325 parts n-Butyl acrylate (Wako Pure Chemical Industries): 100 parts Acrylic acid (Rhodia Nikka Co., Ltd.): 13 parts 1,10-decanediol diacrylate ( Shin-Nakamura Chemical Co., Ltd.): 1.5 parts · Dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.): 3 parts The above components are mixed in advance and dissolved to prepare a solution. An anionic surfactant (Dow Chemical Co., Ltd.) A surfactant solution prepared by dissolving 9 parts of Dowfax A211) in 580 parts of ion-exchanged water is placed in a flask, 400 parts of the above solution is added and dispersed, emulsified, and stirred slowly for 10 minutes. While mixing, 50 parts of ion-exchanged water in which 6 parts of ammonium persulfate was dissolved was added.
Next, after sufficiently replacing the inside of the flask with nitrogen, the flask was heated with an oil bath while stirring the flask until it reached 75 ° C., and emulsion polymerization was continued for 5 hours to obtain a resin particle dispersion (1). It was.
When the resin particles were separated from the resin particle dispersion (1) and examined for physical properties, the number average particle diameter was 195 nm, the solid content in the dispersion was 42%, the glass transition temperature was 51.5 ° C., and the weight average molecular weight ( Mw) was 32000.
[Resin particle dispersion (2)]
The amorphous polyester (APES16) was dispersed using a disperser in which Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) was modified to a high temperature and high pressure type. Specifically, the composition ratio is 79% ion-exchanged water, 1% anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) (as an active ingredient), and 20% amorphous polyester (APES16). Then, the Cavitron was operated under the conditions that the pH was adjusted to 8.5 with ammonia, the rotational speed of the rotor was 60 Hz, the pressure was 5 kg / cm ² , and the heat exchanger was heated to 140 ° C., and the number average particle diameter Yielded a resin fine particle dispersion (2) having a thickness of 200 nm.
[Colorant dispersion]
Carbon black: 20 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R): 2 parts Ion-exchanged water: 78 parts The above ingredients were homogenized (IKA, Ultra Turrax T50). Dissolve the pigment in water at 3000 rpm for 2 minutes, and further disperse at 5000 rpm for 10 minutes, then stir for one day with a normal stirrer to defoam, then high pressure impact disperser Ultimateizer (Sugino Machine Co., Ltd.) A colorant dispersion was obtained by dispersing for about 1 hour at a pressure of 240 MPa using HJP 30006). Further, the pH of the dispersion was adjusted to 6.5.
(Release agent dispersion)
Hydrocarbon wax: 45 parts (Fischer-Tropsch wax, maximum endothermic peak temperature 78 ° C., weight average molecular weight 750)
・ Cationic surfactant (Neogen RK, Daiichi Kogyo Seiyaku): 5 parts ・ Ion-exchanged water: 200 parts The above components are heated to 95 ° C. and sufficiently dispersed with a homogenizer (IKA, Ultra Turrax T50). Thereafter, the mixture was dispersed with a pressure discharge type gorin homogenizer to obtain a release agent dispersion having a number average diameter of 190 nm and a solid content of 25%.

[Production example of toner particles]
-Ion exchange water: 400 parts-Resin particle dispersion (1): 620 parts (resin particle concentration: 42%)-Resin particle dispersion (2): 279 parts (resin particle concentration: 20%)-Anionic surface activity Agent: 1.5 parts (0.9 parts as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, active ingredient amount: 60%)
The above components were put into a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside.
Thereafter, 88 parts of the colorant dispersion and 60 parts of the release agent dispersion were added and held for 5 minutes. As it was, a 1.0% nitric acid aqueous solution was added to adjust the pH to 3.0.
Next, the stirrer and the mantle heater were removed, and 0.33 parts of polyaluminum chloride and 37.5 parts of 0.1% nitric acid aqueous solution were dispersed while being dispersed at 3000 rpm with a homogenizer (manufactured by IKA Japan: Ultratarax T50). After adding 1/2 of the mixed solution, the dispersion speed was set to 5000 rpm, the remaining 1/2 was added over 1 minute, and the dispersion speed was set to 6500 rpm, and dispersed for 6 minutes.
A reactor is equipped with a stirrer and a mantle heater, and the temperature is increased to 42 ° C. at 0.5 ° C./min while appropriately adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred. After maintaining for 15 minutes, the particle size was measured with a Coulter Multisizer every 10 minutes while raising the temperature at 0.05 ° C./min. When the weight average particle size became 7.8 μm, 5% water The pH was adjusted to 9.0 using an aqueous sodium oxide solution.
Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 96 ° C. at a temperature rising rate of 1 ° C./min and maintained at 96 ° C. When the particle shape and surface properties were observed every 30 minutes with an optical microscope and a scanning electron microscope (FE-SEM), the particles were almost spherical in the second hour. Solidified.
Thereafter, the reaction product is filtered and washed with ion-exchanged water, and when the filtrate has a conductivity of 50 mS or less, cake-like particles are taken out and ion-exchanged water having an amount 10 times the mass of the particles is taken out. When the particles were sufficiently loosened by stirring with a three-one motor, the pH was adjusted to 3.8 with a 1.0% nitric acid aqueous solution and held for 10 minutes.
Then, filtration and water washing were performed again, and when the filtrate had a conductivity of 10 mS or less, water flow was stopped and solid-liquid separation was performed.
The obtained cake-like particles were pulverized by a sample mill and dried in an oven at 40 ° C. for 24 hours. Further, the obtained powder was pulverized by a sample mill and then further vacuum dried in an oven at 40 ° C. for 5 hours to obtain comparative toner particles 6.

表２中、Ａ、Ｂ、Ｃ及びＣＢは、以下の通り。
Ａ：重合反応終了後、着色樹脂粒子が分散された水系媒体を１００℃まで昇温させた後の保持時間［分］
Ｂ：着色樹脂粒子のガラス転移温度以下の温度（５０℃）までの冷却速度［℃／分］
Ｃ：着色樹脂粒子のガラス転移温度以下の温度（５０℃）での保持時間［分］
ＣＢ：カーボンブラック（商品名：ＭＡ−１００、三菱化学製）

In Table 2, A, B, C and CB are as follows.
A: After completion of the polymerization reaction, holding time after raising the temperature of the aqueous medium in which the colored resin particles are dispersed to 100 ° C. [min]
B: Cooling rate [° C./min] to a temperature (50 ° C.) below the glass transition temperature of the colored resin particles
C: Holding time [minute] at a temperature (50 ° C.) or lower of the glass transition temperature of the colored resin particles
CB: Carbon black (trade name: MA-100, manufactured by Mitsubishi Chemical)

<Example of production of silica fine particles A1>
In an autoclave equipped with a stirrer, dry silica (number average particle diameter of primary particles: 8 nm) with a BET specific surface area of 300 m ² / g is placed, and dimethyl silica oil (kinematic viscosity: 50 mm ² / s) is added to the dry silica in a nitrogen atmosphere. 20 parts were added to 100 parts and held at 250 ° C. for 30 minutes.
Subsequently, after adding 10 parts of hexamethyldisilazane (hereinafter referred to as HMDS in the table) to 100 parts of dry silica, the inside of the reactor was replaced with nitrogen gas, and the reactor was sealed and heated to 200 ° C. Then, the silane compound treatment was performed in a fluidized state of silica. This reaction was continued for 60 minutes, and then 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 resulting hydrophobic silica.
Then, it took out and crushed, and obtained silica fine particle A1. Table 3-1 shows the physical properties of the silica fine particles A1.

<Example of production of silica fine particles A2>
In the production example of silica fine particles A1, silica fine particles A2 were obtained in the same manner except that the treatment amount of silicone oil and the treatment amount of HMDS were changed as shown in Table 3-1, and the crushing treatment strength was appropriately adjusted. It was. Table 3-1 shows the physical properties of the silica fine particles A2.

<Example of production of silica fine particles B1>
Silica fine particles B1 were produced by a sol-gel method.
In a 3 L glass reactor equipped with a stirrer, a dropping funnel and a thermometer, 687.9 g of methanol, 42.0 g of pure water and 47.1 g of 28 mass% ammonia water were added 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 ammonia water was added over 4 hours.
Even after completion of the dropwise addition, the suspension was further stirred for 0.2 hours for hydrolysis to obtain a suspension of hydrophilic spherical sol-gel silica fine particles.
Thereafter, after adjusting the pH of the obtained suspension to about 3.5, the reactor was heated to 75 ° C., and a solution of 8.8 g of octyltriethoxysilane dissolved in 220 mL of isopropyl alcohol was placed inside the reactor. The solution was added dropwise with stirring. After the dropwise addition, stirring was continued for 5 hours.
After completion of stirring, the mixture was cooled to room temperature and filtered. The obtained filtrate was washed with ion-exchanged water and then dried by heating at 120 ° C. overnight. Then, crushing processing was performed with a pulverizer (manufactured by Hosokawa Micron Corporation) to obtain silica fine particles B1. The true specific gravity of the silica fine particles B1 was 2.0 g / mL. Other physical properties are shown in Table 3-2.

<Production example of silica fine particles B2 and B3>
In the production example of silica fine particles B1, silica was used except that the dropping time of tetramethoxysilane and aqueous ammonia, the pH of the suspension, and the heating temperature of the suspension were appropriately adjusted so as to have the physical properties shown in Table 3-2. Silica fine particles B2 and B3 were obtained in the same manner as fine particle B1. The true specific gravity of silica fine particles B2 and B3 were both 2.0 g / mL.

<Production Example of Toner 1>
100 parts of the toner particles 1 and 0.3 parts of the silica fine particles B1 are put into a Mitsui Henschel mixer (FM10C: Mitsui Miike Chemical Co., Ltd.), and the premixing conditions and external addition conditions shown in Table 4 are used. The first stage external additive mixing treatment was performed.
Thereafter, the processed product is once taken out, and the processed product and 0.6 parts of silica fine particles A1 are combined with the apparatus shown in FIG. 1 (the diameter of the inner peripheral portion of the main body casing 301 is 130 mm, and the volume of the processing space 309 is 2. A device of 0 × 10 ⁻³ m ³ was used, the rated power of the drive unit 308 was 5.5 kW, and the shape of the stirring member 303 was that of FIG. The overlap width d is 0.25 D with respect to the maximum width D of the stirring member 303, and the clearance between the stirring member 303 and the inner periphery of the main body casing 301 is 3.0 mm. A second-stage external mixing process was performed under premixing conditions and external addition conditions.
After charging the toner particles and the silica fine particles A1, premixing was performed in order to mix them uniformly. The premixing conditions were such that the power of the drive unit 308 was 0.10 W / g (the rotation speed of the drive unit 308 was 150 rpm), and the processing time was 1 minute.
After the pre-mixing, an external additive mixing process was performed. The external mixing process conditions were such that the power of the drive unit 308 was 0.30 W / g (the rotational speed of the drive unit 308 was 1200 rpm), and the processing time was 5 minutes.
After the external addition and mixing treatment, coarse particles and the like were removed with a circular vibrating sieve equipped with a screen having a diameter of 500 mm and an opening of 75 μm, whereby Toner 1 was obtained. Table 4-1 shows the external mixing conditions, and Table 5 shows the physical properties of the obtained toner.

<Production Examples of Toners 2 to 30 and Comparative Toners 1 to 7>
In the production example of the toner 1, the same except that the type and amount of silica fine particles, the type of toner particles, the external addition device, the external treatment mixing conditions, etc. are changed as shown in Table 4-1 or Table 4-2. Thus, toners 2 to 30 and comparative toners 1 to 7 were produced. Table 5 shows the physical properties of the obtained toner and the comparative toner.
In Table 4-1 or Table 4-2, HM means Mitsui Henschel Mixer FM10C (Mitsui Miike Chemical Co., Ltd.).

表５中、Ｄ、Ｅ、Ｆ、Ｇ、Ｈ、Ｉ、Ｊ、Ｋ、Ｌ、Ｍ、Ｎ、Ｏ、Ｐ、及びＱ、及び、ＮＤは、以下の通り。
Ｄ：トナーの重量平均粒径（Ｄ４）［μｍ］
Ｅ：トナーのアスペクト比
Ｆ：トナーのガラス転移温度（Ｔｇ）［℃］
Ｇ：トナーのピーク分子量（Ｍｐ（Ｔ））
Ｈ：非晶性ポリエステルの含有量［質量部］
Ｉ：トナーの軟化点［℃］
Ｊ：ｆ_Ａ［ｎＮ］
Ｋ：Ｆ_１［ｋＮ／ｍ^２］
Ｌ：Ｆ_２［ｋＮ／ｍ^２］
Ｍ：２５％面積率［面積％］
Ｎ：５０％面積率［面積％］
Ｏ：ドメインの面積比
Ｐ：非晶性ポリエステルのドメインの個数平均径［μｍ］
Ｑ：Ｓ２１１／Ｓ８５
ＮＤ：観察されず

In Table 5, D, E, F, G, H, I, J, K, L, M, N, O, P, and Q, and ND are as follows.
D: Weight average particle diameter of toner (D4) [μm]
E: Toner aspect ratio F: Glass transition temperature (Tg) of toner [° C.]
G: Peak molecular weight of toner (Mp (T))
H: Content of amorphous polyester [parts by mass]
I: toner softening point [° C.]
J: f _A [nN]
K: F ₁ [kN / m ² ]
L: F ₂ [kN / m ² ]
M: 25% area ratio [area%]
N: 50% area ratio [area%]
O: Domain area ratio P: Amorphous polyester domain number average diameter [μm]
Q: S211 / S85
ND: not observed

<Example 1>
A Canon printer LBP7700C was modified and used for image output evaluation. As a remodeling point, the toner carrier is changed to the toner carrier 1, and the toner supply member of the developing device is rotated reversely to the toner carrier as shown in FIG. The application was turned off.
The contact pressure was adjusted so that the width of the contact portion between the toner carrier and the electrostatic latent image carrier was 0.9 mm, and the size of the developing device was adjusted so that 150 g of toner was contained.
Furthermore, the toner carrier was modified so that the voltage applied to the toner carrier could be 200 V higher than the product conditions. (For example, when the voltage applied to the toner carrier of the product is -600V, the condition that is 200V higher than the product condition is -400V.)
Further, as shown in FIG. 4, the cleaning blade was removed, and the process speed was further modified to 32 ppm.
By doing so, the area of the contact portion between the toner carrier and the electrostatic latent image carrier is reduced, and the process speed is further increased, so that the conditions are more severe with respect to the occurrence of fog and ghost. It was adjusted.
150 g of toner 1 was filled in the developing device modified as described above, and the developing device was set on a black station, and image evaluation was performed in a high temperature and high humidity environment. As a result, it was possible to obtain a good image without image defects even without cleaner.
Further, in a room temperature and high humidity environment (23 ° C./55% RH), the following fixing evaluation and a winding test on a fixing film were performed.
The evaluation methods for each evaluation performed in the examples and comparative examples of the present invention and the criteria for the evaluation will be described below.

<Fixing evaluation (whiteout evaluation)>
In the fixing evaluation, the fixing device was once removed from the image forming apparatus and remodeled so that an unfixed image could be output. Evaluation paper includes Business 4200 (manufactured by Xerox Co., Ltd., Beck smoothness 56, basis weight 105 g / m ² , hereinafter, plain paper), and NEENAH CLASSIC.
LAID TEXT (manufactured by Neenah Paper, Beck smoothness 5, basis weight 105 g / m ² , hereinafter rough paper) was used.
The Beck smoothness indicating the roughness of the paper surface is NEENAH compared to Business 4200.
CLASSIC LAID TEXT is small, and the presence of more paper recesses allows more severe evaluation of white spots during fixing.
The fixing evaluation image was a solid black image, which was adjusted so that the left and right margins were 80 mm and the top and bottom margins were 10 mm. At this time, the applied voltage of the solid black image was adjusted so that the applied amount of toner was 0.8 mg / cm ² .
While changing the temperature range from 160 ° C. to 220 ° C. at intervals of 5 ° C., the presence or absence of white spots at each temperature was visually checked, and the rank was determined based on the temperature at which no white spots occurred. Went.
(Evaluation criteria)
A ⁺ : No white spot occurs at 165 ° C. A: No white spot occurs at 170 ° C. A ⁻ : No white spot occurs at 175 ° C. B: No white spot occurs at 180 ° C. and a fixed image at 180 ° C. C: White spots do not occur at 180 ° C, but slightly peel off when a fixed image at 180 ° C is rubbed D: White spots occur even at 180 ° C

<Test for winding around fixing film>
A solid black unfixed image having a width of 60 mm at a position 3 mm from the leading end of the recording paper is output on a NEENAH BOND SUB16 (manufactured by Neenah Paper, basis weight 60 g / m ² ) paper, and two fixing temperatures of 180 ° C. and 200 ° C. are output. In setting the fixing temperature, one sheet was passed every 10 seconds and intermittently 100 sheets, and the winding around the fixing film was evaluated according to the following criteria.
A: No winding occurs even at a fixing temperature of 200 ° C. B: Winding occurs at a fixing temperature of 200 ° C. C: Winding occurs at a fixing temperature of 180 ° C.

  In a high temperature and high humidity environment (32.5 ° C./80% RH), a cartridge filled with 150 g of toner was allowed to stand for 72 hours, and then a horizontal line with a printing rate of 1% was printed on 4000 sheets and 6000 sheets with two intermittent sheets. Sheet fogging was performed, and fog evaluation after outputting a solid black image and ghost evaluation were performed.

<Fog evaluation on electrostatic latent image carrier after output of solid black image>
The fog was measured using a REFECTMETER MODEL TC-6DS manufactured by Tokyo Denshoku. A green filter was used as the filter.
The fog on the electrostatic latent image carrier after the output of the solid black image is a polyester tape (trade name: polyester tape No. 5511, supplier: Nichiban Co., Ltd.) on the electrostatic latent image carrier immediately after the transfer of the solid black image. Calculated by subtracting the reflectance B of the polyester affixed on the unused paper from the reflectance A of the tape affixed on the paper.
That is, fog (%) = reflectance A (%) − reflectivity B (%).
(Evaluation criteria)
A: Less than 5% B: 5% or more and less than 10% C: 10% or more and less than 20% D: 20% or more

<Ghost evaluation>
A plurality of solid black images of 10 mm x 10 mm are formed on the front half of an evaluation paper (trade name Business 4200, basis weight 75 g / m ² , manufactured by Xerox Corporation), and a halftone image of 2 dots 3 spaces is formed on the back half did. It was visually determined how much trace of the solid black image appeared on the halftone image.
(Evaluation criteria)
A: No ghost occurred B: Very little ghost occurred C: Little ghost occurred D: Most ghost occurred

<Examples 2 to 30>
The toner was changed according to Table 6, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 6.

<Comparative Examples 1-7>
The toner was changed according to Table 6, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 6.

301: Main body casing, 302: Rotating body, 303, 303a, 303b: Stirring member, 304: Jacket, 305: Raw material inlet, 306: Product outlet, 307: Central shaft, 308: Drive unit, 309: Processing space, 310: Rotating body end side surface, 311: Rotating direction, 312: Return direction, 313: Feeding direction, 316: Inner piece for raw material inlet, 317: Inner piece for product outlet, d: Overlapping part of stirring member Interval, D: Width of stirring member, 45: Electrostatic latent image carrier, 46: Charging roller, 47: Toner carrier, 48: Toner supply member, 49: Developing device, 50: Transfer roller, 51: Film fixing device , 52: pickup roller, 53: transfer material (paper), 54: laser generator, 55: toner regulating member, 56: fixing member,
57: toner, 58: stirring member, 59: magnet, 61: fixing film, 62: pressure roller, P: paper feeding direction

Claims (12)

A toner having toner particles containing a binder resin, amorphous polyester and a colorant, and inorganic fine particles,
The softening point of the toner is 110 ° C. or higher and 140 ° C. or lower
The toner satisfying all of the following formulas (1) to (3):
Formula (1) f _A ≦ 25.0
Formula (2) 2.0 ≦ F ₁ ≦ 5.0
Formula (3) F ₂ ≦ 5.0
[In the formulas (1) to (3),
f _A is a force between two particles (nN) calculated from the maximum tensile breaking force when a toner compact is formed by applying a load of 78.5 N at 25 ° C. and the toner compact is broken. ).
F ₁ is a maximum tensile stress (kN / m ² ) when a toner compact is formed by applying a load of 78.5 N to the toner left at 55 ° C. for 10 minutes, and the toner compact is broken. Show.
F ₂ represents a maximum tensile stress (kN / m ² ) when a toner compact is formed by applying a load of 1962.5 N at 55 ° C. for 5 minutes and the toner compact is broken. ] The binder resin contains a vinyl resin;
The amorphous polyester has a monomer unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms, and a monomer unit derived from an alcohol component,
The content ratio of the monomer unit derived from the linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms is 10 mol% or more and 50 mol% or less with respect to all the monomer units derived from the carboxylic acid component constituting the amorphous polyester. The toner according to claim 1, wherein The peak molecular weight of the amorphous polyester is 8000 to 13000,
The toner according to claim 1, wherein a softening point of the amorphous polyester is 85 ° C. or higher and 105 ° C. or lower.   The toner according to claim 1, wherein a content of the amorphous polyester is 5.0 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin. . When the toner was subjected to time-of-flight secondary ion mass spectrometry,
The peak intensity derived from the vinyl resin is S85,
When the peak intensity derived from the amorphous polyester is S211,
The toner according to any one of claims 2 to 4, wherein S85 and S211 satisfy a relationship represented by the following formula (4).
Formula (4) 0.30 <= S211 / S85 <= 3.00   The toner according to claim 1, wherein an acid value of the amorphous polyester is 1.0 mgKOH / g or more and 10.0 mgKOH / g or less. In the cross section of the toner observed with a transmission electron microscope,
The vinyl resin forms a matrix, the amorphous polyester forms a domain,
The amorphous polyester domain is within a range of 30% to 70% with respect to the total area of the amorphous polyester domain within 25% of the distance between the contour and the center point of the cross section from the contour of the cross section. The toner according to claim 2, wherein the toner is present in an amount of not more than%. In the cross section of the toner observed with a transmission electron microscope,
The vinyl resin forms a matrix, the amorphous polyester forms a domain,
The domain of the amorphous polyester is 80 area% or more and 100 area with respect to the total area of the domain of the amorphous polyester within 50% of the distance between the outline and the center point of the cross section from the outline of the cross section. The toner according to claim 2, wherein the toner is present in an amount of not more than%. In the cross section of the toner observed with a transmission electron microscope,
The vinyl resin forms a matrix, the amorphous polyester forms a domain,
From the contour of the cross section, the area of the domain of the amorphous polyester existing within 25% of the distance between the contour and the center point of the cross section is A,
From the contour of the cross section, when the area of the domain of the amorphous polyester existing in 25% to 50% of the distance between the contour and the center point of the cross section is B,
The toner according to claim 2, wherein A and B satisfy a relationship represented by the following formula (5).
Formula (5) A / B ≧ 1.05 In the cross section of the toner observed with a transmission electron microscope,
The vinyl resin forms a matrix, the amorphous polyester forms a domain,
The toner according to claim 2, wherein the number average diameter of domains of the amorphous polyester is 0.3 μm or more and 3.0 μm or less. The inorganic fine particles contain silica fine particles;
The silica fine particles have a number average particle size of primary particles of 80 nm or more and 200 nm or less,
The toner according to any one of claims 1 to 10, wherein the silica fine particles have a maximum peak half-value width of 25.0 nm or less in the particle size distribution of primary particles. Toner for developing the electrostatic latent image formed on the electrostatic latent image carrier;
A toner carrier that carries the toner and conveys the toner to the electrostatic latent image carrier,
The developing device according to claim 1, wherein the toner is the toner according to claim 1.

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