JP6459018B2 - Toner for electrostatic charge development and toner cartridge - Google Patents

Description

  The present invention relates to an electrostatic charge image developing toner used for electrophotographic image formation such as a copying machine, electrostatic printing, facsimile, printer, electrostatic recording, and the like, and a toner cartridge.

An external additive is used to impart fluidity and chargeability to the toner and improve toner replenishability, developability, and transferability. As the external additive, hydrophobic finely-treated inorganic fine particles such as silica, titania and alumina, as well as resin fine particles are used.
For example, Patent Document 1 discloses a toner composition for developing an electrostatic image obtained by adding spherical silicone rubber fine particles having a rubber hardness of 10 to 70 surface-treated with silicone oil to toner particles containing a binder and a colorant. It is disclosed. To obtain a toner for developing an electrostatic charge image having stable characteristics without damaging the surface of the photoreceptor or the dielectric, or causing filming phenomenon on the surface of the photoreceptor or the cleaning member in the cleaning process. It is aimed. The resin fine particles having an average particle diameter in the range of 0.05 to 5 μm, preferably in the range of 0.1 to 2 μm, are used. In addition, since the resin fine particles and the toner particles are unlikely to cause a difference in contact potential, there is a problem that the resin fine particles alone cannot sufficiently obtain a covering effect and cannot secure the chargeability.

Also, as an abnormal image starting from the external additive, the external additive adheres to the surface of the photoconductor or is damaged, and the external additive or toner accumulates and is pressed by a cleaning blade or the like and repeatedly accumulated. Fixed matter may grow and abnormal images may be generated.
Resin fine particles have lower hardness than inorganic fine particles such as silica, and have no sharp projections, so there is little effect as an abrasive, and it has the advantage that the surface layer of the photoconductor is excessively worn and the photoconductor is not easily damaged. However, even if resin fine particles are used, the occurrence of abnormal images (toner fixation containing a large amount of external additives on the photoreceptor) cannot be sufficiently prevented.

  The present invention has been made in view of the above problems in the prior art, and provides an electrostatic charge image developing toner that has excellent chargeability and can sustain the output of a high-quality image that does not cause abnormal images over a long period of time. Objective.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following toner for developing an electrostatic image, and have reached the present invention.
That is, the present invention is as follows.
(1) It contains resin fine particles surface-treated with silicone oil as an external additive, and the resin fine particles have a number average particle size of 50 to 200 nm and contain silica fine particles on the surface. Toner for developing electrostatic image.

  By using the toner for developing an electrostatic charge image of the present invention, it is possible to output a high-quality image that has excellent chargeability and does not generate an abnormal image over a long period of time.

FIG. 3 is a schematic view of an apparatus used for measuring the charge amount of toner. 3 is a chart used for evaluation of cleaning properties and photoreceptor adhesion in Examples. It is the schematic which shows an example of the process cartridge which concerns on this invention.

(Silicon oil surface treatment resin fine particles)
The electrostatic image developing toner of the present invention is characterized by containing resin fine particles surface-treated with silicone oil as an external additive.
By using the silicone oil surface-treated resin fine particles, the above-described abnormal image generation can be prevented.
Silicone oil has been conventionally used as a hydrophobic surface treatment agent to impart hydrophobicity to the surface of silica.
The inventors have found that by using this silicone oil for the surface treatment of resin fine particles, the toner can be sufficiently charged without using silica. Among these, the fine resin particles using fluorine-containing silicone oil, in particular, can prevent the occurrence of abnormal images (fixing of toner containing a large amount of external additives to the photoreceptor) even when combined with toner containing crystalline polyester. I found it. An effect not found in conventional resin fine particles can be obtained.

(Effects of silicone oil surface-treated resin fine particles containing inorganic fine particles)
In addition, the present inventors can further suppress the occurrence of abnormal images by applying silicone oil treatment to resin fine particles containing inorganic fine particles such as silica, titania, and alumina on the surface or inside of the resin fine particles. I found it.
Compared to the case where only the resin fine particles are treated with silicone oil, by adding inorganic fine particles to the resin fine particles, the ability to hold the silicone oil in the resin fine particles is increased. It is thought that there is an effect such as being difficult to adhere to the surface.

In toner containing crystalline polyester resin, a small amount of crystalline polyester component that remains as a low melting point component without being crystallized adheres and accumulates on the surface properties of the photoreceptor, and is the starting point for silica and toner fixation I think that the.
For the problems inherent to the toner containing the crystalline polyester resin, even if the resin fine particles are added externally, there is no effect of preventing the sticking. However, when the silicone oil surface treatment resin fine particles are added externally, the sticking is suppressed and more inorganic. The effect becomes more remarkable with the silicone oil surface-treated resin fine particles containing fine particles.

<Resin fine particle substrate>
The resin fine particles used as an external additive in the present invention are preferably fine particles made of a resin usually used for a binder resin for a toner base to be described later. From the viewpoint of producing fine particles, a styrene monomer, an acrylate ester Resin fine particles that contain a polymer obtained using at least one monomer selected from a monomer and a methacrylic acid ester monomer and are crosslinked are more preferably used.
Further, regarding the surface property / manufacturing method of the resin fine particles, it is preferable that the resin fine particles have a hydrophilic surface since the fixing solution is aqueous. From this aspect, it is preferably produced by a polymerization method / manufacturing method in which a monomer is polymerized / particles in an aqueous system. Specifically, a soap-free polymerization method is mentioned as a production method that satisfies the above requirements.

The particle diameter and specific gravity of the resin fine particles are preferably a number average particle diameter of 30 to 300 nm, preferably 50 to 200 nm, and a true specific gravity of 0.8 to 2.0 g / cm ³ from the viewpoint of adhesion to the toner surface. .
If the particle size is less than 30 nm, the effect of preventing sticking is small, and if it exceeds 300 nm, adhesion between the toner and the resin fine particles hardly occurs. When the true specific gravity is less than 0.8 g / cm ³ , the strength of the material may be insufficient, and when it exceeds 2.0 g / cm ³ , the mixing property (mixing uniformity) may be inferior.

Here, for example, the number average particle diameter is determined by, for example, attaching an externally added toner to an observation substrate for an electron microscope, coating the observation substrate to which the toner is attached with gold, and then applying an electron microscope (manufactured by Hitachi, Ltd.) It was observed with a scanning electron microscope S-4500).
An image obtained by enlarging the toner surface at 30,000 times was printed, and 50 samples were arbitrarily extracted using primary particles as samples. The number average value of the major axis diameters was used as the particle diameter of the resin fine particles. The particle size of the inorganic fine particles was determined in the same manner. The true specific gravity can be measured by, for example, a dry automatic densimeter (manufactured by Shimadzu Corporation, Accupic 1330).

If the glass transition temperature of the resin particle microparticles is less than 65 ° C., there may be a problem in storage stability as a toner under high temperature and high humidity, which is not preferable.
Specific examples of the fine resin particles include MP-300, MP-1451, MP-2200, MP-1000, MP-2701, MP-5000, MP-5500, MP-409, MP-1600, etc. from Soken Chemical Co., Ltd. Can be mentioned.

<Surface treatment resin fine particles containing inorganic fine particles>
The resin fine particles used as an external additive in the present invention preferably contain inorganic fine particles on the surface or inside, and in particular, a resin in which inorganic fine particles are attached to the surface of the resin fine particles and these are covered with silicone oil. Fine particles are preferred.
In order to contain inorganic fine particles in the resin fine particles, the inorganic fine particle coating layer is formed on the surface by adhering or precipitating inorganic fine particles having a particle diameter smaller than the resin fine particles on the surface of the resin fine particles. It is done. Alternatively, it can also be obtained by synthesizing resin fine particles in the presence of inorganic fine particles.

In the following, an example using silica as the inorganic fine particle coating layer will be described as a particularly preferable example, but the present invention is not limited to this.
That is, the inorganic fine particle coating layer may be formed using a known and commonly used inorganic material other than the silica layer. For example, titanium oxide (titania), aluminum oxide (alumina), barium titanate, magnesium titanate, titanate Calcium, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, Examples include calcium carbonate, silicon carbide, and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.

Specific examples of the production method include the methods described in (i) and (ii) below.
(I) Method of adhering silica fine particles to the surface of resin fine particles Silica fine particles having a particle diameter smaller than the resin fine particles are added to the resin fine particles, and a powder mixing apparatus such as an OM dizer, a turbuler mixer, a Ladige mixer, a Henschel Put it in a mixer, mix and stir to electrostatically attach silica particles to the surface of the resin fine particles, then transfer the uniform mixture of resin fine particles and silica fine particles to a device improved from the usual impact pulverizer, and mix This is a method in which an impact force is repeatedly applied to 1 to 20 minutes.

In this method, small silica fine particles are adhered to the surface of large resin fine particles with a mechanical impact force.
As silica fine particles, silica (silicon oxide) or hydrophobized silica can be used. Specific examples thereof include those used for inorganic fine particle external additives described later.
Here, the surface coating of the resin fine particles with the silica fine particles is preferably less than the amount that completely covers the surface.
This is because silica fine particles (coated portion) and resin fine particles (uncoated portion) are simultaneously present on the surface of the resin fine particles, thereby imparting the characteristics of the silica fine particles to the surface of the resin fine particles.
From this, the amount of silica fine particles added during the production of resin fine particles having silica fine particles on the surface is defined by the following equation, assuming that the resin fine particles and the silica fine particles are spherical particles each having a diameter of the primary particle diameter. It is obtained from the coverage ratio.
Coverage ratio = (total projected area of input silica fine particles) / (total surface area of input resin fine particles)
In this formula, the amount of silica fine particles that can be coated with resin fine particles is calculated so that the coverage is in the range of 1 or less, preferably 0.01 to 0.4.
If the coverage is less than 0.01, the coating of silica fine particles becomes insufficient, and the coating effect by the silica fine particles becomes small.
On the other hand, if it exceeds 0.4, the coating amount of the silica fine particles becomes excessive, and the characteristics of the resin fine particles are difficult to appear.

(Ii) Method of depositing silica on the surface of resin fine particles to form a silica coating layer Dissolve silane alkoxide in an aqueous solvent and add alkali in a state where resin fine particles are dispersed to hydrolyze silane alkoxide. How to make.
In this method, hydrolyzed and polycondensed silane alkoxide is deposited on resin fine particles to form a silica coating layer.

  The resin fine particles surface-treated with the silicone oil of the present invention are different from the inorganic fine particles (silica) surface-treated with the conventional silicone oil, and the resin fine particles or silica is fixed to the resin base material. Thus, the durability over time in the printing press is greatly obtained.

<Silicone oil fluorinated treatment agent and treatment method>
For resin fine particles surface-treated with silicone oil, untreated resin fine particles or resin fine particles with inorganic fine particles adhered to the surface are suspended in silicone oil dissolved in alcohol, and then the solvent alcohol is depressurized. It can be obtained by a method of evaporating and drying.
Examples of the silicone oil used for the treatment include dimethyl silicone oil, methylphenyl silicone oil, amino group-containing silicone oil, fluorine-modified silicone oil, epoxy-modified silicone oil, and mercapto-modified silicone oil.
The amount of silicone oil used for the treatment is preferably in the range of 0.5 to 5% by mass, more preferably in the range of 3 to 5% by mass with respect to the resin fine particles. When the amount is more than 5% by mass, there may be a problem that the silicone oil adheres to other members. On the other hand, if the amount is less than 0.5% by mass, the effect is not significant.
The resin fine particles treated with the silicone oil of the present invention are not intended to supply silicone oil. Therefore, if the amount of silicone oil is excessive from the above range, problems associated with the adhesion of silicone oil to other members (contamination of the member surface), fluidity as an external additive, and changes in the charging function will occur. There is a case.
As specific examples of the silicone oil, those having a desired viscosity can be used from KF-99 series of Shin-Etsu Silicone Co., Ltd. and non-reactive silicone oil modified with fluoroalkyl.

<Inorganic fine particle external additive>
In the present invention, together with the resin fine particles surface-treated with the above-mentioned silicone oil (that is, resin particles consisting of resin alone or resin fine particles containing inorganic fine particles on the surface or inside), the following inorganic fine particle external additives (inorganic fine particles) Can be used. However, in order to prevent adhesion to these photoreceptors, it is preferable to externally add only the resin fine particles surface-treated with the aforementioned silicone oil to the toner base without using these inorganic fine particle external additives in combination. .

The inorganic fine particle external additive referred to in the present invention refers to inorganic fine particles and fine particles subjected to hydrophobic treatment.
For example, silicon oxide (silica), titanium oxide (titania), aluminum oxide (alumina), barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, silica Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
These may be used individually by 1 type and may use 2 or more types together.
Of these, silicon oxide (silica), titanium oxide, and aluminum oxide (alumina) are particularly preferably used.

These inorganic fine particles can be produced by any method, and can be obtained by a vapor phase method, a wet method (precipitation method), a sol-gel method, or the like.
Examples of the hydrophobizing agent include the following. Dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, p-chloroethyltrichlorosilane, chloro Methyldimethylchlorosilane, chloromethyltrichlorosilane, p-chlorophenyltrichlorosilane, 3-chloropropyltrichlorosilane, 3-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinylmethoxysilane, vinyl-tris (β-methoxyethoxy) Silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinyldichlorosilane, dimethylvinylchlorosilane, octyl- Lichlorosilane, decyl-trichlorosilane, nonyl-trichlorosilane, (4-t-propylphenyl) -trichlorosilane, (4-t-butylphenyl) -trichlorosilane, dibenzyl-dichlorosilane, dihexyl-dichlorosilane, dioctyl-dichlorosilane, dinonyl- Dichlorosilane, didecyl-dichlorosilane, didodecyl-dichlorosilane, dihexadecyl-dichlorosilane, (4-tert-butylphenyl) -octyl-dichlorosilane, dioctyl-dichlorosilane, dibuthenyl-dichlorosilane, divinyldichlorosilane, di-2-ethylhexyl-dichlorosilane, di- 3,3-dimethylpentyl-dichlorosilane, trihexyl-chlorosilane, trioctyl-chlorosilane, tridecyl-chlorosilane, geo Tyl-methyl-chlorosilane, octyl-dimethyl-chlorosilane, (4-t-propylphenyl) -diethyl-chlorosilane, octyltrimethoxysilane, hexamethyldisilazane, hexaethyldisilazane, diethyltetramethyldisilazane, hexaphenyldisilazane , Hexatolyl disilazane, aminosilane, silicone oil and so on.

The resin fine particle external additive is preferably added in an amount of 0.1 to 7% by mass, more preferably 0.3 to 4% by mass with respect to the base toner. When the inorganic fine particle external additive is used in combination with the resin fine particle external additive, the inorganic fine particle external additive is preferably added in an amount of 0.1 to 7% by mass with respect to the base toner, and 0.3 to 4% by mass. More preferred.
For mixing external additives, a general powder mixer can be appropriately selected and used. Examples thereof include a Laedige mixer, a Nauter mixer, a Henschel mixer, and a super mixer.

(Crystalline polyester-containing toner)
The toner for developing an electrostatic charge image of the present invention preferably contains a crystalline polyester resin as a binder resin in order to achieve both low-temperature fixability and heat-resistant storage stability. It is more preferable that a crystalline resin having a melting point of 50 ° C. or more and 70 ° C. or less is contained in an amount of 45 parts by mass or less with respect to 100 parts by mass of the total binder resin and the glass transition temperature of the toner is 45 ° C. or more. As a result, the glass transition temperature at the first temperature increase measured by a differential scanning calorimeter (DSC) as the toner is 45 to 65 ° C., and the maximum peak temperature of the heat of fusion at the first temperature increase is 50 ° C. or more and 70 ° C. or less. The heat of fusion of the maximum peak is 4 J / g or more and 14 J / g or less.

In a toner containing a crystalline polyester resin, the resistance of the crystalline polyester resin is low, and the resistance further decreases in a state where it is not sufficiently crystallized. For this reason, the volume resistivity of the toner containing the crystalline polyester resin is lower than the volume resistivity compared to the case of not containing it, and the charge amount of the toner is lowered due to deterioration by printing in the printing machine for a long period of time, and the toner There is a problem derived from electrification such as scattering.
In addition, a toner containing crystalline polyester has a problem that abnormal images are likely to be generated (toner fixing containing a large amount of external additives to the photosensitive member) as compared with a toner not containing crystalline polyester. The reason may be that a part of the crystalline polyester appears on the toner surface, so that the photoreceptor is contaminated and the toner and silica are easily fixed, or are not easily removed by the cleaning blade.
By using silicone oil surface-treated resin fine particles as an external additive, even in a toner containing a crystalline polyester resin, the toner can be sufficiently charged, and an abnormal image can be prevented.

(Crystalline polyester resin)
Examples of the crystalline polyester resin include saturated aliphatic diol compounds having 2 to 12 carbon atoms as alcohol components, particularly 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10- Decanediol, 1,12-dodecanediol, and derivatives thereof, and a dicarboxylic acid having 2 to 12 carbon atoms or a saturated dicarboxylic acid having 2 to 12 carbon atoms having at least a double bond (C═C bond) as an acidic component Acids, in particular fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid and their derivatives Crystalline polyesters synthesized using them are preferred.
Among them, in particular, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12 in terms of reducing the difference between the endothermic peak temperature and the endothermic shoulder temperature. Any one alcohol component of dodecanediol, fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, 1, It is preferably composed of only one kind of dicarboxylic acid component of 12-dodecanedioic acid.

The acid value of the crystalline polyester resin is 5 mgKOH / g or more, more preferably 10 mgKOH / g or more in order to achieve the desired low-temperature fixability from the viewpoint of the affinity between paper and resin. On the other hand, in order to improve the hot offset property, it is preferably 45 mgKOH / g or less.
Further, the hydroxyl value of the crystalline polymer is preferably 0 to 50 mgKOH / g, more preferably 5 to 50 mgKOH / g in order to achieve a predetermined low-temperature fixability and to achieve good charging characteristics. .

The molecular structure of the crystalline polyester resin of the present invention can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid. In the above, an example is one having absorption at 965 ± 10 cm ⁻¹ or 990 ± 10 cm ⁻¹ based on δCH (out-of-plane variable angular vibration) of the olefin.

  As for the molecular weight, the above-mentioned molecular weight distribution having a sharp and low molecular weight is excellent in low-temperature fixability, and if many components having a low molecular weight are used, the heat-resistant storage stability is deteriorated. The molecular weight distribution by GPC of the solute is such that the peak position of the molecular weight distribution diagram in which the horizontal axis represents log (M) and the vertical axis represents mass% is in the range of 3.5 to 4.0, and the peak half-value width is 1 It is preferable that the weight average molecular weight (Mw) is 3000 to 30000, the number average molecular weight (Mn) is 1000 to 10,000, and Mw / Mn is 1 to 10. Furthermore, it is more preferable that the weight average molecular weight (Mw) is 5000 to 15000, the number average molecular weight (Mn) is 2000 to 10000, and Mw / Mn is 1 to 5.

(Other physical property controlling components that can be added to crystalline polymer materials)
In addition, as a method for controlling the crystallinity, softening point, hot offset resistance, and the like of the crystalline polyester resin, a trihydric or higher polyhydric alcohol such as glycerin as an alcohol component at the time of polyester synthesis, or trimellitic anhydride as an acid component Examples thereof include a method of designing and using a non-linear polyester obtained by condensation polymerization by adding a trivalent or higher polyvalent carboxylic acid.

(Determination method of crystallinity)
The crystallinity of the crystalline polyester resin of the present invention was determined by the following method.
Presence or absence of crystallinity can be confirmed by a crystal analysis X-ray diffractometer (X'Pert Pro MRD Phillips). The measurement method is described below.
First, a target sample is ground with a mortar to prepare a sample powder, and the obtained sample powder is uniformly applied to a sample holder. Thereafter, a sample holder is set in the diffractometer and measurement is performed to obtain a diffraction spectrum.
Of the peaks obtained in the range of 20 ° <2θ <25 ° in the obtained diffraction peak, the peak having the highest peak intensity was judged to have crystallinity when the peak half width was 2.0 or less.

The measurement conditions for X-ray diffraction are described below.
〔Measurement condition〕
Tention kV: 45kV
Current: 40mA
MPSS
Upper
Gonio
Scannode: continuuos
Start angle: 3 °
End angle: 35 °
Angle Step: 0.02 °
Lucent beam optics
Divergence slit: Div slit 1/2
Difference beam optics
Anti scatter slit: As Fixed 1/2
Receiving slit: Prog rec slit

<Amorphous polyester resin>
The toner for developing an electrostatic charge image of the present invention preferably contains an amorphous resin as a binder resin together with the crystalline polyester resin.

  Any conventionally known resin can be used as the amorphous (non-crystalline) resin used in combination with the polyester resin having crystallinity. For example, styrene, α-methylstyrene, chlorostyrene, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, Styrene resins such as styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-acrylonitrile-acrylic acid ester copolymer, polyester resin, vinyl chloride resin, rosin modified maleic acid resin, phenol resin, There are epoxy resins, polyethylene resins, polypropylene resins, ionomer resins, polyurethane resins, silicone resins, ketone resins, xylene resins, petroleum resins, hydrogenated petroleum resins, and the like. Of these, styrene resins and polyester resins containing an aromatic compound as a component are preferred. Particularly preferred are polyester resins.

The amorphous polyester resin is synthesized from a polyhydric alcohol and a polyvalent carboxylic acid. As the polyhydric alcohol and polyhydric carboxylic acid, components used in the crystalline polyester resin can be used. Besides these, there are alkylene oxide adducts of bisphenol A, isophthalic acid, terephthalic acid, and derivatives thereof.
These resins are not limited to single use but can be used in combination of two or more.

The molecular weight of the polyester resin used in the present invention is such that its weight average molecular weight (Mw) is 3000 to 100,000, its number average molecular weight (Mn) is 1500 to 4000, and its Mw / Mn in the molecular weight distribution by GPC of its THF soluble content. The ratio is preferably 2-50.
The molecular weight distribution of the polyester resin is based on a molecular weight distribution chart in which the horizontal axis is log (M: molecular weight) and the vertical axis is mass%. In the case of the polyester resin used in the present invention, it is preferable to have a molecular weight peak in the range of 2.5 to 4.5 (mass%) in this molecular weight distribution diagram.

  In the polyester resin, the glass transition temperature (Tg) and the softening temperature [T (F1 / 2)] are desirably low as long as the heat-resistant storage stability of the toner is not deteriorated. 70 degreeC is preferable, More preferably, it is 45-65 degreeC. The T (F1 / 2) is preferably 120 to 160 ° C, more preferably 130 to 150 ° C. When Tg and T (F1 / 2) are higher than the above ranges, the lower limit fixing temperature of the toner is increased, so that the low temperature fixing property of the toner is deteriorated.

The content of the amorphous polyester resin is preferably 50% by mass or more since it is preferable that the amorphous polyester is substantially contained as a main component in the present invention. More preferably, it is 60 mass% or more and less than 90 mass%.
When the content is less than 50% by mass, the dispersibility of each material existing in a dispersed state inside the toner, such as crystalline polyester, pigment, and release agent in the toner is deteriorated, and low temperature fixability and heat resistant storage are obtained. It may cause deterioration of sex, fogging of images, and disturbance. When the content is in the more preferable range, it is advantageous in that it is excellent in all of high image quality, high stability, low temperature fixability, and high temperature and high humidity resistance.
The content of the amorphous polyester resin in the toner can be determined from the composition of the material used when the toner is produced. Further, when the material composition at the time of toner production is not clear, the content of the amorphous polyester resin in the present invention can be determined by, for example, the following method.
A toner solution is obtained by sufficiently stirring 50 parts by mass of toner and 50 parts by mass of methyl ethyl ketone with a magnetic stirrer at 23 ° C. for 1 hour. The obtained toner solution is filtered through a membrane filter, the filtrate is heated at 150 ° C. for 1 hour, and the solid content concentration in the filtrate is calculated from the mass change before and after overheating. The solid content of the obtained filtrate can be determined as the content of the amorphous polyester resin.

The molecular structure of the amorphous polyester resin includes NMR (Nuclear Magnetic Resonance) measurement by solution and solid, X-ray diffraction, GC / MS (Gas Chromatography Mass Spectrometer), LC / MS (Liquid Chromatography Mass Spectrometer) It can be confirmed by (Infrared Spectroscopy) measurement or the like. At a convenient infrared absorption spectrum, and a method of detecting the 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 and having no absorption based on olefin? Ch (out-of-plane deformation vibration) as an amorphous polyester resin .

(Mixing ratio of crystalline / amorphous polyester resin)
The compounding ratio (mass ratio) of the crystalline polyester resin and the amorphous polyester resin in the present invention is preferably 3% by mass to 45% by mass of the former with respect to 55% by mass to 97% by mass of the latter. It is more preferable that the former is blended in an amount of 5% by mass to 20% by mass with respect to 80% by mass to 95% by mass. If the amount of the crystalline polyester resin is less than this, the low-temperature fixability is inferior, and if it is more than this, the fixing offset resistance and the heat-preserving stability are often inferior.

(Coloring agent)
The toner of the present invention can contain a colorant. As the colorant, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow Lead, Titanium Yellow, Polyazo Yellow, Oil Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R) , Tartrazine lake, quinoline yellow lake, anthracene yellow BGL, isoindolinone yellow, bengara, red lead, lead vermilion, cadmium red, cadmium mercurial red, antimon vermilion, permanent red 4R, para red, fise red, parachlor ortho Nitroani Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, poly Zored, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phtha Russia Nin green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by mass, preferably 3 to 10% by mass with respect to the toner.

The colorant used in the present invention can also be used as a master batch combined with a resin.
As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the polyester resin, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene and its substituted polymers; styrene-p-chlorostyrene Polymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer Polymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer , Styrene-acryloni Ryl copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid Resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be used, and these can be used alone or in combination.

This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin.
In addition, a so-called flushing method called an aqueous paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and the organic solvent component. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
The toner of the present invention can contain a release agent.
The release agent is preferably a wax having a melting point of 50 to 120 ° C.
Since such a wax can effectively act as a release agent between the fixing roller and the toner interface, high temperature offset resistance can be improved without applying a release agent such as oil to the fixing roller. be able to.
In addition, melting | fusing point of wax is calculated | required by measuring the maximum endothermic peak using TG-DSC system TAS-100 (made by Rigaku Corporation) which is a differential scanning calorimeter.

As the mold release agent, the following materials can be used.
As waxes and waxes, plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin, microcrystalline, petrolatum, etc. And petroleum wax.
In addition, examples of mold release agents other than these natural waxes include synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; and synthetic waxes such as esters, ketones, and ethers.
Furthermore, fatty acid amides such as 1,2-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; low molecular weight crystalline polymer, poly (n-stearyl methacrylate), poly (methacrylic acid n) -A crystalline polymer having a long-chain alkyl group in the side chain, such as a homopolymer or copolymer of polyacrylate such as lauryl (for example, n-stearyl acrylate-ethyl methacrylate copolymer) is also used as a release agent. Can do.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary.
All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives.

  Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84, phenolic condensate E-89 (above, Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary Copy charge PSY VP2038 of ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR- which is a boron complex 147 (Nippon Carlit), copper phthalocyanine, perylene, quinacrid And azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

  The amount of the charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, but is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. Preferably, the range of 0.2-5 mass parts is good. When the amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. It may cause a decrease.

  These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, or of course, may be added when directly dissolving or dispersing in an organic solvent, or may be fixed on the toner surface after preparation of toner particles. May be.

The toner of the present invention is obtained by melting and kneading toner constituent materials and then pulverizing and classifying, and is generally used as a conventional method, but is not limited to this method, and various methods including a polymerization method are possible. It is.
The polymerization method is different from the other polymerization methods such as suspension polymerization method, emulsion polymerization method, dispersion polymerization method, etc., but other than dissolution suspension method, polymer suspension method, etc., extension reaction method and the like can be used.

<Career>
The toner for developing an electrostatic charge image according to the present invention may be mixed with a carrier and used as a two-component developer.
As the carrier, ordinary carriers such as ferrite and magnetite and resin-coated carriers can be used.
The resin-coated carrier comprises a carrier core particle and a coating material that is a resin that coats (coats) the surface of the carrier core particle.

Examples of the resin used in the coating material include styrene-acrylic ester copolymers, styrene-acrylic resins such as styrene-methacrylic ester copolymers, acrylic ester copolymers, methacrylic ester copolymers, and the like. Preferable examples include fluorine-containing resins such as acrylic resins, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, and polyvinylidene fluoride, silicone resins, polyester resins, polyamide resins, polyvinyl butyral, and aminoacrylate resins.
In addition to these, resins that can be used as a coating (coating) material for carriers such as an ionomer resin and a polyphenylene sulfide resin can be used.
These resins may be used alone or in combination of two or more.
A binder type carrier core in which magnetic powder is dispersed in a resin can also be used.

Among the resins, a styrene-methyl methacrylate copolymer, a mixture of a fluorine-containing resin and a styrene copolymer, and a silicone resin are preferably used, and a silicone resin is particularly preferable. Examples of the mixture of the fluorine-containing resin and the styrene copolymer include, for example, a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, a mixture of polytetrafluoroethylene and a styrene-methyl methacrylate copolymer, Vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10:90 to 90:10), styrene-2-ethylhexyl acrylate copolymer (copolymer mass ratio 10:90 to 90:10) and styrene A mixture with 2-ethylhexyl acrylate-methyl methacrylate copolymer (copolymer mass ratio 20 to 60: 5 to 30:10:50) is mentioned.
Examples of the silicone resin include modified silicone resins produced by reacting a nitrogen-containing silicone resin and a nitrogen-containing silane coupling agent with a silicone resin.
The ratio of the resin coating material to the resin-coated carrier may be appropriately determined, but is preferably 0.01 to 5% by mass and more preferably 0.1 to 1% by mass with respect to the resin-coated carrier.

  In the resin-coated carrier, as a method for coating the surface of the carrier core with at least a resin coating agent, a method in which the resin is dissolved or suspended in a solvent and adhered to the applied carrier core, or a method in which the resin core is simply mixed in a powder state Is applicable.

Examples of the magnetic material for the carrier core include oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof.
The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. It is done.
Among these, copper-zinc-iron-based ferrites mainly composed of copper, zinc, and iron components, and manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium, and iron components are preferable.

The resistance value of the carrier is preferably 10 ⁶ to 10 ¹⁰ Ω · cm by adjusting the unevenness of the surface of the carrier and the amount of resin to be coated.
The carrier having a particle size of 4 to 200 μm can be used, preferably 10 to 150 μm, more preferably 20 to 100 μm.
In particular, the resin-coated carrier preferably has a 50% particle size of 20 to 70 μm.

  The two-component developer is preferably used in an amount of 1 to 200 parts by weight of the electrostatic image developing toner of the present invention with respect to 100 parts by weight of the carrier, and with respect to 100 parts by weight of the carrier. It is more preferable to use in 2-50 mass parts.

Next, the physical properties of the toner of the present invention will be described.
(About toner shape)
It is preferable that the average circularity of the toner having a spherical shape is 0.98 to 1.0.
The inventors have found that it is effective in the present invention to make the adhesion state of the additive to the toner surface appear as it is in the flow characteristics of the toner, and it is preferable that the toner is spherical.

(Sphericalizing of pulverized toner)
The toner by the pulverization / classification method is indefinite as it is, and depending on the pulverization method, the circularity is 0.930 to 0.950, and the circularity is not 0.960 to 0.998. The degree of circularity can be increased by mechanical spheroidizing treatment or heat treatment as described below, and spherical toner having a circularity of 0.960 to 0.998 can be obtained.
The circularity is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area.
[Mechanical processing]
For example, as described in JP-A-09-085741, a method using a turbo mill (manufactured by Turbo Industry), a kryptron (manufactured by Kawasaki Heavy Industries), a Q-type mixer (manufactured by Mitsui Mining), a hybridizer The shape of the pulverized toner can be made spherical by continuous treatment with a mechano-fusion device (manufactured by Nara Machinery Co., Ltd.) or a mechano-fusion device (manufactured by Hosokawa Micron Co., Ltd.).
[Heat treatment (dry type)]
For example, the shape of the pulverized toner can be made spherical by semi-melting the toner particle surface with hot air of 100 to 300 ° C. using a surffusion system (manufactured by Nippon Pneumatic Industry Co., Ltd.).
[Heat treatment (wet)]
The shape of the pulverized toner can be made spherical by immersing the toner obtained by the pulverization method in a high-temperature liquid at a temperature (about 200 ° C.) at which the toner has plasticity.

(Polymerized toner)
In the case of the polymer toner, a spherical toner can be obtained unless shape control is performed.

(Average circularity measurement method)
In the present invention, the average circularity is measured using a flow particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation), and analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10) is used. And analyzed. Specifically, 0.1 to 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a glass 100 ml beaker, and each toner 0.1 to 0 is added. 0.5 g was added and stirred with a microspatel, and then 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured using the FPIA-2100 until the density of the dispersion was 5000 to 15000 / μl. In this measurement method, it is important that the concentration of the dispersion liquid is 5000 to 15000 / μl from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated. If the amount is too small, the toner cannot be sufficiently wetted. It becomes insufficient. Further, the toner addition amount differs from the particle size, and it is necessary to decrease the small particle size and increase the large particle size. When the toner particle size is 3 to 7 μm, the toner amount is 0.1 to 0. By adding 0.5 g, the dispersion concentration can be adjusted to 5000 to 15000 / μl.

<Acid value>
The acid value of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of controlling low temperature fixability (fixing lower limit temperature), hot offset occurrence temperature, etc., 0.5 mgKOH / g It is preferably ˜40 mg KOH / g. When the acid value is less than 0.5 mg KOH / g, the effect of improving the dispersion stability by the base during production cannot be obtained, or when the prepolymer is used, an extension reaction and / or a crosslinking reaction proceeds. Manufacturing stability may be reduced. When the acid value exceeds 40 mgKOH / g, when the prepolymer is used, the extension reaction and / or the crosslinking reaction may be insufficient, and the high temperature offset resistance may be lowered.

<Glass transition temperature (Tg)>
The glass transition temperature (Tg) of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. However, the glass transition temperature (Tg1st) calculated at the first temperature increase in differential scanning calorimetry (DSC). ) Is preferably 20 ° C. or higher and lower than 60 ° C., more preferably 30 ° C. or higher and 50 ° C. or lower. Thereby, low temperature fixability, heat resistant storage stability and high durability can be obtained. If the Tg1st is less than 20 ° C., blocking in the developing machine or filming on the photoreceptor may occur, and if it is 60 ° C. or more, the low-temperature fixability may be deteriorated.

  The glass transition temperature (Tg2nd) calculated at the second temperature increase in the differential scanning calorimetry (DSC) of the toner is preferably 10 ° C. or higher and lower than 30 ° C. If the Tg2nd is less than 10 ° C., the image blocking property of the printed matter may be deteriorated, blocking in the developing machine or filming on the photoreceptor may occur, and if it is 30 ° C. or more, the low-temperature fixability is deteriorated. Sometimes.

Further, it is preferable that the difference between the glass transition temperature Tg1st at the first temperature increase of the toner and the glass transition temperature Tg2nd at the second temperature increase is 10 ° C. or more and less than 30 ° C. If the difference between Tg1st and Tg2nd is less than 10 ° C., the softening effect of the crystalline polyester on the amorphous polyester is low, and the low-temperature fixability may not be sufficiently exhibited. Further, if the difference between Tg1st and Tg2nd is 30 ° C. or more, the crystalline polyester is difficult to recrystallize after fixing, and the blocking property of the printed matter may deteriorate.
The details of the glass transition temperature (Tg1st) calculated at the first temperature increase and the glass transition temperature (Tg2nd) calculated at the second temperature increase in differential scanning calorimetry will be described later.

<Volume average particle diameter>
The volume average particle size of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a small particle size from the viewpoint of image quality, and is preferably 4 μm or more and 6 μm or less. The ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. Further, it is preferable to contain 1% by number or more and 10% by number or less of a component having a volume average particle diameter of 2 μm or less.

(Measurement method)
<< Method for measuring gel permeation chromatography >>
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the crystalline polyester resin and the amorphous polyester resin by gel permeation chromatography measurement can be measured by the following means, for example.
<Measurement conditions>
Gel permeation chromatography (GPC) measuring device: GPC-8220 GPC (manufactured by Tosoh Corporation)
・ Column: TSKgel SuperHZM-H 15cm triple (manufactured by Tosoh Corporation)
・ Temperature: 40 ℃
・ Solvent: Orthodichlorobenzene ・ Flow rate: 0.35 ml / min
-Sample: 0.4 ml of 0.15% sample was injected-Sample pretreatment: The target sample was dissolved in orthodichlorobenzene at 0.15 wt% and filtered through a 0.2 µm filter, and the filtrate was used as a sample. 100 μl of the sample solution is injected and measured.

  In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Showd STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580 were used. An RI (refractive index) detector was used as the detector.

<< Measurement Method of Melting Point and Glass Transition Temperature (Tg) >>
The toner and the melting point and glass transition temperature (Tg) of each material in the present invention can be measured using, for example, a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation).
Specifically, the exothermic peak temperature, melting point, and glass transition temperature of the target sample can be measured by the following procedure.

First, about 5.0 mg of a target sample is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, heating is performed from 0 ° C. to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. Thereafter, the temperature is lowered from 150 ° C. to 0 ° C. at a temperature drop rate of 10 ° C./min, and further heated to 150 ° C. at a temperature rise rate of 10 ° C./min, and a differential scanning calorimeter (“DSC-60”, manufactured by Shimadzu Corporation) ) To measure the DSC curve.
From the obtained DSC curve, using the analysis program “endothermic shoulder temperature” in the DSC-60 system, the DSC curve at the first temperature rise is selected, and the glass transition temperature at the first temperature rise of the target sample is obtained. Can do. Further, by using the “endothermic shoulder temperature”, a DSC curve at the second temperature rise can be selected, and the glass transition temperature at the second temperature rise of the target sample can be obtained.
Also, from the obtained DSC curve, using the analysis program “endothermic peak temperature” in the DSC-60 system, the DSC curve at the first temperature increase is selected, and the melting point at the first temperature increase of the target sample is obtained. Can do. Further, by using the “endothermic peak temperature”, a DSC curve at the second temperature rise can be selected, and the melting point at the second temperature rise of the target sample can be obtained.
In the present invention, the glass transition temperature at the first temperature rise when the toner is used as the target sample is Tg1st, and the glass transition temperature at the second temperature rise is Tg2nd.
Moreover, in this invention, melting | fusing point and Tg at the time of the 2nd temperature rise of each structural component are made into melting | fusing point and Tg of each object sample.
In the present invention, when the toner is simply referred to as the glass transition temperature Tg, it is all Tg1st, and when it is referred to as the glass transition temperature Tg for the resin, it is Tg2nd.

<< Measurement Method of Particle Size Distribution >>
For the volume average particle diameter (D4) and number average particle diameter (Dn) of the toner, the ratio (D4 / Dn) is, for example, Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter Co., Ltd.), etc. Can be measured. In the present invention, Coulter Multisizer II is used as a measuring device. The measurement method is described below.
First, 0.1 mL to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) as a dispersant is added to 100 mL to 150 mL of the electrolytic aqueous solution. Here, the electrolytic aqueous solution is a 1 mass% NaCl aqueous solution prepared using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 mg to 20 mg of a measurement sample is added. The electrolytic aqueous solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Calculate volume distribution and number distribution. From the obtained distribution, the volume average particle diameter (D4) and the number average particle diameter (Dn) of the toner can be obtained.
As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted.

<< Softening temperature [T (F1 / 2) >>
The softening temperature [T (F1 / 2)] of the amorphous resin is obtained by using an elevated flow tester CF-500 manufactured by Shimadzu Corporation, with a die diameter of 1 mm, a pressure of 10 kgf / cm ² , and a temperature rising rate of 3 ° C./min. This is the temperature at which the stroke when a sample of 1 cm ³ is melted and flowed out under the conditions is ½ of the stroke change amount from the outflow start point to the outflow end point.

Since the toner of the present invention is excellent in fluidity, it can be sufficiently stored in a cartridge container and is also suitable for an apparatus configured to convey toner from the cartridge container to the developing unit.
Examples of the cartridge container include a toner cartridge that fills toner, and a process cartridge that includes at least a photosensitive member and a developing unit, and that fills a toner storage portion of the developing unit. An image is formed by attaching the cartridge to the image forming apparatus.

(Image forming apparatus and image forming method)
The image forming apparatus (not shown) is not particularly limited as long as it uses the toner for developing an electrostatic image of the present invention, and can be appropriately selected according to the purpose. And at least an electrostatic charge image forming unit, a developing unit, a transfer unit, and a fixing unit, preferably a cleaning unit, and other units appropriately selected as necessary, for example, a neutralizing unit, Recycling means, control means, etc.
These means are not particularly limited and can be appropriately selected according to the purpose.

The image forming step (image forming method) is not particularly limited as long as it uses the toner for developing an electrostatic image of the present invention, and can be appropriately selected according to the purpose. It includes at least a forming process, a developing process, a transferring process, and a fixing process, preferably including a cleaning process, and further including other processes appropriately selected as necessary, for example, a static elimination process, a recycling process, a control process, and the like. .
In addition, these steps are not particularly limited and can be appropriately selected according to the purpose.

(Process cartridge)
An image forming apparatus according to the present invention integrally includes at least an electrostatic latent image carrier and a developing unit, and further, a charging unit, an exposure unit, a transfer unit, a cleaning unit, and a discharging unit, which are appropriately selected as necessary. It is also possible to provide a process cartridge that integrally supports other means such as detachable to the main body of the image forming apparatus.
The developing means is means for developing an electrostatic latent image carried on the electrostatic latent image carrier with toner to form a visible image, and the toner is the toner of the present invention. I need.

The developing means includes at least a toner container that contains the toner, and a toner carrier that carries and conveys the toner contained in the toner container, and further carries the toner. You may have the layer thickness control member etc. for controlling layer thickness. The developing means includes at least a developer container that contains the two-component developer, and a developer carrier that carries and conveys the two-component developer contained in the developer container. preferable.
Further, as the charging unit, the exposure unit, the transfer unit, the cleaning unit, and the charge eliminating unit, the same ones as those of the above-described image forming apparatus can be appropriately selected and used.

  The process cartridge can be detachably provided in various electrophotographic image forming apparatuses, facsimiles, and printers, and it is particularly preferable that the process cartridge is detachably provided in the image forming apparatus.

  Here, for example, as shown in FIG. 3, the process cartridge includes an electrostatic latent image carrier 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and further, if necessary. And other means. In FIG. 3, reference numeral 103 denotes exposure by exposure means, and 105 denotes a recording medium.

Next, the image forming process using the process cartridge shown in FIG. 3 will be described. The electrostatic latent image carrier 101 is charged by the charging unit 102 while being rotated in the direction of the arrow, and exposure 103 by the exposure unit (not shown). An electrostatic latent image corresponding to the exposure image is formed on the surface.
The electrostatic latent image is developed with toner by the developing unit 104, and the developed toner image is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the latent electrostatic image bearing member after the image transfer is cleaned by the cleaning unit 107, further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

Further, the present invention relates to the following electrostatic charge image developing toner (1), and includes the following (2) to (9) as embodiments.
(1) An electrostatic charge image developing toner comprising resin fine particles surface-treated with silicone oil as an external additive.
(2) The electrostatic image developing toner according to (1), wherein the silicone oil is a fluorine-containing silicone oil.
(3) The electrostatic image developing toner according to (1) or (2), wherein the resin fine particles contain inorganic fine particles.
(4) The resin base material of the resin fine particles includes a polymer obtained by using at least one monomer selected from a styrene monomer, an acrylate monomer, and a methacrylate monomer, and is crosslinked. The electrostatic image developing toner according to any one of (1) to (3).
(5) The electrostatic image developing toner according to any one of (1) to (4), wherein the resin fine particles have a number average particle diameter of 50 to 200 nm.
(6) The electrostatic image developing toner according to any one of (1) to (5) above, which does not contain an external additive based on inorganic fine particles as an external additive.
(7) The electrostatic image developing toner according to any one of (1) to (6), wherein the electrostatic image developing toner contains a crystalline polyester resin as a binder resin.
(8) The electrostatic image developing toner according to any one of (1) to (7), wherein the electrostatic image developing toner has an average circularity of 0.98 to 1.0.
(9) A process cartridge that integrally supports at least the electrostatic latent image carrier and the developing unit and is detachable from the main body of the image forming apparatus, wherein the developing unit includes the above (1) to (8). A process cartridge comprising the toner for developing an electrostatic image according to any one of the above.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. “Parts” represents parts by mass.

(Production example of resin fine particles)
(Production Example 1 of Resin Fine Particles)
After 5 parts of dimethyl silicone oil (KF-96-50CPS) was dissolved in 500 parts of ethanol and stirred and mixed with 100 parts of acrylic resin fine particles (MP-300, average primary particle size 100 nm, Soken Chemical) having a crosslinked structure, The solvent ethanol was distilled off using an evaporator and dried.
Next, resin particles 1 surface-treated with dimethyl silicone oil were obtained by crushing using a Henschel mixer.

(Production Example 2 of Resin Fine Particles)
Acrylic resin fine particles (MP-300, average primary particles) having a crosslinked structure in which 4 parts of dimethyl silicone oil (KF-96-50CPS) and 1 part of fluoroalkyl silicone oil (X-22-822) are dissolved in 500 parts of ethanol. After stirring and mixing with 100 parts (diameter 100 nm, Soken Chemical Co., Ltd.), the solvent ethanol was distilled off using an evaporator and dried.
Next, it was put into a Henschel mixer, and the surface treatment was carried out with dimethyl silicone oil and fluoroalkyl silicone oil by repeatedly crushing the cycle of stirring for 10 minutes at a stirring peripheral speed of 33 m / s and then standing for 10 minutes 5 times. Resin fine particles 2 were obtained.

(Production Example 3 of Resin Fine Particles)
Hydrophobized silica HDK H-2000 (Hoechst Japan, average particle size 0.012 μm) 6 parts by mass, cross-linked acrylic resin fine particles (MP-300, average particle size 100 nm, Soken Chemical Co., Ltd.) 100 parts by mass Was put into a Henschel mixer, and a cycle of stirring for 10 minutes at a stirring peripheral speed of 44 m / s and then standing for 10 minutes was repeated 10 times to obtain silica-coated resin fine particles. In addition, about H-2000, H-2000 was made to adhere uniformly on MP-300 by dividing | segmenting into 5 times by 1/5 quantity for every first 5 stirring cycles. The surface coverage of the resin fine particles by the silica fine particles was 0.07.
After 4 parts of dimethyl silicone oil (KF-96-50CPS) and 1 part of fluoroalkyl silicone oil (X-22-822) are dissolved in 500 parts of ethanol and mixed with 100 parts of the silica-coated fine particles, the evaporator is used. The solvent ethanol was distilled off and dried.
Next, by crushing using a Henschel mixer, resin fine particles 3 surface-treated with dimethyl silicone oil and fluoroalkyl silicone oil were obtained.

(Production Example 4 of Resin Fine Particles)
100 parts of acrylic resin fine particles having a crosslinked structure (MP-300, average primary particle size 100 nm, Soken Chemical) 100 parts of acrylic resin fine particles having no cross-linked structure (MP-1451, average primary particle size 150 nm, Soken Chemical) Resin fine particles 4 were obtained in the same manner as in Production Example 3 of resin fine particles, except for the above. The surface coverage of the resin fine particles by the silica fine particles was 0.10.

(Production Example 5 of Resin Fine Particles)
100 parts of acrylic resin fine particles having a crosslinked structure (MP-300, average primary particle size 100 nm, Soken Chemical) and 100 parts of acrylic resin fine particles not having a crosslinked structure (MP-2200, average primary particle size 350 nm, Soken Chemical) Resin fine particles 5 were obtained in the same manner as in Production Example 3 of resin fine particles, except for the above. The surface coverage of the resin fine particles by the silica fine particles was 0.24.

(Production Example 6 of Resin Fine Particles)
Acrylic resin fine particles having a crosslinked structure (MP-300, average primary particle size 100 nm, Soken Chemical) were used as resin fine particles 6.

(Production Example 7 of Resin Fine Particles)
Hydrophobized silica HDK H-2000 (Hoechst Japan, average particle size 0.012 μm) 6 parts by mass, cross-linked acrylic resin fine particles (MP-300, average particle size 100 nm, Soken Chemical Co., Ltd.) 100 parts by mass Was put into a Henschel mixer, and a resin fine particle 7 coated with silica was obtained by repeating a cycle of stirring for 10 minutes at a stirring peripheral speed of 44 m / s and then standing for 10 minutes 5 times. In addition, about H-2000, H-2000 was made to adhere uniformly on MP-300 by dividing | segmenting into 5 times by 1/5 quantity for every first 5 stirring cycles.

The components of the obtained resin fine particles 1 to 7 are collectively shown in Table 1 below.

(Production example of crystalline polyester)
Into a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 2,300 g of 1,10-decanediol, 2530 g of 1,8-octanediol and 4.9 g of hydroquinone were added, and 180 ° C. And then reacted at 8.3 kPa for 2 hours, Tg in DSC measurement was 65 ° C., melting point peak temperature was 70 ° C., Mw 10000, Mn 3000, A crystalline polyester resin A1 having Mw / Mn = 3.3 was obtained.

(Example of production of amorphous polyester resin)
Table 2 shows components of amorphous polyester resins B-H1 and B-L1, and Table 3 shows physical property values of amorphous polyester resins B-H1 and B-L1.
BPA / EO shown in Table 2 represents an ethylene oxide adduct of bisphenol A (2.2 mol adduct), and BPA / PO represents a propylene oxide adduct of bisphenol A (2.2 mol adduct). Indicates.
Amorphous polyester resins B-H1 and B-L1 were prepared by putting 4000 g of the composition shown in Table 2 into a 5-L four-necked round bottom flask equipped with a thermometer, a stirrer, and a condenser. It was set on a mantle heater, 4 g of dibutyltin oxide was added, the temperature was raised, the temperature was kept at 220 ° C., the reaction was carried out for 8 hours, and the reaction was carried out at 8.3 kPa until a predetermined softening point was reached.

(Toner base production example 1)
Crystalline polyester resin A1 20 parts Amorphous polyester resin B-H1 20 parts Amorphous polyester resin B-L1 60 parts Salicylic acid Zr salt (Hodogaya Chemical TN-105) 1 part Desorbed free fatty acid type carnauba wax (Tg: 83 7 parts Carbon black (Mitsubishi Chemical # 44) 13 parts The above toner constituent materials were sufficiently stirred and mixed in a Henschel mixer and then melt-kneaded in a twin-screw extruder. Regarding the kneading conditions, as a result of setting the temperature of the kneader to knead the kneaded material at a low temperature (minimum temperature within the range where the kneaded material is in a molten state), the kneading material is mixed at the kneader outlet. The temperature of the kneader was set so that the temperature of the smelted product was 120 ° C. Next, this kneaded product is coarsely pulverized to a particle size of 1 mm or less using an AP pulperizer manufactured by Hosokawa Micron Co., and then finely pulverized and classified using a turbo mill manufactured by Turbo Industry Co., to obtain a toner base having a weight average particle size of 6.5 μm. It was.
Subsequently, using surffusion (manufactured by Nippon Pneumatic Co., Ltd.), toner having an average circularity of 0.98 is passed through the apparatus set at a temperature of 300 ° C., a hot air flow rate of 1000 l / min, a supply air flow rate of 100 l / min, and a rotation speed of 600 rpm. Mother 1 was obtained.
The maximum peak temperature of heat of fusion was 68 ° C., and the amount of heat was 7 J / g.

(Toner base production example 2)
A toner base was produced in the same manner as in Toner Production Example 1 except that the formulation was changed to the following, and a toner base 2 having an average circularity of 0.98 was obtained.
Crystalline polyester resin A1 0 part Amorphous polyester resin B-H1 20 parts Amorphous polyester resin B-L1 80 parts Salicylic acid Zr salt (Hodogaya Chemical TN-105) 1 part Desorbed free fatty acid type carnauba wax (Tg: 83 ° C) 7 parts Carbon black (Mitsubishi Chemical # 44) 13 parts The maximum peak temperature of heat of fusion was 82 ° C and the amount of heat was 2 J / g.

Examples 3 to 6, Reference Examples 1 and 2, Comparative Examples 1 to 4 (Examples 1 and 2 are missing numbers)
(Example of toner production)
External additives were mixed in the combinations of toner bases and external additives shown in Table 4 below to obtain toners of Examples 3 to 6, Reference Examples 1 and 2 , and Comparative Examples 1 to 4.
(External additive mixing conditions)
In toners 1 to 7 and 9, with respect to 100 parts by mass of toner base particles, 3.0 parts by mass of resin fine particles were stirred with a Henschel mixer at a stirring peripheral speed of 33 m / s for 10 seconds, and then allowed to stand for 10 seconds for 5 cycles. The toner was repeated twice.
For toner 8 and toner 10, toners were produced in the same manner except that 3.0 parts by mass of the resin fine particles were changed to 3.0 parts by mass of silicone oil-treated silica RY50 manufactured by Nippon Aerosil Co., Ltd.

(Developer production example)
The toners of Examples 3 to 6, Reference Examples 1 and 2 and Comparative Examples 1 to 4 and the carrier of the following production method were stirred with a tumbler mixer so that the total amount of toner and carrier was 1 kg and the toner concentration was 7% by mass. It was mixed for 10 minutes at the strongest strength and used for the evaluation described in Table 4.

Carrier production method Acrylic resin solution (solid content 50 wt%) 21.0 parts Guanamin solution (solid content 70 wt%) 6.4 parts Alumina particles [0.3 μm, specific resistance 10 ¹⁴ (Ω · cm)] 7.6 parts Silicon Resin solution [solid content 23 wt%
(SR2410: manufactured by Toray Dow Corning Silicone Co., Ltd.)] 65.0 parts aminosilane [solid content: 100 wt%
(SH6020: manufactured by Toray Dow Corning Silicone Co., Ltd.)] 0.3 parts Toluene 60 parts Butyl cellosolve 60 parts are dispersed with a homomixer for 10 minutes to obtain a blend coating film forming solution of acrylic resin and silicon resin containing alumina particles. It was. Using the sintered ferrite powder [(MgO) _1.8 (MnO) _49.5 (Fe ₂ O ₃ ) _48.0 : average particle size; 35 μm] as the core material, the coating film forming solution has a thickness of 0.15 μm on the surface of the core material. Thus, it was applied and dried with a Spira coater (Okada Seiko Co., Ltd.). The obtained carrier was baked by standing in an electric furnace at 150 ° C. for 1 hour. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 106 μm to obtain [Carrier 1]. The measurement of the binder resin film thickness was performed by observing the cross section of the carrier with a transmission electron microscope so that the coating film covering the carrier surface could be observed.

(Evaluation method in Examples)
(Evaluation of cleaning property and adhesion of photoconductor)
1. The obtained toner, developer, and apparatus are all left in an environmental room at 25 ° C. for 50 days.
2. The developer is extracted from the Imageo neo C600 commercial product developing apparatus, and 400 g of the developer of the example or the comparative example is used instead.
3. A developing device is attached to the main body of Imagio neo C600, and only the developing device is idled for 5 minutes at a developing sleeve linear velocity of 300 mm / s.
4). Both the developing sleeve and the photosensitive member were rotated at 300 mm / s trailing, and the charging potential and the developing bias were adjusted so that the toner on the photosensitive member was 0.6 ± 0.05 mg / cm ² .
5. The cleaning blade was only one cleaning blade mounted on a commercially available Imagio neo C600 PCU, its elastic modulus was 70%, the thickness was 2 mm, and the contact angle with the image carrier at the counter was 20 °.
6). Under the above development conditions, the transfer current is adjusted so that the transfer rate is 96 ± 2%.
7). Using the set values, 1000 sheets of a chart (FIG. 2) including a band of 4 cm in the sheet passing direction and 25 cm in the sheet passing width direction were output.
8). The image output at the end was evaluated for the image quality in the central portion of the printing paper passing direction and the central portion in the width direction, which is a white background portion, and was evaluated based on whether or not an abnormal image was generated due to poor cleaning.
9. For evaluation of the output image, an image ID (X-RITE 938, v-value manufactured by X-RITE) was measured.
10. When the image ID after passing paper is 0.01 or less compared to the image ID of paper that has not passed, the cleaning performance is OK (◯), and when it is more than that, the cleaning performance is NG (×) and rank evaluation did.
11. After that, the surface of the photoconductor is observed with a VK-8700 microscope, and each 4.5 mm width at the center in the axial direction of the photoconductor and both left and right ends is observed at Vk8500 (magnification 10 times), and exists on the photoconductor. The presence or absence of fixed matter to be observed was observed. The case where 5 or more fixed objects existed in one visual field was indicated as “x”, the case where 1 to 5 or more fixed objects existed in one visual field was indicated as “Δ”, and the case where no fixed material existed was indicated as “◯”.

(Decrease in charging ability of carrier)
1. After the evaluation, only the developing device is idled for 60 minutes at a developing sleeve linear velocity of 300 mm / s.
2. A part of the developer was sampled and the charge amount was measured by the blow-off method to evaluate the amount of decrease in the charging ability of the carrier. In comparison with the charge amount immediately after the development of the developer, the case where the decrease amount of the charge amount was less than 5 μc / g was evaluated as ◯, the case where the charge amount was 10 μc / g, and the case where it exceeded 5-10 μc /.

The charge amount of the toner can be measured by the following method. A method for measuring the charge amount of toner will be described with reference to FIG.
First, a certain amount of developer is put into a conductor container (cage) 102 having a stainless steel mesh 101 at both ends. The mesh 101 has a mesh size between the toner 103 and the carrier 104 (mesh size 20 μm), and is set so that the toner 103 passes between the meshes 101. When a compressed nitrogen gas (1 kgf / cm ² ) 106 is blown from the nozzle 105 for 60 seconds to cause the toner 103 to jump out of the gauge 102, a carrier 104 having a polarity opposite to the charge of the toner is left in the cage. In FIG. 1, 107 is an electrometer.
The charge amount Q of the toner and the mass M of the protruding toner are measured, and the charge amount per unit mass is calculated as the charge amount Q / M. The toner charge amount is expressed in μc / g.

(Evaluation of lower limit of fixing)
A copy test was performed on type 6200 paper (manufactured by Ricoh) using an apparatus in which the fixing unit of a digital full-color copier (imageoMP C4500 manufactured by Ricoh) was modified.
Specifically, the cold offset temperature (fixing lower limit temperature) was determined by changing the fixing temperature.
The evaluation conditions were a paper feed linear velocity of 200 to 220 mm / second, a surface pressure of 1.0 kgf / cm ² , and a nip width of 10.0 mm.
The fixing lower limit temperature was ranked by setting the fixing machine temperature in increments of 2 ° C. to pass an unfixed image, and setting the lowest temperature at which no cold offset occurred as the fixing lower limit temperature.
100-115 ° C: ○
115-130 ° C: △
130 ° C or higher: ×

(Evaluation results)
The evaluation results are shown in Table 4 below.

101 mesh 102 conductive container (cage)
103 Toner 104 Carrier 105 Nozzle 106 Compressed nitrogen gas 107 Electrometer

Japanese Patent No. 3500755

Claims (5)

Electrostatic charge characterized by containing resin fine particles surface-treated with silicone oil as an external additive, the resin fine particles having a number average particle diameter of 50 to 200 nm and containing silica fine particles on the surface. Toner for image development.   The electrostatic image developing toner according to claim 1, wherein the silicone oil is a fluorine-containing silicone oil.   The base resin of the resin fine particles contains a polymer obtained by using at least one monomer selected from styrene monomer, acrylate monomer and methacrylate ester monomer, and is crosslinked. Or the electrostatic image developing toner according to 2;   The electrostatic image developing toner according to claim 1, wherein the electrostatic image developing toner contains a crystalline polyester resin as a binder resin.   5. A process cartridge that integrally supports at least the electrostatic latent image carrier and the developing unit and is detachable from the main body of the image forming apparatus, wherein the developing unit is a static cartridge according to claim 1. A process cartridge comprising a toner for developing a charge image.

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