JP2013205793A - Toner for electrostatically charged image development and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatically charged image development, which extends the lifetime of a photoreceptor and is superior in fixability, cleanability, environment resistance, sticking resistance, and heat resistant preservability and allows acquisition of high quality images.SOLUTION: The toner for electrostatically charged image development includes: toner base particles each of which comprises a core particle including a binder resin, a release agent, and a colorant and projections formed of resin fine particles on the surface of the base particle; and an external additive. The external additive comprises organic fine particles, and the binder resin contains a crystalline polyester resin and a non-crystalline polyester resin. The toner for electrostatically charged image development satisfies 0≤A-Z≤3.0, 0.5≤B-Z≤4.0, and 4.0≤C-Z≤8.0 where Z, A, B, and C are abundance ratios (number%) of particles having a particle size of 0.6 to 2.0 μm when measured by a flow type particle image analyzer before irradiation of an ultrasonic wave of 20 kHz and 80 W/10 cmto a dispersion containing 1 mg/mL of the toner for electrostatically charged image development, after the irradiation for one minute, after the irradiation for 5 minutes, and after the irradiation for 10 minutes respectively.

Description

  The present invention relates to an electrostatic charge image developing toner and a process cartridge for developing an electrostatic latent image formed in electrophotography, electrostatic recording method, and electrostatic printing method.

In recent years, spherical toner has been developed as a toner for printers in order to improve image quality. In particular, it has already been known to improve the image quality of a single-component developer toner by making the toner spherical to faithfully reproduce an electrostatic latent image.
In recent years, it has been required that the image forming apparatus can perform printing at low cost. In order to satisfy this requirement, it is essential to extend the life of the functional members of the image forming apparatus. Among the functional members, spherical toner has been developed as a technique that can extend the life of the photoreceptor.

However, when the spherical toner is used, it is difficult to remove the toner remaining on the photosensitive member, and there is a problem that the charging roller is contaminated or the image is lost due to the toner remaining on the photosensitive member. . As a method for solving this problem, for example, it is conceivable to increase the amount of the external additive added to the toner. However, this method has a problem that the low-temperature fixability is hindered.
Further, from the viewpoint of extending the life of the photoreceptor, there has been a problem that the surface of the photoreceptor is scraped due to friction with the cleaning blade, and the photoreceptor is scraped (hereinafter also referred to as “film scraping”).

As a method for solving the above problem, for example, it has been proposed to achieve both toner cleaning properties and low-temperature fixability by forming resin protrusions on the surface of toner base particles to form protrusions (patent). Reference 1).
However, this proposal does not consider the removal of the resin fine particles (protrusions) and the removal of external additives, and problems such as background contamination, charge reduction during long-term use, and toner sticking to toner regulating members, etc. The problem was not solved at the same time. In particular, in a one-component development system, the inorganic fine particles as external additives and the resin fine particles are detached from the toner particle surface by the pressure applied to the toner by a stirring blade in the developing device or a regulating blade as a regulating member. However, it is indispensable for extending the life of the one-component development system to firmly adhere these fine particles to the toner surface.

To solve the above problem, for example, it is proposed to define the amount of change of fine powder (small particle size particles) separated from the toner when the toner is irradiated with ultrasonic waves, and to keep the amount of change within a specific range. (See Patent Document 2). That is, among the toner physical properties, the abundance ratio A of the small particle size at the initial evaluation and the abundance ratio B of the small particle size at the long-term evaluation schematically represent the share of the toner in the developing container, It has been proposed to keep the toner in the developing container in a good state continuously during initial evaluation and long-term evaluation.
However, in this proposal, since the toner base particle does not have a structure having a protrusion as the toner structure, the surface shape in which the resin fine particles are adhered to the surface of the toner core particle as described above to form the protrusion. However, this does not solve the problem of the separation of the resin fine particles, which is a problem with the toner having toner. In addition, when the ratio of the small particle size particles in the toner dispersion liquid is measured under the conditions of ultrasonic irradiation prescribed in the above proposal for the toner in which the resin fine particles are adhered to the surface of the toner core particles to form the protrusions, The inventors have found that there is almost no difference in the abundance ratio between the toner dispersion before ultrasonic irradiation and the toner dispersion after ultrasonic irradiation, and the correlation with image quality cannot be obtained. That is, there is a problem that it cannot be used as a technique for evaluating that the resin fine particles as the protrusions are firmly attached to the surface of the toner base particles so as not to be detached.
Further, in this proposal, since the ratio of small particle size particles in the toner dispersion before ultrasonic irradiation is not defined, the release rate before and after ultrasonic irradiation cannot be determined. Judgment was difficult.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention does not hinder the low-temperature fixability, improves the cleaning property of the toner, realizes a longer life of the photosensitive member, and reduces the decrease in charging due to environmental changes, so that the toner is applied to the regulating blade as a regulating member. No sticking, no contamination by toner, excellent heat-resistant storage, high-quality images, especially images that have very low background stains at an appropriate image density even when used repeatedly for a long period of time. It is an object of the present invention to provide a toner for developing an electrostatic charge image that can be developed.

As a result of intensive studies to achieve the above object, the present inventors have controlled the amount of change in fine particles when irradiated with a specific ultrasonic wave within a certain range, so that the toner surface The adhesion of inorganic fine particles to be dispersed and fine resin fine particles to be dispersed on the surface of the toner core particles is strong, and the release of free fine particles in the development system is suppressed, and the sticking to the regulating member is eliminated. It was found that the life could be extended.
In addition, since the toner has the specific powder characteristics as described above, the rubbing force between the photoconductor and the cleaning blade is reduced, and film abrasion of the surface of the photoconductor can be prevented, and the life of the photoconductor is extended. Also found that it would be possible.
Furthermore, it has been found that a high-quality image can be obtained by using the toner in an image forming apparatus. Based on the above findings, the present invention has been completed.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
The toner for developing an electrostatic charge image of the present invention includes a core particle containing a binder resin, a release agent and a colorant, toner base particles composed of convex portions formed by resin fine particles on the surface of the core particle, An electrostatic charge image developing toner comprising an agent, wherein the external additive is inorganic fine particles, the binder resin contains a crystalline polyester resin and an amorphous polyester resin, Particles having a particle size of 0.6 μm to 2.0 μm as measured by a flow type particle image analyzer when a 1 mg / mL dispersion of toner for developing an electrostatic image is irradiated with ultrasonic waves of 20 kHz and 80 W / 10 cm ² In the abundance ratio (number%), the abundance ratio before irradiation with the ultrasonic waves is Z, the abundance ratio when irradiated for 1 minute is A, and the abundance ratio when irradiated for 5 minutes is B. When irradiated for 10 minutes The abundance ratio when is C, and satisfies all the following relational expression (1) to (3).
0 ≦ A−Z ≦ 3.0 Formula (1)
0.5 ≦ B−Z ≦ 4.0 Formula (2)
4.0 ≦ C−Z ≦ 8.0 Formula (3)

  According to the present invention, the above-mentioned problems can be solved, the object can be achieved, the low-temperature fixability is not hindered, the toner cleaning property is improved, and the life of the photosensitive member is extended. In addition, there is little decrease in charge due to environmental changes, toner does not adhere to the regulating blade, which is a regulating member, there is no contamination of the member with toner, it has excellent heat-resistant storage stability, and high-quality images, especially for a long period of time It is possible to provide a toner for developing an electrostatic charge image that can obtain an image having an appropriate image density and extremely low background stain even when used.

FIG. 1 is an explanatory diagram of a deformation start point TgA measured by a flow tester in the electrostatic image developing toner of the present invention. FIG. 2 is an explanatory diagram showing the relationship between the diameter (a) of the stirring container used in the production of the electrostatic image developing toner of the present invention and the blade diameter (b) of the stirring blade. FIG. 3 is an explanatory diagram showing a main part of an embodiment of an image forming apparatus in which the toner for developing an electrostatic latent image of the present invention is used. FIG. 4 is an explanatory diagram showing a configuration of a fixing device used in an image forming apparatus in which the electrostatic latent image developing toner of the present invention is used. FIG. 5 is an explanatory diagram showing another example of an image forming apparatus in which the electrostatic latent image developing toner of the present invention is used. FIG. 6 is an explanatory view showing another example of an image forming apparatus in which the electrostatic latent image developing toner of the present invention is used. FIG. 7 is an explanatory view showing an example of the process cartridge of the present invention. FIG. 8 is an example of a scanning electron microscope (SEM) photograph of toner base particles in Example 1.

(Static image developing toner)
The toner for developing an electrostatic charge image of the present invention contains at least toner base particles and an external additive, and further contains other components as necessary.

<Toner base particles>
The toner base particles have a structure composed of core particles and convex portions formed by attaching resin fine particles to the surfaces of the core particles. The electrostatic image developing toner of the present invention has a surface structure in which a large number of convex portions are formed on the surface of the core particles (see FIG. 8).
Hereinafter, the core particle is referred to as a core, the resin fine particles forming the convex portions themselves, or an aggregate thereof may be referred to as a shell, and the toner may be referred to as a core-shell type toner.

<Core particles>
The core particles include a binder resin, a release agent, and a colorant, and appropriately include other components as necessary. Examples of the other components include a charge control agent and a dispersant.
The core particles can be preferably produced by a method for producing a toner for developing an electrostatic image described later.

<< Binder resin >>
The binder resin is not particularly limited as long as it includes a crystalline polyester resin and an amorphous polyester resin, and can be appropriately selected from resins conventionally used in toners. For example, polyester resin, styrene-acrylic resin Examples thereof include resins, polyol resins, vinyl resins, polyurethane resins, epoxy resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. Among these, a polyester resin is preferable from the viewpoint of fixability. These may be used individually by 1 type and may use 2 or more types together.

-Crystalline polyester resin-
The crystalline polyester resin is not particularly limited as long as it is a polyester resin having crystallinity, and conventionally known ones can be appropriately used depending on the purpose.
The crystalline polyester resin has an advantage that a linear unsaturated aliphatic dicarboxylic acid is used as an acid component thereof, so that a crystalline structure can be formed more easily than when an aromatic dicarboxylic acid is used. The function of the resin can be exhibited more effectively.
The crystalline polyester resin is, for example, from (I) a linear unsaturated aliphatic divalent carboxylic acid or a reactive derivative thereof (for example, an acid anhydride, a lower alkyl ester having 1 to 4 carbon atoms, an acid halide, etc.). And a polyhydric alcohol component comprising (II) a linear aliphatic diol can be produced by a polycondensation reaction.

If necessary, a small amount of other polyvalent carboxylic acid may be added to the polyvalent carboxylic acid component. Examples of the other polyvalent carboxylic acid include (i) an unsaturated aliphatic having a branched chain. Divalent carboxylic acids, (ii) saturated aliphatic polyvalent carboxylic acids such as saturated aliphatic divalent carboxylic acids, saturated aliphatic trivalent carboxylic acids, (iii) aromatic divalent carboxylic acids, aromatic trivalent carboxylic acids, etc. Aromatic polyvalent carboxylic acid and the like.
There is no restriction | limiting in particular as content of these polyhydric carboxylic acid, Although it can select suitably according to the objective, 30 mol% or less is preferable with respect to all the carboxylic acids, and 10 mol% or less is more preferable. The obtained polyester resin is appropriately added within the range having crystallinity.

  Examples of the polyvalent carboxylic acid added as necessary include divalent carboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, citraconic acid, phthalic acid, isophthalic acid, and terephthalic acid. Acid; trimellitic anhydride, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2 , 5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, trivalent or higher polyvalent carboxylic acid such as 1,2,7,8-octanetetracarboxylic acid and the like.

If necessary, the polyhydric alcohol component may further contain a trivalent or higher polyhydric alcohol in addition to a small amount of an aliphatic branched dihydric alcohol or cyclic dihydric alcohol.
There is no restriction | limiting in particular as content of these polyhydric alcohol, Although it can select suitably according to the objective, 30 mol% or less is preferable with respect to all the alcohols, and 10 mol% or less is more preferable, and obtained. The polyester to be added is appropriately added within the range having crystallinity.

  Examples of the polyhydric alcohol added as necessary include 1,4-bis (hydroxymethyl) cyclohexane, polyethylene glycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, and glycerin.

Whether or not the polyester resin has crystallinity can be confirmed by whether or not there is a peak in the X-ray diffraction pattern by the powder X-ray diffractometer.
In the diffraction pattern, the crystalline polyester resin preferably has at least one diffraction peak at a position where 2θ is 19 ° to 25 °, and 2θ is (i) 19 ° to 20 °, (ii) 21 °. More preferably, diffraction peaks exist at positions of ˜22 °, (iii) 23 ° to 25 °, and (iv) 29 ° to 31 °.
The powder X-ray diffraction measurement is performed using, for example, a powder X-ray diffractometer RINT1100 (manufactured by Rigaku Electric Co., Ltd.) using a wide-angle goniometer under conditions of Cu as a tube and tube voltage-current as 50 kV-30 mA. Can do.

  There is no restriction | limiting in particular as content in the binder resin of the said crystalline polyester resin, Although it can select suitably according to the objective, 1 mass%-15 mass% are preferable, and 1 mass%-10 mass% are preferable. Is more preferable. When the content is within the preferable or more preferable range, the amount of the crystalline polyester resin present on the surface of the toner core particles becomes appropriate, and it is difficult to be affected by the low viscosity component, and the heat resistance performance is improved. However, it is advantageous in that the anti-adhesion performance due to stirring heat generation in the developing device and stress around the regulating blade is improved.

-Amorphous polyester resin-
The amorphous polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, those usually obtained by condensation polymerization of alcohol and carboxylic acid can be used.
There is no restriction | limiting in particular as said alcohol, According to the objective, it can select suitably, For example, glycols, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1, 4-bis (hydroxymethyl) cyclohexane, And ethylated bisphenols such as bisphenol A, other divalent alcohol monomers, and trivalent or higher polyhydric alcohol monomers.
The carboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include divalent organic compounds such as maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid. Acid monomer, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5 -Trivalent or higher polyvalent carboxylic acid monomers such as hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,2,7,8-octanetetracarboxylic acid and the like.

  It can be confirmed that the non-crystalline polyester resin does not have crystallinity because there is no peak in the X-ray diffraction pattern by the powder X-ray diffractometer described above.

-Isocyanate-modified polyester resin-
In addition, in order to obtain a toner in which the core particles and the resin fine particles are firmly attached, an isocyanate-modified polyester resin having an isocyanate group at the terminal of the polyester resin is used, and the isocyanate groups are reacted with each other in the toner production process. It is preferable that the toner is stretched to have an appropriate crosslinking structure in the toner. A modified polyester resin having at least one of a urethane group and a urea group is obtained by reacting the isocyanate group with at least one of amines and polyols.

  There is no restriction | limiting in particular as said isocyanate modified polyester resin, Although it can select suitably according to the objective, For example, the polyester which has a polycondensate of a polyol (1) and a polycarboxylic acid (2), and has an active hydrogen group Examples include those obtained by further reacting a resin with polyisocyanate (3). Examples of the active hydrogen group include hydroxyl groups such as alcoholic hydroxyl groups and phenolic hydroxyl groups, amino groups, carboxyl groups, mercapto groups, and the like. Among these, an alcoholic hydroxyl group is preferable.

--Polyol--
Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or a small amount of (1-2) ) Is preferred.
Examples of the diol (1-1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether Glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol) A, bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenols (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts.
Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable, and the combination of alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms is particularly preferable.

  Examples of the trihydric or higher polyol (1-2) include trihydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols ( Trisphenol PA, phenol novolac, cresol novolac, etc.); alkylene oxide adducts of the above trivalent phenols and the like.

--Polycarboxylic acid--
Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2), and (2-1) alone or a small amount with (2-1). The mixture of (2-2) is preferred.
Examples of the dicarboxylic acid (2-1) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid). , Terephthalic acid, naphthalenedicarboxylic acid, etc.). Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.
Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.).
In addition, as said polycarboxylic acid (2), you may make it react with a polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  There is no restriction | limiting in particular as a compounding ratio of the said polyol (1) and the said polycarboxylic acid (2), Although it can select suitably according to the objective, The equivalent ratio of hydroxyl group [OH] and carboxyl group [COOH] [OH] / [COOH] is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1, and more preferably 1.3 / 1 to 1.02 / 1.

--Polyisocyanate--
Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) ); Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; And those blocked with caprolactam. These may be used individually by 1 type and may use 2 or more types together.

  The blending ratio of the polyisocyanate (3) is not particularly limited and may be appropriately selected depending on the intended purpose. The equivalent ratio of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester resin having a hydroxyl group. [NCO] / [OH] is usually 1/1 to 5/1, preferably 1.2 / 1 to 4/1, and more preferably 1.5 / 1 to 2.5 / 1. If the [NCO] / [OH] exceeds 5/1, the remaining polyisocyanate compound may adversely affect the chargeability of the toner.

In order to extend the isocyanate-modified polyester resin, amines (B) may be used as an extender.
There is no restriction | limiting in particular as said amine (B), According to the objective, it can select suitably, For example, diamine (B1), trivalent or more polyamine (B2), amino alcohol (B3), amino mercaptan ( B4), amino acids (B5), and those in which the amino groups of B1 to B5 are blocked (B6).
Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, tetrafluoro-p-phenylenediamine, etc.), alicyclic Diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc.) and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecafluorohexylenediamine, tetracosafluorododeci Range amine etc.).
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). It is done.
Among these, B1 and a mixture of B1 and a small amount of B2 are preferable.

  There is no restriction | limiting in particular as a compounding ratio of the said amines (B), According to the objective, it can select suitably, For example, the isocyanate group [NCO] in isocyanate modification polyester, and the amino in amines (B) The equivalent ratio [NCO] / [NHx] of the group [NHx] is usually 1/2 to 2/1, preferably 1 / 1.5 to 1.5 / 1, and preferably 1/1/2 to 1.2. / 1 is more preferable. If the [NCO] / [NHx] is less than 1/2 or exceeds 2/1, the elongation reaction of the isocyanate-modified polyester does not proceed sufficiently and the characteristics of the toner of the present invention may not be obtained.

As the binder resin, other than the above resins, conventionally known materials can be appropriately used according to the purpose. For example, polystyrene, chloropolystyrene, poly α-methylstyrene, styrene-chlorostyrene copolymer, styrene- Propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (styrene-methyl acrylate copolymer) Copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylate copolymer (Styrene-methyl methacrylate copolymer, styrene-methacrylic acid ester Copolymer, styrene-butyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, etc.), styrene-alpha-methyl acrylate copolymer, styrene-acrylonitrile-acrylate copolymer, etc. Resin (homopolymer or copolymer containing styrene or styrene-substituted product), vinyl chloride resin, styrene-vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyethylene resin, polypropylene resin, ionomer Examples thereof include petroleum resins such as resins, polyurethane resins, silicone resins, ketone resins, ethylene-ethyl acrylate copolymers, xylene resins, and polyvinyl butyral resins, and hydrogenated petroleum resins. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as a manufacturing method of these resin, Any of block polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be utilized.

<< Releasing agent >>
The release agent is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, Fischer-Tropsch) Wax, sasol wax and the like); carbonyl group-containing wax and the like. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate. , 1,18-octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid trimethylate) Stearylamide, etc.); and dialkyl ketones (distearyl ketone, etc.), mono / diesters, and the like. Among these, polyolefin wax and long-chain hydrocarbon are preferable because of their low polarity and low melt viscosity, and they are easily compatible with the polyester resin as the binder resin, and are excellent in environmental resistance, fixing property and anti-sticking property. In this respect, ester wax is particularly preferable.

  There is no restriction | limiting in particular as content in the toner base particle of the said mold release agent, Although it can select suitably according to the objective, 6.0 mass%-8.0 mass% are preferable. When the content is less than 6.0% by mass, the fixability may be deteriorated. When the content exceeds 8.0% by mass, the toner may adhere to a regulating member such as a developing blade. On the other hand, when the content is 6.0% by mass or more, the fixing property can be improved, and when the content is 8.0% by mass or less, the toner can be well prevented from being fixed to the developing blade.

<< Colorant >>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select from a conventionally well-known coloring agent suitably.
There is no restriction | limiting in particular as content in the toner particle of the said coloring agent, Although it can select suitably according to the objective, 2 mass parts-15 mass parts are preferable with respect to 100 mass parts of said binder resins.

The colorant is preferably used in the form of a masterbatch dispersed in a resin from the viewpoint of dispersibility. As the resin for the masterbatch, conventionally known resins can be used, and the same resins as the binder resin and the resin fine particles may be used.
There is no restriction | limiting in particular as content of the said coloring agent in the said masterbatch, Although it can select suitably according to the objective, 20 mass%-50 mass% are preferable.
The addition amount of the master batch is not particularly limited and may be appropriately selected depending on the intended purpose. However, the amount of the colorant contained in the toner particles may be within the above range. preferable.

<Convex>
The convex portion is formed by adhering the resin fine particles to the surface of the core particle.
The shape of the convex part is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a spherical shape, an elliptical spherical shape and a polyhedron. From the viewpoint of shaving, a shape without corners is preferable.
A method for attaching the resin fine particles to the surface of the core particle will be described in a toner manufacturing method described later.

<< Resin fine particles >>
The resin fine particles are not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of environmental resistance (charging stability), vinyl resins are preferable. The vinyl resin can be obtained, for example, by polymerizing a monomer mixture containing an aromatic compound having a vinyl polymerizable functional group as a monomer.
In order to use the resin fine particles as particles that function by charging the resin fine particles in the electrostatic latent image developing toner of the present invention, the surface of the resin fine particles preferably has a structure that is easily charged. It is preferable to include an aromatic compound having a vinyl polymerizable functional group having an electron orbital such that an electron can exist stably such as an aromatic ring structure. There is no restriction | limiting in particular as content of the aromatic compound which has a vinyl polymerizable functional group in the said monomer mixture, Although it can select suitably according to the objective, 50 mass%-100 mass% are preferable, and 80 mass% -100 mass% is more preferable. If the content is less than 50% by mass, the resulting resin fine particles may have poor chargeability.

Examples of the polymerizable functional group in the aromatic compound having a vinyl polymerizable functional group include a vinyl group, an isopropenyl group, an allyl group, an acryloyl group, and a methacryloyl group.
Specific examples of the monomer include styrene, α-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, 4-methoxystyrene, 4-ethoxystyrene, 4-carboxystyrene, and metals thereof. Salts, 4-styrenesulfonic acid or metal salts thereof, 1-vinylnaphthalene, 2-vinylnaphthalene, allylbenzene, phenoxyalkylene glycol acrylate, phenoxyalkylene glycol methacrylate, phenoxy polyalkylene glycol acrylate, phenoxy polyalkylene glycol methacrylate, and the like. . Among these, styrene is preferable in terms of high chargeability. These may be used individually by 1 type and may use 2 or more types together.

A compound having a vinyl polymerizable functional group and an acid group may be used for the vinyl resin.
The compound having a vinyl polymerizable functional group and an acid group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a carboxyl group-containing vinyl monomer and a salt thereof ((meth) acrylic acid, ( Anhydride) maleic acid, monoalkyl maleate, fumaric acid, monoalkyl fumarate, crotonic acid, itaconic acid, itaconic acid monoalkyl, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl, cinnamic acid, etc.), sulfonic acid Examples thereof include group-containing vinyl monomers, vinyl sulfate monoesters and salts thereof, and phosphate group-containing vinyl monomers and salts thereof. Among these, (meth) acrylic acid, alkyl acrylate (anhydrous) maleic acid, monoalkyl maleate, fumaric acid and monoalkyl fumarate are preferred, and butyl acrylate is particularly preferred. These may be used individually by 1 type and may use 2 or more types together.

  When the aromatic compound (α) having a vinyl polymerizable functional group and the compound (β) having a vinyl polymerizable functional group and an acid group are used in combination, the mixing ratio (α / β) is not particularly limited. However, 75/25 to 85/15 is preferable.

The content of the resin fine particles in the toner base particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 4.0% by mass to 6.0% by mass, and is preferably 5.1% by mass. ~
5.9 mass% is more preferable. When the content is less than 4.0% by mass, the background stain may be deteriorated due to insufficient coating of the toner base particles. When the content is more than 6.0% by mass, the fixing property is deteriorated as the vinyl resin component is increased. There are things to do. On the other hand, when the content is within the more preferable range, it is advantageous in terms of preventing background stains and improving fixability.

There is no restriction | limiting in particular as a method of obtaining the said vinyl-type resin, Although it can select suitably according to the objective, For example, the following methods (a)-(f) etc. are mentioned.
(A) The monomer mixture is reacted by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method to produce a dispersion of vinyl resin fine particles.
(B) The monomer mixture is polymerized in advance, and the resulting resin is pulverized using a mechanical pulverizer or jet pulverizer and then classified to produce resin fine particles.
(C) Resin fine particles are produced by polymerizing the monomer mixture in advance and spraying the resulting resin solution in a solvent in the form of a mist.
(D) polymerizing the monomer mixture in advance and adding the solvent to the resin solution obtained by dissolving the obtained resin in a solvent, or cooling the resin solution previously dissolved in the solvent to precipitate resin fine particles; Resin fine particles are produced by removing the solvent.
(E) A monomer solution is polymerized in advance, and a resin solution obtained by dissolving the obtained resin in a solvent is dispersed in an aqueous medium in the presence of a suitable dispersant, and the solvent is removed by heating or decompression.
(F) A monomer mixture is polymerized in advance, an appropriate emulsifier is dissolved in a resin solution obtained by dissolving the obtained resin in a solvent, and water is added to perform phase inversion emulsification.
Among these, the method (a) is preferable in that the production is easy, the resin fine particles are obtained as a dispersion, and the application to the next step can be performed smoothly.

  In the method (a), when performing the polymerization reaction, a dispersion stabilizer can be added to the aqueous medium, or the dispersion stability of the resin fine particles obtained by polymerization can be imparted to the monomer that performs the polymerization reaction. It is preferable to add such a monomer (so-called reactive emulsifier), or to use these two means in combination to impart dispersion stability of the resulting vinyl resin fine particles. If a dispersion stabilizer or reactive emulsifier is not used, the dispersion state of the particles cannot be maintained, so the vinyl resin cannot be obtained as fine particles, or the dispersion stability of the obtained resin fine particles is low, so that the storage stability The resin particles are agglomerated during storage, or the dispersion stability of the particles in the resin fine particle adhesion step described later is reduced, so that the core particles are easily aggregated or united, and the resin fine particles finally obtained The uniformity of the particle size, shape, surface, and the like may deteriorate.

There is no restriction | limiting in particular as said dispersion stabilizer, According to the objective, it can select suitably, For example, surfactant, an inorganic dispersing agent, etc. are mentioned.
Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, and phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and amine salts such as imidazoline. Type cationic surfactant, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, quaternary ammonium salt type cationic surfactant such as benzethonium chloride , Nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives (for example, alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine) Amphoteric surfactants), and the like.
Examples of the inorganic dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.

<External additive>
In the electrostatic image developing toner of the present invention, the external additive is inorganic fine particles.
The inorganic fine particles are not particularly limited and may be appropriately selected depending on the intended purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide , Copper oxide, 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, calcium carbonate , Silicon carbide, silicon nitride and the like. Of these, silica and titanium oxide are particularly preferable. These may be used individually by 1 type and may use 2 or more types together.

  The amount of the external additive added is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1% by mass to 6% by mass, and preferably 0.3% by mass to the toner particles. 5 mass% is more preferable.

<< Inorganic fine particles containing silicone oil (external additive I) >>
The external additive preferably includes external additive I which is inorganic fine particles containing silicone oil.
The external additive I is obtained by surface-treating inorganic fine particles with silicone oil.
The silicone oil is not particularly limited and may be appropriately selected depending on the intended purpose. For example, dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine Modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, epoxy and polyether modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, acrylic, Examples include methacryl-modified silicone oil and α-methylstyrene-modified silicone oil. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said external additive I in a toner, Although it can select suitably according to the objective, 2.7 mass%-3.3 mass% are preferable. When the content is less than 2.7% by mass, the life of the photosensitive member may be inferior in terms of life and cleaning properties, and when it exceeds 3.3% by mass, background stains may occur.

<< Inorganic fine particles containing silicone oil and containing amino group-containing silane coupling agent (external additive II) >>
It is preferable that the external additive further includes an external additive II that includes silicone oil and is inorganic fine particles including an amino group-containing silane coupling agent.
The external additive II is obtained by surface-treating the external additive I with an amino group-containing silane coupling agent.
The amino group-containing silane coupling agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylamino Propyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, monobutylaminopropyltrimethoxysilane, dioctylaminopropyltrimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylamino Phenyltriethoxysilane, trimethoxysilyl-γ-propylphenylamine, trimethoxysilyl-γ-propylbenzidineamine, trimethoxy Examples include silyl-γ-propylpiperidine, trimethoxysilyl-γ-propylmorpholine, and trimethoxysilyl-γ-propylimidazole. These may be used individually by 1 type and may use 2 or more types together.

  When the external additive II is used as an external additive, the content of the external additive II in the external additive is not particularly limited and may be appropriately selected depending on the intended purpose. Is preferably less than 10% by mass and less than 30% by mass. If the content is less than 5% by mass, the effect may not be exhibited. Further, when the content is 50% by mass or more, the positive chargeability of the external additive becomes strong, so that it may not function normally as the required toner. Further, since the external additive II contains an amino group, it is relatively susceptible to environmental resistance due to humidity and the like, and from the viewpoint of toner charge control, the content is preferably kept to the minimum necessary. As content of the said external additive II in 0.7 mass%-1.3 mass% are preferable.

  The particle size of the external additive can be measured by a particle size distribution measuring device using dynamic light scattering, for example, DLS-700 manufactured by Otsuka Electronics Co., Ltd., Coulter N4 manufactured by Coulter Electronics. However, since it is difficult to dissociate the secondary aggregation of the particles after the silicone oil treatment with these apparatuses, the primary particle diameter of the external additive is directly obtained from a photograph obtained by a scanning electron microscope or a transmission electron microscope. It is preferable. In this case, at least 100 particles of the external additive are observed, and the average value of the major axis is obtained. Similarly, for the particle diameter of the external additive on the toner surface, at least 100 external additives are observed, and the average value of the long diameters is obtained.

<Evaluation of adhesion strength of resin fine particles to core particles using ultrasonic irradiation>
The electrostatic charge image developing toner of the present invention is a particle measured by a flow type particle image analyzer in the case where a 1 mg / mL dispersion of the electrostatic charge image developing toner is irradiated with ultrasonic waves of 20 kHz and 80 W / 10 cm ^2. In the abundance ratio (number%) of particles having a diameter of 0.6 μm to 2.0 μm, the abundance ratio before irradiation with the ultrasonic wave is Z, and the abundance ratio when irradiated for 1 minute is A. When the abundance ratio when irradiated for 5 minutes is B and the abundance ratio when irradiated for 10 minutes is C, it is essential to satisfy all of the following relational expressions (1) to (3).
0 ≦ A−Z ≦ 3.0 Formula (1)
0.5 ≦ B−Z ≦ 4.0 Formula (2)
4.0 ≦ C−Z ≦ 8.0 Formula (3)
When the (A-Z), the (B-Z), and the (C-Z) are less than the lower limit values of the formulas (1) to (3), the core particles and the resin fine particles are strong. If the toner adheres too much, the fluidity of the toner decreases, and a conveyance failure occurs. Further, when the upper limit value of the formulas (1) to (3) is exceeded, the amount of free components increases, and sticking to a regulating blade or the like that is a regulating member occurs.

The Z and A preferably satisfy the following relational expression (4), and the B and C preferably satisfy the following relational expression (5).
1 ≦ Z ≦ A ≦ 5 Formula (4)
2 ≦ B ≦ 7 ≦ C ≦ 12 Formula (5)
When Z or A exceeds 5, the free component increases, and sticking to a regulating blade or the like as a regulating member may occur. Defects may occur.
Further, when B exceeds 7 or C exceeds 12, free components increase, and sticking to a regulating blade or the like that is a regulating member may occur. On the other hand, if the B is less than 2 or the C is less than 7, the fluidity of the toner may be deteriorated and a conveyance failure may occur.

Here, the A, B, C, D, and Z parameters are indices indicating the difficulty of peeling of the resin fine particles from the core particles, that is, the adhesion strength between the core particles and the resin fine particles. The ultrasonic irradiation treatment simulates the stress on the toner due to the friction between the toners actually performed in the developing device and the friction between the toner and the developing member. There is a high correlation with the durability of
Specifically, the ultrasonic wave is irradiated under the above-mentioned conditions for 1 minute, when it is irradiated for 5 minutes, and when it is irradiated for 10 minutes, the durable life of the developing device is taken into consideration, respectively. It can be considered that the toner surface state is at the stage (level equivalent to 1,000 durable prints), when the durability is stable (level equivalent to 5,000 durable prints), and at the end of durability (level equivalent to 10,000 or more durable prints).

Differences (A−Z), (B−Z), and (C−Z) indicate an increase amount of toner detachment particles generated when the toner is destroyed by the ultrasonic stress. Among the particles, particles having a size of 0.6 μm to 2.0 μm can be evaluated to be derived from the resin fine particles.
As the actual number of printed sheets increases, the resin surface is affected by various stresses such as the agitation stress associated with the supply and the stress associated with the pressure at the regulating section in the developing unit, and the resin fine particles are dispersed on the toner surface. As the number of printed sheets increases, the toner may be separated from the toner and adhere to the regulating blade of the developing unit, the developing roller, and the photosensitive member, leading to an image defect.

The toner of the present invention that satisfies the above parameters is in a state where the resin fine particles are more firmly adhered to the surface of the core particles than the conventional toner, and the toner has high chargeability and durability due to less separation of the resin fine particles. can do.
The separation of the resin fine particles from the toner occurs when the thickness of the toner layer is regulated by the blade in the developing device. The above-mentioned ultrasonic irradiation conditions correspond to the conditions for regulating the thickness of the toner layer. To do.

The details of the procedure for measuring the abundance ratio of the particles having a size of 0.6 μm to 2.0 μm are as follows.
First, about 990 g of ion-exchanged water from which impure solids and the like have been removed in advance is put in a 1 L polypropylene container, and 10 g of sodium dodecyl sulfate (manufactured by Kanto Chemical Co., Inc.) is added as a dispersing agent to 1.0 mass%. A dispersion is prepared.
60 mL of this dispersion is weighed, 60 mg of toner as a measurement sample is added, and the mixture is stirred for 90 minutes with a stirrer. After confirming that the toner is sufficiently dispersed in the dispersion and that the toner does not float on the surface of the dispersion, the toner is transferred to a 100 mL capacity stainless steel cup (manufactured by TOP). %).
After measuring the reference Z, 60 mL of the dispersion is weighed again in another container, 60 mg of the measurement sample is added, and the mixture is stirred for 90 minutes with a stirrer. After confirming that the toner is sufficiently dispersed in the dispersion liquid and that the toner does not float on the liquid surface of the dispersion liquid, the toner is transferred to a 100 mL capacity stainless cup (manufactured by TOP), and then the output is 80 W / 10 cm ² . Ultrasonic waves are applied with the adjusted ultrasonic irradiation device for 1 minute (in the case of A), 5 minutes (in the case of B), and 10 minutes (in the case of C). Dispersions for measuring B and C were used.
As the ultrasonic irradiation device, for example, “VCX-750” (manufactured by Sonics & Materials) can be used.
The measurement of A, B, C, and Z can be performed by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation).

As a specific measurement method, the prepared dispersion is introduced into the flow particle image analyzer, and 3,000 toner particles are measured in the HPF measurement mode and in the total count mode. The binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the equivalent circle diameter of 0.60 μm or more and less than 39.69 μm, and the arithmetic mean value of the equivalent circle diameter of the toner (number average particle diameter D1) The mode diameter Dm and the average circularity are obtained.
The abundance ratio of particles having a particle size of 0.6 μm or more and 2.0 μm or less is calculated from the obtained Dm, and is set as Z, A, B, and C, respectively. Further, when obtaining the values of Z, A, B, and C, the same sample is measured five times and the average value is adopted in order to suppress the in-sample error as much as possible.

<Toner aggregation degree>
The toner for developing an electrostatic charge image of the present invention preferably has a degree of toner aggregation measured by the following method of 60% to 90%. When the aggregation degree is less than 60%, the sticking resistance may be deteriorated, and when it exceeds 90%, the heat resistant storage stability may be deteriorated.
The toner aggregation degree can be measured as follows.
As a measuring device, a powder tester manufactured by Hosokawa Micron Corporation is used, and attached parts are set on a vibration table in the following procedure.
(B) Vibro chute, (b) Packing, (c) Space ring, (d) Fluey (3 types, arranged in order from the largest opening to the top, middle and bottom), (e) Osaba Next, the knob nut is fixed, and the shaking table is operated.
The measurement conditions are as follows.
Sieve opening: (upper) 75 μm, (middle) 45 μm, (lower) 20 μm
Swing scale: 1mm
Sampling amount: 2g
Vibration time: 10 seconds After the measurement based on the above procedure, the following formula using the following calculated values (x), (y) and (z) is defined as the degree of aggregation [%].
Aggregation degree [%] = 100 × {(x) × 1 + (y) × 0.6 + (z) × 0.2} / 2
(X): Remaining amount of powder (mass%) remaining on the upper sieve
(Y): Remaining amount of powder (mass%) remaining on the middle sieve
(Z): Remaining amount of powder (mass%) remaining on the lower sieve

<Deformation start point TgA>
The electrostatic charge image developing toner of the present invention preferably has a deformation start point TgA measured by a flow tester of 57.0 ° C. to 61.0 ° C. When the TgA is less than 57.0 ° C., the heat resistant storage stability may be deteriorated, and when it exceeds 61.0 ° C., the fixability may be deteriorated.
Here, as shown in FIG. 1, the TgA is a profile in a temperature test method of a flow tester, and is a softening temperature Ts when moving from a fixed region to a shift region and an outflow start temperature Tfb from which a sample flows out. In contrast, a first profile having a minute profile that occurs at a temperature near the glass transition temperature Tg of a DSC (differential scanning calorimeter) (a difference ΔT from the Tg is in the range of about 1 ° C. to 2 ° C. before the Ts). It is the displacement point (in the region where it starts to rise, the contact point between the baseline and the tangent of the rising curve).

As a specific method for measuring TgA, a flow tester (CFT-500, manufactured by Shimadzu Corporation) was used, and 1.5 g of a measurement sample was weighed, and a die having a height of 1.0 mm and a diameter of 1.0 mm was used. Measurement is performed under the conditions of a heating rate of 3.0 ° C./min, a preheating time of 180 seconds, a load of 30 kg, a measurement temperature range of 20 ° C. to 140 ° C., and the point at which the above sample starts to deform under a compressive load. TgA.
As a more detailed method of obtaining TgA, the extension line of the BC line, which is the internal void reduction stage in the sample from the softening temperature Ts point C, and the sample AB is still in an undeformed state while receiving a compressive load. The point of intersection with the line is TgA.

<Method for producing toner>
The method for producing the toner for developing an electrostatic charge image of the present invention is not particularly limited as long as it has a structure comprising the core particles and convex portions formed by adhering resin fine particles to the surfaces of the core particles. The toner can be selected from known toner production methods, but can be suitably produced by an emulsion aggregation method, a dissolution suspension method, an ester elongation method, or the like. In these methods, the binder resin that can be dissolved in a solvent among the binder resins can be used in production.

  The method for producing the electrostatic image developing toner of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. The oil phase preparation step, core particle preparation step, and resin fine particle adhesion step described below A production method including a demelting step is preferable.

<< Oil phase preparation process >>
The oil phase preparation step is a step of obtaining a solution or dispersion in which at least a binder resin, a release agent and a colorant are dissolved or dispersed in an organic solvent. As a method for preparing an oil phase in which a binder resin, a release agent and a colorant are dissolved or dispersed in an organic solvent, the binder resin, the release agent and the colorant are gradually added while stirring in the organic solvent. It may be added to and dissolved or dispersed. However, when pigments are used as colorants, or when wax or charge control agents that are difficult to dissolve in organic solvents (dispersoids) are added, the particles are added prior to addition to the organic solvent. You may keep it small.
As another means, if a material that melts below the boiling point of the organic solvent is dispersed, a dispersion aid is added in the organic solvent as necessary, and the mixture is heated while stirring with the dispersoid. It is possible to carry out a method in which, after being dissolved and once dissolved, crystallization is performed by cooling with stirring or shearing to produce dispersoid microcrystals.
The colorant, wax, and charge control agent dispersed as described above may be further dispersed after being dissolved or dispersed together with the binder resin in an organic solvent. For dispersion, a known disperser such as a bead mill or a disk mill can be used.

  There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, In order to make it possible to remove easily at a subsequent desolubilization process, the thing whose boiling point is less than 100 degreeC is used. It is preferable. Examples of such organic solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Examples include ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as said dispersion | distribution adjuvant, According to the objective, it can select suitably, For example, an inorganic dispersing agent etc. are mentioned.
Examples of the inorganic dispersant include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, and barium sulfate. Bentonite, alumina, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite, and the like can be used.

<< Core particle production process >>
The core particle preparation step is a step of suspending the dissolved product or the dispersion in an aqueous medium having an inorganic base to generate a core particle dispersion. There is no particular limitation on the method for preparing the dispersion liquid in which the oil phase obtained in the above-described step is dispersed in an aqueous medium having an inorganic base, and the core particles composed of the oil phase are dispersed, and is appropriately selected depending on the purpose. For example, known equipment such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable in that the particle diameter of the core particles (dispersion) dispersed in the dispersion liquid is 2 μm to 20 μm.
When the high-speed shearing type disperser is used, the rotation speed is not particularly limited and can be appropriately selected according to the purpose, but is usually 1,000 rpm to 30,000 rpm, and 5,000 rpm to 20,000 rpm is preferred. There is no restriction | limiting in particular as dispersion time, According to the objective, it can select suitably, However, In the case of a batch system, it is 0.1 minute-5 minutes normally. If the dispersion time exceeds 5 minutes, particles having an undesirably small diameter may remain, or the dispersion may be overdispersed, resulting in an unstable system and generation of aggregates and coarse particles. There is no restriction | limiting in particular as temperature at the time of dispersion | distribution, Although it can select suitably according to the objective, Usually, it is 0 to 40 degreeC, and 10 to 30 degreeC is preferable. When the temperature exceeds 40 ° C., molecular motion becomes active, so that the dispersion stability is lowered, and aggregates and coarse particles may be easily generated. On the other hand, when the temperature is less than 0 ° C., the viscosity of the dispersion increases, and the shear energy required for dispersion increases, so the production efficiency may decrease.

  There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, Although water may be independent, the solvent miscible with water can also be used together. Examples of the water-miscible solvent include alcohols such as methanol, isopropanol and ethylene glycol, cellosolves such as dimethylformamide, tetrahydrofuran and methyl cellosolv, and lower ketones such as acetone and methyl ethyl ketone. The amount of the aqueous medium used relative to 100 parts by mass of the toner material is usually 50 parts by mass to 2,000 parts by mass, and preferably 100 parts by mass to 1,000 parts by mass. If the amount used is less than 50 parts by mass, the dispersion state of the toner material may be deteriorated, and if it exceeds 2,000 parts by mass, it is not economical.

The inorganic base is not particularly limited and may be appropriately selected depending on the intended purpose. However, the dispersion state can be stabilized, toner base particles having a stable particle size distribution can be obtained, and adhesion of resin fine particles to the core particles Sodium hydroxide is preferable in terms of good properties.
The inorganic base may not be dropped into the aqueous phase but may be dropped during the oil phase, which is the previous step.

  There is no restriction | limiting in particular as content in the aqueous medium of the said inorganic base, Although it can select suitably according to the objective, 1 mass%-10 mass% are preferable, and 2 mass%-8 mass% are more. Preferably, 3% by mass to 7% by mass is more preferable. When the content exceeds 10% by mass, the oil droplets may become too small, or the dispersion stability may be lowered and the oil droplets may be coarsened. Moreover, when the content is less than 1% by mass, the oil droplets may not be stably dispersed and the oil droplets may become coarse.

<< Resin fine particle adhesion process >>
The resin fine particle adhesion step is a step of adding a resin fine particle dispersion to the core particle dispersion to form a convex portion made of resin fine particles on the surface of the core particle. The core particle dispersion obtained in the core particle preparation step can stably keep the core particle droplets while stirring, and in this state, the resin fine particle dispersion is charged. Can be deposited on the core particles.
The charging speed of the resin fine particle dispersion is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably more than 15 g / min and not more than 30 g / min, more preferably from 18 g / min to 25 g / min. 20 g / min is particularly preferred.
When the charging speed is less than 15 g / min, the resin fine particles may not be sufficiently adhered to the core particles, and the effects of the present invention may not be exhibited. If the charging speed exceeds 30 g / min, the dispersion system may change rapidly, causing agglomerated particles and uneven adhesion of resin fine particles.

  The resin fine particle dispersion may be diluted or concentrated to adjust the concentration as appropriate before being added to the core particle dispersion. The concentration of the resin fine particle dispersion is preferably 5% by mass to 30% by mass, and more preferably 8% by mass to 20% by mass. When the concentration is less than 5%, the change in the concentration of the organic solvent accompanying the introduction of the dispersion is large, and the adhesion of the resin fine particles may be insufficient. If the concentration exceeds 30% by mass, the resin fine particles are likely to be unevenly distributed in the core particle dispersion, and as a result, the resin fine particles may not adhere uniformly.

  The resin fine particle dispersion may be a mixture of a low molecular weight resin fine particle dispersion and a high molecular weight resin fine particle dispersion mixed before addition, or the low molecular weight resin fine particle dispersion. The dispersion of the high molecular weight resin fine particles may be added 5 to 60 minutes after the addition. As a reason that pre-mixing may be performed before the addition, low-molecular resin fine particles having high compatibility with the core particles first form a shell layer on the surface of the core particles containing the solvent. This is because after the low molecular weight resin fine particles form the shell layer, the high molecular weight resin fine particles form the shell layer on the surface of the core particle.

  The resin fine particles adhere to the core particles with sufficient strength by the above-described method because the core particles can freely deform when the resin fine particles adhere to the droplets of the core particles. This is presumably because the contact surface can be sufficiently formed and the resin fine particles are swollen or dissolved by the organic solvent, and the vinyl resin fine particles and the resin in the core particles are likely to adhere to each other. Therefore, in this state, the organic solvent needs to be sufficiently present in the system. Specifically, the content of the organic solvent in the state of the core particle dispersion is 50% by mass with respect to the solid content (binder resin, release agent, colorant, and charge control agent as required). -150 mass% is preferable, and 70 mass%-125 mass% is more preferable. When the content exceeds 150% by mass, resin fine particles obtained in a single production process may be reduced and production efficiency may be lowered, and dispersion stability may be lowered and stable production may be difficult.

  The temperature at which the resin fine particles are adhered to the core particles is preferably 10 ° C to 60 ° C, more preferably 20 ° C to 45 ° C. When the temperature exceeds 60 ° C., the energy required for production increases and the production environmental load increases. In addition, low acid value vinyl resin fine particles may be present on the surface of the droplets, resulting in poor dispersion. It may become stable and coarse particles may be generated. When the temperature is less than 10 ° C., the viscosity of the dispersion increases, and adhesion of resin fine particles may be insufficient.

As a method for adhering the resin fine particles to the core particles, there is a method in which the core particles and the resin fine particles are mixed and stirred and mechanically adhered or coated.
The mixing and stirring can be performed, for example, by stirring the core particles and the resin fine particles in a stirring container using a motor equipped with stirring blades. In order to improve the adhesion strength of the resin fine particles to the core particles, the rotation speed of the stirring blade (motor), the ratio of the diameter (a) of the stirring vessel to the blade diameter (b, maximum diameter) of the stirring blade (b / A) is an important factor.

  As said rotation speed, 250 rpm-600 rpm are preferable, 300 rpm-500 rpm are more preferable, 350 rpm-450 rpm are still more preferable. If the rotational speed is less than 250 rpm, the shearing force by stirring may not be sufficient, and adhesion of resin fine particles to the core particles may not be sufficient. On the other hand, when the rotational speed exceeds 600 rpm, the shearing force due to stirring is too strong, and the adhesion state of the resin fine particles to the core particles becomes uneven, and the effects of the present invention may not be exhibited.

The ratio (b / a) between the diameter (a) of the stirring vessel and the blade diameter (b) of the stirring blade is preferably 0.9 or more and less than 1.0.
When the ratio (b / a) is less than 0.9, the shearing force by stirring is not sufficient, and the resin fine particles may not be sufficiently adhered to the core particles. On the other hand, when the ratio (b / a) exceeds 1, the stirring blades and the stirring container come into contact with each other, turbulent flow is generated in the dispersion, and the adhesion state of the resin fine particles to the core particles becomes uneven. It may not be effective.
In addition, said (a) and (b) represent the diameter of a cylindrical stirring container and the maximum diameter of a stirring blade, respectively, as FIG. 2 shows.

  In order to firmly attach the resin fine particles to the core particles, it is considered that an important factor is how uniform the stirring state of the droplets in the aqueous phase when the resin fine particles are dropped. That is, it is considered that the stirring state of the droplets is not uniform but becomes a turbulent flow, so that the uniform and strong adhesion of the resin fine particles is greatly inhibited. As factors for controlling these, the rotational speed of the stirring blade and the ratio (b / a) between the diameter (a) of the stirring vessel and the blade diameter (b, maximum diameter) of the stirring blade are important. In addition to the shape, number, angle, position, and size of the stirring blade, and the shape and volume of the stirring vessel, the composition of the resin fine particles, the amount of the resin fine particles, the dilution ratio with water, etc. are appropriately optimized. It is also related.

<< Demelting process >>
The desolvation step is a step of removing the organic solvent. The method for removing the organic solvent from the toner base particles obtained in the resin fine particle adhesion step is not particularly limited and may be appropriately selected from known methods according to the purpose. For example, the entire system is stirred. While gradually elevating the temperature, completely evaporating and removing the organic solvent in the droplets, and stirring the resulting dispersion of toner base particles into a dry atmosphere to completely remove the organic solvent in the droplets Examples thereof include a method of removing, a method of reducing the pressure while stirring the colored resin dispersion, and evaporating and removing the organic solvent. Of the above methods, the latter two methods can be used in combination with the first method.
The drying atmosphere in which the dispersion of the toner base particles is sprayed is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a gas heated with air, nitrogen, carbon dioxide gas, combustion gas, and the like. It is done. The temperature of these gases is preferably higher than the boiling point of the highest boiling solvent used.
For example, a spray dryer, a belt dryer, a rotary kiln or the like can be used for spraying the dispersion of the toner base particles.

<< Aging process >>
In the case where a modified resin having an isocyanate group at the terminal is added as the binder resin, an aging step may be performed in order to advance the elongation or crosslinking reaction of the isocyanate group.
The aging time is not particularly limited and may be appropriately selected depending on the intended purpose, but is usually 10 minutes to 40 hours, and preferably 2 hours to 24 hours.
There is no restriction | limiting in particular as reaction temperature of the said aging, Although it can select suitably according to the objective, Usually, it is 0 to 65 degreeC, and 35 to 50 degreeC is preferable.

<< Cleaning process >>
Since the dispersion of the toner base particles obtained in the above-mentioned process contains secondary materials such as a surfactant and other dispersants in addition to the toner base particles, only the toner base particles are taken out from the dispersion. Therefore, it is preferable to include a cleaning process for performing cleaning.
The cleaning method for the toner base particles is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a centrifugal separation method, a vacuum filtration method, and a filter press method. In any of the above methods, a cake body of toner base particles can be obtained. However, if the cake body cannot be sufficiently washed by a single operation, the obtained cake body is again dispersed in an aqueous solvent to form a slurry, and any of the above methods The step of taking out the resin fine particles may be repeated. Further, when washing is performed by a vacuum filtration method or a filter press method, a method may be used in which an aqueous medium is passed through the cake body to wash away the auxiliary material that is held by the toner base particles.
There is no restriction | limiting in particular as an aqueous solvent used for the said washing | cleaning, According to the objective, it can select suitably, For example, the mixed solvent etc. which mixed alcohol, such as water and methanol, ethanol, etc. are mentioned. Among these, water is preferable from the viewpoint of environmental load due to cost and wastewater treatment.
As one of means for adjusting the adhesion strength between the core particles and the resin fine particles, there is a method of previously removing resin fine particles that are easily detached in a cleaning process. For example, in the above-described cleaning step, by applying ultrasonic waves to the slurry of resin fine particles, the resin fine particles that are easily detached can be taken and removed during cleaning.

<< Drying process >>
Since the toner base particles cleaned in the cleaning step include a large amount of an aqueous medium, it is preferable to obtain only the toner base particles by drying and removing the aqueous medium. The drying method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a spray dryer, a vacuum freeze dryer, a vacuum dryer, a stationary shelf dryer, a mobile shelf dryer, a flow Examples thereof include a method using a dryer such as a tank dryer, a rotary dryer, and a stirring dryer.
The drying is preferably performed until the water content in the toner base particles finally becomes less than 1% by mass.

<< Crushing process >>
If the toner base particles are softly agglomerated and inconvenience occurs during use, they are crushed using a device such as a jet mill, a Henschel mixer, a super mixer, a coffee mill, an auster blender, or a food processor, and then soft agglomerated. You may loosen.
As one means for increasing the adhesion strength between the core particles and the resin fine particles, there is a method in which a higher mechanical stress is applied in the crushing step to firmly fix the resin fine particles to the core particles. For example, the adhesion strength can be adjusted by controlling the peripheral speed of the mixer, the angle of the deflector, the charged amount of resin fine particles, the temperature during crushing, and the like.

In addition, the following method is mentioned as another method of adjusting the adhesion strength of the said core particle and resin fine particle.
As a means for removing the weakly adhesive shell from the toner surface in advance and firmly bonding the shell onto the core surface to the blade, a core-shell type toner is mixed using a known mixer and resin fine particles (shell) on the toner surface. And a method of improving the adhesion strength between the shell and the core by heating to near the Tg of the toner at the time of toner preparation (solvent removal). In addition, as a method for removing in advance a shell having low adhesion strength to the core, ultrasonic cleaning of toner can be raised. Through these processes, a toner in a state where a certain amount of shell is peeled off can be produced.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes a latent image carrier, a charging unit, an exposure unit, a developing unit, a transfer unit, and a fixing unit. Further, other units selected as necessary, for example, a cleaning unit. , Static elimination means, recycling means, control means, and the like.
The image forming method of the present invention includes a charging step, an exposure step, a development step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a cleaning step, a charge removal step, and a recycling step. And a control process.

FIG. 3 shows an example of an image forming apparatus in which the toner for developing an electrostatic latent image of the present invention is used. In this image forming apparatus, a latent image carrier 1 that is rotationally driven in a clockwise direction is housed in a main body housing (not shown), and charging means 2 and exposure are provided around the latent image carrier 1. Means 3, a developing device 4 having the toner T for developing an electrostatic charge image of the present invention, a cleaning unit 5, an intermediate transfer member 6, a support roller 7, a transfer roller 8, a charge eliminating unit (not shown), and the like.
This image forming apparatus includes a paper feed cassette (not shown) that stores a plurality of recording papers P as an example of a recording medium. One recording paper P in the paper feeding cassette is fed by a paper feeding roller (not shown). After the timing is adjusted by a pair of registration rollers (not shown), the sheet is sent between a transfer roller 8 serving as a transfer unit and the intermediate transfer member 6.

  In this image forming apparatus, the latent image carrier 1 is rotated in the clockwise direction, and the latent image carrier 1 is uniformly charged by the charging unit 2, and then irradiated with a laser modulated by image data by the exposure unit 3. Then, an electrostatic latent image is formed on the latent image carrier 1, and toner is attached to the latent image carrier 1 on which the electrostatic latent image is formed by the developing device 4 and developed. Next, a transfer bias is applied from the latent image carrier 1 on which the toner image is formed by the developing device 4 to the intermediate transfer member 6 to transfer the toner image onto the intermediate transfer member 6, and the intermediate transfer member 6 and the transfer roller are further transferred. The toner image is transferred to the recording paper P by conveying the recording paper P between the recording paper P and the recording paper P. Further, the recording paper P on which the toner image is transferred is conveyed to a fixing unit (not shown).

The fixing unit includes a fixing roller heated to a predetermined fixing temperature by a built-in heater and a pressure roller pressed against the fixing roller with a predetermined pressure, and heats and pressurizes the recording paper conveyed from the transfer roller 8. The toner image on the recording paper is fixed on the recording paper and then discharged onto a paper discharge tray (not shown).
On the other hand, the image forming apparatus further rotates the latent image carrier 1 having the toner image transferred onto the recording paper by the transfer roller 8, and scrapes and removes toner remaining on the surface of the latent image carrier 1 by the cleaning unit 5. After that, the charge is removed by a charge removal device (not shown). The image forming apparatus uniformly charges the latent image carrier 1 neutralized by the static eliminator with the charging unit 2, and then performs the next image formation in the same manner as described above.

Hereinafter, each step of the image forming method and each unit of the image forming apparatus in which the toner for developing an electrostatic charge image of the present invention is used will be described in detail.
The material, shape, structure, size and the like of the latent image carrier 1 are not particularly limited, and can be appropriately selected from known ones. Preferred examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon and organic photoreceptors are preferable from the viewpoint of long life.

The charging step is a step of uniformly charging the surface of the latent image carrier that carries the latent image. For example, the charging step is performed by applying a voltage to the surface of the latent image carrier 1 using the charging unit 2. it can.
The charging means 2 is not particularly limited and can be appropriately selected depending on the purpose. For example, the charging means 2 includes a conductive or semiconductive roller, a brush, a film, a rubber blade, and the like, which is known per se. Non-contact chargers using corona discharge such as chargers, corotrons, scorotrons and the like can be mentioned.
The shape of the charging means 2 may be in the form of a magnetic brush, a fur brush or the like in addition to the roller, and can be selected according to the specifications and form of the electrophotographic apparatus. In the case of using a magnetic brush, the magnetic brush is composed of, for example, various ferrite particles such as Zn-Cu ferrite as a charging member, and a non-magnetic conductive sleeve for supporting the same, and a magnet roll included therein. . In addition, when using a brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound around a metal or other conductive core. It is configured by pasting.
The charging unit 2 is not limited to the contact type charger as described above. However, since an image forming apparatus in which ozone generated from the charger is reduced is obtained, a contact type charger is used. preferable.

  The exposure step is a step of writing an electrostatic latent image by exposing the surface of the charged latent image carrier, for example, by exposing the surface of the photosensitive member imagewise using the exposure means 3. Can do. The exposure unit 3 is not particularly limited as long as the surface of the latent image carrier 1 charged by the charging unit 2 can be exposed like an image to be formed, and can be appropriately selected according to the purpose. Examples thereof include various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.

The developing step is a step of developing the electrostatic latent image formed on the surface of the latent image carrier using a toner to form a visible image, and using the toner of the present invention, the electrostatic latent image For example, by the developing device 4. The developing device 4 is not particularly limited as long as it can be developed using, for example, the toner of the present invention, and can be appropriately selected from known ones. Preferable examples include those having at least a developing unit that can apply toner to a latent image in a contact or non-contact manner.
The developing device 4 carries toner on its peripheral surface, rotates in contact with the latent image carrier 1, and supplies toner to the electrostatic latent image formed on the latent image carrier 1 for development. An embodiment having a roller 40 and a thin layer forming member 41 that contacts the peripheral surface of the developing roller 40 and thins the toner on the developing roller 40 is preferable.

  As the developing roller 40, either a metal roller or an elastic roller is preferably used. There is no restriction | limiting in particular as a metal roller, Although it can select suitably according to the objective, For example, an aluminum roller etc. are mentioned. By performing a blasting process on the metal roller, the developing roller 40 having an arbitrary surface friction coefficient can be produced relatively easily. Specifically, by treating the aluminum roller with glass bead blasting, the roller surface can be roughened, and an appropriate toner adhesion amount can be obtained on the developing roller.

As the elastic roller, a roller coated with an elastic rubber layer is used, and a surface coat layer made of a material that is easily charged to a polarity opposite to that of the toner is provided on the surface. The elastic rubber layer is set to a hardness of 60 degrees or less according to JIS-A in order to prevent toner deterioration due to pressure concentration at the contact portion with the thin layer forming member 41. The surface roughness (Ra) is set to 0.3 μm to 2.0 μm, and a necessary amount of toner is held on the surface. Further, since the developing roller 40 is applied with a developing bias for forming an electric field with the latent image carrier 1, the elastic rubber layer is set to a resistance value of 10 ³ Ω to ^{10 10} Ω. . The developing roller 40 rotates in the clockwise direction, and conveys the toner held on the surface to a position facing the thin layer forming member 41 and the latent image carrier 1.

  The thin layer forming member 41 is provided at a position lower than the contact position between the supply roller 42 and the developing roller 40. The thin layer forming member 41 is made of a metal leaf spring material such as stainless steel (SUS) or phosphor bronze, and the free end is brought into contact with the surface of the developing roller 40 with a pressing force of 10 N / m to 40 N / m. Then, the toner that has passed under the pressure is thinned and a charge is applied by triboelectric charging. Further, a regulation bias having a value offset in the same direction as the toner charging polarity with respect to the developing bias is applied to the thin layer forming member 41 in order to assist frictional charging.

There is no restriction | limiting in particular as a rubber elastic body which comprises the surface of the developing roller 40, Although it can select suitably according to the objective, For example, a styrene-butadiene-type copolymer rubber, an acrylonitrile-butadiene-type copolymer rubber Acrylic rubber, epichlorohydrin rubber, urethane rubber, silicone rubber, or a blend of two or more thereof. Among these, a blend rubber of epichlorohydrin rubber and acrylonitrile-butadiene copolymer rubber is particularly preferable.
The developing roller 40 is manufactured, for example, by covering the outer periphery of the conductive shaft with a rubber elastic body. The conductive shaft is made of a metal such as stainless steel (SUS), for example.

The transfer step is a step of transferring the visible image on the surface of the latent image carrier to a transfer target, and can be performed by, for example, a transfer roller as transfer means. The transfer roller has primary transfer means for transferring the toner image onto the intermediate transfer body 6 to form a transfer image, and secondary transfer means (transfer roller 8) for transferring the transfer image onto the recording paper P. Embodiments are preferred. At this time, two or more colors, preferably full color toners are used as the toner, and a primary transfer means for transferring the toner image onto the intermediate transfer body 6 to form a composite transfer image, and the composite transfer image on the recording paper P An embodiment having a secondary transfer means for transferring on is further preferred.
The intermediate transfer member 6 is not particularly limited, and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (primary transfer means, secondary transfer means) preferably has at least a transfer unit that peels and charges the toner image formed on the latent image carrier 1 to the recording paper P side. There may be one transfer means, or two or more transfer means. Examples of the transfer means include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording paper P is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. A PET base for OHP can also be used.

The fixing step is a step of fixing the transferred image transferred onto the transfer target. For example, the fixing step can be performed on the toner image transferred to the recording paper P using a fixing unit. It may be performed each time the toner image is transferred to the recording paper P, or may be performed simultaneously at the same time in a state where the toner images of the respective colors are laminated.
The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose, but a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. In addition, as for the heating temperature by a heating-pressing means, 80 to 200 degreeC is preferable.

The fixing unit may be a soft roller type fixing device having a fluorine-based surface layer structure as shown in FIG. The heating roller 9 has an elastic body layer 11 made of silicone rubber and a PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) surface layer 12 on an aluminum core bar 10, Is provided with a heater 13. The pressure roller 14 has an elastic layer 16 made of silicone rubber and a PFA surface layer 17 on an aluminum core 15. The recording paper P on which the unfixed image 18 is printed is passed as shown in the figure.
In the present invention, for example, a known optical fixing device may be used together with or instead of the fixing unit depending on the purpose.

  The neutralization step is a step of performing neutralization by applying a neutralization bias to the latent image carrier, and can be suitably performed by a neutralization unit. The neutralization unit is not particularly limited, and may be appropriately selected from known neutralization units as long as it can apply a neutralization bias to the latent image carrier. For example, a neutralization lamp is preferable. It is mentioned in.

The cleaning step is a step of removing the toner remaining on the latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as the toner remaining on the latent image carrier can be removed, and can be appropriately selected from known cleaners. For example, a magnetic brush cleaner or an electrostatic brush cleaner A magnetic roller cleaner, a blade cleaner, a brush cleaner, a web cleaner, and the like are preferable.
In addition, it is also possible to employ a method in which the charge of the residual toner is made uniform by the rubbing member and collected by the developing roller without using the cleaning means.

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

FIG. 5 is a schematic diagram showing an example of a tandem type full-color image forming apparatus as another example of an image forming apparatus using the electrostatic latent image developing toner of the present invention.
In FIG. 5, the image forming apparatus stores a latent image carrier 1 that is rotated in a clockwise direction in a main body housing (not shown). A charging unit 2 and an exposure unit 3 are disposed around the latent image carrier 1. A developing device 4, an intermediate transfer member 6, a support roller 7, a transfer roller 8, and the like are arranged. Although not shown, the image forming apparatus includes a paper feeding cassette that stores a plurality of recording papers. The recording paper P in the paper feeding cassette is timed by a pair of registration rollers (not shown) one by one by a paper feeding roller (not shown). After the adjustment, the sheet is fed between the intermediate transfer member 6 and the transfer roller 8 and fixed by a fixing unit 19 having a heating roller 9 and a pressure roller 14.

  The image forming apparatus rotates the latent image carrier 1 in the clockwise direction, uniformly charges the latent image carrier 1 with the charging unit 2, and then irradiates the laser modulated with the image data by the exposure unit 3. Then, an electrostatic latent image is formed on the latent image carrier 1, and toner is attached to the latent image carrier 1 on which the electrostatic latent image is formed by the developing device 4 and developed. The image forming apparatus transfers the toner image formed by attaching the toner to the latent image carrier with the developing device 4 from the latent image carrier 1 to the intermediate transfer member. This is performed for each of the four colors of cyan (C), magenta (M), yellow (Y), and black (K) to form a full-color toner image.

Next, FIG. 6 is a schematic view showing an embodiment of a revolver type full color image forming apparatus which is another example of an image forming apparatus using the electrostatic latent image developing toner of the present invention.
In this image forming apparatus, a charging unit 2, an exposure unit 3, a developing device 4, an intermediate transfer body 6, a support roller 7, a transfer roller 8, and the like are disposed around the latent image carrier 1. By switching the operation, a plurality of color toners are successively developed on one latent image carrier 1. Then, the color toner image on the intermediate transfer body 6 is transferred to the recording paper P by the transfer roller 8, and the recording paper P to which the toner image has been transferred is conveyed to the fixing unit to obtain a fixed image.

On the other hand, the image forming apparatus further rotates the latent image carrier 1 having the toner image transferred onto the recording paper P by the intermediate transfer member 6, and scrapes the toner remaining on the surface of the latent image carrier 1 with the blade by the cleaning unit 5. After removing by dropping, the charge is removed by the charge removal unit. The image forming apparatus uniformly charges the latent image carrier 1 neutralized by the neutralization unit with the charging unit 2, and then performs the next image formation as described above. The cleaning unit 5 is not limited to the one that scrapes the residual toner on the latent image carrier 1 with a blade, and may be one that scrapes the residual toner on the latent image carrier 1 with a fur brush, for example. .
In the image forming apparatus and the image forming method of the present invention, since the toner of the present invention is used as the developer, a good image can be obtained.

  In the image forming apparatus of the present invention, the latent image carrier, the developing unit, the cleaning unit, and the like may be configured as a process cartridge, and the process cartridge may be configured to be detachable from the image forming apparatus main body. . Further, at least one of a charging unit, an exposure unit, a developing unit, a transfer unit, and a cleaning unit is supported together with a photosensitive member to form a process cartridge, and a single unit that is detachable from the main body of the image forming apparatus is formed. It is good also as a structure which can be attached or detached using guide means, such as a rail of a main body.

(Process cartridge)
The process cartridge of the present invention includes a latent image carrier that carries a latent image, and a developing unit that develops the latent image carried on the latent image carrier using the toner of the present invention to form a visible image. , And other means such as a charging unit, a developing unit, a transfer unit, a cleaning unit, and a static elimination unit, which are appropriately selected as necessary.

  The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried. The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, facsimiles, and printers, and is preferably detachably provided in the image forming apparatus of the present invention described later.

  For example, as shown in FIG. 7, the process cartridge includes a latent image carrier 1 and includes a charging unit 2, a developing device 4, a transfer roller 8, and a cleaning unit 5, and other units as necessary. It has. In FIG. 7, L indicates exposure from the exposure means, and P indicates recording paper. As the latent image carrier 1, the same one as the image forming apparatus can be used. An arbitrary charging member is used for the charging means 2.

  Next, the image forming process using the process cartridge shown in FIG. 7 will be described. The latent image carrier 1 is rotated in the direction of the arrow while being charged by the charging unit 2 and exposed 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 device 4, and the toner development is transferred onto the recording paper P by the transfer roller 8 and printed out. Next, the surface of the latent image carrier after the image transfer is cleaned by the cleaning unit 5 and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples.
In the following, “parts” and “%” indicate parts by mass and mass%, respectively, unless otherwise specified.
In the following, the case where the toner of the present invention is used as a one-component developer was evaluated. Can also be used.

<Synthesis of Amorphous Polyester Resin (Polyester 1)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1,290 parts of bisphenol A ethylene oxide 2 mol adduct, 2,700 parts of bisphenol A propylene oxide 3 mol adduct, 900 parts of terephthalic acid, adipic acid 190 parts and 10 parts of dibutyltin oxide were added, reacted at normal pressure at 230 ° C. for 8 hours, and further reacted at reduced pressure of 10 mmHg to 15 mmHg for 5 hours. Then, 250 parts of trimellitic anhydride was added to the reaction vessel, Reaction was performed at 180 ° C. for 2 hours to obtain [Polyester 1]. [Polyester 1] had a number average molecular weight of 3,100, a weight average molecular weight of 6,700, a Tg of 52 ° C., a Tm of 98 ° C., and an acid value of 21 mgKOH / g. In addition, it was confirmed by the presence or absence of the above-mentioned X-ray diffraction peak that the [Polyester 1] was non-crystalline.

<Synthesis of Amorphous Polyester Resin (Polyester 2)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 270 parts of bisphenol A ethylene oxide 2-mole adduct, 520 parts of bisphenol A propylene oxide 2-mole adduct, 120 parts of terephthalic acid, 170 parts of adipic acid and dibutyl 1 part of tin oxide was added and reacted at normal pressure at 230 ° C. for 8 hours, and further reacted at a reduced pressure of 10 mmHg to 15 mmHg for 8 hours. Thereafter, 30 parts of trimellitic anhydride was put in a reaction vessel and reacted at normal pressure and 180 ° C. for 2 hours to obtain [Polyester 2]. [Polyester 2] had a number average molecular weight of 4,000, a weight average molecular weight of 45,000, a Tg of 67 ° C., a Tm of 115 ° C., and an acid value of 17 mgKOH / g. In addition, it was confirmed by the presence or absence of the X-ray diffraction peak that the [polyester 2] was non-crystalline.

<Synthesis of Amorphous Polyester Resin (Polyester 3)>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 350 parts of bisphenol A ethylene oxide 2-mole adduct, 326 parts of bisphenol A propylene oxide 3-mole adduct, 260 parts of terephthalic acid, 50 parts of phthalic anhydride, and As a polycondensation catalyst, 1.5 parts of potassium titanyl oxalate was added and reacted at 230 ° C. for 10 hours while distilling off the water generated in a nitrogen stream. Next, the reaction is carried out under reduced pressure of 5 mmHg to 20 mmHg, and when the acid value becomes 2 or less, it is cooled to 180 ° C., 60 parts of trimellitic anhydride is added, and the mixture is reacted for 2 hours under normal pressure sealing, then taken out, After cooling to room temperature, it was pulverized to obtain [Polyester 3].
[Polyester 3] does not contain THF (tetrahydrofuran) insoluble matter, has an acid value of 35 mgKOH / g, Tg of 68 ° C., Tm of 125 ° C., number average molecular weight of 4,100, and weight average molecular weight. It was 57,000.
In addition, it was confirmed by the presence or absence of the X-ray diffraction peak that the [polyester 3] was non-crystalline.

<Synthesis of crystalline polyester resin (polyester 4)>
Into a 5 liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, 2,300 g of 1,10-decanedioic acid, 2,530 g of 1,8-octanediol, and 4.9 g of hydroquinone The mixture was reacted at 180 ° C. for 10 hours, heated to 200 ° C., reacted for 3 hours, and further reacted at 8.3 kPa for 2 hours to obtain crystalline [Polyester 4]. [Polyester 4] had a number average molecular weight of 3,000 and a weight average molecular weight of 10,000, and exhibited an endothermic peak at about 70 ° C. by DSC measurement. In addition, it was confirmed by the presence or absence of the X-ray diffraction peak that the [polyester 4] was crystalline.

<Preparation of dispersion of crystalline polyester resin (polyester 4)>
100 g of [Polyester 4] and 400 g of ethyl acetate were placed in a metal 2 L container, heated and dissolved at 75 ° C., and then rapidly cooled in an ice water bath at a rate of 27 m / min. To this, 500 mL of glass beads (diameter 3 mm) was added, and pulverized for 10 hours with a batch type sand mill (manufactured by Campehapio) to obtain [Crystalline Polyester Dispersion 1].

<Synthesis of prepolymer>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 366 parts of 1,2-propylene glycol, 566 parts of terephthalic acid, 44 parts of trimellitic anhydride and 6 parts of titanium tetrabutoxide were placed at normal pressure, 230 The mixture was reacted at 0 ° C. for 8 hours and further reacted at a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate polyester 1] had a number average molecular weight of 3,200, a weight average molecular weight of 12,000, and a Tg of 55 ° C.
Next, 420 parts of the [intermediate polyester 1], 80 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. [Prepolymer] was obtained. The content of free isocyanate in the [prepolymer] was 1.34%.

<Preparation of dispersion of vinyl resin fine particles D1>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1.6 parts of sodium dodecyl sulfate and 492 parts of ion-exchanged water are heated to 80 ° C., and then 2.5 parts of potassium persulfate is ion-exchanged. A solution dissolved in 100 parts of water is added, and after 15 minutes, a mixed solution of 170 parts of styrene monomer, 30 parts of butyl acrylate, and 1.4 parts of n-octyl mercaptan is added dropwise over 90 minutes, and then for another 60 minutes, 80 minutes. Kept at ℃. Thereafter, the mixture was cooled to obtain a dispersion of [vinyl resin fine particles D1]. The solid content concentration of this dispersion was measured and found to be 25%. The volume average particle diameter (Dv) of the [vinyl resin fine particles D1] was 90 nm. When the solid obtained by taking the dispersion in a small petri dish and evaporating the dispersion medium was measured, the number average molecular weight was 22,500, the weight average molecular weight was 42,000, and the glass transition temperature Tg was 69 ° C.
The volume average particle diameter (Dv) was measured using Multisizer 3 (manufactured by Beckman Coulter).

<Preparation of dispersion of vinyl resin fine particles D2>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1.6 parts of sodium dodecyl sulfate and 492 parts of ion-exchanged water are heated to 80 ° C., and then 2.5 parts of potassium persulfate is ion-exchanged. What was dissolved in 100 parts of water was added, and 15 minutes later, a mixture of 180 parts of styrene monomer, 20 parts of butyl acrylate, and 1.4 parts of n-octyl mercaptan was added dropwise over 90 minutes, and then a further 60 minutes, 80 minutes Kept at ℃. Thereafter, the mixture was cooled to obtain a dispersion of [vinyl resin fine particles D2]. The solid content concentration of this dispersion was measured and found to be 25%. The volume average particle size of the [vinyl resin fine particles D2] was 85 nm. The dispersion was taken in a small petri dish, and the solid obtained by evaporating the dispersion medium was measured. The number average molecular weight was 21,000, the weight average molecular weight was 40,000, and Tg was 75 ° C.

<Preparation of dispersion of vinyl resin fine particles D3>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1.6 parts of sodium dodecyl sulfate and 492 parts of ion-exchanged water are heated to 80 ° C., and then 2.5 parts of potassium persulfate is ion-exchanged. A solution dissolved in 100 parts of water is added, and after 15 minutes, a mixed solution of 170 parts of styrene monomer, 30 parts of methoxydiethylene glycol methacrylate, and 1.4 parts of n-octyl mercaptan is dropped over 90 minutes, and then for another 60 minutes. Maintained at 80 ° C. Thereafter, the mixture was cooled to obtain a dispersion of [vinyl resin fine particles D3]. The solid content concentration of this dispersion was measured and found to be 25%. The volume average particle size of the [vinyl resin fine particles D3] was 85 nm. The dispersion was taken in a small petri dish, and the solid obtained by evaporating the dispersion medium was measured. The number average molecular weight was 21,500, the weight average molecular weight was 41,300, and Tg was 72 ° C.

<Synthesis of master batch>
40 parts of pigment (CI. Pigment Red (PR) -269), 60 parts of polyester resin (RS-801 manufactured by Sanyo Chemical Industries, Ltd., acid value 10 mg KOH / g, weight average molecular weight 20,000, Tg 64 ° C.), 30 parts of water The mixture was mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. and pulverized to a size of 1 mm in diameter with a pulverizer to obtain [Masterbatch 1].

Example 1
<Oil phase preparation process>
Ester wax (melting point 70 ° C.) and [Polyester 1] are adjusted and distributed so as to be 7% by mass with respect to 100 parts by mass of the total resin in a container in which a stir bar and a thermometer are set. Was added so that the solid content concentration (measured with an infrared moisture meter at 130 ° C. for 30 minutes) was 50%, the temperature was raised to 80 ° C. with stirring, and the temperature was maintained at 80 ° C. for 5 hours. Cooled to 30 ° C. in 1 hour. Next, after adding [Masterbatch 1] to 6 parts by mass with respect to 100 parts by mass of the total resin and mixing for 1 hour, the container was changed, and a bead mill (Ultra Visco Mill, manufactured by Imex Corporation) was used. Using this, dispersion was carried out under the conditions of a liquid feed speed of 1 kg / hour, a disk peripheral speed of 6 m / second, 0.5% zirconia beads filled with 80% by volume, and three passes to obtain [Raw Material Solution 1]. Next, [Polyester 1] and [Polyester 2] are adjusted and distributed to the composition of Table 2-1 in [Raw Material Solution 1], and [Crystalline Polyester Dispersion 1] is further added to 100% by mass of the total resin. In addition, it is adjusted and distributed to a substantial amount ratio so that it becomes 4% by mass, and further, an ethyl acetate solution is added, and the solid content concentration (measured with an infrared moisture meter at 130 ° C. for 30 minutes) becomes 50%. As such, the mixture was stirred for 8 hours with a three-one motor to obtain [Oil Phase 1].
After mixing 976 parts of [Oil Phase 1] with a TK homomixer (manufactured by Special Machine Engineering Co., Ltd.) at 5,000 rpm for 1 minute, 88 parts of [Prepolymer] were added and TK homomixer (manufactured by Special Machine Co., Ltd.). Was mixed at 5,000 rpm for 1 minute to obtain [Prepolymer-containing oil phase 1]. The solid content concentration of the obtained [prepolymer-containing oil phase 1] was measured and found to be 52.0% by mass, and the amount of ethyl acetate based on the solid content was 92% by mass.

<Aqueous phase preparation process>
When 472 parts of ion-exchanged water, 65 parts of a 1% aqueous solution of carboxymethylcellulose as a thickener, 80 parts of a 50% aqueous solution of sodium dodecyl diphenyl ether disulfonate, and 55 parts of ethyl acetate were mixed and stirred, the pH reached 6.0. While stirring this, a 4% aqueous sodium hydroxide solution was added dropwise to adjust the pH to 12.0 to obtain [Aqueous Phase 1].

<Core particle production process>
[Prepolymer-containing oil phase 1] that has been stirred in advance is added to the obtained [aqueous phase 1], and the temperature in the liquid is reduced to 20 by cooling in a water bath in order to suppress the temperature rise due to the shear heat of the mixer. While adjusting to a temperature in the range of ℃ to 23 ℃, using a TK homomixer, adjust the granulation at a rotational speed of 4,000 rpm to 12,000 rpm and mix for 3 minutes. The mixture was stirred for 10 minutes while adjusting the rotation speed to 200 rpm to obtain [core particle slurry 1] in which droplets of an oil phase serving as core particles were dispersed in an aqueous phase.

<Resin fine particle adhesion process to core particle>
While the [core particle slurry 1] is stirred at a rotational speed of 400 rpm with a three-one motor equipped with a stirring blade, the [resin fine particle dispersion D1] is mixed at a core particle mass ratio while the liquid temperature is 22 ° C. What was mixed with ion-exchanged water so as to be 5.5% (solid content concentration 10%) was added dropwise at a rate of 20 g / min. After the dropping, the rotation speed was maintained at 400 rpm and stirring was continued for 30 minutes to obtain [Composite Particle Slurry 1]. In the stirring, a cylindrical stirring vessel is used, and the ratio (b / a) between the diameter (a) of the stirring vessel and the blade diameter (b, maximum diameter) of the stirring blade is 0.9 or more and 1. It was less than 0.

<Demelting process>
[Composite particle slurry 1] was charged into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours while stirring to obtain [Dispersion slurry 1]. When the obtained [Dispersion Slurry 1] was placed on a small amount of slide glass, sandwiched between cover glasses and observed with an optical microscope at a magnification of 200, uniform colored particles were observed.

<Washing process and drying process>
After filtering 100 parts of [Dispersion Slurry 1] under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry liquid of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filter Cake 1].
The obtained [Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh of 75 μm, and [Toner base particle 1] (volume average particle diameter (Dv) was 6.0 μm, Dv). / Dn was 1.15). FIG. 8 shows an SEM photograph of [Toner Base Particle 1] obtained. [Toner base particle 1] has a surface structure in which a large number of convex portions are formed on the surface of the core particle.

  Commercially available silica fine powder RY50 (manufactured by Nippon Aerosil Co., Ltd .; average primary particle size 40 nm, with silicone oil treatment) is added to 50 parts of this [toner base particle 1] as external additive I, and MSP009 [Taika] is used as external additive II. 1 part of average primary particle size 80 nm, with silicone oil treatment, with aminosilane treatment], and 1.5 parts of H20TM [manufactured by Clariant Japan; average primary particle size 12 nm, without silicone oil treatment] as external additive C 15 kg was charged with a 100 L Henschel mixer, and mixed at a peripheral speed of 35 m / s for 15 minutes to obtain [Toner 1]. In the mixing, continuous operation is performed while cooling appropriately so that the temperature of the actual powder becomes 40 ° C. or less.

(Example 2)
In Example 1, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 2 was obtained in the same manner as in Example 1 except that the same amount of [Polyester 3] as the content of [Prepolymer] was added to prepare an oil phase.

(Example 3)
In Example 1, the [resin fine particle dispersion D1] in the resin fine particle adhesion step is changed from 5.5% to 5% in terms of the mass ratio of the core particles, and the external additives I, II, and III to be added to the toner base particles, respectively. The toner of Example 3 was obtained in the same manner as in Example 1 except that the ratio was changed as shown in Table 2-2, and the mixing time during external addition was changed from 15 minutes to 20 minutes. It was.

Example 4
In Example 3, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 4 was obtained in the same manner as in Example 3, except that the same amount of [Polyester 3] as the prepolymer content was added to prepare an oil phase.

(Example 5)
In Example 1, the resin fine particle dispersion D1 in the resin fine particle adhering step is changed from 5.5% to 6% in terms of the mass ratio of the core particles, and external additives I, II, and III added to the toner base particles, respectively. The toner of Example 5 was obtained in the same manner as in Example 1 except that the ratio was changed as shown in Table 2-2, and the mixing time during external addition was changed from 15 minutes to 10 minutes. It was.

(Example 6)
In Example 5, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 6 was obtained in the same manner as in Example 5, except that the same amount of [Polyester 3] as the prepolymer content was added to prepare an oil phase.

(Example 7)
In Example 1, the volume average particle diameter (Dv) of the toner base particles is changed from 6.0 μm to 6.5 μm, and the peripheral speed at the time of external addition mixing in which the toner base particles and the external additive are mixed is 35 m. The toner of Example 7 was obtained in the same manner as in Example 1, except that the mixing time was changed from 15 / s to 30 m / s and the mixing time was changed from 15 minutes to 10 minutes.

(Example 8)
In Example 7, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 8 was obtained in the same manner as in Example 7 except that an oil phase was prepared by adding [Polyester 3] in the same amount as the prepolymer content.

Example 9
In Example 1, the volume average particle diameter (Dv) of the toner base particles is changed from 6.0 μm to 5.5 μm, and the peripheral speed at the time of external addition mixing in which the toner base particles are mixed with an external additive is 35 m / The toner of Example 9 was obtained in the same manner as in Example 1, except that the mixing time was changed from 15 to 40 m / s and the mixing time was changed from 15 to 20 minutes.

(Example 10)
In Example 9, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 10 was obtained in the same manner as in Example 9, except that the same amount of [Polyester 3] as the prepolymer content was added to prepare an oil phase.

(Example 11)
Example 1 is the same as Example 1 except that the ratio of [Polyester 1] and Polyester 2] put into [Raw Material Solution 1] in the oil phase preparation step is changed as shown in Table 2-1 in terms of mass ratio. Thus, the toner of Example 11 was obtained.

(Example 12)
In Example 11, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 12 was obtained in the same manner as in Example 11 except that the same amount of [Polyester 3] as the prepolymer content was added to prepare an oil phase.

(Example 13)
Example 1 is the same as Example 1 except that the ratio of [Polyester 1] and Polyester 2] put into [Raw Material Solution 1] in the oil phase preparation step is changed as shown in Table 2-1 in terms of mass ratio. Thus, a toner of Example 13 was obtained.

(Example 14)
In Example 13, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 14 was obtained in the same manner as in Example 13, except that an oil phase was prepared by adding [Polyester 3] in the same amount as the prepolymer content.

(Example 15)
Example 1 The toner of Example 15 was obtained.

(Example 16)
In Example 15, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 16 was obtained in the same manner as in Example 15, except that the same amount of [Polyester 3] as the prepolymer content was added to prepare an oil phase.

(Example 17)
In Example 1, the external additive II was changed from MSP009 to commercially available silica MSN005 (manufactured by Teica; average primary particle size 80 nm, with silicone oil treatment, without aminosilane treatment), in the same manner as in Example 1, A toner of Example 17 was obtained.

(Example 18)
In Example 17, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 18 was obtained in the same manner as in Example 17, except that the same amount of [Polyester 3] as the prepolymer content was added to prepare an oil phase.

(Example 19)
In Example 1, a toner of Example 19 was obtained in the same manner as in Example 1, except that the addition amount of the external additive I was changed from 3.0% to 2.5%.

(Example 20)
In Example 19, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 20 was obtained in the same manner as in Example 19, except that the same amount of [Polyester 3] as the prepolymer content was added to prepare an oil phase.

(Example 21)
In Example 1, the toner of Example 21 was obtained in the same manner as in Example 1, except that the addition amount of the external additive I was changed from 3.0% to 3.5%.

(Example 22)
In Example 21, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline polyester dispersion 1] in [Raw material solution 1], by mass ratio A toner of Example 22 was obtained in the same manner as in Example 21, except that the same amount of [Polyester 3] as the prepolymer content was added to prepare an oil phase.

(Example 23)
In Example 1, a toner of Example 23 was obtained in the same manner as in Example 1, except that the addition amount of the external additive II was changed from 1.0% to 0.5%.

(Example 24)
In Example 23, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 24 was obtained in the same manner as in Example 23, except that the same amount of [Polyester 3] as the prepolymer content was added to prepare an oil phase.

(Example 25)
In Example 1, a toner of Example 25 was obtained in the same manner as in Example 1, except that the addition amount of the external additive II was changed from 1.0% to 1.5%.

(Example 26)
In Example 25, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 26 was obtained in the same manner as in Example 25 except that the same amount of [Polyester 3] as the prepolymer content was added to prepare an oil phase.

(Example 27)
A toner of Example 27 was obtained in the same manner as in Example 1, except that the type of wax was changed from ester wax to paraffin wax having a melting point of 75 ° C. in Example 1.

(Example 28)
In Example 27, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 28 was obtained in the same manner as in Example 27, except that [Polyester 3] having the same amount as the prepolymer content was added to prepare an oil phase.

(Example 29)
In Example 1, 976 parts of [Oil Phase 1] in the oil phase preparation step was mixed with TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute. A toner of Example 29 was obtained in the same manner as in Example 1, except that the aqueous solution was added to [Oil Phase 1] instead of being dropped into the aqueous phase and stirred, and then [Prepolymer] was stirred again.

(Example 30)
In Example 29, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 30 was obtained in the same manner as in Example 29 except that [Polyester 3] having the same amount as the prepolymer content was added to prepare an oil phase.

(Example 31)
The toner of Example 31 was obtained in the same manner as in Example 1, except that [resin fine particle dispersion D1] was changed to [resin fine particle dispersion D3].

(Example 32)
In Example 31, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 32 was obtained in the same manner as in Example 31 except that the same amount of [Polyester 3] as the prepolymer content was added to prepare an oil phase.

(Example 33)
A toner of Example 33 was obtained in the same manner as in Example 1, except that [resin fine particle dispersion D1] was changed to [resin fine particle dispersion D2] in Example 1.

(Example 34)
In Example 33, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Example 34 was obtained in the same manner as in Example 33, except that [Polyester 3] having the same amount as the prepolymer content was added to prepare an oil phase.

(Example 35)
In Example 1, except that [Core Particle Slurry 1] was changed so that the rotation speed of the three-one motor with the stirring blades was continuously stirred at 200 rpm in <resin fine particle adhesion step to core particles>. In the same manner as in Example 1, the toner of Example 35 was obtained.

(Example 36)
In Example 35, instead of adding [Prepolymer] in <Oil phase preparation step>, in addition to [Polyester 1], [Polyester 2] and [Crystalline polyester dispersion 1] in [Raw material solution 1] A toner of Example 36 was obtained in the same manner as in Example 35 except that [Polyester 3] having the same amount as the prepolymer content was added to prepare an oil phase.

(Example 37)
In Example 1, the liquid temperature is 22 ° C. while the [core particle slurry 1] is adjusted to a rotation speed of 400 rpm with a three-one motor equipped with a stirring blade in the <resin particle adhesion step to the core particles> and stirred. Then, [resin fine particle dispersion D1] was mixed with ion-exchanged water so that the core particle mass ratio was 5.5% (solid content concentration 10%) was changed so as to be dropped at a rate of 15 g / min. A toner of Example 37 was obtained in the same manner as Example 1 except for the above.

(Example 38)
In Example 37, instead of adding [Prepolymer] in <Oil phase preparation step>, in addition to [Polyester 1], [Polyester 2] and [Crystalline polyester dispersion 1] in [Raw material solution 1] A toner of Example 38 was obtained in the same manner as in Example 37, except that [Polyester 3] having the same amount as the prepolymer content was added to prepare an oil phase.

(Comparative Example 1)
A toner of Comparative Example 1 was obtained in the same manner as in Example 1 except that [Resin fine particle dispersion D1] was not added.

(Comparative Example 2)
In Comparative Example 1, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Comparative Example 2 was obtained in the same manner as Comparative Example 1 except that an oil phase was prepared by adding [Polyester 3] in the same amount as the prepolymer content.

(Comparative Example 3)
A toner of Comparative Example 3 was obtained in the same manner as in Example 1 except that the content of [resin fine particle dispersion D1] was changed from 5% to 9% in terms of the mass ratio of the core particles in Example 1.

(Comparative Example 4)
In Comparative Example 3, instead of adding [Prepolymer] in the oil phase preparation step, in addition to [Polyester 1], [Polyester 2] and [Crystalline Polyester Dispersion 1] in [Raw Material Solution 1], by mass ratio A toner of Comparative Example 4 was obtained in the same manner as Comparative Example 3 except that the same amount of [Polyester 3] as the prepolymer content was added to prepare an oil phase.

(Comparative Example 5)
In Example 2, a toner of Comparative Example 5 was obtained in the same manner as in Example 2, except that the production method was changed from the dissolution suspension method to the mixing, kneading and pulverizing method. Specifically, the toner materials described in Tables 2-1 and 2-2 are mechanically mixed with a mixing mixer, then cooled and solidified while being melted with a melt kneader, and further with a mechanical pulverizer. After grinding to an average particle size of 6 μm, the fine powder component was removed by a classifier to obtain toner base particles having a volume average particle size of 7.0 μm.

  The following evaluations were performed on the toners of Examples 1 to 38 and Comparative Examples 1 to 5. The results are shown in Table 3.

<Measurement of abundance ratio of particles having a particle size of 0.6 μm to 2.0 μm during ultrasonic irradiation>
The specific measuring method in the present invention is as follows. Measurement and analysis conditions were measured under the calibration and measurement conditions.

<< Preparation of dispersion and irradiation with ultrasonic waves >>
First, about 990 g of ion-exchanged water from which impure solids have been removed in advance is placed in a 1 L polypropylene container. 10 g of sodium dodecyl sulfate (manufactured by Kanto Chemical Co., Inc.) was added as a dispersant to prepare a 1.0 mass% dispersion.
60 mL of this dispersion was weighed, 60 mg of toner as a measurement sample was added, and the mixture was stirred for 90 minutes with a stirrer. After confirming that the toner is sufficiently dispersed in the dispersion and that the toner does not float on the surface of the dispersion, the toner is transferred to a 100 mL stainless steel cup (manufactured by TOP). taking measurement.
After measuring the value of Z, 60 mL of the dispersion is weighed again in another container, 60 mg of a measurement sample is added, and the mixture is stirred for 90 minutes with a stirrer. After confirming that the toner is sufficiently dispersed in the dispersion liquid and that the toner does not float on the liquid surface of the dispersion liquid, the toner is transferred to a 100 mL capacity stainless cup (manufactured by TOP), and then the output is 80 W / 10 cm ² . With the adjusted ultrasonic irradiation device, ultrasonic waves are irradiated for 1 minute (in the case of A), 5 minutes (in the case of B), and 10 minutes (in the case of C) to perform dispersion treatment, respectively, Z, A, A dispersion for measurement of B and C was obtained.
In addition, when irradiating the said ultrasonic wave, it confirmed that the generation | occurrence | production source of the said ultrasonic wave was fully immersed in the dispersion liquid (it was immersed 1 cm or more from the liquid surface). Moreover, it cooled suitably so that the temperature of a dispersion liquid might be 10 degreeC or more and 40 degrees C or less.
As the ultrasonic irradiation device, “VCX-750” (manufactured by Sonics & Materials) was used.

<< FPIA measurement >>
The average circularity of the toner particles was measured with a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.
For the measurement, the flow type particle image analyzer equipped with “UPlanApro” (magnification: 10 ×, numerical aperture: 0.40) as an objective lens is used, and the particle liquid “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. )It was used.
The dispersion prepared according to the above procedure was introduced into the flow type particle image analyzer, and 3,000 toner particles were measured in the HPF measurement mode and in the total count mode.
Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the circle equivalent diameter of 0.60 μm or more and less than 39.69 μm, and the arithmetic average value of the toner equivalent circle diameter (number average particle diameter) D1), the mode diameter Dm and the average circularity were determined.
The abundance ratio of particles having a particle size of 0.6 μm or more and 2.0 μm or less was calculated from the determined Dm, and were set as Z, A, B, and C, respectively. Further, when obtaining the values of Z, A, B, and C, the same sample was measured five times and the average value was adopted in order to suppress the error in the sample as much as possible.
In the measurement, automatic focus adjustment was performed using standard latex particles (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
Further, in this embodiment, a flow type particle image analyzer which has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 0.60 μm or more and less than 39.69 μm.

<Measurement of TgA>
<< Definition of deformation start point TgA of flow tester >>
Hereinafter, details of the toner TgA will be described again.
Here, TgA is a profile in the temperature test method of the flow tester, and is different from the softening temperature Ts when moving from the fixed region to the shift region and the outflow start temperature Tfb from which the sample flows out. ) In the vicinity of the glass transition temperature Tg (a region where the difference ΔT from the Tg is in the range of about 1 ° C. to 2 ° C. before the Ts) It is the point of contact between the baseline and the tangent of the rising curve).

<< Measurement Method of TgA >>
Using a flow tester (CFT-500, manufactured by Shimadzu Corporation), 1.5 g of a measurement sample is weighed, using a die having a height of 1.0 mm and a diameter of 1.0 mm, a heating rate of 3.0 ° C./min, preheating Measurement was performed under conditions of a load of 30 kg, a measurement temperature range of 20 ° C. to 140 ° C. for a time of 180 seconds, and a point at which the above sample started to deform under a compressive load was defined as a deformation start point TgA (see FIG. 1).
As a more detailed method of obtaining TgA, the extension line of the BC line, which is the internal void reduction stage in the sample from the softening temperature Ts point C, and the sample AB is still in an undeformed state while receiving a compressive load. The point of intersection with the line is TgA.

<Measuring method of toner aggregation degree>
The method for measuring the degree of aggregation of the toner was as follows.
As a measuring device, a powder tester manufactured by Hosokawa Micron Co., Ltd. was used, and attached parts were set on a vibration table in the following procedure.
(T1) Vibro chute, (T2) Packing, (T3) Space ring, (T4) Fluey (Three types, arranged so that the openings are in order from the largest, middle, and lower), (T5) Osaba Next, it was fixed with a knob nut and the shaking table was operated.
Measurement conditions were as follows.
Sieve opening: (upper) 75 μm, (middle) 45 μm, (lower) 20 μm
Swing scale: 1mm
Sampling amount: 2g
Vibration time: 10 seconds After the measurement based on the above procedure, the following formula using the following calculated values (x), (y) and (z) was used as the degree of aggregation [%].
Aggregation degree [%] = 100 × {(x) × 1 + (y) × 0.6 + (z) × 0.2} / 2
(X): Remaining amount of powder (mass%) remaining on the upper sieve
(Y): Remaining amount of powder (mass%) remaining on the middle sieve
(Z): Remaining amount of powder (mass%) remaining on the lower sieve

<Photoconductor shaving>
Using a color electrophotographic apparatus (IPSiO SP C220, manufactured by Ricoh Co., Ltd.), 3,000 image charts having a 1% image area were output, and then the surface of the photoconductor was visually evaluated in four stages.
-Evaluation criteria-
A: State without streaking ○: Streaking is 1 or more and less than 5 but practically acceptable level Δ: Streaking is 5 or more and less than 10 and practically acceptable level X: There are 10 or more streaks, and the level is not practical.

<Cleanability>
Using a color electrophotographic apparatus (IPSiO SP C220, manufactured by Ricoh Co., Ltd.), the transfer residual toner on the photoreceptor after passing through the cleaning process after outputting 1,000 sheets of an image area ratio of 95% is scotch tape. It was transferred to a white paper (manufactured by Sumitomo 3M Co., Ltd.) and measured with a Macbeth reflection densitometer RD514 type to evaluate the cleaning property according to the following evaluation criteria. The numerical value of the evaluation standard represents a difference from the numerical value of the blank (when there is no toner and only the scotch tape).
-Evaluation criteria-
◎: Less than 0.005 ○: 0.005 or more and less than 0.01 Δ: 0.01 or more and less than 0.02 ×: 0.02 or more

<Environment resistance>
Using a color electrophotographic apparatus (IPSiO SP C220, manufactured by Ricoh Co., Ltd.), a predetermined print pattern having a black solid to white solid ratio (B / W ratio: black dot area ratio to white paper) of 6% Continuous printing was performed in an L environment (temperature 10 ° C., relative humidity 15%). After 1,000 sheets of continuous printing in the L / L environment (after endurance), it was changed to the H / H environment (temperature 27 ° C., relative humidity 80%), and 1,000 sheets of continuous printing were performed. After that, the toner on the developing roller during the printing of the blank paper pattern after 1,000 sheets of durability under each environment is sucked, and the charge amount is measured with an electrometer, under the L / L environment and the H / H environment. Each charge amount difference was evaluated.
-Evaluation criteria-
A: Absolute value of difference in charge amount is less than 10 μC / g. ○: Absolute value of difference in charge amount is from 10 μC / g to less than 15 μC / g. Δ: Absolute value of difference in charge amount is from 15 μC / g to less than 20 μC / g. Absolute value of quantity difference is 20μC / g or more

<Skin dirt>
Using a color electrophotographic apparatus (IPSiO SP C220, manufactured by Ricoh Co., Ltd.), after outputting 3,000 image charts with a 1% image area, the toner adhering to the white solid image printed is peeled off with a scotch tape. What was taken was affixed to white paper, and ΔE (density difference) was measured using a spectral densitometer (manufactured by X-Rite), and evaluated in four stages.
-Evaluation criteria-
◎: ΔE is less than 3 ○: ΔE is 3 or more and less than 5 Δ: ΔE is 5 or more and less than 10 ×: ΔE is 10 or more

<Fixability>
The toner is put into IPSiO SP C220 (manufactured by Ricoh Co., Ltd.) which has been made to be able to control the toner adhesion amount by removing the fixing means, and the adhesion amount becomes 11 g / m ² on the Ricoh Co., Ltd. My Recycle Paper 100T paper. Thus, 19 sheets of 50 mm square unfixed solid images were prepared.
Next, using the modified fixing unit, the system speed was set to 180 mm / sec, and the prepared unfixed solid image was passed through to fix the image. The fixing temperature was tested from 120 ° C to 200 ° C in 10 ° C increments. The fixed image was folded inward, spread again, and then lightly rubbed with an eraser. The lowest temperature at which the crease did not disappear was defined as the minimum fixing temperature.
-Evaluation criteria-
A: Fixing lower limit temperature is less than 130 ° C.
○: Fixing lower limit temperature is 130 ° C. or more and less than 140 ° C. Δ: Fixing lower limit temperature is 140 ° C. or more and less than 150 ° C. ×: Fixing lower limit temperature is 150 ° C. or more.

<Fixing resistance>
Using a color electrophotographic apparatus (IPSiO SP C220, manufactured by Ricoh Co., Ltd.), after outputting 3,000 image charts with a 1% image area, a black solid image was printed, and a black solid image (7.8 cm × 1. 0 cm) was compared with the stage sample, and the sticking resistance was evaluated in four stages.
-Evaluation criteria-
◎: Very good level without white streaks ○: Level where white streaks are not noticeable and does not affect image quality △: Level that white streaks affect image quality ×: Level that has white streaks and greatly affects image quality

<Heat resistant storage>
A 1 mg sample of toner was placed between two slide glasses (manufactured by MATSANAMI, S-1111), a 1 kg load was applied from above, and the sample was left at 40 ° C. and 90% relative humidity for 3 days. Thereafter, the deformation rank of the toner was determined from the SEM image of the extracted toner.
-Evaluation criteria-
◎: No deformation of the toner is observed. ○: The contact surface with the glass is slightly deformed. △: The toner is deformed and the toner surface is smooth, but voids are also observed. ×: The toner is deformed. Fused, no voids seen

The aspect of the present invention is as follows.
<1> Toner base particles composed of core particles containing a binder resin, a release agent and a colorant, and convex portions formed by resin fine particles on the surface of the core particles;
An electrostatic charge image developing toner comprising an external additive,
The external additive is inorganic fine particles,
The binder resin contains a crystalline polyester resin and an amorphous polyester resin;
The particle diameter measured by a flow type particle image analyzer when the 1 mg / mL dispersion of the electrostatic charge image developing toner is irradiated with ultrasonic waves of 20 kHz and 80 W / 10 cm ² is 0.6 μm to 2.0 μm. In the presence ratio (number%) of particles, the ultrasonic wave is
The abundance ratio before irradiation is Z,
The abundance ratio when irradiated for 1 minute is A,
The existence ratio when irradiated for 5 minutes is B,
When the existence ratio when irradiated for 10 minutes is C,
An electrostatic charge image developing toner characterized by satisfying all of the following relational expressions (1) to (3):
0 ≦ A−Z ≦ 3.0 Formula (1)
0.5 ≦ B−Z ≦ 4.0 Formula (2)
4.0 ≦ C−Z ≦ 8.0 Formula (3)
<2> The electrostatic image developing toner according to <1>, wherein Z and A satisfy the following relational expression (4).
1 ≦ Z ≦ A ≦ 5 Formula (4)
<3> The electrostatic image developing toner according to any one of <1> to <2>, wherein B and C satisfy the following relational expression (5).
2 ≦ B ≦ 7 ≦ C ≦ 12 Formula (5)
<4> The electrostatic image developing toner according to any one of <1> to <3>, wherein the aggregation degree of the electrostatic image developing toner is 60% to 90%.
<5> The electrostatic charge image according to any one of <1> to <4>, wherein a glass transition temperature TgA measured by a flow tester of the electrostatic charge image developing toner is 57.0 ° C. to 61.0 ° C. Development toner.
<6> The electrostatic image developing toner according to any one of <1> to <5>, wherein the external additive contains an external additive I which is inorganic fine particles containing silicone oil.
<7> The electrostatic image developing toner according to <6>, wherein the content of the external additive I in the electrostatic image developing toner is 2.7% by mass to 3.3% by mass.
<8> The electrostatic image developing toner according to <6>, wherein the external additive further includes an external additive II which is an inorganic fine particle containing a silicone oil and containing an amino group-containing silane coupling agent.
<9> The electrostatic image developing toner according to <8>, wherein the content of the external additive II in the electrostatic image developing toner is 0.7% by mass to 1.3% by mass.
<10> The electrostatic image developing toner according to any one of <1> to <9>, wherein the release agent is an ester wax.
<11> The electrostatic image developing toner according to any one of <1> to <10>, wherein the binder resin further contains a modified polyester resin having at least one of a urethane group and a urea group.
<12> A solution or dispersion in which at least a binder resin, a release agent, and a colorant are dissolved or dispersed in an organic solvent is obtained, and the solution or the dispersion is suspended in an aqueous medium having an inorganic base. A core particle dispersion was produced by turbidity, and a resin fine particle dispersion was added to the core particle dispersion to form a convex portion made of resin fine particles on the surface of the core particles, and the organic solvent was removed. The toner for developing an electrostatic charge image according to any one of <1> to <11>.
<13> The electrostatic charge image development according to <12>, wherein the core particle dispersion and the resin fine particle dispersion are stirred with a stirring blade in the formation of the convex portion, and the rotation speed of the stirring blade is 250 rpm to 600 rpm. Toner.
<14> The electrostatic charge image according to any one of <12> to <13>, wherein in the formation of the convex portion, the addition rate of the resin fine particle dispersion with respect to the core particle dispersion is more than 15 g / min and not more than 30 g / min. Development toner.
<15> In the formation of the convex portion, the core particle dispersion and the resin fine particle dispersion are stirred by a stirring blade in a stirring vessel, and the ratio of the diameter (a) of the stirring vessel to the blade diameter (b) of the stirring blade The toner for developing an electrostatic charge image according to any one of <12> to <14>, wherein (b / a) is 0.9 or more and less than 1.0.
<16> Any one of <1> to <15>, wherein the resin fine particles are obtained by polymerizing a vinyl polymerizable monomer having a vinyl polymerizable functional group, and the vinyl polymerizable monomer is styrene and butyl acrylate. The toner for developing an electrostatic image described in 1.
<17> The electrostatic charge image according to <16>, wherein the content of styrene in the vinyl polymerizable monomer is 75% by mass to 85% by mass and the content of butyl acrylate is 15% by mass to 25% by mass. Development toner.
<18> A latent image carrier that carries a latent image, and a developing unit that develops an electrostatic latent image formed on the surface of the latent image carrier using toner to form a visible image, are integrated. A process cartridge that is supported and detachable from the main body of the image forming apparatus, wherein the developing means is accommodated in the toner container, a toner conveying member that rotates, and the toner conveying member. A developing device having at least a toner supply member for supplying toner, wherein the toner is the electrostatic image developing toner according to any one of <1> to <17>.
<19> A latent image carrier that carries a latent image, a charging unit that uniformly charges the surface of the latent image carrier, and an exposure that exposes the surface of the charged latent image carrier to write an electrostatic latent image Means, developing means for developing the electrostatic latent image formed on the surface of the latent image carrier with a toner to form a visible image, and the visible image on the surface of the latent image carrier. The transfer device according to any one of <1> to <17>, further comprising: a transfer unit that transfers the image to a transfer target; and a fixing unit that fixes the transfer image transferred onto the transfer target. An image forming apparatus characterized by being an electrostatic charge image developing toner.
<20> A charging step for uniformly charging a surface of a latent image carrier that carries a latent image, an exposure step for exposing the charged surface of the latent image carrier to write an electrostatic latent image, and the latent image Developing the electrostatic latent image formed on the surface of the carrier with a toner to form a visible image; and transferring the visible image on the surface of the latent image carrier to the transfer target An electrostatic image developing toner according to any one of <1> to <17>, wherein the toner includes a transfer step and a fixing step of fixing the transferred image transferred onto the transfer target. An image forming method is characterized in that there is an image forming method.

DESCRIPTION OF SYMBOLS 1 Latent image carrier 2 Charging means 3 Exposure means 4 Developing apparatus 5 Cleaning part 6 Intermediate transfer body 7 Support roller 8 Transfer roller 9 Heating roller 10 Aluminum core metal 11 Elastic body layer 12 PFA surface layer 13 Heater 14 Pressure roller 15 Aluminum core Gold 16 Elastic layer 17 PFA surface layer 18 Unfixed image 19 Fixing means 40 Developing roller 41 Thin layer forming member 42 Supply roller 50 Stirring vessel 51 Stirring blade L Exposure P Recording paper T Toner for electrostatic image development

JP 2011-123483 A Japanese Patent No. 4817996

Claims (10)

Core particles containing a binder resin, a release agent and a colorant, and toner base particles composed of convex portions formed by resin fine particles on the surface of the core particles;
An electrostatic charge image developing toner comprising an external additive,
The external additive is inorganic fine particles,
The binder resin contains a crystalline polyester resin and an amorphous polyester resin;
The particle diameter measured by a flow type particle image analyzer when the 1 mg / mL dispersion of the electrostatic charge image developing toner is irradiated with ultrasonic waves of 20 kHz and 80 W / 10 cm ² is 0.6 μm to 2.0 μm. In the presence ratio (number%) of particles, the ultrasonic wave is
The abundance ratio before irradiation is Z,
The abundance ratio when irradiated for 1 minute is A,
The existence ratio when irradiated for 5 minutes is B,
When the existence ratio when irradiated for 10 minutes is C,
An electrostatic charge image developing toner characterized by satisfying all of the following relational expressions (1) to (3):
0 ≦ A−Z ≦ 3.0 Formula (1)
0.5 ≦ B−Z ≦ 4.0 Formula (2)
4.0 ≦ C−Z ≦ 8.0 Formula (3) 2. The electrostatic image developing toner according to claim 1, wherein Z and A satisfy the following relational expression (4), and B and C satisfy the following relational expression (5).
1 ≦ Z ≦ A ≦ 5 Formula (4)
2 ≦ B ≦ 7 ≦ C ≦ 12 Formula (5)   The electrostatic image developing toner according to claim 1, wherein the aggregation degree of the electrostatic image developing toner is 60% to 90%.   The electrostatic image developing toner according to any one of claims 1 to 3, wherein a deformation start point TgA of the electrostatic image developing toner measured by a flow tester is 57.0 ° C to 61.0 ° C.   The external additive contains the external additive I which is inorganic fine particles containing silicone oil, and the content of the external additive I in the toner for developing an electrostatic charge image is 2.7% by mass to 3.3% by mass. The electrostatic charge image developing toner according to claim 1, wherein:   The external additive further includes an external additive II which is an inorganic fine particle containing a silicone oil and containing an amino group-containing silane coupling agent, and the content of the external additive II in the toner for developing an electrostatic charge image is The toner for developing an electrostatic image according to claim 5, wherein the toner is 0.7% by mass to 1.3% by mass.   The electrostatic image developing toner according to claim 1, wherein the binder resin further contains a modified polyester resin having at least one of a urethane group and a urea group. Obtain a dissolved or dispersed material in which at least a binder resin, a release agent and a colorant are dissolved or dispersed in an organic solvent,
Suspending the dissolved product or the dispersion in an aqueous medium having an inorganic base to produce a core particle dispersion,
A resin fine particle dispersion is added to the core particle dispersion to form convex portions made of resin fine particles on the surface of the core particles,
The electrostatic image developing toner according to claim 1, obtained by removing the organic solvent. The resin fine particles are obtained by polymerizing a vinyl polymerizable monomer having a vinyl polymerizable functional group,
The vinyl polymerizable monomer is styrene and butyl acrylate;
The styrene content in the vinyl polymerizable monomer is 75% by mass to 85% by mass,
The electrostatic image developing toner according to claim 1, wherein a content of the butyl acrylate in the vinyl polymerizable monomer is 15% by mass to 25% by mass. A latent image carrier that carries a latent image, and a developing unit that develops a visible image by developing the electrostatic latent image formed on the surface of the latent image carrier using toner, are integrally supported, A process cartridge that is detachable from the main body of the image forming apparatus,
The developing means is a developing device having at least a toner container, a rotating toner conveying member, and a toner supply member that supplies toner accommodated in the toner container to the toner conveying member;
A process cartridge, wherein the toner is the electrostatic image developing toner according to claim 1.