JP2018004894A - Toner and developing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that exhibits a good fogging suppressing characteristic and development ghost suppressing characteristic over a long period of use in the present low-temperature and low-humidity environment, and suppresses fixation tailing in a normal-temperature and high-humidity environment.SOLUTION: A toner includes toner particles each containing a binder resin containing a vinyl resin, colorant, and an amorphous polyester resin. The vinyl resin forms a matrix; the amorphous polyester resin forms domains; the domains are present at a ratio of 30 area% or more and 70 area% or less in an area within 25% of the distance between the contour of a cross section and the central point of the cross section from the contour; Mw of the toner when an orthodichlorobenzene soluble is measured by SEC-MALLS is 100000 or more and 500000 or less; Mw and Rw satisfy the formula (1).SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electrophotographic toner, a toner used in an image forming method for developing an electrostatic image, and a developing device.

  In recent years, the usage of copiers and printers has been changed from a mode in which a single copier or printer is placed in a section of the office and used by multiple people. It has changed to the form that uses the printer. Due to this change, it has been required to further reduce the size and speed of the printer. Regarding the downsizing of the printer, it is effective to reduce the size of the process cartridge in which the developer is accommodated and the fixing unit mounted on the main body.

  One effective means for reducing the size of the process cartridge is to employ a cleanerless system. The cleanerless system does not have a cleaning blade or waste toner box, and can greatly contribute to downsizing of the main body. However, in order to employ a cleanerless system, there are many performances required for toner. In the cleanerless system, since there is no cleaning blade, the transfer residual toner passes through the charging process, is collected in the toner container, and is sent to the developing process again. Therefore, compared with a printer having a cleaning blade, the stress applied to the toner particles is increased, and there is a possibility that the toner particles may be broken or crushed. The cracking and crushing of the toner particles occur remarkably when members such as the toner carrier and the regulation blade become hard, particularly in a low temperature and low humidity environment. As a result, with a long-term use, the toner particle size distribution in the toner container is broadened and the external additive is embedded, so that the fluidity of the toner is lowered, and the toner is sufficiently charged by rubbing between the toner carrier and the blade. It becomes hard to be broken. As a result, the toner charge distribution becomes broad, and fogging is likely to occur when toner having a low charge amount is developed in the non-image area on the photosensitive member. On the other hand, due to the charged-up toner, it is easy for a toner regulation unit in the image forming apparatus to cause a regulation failure, and a development ghost is likely to occur. In order to suppress such fog and development ghost, it is necessary to improve the brittleness of the toner particles more than ever.

  In addition, miniaturization of a fixing device attached to the main body is considered to be one effective means for miniaturization of the printer. In order to reduce the size of the fixing device, it is easy to apply the film fixing because the heat source and the apparatus configuration can be easily simplified. However, in film fixing, a toner that can be fixed with a small amount of heat and low pressure is required. In recent years, there are many cases where printers are used in various environments, and in particular, in a normal temperature and high humidity environment, an image problem called “fixing tailing” tends to occur. Fixing tailing is an image detriment caused by the occurrence of a water vapor flow from a medium such as paper and the toner being blown off when a horizontal line image or the like with a large amount of applied toner is produced.

  From the above, cleaner-less systems and film fixing are effective for downsizing printers, but in order to apply to these systems, there are few while suppressing cracking and crushing of toner particles in a low-temperature and low-humidity environment. Toners that can be fixed with heat and light pressure are required.

  Patent Document 1 describes that a toner in which a styrene acrylic resin and a polyester resin are dispersed at a micro level can achieve both charging stability and fixability.

  In Patent Document 2, as a toner having improved fixability, a domain-matrix in which toner particles are dispersed in a matrix phase composed of an amorphous resin (A) and an amorphous polyester resin (B) as a domain phase. A toner having a structure is described. In this observed image of the toner particle cross section, it is described that the number average domain diameter of the amorphous polyester resin (B) having a domain diameter of 100 nm or more is 100 to 200 nm. Furthermore, it is described that the area ratio of the domain phase having a domain diameter of 500 nm or more with respect to the total area of the domain phase is 0 to 10%.

  Patent Document 3 describes a toner in which low temperature fixability and offset resistance are improved by physically cross-linking a binder resin in a toner using a macromonomer.

JP 2004-295105 A Japanese Patent Laying-Open No. 2015-152703 JP 2002-365849 A

  However, as a result of the study by the present inventors, there was still room for improvement when considering the use of a cleanerless system and film fixing for miniaturization of any of the toners described in the above documents. . In the toner described in Patent Document 1, polyester resin and styrene acrylic resin are dispersed up to the toner surface, and when applying a cleanerless system, there is a possibility that embedding of external additives or cracking or crushing of the toner may occur. There is room for improvement. Similarly, in the toner described in Patent Document 2, since a small domain diameter is finely dispersed throughout the toner, when a cleaner-less system is applied, the toner has poor brittle resistance, and the toner is not cracked or crushed. It can happen and there is room for improvement. In the toner described in Patent Document 3, when the fixing device is further reduced in size and speeded up, the toner is insufficiently melted and fixing tailing may occur, and there is room for improvement.

  An object of the present invention is to provide a toner that solves the above problems. That is, an object of the present invention is to provide a toner that has good fog characteristics and excellent development ghost characteristics over a long period of use in a low temperature and low humidity environment, and suppresses fixing tailing even in a normal temperature and high humidity environment. There is.

The present invention is a toner having toner particles containing a binder resin, a colorant, and an amorphous polyester,
The binder resin contains a vinyl resin,
The softening point of the toner is 110 ° C. or higher and 140 ° C. or lower;
In the cross section of the toner observed with a transmission electron microscope,
The vinyl resin forms a matrix and the amorphous polyester forms a domain;
The area of the amorphous polyester is 30% by area or more based on the total area of the domains of the amorphous polyester in the region from the outline of the cross section to within 25% of the distance between the outline and the center point of the cross section. 70 area% or less exists,
In the weight average molecular weight (Mw) and average radius of rotation (Rw) of the toner's orthodichlorobenzene solubles measured using size exclusion chromatography-multi-angle light scattering (SEC-MALLS),
The Mw is 100,000 or more and 500,000 or less,
The Mw and the Rw are represented by the formula (1)
1.0 × 10 ⁻⁴ ≦ Rw / Mw ≦ 5.0 × 10 ⁻⁴ (1)
The present invention relates to a toner characterized by satisfying

  According to the present invention, it is possible to provide a toner that has good fog characteristics and excellent development ghost characteristics over a long period of use in a low temperature and low humidity environment, and suppresses fixing tailing even in a normal temperature and high humidity environment. it can.

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 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.

  As described above, when a stress is applied to the toner between the members as in the cleanerless system, the toner particles are likely to be broken or crushed. Therefore, it is necessary to improve the brittleness of the toner.

On the other hand, considering the application of film fixing, a toner that can be fixed with a light pressure and with a smaller amount of heat is required, and fixing tailing tends to be a problem as described above. As a result of studies by the present inventors, it has been found that fixing tailing deteriorates in the following cases.
1) When an image with a large amount of applied toner (for example, a horizontal line image) is output.
2) When the paper is uneven.
3) When the toner on the media is loaded unevenly.
4) The toner has a melt viscosity that is too low.

  It has been found that in order to suppress such fixing tailing, it is necessary to increase the surface adhesion between toner toners and between toner media.

  Conventionally, a core-shell type toner has been studied in order to achieve both improvement in brittleness and fixing property of the toner. The core-shell type toner has a structure in which a shell portion has a high softening point material and a core portion has a low softening point material and a plasticizer such as a release agent. However, when used for a long time in an image forming apparatus that is prone to stressing toner, such as cleaner-less, even if the shell has a high softening point material, the core part is soft, so the toner cracks and breaks Such toner deterioration was easy to be seen. Also, with regard to fixing tailing in a room temperature and high humidity environment for film fixing, since the shell portion has a high softening point material, adhesion between toner toners or between toner media is poor, and fixing tailing is difficult. It was difficult to improve.

  As described above, when a cleaner-less system and film fixing are applied to reduce the size of the apparatus main body, it has been difficult to achieve both suppression of toner chipping and crushing and suppression of fixing tailing.

  As a result of detailed investigations by the present inventors, it has been found that the toner has the following characteristics, so that it is possible to achieve both suppression of cracking and crushing of the toner and suppression of fixing tailing.

That is, a toner having toner particles containing a binder resin, a colorant, and amorphous polyester, wherein the binder resin contains a vinyl resin, and the softening point of the toner is 110 ° C. or higher and 140 ° C. or lower.
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,
Amorphous polyester domains in a region from the contour of the cross section to within 25% of the distance between the contour and the center point of the cross section are 30 to 70 area% with respect to the total area of the amorphous polyester domain The following exist.

Then, in the weight average molecular weight (Mw) and the average radius of rotation (Rw) measured using size exclusion chromatography-multi-angle light scattering (SEC-MALLS) of the toner's orthodichlorobenzene-soluble matter,
Mw is 100,000 or more and 500,000 or less, and Mw and Rw are represented by the formula (1)
1.0 × 10 ⁻⁴ ≦ Rw / Mw ≦ 5.0 × 10 ⁻⁴ (1)
It is characterized by satisfying.

  The toner of the present invention has a vinyl resin and an amorphous polyester. By having the vinyl resin as the binder resin, for example, maintenance of the rigidity and viscosity of the toner can be easily achieved, and cracking and crushing of the toner can be suppressed. Furthermore, by containing amorphous polyester, for example, it is possible to introduce a part that melts in a specific temperature range, and it is easy to improve the adhesion strength between toner toner at a lower temperature, and to improve the fixing tailing Easy to make. Further, the softening point of the toner can be controlled by the presence state of the vinyl resin and the amorphous polyester in the toner. Furthermore, as will be described later, by controlling the positions where the vinyl resin and the amorphous polyester are present, it is easy to achieve both cracking and crushing of the toner and fixing tailing.

  In the cross section of the toner observed with a transmission electron microscope, the vinyl resin forms a matrix and the amorphous polyester forms a domain. The domain of the amorphous polyester is in the region from the contour of the cross section to within 25% of the distance between the contour and the center point of the cross section (hereinafter also referred to as “25% area ratio”). It is 30 area% or more and 70 area% or less with respect to the total area of the domain. In this way, fixing the tailing can be improved by dispersing amorphous polyester as a domain in a vinyl resin matrix and controlling the dispersion state of the domain as described above.

  When the 25% area ratio is less than 30 area%, the toner surface melting becomes dull, the adhesion between the toner and the toner medium is lowered, and the fixing tail is deteriorated. On the other hand, if the 25% area ratio is greater than 70 area%, the amorphous polyester present in the vicinity of the toner surface tends to absorb moisture in a room temperature and high humidity environment, resulting in poor transferability. Along with this, the toner is not uniformly applied on the medium, and the fixing tail is deteriorated. Further, when used for a long time, the toner is liable to be broken and broken, and fog and development ghost may be deteriorated.

  The toner of the present invention has a weight average molecular weight Mw measured by SEC-MALLS of 100,000 or more and 500,000 or less, and the weight average molecular weight Mw and the average rotation radius Rw must satisfy the above formula (1). The unit of the average rotation radius Rw is “nm”.

Here, the inertial square radius (Rg ² ) is generally a value indicating the spread per molecule, and the average rotation radius (Rw = (Rg ² ) ^1/2 ), which is the square root, is divided by the weight average molecular weight. The value (Rw / Mw) obtained by is considered to indicate the degree of branching per molecule. Therefore, the smaller the (Rw / Mw), the smaller the spread with respect to the molecular weight, so the degree of branching of the molecule is larger, and conversely, the larger the (Rw / Mw), the greater the spread with respect to the molecular weight. It is believed that there is.

  The weight average molecular weight and inertial square radius determined from the SEC-MALLS will be described. The molecular weight distribution measured by SEC is based on the molecular size, and the intensity is its abundance. On the other hand, when using the light scattering intensity obtained by SEC-MALLS (by combining SEC as a separating means and a multi-angle light scattering detector, the weight average molecular weight and molecular spread (inertial square radius) can be measured). The molecular weight distribution not based on the molecular size can be obtained.

In the conventional SEC, when a molecule to be measured passes through a column, the molecule is subjected to a molecular sieving effect, and the molecules having a large molecular size are eluted in order, and the molecular weight is measured. In this case, the linear polymer and the branched polymer having the same molecular weight are eluted earlier because the former has a larger molecular size in the solution. Therefore, the molecular weight of the branched polymer measured by SEC is usually measured smaller than the true molecular weight. On the other hand, the light scattering method used in the present invention utilizes Rayleigh scattering of the measurement molecule. And, by measuring the dependence of light incident angle and sample concentration on the intensity of light scattered light, and analyzing by Zimm method, Berry method, etc., it is more true for all molecular forms of linear polymers and branched polymers. Close molecular weight (absolute molecular weight) can be determined. In the present invention, as will be described later, the intensity of light scattered light is measured by the SEC-MALLS measurement method, the relationship represented by the following Zimm equation is analyzed using Debye Plot, and the weight average based on the absolute molecular weight The molecular weight (Mw) and the inertial square radius (Rg ² ) are derived. The Debye Plot is a graph in which the vertical axis is K · C / R (θ) and the horizontal axis is sin ² (θ / 2), and the weight average molecular weight (Mw) from the intercept of the vertical axis at that time. And the inertial square radius (Rg ² ) can be calculated from the slope. However, since the above Mw and Rg ² are calculated for each component for each elution time, in order to obtain Mw and Rg ^{2 of the} entire sample, it is necessary to further calculate the respective average values. In addition, when it measures using the apparatus mentioned later, the value of the weight average molecular weight (Mw) of the whole sample and an average rotation radius (Rw) is obtained as a direct output from an apparatus.

Ｋ：光学定数
Ｃ：ポリマーの濃度（ｇ／ｍＬ）
Ｒ（θ）：散乱角θにおける散乱光の相対強度
Ｍｗ：重量平均分子量
Ｐ（θ）：散乱光の角度依存性を表すファクター
Ｐ（θ）＝Ｒ（θ）／Ｒ_０＝１−〈Ｒｇ^２〉［（４π／λ）ｓｉｎ（θ／２）］^２／３
〈Ｒｇ^２〉：慣性自乗半径
λ：溶液中のレーザー光の波長（ｎｍ）

K: Optical constant C: Polymer concentration (g / mL)
R (θ): relative intensity of scattered light at scattering angle θ: weight average molecular weight P (θ): factor P (θ) = R (θ) / R ₀ = 1− <Rg representing angle dependency of scattered light ^{2> [(4π / λ)} sin (θ / 2)] 2/3
<Rg ² >: inertial radius λ: wavelength of laser light in solution (nm)

In the present invention, orthodichlorobenzene is used as the extraction solvent.
The reason for this is that there is a correlation between the soluble content of orthodichlorobenzene and the level of fixing tail in the toner of the present invention. Because ortho-dichlorobenzene has a boiling point as high as 180 ° C, it can be extracted at a high temperature such as 135 ° C, and since it is a polar solvent, it has a high extraction capability and extracts a wide molecular weight band related to melting during fixing. I think it is possible.

  In the present invention, the Mw measured by the size exclusion chromatography-multi-angle light scattering (SEC-MALLS) is 100,000 or more and 500,000 or less. When Mw is smaller than 100,000, the melt viscosity of the toner is remarkably lowered, the toner is liable to be broken or crushed during long-term use, and fog and development ghost are deteriorated. On the other hand, when Mw is larger than 500,000, the adhesion strength between toner toners and between toner media is weakened, and fixing tailing is deteriorated. More preferably, the weight average molecular weight is 200000 or more and 400000 or less.

Subsequently, the ratio (Rw / Mw) of the average rotation radius (Rw) to the weight average molecular weight (Mw) of the toner of the present invention is 1.0 × 10 ⁻⁴ or more and 5.0 × 10 ⁻⁴ or less. When Rw / Mw is smaller than 1.0 × 10 ^{−4, the} degree of branching of the polymer molecules becomes too high, surface melting in a lower temperature range becomes difficult, the adhesive strength between toners becomes small, and the media having low smoothness. In this case, the fixing tail is worsened. On the other hand, when it is larger than 5.0 × 10 ^{−4, the} degree of branching of the polymer molecules becomes too low, and the entanglement between the polymer molecules is reduced, so that the melt viscosity is remarkably lowered. As a result, cracking and crushing of the toner become prominent, and fogging and ghosting due to long-term use deteriorate. More preferably, (Rw / Mw) is 1.2 × 10 ⁻⁴ or more and 4.8 × 10 ⁻⁴ or less.

  In addition, the said weight average molecular weight (Mw) can be controlled to the said range by adjusting the density | concentration of the vinyl-type monomer with respect to the dispersion medium at the time of a polymerization reaction, the kind and addition amount of a polymerization initiator, and a polymerization reaction. . On the other hand, (Rw / Mw) is the type and addition amount of the polymerization initiator, the polymerization reaction temperature, the concentration of the vinyl monomer relative to the dispersion medium during the polymerization reaction, the adjustment of the type and addition amount of the chain transfer agent, and the polymerization inhibitor It is possible to control by adding a reactive resin such as a macromonomer.

  The toner of the present invention has a softening point of 110 ° C. or higher and 140 ° 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 less than 110 ° C., toner deterioration such as embedding of an external additive or toner cracking occurs, and fog and development ghost are deteriorated. On the other hand, when the softening point of the toner is higher than 140 ° C., the surface melt viscosity of the toner is remarkably high in the lower temperature range, and the fixing tailing is deteriorated. More preferably, it is 120 degreeC or more and 140 degrees C or less, More preferably, it is 125 degreeC or more and 135 degrees C or less.

  In order to adjust the softening point of the toner within the above range, the molecular weight of the toner, the amount of insoluble THF in the toner, the type and molecular weight of the binder resin constituting the toner, the type and content of the plasticizer such as wax It is controllable by adjusting.

  As described above, by satisfying these characteristics, it is possible to obtain a toner that suppresses fogging and development ghosts caused by toner cracking and crushing in a low temperature and low humidity environment through long-term use and further suppresses fixing tailing in a normal temperature and high humidity environment. .

  The binder resin of the toner contains a vinyl resin. When the binder resin contains a vinyl resin, it is easy to achieve maintenance of rigidity and viscosity, and it is easy to suppress toner deterioration during long-term use. 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, the toner contains amorphous polyester. With this amorphous polyester, it is possible to easily introduce a portion that melts in a specific temperature range. As a result, the adhesive strength between the toner and the toner medium can be increased from a lower temperature range. Further, in order to suppress cracking and crushing of the toner, a domain of amorphous polyester is present in the vicinity of the toner surface in the vinyl resin matrix.

  Examples of the vinyl resin include the following.

Homopolymers of styrene and substituted products thereof such as polystyrene and polyvinyltoluene;
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, polyester resin, polyamide resin, epoxy resin, and polyacrylic acid resin can be used. These can be used alone or in combination of two or more. Among these, a styrene copolymer, particularly a styrene-butyl acrylate copolymer is preferable from the viewpoints of development characteristics and ease of control of fixability.

  The content of the amorphous polyester in the toner is preferably 5.0% by mass or more and 30.0% by mass or less with respect to the binder resin. When the content of the amorphous polyester resin is 5.0% by mass or more, the adhesion strength between the toners and between the toner media is easily improved, and the fixing tailing is easily improved. When the content of the amorphous polyester is 30.0% by mass or less, toner cracking and crushing during long-term use is suppressed, and further, transferability is improved over long-term use, and fixing tailing is likely to be improved.

  From the viewpoint of surface melting of the toner for improving the adhesion strength of the toner particles, the amorphous polyester is a unit derived from an alcohol component and a unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms. It is preferable to have. Furthermore, it is preferable to contain 10 mol% or more and 50 mol% or less of a unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms with respect to units derived from all carboxylic acid components in the amorphous polyester. As described above, the amorphous polyester is preferably a low softening point material in order to improve the surface melting. As the method, the amorphous polyester is a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms. It is preferable to have a unit derived from. This makes it easier to lower the softening point of the amorphous polyester while the molecular weight of the amorphous polyester is increased, so that the surface melting of the toner can be easily controlled while suppressing cracking and crushing of the toner.

  In addition, since the amorphous polyester contains a specific amount of units derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms, it can be melted instantaneously at the time of fixing, so that surface melting is easily promoted. Become. As a result, the adhesive strength between the toner and the toner medium is likely to be improved, and the fixing property and the fixing tail are likely to be improved. This is presumed to be caused by the fact that the unit derived from the linear aliphatic dicarboxylic acid 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, the adhesion between the toner and toner becomes good. When the linear aliphatic dicarboxylic acid has 12 or less carbon atoms, it becomes easy to control the softening point and molecular weight of the amorphous polyester, so that the cracking and crushing of the toner are well suppressed, and the adhesive strength between the toner and the toner is improved. It is easy to improve.

  When the content of the unit derived from the linear aliphatic dicarboxylic acid is 10 mol% or more, the softening point of the amorphous polyester tends to be lowered. On the other hand, when the content of the unit derived from the linear aliphatic dicarboxylic acid is 50 mol% or less, it is difficult to reduce the molecular weight of the amorphous polyester, and thus it is easy to suppress cracking and crushing of the toner. The content of the unit derived from the linear aliphatic dicarboxylic acid is more preferably 30 mol% or more and 50 mol% or less.

  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 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 thereof, 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. Or lower alkyl esters thereof. Among these, terephthalic acid is preferably used because it can maintain a high 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. Moreover, it is preferable that the molar ratio (carboxylic acid component / alcohol component) of the alcohol component which is a raw material monomer of amorphous polyester and a carboxylic acid component is 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 point (Tg) can be known by measuring a differential scanning calorimeter (DSC).

  In the weight average molecular weight (Mw (P)) and average radius of rotation (Rw (P)) measured with SEC-MALLS, the Mw (P) is 3500 or more and 20000 in the soluble part of orthodichlorobenzene of amorphous polyester. The following is preferable. In addition, it is preferable that Mw (P) and Rw (P) satisfy the formula (2).

1.5 × 10 ⁻³ ≦ Rw (P) / Mw (P) ≦ 7.0 × 10 ⁻³ (2)
When Mw (P) of the amorphous polyester is 3500 or more, it becomes easy to suppress cracking and crushing of the toner during long-term use. Further, when Mw (P) of the amorphous polyester is 20000 or less, melting by heat occurs instantaneously, so that the temperature at which the toner surface starts to melt can be easily controlled. Further, when Rw (P) / Mw (P) is 1.5 × 10 ⁻³ or more, the brittleness of the surface is easily increased, cracking of the toner and embedding of external additives are easily suppressed, and development ghosts and The fog is easily improved. When Rw (P) / Mw (P) is 7.0 × 10 ⁻³ or less, the polymer chain of the binder resin existing around the amorphous polyester resin can be instantly loosened, and the fixing tailing can be prevented. Easy to improve.

  The softening point of the amorphous polyester is preferably 85 ° C. or higher and 105 ° C. or lower. When the amorphous polyester has a softening point of 85 ° C. or higher, it becomes easy to suppress cracking and crushing of the toner during long-term use. Further, when the softening point of the amorphous polyester is 105 ° C. or lower, the toner can be melted instantaneously at the time of fixing, so that the adhesiveness of the toner is improved and the fixing tailing is easily improved.

  In order to control the weight average molecular weight, Rw (P) / Mw (P), and softening point of the amorphous polyester within the above ranges, a unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms is used. It is good to contain in said range.

  Further, the area of the amorphous polyester is 80 areas relative to the total area of the amorphous polyester domains in the region from the outline of the cross section of the toner to within 50% of the distance between the outline and the center point of the cross section. % Or more and 100 area% or less is preferable. Furthermore, it is more preferable that it is 90 area% or more and 100 area% or less.

  The ratio of the area of the amorphous polyester domain existing within 50% of the distance between the outline and the center point of the cross section to the total area of the amorphous polyester domain (hereinafter referred to as “50% area”). If the ratio is also 80% by area or more, melting can be instantaneously performed at the time of fixing, so that fixing tailing can be easily suppressed. The fact that the 50% area ratio is 80 area% or more means that the amorphous polyester domain has a distance from the center point of the toner cross section to the distance between the center point of the cross section from the outline of the toner cross section. In other words, it can be said that 20% by area or less of the total area of the amorphous polyester domain is present in the region up to “% boundary line”. In this case, the softening point of the toner can be easily controlled to 110 ° C. or more, cracking and breaking of the toner during long-term use can be suppressed, and fog and development ghost can be easily suppressed.

Further, from the contour of the cross section of the toner, the area of the amorphous polyester domain existing within 25% of the distance between the contour and the center point of the cross section is A,
When 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 is defined as B from the contour of the cross section, A and B are expressed by the following formula (4): It is preferable to satisfy.
A / B ≧ 1.05 (4)
[A / B] (hereinafter also referred to as domain area ratio) is not particularly limited, but is preferably 3.00 or less. Further, it is more preferable that A and B satisfy the relationship of the following formula (1) ′.
3.00 ≧ A / B ≧ 1.20 (Formula (4) ′)
When A and B satisfy the above formula (4), it indicates that the amorphous polyester domains are unevenly distributed on the toner surface. Since the amorphous polyester domains are unevenly distributed on the toner surface, melting can be instantaneously performed at the time of fixing, so that fixing tailing can be easily suppressed.

  In the cross section of the toner, the number average diameter of the amorphous polyester domains 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 is 0.3 μm or more, it is preferable because both the control of the existence state of the domains and the suppression of the burying of the external additive are easily achieved. Further, when the number average diameter of the domains is 3.0 μm or less, the surface area of the interface between the domain and the matrix existing in the toner is increased, so that the adhesion between the toner and the toner medium is easily improved.

  Examples of a method for forming an amorphous polyester domain in the vicinity of the toner surface and controlling the number average diameter of the domain diameters include the following methods. For example, adjustment of acid value and hydroxyl value of amorphous polyester, addition of lipophilic part to molecular chain terminal of amorphous polyester, adjustment of softening point of amorphous polyester and toner, and production conditions of toner particles There is a way to adjust.

  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 1.0 mgKOH / g or more, the 25% area ratio is easily controlled to 30 area% or more. On the other hand, when the acid value of the amorphous polyester is 10.0 mgKOH / g or less, the 25% area ratio can be easily controlled to 70 area% or less.

  The hydroxyl value of the amorphous polyester is preferably 40.0 mgKOH / g or less. More preferably, it is 30 gKOH / g or less. The lower limit is not particularly limited, but is preferably 5 mgKOH / g or more, and more preferably 10 mgKOH / g or more. When the hydroxyl value of the amorphous polyester is 40.0 mgKOH / g or less, it becomes easy to form a domain of the amorphous polyester near the toner surface.

  In order to control the acid value of the amorphous polyester to be 1.0 mgKOH / g or more and 10.0 mgKOH / g or less and the hydroxyl value to 40.0 mgKOH / g or less, the terminal chain of the amorphous polyester is lipophilic. It is preferable to have a site. By having an oleophilic part at the molecular chain terminal of the amorphous polyester, it becomes easy to interact with the vinyl resin, so that the size and position of the domain can be easily controlled.

  In order to have a lipophilic part at the molecular chain terminal of the amorphous polyester, it is preferable to react with a compound having a monovalent or higher functional group capable of reacting with the molecular chain terminal of the amorphous polyester resin.

  The compound having a monovalent or higher functional group is preferably an aliphatic monoalcohol having 10 to 50 carbon atoms and an aliphatic monocarboxylic acid having 11 to 51 carbon atoms. These compounds include dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanoic acid (Lignoceric acid), caprin alcohol, lauryl alcohol, mystyryl alcohol, cetanol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol and the like.

  The binder resin preferably has a site derived from a macromonomer having an unsaturated double bond capable of radical polymerization reaction. As described above, amorphous polyester domains are present in the vicinity of the toner surface to promote melting in the vicinity of the surface layer. If the binder resin has a part derived from the macromonomer, a part of the macromonomer part existing in the vicinity of the surface layer exists so as to be entangled with both the binder resin and the amorphous polyester part. Conceivable. The toner configured as described above is improved in brittleness by improving the elasticity of the toner as the density of the entanglement of the resin chain of the binder resin by the macromonomer site is improved, and the fog and the development ghost are improved. Not only that, the macromonomer part entangled with the amorphous polyester part that melts sharply when the toner passes through the fixing roller acts as a viscosity improver on the toner surface, and increases the adhesive strength between the toner and the toner medium. Improve dramatically. As a result, the present inventors speculate that the fixing tail will be significantly improved.

  The number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the macromonomer is preferably from 4,000 to 8,000, more preferably from 5,000 to 8,000. By adjusting the number average molecular weight (Mn) of the macromonomer to the above range, the compatibility of the binder resin and the amorphous polyester can be further improved.

  Specific examples of the macromonomer include a polymer obtained by polymerizing one or more selected from the group consisting of styrene, styrene derivatives, methacrylic acid esters, acrylic acid esters, acrylonitrile, and methacrylonitrile. And a macromonomer having a vinyl group at the end of the molecular chain. Alternatively, a macromonomer having a polysiloxane skeleton and having a vinyl group at the end of the molecular chain can be used. The macromonomer is a polymer obtained by polymerizing one or more selected from the group consisting of styrene, acrylonitrile, n-butyl acrylate and methyl methacrylate, and has a vinyl group at the end of the molecular chain It is preferable that Such a macromonomer is easy to be compatible with the binder resin and the amorphous polyester. Furthermore, it is a polymer obtained by polymerizing one or more selected from the group consisting of styrene and n-butyl acrylate, and a macromonomer having a vinyl group at the end of the molecular chain is more preferable.

  The addition amount of the macromonomer is preferably 0.01 parts by mass or more and 5.0 parts by mass or less, more preferably 0. 0 parts by mass with respect to 100 parts by mass of the polymerizable monomer capable of generating the binder resin. It is 05 mass parts or more and 3.0 mass parts or less. By adjusting the addition amount within this range, it is easy to become familiar with both the binder resin and the amorphous polyester, and the above-described effects are easily exhibited to the maximum extent.

When the toner is subjected to time-of-flight secondary ion mass spectrometry (TOF-SIMS), when the peak intensity derived from the vinyl resin is S85 and the peak intensity derived from the amorphous polyester is S211, the following formula (3) is satisfied. Is preferred.
0.30 ≦ S211 / S85 ≦ 3.00 (3)

  In the time-of-flight secondary ion mass spectrometry, since information of several nm can be obtained from the toner surface, the constituent material of the outermost layer of the toner can be specified. It is preferable that the amorphous polyester contains a unit derived from bisphenol A as an alcohol component, and S211 is a peak derived from the bisphenol A. 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 an amorphous polyester in the vicinity of the toner surface layer, so that the adhesive strength of the toner can be easily controlled, and the fixing tailing is easily improved. Further, when S211 / S85 is 3.00 or less, embedding of external additives can be suppressed, and toner deterioration due to long-term use can be easily suppressed, so that fog and ghost are improved and transferability is improved. However, it becomes easy to improve the fixing tail. In order to adjust so that the said Formula (3) may be satisfy | filled, the following are mentioned, for example. From the viewpoint of the production method of the toner, there are a method of controlling by a suspension polymerization method which is a preferable production method as described later, and a method of controlling annealing conditions including a temperature holding step and a cooling step after polymerization. From the viewpoint of the material of the toner, a method of controlling the acid value or hydroxyl value of the amorphous polyester can be mentioned.

  Next, the tetrahydrofuran (THF) insoluble content derived from the binder resin of the toner is preferably 3% by mass or more and 50% by mass or less based on the total amount of the binder resin. When the content is 3% by mass or more, an appropriate gel component is present in the binder resin, and the brittleness of the toner is improved, and cracking and crushing of the toner are easily suppressed through long-term use, and fog and development ghost are improved. . When the amount is 50% by mass or less, the amount of the gel component in the binder resin is not excessive, and the adhesive strength of the toner is improved, so that the fixing tailing is improved.

  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. If the weight average particle diameter (D4) is in the above range, good fluidity can be obtained, and it is easy to be frictionally charged uniformly at the regulating portion, so that fog and development ghost are easily improved.

  The average circularity of the toner is preferably 0.950 or more and 1.000 or less. When the average circularity of the toner is 0.950 or more, the shape of the toner becomes a sphere or a shape close to this, and it becomes easy to obtain uniform triboelectric chargeability with excellent fluidity, and it becomes easy to suppress fogging, In addition, transferability is easily improved.

  The glass transition temperature (Tg) of the toner is preferably 40.0 ° C. or higher and 70.0 ° C. or lower. If the glass transition temperature is within the above range, the storage stability and durability of the toner can be improved while maintaining good fixability. The glass transition point (Tg) can be measured using a differential scanning calorimeter (DSC).

  If necessary, the toner particles of the present invention 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 group 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. The amount is 5.0 parts by mass or less. Further, when added outside the toner particles, it is preferably 0.005 parts by mass or more and 1.00 parts by mass or less, more preferably 0.01 parts by mass or more and 0.30 parts by mass or less with respect to 100 parts by mass of the toner. is there.

  The toner particles may contain a release agent for improving the fixing property. The content of the release agent in the toner particles is preferably 1.0% by mass or more and 30.0% by mass or less, and 3.0% by mass or more and 25.0% by mass or less with respect to the binder resin. It is more preferable. When the content of the release agent is 1.0% by mass or more, the releasability from the fixing film is improved, and the fixability is improved. Moreover, if it is 30.0 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 and derivatives thereof such as paraffin wax, microcrystalline wax and petrolactam; 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 derivatives thereof.

  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, hydrogenated 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, and the fixability and fixing tailing are improved, and further, toner cracking and crushing are easily suppressed.

  Further, the melting point defined by the maximum endothermic peak temperature 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, and 65 ° C. or higher and 120 ° C. or lower. The following is more preferable. When the melting point is 60 ° C. or higher, it is easy to suppress toner deterioration during long-term use. When the melting point is 140 ° C. or lower, the low-temperature fixability is hardly lowered.

  The melting point of the release agent is the peak top of the endothermic peak when measured by DSC. Moreover, the measurement of the peak top of the endothermic peak is performed according to ASTM D 3417-99. 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. As a measurement sample, an aluminum pan is used, and an empty pan is set as a control and measured.

  The toner particles contain a colorant.

  As the black colorant, a carbon black, magnetic fine particles, yellow, magenta, and cyan colorants that are toned to black are used.

  Another effective means for reducing the size of the printer is a one-component development system. It is also effective to omit the supply roller for supplying the toner in the cartridge to the toner carrier. As such a one-component developing method in which the supply roller is omitted, a magnetic one-component developing method is preferable, and a magnetic toner using a magnetic material is preferable as a toner colorant. By using such a magnetic toner, it is possible to have high transportability and colorability.

The magnetic fine particles are 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. BET specific surface area by nitrogen adsorption method of the magnetic fine particles is preferably 2~30m ² / g, more preferably 3~28m ² / g. A Mohs hardness of 5 to 7 is preferred. The shape of the magnetic fine particle includes polyhedron, octahedron, hexahedron, spherical shape, needle shape, scale shape, and the like, but those having low anisotropy such as polyhedron, octahedron, hexahedron, and spherical shape increase the image density. Preferred above.

  The magnetic fine particles preferably have a number average particle diameter of 0.10 μm to 0.40 μm. When the number average particle diameter is 0.10 μm or more, the magnetic fine particles are difficult to aggregate, and the uniform dispersibility of the magnetic fine particles in the toner is improved. A number average particle diameter of 0.40 μm or less is preferably used because the coloring power of the toner is improved.

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

  Magnetic fine particles can be produced, for example, by the following method. An aqueous solution containing ferrous hydroxide is prepared by adding an alkali such as sodium hydroxide 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 the magnetic iron oxide particles were formed. Generate.

  Next, an aqueous solution containing about 1 equivalent of ferrous sulfate is added to the slurry-like liquid containing seed crystals based on the amount of alkali added previously. And the pH of the obtained liquid mixture is maintained at 5-10, reaction of ferrous hydroxide is advanced, blowing in air, and a magnetic iron oxide powder is grown by making a seed crystal into a core. At this time, the shape and magnetic characteristics of the magnetic fine particles can be controlled by selecting an arbitrary pH, reaction temperature, and stirring conditions. As the oxidation reaction proceeds, the pH of the liquid shifts to the acidic side, but it is preferable that the pH of the mixed liquid not be less than 5. The magnetic fine particles can be obtained by filtering, washing, and drying the magnetic fine particles thus obtained by a conventional method.

  Further, when the toner particles are produced in an aqueous medium such as a suspension polymerization method, it is preferable that the surface of the magnetic fine particles is hydrophobized because the magnetic fine particles are easily included in the toner. When the surface treatment is carried out by a dry method, the coupling agent treatment is performed on the washed, filtered and dried magnetic fine particles. When the surface 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 but in another aqueous medium. And re-dispersed in the solution and treated with a coupling agent. Specifically, a silane coupling agent or a silane compound is added while sufficiently stirring the redispersion, and the temperature is increased after hydrolysis, or coupling is performed by adjusting the pH of the dispersion to an alkaline region after hydrolysis. Process.

Examples of the coupling agent or silane compound used for the hydrophobic treatment of the magnetic fine particles include a silane coupling agent, a titanium coupling agent, and a silane compound. More preferably used are silane coupling agents or silane compounds, which are represented by the general formula (I).
R _m SiY _n general formula (I)
[Wherein, R represents an alkoxy group, m represents an integer of 1 to 3, Y represents a functional group such as an alkyl group, a vinyl group, an epoxy group, an acrylic group, or a methacryl group, and n represents 1 to 3] Indicates an integer. However, m + n = 4. ]

  Examples of the silane coupling agent or silane compound represented by the general formula (1) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4 epoxy cyclohexyl) ethyltri Methoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltri Methoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxy Silane, diphenyldiethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, trimethylmethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane , Hydroxypropyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, and hydrolysates thereof.

  Those where Y in the above formula (I) is an alkyl group are preferred. Among these, an alkyl group having 3 to 6 carbon atoms is preferable.

  When the silane coupling agent is used, it can be used alone or in combination. When using together, you may process separately with each silane coupling agent, and may process simultaneously.

  The total processing amount of the coupling agent is preferably 0.9 to 3.0 parts by mass with respect to 100 parts by mass of the magnetic substance, depending on the surface area of the magnetic substance and the reactivity of the silane coupling agent. Adjust the amount.

  The content of the magnetic substance in the toner particles is preferably 40 parts by mass or more and 90 parts by mass or less, and more preferably 50 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the binder resin. If it is 40 parts by mass or more, the coloring power is increased, so that the image density is easily improved. On the other hand, if it is 90 parts by mass or less, fixing tailing can be easily suppressed. The content of the magnetic substance in the toner particles can be measured using a thermal analyzer [TGA7] manufactured by PerkinElmer. The measurement method is as follows.

  In a nitrogen atmosphere, the toner is heated from room temperature to 900 ° C. at a temperature rising rate of 25 ° C./min. The weight loss mass% between 100 ° C. and 750 ° C. is the amount of the binder resin, and the remaining mass is approximately the amount of the magnetic material.

  Examples of the yellow colorant include compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155, 168, 180, 185, 214.

  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. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. And CI Pigment Bio Red 19.

  Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant is selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner particles. The added amount of the colorant is used by adding 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin.

  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, 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 dispersed or dissolved by 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. 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.

  In order to form amorphous polyester domains near the toner surface and to control the number average diameter of the amorphous polyester domains, the toner particles are used in an aqueous medium such as a solution suspension method or a suspension polymerization method. It is preferred to produce toner particles. Among these, it is more preferable to use a suspension polymerization method.

  In the suspension polymerization method, a polymerizable monomer capable of producing 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. A polymerizable monomer composition is obtained by dissolving or dispersing with a disperser. Examples of the disperser include a homogenizer, a ball mill, and an ultrasonic disperser. Next, the polymerizable monomer composition is suspended in an aqueous medium containing a dispersion stabilizer 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. Then, 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 obtained toner particles are almost spherical in shape, so the fluidity at the regulating part is easy to improve, and uniform frictional charging is easy, which suppresses fogging and improves image quality. It becomes easy.

  The following are mentioned as a polymerizable monomer.

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 above-mentioned polymerizable monomers, styrene monomers, acrylate monomers, and methacrylate monomers can be preferably exemplified.

  The polymerizable monomer composition preferably contains a polar resin. In the suspension polymerization method, toner particles are produced in an aqueous medium, and therefore by adding a polar resin, the surface of the toner particles can have a polar resin, which can easily improve the chargeability and suppress fogging. Cheap.

As the polar resin, for example,
Homopolymers of styrene and substituted products thereof such as polystyrene and polyvinyltoluene;
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, styrene-polyester copolymer, polyacrylate-polyester copolymer, polymethacrylate-polyester copolymer, 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 carboxyl group, a hydroxyl group, a sulfonic acid group, a glycidyl group, a nitrile group, into 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 Peroxide-based polymerization initiators such as peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, tert-butylperoxy 2-ethylhexanoate, and t-butylperoxypivalate are listed.

  When the toner used in the present invention is produced by a polymerization method, a crosslinking agent may be added. A preferable addition amount is 0.01 parts by mass or more and 5.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Or less.

  As the crosslinking 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; divinylaniline and divinyl ether , Divinyl sulfide, divinyl sulfone and other divinyl compounds; compounds having three or more vinyl groups. These are used alone or as a mixture of two or more.

  As the dispersion stabilizer, various surfactants, organic dispersants, or inorganic dispersants can be used. Among these, inorganic dispersants can be preferably used because they do not easily generate ultrafine powder and have obtained dispersion stability due to their steric hindrance. Examples of inorganic dispersants include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, hydroxyapatite and other polyvalent metal phosphates, carbonates such as calcium carbonate and magnesium carbonate, calcium metasilicate, calcium sulfate, and barium sulfate. And inorganic salts such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

  The amount of the inorganic dispersant added 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. A dispersion stabilizer may be used independently and may use multiple types together. Further, a surfactant may be used in combination.

  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, it is preferable to have the following steps.

  The polymerizable monomer is polymerized to form colored particles, and the dispersion in which the colored particles are dispersed in an aqueous medium is heated to a temperature near the softening point of the amorphous polyester, specifically about 100 ° C. The temperature is preferably maintained for 30 minutes or more. The vicinity of the softening point of the amorphous polyester is, for example, a range of ± 10 ° C. of the softening point of the amorphous polyester. The holding time is more preferably 120 minutes or more, and further preferably 180 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 5.0 ° C./min or more, more preferably at a cooling rate of 20.0 ° C./min or less, to a glass transition temperature (Tg) or less of the colored particles, It is more preferable to cool at a cooling rate of 100.0 ° C./min or more. The upper limit of the cooling rate is about 500.0 ° C./min or less from the viewpoint of production efficiency. Moreover, after cooling at the above cooling temperature, 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. The glass transition temperature (Tg) or lower refers to a glass transition temperature of about −5 ° C. from the glass transition temperature (Tg), and the glass transition temperature of the colored particles is the same as the glass transition temperature of the toner particles obtained in this step. It is almost the same.

  Toner particles are obtained by filtering, washing, and drying the colored particles obtained through the above steps. The toner particles can be obtained by mixing the toner particles with inorganic fine particles as necessary and attaching them to the surface of the toner particles. 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.

  When inorganic fine particles are used for improving the fluidity of the toner and making the charge uniform, the number average particle size of the primary particles of the inorganic fine particles is preferably 4 nm or more and 80 nm or less, more preferably 6 nm or more and 40 nm or less. Furthermore, it is more preferable to use inorganic fine particles having a primary particle number average particle size of 80 nm to 200 nm in combination. By doing so, the fluidity of the toner can be ensured through long-term use, uniform and stable triboelectric charging performance can be obtained, and fog can be easily improved.

  The method for measuring the number average particle size of the primary particles of the inorganic fine particles is performed using a photograph of the toner magnified by a scanning electron microscope. The content of the inorganic fine particles is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the toner particles. The content of inorganic fine particles can be quantified using a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

  Examples of the inorganic fine particles include fine particles such as silica, titanium oxide, and alumina. Examples of the silica fine particles include so-called dry silica produced by vapor phase oxidation of silicon halides or dry silica called fumed silica, and so-called wet silica produced from water glass.

Dry silica is preferred because there are few silanol groups on the surface and inside the silica fine particles, and there are few production residues such as Na ₂ O and SO ₃ ²⁻ . In dry silica, it is also possible to obtain fine particles of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. , Including them.

  The inorganic fine particles are preferably hydrophobized from the viewpoints of adjusting the charge amount of the toner and improving environmental stability. Examples of the treating agent used for the hydrophobizing treatment include silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, and silane coupling agents. In addition, treatment agents such as other organosilicon compounds and organotitanium compounds are listed. These can be used alone or in combination of two or more.

  Among the above-mentioned treatment agents, those treated with silicone oil are preferred, and those treated with silicone oil are more preferred at the same time as or after hydrophobizing inorganic fine particles with a silane compound. As the treatment method, as a first stage reaction, a silylation reaction is performed with a silane compound, silanol groups are eliminated by chemical bonding, and then a hydrophobic thin film is formed on the surface with silicone oil as a second stage reaction. be able to.

Silicone oil, preferably a viscosity at 25 ° C. is 10 mm ² / s or more 200,000 mm ² / s or less things, 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.

  As a method for treating inorganic fine particles with silicone oil, there are a method of directly mixing inorganic fine particles treated with a silane compound and silicone oil using a mixer such as a Henschel mixer, and a method of spraying silicone oil on inorganic fine particles. Can be mentioned. Or, 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 to 40 parts by mass, more preferably 3 to 35 parts by mass with respect to 100 parts by mass of the inorganic fine particles.

Of hydrophobized inorganic fine particles, specific surface area measured by the BET method by nitrogen adsorption is preferably 20~350m ² / g, more preferably 25~300m ² / g. The specific surface area is calculated using the BET multipoint method by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics Co., Ltd.) according to the BET method.

  In addition to the inorganic fine particles, a small amount of other additives may be used. For example, 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; fluidity imparting such as titanium oxide particles and aluminum oxide particles Agents; anti-caking agents; organic fine particles of opposite polarity and inorganic fine particles. These additives can also be used after being hydrophobized.

  The developing device will be described in detail with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view illustrating an example of a developing device. FIG. 2 is a schematic cross-sectional view showing an example of an image forming apparatus in which a developing device is incorporated. In FIG. 1 or 2, the electrostatic latent image carrier 45, which is an image carrier, 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. A toner supply member 48 is in contact with the toner carrier 47, 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 fixing device 51, a pickup roller 52, and the like are provided. 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 to the fixing device 51 and fixed on the transfer material (paper) 53.

  In the charging process of 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 has a predetermined potential. It is preferable to use a contact charging method in which the battery is charged. By performing contact charging in this manner, stable and uniform charging can be performed, and generation of ozone can be reduced. It is more preferable to use a charging roller that rotates in the same direction as the electrostatic latent image carrier in order to maintain uniform contact with the electrostatic latent image carrier and perform uniform charging.

  In the transfer process of the image forming apparatus, a contact transfer process is preferable. The contact transfer process is to electrostatically transfer the toner image onto the transfer material while the electrostatic latent image carrier is in contact with the transfer roller to which a voltage having a polarity opposite to that of the toner is applied via the transfer material.

  Further, it is preferable that the thickness of the toner layer on the toner carrying member is regulated by the toner regulating member 55 coming into contact with the toner carrying member 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.

  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. As the waveform of the alternating electric field, a sine wave, a rectangular wave, a triangular wave, or the like can be used as appropriate. Further, it may be a pulse wave formed by periodically turning on / off a DC power source. As described above, a bias whose voltage value periodically changes can be used as the waveform of the alternating electric field.

  Further, in the case of using a method of conveying toner by magnetism without using a toner supply member, a magnet is arranged inside the toner carrier (reference numeral 59 in FIG. 3). In this case, the toner carrier preferably has a fixed magnet having multiple poles inside, and preferably has 3 to 10 magnetic poles.

  Hereinafter, it describes regarding the measuring method of each physical property which concerns on this invention.

<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 (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 magnified 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 particles was observed using EDX. Perform element 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 specifying the amorphous polyester domain, binarization is performed. Thereafter, the ratio of the domain area of the amorphous polyester existing within 25% of the distance between the outline and the center point of the cross section from the outline of the cross section of the toner to the total area of the amorphous polyester domains existing in the toner cross section ( Area%). 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.

<Measurement method of SEC-MALLS>
After 0.03 g of toner or amorphous polyester is dispersed and dissolved in 10 ml of orthodichlorobenzene, it is shaken with a shaker at 135 ° C. for 24 hours, filtered through a 0.2 μm filter, and the filtrate is used as a sample.

[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) × 2
Column temperature: 135 ° C
Mobile phase solvent: orthodichlorobenzene Mobile phase flow rate: 1.0 ml / min.
Sample concentration: About 0.3% by mass
Injection volume: 300 μl
Detector 1: Multi-angle light scattering detector Wyatt DAWN EOS
Detector 2: Differential refractive index detector Shodex RI-71

[Measurement theory]
(LS) = (dn / dc) ² × C × Mw × KLS (1)
(LS); Measurement voltage value of the detector (v)
(Dn / dc): Increment of refractive index per 1 g of sample (ml / g)
C: Concentration (g / ml)
K _LS ; Coefficient of measurement voltage and scattering intensity (reduction Rayleigh ratio) (equipment constant)
(Dn / dc) was set to 0.068 ml / g from the literature value of polystyrene.

In SEC-MALLS, the molecular size is separated by the molecular sieve of the SEC column, and Mw (absolute molecular weight) and C (concentration) are changed and eluted, so it is necessary to separately measure the concentration detector in combination with MALLS. The signal intensity is converted into a concentration C to determine the molecular weight Mw. In the present invention, a differential refractive index detector (RI) is used as a concentration detector, and the signal intensity (RI) of the RI detector is converted into a concentration C and used.
(RI) = (dn / dc) × C × KRI (2)
KRI: Coefficient of measurement voltage and refractive index (RI constant, calibrated with polystyrene standard)
The molecular size (radius of inertia) was calculated by Debye Plot.

<Method for measuring softening point of toner and amorphous polyester>
The softening point of the toner and the 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 1/2 method (a schematic diagram of the flow curve is shown in FIG. 4).

  The measurement sample was about 1.0 g of toner or amorphous polyester in an environment of 25 ° C. using a tablet molding compressor (for example, NT-100H, manufactured by NP System Co., Ltd.) at about 10 MPa, 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 determined based on the precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube. Using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for setting and analyzing the measurement data, the measurement data is measured with 25,000 effective channels. Analyze and calculate.

  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 aqueous solution is put in a glass 250 ml round bottom beaker for exclusive use with the ultisizer 3 and 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 about 0.3 ml of a diluted solution obtained by diluting “Contaminone N” with ion-exchanged water 3 times as a dispersant is added thereto. Contaminone N is a 10% by weight aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) of a neutral detergent for pH 7 precision measuring instrument cleaning comprising a nonionic surfactant, an anionic surfactant and an organic builder.

  (3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic dispersion device “Ultrasonic Disposition System Tetora 150” (manufactured by Nikka Ki Bios Co., Ltd.) having an electrical output of 120 W. A fixed amount of ion-exchanged water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.

  (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. 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 the 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) aqueous electrolyte 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 average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Measuring method of average circularity of toner>
The average circularity 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 are removed in advance is put 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 the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and 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 added, 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 2000 toners are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the equivalent circle diameter of 1.977 μm or more and less than 39.54 μm, and the average circularity of the toner 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.

  In the measurement, a flow type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, is used. The measurement is performed under the measurement and analysis conditions when the calibration certificate is received, except that the analysis particle diameter is limited to a circle equivalent diameter of 1.977 μm or more and less than 39.54 μm.

<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 vol%), 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 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide 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 2.0 g of the crushed amorphous polyester sample is precisely weighed into 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 a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<Measuring method of hydroxyl value of amorphous polyester>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl 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 25 g of special grade acetic anhydride is placed in a 100 ml volumetric flask, pyridine is added to make a total volume of 100 ml, and shaken sufficiently to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.

  Dissolve 1.0 g of phenolphthalein in 90 ml of ethyl alcohol (95 vol%) and add ion exchange water to make 100 ml to obtain a phenolphthalein solution.

  Dissolve 35 g of special grade potassium hydroxide in 20 ml of water and add ethyl alcohol (95 vol%) to make 1 liter. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.5 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.5 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 1.0 g of a crushed amorphous polyester sample is precisely weighed into a 200 ml round bottom flask, and 5.0 ml of the acetylating reagent is accurately added to the sample using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.

  A small funnel is placed on the mouth of the flask, and the bottom of the flask is immersed in a glycerin bath at about 97 ° C. and heated. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole.

  After 1 hour, the flask is removed from the glycerin bath and allowed to cool. After standing to cool, 1 ml of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further complete hydrolysis. After cooling, wash the funnel and flask walls with 5 ml of ethyl alcohol. Add several drops of the phenolphthalein solution as an indicator and titrate with 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 similar to the above operation is performed except that a sample of amorphous polyester is not used.
(3) Substituting the obtained results into the following formula to calculate the hydroxyl value.
A = [{(BC) × 28.05 × f} / S] + D
Here, A: hydroxyl value (mg KOH / g), B: addition amount (ml) of potassium hydroxide solution in blank test, C: addition amount (ml) of potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g), D: acid value of amorphous polyester (mgKOH / 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. It was used. Analysis conditions were as follows.
Sample preparation: Toner particles were adhered to an indium sheet.
Sample pretreatment: None Primary ion: Au +
Acceleration voltage: 30 kV
Charge neutralization mode: On
Measurement mode: Negative
Raster: 100 μm
Calculation of peak intensity derived from vinyl resin (S85): In accordance with ULVAC-PHI standard software (Win CAD), the total count number of mass numbers 84.5 to 85.5 was defined as peak intensity (S85).

  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 was defined as peak intensity (S211).

  Calculation of intensity ratio (S211 / S85): Using S85 and S211 calculated as described above, the intensity ratio (S211 / S85) was calculated.

  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.

<Preparation of Toner Carrier 1>
(Preparation of substrate)
As a substrate, a SUS304 core metal having a diameter of 6 mm is coated with a primer (trade name, DY35-051; manufactured by Toray Dow Corning) and baked.

(Production of elastic roller)
The substrate is placed in a mold, and an addition type silicone rubber composition in which the following materials are mixed is injected into a cavity formed in the mold.
・ Liquid silicone rubber material (trade name, SE6724A / B; manufactured by Toray Dow Corning)
100 parts carbon black (trade name, Toka Black # 4300; manufactured by Tokai Carbon Co., Ltd.)
15 parts / silica particles as heat resistance imparting agent 0.2 parts / platinum catalyst 0.1 part Subsequently, the mold is heated to cure and cure the silicone rubber at a temperature of 150 ° C. for 15 minutes. After the base body 1 having the silicone rubber layer cured on the peripheral surface is removed from the mold, the base body 1 is 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 is produced.

(Preparation of surface layer 1)
(Synthesis of isocyanate group-terminated prepolymer 1)
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 g is gradually added dropwise while maintaining the temperature in the reaction vessel at 65 ° C. After completion of dropping, the reaction is carried out at a temperature of 65 ° C. for 2 hours. The obtained reaction mixture is cooled to room temperature to obtain an isocyanate group-terminated prepolymer 1 having an isocyanate group content of 3.8% by weight.

(Synthesis of amino compound 1)
While stirring, 100.0 parts (1.67 mol) of ethylenediamine and 100 parts of pure water are 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 control device. Next, 425.3 parts (7.35 mol) of propylene oxide is gradually added dropwise over 30 minutes while maintaining the reaction temperature at 40 ° C. or lower. The reaction is further stirred for 1 hour to obtain a reaction mixture. The obtained reaction mixture is heated under reduced pressure to distill off water, and 426 g of amino compound 1 is obtained.

<Preparation of Toner Carrier 1>
-Isocyanate-terminated prepolymer 1 617.9 parts-Amino compound 1 34.2 parts-Carbon black (trade name, MA230; manufactured by Mitsubishi Chemical Corporation) 117.4 parts-Urethane resin fine particles (trade name, Art Pearl C-400 ; Negami Kogyo Co., Ltd.) 130.4 parts are stirred and mixed.

Next, methyl ethyl ketone (hereinafter also referred to as “MEK”) is added so that the total solid content is 30% by mass, and then mixed in a sand mill. Next, the viscosity is further adjusted to 10 cps or more and 13 cps or less with MEK to prepare a coating material for forming a surface layer.
C The elastic roller 1 produced first is dipped 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 surface layer having a thickness of 15 μm is provided on the outer periphery of the elastic layer by heat treatment at a temperature of 150 ° C. for 1 hour, whereby the toner carrier 1 is manufactured.

<Example of production of long-chain monomer 1>
1200 g of an aliphatic hydrocarbon having a peak value of 35 carbon atoms was placed in a glass cylindrical reaction vessel, and 38.5 g of boric acid was added at a temperature of 140 ° C. Immediately after that, a mixed gas of 50 volume% air and 50 volume% nitrogen with an oxygen concentration of about 10 volume% was blown at a rate of 20 liters per minute, reacted at 200 ° C. for 3.0 hours, and then hot water was added to the reaction solution. Then, hydrolysis was performed at 95 ° C. for 2 hours, and after standing, an upper layer reaction product was taken. 20 parts by mass of the modified product was added to 100 parts by mass of n-hexane to obtain a long-chain monomer 1 in which unmodified components were dissolved and removed. The obtained long-chain monomer 1 was an alcohol component having a modification rate of 94% and a hydroxyl value of 92.4 mgKOH / g.

<Production Example of Amorphous Polyester APES1>
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, carboxylic acid component and alcohol component are adjusted as shown in Table 1 as raw material monomers, and then dibutyltin is used as a catalyst as a monomer. 1.5 parts were added to 100 parts in total. Next, the temperature is rapidly raised to 180 ° C. at normal pressure in a nitrogen atmosphere, and then polycondensation is performed by distilling off water while heating from 180 ° C. to 210 ° C. at a rate of 10 ° C./hour. 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.

<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 25 g of acid and 2 g of esterification catalyst (tin octylate) were added, subjected to condensation polymerization reaction at 230 ° C. for 8 hours, further reacted at 8 kPa for 1 hour, cooled to 160 ° C., 6 g of acrylic acid, 70 g of styrene, n- A mixture of 31 g of butyl acrylate and 20 g of a polymerization initiator (di-t-butyl peroxide) was added dropwise over 1 hour using a dropping funnel, and after the addition, the addition polymerization reaction was continued for 1 hour while maintaining at 160 ° C. The temperature is raised to 200 ° C. and held at 10 kPa for 1 hour, and then unreacted acrylic acid, By removing the emissions and butyl acrylate, to give a non-crystalline polyester 16 (APES16) is a composite resin formed by bonding a vinyl polymer segment and a polyester polymerized segment.

  The numerical value of the raw material monomer indicates mol%.

<Preparation of reactive resin macromonomer 1>
A macromonomer AS-6 manufactured by Toa Gosei Co., Ltd. is prepared as the macromonomer 1. The terminal unsaturated double bond group of AS-6 is a methacryloyl group, and the main chain skeleton is a styrene skeleton. In addition, the number average molecular weight (Mn) of AS-6 is 6000.

<Preparation of reactive resin macromonomers 2-7>
A macromonomer 1 having a number average molecular weight (Mn) and a main chain skeleton changed as shown in Table 2 is prepared.

  In Table 2, “MMA” is a methyl methacrylate skeleton.

<Production example of treated magnetic material>
In a ferrous sulfate aqueous solution, 1.0 to 1.1 equivalent of NaOH 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, On the other hand, SiO ₂ in an amount of 0.50% by mass in terms of silicon element is mixed to prepare an aqueous solution containing ferrous hydroxide. The pH of the aqueous solution is set to 8.0, and an oxidation reaction is performed at 85 ° C. while blowing air to prepare a slurry liquid having seed crystals.

  Subsequently, ferrous sulfate aqueous solution is added to this slurry liquid so that it may become 0.9-1.2 equivalent with respect to the original amount of alkalis (Na component of NaOH), the slurry liquid is maintained at pH 7.6, and air is supplied. The oxidation reaction is promoted while blowing to obtain a slurry liquid containing magnetic iron oxide. After this slurry liquid is filtered and washed, the water-containing slurry is once taken out. At this time, a small amount of water-containing slurry is collected and the water content is measured. Next, this water-containing slurry is put into another aqueous medium without being dried, stirred and re-dispersed with a pin mill while circulating the slurry, and the pH of the re-dispersed liquid is adjusted to about 4.8. Then, 1.6 parts of n-hexyltrimethoxysilane coupling agent is added to 100 parts of magnetic iron oxide with stirring (the amount of magnetic iron oxide is calculated as a value obtained by subtracting the water content from the water-containing slurry). Disassemble. Thereafter, the surface treatment is carried out by sufficiently stirring and adjusting the pH of the dispersion to 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 at 90 ° C. for 30 minutes, and the resulting particles are crushed to obtain a treated magnetic material. The volume average particle diameter of this treated magnetic material was 0.21 μm.

<Production Example of Toner Particle 1>
After adding 450 parts of 0.1 mol / L-Na ₃ PO ₄ aqueous solution to 720 parts of ion-exchanged water and heating to 60 ° C., 67.7 parts of 1.0 mol / L-CaCl ₂ aqueous solution was added. An aqueous medium containing a dispersion stabilizer was obtained.
-Styrene 75.0 parts-N-butyl acrylate 25.0 parts-Amorphous polyester APES1 10.0 parts-Divinylbenzene 0.4 parts-Iron complex of monoazo dye (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 5 parts, treated magnetic material 65.0 parts, macromonomer 1 0.5 part The above formulation was uniformly dispersed and mixed using an attritor (manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain a monomer composition. This monomer composition was heated to 63 ° C., and 15.0 parts of paraffin wax (melting point: 78 ° C.) was added and mixed therein to be dissolved. Thereafter, 5.0 parts of a polymerization initiator tert-butyl peroxypivalate was dissolved.

The aqueous medium of the above monomer composition was charged in, 60 ° C., T. under N ₂ atmosphere K. The mixture was stirred at 12000 rpm for 10 minutes with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) and granulated. Then, it was made to react at 70 degreeC for 4 hours, stirring with a paddle stirring blade. After completion of the reaction, it is confirmed that colored particles are dispersed in the aqueous medium obtained here, and calcium phosphate is adhered to the surface of the colored particles as an inorganic dispersant. At this time, hydrochloric acid was added to the aqueous medium to remove calcium phosphate by washing, followed by filtration and drying to analyze the colored particles. As a result, the glass transition temperature Tg of the binder resin was 54 ° 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. Table 3 shows the production conditions of the toner particles 1.

<Production Example of Toner Particles 2-33>
In the production example of the toner particles 1, the toner particles 2 to 33 are produced in the same manner except that the amorphous polyester, the colorant, and the production conditions are changed as shown in Table 3. Table 3 shows the production conditions of each toner particle.

<Production Example of Toner Particles 34>
<< Preparation of each dispersion liquid >>
(Resin particle dispersion (1))
-Styrene: 325 parts-n-butyl acrylate: 100 parts-Acrylic acid (manufactured by Rhodia Nikka Co., Ltd.): 13 parts-1,10-decanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.): 1.5 parts-Dodecanethiol ( Wako Pure Chemical Industries, Ltd.): 3.0 parts The above components are mixed in advance and dissolved to prepare a solution, and 9 parts of an anionic surfactant (Dowfax A211 manufactured by Dow Chemical Co., Ltd.) is added to ion-exchanged water 580. The surfactant solution dissolved in the part was placed in a flask. Next, 400 parts of the above-mentioned premixed solution was added, dispersed and emulsified, and slowly stirred and mixed for 10 minutes, and then 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 point was 51.5 ° C., and the weight average molecular weight Mw. Was 32,000.

(Resin particle dispersion (2))
The amorphous polyester (APES18) 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 of 79% by mass of ion-exchanged water, 1% by mass (as an active ingredient) of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK), and 20% by mass of an amorphous polyester resin 18 Mix with. Thereafter, the mixture was adjusted to pH 8.5 with ammonia, the Cavitron was operated under the conditions of a rotor rotation speed of 60 Hz, a pressure of 5 kg / cm ² , and heating by a heat exchanger at 140 ° C. A resin fine particle dispersion (2) having a diameter of 290 nm was obtained.

(Colorant dispersion)
・ 20 parts of carbon black ・ 2 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) ・ 78 parts of ion-exchanged water The above components were used at 3000 rpm using a homogenizer (IKA Corporation, Ultra Turrax T50). The pigment was blended in water for 2 minutes, further dispersed at 5000 rpm for 10 minutes, and then stirred for a whole day and night with a normal stirrer to degas. Thereafter, using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006), dispersion was performed at a pressure of 240 MPa for about 1 hour to obtain a colorant dispersion (1). Further, the pH of the dispersion was adjusted to 6.5.

(Release agent dispersion)
・ 45 parts of hydrocarbon wax
(Fischer-Tropsch wax, maximum endothermic peak; 78 ° C., Mw; 750)
・ Cationic surfactant (Neogen RK, Daiichi Kogyo Seiyaku) 5 parts ・ Ion-exchanged water 200 parts The above components were heated to 95 ° C. and sufficiently dispersed with a homogenizer (manufactured by IKA, Ultra Tarax T50). Dispersion treatment was performed 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%.

(Example of toner particle production)
・ Ion-exchanged water 400 parts ・ Resin particle dispersion (1) 620 parts (resin particle concentration: 42%)
Resin particle dispersion (2) 279 parts (resin particle concentration: 20%)
Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, active ingredient amount: 60%) 1.5 parts (0.9 parts as active ingredient)

  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 with a homogenizer (manufactured by IKA Japan: Ultra Tarax T50) at 3000 rpm. Half of the mixed solution was added. Thereafter, the dispersion rotational speed was set to 5000 rpm, the remaining ½ was added over 1 minute, and the dispersion rotational speed was set to 6500 rpm to disperse 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. Hold for 15 minutes. Thereafter, 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 reached 7.8 μm, a 5% sodium hydroxide aqueous solution was added. Used to bring the pH to 9.0. 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. The mixture was added and stirred with a three-one motor. When the particles were sufficiently loosened, the pH was adjusted to 3.8 with a 1.0% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 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 toner particles 34.

In Table 3, A, B and C are as follows.
A: After completion of the polymerization reaction, the holding time after raising the temperature of the aqueous medium in which the colored particles are dispersed to 100 ° C. [minutes]
B: Cooling rate [° C./min] to a temperature (50 ° C.) below the glass transition temperature of the colored particles
C: Holding time [minutes] at a temperature (50 ° C.) or lower of the glass transition temperature of the colored particles

<Production Example of Toner 1>
100 parts of toner particles 1 and 0.3 part of sol-gel silica fine particles having a primary particle size of 115 nm are mixed using a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.). Thereafter, 0.9 parts of hydrophobic silica fine particles having a BET specific surface area value of 120 m ² / g (the silica fine particles having a primary particle diameter of 12 nm treated with hexamethyldisilazane and then treated with silicone oil) were added. In the same manner, the toner 1 was prepared by mixing using a Mitsui Henschel mixer. Table 4 shows the physical properties of Toner 1.

<Production Example of Toners 2 to 27>
Toners 1 to 27 were obtained in the same manner as in Production Example of Toner 1 except that the toner particles were changed as shown in Table 4. Table 4 shows the physical properties of Toners 2 to 27.

<Production Example of Toners 28 to 34>
In the production example of the toner 1, toners 28 to 33 were obtained in the same manner except that the toner particles were changed as shown in Table 4. Table 4 shows the physical properties of Toners 28 to 34. In the toners 28 and 29, amorphous polyester domains did not exist, and a shell of amorphous polyester was formed.

In Table 4, “D4” is the weight average particle diameter of the toner,
“Tg” is the glass transition temperature of the toner,
“25% area ratio” is the 25% area ratio of the amorphous polyester domain,
“50% area ratio” means 50% area ratio of the amorphous polyester domain,
“THF insoluble matter” means the THF insoluble matter of the toner,
“Domain diameter” indicates the number average diameter of domains of amorphous polyester.

<Image forming apparatus>
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. 1, and the voltage to the toner supply member is changed. Turn off application. The contact pressure was adjusted so that the width of the contact portion between the toner carrier and the electrostatic latent image carrier was 1.0 mm. Further, as shown in FIG. 2, the cleaning blade was removed, and the process speed was modified to 35 ppm. By doing so, the area of the contact portion between the toner carrying member and the electrostatic latent image carrying member is reduced, and the process speed is increased, whereby strict image forming conditions are obtained. Next, the fixing device was once removed from the image forming apparatus and remodeled so that an unfixed image could be output.

The developing device modified as described above was charged with 100 g of toner 1 and subjected to an image formation test in a low temperature and low humidity environment (15.0 ° C./10% RH), and evaluation based on the following evaluation method was performed. As an image forming test, 4000 horizontal line images with a printing rate of 1% are printed on two intermittent sheets. The evaluation paper used for the image formation test is a business 4200 (manufactured by Xerox) having a basis weight of 75 g / m ² .

  The evaluation methods and judgment criteria for each evaluation performed in the examples and comparative examples of the present invention will be described below.

<Fog on photoreceptor drum after solid black image output>
After printing 2000 sheets of the image formation test and after printing 4000 sheets, a solid black image was output, and the non-image area (white background portion) on the photosensitive drum after the transfer of the solid black image was removed by taping with a Mylar tape. . Each difference was calculated by subtracting the reflectance of the mylar tape only on the unused paper from the reflectance of the peeled mylar tape on the unused paper. In the present invention, ranks A, B, and C were set to levels at which the effects of the present invention were obtained.

The reflectivity was measured using a REFECTMETER MODEL TC-6DS manufactured by Tokyo Denshoku. A green filter was used as the filter.
A: Reflectance difference is less than 5.0% B: Reflectance difference is 5.0% or more and less than 10.0% C: Reflectance difference is 10.0% or more and less than 20.0% D : Reflectance difference is 20.0% or more

<Development ghost>
After printing 4000 sheets of the image formation test, a plurality of solid black images of 10 mm × 10 mm were formed on the front half of the transfer paper, and a halftone image of 2 dots and 3 spaces was formed on the back half. It was visually determined how much trace of the solid black image appeared on the halftone image. In the present invention, ranks A, B, and C were set to levels at which the effects of the present invention were obtained.
A: No development ghost occurred.
B: Development ghost is very slight.
C: Development ghost is slightly generated.
D: Development ghost is remarkably generated.

<Transferability>
After printing 4000 sheets of the image formation test, the image forming apparatus and the developing apparatus are moved to a room temperature and high humidity environment (23.0 ° C./85% RH) and allowed to stand overnight. Subsequently, the transfer residual toner on the electrophotographic photosensitive drum when the solid black image was formed was removed by taping with a transparent polyester adhesive tape (polyester tape No. 5511, manufactured by Nichiban Co., Ltd.). Each density difference was calculated by subtracting the density of the adhesive tape only on the paper from the density of the adhesive tape peeled off on the paper. The concentration was measured using a REFECTMETER MODEL TC-6DS manufactured by Tokyo Denshoku. A green filter was used as the filter. In the present invention, ranks A, B, and C were set to levels at which the effects of the present invention were obtained.
A: Density difference is less than 0.05
B: Density difference is 0.05 or more and less than 0.10 C: Density difference is 0.10 or more and less than 0.15 D: Density difference is 0.15 or more.

<Fixing trail>
After printing 4000 sheets of the image formation test, the image forming apparatus and the developing apparatus are moved to a room temperature and high humidity environment (23.0 ° C./85% RH) and allowed to stand overnight. Subsequently, when 50 horizontal line images having a printing rate of 1% were passed, the frequency and degree of fixing tailing were visually evaluated. Two types of evaluation paper were prepared, Canon color laser (80 g / m ² ) was prepared as smooth paper, and FOX RIVER BOND paper (75 g / m ² ) was prepared as rough paper. The criteria for evaluating the fixing tail on each evaluation paper are shown below. In the present invention, ranks A, B, and C were set to levels at which the effects of the present invention were obtained.
A: Fixation tailing has not occurred.
B: The occurrence of fixing tailing is 1 to 5 sheets.
C: The occurrence of fixing tailing is 6 or more and 10 or less.
D: 11 or more fixing tails are generated.

<Examples 2 to 27>
The toner was changed according to Table 5, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.

<Comparative Examples 1-7>
The toner was changed according to Table 5, and each evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.

45 Electrostatic latent image carrier (photoconductor)
46 Charging roller 47 Toner carrier 48 Toner supply member 49 Developer 50 Transfer member (transfer roller)
51 Fixing Unit 52 Pickup Roller 53 Transfer Material (Paper)
54 Laser generator 55 Toner regulating member 56 Metal plate 57 Toner 58 Stirring member

Claims (13)

A toner having toner particles containing a binder resin, a colorant, and amorphous polyester,
The binder resin contains a vinyl resin,
The softening point of the toner is 110 ° C. or higher and 140 ° C. or lower;
In the cross section of the toner observed with a transmission electron microscope,
The vinyl resin forms a matrix and the amorphous polyester forms a domain;
The area of the amorphous polyester is 30% by area or more based on the total area of the domains of the amorphous polyester in the region from the outline of the cross section to within 25% of the distance between the outline and the center point of the cross section. 70 area% or less exists,
In the weight average molecular weight (Mw) and average radius of rotation (Rw) of the toner's orthodichlorobenzene solubles measured using size exclusion chromatography-multi-angle light scattering (SEC-MALLS),
The Mw is 100,000 or more and 500,000 or less,
The Mw and the Rw are represented by the formula (1)
1.0 × 10 ⁻⁴ ≦ Rw / Mw ≦ 5.0 × 10 ⁻⁴ (1)
A toner characterized by satisfying In the weight average molecular weight (Mw (P)) and average turning radius (Rw (P)) measured using SEC-MALLS of the ortho-dichlorobenzene soluble part of the amorphous polyester,
Mw (P) of the amorphous polyester is 3500 or more and 20000 or less,
Mw (P) and Rw (P) of the amorphous polyester are represented by the formula (2)
1.5 × 10 ⁻³ ≦ Rw (P) / Mw (P) ≦ 7.0 × 10 ⁻³ (2)
The toner according to claim 1, wherein:   The toner according to claim 1, wherein the binder resin has a part derived from a macromonomer having an unsaturated double bond capable of radical polymerization reaction.   The toner according to claim 1, wherein the 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% by mass or more and 30.0% by mass or less with respect to the binder resin. The amorphous polyester has a unit derived from an alcohol component and a unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms,
The unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms is contained in an amount of 10 to 50 mol% with respect to units derived from all carboxylic acid components in the amorphous polyester. The toner according to any one of the above.   The toner according to any one of claims 1 to 6, wherein a tetrahydrofuran (THF) insoluble content derived from the binder resin of the toner is 3% by mass or more and 50% by mass or less based on the total amount of the binder resin. The toner according to claim 1, wherein the toner satisfies the following formula (3).
0.30 ≦ S211 / S85 ≦ 3.00 (3)
(Where
S85 represents the peak intensity derived from the vinyl resin obtained by time-of-flight secondary ion mass spectrometry (TOF-SIMS) of the toner,
S211 indicates the peak intensity derived from the amorphous polyester obtained by TOF-SIMS of the toner. )   The toner according to claim 1, wherein the amorphous polyester has an acid value of 1.0 mgKOH / g or more and 10.0 mgKOH / g or less. In the cross section of the toner,
The area of the amorphous polyester is 80 area% with respect to the total area of the domain of the amorphous polyester in the area from the outline of the cross section to within 50% of the distance between the outline and the center point of the cross section. The toner according to claim 1, wherein the toner is present in an amount of 100 area% or less. 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 1, wherein A and B satisfy a relationship represented by the following formula (4).
A / B ≧ 1.05 (4)   The toner according to claim 1, wherein the amorphous polyester has a number average diameter of domains of 0.3 μm or more and 3.0 μm or less. Toner for developing the electrostatic latent image formed on the image carrier;
A toner carrying body that carries the toner and conveys the toner to the image carrier,
The developing device according to claim 1, wherein the toner is the toner according to claim 1.

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