JP5911235B2 - toner - Google Patents

Description

  The present invention relates to a toner used in electrophotography and electrostatic recording.

A full-color image forming apparatus such as a full-color copying machine or a full-color printer that requires high image quality is required to support not only plain paper but also paper with large surface irregularities such as recycled paper. Therefore, a transfer method using an intermediate transfer member has become mainstream.
Usually, in a transfer method using an intermediate transfer member, it is necessary to transfer a toner image visualized on an image carrier to the intermediate transfer member and then transfer the toner image from the intermediate transfer member onto a transfer material. Therefore, the number of times of transfer increases as compared with the conventional method, and it is desired that the toner has higher transfer efficiency.
As one method for increasing the transfer efficiency, toner spheroidization has been studied.
Examples thereof include polymerized toner such as suspension polymerization and emulsion polymerization, and toner obtained by spheroidizing pulverized toner.
However, in the polymerized toner, the wax is encapsulated in the toner particles, so that the wax does not easily come out on the surface of the toner at the time of fixing, so that the fixability may be inferior, and the scattering of the line image may deteriorate. there were.
On the other hand, in the pulverized toner that has been spheroidized by heat, excessive wax easily elutes on the surface of the toner, which may cause poor cleaning.
Therefore, it contains a polymer having a structure in which a vinyl resin component and a hydrocarbon compound are reacted, and surface treatment is performed with hot air to suppress the exudation of an excessive amount of wax on the toner surface and improve cleaning properties. Proposed toners have been proposed. (See Patent Document 1)
However, when printing is performed for a long time at a low image density, the fluidity of the toner is lowered, the amount of developer on the sleeve is changed, and the image density may be lowered.
In addition, 0.5-6 parts by weight of silica having an average primary particle size of 35-300 nm for the purpose of coalescence of toner particles during heat spheroidization, blade fusion in a developing machine, and suppression of contamination of a charging roller, There has been proposed a toner using toner particles that are made spherical by heat treatment after adding 0.1 to 3 parts by weight of silica having an average primary particle size of 4 to 30 nm. (Patent Document 2)
However, in order to improve the low-temperature fixability and hot offset resistance, when using a resin or wax with a low softening point, if many sheets are printed at a low image density, the image density decreases or hot offset resistance There was a case where the sex deteriorated.
For this reason, full-color image forming apparatuses such as full-color copying machines or full-color printers are expected to have excellent low-temperature fixability, hot offset resistance, and durability while achieving transferability corresponding to paper with large unevenness. Yes.

JP 2009-237007 A JP 2007-279239 A

  The present invention provides a toner having excellent low-temperature fixability, hot offset resistance, and durability while achieving transferability even on paper with large irregularities such as recycled paper.

The above problem can be solved by the toner having the following configuration.
That is, the present invention is as follows.
In the toner having toner particles containing at least a binder resin, a colorant, wax, and silica particles A, the silica particles A have a number average particle size of primary particles of 60 nm or more and 300 nm or less. The surface of the toner particles is fixed to the surface of the toner particles by surface treatment with hot air, and the theoretical coverage of the silica particles A on the toner surface obtained from the following formula (I) is calculated by A (%) by X-ray photoelectron spectroscopy. coating rate B (%) of the silica particles a in the toner particle surfaces, the number average particle diameter of primary particles of the silica particles a is taken as D _a, the exposed height of the silica (D _{a / 2-D} a / 2 and the ^{(1-B / A) 1/2} ) is 30nm or more state, and are the silica particles A coverage A 5% or more and 45% or less, an average circularity of 0.955 or more 0.980 or less Oh toner characterized by Rukoto -.
Formula (I) Theoretical coverage [A] = (3 ^1/2 × D ₄ × ρt) / (2π × D _A × ρ _A ) × C
[Wherein D ₄ is the weight average particle diameter of the toner, ρt is the true density of the toner, D _A is the number average particle diameter of the primary particles of the silica particles A, ρ _A is the true density of the silica particles A, and [C] is The addition amount [parts by mass] of silica particles A with respect to 100 parts by mass of toner particles is represented . ]

  According to the present invention, it is possible to provide a toner having excellent low-temperature fixability, hot offset resistance, and durability while achieving transferability even on paper with large unevenness.

The figure for demonstrating the calculation method of the exposure height of the silica particle A Sectional view of surface treatment equipment using hot air

Hereinafter, modes for carrying out the present invention will be described.
The toner of the present invention is a toner having toner particles containing at least a binder resin, a colorant, a wax, and silica particles A. The silica particles A have a number average particle size of primary particles of 60 nm or more and 300 nm or less. The surface of the toner particles is fixed to the surface of the toner particles by treatment with hot air, and the surface coverage of the toner particles by the silica particles A is A (%) and is calculated by X-ray photoelectron spectroscopic analysis. the coverage by the silica particles a and B (%), number average particle diameter of primary particles of the silica particles a is taken as D _a, the exposed height of the silica particles a, [D a _/ 2- D _A / 2 (1-B / A) ^1/2 ] is 30 nm or more, and the coverage B is 5% or more and 45% or less.
In order to improve transferability, the inventors of the present invention have used toner particles containing a binder resin, a colorant, and a wax that have been spheroidized by surface treatment with hot air to provide low-temperature fixability, hot offset resistance, and durability. We examined whether we could improve sex.
As a result, toner particles in which silica particles having a number average particle size of primary particles of 60 nm to 300 nm (hereinafter also simply referred to as silica particles A) are added to the binder resin, the colorant, and the wax using hot air. It was found that the durability was improved (for example, the image density was maintained) by fixing the toner particles to the surface of the toner particles in a specific form by the treatment.
Conventionally, when a two-component developer composed of a toner and a carrier is mixed by agitation in the developing machine and the fluidity is lowered, the amount of developer loaded on the developer carrier is reduced, and as a result, the image Concentration may decrease.
In addition, if the silica particles are simply present on the surface of the toner particles, the silica particles detached from the toner particles may contaminate members such as the carrier and the sleeve, and the charge amount of the toner may change and the image density may change. there were.
On the other hand, it has been found that in the case of toner in which silica particles A are fixed on the surface of the toner particles, a decrease in image density can be prevented.
The reason for this is not clear, but the inventors have been able to reduce the fluidity of the toner even when the toner is stirred for a long period of time in the developing machine by the silica particles A entering between the toner particles and acting as a spacer. This is because the image density is maintained as a result.
On the other hand, by fixing the silica particles A to the toner particle surfaces by surface treatment with hot air, it was possible to reduce the separation of the silica particles from the toner and to suppress the change in the image density.
The inventors have studied the mechanism, and the effect is that the number average particle size of the primary particles is 6%.
Silica particles having a particle size of 0 nm or more and 300 nm or less are not simply fixed to the surface of the toner particles, and the above effect is exhibited only by controlling the exposure height and the exposed area of the silica particles from the toner particles. I found out.
Specifically, the exposed height of the silica particles from the toner particles needs to be 30 nm or more. Moreover, it is preferable that this exposure height is 35 nm or more.
As a method for measuring the exposure height, conventionally, a method such as observation with a scanning electron microscope (SEM) has been devised, but the durability of the toner is not based on the exposure condition of each silica particle. It was found that the silica exposed height of the toner particles as a whole and the coverage (%) by the silica particles A on the surface of the toner particles are involved.
A specific method for measuring the coverage is as follows.
The coverage [B] (%) of the silica particles A on the toner particle surface was calculated by X-ray photoelectron spectroscopy (ESCA (Electron Spectroscopy for Chemical Analysis)).
On the other hand, the theoretical coverage [A] (%) by the silica particles A on the surface of the toner particles can be obtained from the following formula (I).
Formula (I) Theoretical coverage [A] = (3 ^1/2 × D ₄ × ρt) / (2π × D _A × ρ _A ) × C
[Wherein D ₄ is the weight average particle diameter of the toner, ρt is the true density of the toner, D _A is the number average particle diameter of the primary particles of the silica particles A, ρ _A is the true density of the silica particles A, and [C] is The amount of silica particles A added [parts by mass] with respect to 100 parts by mass of toner particles. ]
Here, by calculating the ratio of the theoretical coverage [A] by the silica particles A on the toner particle surface and the actual coverage [B], the exposed height of the silica particles A on the toner particle surface can be calculated. it can. (See Figure 1)
Specifically, when the number average particle diameter of primary particles of the silica particles A was D _A, theoretical projected area of A1 per silica particles, a [pi] D A ^_2/4.
In contrast, actually when the diameter of the portion exposed on the surface of the toner particles and D _B, the exposed area of A1 per actual silica particles of the silica particles A becomes πD B ^_2/4.
At this time, the relationship between the theoretical projected area per silica particle A and the actual exposed area is such that the theoretical exposure rate [A] and actual coverage [B] by the silica particles A on the toner particle surface are as follows.
^{_{A: B = πD A 2/}} 4: a relation that πD _B ^2/4.
When this equation is solved, D _B = D _A (B / A) ^1/2 .
By using the D _B , D _A, and the square theorem, the exposed height of the silica particles A on the toner particle surface is [D _A / 2-D _A / 2 (1-B / A) ^1/2 ]. Is calculated.
SEM observation of the surface of the toner particles after the hot air treatment is that when the surface treatment of the toner particles is performed using hot air under conditions such that the toner particles are spheroidized, up to about half of the silica particles A are buried quickly. I know more.
The reason for this is not clear, but the situation in which more than half of the silica particles A are exposed results in a large surface area of the toner particles. During the surface treatment using hot air, a force is applied to the toner particles to reduce the surface area as much as possible in order to reduce the surface free energy. As a result, the toner particles are spheroidized, but when the silica particles A are completely exposed from the fully exposed state, the surface area is greatly reduced. For this reason, the silica particle A is rapidly embedded up to half.
Thus, when the surface treatment with hot air is performed under the condition that the toner particles are spheroidized, the silica particles A are more than half buried. Was calculated.

As a result of intensive investigations, the inventors have first discovered that when the exposed height of the silica particles A on the toner particle surface is 30 nm or more, the silica particles A act as a spacer and the toner is stirred in the developing machine. It was found that the decrease in the fluidity of the toner was suppressed.
This is because the exposed height of the silica particles A on the toner particle surface, [D _A / 2-D _A / 2 (1-B / A) ^1/2 ] is 30 nm or more, and the spacer effect can be exhibited. It seems to be because.
When the exposed height of the silica particles A is less than 30 nm, it cannot act as a spacer effect, and when the toner is stirred for a long time in the developing machine, the amount of the developer loaded on the developer carrier of the developing machine varies. As a result, the image density decreases.
As a method of changing the exposed height of the silica particles A, spheroidization by hot air can be performed by changing the treatment conditions using hot air, the addition conditions of the silica particles A to the toner particle surfaces, the melting point of the wax and the softening point of the resin. It is preferable to control the embedding speed of silica particles A.

In addition to the exposed height of the silica particles A, the coverage [B] of the silica particles A on the surface of the toner particles calculated by X-ray photoelectron spectroscopic analysis is set to 5% or more and 45% or less. At the same time, hot offset resistance can be improved. The coverage [B] is preferably 10% or more and 45% or less.
When the coverage [B] is less than 5%, there are few portions that contribute as spacers, and as a result, the image density fluctuation cannot be suppressed.
If the coverage [B] is greater than 45%, the toner may be prevented from seeping out of the wax at the time of fixing, and when it is fixed at a high temperature, the toner may partially remain on the fixing member. Occur.
As a method of changing the coverage [B], hot air can be used by changing the treatment conditions using hot air, the addition conditions and addition amount of silica particles A to the toner particle surface, the melting point of the wax, and the softening point of the resin. Preferably, the spheroidization by the control and the embedding speed of the silica particles A are controlled.

As described above, the silica particles A have a number average particle diameter (D _A ) of primary particles of 60 nm or more and 300 nm or less. Also, the _{D A} is, 100 nm or more and 250nm or less.
When the D _A is less than 60 nm, since the filler effect by silica particles A is too high, viscoelastic in the surface layer region of the toner particles is too high, the low temperature fixability of the toner deteriorates.
On the other hand, if the D _A is greater than 300 nm, since the silica particles A are not sufficiently embedded in the surface of the toner particles, can not be suppressed free silica particles A, the silica particles A is and carrier from the toner particles developer By moving to the carrier, the charge amount of the toner changes and the image density decreases.

In the present invention, the number average particle diameter (D _A ) of the primary particles of the silica particles A, the BET specific surface area (BET _A ) (m ² / g) of the silica particles A, the true density (ρ _A ) of the silica particles A (g / Cm ³ ) is preferable when the relationship of the following formula (II) is satisfied, because the fixing strength between the toner particle surface and the silica particles A is dramatically increased by the treatment using hot air.
Formula _{(II) 0.85 ≦ BET A /} [6 / (D A × ρ A)] ≦ 1.50
Here, BET _A / [6 / (D _A × ρ _A )] is defined as the BET ratio. The meaning of the BET ratio will be described below.
As for the BET ratio, the measured value (BET _A ) of the BET specific surface area of the silica particles A is assumed, and the number average particle diameter (D _A ) of the primary particles is calculated assuming that the silica particles A are ideal spherical monodisperse particles. It is the value normalized by the calculated value of BET specific surface area calculated using (theoretical BET specific surface area).
The theoretical BET specific surface area means that the BET specific surface area of a spherical particle (one particle) is obtained by the following formula (III) from the particle size (d1) and the true density. Calculated from the number average particle diameter (D _A ) and the true density of the silica particles A,
Formula (III) Theoretical BET specific surface area = 6 / [d1 (μm) × true density of spherical particles (g / cm ³ )]
When the BET specific large, number average particle diameter as compared with the ideal spherical monodisperse particles is _{D A,} BET specific surface area of the silica particles A (BET _A) is large. Therefore, the silica particles A are not perfectly spherical, have irregular shapes such as irregularities on the surface, and have a large specific surface area compared to spherical monodisperse particles, so the surface free energy is high and they are likely to aggregate. It has properties.
On the other hand, if the BET ratio is less than ideal spherical monodisperse particles the number average particle size of D _A, BET specific surface area of the silica particles A (BET _A) is small, the silica particles A and the particle size distribution It is thought to have.
In other words, the silica particles A used in the toner of the present invention preferably have a BET ratio of 0.85 or more and 1.50 or less. When the BET ratio is within this range, the release of the silica particles A from the toner particles can be easily suppressed even when a strong stress is applied.
When the BET ratio of the silica particles A exceeds 1.50, the surface free energy of the silica particles A is too high, so that the silica particles A are easily aggregated, and the silica particles A are mixed and adhered to the surface of the toner particles before treatment with hot air. At this time, an aggregate of silica particles A is formed. Therefore, even if surface treatment with hot air is performed, silica particles A that are not embedded in the surface of the toner particles and are not fixed to the surface of the toner particles exist in the aggregate. Therefore, the release of the silica particles A from the toner particles cannot be suppressed, image defects due to contamination of the charging roller are likely to occur, and offset resistance tends to decrease.
On the other hand, when the BET ratio of the silica particles A is less than 0.85, the particle size distribution of the silica particles A is too wide, and thus the BET specific surface area and mass have a large distribution. For this reason, the exposed height of the silica particles A on the surface of the toner particles when the surface treatment is performed with hot air is non-uniform, the function as the spacer particles is likely to be lowered, and the image density may be lowered during long-term use. .
In order to obtain silica particles A having a BET ratio in the above range, for example, a method of obtaining silica particles A having a nearly spherical shape by adjusting raw materials, production steps, and production conditions of silica particles A, or silica particles A When the surface treatment is performed, a processing agent, a treatment amount, and treatment conditions are appropriately selected to obtain a silica particle A with less surface irregularities, or a silica particle A having a narrow particle size distribution by classification treatment and / or pulverization treatment. And the like.

The silica particles A are not particularly limited as long as the number average particle diameter (D _A ) of the primary particles is 60 nm or more and 300 nm or less, and conventionally known silica particles can be adopted.
For example, silica particles produced by an arbitrary method such as a wet method, a flame melting method, and a gas phase method are preferably used. However, in terms of easy obtaining silica particles having a desired BET ratio, D _A and BET _A , the wet method, Silica particles produced by a flame melting method are more preferable.
Moreover, it is preferable that the surface of the said silica particle A is hydrophobized by surface treatment. Since the surface is hydrophobized, moisture absorption of the silica particles A in a high-temperature and high-humidity environment is suppressed, toner chargeability is increased, and fogging is suppressed.
Examples of the surface treatment include silane coupling treatment, oil treatment, fluorine treatment, surface treatment for forming an alumina coating, and the like, and can be appropriately selected. It is also possible to select a plurality of types of surface treatments, and the order of these treatments is also arbitrary.
In the present invention, the addition amount of the silica particles A to the toner particles before treatment with hot air is preferably 1.0 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the toner particles. It is more preferable that the amount be 0.0 parts by mass or more and 10.0 parts by mass or less.

The toner of the present invention preferably further contains at least one of silica particles and titanium oxide particles whose primary particles have a number average particle size of 5 nm or more and 50 nm or less. The particles are preferably externally added after the toner particles are subjected to a surface treatment using hot air.
By containing the particles, the fluidity of the toner can be further improved.
As the silica particles having a primary particle number average particle size of 5 nm or more and 50 nm or less, known silica particles used for toner manufactured by any method such as a wet method, a flame melting method, and a gas phase method should be used. Is possible. On the other hand, titanium oxide particles having a primary particle number average particle diameter of 5 nm or more and 50 nm or less can also be known titanium oxide particles used for toner.
The addition amount of the particles is preferably 0.1 parts by mass or more and 5.0 parts by mass or less, and 0.3 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the toner particles. It is more preferable.

The toner of the present invention contains toner particles containing a binder resin, a colorant, wax, and silica particles A.
The wax used in the toner of the present invention is not particularly limited, and a known wax can be used. Examples of waxes that can be suitably used are shown below. Low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, microcrystalline wax, paraffin wax, aliphatic hydrocarbon wax such as Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; aliphatic carbonization A wax mainly composed of a fatty acid ester such as a hydrogen ester wax; and a fatty acid ester such as a deoxidized carnauba wax that has been partially or fully deoxidized. Partially esterified products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and the like.
In particular, when the toner particles include a polyester resin as a binder resin and a hydrocarbon wax having a melting point of 60 ° C. or higher and 110 ° C. or lower as a wax, the toner particles exhibit good releasability, thereby achieving low temperature fixability. However, it is particularly preferable because the hot offset resistance can be further improved.
The amount of the wax added is preferably 1.0 part by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the toner particles.

Next, the binder resin used for the toner of the present invention will be described. The toner of the present invention preferably contains a polyester resin having a high sharp melt property as a binder resin from the viewpoint of low-temperature fixability. Moreover, even if it is other than polyester resin, other resin can also be included in the range which does not affect low-temperature fixability.
As the polyester resin, a resin obtained by condensation polymerization of an alcohol monomer and a carboxylic acid monomer is used. The following are mentioned as an alcohol monomer.
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2. 0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) alkylene oxide adducts of bisphenol A such as -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1 , 4-butanediol, neopentyl glycol, 1,4-butenediol 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A, sorbitol, 1,2 , 3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropane Triol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene.
On the other hand, examples of the carboxylic acid monomer include the following.
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or their anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides; alkyl group or alkenyl having 6 to 18 carbon atoms Group-substituted succinic acid or anhydride; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof.
In addition, the following monomers can be used.
Glycerin, sorbit, sorbitan, and polyhydric alcohols such as oxyalkylene ethers of novolac-type phenol resins; polyhydric carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and anhydrides thereof.
Among these, in particular, a bisphenol derivative represented by the following general formula (1) is a dihydric alcohol monomer component, and a carboxylic acid component comprising a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof ( For example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) are used as acid monomer components, and resins obtained by condensation polymerization with these polyester unit components have good charging characteristics. Therefore, it is preferable.

（式中、Ｒはエチレン基又はプロピレン基を示し、ｘ及びｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。）

(In the formula, R represents an ethylene group or a propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10).

The toner particles used in the present invention have a “melting temperature in 1/2 method” (hereinafter simply referred to as softening point (1/2 method)) measured by a constant load extrusion type capillary rheometer of 90 ° C. or more. It is preferable that it is 110 degrees C or less.
When the toner particles satisfy the softening point (1/2 method) in this range, it becomes easier to achieve both low-temperature fixability and hot offset resistance.
Further, when the softening point (1/2 method) of the toner particles is higher than the melting point of the wax by 40 ° C. or more, the silica particles are formed by the wax before the toner particles are spheroidized during the surface treatment of the toner particles using hot air. A may be excessively buried, resulting in a decrease in durability. That is, the value obtained by subtracting the melting point of the wax from the softening point (1/2 method) of the toner particles is preferably less than 40 ° C.

The colorant used in the toner of the present invention is not particularly limited, and a known colorant can be used. Specific examples include the following. As the colorant, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.
Examples of the black colorant include carbon black; a magnetic material; a black colorant using a yellow colorant, a magenta colorant, and a cyan colorant.
Examples of the color pigment for magenta toner include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 185, 202, 206, 207, 209, 238, 269, 282; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.
Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disper thread 9; I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24
27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.
Examples of the color pigment for cyan toner include the following. C. I. Pigment blue 2, 3, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton. Examples of the coloring dye for cyan include C.I. I. There is Solvent Blue 70.
Examples of the color pigment for yellow include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat yellow 1, 3, 20 Examples of the coloring dye for yellow include C.I. I. There is Solvent Yellow 162.
The amount of the colorant used is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

In the toner of the present invention, a charge control agent can be added and used. As the charge control agent for negative charging, for example, organometallic complexes and chelate compounds are effective. Examples thereof include monoazo metal complexes; acetylacetone metal complexes; aromatic hydroxycarboxylic acid or aromatic dicarboxylic acid metal complexes and Examples thereof include phenol derivatives such as metal salts, anhydrides, esters, and bisphenol.
On the other hand, as a charge control agent for positive charge, modified products such as nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, And onium salts such as phosphonium salts which are analogs thereof, and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (phosphorungstic acid, phosphomolybdate, phosphotungsten molybdate, tannin Acids, lauric acid, gallic acid, ferricyanic acid, ferrocyanic compounds, etc.); metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dibutyl Cu Chi Angeles trousers rate, include such as organo-tin borate of dicyclohexyl tin borate.
These charge control agents can be used alone or in combination of two or more. The amount of these charge control agents used is preferably 0.1 to 5.0 parts by mass per 100 parts by mass of the binder resin.

The toner particles and the method for producing the toner are not particularly limited, except that there is a step of fixing the silica particles A to the surface of the toner particles by treatment with hot air, and conventionally known production methods can be used.
Here, a toner manufacturing procedure using a pulverization method will be described.
In the raw material mixing step, as a material constituting the toner particles, a binder resin, a colorant, a wax, and, if necessary, other components such as a charge control agent are weighed and mixed in a predetermined amount and mixed. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a nauter mixer, and a mechano-hybrid (manufactured by Nippon Coke Kogyo Co., Ltd.).
Next, the mixed material is melt-kneaded to disperse wax or the like in the binder resin. In the melt-kneading step, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. Due to the advantage of continuous production, single-screw or twin-screw extruders are the mainstream. For example, KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Tekko), twin screw extruder (manufactured by Kay Sea Kay Co., Ltd.) ), Co-kneader (manufactured by Buss), and kneedex (manufactured by Nippon Coke Industries).
Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.
Next, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization process, after coarse pulverization with a pulverizer such as a crusher, hammer mill, or feather mill, kryptron system (manufactured by Kawasaki Heavy Industries), super rotor (manufactured by Nissin Engineering Co., Ltd.), turbo mill (manufactured by Turbo Industry) ) And air jet type fine pulverizer.
After that, if necessary, classification such as elbow jet with inertia classification (manufactured by Nippon Steel Mining), turboplex with centrifugal classification system (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), Faculty (manufactured by Hosokawa Micron) Classification using a machine or sieving machine to obtain base particles.
After passing through an adhesion step for attaching silica particles A to the surface of the base particles thus obtained, surface treatment with hot air is performed, and classification is performed using a classifier or a sieving machine as necessary, and silica is applied to the surface. Toner particles to which the particles A are fixed can be obtained.
The method for attaching the silica particles A to the surface of the base particles in the attaching step is not particularly limited, and a predetermined amount of the base particles and the silli particles A are weighed, mixed, and mixed.
Further, other inorganic fine particles, a charge control agent, a fluidity imparting agent and the like can be blended at the same time as long as the effects of the present invention are not impaired.
As an example of the mixing apparatus, there are a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer, which are preferably used.
It is more preferable to use a Henschel mixer as a mixing device in that the silica particles A can be more uniformly attached to the surface of the base particles.
As mixing conditions, the higher the rotation speed of the mixing blade and the longer the mixing time, the more preferable it is because silica particles A are more easily adhered uniformly to the surface of the base particles.
However, if the rotation speed of the mixing blade is too high or the mixing time is too long, the frictional heat between the toner and the mixing blade becomes high, and the toner may be heated and fused.
Therefore, it is preferable to actively cool the mixer by providing a mixing blade or a water cooling jacket in the mixer.
And it is preferable to adjust the rotation speed of the mixing blade and the mixing time in a range where the temperature in the mixer is 45 ° C. or less. Specifically, the maximum peripheral speed of the mixing blade is 10.0 m / sec or more, It is preferable that it is 150.0 m / sec or less, and it is preferable to adjust mixing time in the range of 0.5 minute-60 minutes.
Further, the adhesion process may be performed in one stage or in multiple stages of two or more stages, and the mixing apparatus, mixing conditions, and blending of base particles used in each stage are the same or different. May be.
In the present invention, the apparatus used for the treatment using hot air has means for bringing the surface of the toner particles before the treatment into a molten state using hot air, and the toner particles treated using the hot air are used. Any device may be used as long as it has means capable of cooling with cold air.
As such an apparatus, for example, Meteoleinbo MR Type (manufactured by Nippon Pneumatic Co., Ltd.) can be exemplified.

Next, one embodiment of a surface treatment method using hot air will be described with reference to FIG. 2, but the present invention is not limited to this.
In the present invention, the base particles having the silica particles A attached to the surface are subjected to a surface treatment using hot air, and the particles having the silica particles A fixed on the surface are referred to as toner particles. For convenience, the particles before the silica particles A are fixed to the surface may also be expressed as toner particles.
FIG. 2 is an example of a cross-sectional view of the surface treatment apparatus used in the present invention. Specifically, as the surface treatment method, a material obtained by previously attaching the silica particles A to the surfaces of the base particles is used as a raw material, and the raw material is supplied to the surface treatment apparatus.
The toner particles (114) supplied from the toner particle supply port (100) are accelerated by the injection air injected from the high-pressure air supply nozzle (115) and travel toward the airflow injection member (102) below the injection air.
Diffusion air is ejected from the airflow ejecting member (102), and the toner particles are diffused outward by the diffusion air. At this time, the diffusion state of the toner particles can be controlled by adjusting the flow rate of the injection air and the flow rate of the diffusion air.
Further, for the purpose of preventing fusion of the toner particles, a cooling jacket (106) is provided on the outer periphery of the toner particle supply port (100), the outer periphery of the surface treatment apparatus, and the outer periphery of the transfer pipe (116).
In addition, it is preferable to pass cooling water (preferably antifreeze such as ethylene glycol) through the cooling jacket.
On the other hand, the toner particles diffused by the diffusion air are treated on the surface of the toner particles by the hot air supplied from the hot air supply port (101).
At this time, the hot air discharge temperature is preferably 100 ° C. or higher and 300 ° C. or lower, and more preferably 150 ° C. or higher and 250 ° C. or lower.
When the temperature of the hot air is less than 100 ° C., the melting state of the toner particles becomes insufficient, the silica particles A are not sufficiently embedded in the surface of the toner particles, and the silica particles A may not be fixed.
When the temperature of the hot air exceeds 300 ° C., the melting state of the toner particles progresses too much, the degree of embedding of the silica particles A on the toner particle surfaces becomes uneven, or the silica particles A are completely inside the toner particles. In some cases, the fluidity and chargeability of the resulting toner may be deteriorated. In addition, the toner particles are likely to coalesce in the manufacturing process, and the toner particles may be coarsened or the toner particles may be severely fused to the inner wall surface of the apparatus.
Further, the average circularity of the obtained toner can be controlled to 0.955 or more and 0.980 or less by adjusting the hot air discharge temperature in the above temperature range.
The higher the temperature, the higher the average circularity of the resulting toner, and the lower the temperature, the lower the average circularity of the resulting toner. The degree of circularity tends to increase.
Therefore, it can be considered that the degree of embedding of the silica particles A on the surface of the toner particles varies depending on the average circularity of the toner. However, since the number average particle diameter (D _A ) of the primary particles is in a specific range, the silica particles A used in the present invention are appropriately embedded in the surface of the toner particles in the above range. It is preferable because of its high fixing strength.
The toner particles whose surface has been treated with hot air are cooled by cold air supplied from a cold air supply port (103) provided on the outer periphery of the upper part of the apparatus. At this time, it is preferable to introduce cold air from the second cold air supply port (104) provided on the side surface of the main body of the apparatus for the purpose of controlling the temperature distribution in the apparatus and controlling the surface state of the toner particles. The outlet of the second cold air supply port (104) can use a slit shape, a louver shape, a perforated plate shape, a mesh shape, etc., the introduction direction is horizontal to the center direction, and the direction along the apparatus wall surface depends on the purpose. Selectable.
At this time, the cold air temperature is preferably −50 ° C. or higher and 10 ° C. or lower, and more preferably −40 ° C. or higher and 8 ° C. or lower. The cold air is preferably dehumidified air. Specifically, the absolute water content in the cold air is preferably 5 g / m ³ or less. More preferably, it is 3 g / m ³ or less.
When the temperature of the cold air is less than -50 ° C., the temperature in the apparatus is too low, and the heat treatment that is the original purpose is not sufficiently performed, and the surface of the toner particles cannot be made into a molten state. There is a case.
When the temperature exceeds 10 ° C., the toner particles subjected to the surface treatment with hot air cannot be sufficiently cooled, and the toner particles may be coarsened or fused due to coalescence between the toner particles. .
Thereafter, the cooled toner particles are sucked by a blower and collected by a cyclone or the like through a transfer pipe (116).
After performing the surface treatment with hot air in this way, toner particles having silica particles A fixed on the surface can be obtained by classification using a classifier or a sieving machine as necessary.
In the toner of the present invention, at any stage after the surface treatment with hot air, the number average particle size of the primary particles is 5 nm or more and 50 nm or less, and at least one particle of silica particles and titanium oxide particles is present. External addition is preferable from the viewpoint of further improving the fluidity of the toner.

Hereinafter, methods for measuring various physical properties of the toner and the like in the present invention will be described.
<Method for separating inorganic fine particles not fixed>
In the present invention, the fixed inorganic fine particles are measured.
For this reason, it is necessary to remove the inorganic fine particles not fixed by the following method.
In a 50 ml vial, weigh 20 g of a 2% by weight aqueous solution of “Contaminone N” (neutral detergent, anionic surfactant, neutral detergent for pH 7 precision measuring instrument washing comprising an organic builder and 1 g of toner. Set to “KM Shaker” (model: V.SX) manufactured by Iwaki Sangyo Co., Ltd., set speed to 50 and shake for 30 seconds, then centrifuge (1000 rpm for 5 minutes), The toner and the aqueous solution are separated, the supernatant liquid is separated, and the precipitated toner is vacuum-dried to obtain toner particles from which inorganic fine particles not fixed are separated.
<Amount of silica particles A fixed to the toner particle surface>
The addition amount [parts by mass] of the silica particles A with respect to 100 parts by mass of the toner particles of the present invention can be determined with a fluorescent X-ray analyzer. The measurement method in the present invention will be described below.
The Si element in the toner particles is directly measured by the FP method in a He atmosphere using a wavelength dispersive X-ray fluorescence analyzer Axios advanced (manufactured by PANalytical).
In the present invention, among the production examples of the toner particles 1 shown in Examples, the addition amount of silica particles A-1 is 1.0 part by mass, 2.0 parts by mass, 5.0 parts by mass, 10.0 parts by mass. A standard was created instead of the part. The amount of each Si element is measured, and a calibration curve for silica is created.
Thereafter, the toner particles from which the inorganic fine particles that are not fixed are separated are measured with the wavelength dispersion type fluorescent X-ray analyzer, and the obtained fluorescent X-ray intensity is compared with a calibration curve, and the added amount of silica particles A [mass Part] (the above-mentioned [C]).
<Surface composition analysis by X-ray photoelectron spectroscopy (ESCA)>
In the present invention, the coverage of the toner particle surface with silica particles A (ie, [B]) is calculated by performing a surface composition analysis by X-ray photoelectron spectroscopy (ESCA). The ESCA apparatus and measurement conditions are as follows.
Equipment used: Quantum 2000 Scanning ESCA Microprobe, manufactured by PHI (Physical Electronics Industries, Inc.)
Measurement condition:
X-ray source: AlKα (100μ25W15KV)
Angle; 45 °
Pass Energy; 58.70 eV
As a measurement sample, toner particles obtained by separating inorganic fine particles that are not fixed are used.
From the peak intensity of each element measured under the above conditions, the surface atomic concentration (atomic%) is calculated using a relative sensitivity factor provided by PHI.
As measurement elements, seven types of C, O, Si, Ti, Al, Ca, and Sr are measured, and the ratio of Si in these seven types of elements is calculated. For each atom, reference is made to the peak intensities based on C: 1s, O: 1s, Si: 2p, Ti: 2p orbital, Al: 2p orbital, Ca: 2p orbital, and Sr: 3d orbital.
Since the element concentration of Si in silica (SiO ₂ ) is 33%, the Si obtained above
Three times the concentration (atomic%) was considered as the concentration of silica particles, and this value was defined as the coverage [B]. The above seven types of elements are elements present on the surface of the toner particles or representative elements constituting the external additive.

<Method for Measuring Number Average Particle Size of Primary Particles of Silica Particles A and Other Inorganic Fine Particles>
The number average particle diameter of primary particles such as silica particles A is measured using a field emission scanning electron microscope (FE-SEM) S-4700 (manufactured by Hitachi, Ltd.).
The photographing magnification is set to 50,000 times, and after the photographed photograph is further doubled, the silica particles A and the like (primary particles) to which the toner particle surface is adhered are exposed from the obtained FE-SEM photograph image. The maximum diameter (major axis diameter) La of the surface is measured. At the same time, the height Lb of the exposed surface is calculated.
From La and Lb, the maximum diameter of the silica particles is calculated as ^{(La 2/4 + Lb 2} ) / Lb. The same calculation is performed on 100 randomly selected silica particles A and the like (primary particles) to obtain the number average particle diameter of the silica particles A and the like (primary particles).

<Method for Measuring BET Specific Surface Area (BET _A ) of Silica Particle A>
The BET specific surface area (BET _A ) of the silica particles A was measured according to JIS Z8830 (2001).
A specific measurement method is as follows.
As a measuring device, an “automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)” which employs a gas adsorption method by a constant volume method as a measuring method was used.
Setting of measurement conditions and analysis of measurement data were performed using dedicated software “TriStar3000 Version 4.00” attached to the apparatus, and a vacuum pump, nitrogen gas pipe, and helium gas pipe were connected to the apparatus. The value calculated by the BET multipoint method using nitrogen gas as the adsorption gas was defined as the BET specific surface area in the present invention.
Specifically, the BET specific surface area is calculated as follows.
First, nitrogen gas is adsorbed on the silica particles A, and the equilibrium pressure P (Pa) in the sample cell and the nitrogen adsorption amount Va (mol · g ⁻¹ ) of the silica particles A at that time are measured. The relative pressure Pr, which is a value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is plotted on the horizontal axis, and the nitrogen adsorption amount Va (mol · g ⁻¹ ) is plotted on the vertical axis. The adsorption isotherm is obtained. Next, a monomolecular layer adsorption amount Vm (mol · g ⁻¹ ), which is an adsorption amount necessary for forming a monomolecular layer on the surface of the silica particle A, is obtained by applying the following BET equation.
Pr / Va (1-Pr) = 1 / (Vm * C) + (C-1) * Pr / (Vm * C)
(Here, C is a BET parameter, which is a variable that varies depending on the measurement sample type, adsorbed gas type, and adsorption temperature.)
The BET equation is interpreted as a straight line with an inclination of (C-1) / (Vm × C) and an intercept of 1 / (Vm × C), where Pr is X axis and Pr / Va (1-Pr) is Y axis. Yes (this line is called a BET plot).
Straight line slope = (C-1) / (Vm × C)
Straight line intercept = 1 / (Vm × C)
When the measured value of Pr and the measured value of Pr / Va (1-Pr) are plotted on a graph and a straight line is drawn by the least square method, the slope and intercept value of the straight line can be calculated. Vm and C can be calculated by solving the above slope and intercept simultaneous equations using these values.
Furthermore, the BET specific surface area S (m ² · g ⁻¹ ) of the silica particles A is calculated from the Vm calculated above and the molecular occupation cross-sectional area (0.162 nm ² ) of nitrogen molecules based on the following formula.
S = Vm × N × 0.162 × 10 ⁻¹⁸
(N is Avogadro's number (mol- ¹ ).)
The measurement using this apparatus follows the “TriStar 3000 Instruction Manual V4.0” attached to the apparatus, and specifically, the measurement is performed according to the following procedure.
Thoroughly weigh the tare of a dedicated glass sample cell (stem diameter 3/8 inch, volume about 5 ml) that has been thoroughly cleaned and dried. Then, 0.3 g of silica particles A are put into the sample cell using a funnel.
The sample cell containing the silica particles A is set in a “pretreatment device Bacrepprep 061 (manufactured by Shimadzu Corporation)” connected with a vacuum pump and a nitrogen gas pipe, and vacuum degassing is continued at 23 ° C. for about 10 hours. Do it. During vacuum deaeration, the silica particles A are gradually deaerated while adjusting the valve so that the silica particles A are not sucked into the vacuum pump. The pressure in the cell gradually decreases with deaeration and finally becomes about 0.4 Pa (about 3 mTorr). After completion of vacuum degassing, nitrogen gas is gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell is removed from the pretreatment device. Then, the mass of the sample cell is precisely weighed, and the exact mass of the silica particles A is calculated from the difference from the tare. At this time, the sample cell is covered with a rubber plug during weighing so that the silica particles A in the sample cell are not contaminated by moisture in the atmosphere.
Next, a dedicated “isothermal jacket” is attached to the stem portion of the sample cell containing the silica particles A. Then, a dedicated filler rod is inserted into the sample cell, and the sample cell is set in the analysis port of the apparatus. The isothermal jacket is a cylindrical member having an inner surface made of a porous material and an outer surface made of an impermeable material capable of sucking liquid nitrogen to a certain level by capillary action.
Subsequently, the free space of the sample cell including the connection tool is measured. The free space is measured by measuring the volume of the sample cell using helium gas at 23 ° C., and then measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen using helium gas. It is calculated by converting from the difference in volume. The saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using a Po tube built in the apparatus.
Next, after vacuum deaeration in the sample cell, the sample cell is cooled with liquid nitrogen while the vacuum deaeration is continued. Thereafter, nitrogen gas is gradually introduced into the sample cell to adsorb nitrogen molecules on the silica particles A. At this time, the adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) as needed, and the adsorption isotherm is converted into a BET plot. Note that the points of the relative pressure Pr for collecting data are set to a total of 6 points of 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is drawn from the obtained measurement data by the least square method, and Vm is calculated from the slope and intercept of the straight line. Further, using the value of Vm, the BET specific surface area of the silica particles A is calculated as described above.

<Method for Measuring True Density of Silica Particle A and Toner>
Measurement was performed using a dry automatic densimeter AccuPick 1330 (manufactured by Shimadzu Corporation).
First, 5 g of a sample sample left in an environment of a temperature of 23 ° C. and a humidity of 50% RH for 24 hours is weighed, placed in a measurement cell (10 cm ³ ), and inserted into the main body sample chamber. The measurement can be automatically performed by inputting the measurement sample sample mass into the main body and starting the measurement.
The measurement conditions for automatic measurement are as follows: after purging the sample chamber with helium gas adjusted at 2.392 × 10 ² kPa, the pressure change in the sample chamber becomes 3.447 × 10 ⁻² kPa / min. Equilibrate and purge with helium gas repeatedly until equilibrium is reached.
The pressure in the main body sample chamber in the equilibrium state can be measured, and the sample sample volume can be calculated from the pressure change when that state is reached (Boil's law).
The volume of the sample sample was calculated, and the true density of the sample sample was calculated using the following formula.
True density (g / cm ³ ) = sample sample mass (g) / sample sample volume (cm ³ )
The average value of the measurement values repeated five times by this automatic measurement was taken as the true density (g / cm ³ ) of the sample specimen.

<Calculation method of average circularity of toner>
The average circularity of the toner is measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.
The measurement principle of the flow-type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) is to capture flowing particles as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is picked up by a CCD camera, and the picked-up image is image-processed at an image processing resolution of 512 × 512 pixels (0.37 × 0.37 μm per pixel), the contour of each particle image is extracted, and the particle image The projected area S, the peripheral length L, etc. are measured.
Next, the equivalent circle diameter and the circularity are obtained using the area S and the peripheral length L. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity C is a value obtained by dividing the circumference of the circle obtained from the equivalent circle diameter by the circumference of the projected particle image. And is calculated by the following formula.
Circularity C = 2 × (π × S) ^1/2 / L
When the particle image is circular, the circularity is 1.000, and the greater the degree of unevenness around the particle image, the smaller the circularity. After calculating the circularity of each particle, the range of the circularity of 0.200 to 1.000 is divided into 800, the arithmetic average value of the obtained circularity is calculated, and the value is defined as the average circularity.
A specific measurement method is as follows. First, 20 ml of ion-exchanged water from which impure solids and the like have been removed in advance is placed in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. 0.2 ml of a diluted solution obtained by diluting 3) times with ion-exchanged water. Further, 0.02 g of a measurement sample is added, and a dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser (for example, “VS-150” (manufactured by Velvo Crea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchanged water is added, and 2 ml of the contamination N is added to the water tank.
For the measurement, the flow type particle image analyzer equipped with a standard objective lens (10 ×) is used, and the particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion prepared in accordance with the procedure is introduced into the flow particle image analyzer, and 3000 toner particles are measured in the total count mode in the HPF measurement mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the circle equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is obtained.
In the measurement, automatic focus adjustment is performed using standard latex particles (eg, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” 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 embodiment of the present application, a flow type particle image analyzer which has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, is used. 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 1.985 μm or more and less than 39.69 μm.

<Method for Measuring Toner Weight Average Particle Size (D4)>
The weight average particle diameter (D4) of the toner is calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.
The electrolytic aqueous solution used for the measurement has a concentration of 1 by dissolving special grade sodium chloride in ion exchange water.
For example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows.
On the “Change Standard Measurement Method (SOM)” 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 By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush 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) Put 200 ml of the aqueous electrolytic solution into a glass 250 ml round bottom beaker for exclusive use of Multisizer 3, set it on a sample stand, and stir the stirrer rod 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) 30 ml of the electrolytic aqueous solution is placed in a glass 100 ml flat bottom beaker. 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. 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. Into the water tank of the ultrasonic disperser, 3.3 l of ion-exchanged water is added, and 2 ml of Contaminone N is added to the water tank. (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the electrolyte solution liquid surface 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, 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 round bottom beaker of (1) installed in a sample stand, the electrolyte aqueous solution of (5) in which toner is dispersed is dropped using a pipette, and the measured concentration is adjusted to 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 “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle diameter (D4).

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

<Measuring method of melting point of wax, glass transition temperature (Tg) of resin>
The melting point of the wax is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
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. Specifically, 10 mg of wax is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The maximum endothermic peak of the DSC curve in the temperature range of 30 ° C. to 200 ° C. in the second temperature raising process is defined as the maximum endothermic peak of the wax, and the peak temperature of the maximum endothermic peak is defined as the melting point of the wax.
The glass transition temperature (Tg) of the resin is measured by precisely weighing 10 mg of the resin in the same manner as the peak temperature measurement of the maximum endothermic peak of the wax. A specific heat change is obtained in the temperature range of 40 ° C. or higher and 100 ° C. or lower. At this time, the intersection of the midpoint line of the baseline before the specific heat change and after the specific heat change and the DSC curve is defined as the glass transition temperature (Tg) of the resin.

<Measurement method of softening point (1/2 method)>
The softening point (1/2 method) of the sample is measured according to a manual attached to the apparatus using a constant load extrusion type capillary rheometer “flow characteristic evaluation apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation). 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 (1/2 method). The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax when the outflow is completed and the piston lowering amount Smin when the outflow starts is obtained, and the calculated value is X (X = (Smax−Smin)). / 2). Then, the temperature of the flow curve when the piston descending amount is X in the flow curve is the melting temperature in the 1/2 method.
The measurement sample was about 1.0 g of a sample at about 10.0 MPa for about 60 seconds in a 25 ° C. environment using a tablet molding compressor (for example, “NT-100H” manufactured by NP System). A cylindrical shape having a diameter of about 8 mm is used by compression molding.
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

Hereinafter, the present invention will be described more specifically with reference to production examples, examples and comparative examples, but these do not limit the present invention in any way. In addition, the number of parts and% of a manufacture example, an Example, and a comparative example are all mass references | standards unless there is particular notice.
<Example of binder resin production>
[Binder resin 1]
The following materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube.
Terephthalic acid 22.6 parts by weight Trimellitic anhydride 1.8 parts by weight Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
75.6 parts by mass Titanium dihydroxybis (triethanolaminate) 0.2 parts by mass Thereafter, the mixture is heated to 200 ° C. and reacted for 8 hours while removing water generated while introducing nitrogen, and then 10.0 mmHg. Resin 1 was synthesized by reacting under reduced pressure for 1 hour.
The molecular weight of the resin 1 determined by GPC is weight average molecular weight (Mw) 5500, number average molecular weight (Mn) 2500, peak molecular weight (Mp) 3000, glass transition temperature (Tg) is 53 ° C., softening point (1 / (Method 2) was 88 ° C.

[Binder resin 2]
The following materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube.
Terephthalic acid 17.2 parts by weight polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
76.6 parts by mass Titanium dihydroxybis (triethanolamate) 0.2 parts by mass Thereafter, the mixture was heated to 220 ° C. and reacted for 10 hours while removing water produced while introducing nitrogen. Thereafter, 2.0 parts by mass of trimellitic anhydride was added, heated to 180 ° C., and reacted for 4 hours to synthesize resin 2.
The molecular weight of resin 2 determined by GPC is as follows: weight average molecular weight (Mw) 85000, number average molecular weight (Mn) 6000, peak molecular weight (Mp) 18000, glass transition temperature (Tg) 65 ° C., softening point (1/2 method ) Was 140 ° C.

[Silica particle A-1]
A mixed gas of silicon tetrachloride, oxygen, and hydrogen was introduced into a burner, fired at a burner temperature of 1100 ° C., cooled, and collected by a back filter.
The obtained fumed silica fine particles are dispersed in the gas phase, and 10 parts by mass of hexamethyldisilazane as a surface treatment agent is sprayed on 100 parts by mass of the fumed silica fine particles so that the particles do not coalesce. The reaction was allowed to stir well.
Next, 10% by mass of dimethyl silicone oil having a viscosity at 25 ° C. of 70 mm ² / s was added, and the mixture was allowed to react with sufficient stirring so that the particles were not coalesced.
After the obtained reaction product was dried, heat treatment was performed at 130 ° C. for 2 hours, and then adjusted to a desired particle size distribution by classification to obtain silica particles A-1.

[Silica particles A-3 to 10]
As shown in Table 1, the silica particle A is the same as the silica particle A-1, except that the average gas supply rate, the hydrogen supply amount, the oxygen ratio, and the surface treatment amount with hexamethyldisilazane are changed.
-3 to 10 were obtained.

[Silica particle A-2]
To a glass reactor having a stirrer, a dropping funnel and a thermometer, 693.0 g of methanol as an alcohol solvent, 46.0 g of water, and 55.3 g of 28% by mass ammonia water were added. A mixed solution of water and ammonia was prepared.
The obtained mixed solution was adjusted to 35 ° C. (reaction temperature), and the reaction temperature was maintained while stirring, and 1293.0 g (8.5 mol) of tetramethoxysilane and 464.5 g of 5.4 mass% aqueous ammonia were added. At the same time, dripping was started.
At this time, tetramethoxysilane was dropped over 8 hours (dropping time). The dropping speed of ammonia water was adjusted so that dropping was completed one hour earlier than tetramethoxysilane.
After completion of the dropwise addition of tetramethoxysilane, the mixture was stirred for 1 hour for hydrolysis to obtain a methanol-water dispersion of sol-gel silica fine particles.
Next, the dispersion was heated to 75 ° C. to distill off 1320 g of methanol, and then 1320 g of water was added. The mixture was heated to 90 ° C. to distill off 532.4 g of methanol to obtain an aqueous dispersion of sol-gel silica fine particles.
After adding 1584 g of methyl isobutyl ketone to the aqueous dispersion, the mixture was heated to 90 to 110 ° C., and 1474 g of a mixture of methanol and water was distilled off over 15 hours.
After cooling the obtained methyl isobutyl ketone dispersion of sol-gel silica fine particles to 25 ° C., 322 g of hexamethyldisilazane (2.0 mol, 0.24 mol relative to 1 mol of SiO ₂ unit) is added as a surface treatment agent. The sol-gel silica fine particles were subjected to surface treatment by heating to 120 ° C. and reacting for 5 hours.
By removing the solvent from the dispersion under reduced pressure at 80 ° C., silica particles A-2 were obtained. Table 2 shows the physical properties of the resulting silica particle A-2.

[Production Example 1 of toner mother particles]
Resin 1 60.0 parts by mass Resin 2 40.0 parts by mass Paraffin wax (melting point 76 ° C.) 6.0 parts by mass C.I. I. Pigment Blue 15: 3 4.5 parts by mass After the above materials were thoroughly mixed with a Henschel mixer (“FM-75 type”, manufactured by Mitsui Miike Chemical Co., Ltd.), a twin-screw kneader set at a temperature of 130 ° C. ( It knead | mixed with "PCM-30 type | mold", Ikegai Iron Works Co., Ltd. product. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The obtained coarsely crushed material was finely pulverized using a collision-type airflow pulverizer using high-pressure gas. Next, classification was performed with an air classifier (“Elbow Jet Lab EJ-L3”, manufactured by Nittetsu Mining Co., Ltd.) using the Coanda effect, and fine particles and coarse particles were classified and removed at the same time to obtain base particles 1.
The softening point (1/2 method) of toner base particles 1 was 105 ° C.

[Production Example 2 of toner mother particles]
Resin 1 80.0 parts by mass Resin 2 20.0 parts by mass Paraffin wax (melting point 62 ° C.) 8.0 parts by mass C.I. I. Pigment Blue 15: 3 4.5 parts by mass Toner base particles 2 were obtained in the same manner as toner base particles 1 using the above materials.
The softening point (1/2 method) of the toner base particles 2 was 93 ° C.

[Production Example 3 of toner mother particles]
Resin 1 50.0 parts by mass Resin 2 50.0 parts by mass Fischer-Tropsch wax (melting point 105 ° C.) 4.0 parts by mass C.I. I. Pigment Blue 15: 3 4.5 parts by mass Toner base particles 3 were obtained in the same manner as in toner base particles 1.
The softening point (1/2 method) of the toner base particles 3 was 108 ° C.

[Production Example 4 of toner mother particles]
Resin 1 60.0 parts by mass Resin 2 40.0 parts by mass Paraffin wax (melting point: 58 ° C.) 5.0 parts by mass C.I. I. Pigment Blue 15: 3 4.5 parts by mass Toner base particles 4 were obtained in the same manner as toner base particles 1 using the above materials.
The softening point (1/2 method) of the toner base particles 4 was 105 ° C.

[Production Example 5 of toner mother particles]
Resin 1 60.0 parts by mass Resin 2 40.0 parts by mass polypropylene wax (melting point 140 ° C.) 6.0 parts by mass C.I. I. Pigment Blue 15: 3 4.5 parts by mass Toner base particles 5 were obtained in the same manner as the toner base particles 1 using the above materials.
The softening point (1/2 method) of the toner base particles 5 was 105 ° C.

[Production Example 6 of toner mother particles]
Resin 2 100.0 parts by mass Rice wax (melting point 79 ° C.) 3.0 parts by mass carbon black 5.0 parts by mass charge control agent (E-304, Orient Chemical Co., Ltd.) 1.0 part by mass In the same manner as the mother particle 1, toner mother particles 6 were obtained.
The softening point (1/2 method) of the toner base particles 6 was 140 ° C.

[Toner Production Example 1]
Toner base particle 1 100.0 parts by mass Silica particles A-1 4.0 parts by mass The above materials were put into a Henschel mixer ("FM-75 type", manufactured by Mitsui Miike Chemical Co., Ltd.), and the peripheral speed of the rotating blades Was mixed at a mixing time of 5 minutes to obtain toner base particles A-1 having silica particles A-1 attached to the surfaces of the toner base particles 1.
The thus obtained toner base particles A-1 were treated by a surface treatment apparatus using hot air as shown in FIG.
As conditions for the surface modification, the raw material supply rate is 3.0 kg / hr, the hot air flow rate is 4.8 m ³ / min, the hot air discharge temperature is 220 ° C., the cold air temperature is 3 ° C., and the cold air flow rate is 3.5 m ³ / Surface treatment was performed at an absolute moisture content of 3 g / m ³ for min.
Next, classification was performed with an air classifier (“Elbow Jet Lab EJ-L3”, manufactured by Nittetsu Mining Co., Ltd.) using the Coanda effect, whereby fine powder and coarse powder were simultaneously removed to obtain toner particles 1.
To 100.0 parts by mass of the obtained toner particles 1, 0.5 parts by mass of fumed silica particles treated with hexamethyldisilazane (10% by mass) having a number average particle diameter of primary particles of 20 nm are further added. External addition was performed to obtain toner 1.

[Toner Production Example 2]
In addition to 100.0 parts by mass of toner particles 1 thus obtained, 1.0 part by mass of titanium oxide particles having a primary particle number average particle size of 40 nm and treated with i-butyltrimethoxysilane (10% by mass). A toner 2 was obtained in the same manner as in Toner Production Example 1 except that was added externally.

[Toner Production Examples 3 to 19]
Table 3 shows the used toner base particles, silica particles A, the adhesion conditions of silica particles A to the toner base particles (addition amount, peripheral speed of rotating blades in a Henschel mixer), and surface modification conditions (hot air discharge temperature). Toners 3 to 19 were obtained in the same manner as in Toner Production Example 1 except that
The respective conditions are shown in Table 3, and the physical properties are shown in Table 4.

<Example of manufacturing magnetic carrier>
100 parts by mass of 50% particle size 50% particle size (D50) Mn-Mg-ferrite particles, 1 part by mass of silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd .: KR271), 0.5 part by mass of γ-aminopropyltriethoxysilane And 98.5 parts by mass of toluene were added, and the mixture was further dried under reduced pressure at 70 ° C. for 5 hours while stirring and mixing with a solution vacuum kneader to remove the solvent. Then, it baked at 140 degreeC for 2 hours, and sieved with the sieve shaker (300MM-2 type | mold, Tsutsui physics and chemistry machine: 75 micrometer opening), D50 obtained the magnetic carrier of 38 micrometers.

<Example 1>
Next, a two-component developer was prepared using the toner 1 and the magnetic carrier prepared as described above. The two-component developer was mixed at a blending ratio of 9 parts by mass of toner with respect to 100 parts by mass of the magnetic carrier and mixed for 5 minutes with a V-type mixer. Each evaluation mentioned later was implemented about the obtained two-component system developer. The evaluation results are shown in Tables 5 and 6.

<Examples 2 to 15 and Comparative Examples 1 to 4>
A two-component developer was prepared in the same manner as in Example 1 except that the toner 1 was changed to toners 2 to 19, and each evaluation described below was performed on the obtained two-component developer. The evaluation results are shown in Tables 5 and 6.

<Evaluation of two-component developer>
The two-component developer was evaluated using the following evaluation items.
Various evaluations of the low-temperature fixability, hot offset resistance, image density, image density fluctuation, and transferability of the obtained two-component developer were evaluated as temperature 23 ° C./humidity 50% RH (hereinafter “N / N”). The temperature was 30 ° C./humidity was 80% RH (hereinafter “H / H”). Detailed evaluation methods and evaluation criteria will be described later. As an image forming apparatus for various evaluations, a Canon color copying machine imageRUNNER iRC3580 was used. The modified part is that the peripheral speed of the developer carrier relative to the developing drum is 400 mm / sec and the peripheral speed of the photosensitive drum is 245 mm / sec. The two-component developer was evaluated by putting it in a cyan developing device of an image forming apparatus.

<Low temperature fixability>
The paper used was plain paper CS-814 (A4, 81.4 g / m ² ) (sold from Canon Marketing Japan Inc.) for color copiers and printers.
The DC voltage _VDC was adjusted so that the amount of toner applied on the paper of the FFH image (hereinafter, solid portion) was 0.5 mg / cm ² to obtain an unfixed FFH image.
Thereafter, an external fixing device (belt & roller fixing device) of a copy machine “imagePRESS C1 +” for Canon production was remodeled so as to have a process speed of 300 mm / sec.
The fixing temperature in the external fixing device was adjusted every 10 ° C. within the range of 100 to 200 ° C., and the unfixed FFH image was fixed at each temperature to obtain a fixed image. The obtained fixed image is rubbed 5 times with a lens cleaning wiper (Dasper Ozu Sangyo Co., Ltd.) applied with a load of 4.9 kPa, and the density reduction rate of the image density before and after the rubbing is 10% or less. The fixing temperature was evaluated according to the following evaluation criteria.
A: Fixing temperature of 120 ° C. or less (very good)
B: Fixing temperature 130 ° C. (good)
C: Fixing temperature 140 ° C. (Acceptable level in the present invention)
D: Fixing temperature of 150 ° C. or higher (level unacceptable in the present invention)

<Hot offset resistance>
The paper used was plain paper CS-814 (A4, 81.4 g / m ² ) (sold from Canon Marketing Japan Inc.) for color copiers and printers.
The DC voltage _VDC was adjusted so that the amount of toner applied on the paper of the FFH image (hereinafter, solid portion) was 0.2 mg / cm ² to obtain an unfixed FFH image.
Thereafter, an external fixing device (belt & roller fixing device) of a copy machine imagePRESS C1 + for Canon production was remodeled so as to have a process speed of 300 mm / sec, and used for hot offset resistance evaluation.
The reflectivity of the evaluation paper before image printing is reflected by the reflectometer ("REFLECTOMETER"
Measured by “MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.), the average value measured at five locations was defined as D _A (%). The fixing temperature in the external fixing device is adjusted every 10 ° C. within the range of 100 to 200 ° C., the reflectance of the white background portion of the fixed image at each fixing temperature is measured with a reflectometer, and the maximum value is expressed as D _B (%). did.
The difference between D _A (%) and D _B (%) did not exceed 2%, and the highest fixing temperature was set as the fixing upper limit temperature, and hot offset resistance was evaluated according to the following criteria.
A: The fixing upper limit temperature is 190 ° C. or higher (very good)
B: Fixing upper limit temperature is 180 ° C. (good)
C: fixing upper limit temperature is 170 ° C. (acceptable level in the present invention)
D: The upper limit fixing temperature is 160 ° C. or less (a level unacceptable in the present invention).

<Evaluation of image density (evaluation of durability)>
The paper used was plain paper CS-814 (A4, 81.4 g / m ² ) (sold from Canon Marketing Japan Inc.) for color copiers and printers.
The DC voltage _VDC was adjusted so that the amount of solid toner on the paper was 0.5 mg / cm ² . An FFH image was printed and the image density (reflection density) was determined (initial). Thereafter, 50000 sheets were printed at an image ratio of 1%. After printing 50000 sheets, an FFH image was printed again, and the image density (reflection density) was measured (after 1% Duty 50000 sheets). As the paper, CS-814 (A4, 81.4 g / m ² ) (sold from Canon Marketing Japan Inc.) was used. The image density (reflection density) was measured using a spectral densitometer 500 series (manufactured by X-Rite) and judged based on the following criteria.
Further, the same evaluation was performed after printing 50000 sheets with an image ratio of 30% (after 30% Duty 50000 sheets).
A: 1.50 or more B: 1.40 or more and less than 1.50 (good)
C: 1.30 or more and less than 1.40 (acceptable level in the present invention)
D: less than 1.30 (level unacceptable in the present invention)

<Transferability>
The evaluation paper was evaluated using “GF-R070 (A4, basis weight 66.0 g / m ² )” (sold from Canon Marketing Japan Inc.).
The toner loading amount on the paper surface in the solid portion is 0.5 mg / cm ^2, and when 100 images having the solid surface on the entire surface are output, the toner loading amount is again 0.5 mg / cm ^2. Then, one image with the whole surface of the paper being solid was output, the amount of toner on the drum and the amount of toner on the transfer paper were measured, and the transfer efficiency was obtained from the change in the weight (the amount of toner on the drum was all on the paper) The transfer efficiency is 100%).
A: Transfer efficiency is 95% or more (very good)
B: Transfer efficiency is 90% or more and less than 95% (good)
C: Transfer efficiency is 80% or more and less than 90% (acceptable level in the present invention)
D: Transfer efficiency is less than 80% (not acceptable in the present invention)

100: Toner particle supply port, 101: Hot air supply port, 102: Airflow injection member, 103: Cold air supply port, 104: Second cold air supply port, 106: Cooling jacket, 114: Toner particles, 115: High pressure air supply nozzle 116: Transfer piping

Claims (5)

In a toner having toner particles containing at least a binder resin, a colorant, wax and silica particles A,
The silica particles A have a number average particle size of primary particles of 60 nm or more and 300 nm or less, and are fixed to the surface of the toner particles by treatment with hot air.
The theoretical coverage by the silica particles A obtained from the following formula (I) is A (%), and the coverage by the silica particles A calculated by X-ray photoelectron spectroscopy is B ( %), and the number average particle diameter of primary particles of the silica particles a is taken as D _a,
The exposed height of the silica particles A, [D _A / 2-D _A / 2 (1-B / A) ^1/2 ] is 30 nm or more,
The coverage B is 5% or more state, and are 45% or less,
The toner average circularity is characterized der Rukoto 0.955 or 0.980 or less.
Formula (I) Theoretical coverage [A] = (3 ^1/2 × D ₄ × ρt) / (2π × D _A × ρ _A ) × C
[Wherein D ₄ is the weight average particle diameter of the toner, ρt is the true density of the toner, D _A is the number average particle diameter of the primary particles of the silica particles A, ρ _A is the true density of the silica particles A, and [C] is The addition amount [parts by mass] of silica particles A with respect to 100 parts by mass of toner particles is represented . ] The toner according to claim 1, wherein the silica particles A have a number average particle size of primary particles of 100 nm or more and 300 nm or less. The binder resin comprises a polyester resin, wherein the wax is characterized in that it comprises a 110 ° C. or less of the hydrocarbon wax above the melting point 60 ° C., toner according to claim 1 or 2. The relation of the following formula (1) is satisfied, where the BET specific surface area of the silica particles A is BET _A (m ² / g) and the true density is ρ _A (g / cm ³ ). The toner according to any one of 1 to 3 .
Formula (1) 0.85 ≦ BET _A / [6 / (D _A × ρ _A )] ≦ 1.50 The toner is further primary particle number-average particle diameter of 5nm or more, less 50 nm, characterized in that it contains at least one of the particles of the silica particles and titanium oxide particles according to claim 1
5. The toner according to any one of 4 above.

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