JP6272018B2 - toner - Google Patents

Description

  The present invention relates to a toner used in a recording method such as an electrophotographic method, an electrostatic recording method, a magnetic recording method, or a toner jet method.

In an image forming apparatus using an electrophotographic system such as a copying machine or a laser printer, there are various demands such as further downsizing, weight reduction, energy saving and printing speed increase. It is widely known that the one-component contact development method is useful in reducing the size and weight of the apparatus.
In addition, the toner is strongly required to have excellent low-temperature fixability and heat stability in order to satisfy the above performance. Therefore, many methods have been proposed in which a toner contains a crystalline polyester resin that exhibits high heat stability in a high temperature environment and can be quickly melted by heat during fixing (so-called sharp melt property) ( Patent Document 1).
However, a toner containing such a crystalline resin has improved low-temperature fixability but has a tendency to lower the resin strength. As a result, there has been a problem with durability such as adhesion to the developing blade and occurrence of uneven stripes on the developing roller when more mechanical stress is applied as the speed and size are reduced. In order to solve this problem, a toner containing a high molecular weight crystalline polyester has been proposed (Patent Document 2).

Japanese Patent Laid-Open No. 01-161260 JP 2013-127607 A

  Such prior art toners have excellent properties. However, in a low temperature and low humidity environment, there is room for improvement in compatibility between fluidity and fixability in a toner containing a crystalline polyester resin having a high molecular weight.

As a result of intensive studies, the inventors of the present invention have improved the fluidity of the toner by fixing inorganic fine particles containing silica fine particles having a small particle size to the toner surface uniformly and moderately, and the crystallinity existing in the toner surface layer. The present inventors have found that the above problems can be solved without impairing the melting characteristics of the polyester, and have completed the present invention.
That is, the present invention
Toner particles containing a binder resin and crystalline polyester;
Inorganic fine particles,
A non-magnetic toner having
(I) The crystalline polyester has a melting point (Tm) of 60 ° C. or higher and 100 ° C. or lower,
(Ii) In the molecular weight distribution measured by gel permeation chromatography (GPC) of the crystalline polyester, the weight average molecular weight (Mw) is 20,000 to 50,000,
(Iii) The non-magnetic toner contains 1.5 to 3.0 parts by mass of the inorganic fine particles with respect to 100.0 parts by mass of the toner particles.
(Iv) 30% by mass or more of the inorganic fine particles are silica fine particles, and the number average particle diameter (D1) of the primary particles of the silica fine particles is 4.0 nm or more and 15.0 nm or less,
(V) The inorganic fine particles have a liberation rate of 10.0% by mass or more and 25.0% by mass or less,
(Vi) The present invention relates to a non-magnetic toner characterized in that the variation coefficient of the coverage of the toner particles by the inorganic fine particles is 6.0% or less.

  According to the present invention, it is possible to uniformly and moderately fix inorganic fine particles containing silica fine particles having a small particle diameter to a toner, and in a low-temperature and low-humidity environment, while suppressing the generation of streaks, the fixability and fluidity are improved. A toner capable of achieving both can be provided.

Schematic diagram showing an example of a mixing treatment apparatus that can be used for external addition mixing of inorganic fine particles The schematic diagram which shows an example of a structure of the stirring member used for a mixing processing apparatus

The toner of the present invention is
Toner particles containing a binder resin and crystalline polyester;
Inorganic fine particles,
A non-magnetic toner (hereinafter also simply referred to as toner) having
(I) Tm of the crystalline polyester,
(Ii) While Mw measured by GPC is within a certain range,
(Iii) containing 1.5 to 3.0 parts by mass of the inorganic fine particles with respect to 100.0 parts by mass of the toner particles;
(Iv) The inorganic fine particles contain 30% by mass or more of silica fine particles having a small particle diameter. Further, (v) the liberation rate of the inorganic fine particles and (vi) the coefficient of variation of the coverage are within a certain range.
Next, the reason why the above problem is solved in the present invention will be described in detail.
From the viewpoint of suppressing streaks in a one-component contact development method, a method using a toner containing a crystalline polyester having a high weight average molecular weight (Mw) in order to improve the resin strength of the crystalline polyester resin is widely known. ing.
However, simply adding inorganic fine particles including silica fine particles having a small particle diameter to the toner causes, for example, the fixed state of the inorganic fine particles to be non-uniform, insufficient fixation, and release of a large amount of inorganic fine particles. A malfunction occurs. As a result, there has been a problem that the fluidity of the toner is lowered in the initial printing and the latter half of the printing life.
Further, when the inorganic fine particles are strongly fixed to suppress release, the embedded inorganic fine particles form a pseudo shell on the toner surface, and the resin strength of the crystalline polyester as described above is increased. This also becomes a factor, which hinders the melting characteristics of the toner. For this reason, there is a problem that the fixability in a low temperature and low humidity environment is impaired.
Therefore, the present inventors control the coefficient of variation of the inorganic fine particle liberation rate and the toner particle coverage rate, which indicates the state of the inorganic fine particles fixed to the toner particles, and adjust the values within a certain range to adjust the inorganic fine particles to the toner particles. Was successfully fixed uniformly and reasonably well.
Therefore, it has been found that if the above physical properties can be adjusted within a certain range, the toner can be fixed in a low temperature and low humidity environment while having high fluidity, and the present invention has been completed.

The toner of the present invention will be specifically described below.
In the present invention, the liberation rate of the inorganic fine particles is 10.0% by mass or more and 25.0% by mass or less, and the variation coefficient of the coverage of the toner particles by the inorganic fine particles is 6.0% or less.
The liberation rate of the inorganic fine particles indicates a fixed state of the inorganic fine particles to the toner particles. When the inorganic fine particles are less than 10.0% by mass, the inorganic fine particles are strongly driven into the toner particles, and the desired low temperature of the toner. Fixability in a low humidity environment cannot be obtained. On the other hand, when the content exceeds 25.0% by mass, the inorganic fine particles tend to be detached from the toner because of insufficient adhesion to the toner. As a result, the desired fluidity cannot be obtained in the latter half of the printing life.
Further, when the variation coefficient of the coverage of the toner particles exceeds 6.0%, the desired fluidity cannot be obtained because the fixed state of the inorganic fine particles is not uniform.
In the present invention, the liberation rate of the inorganic fine particles is preferably 10.0% by mass or more and 15.0% by mass or less, and the variation coefficient of the coverage of the toner particles by the inorganic fine particles is 5.0% or less. preferable.
The coefficient of variation of the inorganic fine particle liberation rate and toner particle coverage rate is, for example, the type and amount of inorganic fine particles, the number of rotations of the stirring member, and the like when a mixing apparatus as shown in FIG. 1 is used. It is possible to adjust by appropriately changing the conditions.

The toner of the present invention contains toner particles and inorganic fine particles. Further, the toner contains 1.5 to 3.0 parts by mass, preferably 1.5 to 2.5 parts by mass of inorganic fine particles with respect to 100.0 parts by mass of toner particles.
In the present invention, from the viewpoint of developability, 30.0% by mass or more of the inorganic fine particles are preferably silica fine particles, and 40.0% by mass or more of the inorganic fine particles are preferably silica fine particles.
Hereinafter, the silica fine particles will be specifically described.
As the silica fine particles used in the present invention, it is possible to use both a dry process produced by vapor phase oxidation of a silicon halogen compound or dry silica called fumed silica, and wet silica produced from water glass or the like. it can. In the present invention, dry silica having less silanol groups on the surface and inside and no production residue is preferred.
The number average particle size of the primary particles of the silica fine particles is 4.0 nm or more and 15.0 nm or less and 5.0 nm or more and 10.0 nm or less from the viewpoint of imparting excellent fluidity to the toner particles. Is preferred.
Subsequently, a preferable treatment of the silica fine particles used in the toner of the present invention will be specifically described below.
In the present invention, the silica fine particles are preferably obtained by treating the surface of the silica fine particles with at least silicone oil. More preferably, it is obtained by treating the surface of silica fine particles with a silicone oil and then treating with a silane compound or a silazane compound.
When the silica fine particles are silica fine particles treated with silicone oil, it is possible to control chargeability during storage in a high temperature and high humidity environment. In addition, when the silica fine particles are silica fine particles treated with a silicone oil and then treated with a silane compound or a silazane compound, the chargeability during storage in a high temperature and high humidity environment and the fluidity after storage in a high temperature and high humidity environment Can be established at a higher level.
Moreover, it is more preferable that the silica fine particles used in the present invention have been subjected to a crushing treatment after a treatment with silicone oil or the like. By performing the crushing treatment, the fluidity of the toner is further enhanced.

In the present invention, the amount of silicone oil extracted from hexane in the silica fine particle is preferably 0.50% by mass or less, more preferably from the viewpoint of fluidity after storage in a high temperature and high humidity environment. It is 0.10 mass% or less.
The amount of the extracted silicone oil can be appropriately controlled depending on the amount of treatment and the treatment temperature when the silica fine particles are treated with the silicone oil.
Further, in the present invention, the hydrophobization rate of the silica fine particles is preferably 95% or more and 100% or less, more preferably 97% or more and 100% or less, from the viewpoint of chargeability during storage in a high temperature and high humidity environment. is there.
The hydrophobization rate of the silica fine particles can be appropriately controlled depending on the treatment amount when the silica fine particles are treated with the silicone oil and the treatment conditions with the silane compound or the silazane compound.

As the silicone oil used for the treatment of the silica fine particles, a known silicone oil can be used without particular limitation, but straight silicone is preferable.
More specifically, for example, dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, fluorine-modified silicone oil, methyl hydrogen silicone oil and the like can be mentioned. Silicone oils can be used singly or in combination of two or more.
As a treatment method using silicone oil, for example, silica fine particles and silicone oil may be directly mixed using a mixer such as a Henschel mixer. Alternatively, a method of stirring while spraying silicone oil onto silica fine particles may be used. Alternatively, the silicone oil may be dissolved or dispersed in a suitable solvent (preferably adjusted to pH 4 with an organic acid or the like), and then mixed with silica fine particles, and then the solvent may be removed. Also, silica fine particles are put into a reaction vessel, alcohol water is added with stirring in a nitrogen atmosphere, a solvent solution of silicone oil is introduced into the reaction vessel, surface treatment is performed, and the solvent is removed by heating and stirring. You may take
In this invention, when processing with a silicone oil, it is good to use a silicone oil by 1 to 50 mass parts in total with respect to 100 mass parts of silica fine particles.
On the other hand, as a silane compound or silazane compound used for the treatment of silica fine particles, a known silane compound or silazane compound can be used without particular limitation.
Specifically, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchloro. Silane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldi And ethoxysilane. Among these, hexamethyldisilazane is preferably used from the viewpoint of processing uniformity and coupling bond reliability. Silane compounds or silazane compounds can be used alone or in combination of two or more.
Examples of the treatment with the silane compound or the silazane compound include a dry treatment in which the vaporized silane compound or silazane compound is reacted with the silica fine particles made into a cloud by stirring. In addition, a generally known method such as a wet method in which silica fine particles are dispersed in a solvent and a silane compound or a silazane compound is dropped and reacted can be exemplified.
In this invention, when processing with a silane compound or a silazane compound, it is good to use 1 mass part or more and 50 mass parts or less of a silane compound or a silazane compound with respect to 100 mass parts of silica fine particles.

Further, the toner of the present invention may contain inorganic fine particles other than silica fine particles as described above.
As the inorganic fine particles used in the toner of the present invention, conventionally known inorganic fine particles can be used without any particular limitation. Specifically, surface treatment was performed with a treatment agent typified by a silane coupling agent, a titanium coupling agent, and silicone oil; metal oxide fine particles typified by titanium oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles, Or metal oxide fine particles obtained by hydrophobizing the metal oxide; fatty acid metal salts represented by zinc stearate, calcium stearate, zinc stearate, etc .; salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, etc. A metal complex of aromatic carboxylic acid represented; clay mineral represented by hydrotalcite. Among these, it is preferable to use fine titanium oxide particles from the viewpoints of chargeability and fluidity.

Subsequently, as a mixing treatment device for adding inorganic fine particles containing silica fine particles to toner particles and mixing them (hereinafter also referred to as external addition mixing), known mixing treatment devices can be used. An apparatus as shown in FIG. 1 is preferable in that it can easily control the variation coefficient of the liberation rate and the coverage rate.
FIG. 1 is a schematic view showing an example of a mixing treatment apparatus that can be used when externally adding and mixing inorganic fine particles used in the present invention.
The mixing device is configured to take a share in a narrow clearance portion with respect to the toner particles and the inorganic fine particles, so that the inorganic fine particles adhere to the toner particle surface while loosening the inorganic fine particles from the secondary particles to the primary particles. can do.
Further, as will be described later, in the axial direction of the rotating body, the toner particles and the inorganic fine particles are easily circulated, and the coefficient of variation of the free rate and the coverage of the inorganic fine particles is easily reduced before the fixation proceeds. In this invention, it is easy to control to a preferable range.
On the other hand, FIG. 2 is a schematic diagram showing an example of a configuration of a stirring member used in the mixing treatment apparatus.
Hereinafter, the external addition mixing step of the inorganic fine particles will be described with reference to FIGS.
The mixing processing apparatus for externally mixing inorganic fine particles has a rotating body 2 having at least a plurality of stirring members 3 installed on the surface thereof, a drive unit 8 that rotationally drives the rotating body, and a gap between the stirring members 3. The main body casing 1 is provided.
The clearance (clearance) between the inner peripheral portion of the main body casing 1 and the stirring member 3 gives a uniform share to the toner particles and easily adheres to the toner particle surface while loosening the inorganic fine particles from the secondary particles to the primary particles. Therefore, it is preferable to keep it constant and minute.
Further, in this apparatus, the diameter of the inner peripheral portion of the main body casing 1 is not more than twice the diameter of the outer peripheral portion of the rotating body 2. In FIG. 1, an example in which the diameter of the inner peripheral portion of the main casing 1 is 1.7 times the diameter of the outer peripheral portion of the rotating body 2 (the diameter of the body portion obtained by removing the stirring member 3 from the rotating body 2). If the diameter of the inner peripheral portion of the main body casing 1 is less than or equal to twice the diameter of the outer peripheral portion of the rotating body 2, the processing space in which the force acts on the toner particles is appropriately limited. A sufficient impact force is applied to the inorganic fine particles.
Moreover, it is preferable to adjust the said clearance according to the magnitude | size of a main body casing. It is preferable that the diameter of the inner peripheral portion of the main body casing 1 is about 1% or more and 5% or less in that a sufficient share is applied to the inorganic fine particles. Specifically, when the diameter of the inner peripheral part of the main body casing 1 is about 130 mm, the clearance is about 2 mm or more and about 5 mm or less. When the diameter of the inner peripheral part of the main body casing 1 is about 800 mm, the clearance is about 10 mm or more and 30 mm or less. It should be about.
In the external addition mixing process of the inorganic fine particles in the present invention, the rotating body 2 is rotated by the drive unit 8 using the mixing processing device, and the toner particles and the inorganic fine particles charged into the mixing processing device are stirred and mixed. Inorganic fine particles are externally mixed on the surface of the toner particles.
As shown in FIG. 2, at least a part of the plurality of stirring members 3 is formed as a feeding stirring member 3 a that sends toner particles and inorganic fine particles in one axial direction of the rotating body as the rotating body 2 rotates. Is done. At least a part of the plurality of stirring members 3 is formed as a return stirring member 3b that returns the toner particles and the inorganic fine particles to the other direction in the axial direction of the rotating body 2 as the rotating body 2 rotates.
Here, when the raw material inlet 5 and the product outlet 6 are provided at both ends of the main casing 1 as shown in FIG. 1, the direction from the raw material inlet 5 toward the product outlet 6 (in FIG. 1). (Right direction) is called “feed direction”.
That is, as shown in FIG. 2, the plate surface of the feeding stirring member 3a is inclined so as to feed the toner particles in the feeding direction (13). On the other hand, the plate surface of the stirring member 3b is inclined so as to send toner particles and inorganic fine particles in the return direction (12).
Thus, the external addition mixing process of the inorganic fine particles is performed on the surface of the toner particles while repeatedly performing the feed (13) in the “feed direction” and the feed (12) in the “return direction”.
The stirring members 3a and 3b are a set of a plurality of members arranged at intervals in the circumferential direction of the rotating body 2. In the example shown in FIG. 2, the stirring members 3a and 3b form a pair of two members on the rotating body 2 at an interval of 180 degrees, but three members at an interval of 120 degrees or an interval of 90 degrees. It is good also as a set of many members, such as four sheets.
In the example shown in FIG. 2, a total of 12 stirring members 3a and 3b are formed at equal intervals.
Further, in FIG. 2, D indicates the width of the stirring member, and d indicates the interval indicating the overlapping portion of the stirring member. From the viewpoint of efficiently feeding toner particles and inorganic fine particles in the feeding direction and the returning direction, it is preferable that D has a width of about 20% to 30% with respect to the length of the rotating body 2 in FIG. FIG. 2 shows an example of 23%. Furthermore, it is preferable that the stirring members 3a and 3b have some overlap d between the stirring member 3b and the stirring member when an extension line is drawn in the vertical direction from the end position of the stirring member 3a. Thereby, it is possible to efficiently share the inorganic fine particles which are secondary particles. D is preferably 10% or more and 30% or less in terms of applying a share.
Regarding the shape of the blade, in addition to the shape shown in FIG. 2, if the toner particles can be sent in the feeding direction and the returning direction and the clearance can be maintained, the shape having a curved surface and the tip blade portion are A paddle structure coupled to the rotating body 2 with a rod-like arm may be used.
Hereinafter, the present invention will be described in more detail with reference to the schematic views of the apparatus shown in FIGS.
The apparatus shown in FIG. 1 includes a rotating body 2 having at least a plurality of stirring members 3 installed on a surface thereof, a drive unit 8 that rotationally drives the rotating body 2, and a main casing provided with a gap between the stirring member 3 and the main body casing. 1 and a jacket 4 on the inner side of the main body casing 1 and the side surface 10 of the rotating body end, through which a cooling medium can flow.
Further, the apparatus shown in FIG. 1 is used to discharge toner from the main casing 1 and the raw material inlet 5 formed in the upper portion of the main casing 1 and the externally added and mixed toner to introduce toner particles and inorganic fine particles. In addition, a product discharge port 6 formed in the lower part of the main body casing 1 is provided.
Further, in the apparatus shown in FIG. 1, a raw material inlet inner piece 16 is inserted into the raw material inlet 5, and a product outlet inner piece 17 is inserted into the product outlet 6.
In the present invention, first, the raw material inlet inner piece 16 is taken out from the raw material inlet 5, and the toner particles are put into the processing space 9 from the raw material inlet 5. Next, inorganic fine particles are introduced into the treatment space 9 from the raw material inlet 5 and the inner piece 16 for raw material inlet is inserted. Next, the rotating body 2 is rotated by the drive unit 8 (11 indicates the direction of rotation), and the processed material introduced above is externally added while being stirred and mixed by a plurality of stirring members 3 provided on the surface of the rotating body 2. Mix.
The order of charging may be such that the inorganic fine particles are first charged from the raw material charging port 5 and then the toner particles are charged from the raw material charging port 5. Further, after the toner particles and the inorganic fine particles are mixed in advance by a mixer such as a Henschel mixer, the mixture may be supplied from the raw material input port 5 of the apparatus shown in FIG.
Although it does not specifically limit as processing time, Preferably it is 3 to 10 minutes.
Although the rotation speed of the stirring member at the time of external mixing is not particularly limited, the shape of the stirring member 3 in the apparatus in which the volume of the processing space 9 of the apparatus shown in FIG. 1 is 2.0 × 10 ⁻³ m ³ is shown in FIG. The rotation speed of the stirring member when it is made is preferably 1000 rpm or more and 2500 rpm or less. By being 1000 rpm or more and 2500 rpm or less, it becomes easy to obtain the variation coefficient of the free rate of inorganic fine particles and the coverage defined in the present invention.
After completion of the external addition mixing process, the product discharge port inner piece 17 is taken out from the product discharge port 6, the rotating body 2 is rotated by the drive unit 8, and the toner is discharged from the product discharge port 6. From the obtained toner, coarse particles and the like are separated by a sieve such as a circular vibratory sieve as needed to obtain a toner.

  Further, in the toner of the present invention, in order to uniformly fix inorganic fine particles, it is preferable that the surface of the toner particles has a uniform surface with little unevenness. That is, it is preferably 100 or more and 120 or less in SF-2 indicating the degree of unevenness on the surface of the toner particles. The SF-2 calculation method will be described later.

Subsequently, materials used for the toner of the present invention will be specifically described below.
As the binder resin used in the toner of the present invention, a known resin can be used without particular limitation. Specific examples include: vinyl resins; polyester resins; polyamide resins; furan resins; epoxy resins; xylene resins; These resins can be used alone or in combination. As the vinyl resin, styrene monomers represented by styrene, α-methylstyrene, divinylbenzene and the like; methyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, t-methacrylic acid t- Unsaturated carboxylic acid esters typified by butyl, 2-ethylhexyl methacrylate, etc .; Unsaturated carboxylic acids typified by acrylic acid, methacrylic acid, etc .; Unsaturated dicarboxylic acids typified by maleic acid; maleic anhydride, etc. Unsaturated carboxylic acid anhydrides typified by: nitrile vinyl monomers typified by acrylonitrile, etc .; halogen-containing vinyl monomers typified by vinyl chloride, etc .; nitro vinyl monomers typified by nitrostyrene, etc. Monomers or copolymers of monomers such as .

The melting point (Tm) of the crystalline polyester used in the present invention is 60 ° C. or higher and 100 ° C. or lower, preferably 60 ° C. or higher and 90 ° C. or lower, from the viewpoint of fixability in a low temperature and low humidity environment.
The melting point (Tm) of the crystalline polyester can be controlled by the linear length of the polyvalent carboxylic acid and diol that are the raw materials for the crystalline polyester.
From the viewpoint of durability, the crystalline polyester used in the present invention has a weight average molecular weight (Mw) of 20000 or more and 50000 or less, and 20000 or more and 40000 or less in the molecular weight distribution measured by gel permeation chromatography (GPC). It is preferable that In addition, the weight average molecular weight (Mw) of the crystalline polyester can be controlled by various production conditions of the crystalline polyester, for example, the substance amount ratio of the raw polyvalent carboxylic acid and diol, the reaction temperature, the reaction time, etc. It is. A method for measuring the weight average molecular weight (Mw) of the crystalline polyester will be described later.

Further, in order to improve durability during storage in a high temperature and high humidity environment, in the molecular weight distribution chart obtained when measured by GPC of the crystalline polyester, the area with a molecular weight of 3000 or less is relative to the area of the entire chart. It is preferably 15 area% or less, and more preferably 10 area% or less.
The area ratio of the crystalline polyester having a molecular weight of 3000 or less is determined by using a hybrid resin in which an amorphous vinyl moiety or the like is introduced into the crystalline polyester resin, or the area ratio of the amorphous vinyl moiety in the hybrid resin. It can be controlled by adjusting the amount.
The crystalline polyester can be obtained by reacting a divalent or higher polyvalent carboxylic acid with a diol. Among these, a polyester mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid is preferable because of high crystallinity.
As the alcohol monomer for obtaining such a crystalline polyester, a known alcohol monomer can be used. Specifically, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octane Alcohol monomer such as diol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol; divalent alcohol such as polyoxyethylenated bisphenol A An aromatic alcohol such as 1,3,5-trihydroxymethylbenzene and a trivalent alcohol such as pentaerythritol can be used.
On the other hand, a known carboxylic acid monomer can be used as the carboxylic acid monomer for obtaining the crystalline polyester. Specifically, for example, dicarboxylic acids such as oxalic acid and sebacic acid and anhydrides or lower alkyl esters of these acids; trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid Trivalent or higher polyvalent acids such as acid, pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane Carboxylic acid components and derivatives of these acid anhydrides or lower alkyl esters.
The crystalline polyester can be produced by a known polyester synthesis method. For example, a dicarboxylic acid component and a dial alcohol component are esterified or transesterified, and then subjected to a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method to obtain a crystalline polyester.
In the esterification or transesterification reaction, an ordinary esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, and tetrabutyl titanate can be used as necessary. For polymerization, conventional polymerization catalysts such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, and germanium oxide can be used. The polymerization temperature and the amount of catalyst are not particularly limited, and may be arbitrarily selected as necessary.
The crystalline polyester resin may be used as a hybrid resin by introducing an amorphous vinyl moiety into the resin.
A monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used as the vinyl-based polymerizable monomer used when producing the amorphous vinyl moiety in the hybrid resin. Examples of monofunctional polymerizable monomers include styrene; styrene derivatives such as α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso- Acrylic polymerization such as propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate Methacrylic polymerizable monomer in which the acrylic polymerizable monomer is changed to methacrylate.
As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Acrylic polyfunctional polymerizable monomers such as diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate; Methacrylic polyfunctional polymerizable monomer obtained by replacing the acrylic polyfunctional polymerizable monomer with methacrylate; divinylbenzene, divinylnaphthalene, divinylacetate Tell.
As a polymerization initiator used for polymerizing the above-mentioned vinyl-based polymerizable monomer when producing the hybrid resin, as long as it does not inhibit the effects of the present invention other than those used in the present invention, Oil-soluble initiators and / or water-soluble initiators can be used as appropriate.
For example, as an oil-soluble initiator, azo compounds such as 2,2′-azobisisobutyronitrile; t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, lauroyl peroxide, t-butyl Examples thereof include peroxides such as peroxy 2-ethylhexanoate, t-butyl peroxyisobutyrate, di-t-butyl peroxyisophthalate, and di-t-butyl peroxide.
Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloric acid Salt, azobis (isobutylamidine) hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2 -Hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2- (1-hydroxybutyl)]-propionamide}, hydrochloride ferrous sulfate or hydrogen peroxide.
Here, in the present invention, the “crystalline polyester resin” refers to having a clear endothermic peak in the differential scanning calorimetry (DSC) instead of a stepwise endothermic change.
Even when the crystalline polyester resin has an amorphous vinyl moiety introduced into the resin, if the crystalline polyester resin has a clear endothermic peak in differential scanning calorimetry (DSC), this is also crystalline. Contained in the conductive polyester resin.

The toner of the present invention may further contain a polar resin. Specific examples include the following carboxy group-containing vinyl resins; carboxy group-containing polyester resins; carboxy group-containing polyurethane resins; carboxy group-containing polyamide resins. As the carboxy group-containing vinyl resin, a homopolymer of a carboxy group-containing monomer represented by the following; unsaturated carboxylic acid; unsaturated dicarboxylic acid; and the carboxy group-containing monomer; And a copolymer with an unsaturated carboxylic acid ester, an unsaturated dicarboxylic acid anhydride, a nitrile vinyl monomer, a halogen-containing vinyl monomer, a nitro vinyl monomer, and the like. In the present invention, the polar resin refers to a resin containing a carboxy group in its structure.
The content of the polar resin is preferably 1.0 part by mass or more and 20.0 parts by mass or less, more preferably 2.0 parts by mass or more and 10.0 parts by mass with respect to 100.0 parts by mass of the binder resin. Or less.

The toner of the present invention may further contain a colorant. As the colorant, known pigments and dyes of black, yellow, magenta, cyan, and other colors can be used without particular limitation.
Specific examples of the black colorant include black pigments typified by carbon black.
Specific examples of the yellow colorant include the following monoazo compounds; disazo compounds; condensed azo compounds; isoindoline compounds; isoindolinone compounds; benzimidazolone compounds; anthraquinone compounds; azo metal complexes; methine compounds; And yellow pigments and yellow dyes represented by the above.
Specific examples of the magenta colorant include the following monoazo compounds; condensed azo compounds; diketopyrrolopyrrole compounds; anthraquinone compounds; quinacridone compounds; basic dye lake compounds; naphthol compounds: benzimidazolone compounds; thioindigo compounds; And magenta pigments and magenta dyes.
Specific examples of cyan colorants include the following copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds; cyan pigments and cyan dyes typified by basic dye lake compounds and the like.
The colorant is preferably used in an amount of 1.0 to 20.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

The toner of the present invention may further contain a release agent. Specifically, the following: monofunctional ester waxes represented by behenyl behenate, stearyl stearate, palmitic acid palmitate, etc .; difunctional ester waxes represented by dibehenyl sebacate, hexanediol dibehenate, etc .; Trifunctional ester waxes represented by glycerin tribehenate; tetrafunctional ester waxes represented by pentaerythritol tetrastearate, pentaerythritol tetrapalmitate, etc .; dipentaerythritol hexastearate, dipentaerythritol hexapalmi Hexafunctional ester waxes typified by Tate and the like; Multifunctional ester waxes typified by polyglycerin behenate; Natural ester waxes typified by carnauba wax and rice wax; Petroleum waxes such as raffin wax, microcrystalline wax, petrolatum and their derivatives; hydrocarbon waxes and derivatives thereof according to the Fischer-Tropsch method; polyolefin waxes and their derivatives such as polyethylene wax and polypropylene wax; higher aliphatic alcohols; stearic acid, palmitic acid Fatty acids such as acids; acid amide waxes and the like.
The release agent is preferably used in an amount of 1.0 to 30.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

The toner of the present invention may further contain a charge control agent. As the charge control agent, a conventionally known charge control agent can be used without any particular limitation. Specifically, as a negative charge control agent, the following metal complexes of aromatic carboxylic acids represented by salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, etc .; sulfonic acid group, sulfonic acid group or sulfonic acid Examples thereof include polymers or copolymers having an ester group; metal salts or metal complexes of azo dyes or azo pigments; boron compounds, silicon compounds, calixarene, and the like. Examples of the positive charge control agent include the following quaternary ammonium salts, polymer compounds having a quaternary ammonium salt in the side chain; guanidine compounds; nigrosine compounds; imidazole compounds. Examples of the polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group include styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfone. A homopolymer of a sulfonic acid group-containing vinyl monomer typified by acid, vinyl sulfonic acid, methacryl sulfonic acid or the like, or a copolymer of the above-mentioned vinyl polymerizable monomer and the sulfonic acid group-containing vinyl monomer, etc. Can be used.
The addition amount of the charge control agent is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, more preferably 0.5 parts by mass or more and 10.0 parts by mass with respect to 100.0 parts by mass of the binder resin. Or less.

Subsequently, the toner particles used in the present invention and the method for producing the toner will be specifically described below.
As a method for producing toner particles, a conventionally known method can be used without any particular limitation. Specific examples include suspension polymerization method; dissolution suspension method; emulsion aggregation method; spray drying method; Among these, the suspension polymerization method is preferable from the viewpoint of reducing unevenness on the surface layer of the toner particles.
When obtaining toner particles in the suspension polymerization method, the polymerizable monomer and crystalline polyester constituting the binder resin, and, if necessary, a colorant, a release agent, a polar resin, a charge control agent, etc. Other materials are uniformly dissolved or dispersed to form a polymerizable monomer composition. Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer as necessary using a suitable stirrer. Thereafter, the polymerizable monomer is polymerized to obtain toner particles having a desired particle size.
After the polymerization, the toner particles are filtered, washed and dried by a known method, and the inorganic fine particles are externally added and mixed as described above to adhere to the surface of the toner particles, thereby obtaining the toner of the present invention.
Examples of the polymerizable monomer for obtaining toner particles by the suspension polymerization method include the above-described vinyl polymerizable monomers.
When toner particles are obtained by the suspension polymerization method, a polymerization initiator may be further used.
As the polymerization initiator, a known polymerization initiator can be used without particular limitation. Specifically: 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) ), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo-based or diazo-based polymerization initiators typified by azobisisobutyronitrile, etc .; benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroper Peroxides such as oxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, etc. An oxide polymerization initiator is mentioned.
When toner particles are obtained by the suspension polymerization method, known chain transfer agents, polymerization inhibitors and the like can be further used.
When toner particles are obtained by a suspension polymerization method, an inorganic or organic dispersion stabilizer may be further contained in the aqueous medium. As the dispersion stabilizer, a known dispersion stabilizer can be used without any particular limitation. Specifically, as inorganic dispersion stabilizers, the following phosphates represented by hydroxyapatite, tricalcium phosphate, dicalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, etc .; calcium carbonate, magnesium carbonate, etc. Carbonates typified by: metal hydroxides typified by calcium hydroxide, magnesium hydroxide, aluminum hydroxide; sulfates typified by calcium sulfate, barium sulfate, etc., calcium metasilicate, bentonite, silica, alumina Etc. Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and salts thereof, and starch.
When toner particles are obtained by the suspension polymerization method, a surfactant may be further contained in the aqueous medium. As the surfactant, a known surfactant can be used without any particular limitation. Specifically, the following anionic surfactants typified by sodium dodecylbenzene sulfate, sodium oleate and the like; cationic surfactants; amphoteric surfactants; nonionic surfactants and the like can be mentioned.
When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, but in order to obtain finer particles, the inorganic compound may be generated and used in an aqueous medium. For example, in the case of calcium phosphates such as hydroxyapatite and tricalcium phosphate, an aqueous phosphate solution and an aqueous calcium salt solution may be mixed with high stirring.

Subsequently, the measurement method of the present invention will be specifically described below.
<Measurement of weight average molecular weight (Mw) of crystalline polyester and area ratio of molecular weight of 3000 or less>
The molecular weight distribution of the crystalline polyester is measured by gel permeation chromatography (GPC) as follows.
First, 0.03 g of crystalline polyester is dispersed and dissolved in 10 ml of o-dichlorobenzene, and then allowed to stand at 135 ° C. for 24 hours for dissolution. 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. Using this sample solution, measurement is performed under the following conditions.
[Analysis conditions]
Separation column: TSKgel GMHHR-HHT 7.8 cmI. D x 30cm 2 series (Tosoh Corporation)
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene mobile phase flow rate: 1.0 ml / min.
Sample concentration: 0.3%
Injection volume: 300 μl
Detector: Differential refractive index detector Shodex RI-71 (Showa Denko KK)
In calculating the molecular weight of the sample, standard polystyrene resin (TSO standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- manufactured by Tosoh Corporation) was used. 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500).

  The area% of the crystalline polyester having a molecular weight of 3000 or less is an area having a molecular weight of 3000 or less in the molecular weight distribution chart (horizontal axis: retention time, vertical axis: voltage value detected by RI) obtained by the GPC measurement. It is the ratio (%) of the area to the area of the entire chart.

<Measurement of melting point of crystalline polyester>
The melting point (Tm) of the crystalline polyester 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, 5 mg of crystalline polyester is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rises between 30 ° C. and 200 ° C. in the measurement temperature range. Measurement is performed at a temperature rate of 10 ° 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 peak temperature of the maximum endothermic peak of the DSC curve in the temperature range of 30 ° C. or more and 200 ° C. or less in the second temperature raising process is defined as the melting point (Tm: ° C.) of the crystalline polyester.

<Calculation of the release rate of inorganic fine particles>
Calculation of the liberation rate of the inorganic fine particles in the present invention was performed as follows.
(Sample preparation)
Toner before release: Various toners prepared in Examples described later were used as they were.
Toner after release: 30 g of 65% by weight aqueous sucrose solution in a 50 ml vial, “Contaminone N” (Neutral detergent for cleaning precision instruments with a pH of 7 consisting of nonionic surfactant, anionic surfactant and organic builder) 6 g is weighed and mixed with 1 g of toner. This mixture is set in “KM Shaker” (model: V.SX) manufactured by Iwaki Sangyo Co., Ltd., and the speed is set to 50 (amplitude 40 mm, shaking number 350 times / min) and shaken for 20 minutes. Thereafter, the mixture is processed in a centrifuge (3500 rpm for 30 minutes) to separate the toner and the aqueous solution. The toner prepared in the examples described later is separated due to the difference in specific gravity, with the toner in the upper layer and the free external additive precipitated. The toner in the upper layer is collected, filtered and washed, and then dried by vacuum drying to obtain the toner after release.

The measurement of the fluorescent X-ray of each element is in accordance with JISK0119-1969, and is specifically as follows.
As a measuring device, a wavelength dispersion type fluorescent X-ray analyzer “Axios” (manufactured by PANalytical) and attached dedicated software “SuperQ ver. 4.0F” (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data ) Is used.
Note that Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 10 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).
As a measurement sample, about 0.4 g of toner is put in a dedicated aluminum ring for press and leveled, and a tablet molding compressor “BRE-32” (manufactured by Maekawa Tester) is used at 10 MPa. , And pressurizing for 60 seconds and using pellets molded to a thickness of about 2 mm and a diameter of about 17 mm.
The measurement is performed under the above conditions, the element is identified based on the obtained X-ray peak position, and the concentration is calculated from the count rate (unit: cps) which is the number of X-ray photons per unit time.

(Quantitative determination of SiO ₂ in toner)
Silica (SiO ₂ ) fine particles are added to 0.5 parts by mass with respect to 100.0 parts by mass of the toner particles, and sufficiently mixed using a coffee mill. Similarly, silica fine particles are mixed with toner particles so as to be 1.0 part by mass and 1.5 parts by mass, respectively, and these are used as samples for a calibration curve.
About each sample, the pellet of the sample for a calibration curve was produced as mentioned above using a tablet molding compressor, and when PET (pentaerythritol) was used for the spectroscopic crystal, diffraction angle (2θ) = 109.08 The count rate (unit: cps) of Si-Kα rays observed at ° is measured.
At this time, the acceleration voltage and current value of the X-ray generator are 24 kV and 100 mA, respectively. A calibration curve of a linear function is obtained with the X-ray count rate obtained on the vertical axis and the added amount of SiO ₂ in each calibration curve sample on the horizontal axis.
Next, the toner to be analyzed is formed into pellets as described above using a tablet molding compressor, and the Si-Kα ray count rate is measured. Then, the SiO ₂ content in the toner is determined from the above calibration curve.
(Quantitative determination of TiO ₂ in toner)
Titanium dioxide (TiO ₂ ) fine powder is added to 0.5 parts by mass with respect to 100.0 parts by mass of the toner particles, and sufficiently mixed using a coffee mill. Similarly, fine particles of titanium dioxide are mixed with toner particles so as to be 1.0 part by mass and 1.5 parts by mass, respectively, and these are used as samples for a calibration curve.
For each sample, a pellet for a calibration curve was prepared as described above using a tablet molding compressor, and when LiF200 was used for a spectroscopic crystal, a diffraction angle (2θ) = 86.11 ° was observed. The counting rate (unit: cps) of Ti-Kα rays is measured. At this time, the acceleration voltage and the current value of the X-ray generator are 40 kV and 60 mA, respectively. A calibration curve of a linear function is obtained with the X-ray count rate obtained on the vertical axis and the added amount of TiO ₂ in each calibration curve sample on the horizontal axis.
Next, the toner to be analyzed is formed into pellets as described above using a tablet molding compressor, and the counting rate of the Ti-Kα ray is measured. Then, the TiO ₂ content in the toner is obtained from the calibration curve.
(Quantification of other inorganic substances in toner)
Other inorganic substances were quantified in the same manner as the TiO ₂ quantification.
(Calculation method of the free rate of inorganic fine particles from toner particles)
First, the content of each inorganic fine particle in the pre-release toner and the post-release toner is determined by the above method. Thereafter, the silica fine particle content part of the toner before release is Xa, the titanium oxide fine particle content part of the toner before release is Ya, the other inorganic fine particle content part of the toner before release is Za, and the silica fine particle content part of the toner after release is Xb. Based on the following formula, the liberation ratio (% by mass) is calculated based on Yb as the titanium oxide fine particle-containing part of the post-toner and Zb as the other inorganic fine particle-containing part of the post-free toner.
Release rate (mass%) = {(Xa−Xb) + (Ya−Yb) + (Za−Zb)} / (Xa + Ya + Za) × 100

<Measurement of number average particle diameter (D1) of primary particles of silica fine particles>
A photograph of the surface of a toner particle obtained by adding 1.0 part by mass of silica fine particles to 100 parts by mass of the toner particles, magnified 100,000 times by a field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation). , The primary particle diameter of 100 or more silica fine particles is measured using the enlarged photograph, and the number average particle diameter (D1) is obtained from the arithmetic average. In addition, the particle diameter of the primary particle of the silica fine particle was defined as the absolute maximum length when the shape was spherical, and the major axis when the shape had a major axis and a minor axis.

<Calculation of coefficient of variation of inorganic fine particle coverage>
The coefficient of variation of the coverage in the present invention is determined by using a toner surface image photographed with a field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation), image analysis software Image-Pro Plus ver. Calculated by 5.0 (Japan Roper Co., Ltd.). The image capturing conditions of S-4800 are as follows.
(1) Sample preparation A conductive paste is thinly applied to a sample table (aluminum sample table 15 mm × 6 mm), and toner is sprayed thereon. Further, air is blown to remove excess toner from the sample stage and sufficiently dry. The sample stage is set on the sample holder, and the height of the sample stage is adjusted to 36 mm by the sample height gauge.
(2) S-4800 observation condition setting The coefficient of variation of the coverage is calculated using an image obtained by the reflected electron image observation of S-4800. The reflected electron image can be measured with high accuracy because the charge of inorganic fine particles is less than that of the secondary electron image.
Liquid nitrogen is poured into the anti-contamination trap attached to the S-4800 housing until it overflows, and is placed for 30 minutes. The “PC-SEM” of S-4800 is activated and flushing (cleaning of the FE chip as an electron source) is performed. Click the acceleration voltage display part of the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Confirm that the flushing intensity is 2 and execute. Confirm that the emission current by flashing is 20-40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position.
Click the acceleration voltage display section to open the HV setting dialog, and set the acceleration voltage to [0.8 kV] and the emission current to [20 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select [Up (U)] and [+ BSE] for the SE detector, and select [+ BSE] in the selection box on the right. L. A. 100] to select a mode in which observation is performed with a reflected electron image. Similarly, in the [Basic] tab of the operation panel, the probe current of the electron optical system condition block is set to [Normal], the focus mode is set to [UHR], and the WD is set to [3.0 mm]. Press the [ON] button in the acceleration voltage display section of the control panel to apply the acceleration voltage.
(3) Calculation of number average particle diameter (D1) of toner Drag within the magnification display section of the control panel to set the magnification to 5000 (5k). The focus knob [COARSE] on the operation panel is rotated, and the aperture alignment is adjusted when the focus is achieved to some extent. Click [Align] on the control panel to display the alignment dialog and select [Beam]. The STIGMA / ALIGNMENT knob (X, Y) on the operation panel is rotated to move the displayed beam to the center of the concentric circle. Next, [Aperture] is selected, and the STIGMA / ALIGNMENT knobs (X, Y) are turned one by one to stop the movement of the image or adjust the movement to the minimum. Close the aperture dialog and focus with auto focus. Repeat this operation two more times to focus.
Thereafter, the particle diameter of 300 toner particles is measured to determine the number average particle diameter (D1). The particle diameter of each particle is the maximum diameter when the toner particles are observed.
(4) Focus adjustment For the particles with a number average particle diameter (D1) of ± 0.1 μm obtained in (3), inside the magnification display part of the control panel with the midpoint of the maximum diameter aligned with the center of the measurement screen Drag to set the magnification to 10,000 (10k). The focus knob [COARSE] on the operation panel is rotated, and the aperture alignment is adjusted when the focus is achieved to some extent. Click [Align] on the control panel to display the alignment dialog and select [Beam]. The STIGMA / ALIGNMENT knob (X, Y) on the operation panel is rotated to move the displayed beam to the center of the concentric circle. Next, [Aperture] is selected, and the STIGMA / ALIGNMENT knobs (X, Y) are turned one by one to stop the movement of the image or adjust the movement to the minimum. Close the aperture dialog and focus with auto focus. Thereafter, the magnification is set to 50000 (50k), focus adjustment is performed using the focus knob and the STIGMA / ALIGNMENT knob in the same manner as described above, and the focus is again adjusted by autofocus. Repeat this operation again to focus. Here, since the measurement accuracy of the coverage rate tends to be low when the angle of inclination of the observation surface is large, select the one with the smallest possible surface inclination by selecting the one that focuses on the entire observation surface at the same time when adjusting the focus. And analyze.
(5) Image storage Brightness adjustment is performed in ABC mode, and a photograph is taken with a size of 640 × 480 pixels and stored. The following analysis is performed using this image file. 1 photo for each toner particle
A picture is taken to obtain an image of at least 30 particles of toner.
(6) Image Analysis In the present invention, the coverage is calculated by binarizing the image obtained by the above-described method using the following analysis software. At this time, the one screen is divided into 12 squares and analyzed. However, when inorganic fine particles having a particle diameter of 50 nm or more enter the divided section, the coverage is not calculated in the section.
Image analysis software Image-Pro Plus ver. The analysis conditions of 5.0 are as follows.
Software Image-ProPlus 5.1J
Select “Measure” from the tool bar, then select “Count / Size” and “Option” in this order, and set the binarization condition. Select 8 connections in the object extraction option and set smoothing to 0. In addition, sorting, filling holes, and inclusion lines are not selected, and “exclude boundary lines” is set to “none”. Select “Measurement Item” from “Measurement” on the tool bar, and enter 2 to 10 ⁷ in the area selection range.
The coverage is calculated by surrounding a square area. At this time, the area (C) of the region is set to be 24,000 to 26000 pixels. “Processing” —Automatic binarization by binarization, and the total area (D) of the area without inorganic fine particles is calculated.
From the area C of the square area and the total sum D of the areas without the inorganic fine particles, the coverage a is obtained by the following equation.
Coverage a (%) = 100− (D / C × 100)
As described above, the coverage a is calculated for 30 or more toner particles. Let the average value of all the obtained data be the coverage in this invention.
The coefficient of variation of the coverage in the present invention is determined as follows. Assuming that the above-described coverage is A and the standard deviation of the total coverage data used is σ (A), the variation coefficient of the coverage is obtained by the following equation. Coefficient of variation (%) = {σ (A) / A} × 100

<Measurement of extracted silicone oil content of silica fine particles>
The amount of silica oil extracted from silica fine particles is measured as follows. 1.0 g of silica fine particles is weighed into a 50 ml screw tube, and 20 ml of normal hexane is added. Then, it extracts for 10 minutes with the intensity | strength 20 (output 10W) with an ultrasonic homogenizer (VP-050 by TAITEC). The obtained extract is separated with a centrifuge to obtain a supernatant. 10 g of the obtained supernatant is dried with an evaporator, the residue is made into silicone oil, the silicone oil concentration in the supernatant is calculated, and the amount of extracted silicone oil (the amount of extracted silicone oil in silica fine particles [mass%]) is obtained.

<Hydrophobicization rate of silica fine particles>
The hydrophobicity of silica fine particles is measured as follows. First, 1 g of silica fine particles is weighed into a separating funnel (200 ml), 100 ml of pure water is added thereto, stoppered, shaken with a tumbler mixer (T2F manufactured by Shinmaru Enterprises Co., Ltd.) for 10 minutes, and then allowed to stand for 10 minutes. After that, after removing 20 to 30 mL of the lower layer from the funnel, the lower layer mixed solution is dispensed into a 10 mm quartz cell, subjected to a colorimeter using pure water as a blank, and its 500 nm passage rate (%) is hydrophobic. Conversion rate (%).

<Measurement of SF-2 of toner particles>
The SF-2 of the toner particles is measured as follows. Using a field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation), 100 toner particle images magnified at a magnification of 500 times were sampled randomly.
Then, the image information was introduced into an image analysis apparatus (Luxex 3) manufactured by Nicole via an interface and analyzed, and a value was calculated based on the SF-2 formula defined below.
SF-2 = {(PERI) ² / AREA} × (1 / 4π) × 100
AREA: toner particle projected area, PERI: perimeter

The present invention will be specifically described with reference to the following examples and comparative examples. However, this does not limit the present invention in any way. In addition, all the parts and% of an Example and a comparative example are mass references | standards unless there is particular notice.
<Production Example of Silica Fine Particle 1>
As the first treatment step, fumed silica (trade name: AEROSIL 380s, specific surface area by BET method 380 m ² / g, number average particle size of primary particles 6.8 nm, manufactured by Nippon Aerosil Co., Ltd.) 1] To 100.0 parts by mass, 10.0 parts by mass of dimethyl silicone oil was sprayed, and stirring was continued for 30 minutes. Thereafter, the temperature was raised to 300 ° C. with stirring, and the mixture was further stirred for 2 hours, whereby dimethyl silicone oil was baked on the fumed silica surface to complete the reaction.
As the second treatment step, 40.0 parts by mass of hexamethyldisilazane (hereinafter, also referred to as HMDS) is sprayed on the silica fine particles produced in the first treatment step, and the silica fine particles are fluidized in a state where they are fluidized. Processed. This reaction was continued for 60 minutes, and then the reaction was terminated. After completion of the reaction, crushing was performed with a pulverizer (manufactured by Hosokawa Micron Corporation) to obtain silica fine particles 1. Table 1 shows the physical properties of the silica fine particles 1 obtained.

<Production example of silica fine particles 2 to 6>
In the production example of silica fine particles 1, silica fine particles 2 to 6 were obtained in the same manner as in the production example of silica fine particles 1, except that the type and formulation of the raw silica fine particles were changed to those shown in Table 1. The physical properties of the obtained silica fine particles 2 to 6 are similarly shown in Table 1. The raw silica fine particles 2 are fumed silica (trade name: AEROSIL 200, specific surface area 200 m ² / g by BET method,
The number average particle diameter of primary particles is 12.0 nm, manufactured by Nippon Aerosil Co., Ltd.).

<Production Example of Crystalline Polyester 1>
Under a nitrogen atmosphere, 50.0 parts by mass of xylene, 175.0 parts by mass of sebacic acid, and 209.0 parts by mass of 1,12-dodecanediol were added to a pressure resistant reactor equipped with a dropping funnel, a Liebig condenser and a stirrer. The temperature was raised to 210 ° C. The pressure at this time was 0.32 MPa. Thereafter, 0.8 parts by mass of tetrabutoxy titanate was charged, and a polycondensation reaction was performed at 210 ° C. under a nitrogen atmosphere for 3 hours. Thereafter, 0.1 part by mass of tetrabutoxy titanate was added and reacted at 210 ° C. for 2 hours. Then, at normal pressure, 40.2 parts by mass of benzoic acid and 4.0 parts by mass of trimellitic acid were added, and further 220 ° C. For 5 hours to obtain crystalline polyester 1. Table 2 shows the physical properties of the obtained crystalline polyester 1.

<Production Example of Crystalline Polyester 2>
In the production example of the crystalline polyester 1, the reaction was carried out in the same manner as in the production example of the crystalline polyester 1 except that the addition amounts of monomers and other additives were changed as shown in Table 2, and the crystalline resin polyester was reacted. 2 was obtained. Table 2 shows the physical properties of the obtained crystalline polyester 2.

<Production Example of Crystalline Polyester 3>
Under a nitrogen atmosphere, 50.0 parts by mass of xylene, 175.0 parts by mass of sebacic acid, and 210.1 parts by mass of 1,12-dodecanediol were added to a pressure resistant reactor equipped with a dropping funnel, a Liebig condenser and a stirrer. The temperature was raised to 210 ° C. To this, 52.3 parts by mass of styrene, 5.4 parts by mass of acrylic acid, and 3.7 parts by mass of di-tert-butyl peroxide (Perbutyl D, manufactured by NOF Corporation) as a polymerization initiator are added to 10 parts by mass of xylene. What melt | dissolved the mixture prepared in the dropping funnel was dripped under pressure over 2 hours. After the dropping, the reaction was further performed at 210 ° C. for 3 hours to complete the solution polymerization. Thereafter, 0.8 parts by mass of tetrabutoxy titanate was charged, and a polycondensation reaction was performed at 210 ° C. under a nitrogen atmosphere for 3 hours. Thereafter, 0.01 part by mass of tetrabutoxy titanate was added and reacted at 210 ° C. for 2 hours. Thereafter, 33.1 parts by mass of benzoic acid and 4.0 parts by mass of trimellitic acid were added at normal pressure, and the mixture was further reacted at 220 ° C. for 5 hours to obtain crystalline polyester 3. Since the mass ratio of the crystalline polyester part and the amorphous vinyl part in the crystalline polyester 3 was equal to the mass ratio in the raw material, it was confirmed that there was no unreacted amorphous vinyl part. Table 2 shows the physical properties of the obtained crystalline polyester 3.

<Production example of crystalline polyesters 4 and 5>
In the production example of the crystalline polyester 3, the reaction was carried out in the same manner as in the production example of the crystalline polyester 3 except that the addition amounts of monomers, styrene, acrylic acid, initiator and other components were changed as shown in Table 2. The crystalline resin polyesters 4 and 5 were obtained.
Table 2 shows the physical properties of the obtained crystalline polyesters 4 and 5.

<Example of production of amorphous polyester 1>
Under a nitrogen atmosphere, a pressure resistant reactor equipped with a dropping funnel, a Liebig condenser and a stirrer, 100.0 parts by mass of propylene oxide 2-mol adduct of bisphenol A, 100.0 parts by mass of terephthalic acid, and titanium dihydroxybis (triethanol 0.5 parts by mass of (aminate) was added, and the reaction was carried out at 230 ° C. for 10 hours while distilling off the water produced under a nitrogen stream. Next, the reaction is carried out under reduced pressure of 5 to 20 mmHg, and when the acid value becomes 2 mgKOH / g or less, it is cooled to 180 ° C., 4.0 parts by mass of trimellitic anhydride is added, and the reaction is performed for 2 hours under normal pressure sealing. The amorphous polyester 1 was obtained by taking out, cooling to room temperature, and pulverizing. Regarding the physical properties of the obtained amorphous polyester 1, the weight average molecular weight (Mw) was 10,000 and the glass transition temperature (Tg) was 76 ° C.

<Production example of polar resin 1>
After putting 300 parts by mass of xylene (boiling point 144 ° C.) into an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, the inside of the container was sufficiently replaced with nitrogen while stirring. The temperature was raised to reflux. Under this reflux,
・ Styrene 91.5 parts by mass ・ Butyl acrylate 1.0 part by mass ・ Methyl methacrylate 2.5 parts by mass ・ Methacrylic acid 2.5 parts by mass ・ 2-hydroxyethyl methacrylate 2.5 parts by mass ・ Initiator di- After adding 2.0 parts by mass of tert-butyl peroxide, polymerization was carried out for 5 hours at a polymerization temperature of 160 ° C. and a reaction pressure of 0.15 MPa. Thereafter, the solvent removal step is performed under reduced pressure for 3 hours, xylene is removed and pulverized to polar resin 1 (glass transition temperature: 91.9 ° C., acid value: 16.0 mgKOH / g)
Got.

<Production Example of Toner Particle 1>
Toner particles 1 were produced by the suspension polymerization method as follows.
First, the following materials were uniformly dissolved and mixed at 100 r / min with a propeller type stirring device to prepare a polymerizable monomer composition.
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Crystalline polyester 1 10.0 parts by mass Polar resin 1 10.0 parts by mass Pigment Blue 15: 3 7.5 parts by mass Charge control Agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 0.5 parts by mass Subsequently, these mixtures are heated to 60 ° C. and 9.0 parts by mass of paraffin wax (HNP-5: Nippon Seiki, melting point 60 ° C.) added. Next, 5.0 parts by mass of a polymerization initiator perbutyl O (manufactured by NOF Corporation) was added and stirred for 5 minutes.
On the other hand, 850 parts by mass of 0.1 mol / L-Na ₃ PO ₄ aqueous solution and 8.0 parts by mass of 10% hydrochloric acid were added to a container equipped with a high-speed agitator CLEARMIX (M Technique Co., Ltd.) It adjusted to 15000 rpm and heated to 60 degreeC. Here was added 1.0mol / L-CaCl ₂ aqueous solution 68 parts by mass, to prepare an aqueous medium containing a fine sparingly water-soluble dispersing agent _Ca 3 _{(PO 4) 2.}
After 5 minutes from the introduction of the polymerization initiator to the polymerizable monomer composition, the polysynthetic monomer composition at 60 ° C. was introduced into an aqueous medium heated to a temperature of 60 ° C. And granulated for 15 minutes. Thereafter, the stirrer was changed from a high-speed stirrer to a propeller stirring blade, and the mixture was reacted at 60 ° C. for 5 hours while refluxing. The liquid temperature was then adjusted to 80 ° C., and the mixture was further reacted for 5 hours. After completion of the polymerization, the liquid temperature was lowered to about 20 ° C., diluted hydrochloric acid was added to adjust the pH of the aqueous medium to 3.0 or less, and the poorly water-soluble dispersant was dissolved. Further, washing and drying were performed to obtain toner particles 1.

<Production example of toner particles 2 to 5>
In the production example of toner particles 1, toner particles 2 to 5 were obtained in the same manner as in the production example of toner particles 1 except that the type of crystalline polyester was changed to that shown in Table 3.
Table 3 shows the physical properties of Toner Particles 1 to 5.

<Production Example of Toner 1>
The toner particles 1 obtained in the production example of the toner particles 1 were subjected to an external addition mixing process using the apparatus shown in FIG.
In this embodiment, the apparatus shown in FIG. 1 uses an apparatus in which the diameter of the inner peripheral portion of the main casing 1 is 130 mm and the volume of the processing space 9 is 2.0 × 10 ⁻³ m ^3. The rated power was 5.5 kW, and the shape of the stirring member 3 was that shown in FIG. The overlapping width d of the stirring member 3a and the stirring member 3b in FIG. 2 is 0.25D with respect to the maximum width D of the stirring member 3, and the clearance between the stirring member 3 and the inner periphery of the main casing 1 is 3.0 mm. .
With the apparatus configuration described above, 100.0 parts by mass of toner particles 1, 0.8 parts by mass of silica fine particles 1 shown in Table 1, and 0.8 parts by mass of titanium oxide fine particles (number average particle diameter of primary particles: 20 nm) Was put into the apparatus shown in FIG.
The external mixing process conditions were such that the outermost peripheral speed of the stirring member 3 was adjusted so that the rotation speed of the drive unit 8 was constant at 2000 rpm, and the processing time was 5 minutes. Table 4 shows the external additive mixing conditions.
After the external addition mixing process, coarse particles and the like were removed with a vibration sieve equipped with a 200-mesh (aperture 75 μm) screen to obtain toner 1. Table 4 shows the external addition conditions and physical properties of Toner 1.

<Production Examples of Toners 2 to 12 and Comparative Toners 1 to 3 and 6>
In the production example of the toner 1, the toners 2 to 12 and the comparative toner 1 are similarly manufactured except that the type of silica fine particles and the number of addition parts, the toner particles, the external addition device, and the external addition conditions shown in Table 4 are changed. -3, 6 were produced. Table 4 shows the external addition conditions and physical properties of the obtained toners 2 to 12 and comparative toners 1 to 3.

<Production Example of Comparative Toner 4>
Toner particles 1: 0.8 parts by mass of silica fine particles 1 and 0.8 parts by mass of titanium oxide fine particles (number average particle size of primary particles: 20 nm) are added to 100.0 parts by mass of Henschel mixer (Mitsui Mine). Comparative toner 4 was obtained by mixing for 10 minutes at 4000 rpm. Table 4 shows the physical properties of Comparative Toner 4.

<Production Example of Comparative Toner 5>
Comparative toner 5 was obtained in the same manner as in Comparative toner 4 except that the number of silica fine particles added in the production example of comparative toner 4 was changed to that shown in Table 4. Table 4 shows the physical properties of Comparative Toner 5.

<Examples 1-12 and Comparative Examples 1-6>
The following evaluation was performed using toners 1 to 12 and comparative toners 1 to 6. The results are shown in Tables 5 and 6.
The evaluation method and evaluation criteria of the present invention will be specifically described below.
As the image forming apparatus, a remodeling machine of LBP-7700C (manufactured by Canon) which is a commercially available laser printer and a toner cartridge 323 (cyan) (manufactured by Canon) which is a process cartridge were used. This modified machine was modified so that the process speed was 240 mm / sec by changing the internal gear. The product toner was extracted from the inside of the cartridge, cleaned by air blow, and then filled with 160 g of the toner.
Example 10 is referred to as Reference Example 10.

[1] Fluidity in a low-temperature, low-humidity environment (solid followability)
Canon color laser copy paper (A4: 81.4 g / m ²⁾ as a transfer material using a process cartridge filled with toner in a low temperature and low humidity environment (10 ° C./15% RH)
From now on, this paper will be used unless otherwise specified), and three solid images were output (initial evaluation). Thereafter, 20000 images with a printing rate of 1% were output. Thereafter, three solid images were similarly output (evaluation after endurance). The solid followability was evaluated for all the obtained solid images.
As for the evaluation items, it is known that better results are obtained as the fluidity of the toner is higher. The image density is measured by measuring the relative density with respect to the image of the white background portion where the image density is 0.00 using the “Macbeth reflection densitometer RD918” (manufactured by Macbeth) according to the attached instruction manual. The relative density obtained was used as the image density value.
(Evaluation criteria)
A: The difference between the image density of the leading edge of the first sheet of all solid images and the image density of the trailing edge of the third sheet of all solid images is less than 0.10 B: The image density of the first sheet of all solid images and the whole solid image The difference between the image density at the rear end of the third image and the image density is 0.10 or more and less than 0.20 C: The image density at the front end of the first solid image and the image density at the rear end of the third solid image The difference is 0.20 or more and less than 0.30 D: The difference between the image density at the leading edge of the first sheet of all solid images and the image density at the trailing edge of the third sheet of all solid images is 0.30 or more

[2] Durability (Development stripe)
After the solid follow-up evaluation test was completed, the developer container was disassembled, and the surface and edges of the toner carrier were visually observed.
(Evaluation criteria)
A: There is no streak in the circumferential direction due to the foreign matter sandwiched between the toner regulating member and the toner carrying member due to toner destruction or fusion at the surface or end of the toner carrying member.
B: Some foreign matter is caught between the toner carrier and the toner end seal, but there are no circumferential streaks.
C: 1-4 streaks in the circumferential direction can be seen at the ends.
D: Five or more streaks in the circumferential direction are observed in the entire region.

[3] Fixability in low temperature and low humidity environment (rubbing test)
Using a process cartridge filled with toner in a low-temperature and low-humidity environment (10 ° C./15% RH), the toner has a paste amount of 0.90 mg / cm ² and a 10 mm × 10 mm 3-dot 3 for density measurement An image having a large number of space (600 dpi) images is output, and the obtained fixed image is rubbed five times with sylbon paper to which a weight of 50 g / cm ² (0.49 N / cm ² ) is applied. The reduction rate of the image density was evaluated based on the following. The fixing temperature was set to 180 ° C. In addition, the image density is measured by using a Macbeth reflection densitometer (manufactured by Macbeth Co., Ltd.), measuring the relative density with respect to the printout image of the white background portion where the document density is 0.00, and reducing the image density after rubbing. The rate was calculated.
A: Less than 5.0% B: 5.0% or more and less than 10.0% C: 10.0% or more and less than 15.0% D: 15.0% or more

[4] Charging during storage in high temperature and high humidity environment (fogging)
The process cartridge filled with the toner was stored for 30 days in a high temperature and high humidity storage environment (40 ° C./95% RH). After that, moved to a high temperature and high humidity environment (30 ° C / 80% RH), Letter size HP Color Laser Photo Paper, gloss
A solid white image having a printing ratio of 0% was output to sy (220 g / m ² ) (initial evaluation). After the image output, 20000 images with a printing rate of 1% were output. Thereafter, a solid white image was similarly output (endurance evaluation). Further, after storing in a high temperature and high humidity environment (30 ° C./80% RH) for 72 hours, a solid white image was similarly output (evaluation after being left). The fog was evaluated on the obtained solid white image. In addition, as for the said evaluation item, it is known that a favorable result will be obtained, so that it is excellent in the charging property at the time of storage in a high-temperature, high-humidity environment.
The fog density (%) was measured using “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.), and the fog density (from the difference between the whiteness of the white portion of the measured image and the whiteness of the transfer paper) %). An amber filter was used as the filter. Further, the measurement of the image density was calculated as an average value of the image density of the five solid image portions of the obtained sample image.
(Evaluation criteria)
A: fog density of less than 0.5% B: fog density of 0.5% or more and less than 1.0% C: fog density of 1.0% or more and less than 2.0% D: fog density of 2.0% or more

[5] Fluidity after storage in a high temperature and high humidity environment (solid followability)
The process cartridge filled with the toner was stored for 30 days in a high temperature and high humidity storage environment (40 ° C./95% RH). Thereafter, the sheet was moved to a room temperature and humidity environment (25 ° C./50% RH), and three solid images were output on Canon color laser copy paper (initial evaluation). Thereafter, 20000 images with a printing rate of 1% were output. Thereafter, three solid images were similarly output (evaluation after endurance). The solid followability was evaluated for all the obtained solid images.
(Evaluation criteria)
A: The difference between the image density of the leading edge of the first sheet of all solid images and the image density of the trailing edge of the third sheet of all solid images is less than 0.10 B: The image density of the first sheet of all solid images and the whole solid image The difference between the image density at the rear end of the third image and the image density is 0.10 or more and less than 0.20 C: The image density at the front end of the first solid image and the image density at the rear end of the third solid image The difference is 0.20 or more and less than 0.30 D: The difference between the image density at the leading edge of the first sheet of all solid images and the image density at the trailing edge of the third sheet of all solid images is 0.30 or more

[6] Durability after storage in high temperature and high humidity environment (development streak)
After the solid follow-up evaluation test was completed, the developer container was disassembled, and the surface and edges of the toner carrier were visually observed.
(Evaluation criteria)
A: There is no streak in the circumferential direction due to the foreign matter sandwiched between the toner regulating member and the toner carrying member due to toner destruction or fusion at the surface or end of the toner carrying member.
B: Some foreign matter is caught between the toner carrier and the toner end seal, but there are no circumferential streaks.
C: 1-4 streaks in the circumferential direction can be seen at the ends.
D: Five or more streaks in the circumferential direction are observed in the entire region.

  1: main body casing, 2: rotating body, 3, 3a, 3b: stirring member, 4: jacket, 5: raw material inlet, 6: product outlet, 7: central shaft, 8: drive unit, 9: processing space, 10: Rotating body end side surface, 11: Rotating direction, 12: Return direction, 13: Feeding direction, 16: Inner piece for raw material inlet, 17: Inner piece for product outlet, d: Overlapping portion of stirring member Interval, D: Width of stirring member

Claims (3)

Toner particles containing a binder resin and crystalline polyester;
Inorganic fine particles,
A non-magnetic toner having
(I) The crystalline polyester has a melting point (Tm) of 60 ° C. or higher and 100 ° C. or lower,
(Ii) In the molecular weight distribution measured by gel permeation chromatography (GPC) of the crystalline polyester, the weight average molecular weight (Mw) is 20,000 to 50,000,
(Iii) The non-magnetic toner contains 1.5 to 3.0 parts by mass of the inorganic fine particles with respect to 100.0 parts by mass of the toner particles.
(Iv) 30.0% by mass or more of the inorganic fine particles are silica fine particles, and the number average particle diameter (D1) of the primary particles of the silica fine particles is 4.0 nm or more and 15.0 nm or less,
(V) The inorganic fine particles have a liberation rate of 10.0% by mass or more and 25.0% by mass or less,
(Vi) A nonmagnetic toner, wherein a coefficient of variation of the coverage of the toner particles by the inorganic fine particles is 5.0 % or less.   2. The nonmagnetic toner according to claim 1, wherein an area having a molecular weight of 3000 or less is 15 area% or less based on an area of the entire chart in a molecular weight distribution chart obtained by measuring the crystalline polyester by GPC. The silica fine particles are silica fine particles obtained by treating the surface of the silica fine particles with silicone oil,
The hydrophobization rate of the silica fine particles is 95% or more,
The nonmagnetic toner according to claim 1, wherein the amount of silicone oil extracted using hexane in the silica fine particles is 0.50 mass% or less.

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