JP5387951B2 - Toner production method - Google Patents

Description

  The present invention relates to an electrostatic latent image developing toner manufacturing method and manufacturing apparatus.

In an electrophotographic apparatus, an electrostatic recording apparatus, etc., a toner is attached to an electrostatic latent image formed on a photoreceptor, transferred to a recording medium, and then fixed on the recording medium by heat to form a toner image. Is forming. Also, full-color image formation generally involves color reproduction using four color toners of black, yellow, magenta, and cyan. Each color is developed, and each toner layer is superimposed on a recording medium. The toner image is heated and fixed at the same time, thereby forming a full-color image.
However, from the viewpoint of users who are familiar with printing, in general, images on full-color copiers are not yet satisfactory, and there is a demand for higher image quality that satisfies photography, high-resolution, and high resolution. It is known that a toner having a small particle size and a narrow particle size distribution is effective for improving the quality of a photographic image.

Conventionally, an electrical or magnetic latent image has been developed with toner.
The toner used for developing the electrostatic image is generally colored particles in which a binder, a charge control agent, and other additives are contained in a binder resin. The toner production method is roughly classified into a pulverization method and a chemical method (for example, a spray drying method in which an organic solvent liquid in which a binder resin component is dissolved is spray-dried into droplets to prepare a spherical toner particle base material, O / W emulsion method, polymerization method, partial polymerization method, etc. in which an organic solvent liquid in which the binder resin is dissolved is dispersed in an aqueous liquid medium in the form of droplets and the solvent is removed therefrom to prepare a spherical toner particle base material. ) In the pulverization method, a colorant, a charge control agent, an anti-offset agent, etc. are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting toner composition is pulverized and classified to produce a toner. doing.
According to the pulverization method, it is possible to produce a toner having excellent properties to some extent, but there are limitations on the selection of the toner material. For example, a toner composition obtained by melt mixing must be capable of being pulverized and classified by an economically usable apparatus. From this demand, the melt-mixed toner composition must be sufficiently brittle. For this reason, when the toner composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and if an attempt is made to obtain a copy image with good resolution and gradation, for example, A fine powder having a diameter of 3 μm or less and a coarse powder having a diameter of 10 μm or more must be removed by classification, which has a drawback that the yield becomes very low. In many of these classifications, classification is performed using a conventionally known classification device. However, in the classification device using mainly wind power, coarse powder slightly larger than the target particle size due to turbulence of the wind power, etc. Such a dive was inevitable and the coarse powder could not be eliminated.

On the other hand, a chemical method for producing toner base particles or binder resin-containing particles in an aqueous medium such as a polymerization method or an emulsification dispersion method is known. As a polymerization method, a suspension polymerization method is known in which a monomer, a polymerization initiator, a colorant, a charge control agent, and the like are added to an aqueous medium containing a dispersant while stirring to form oil droplets and then polymerized. It has been. Also known is an association method in which particles obtained by emulsion polymerization or suspension polymerization are aggregated and fused.
By such a method, the toner particle size can be reduced and the particle size distribution can be made narrow, and classification may not be necessary. However, in these methods, while achieving a particle size distribution that does not require classification, when they are produced by these production methods, coarse particles are generated due to condensation and aggregation, or particles adhering to the wall surface of the pipe are peeled off. Particles are often generated.
These coarse powders are removed using a strainer in the granulation step, or the residual amount on the sieve (coarse particle quantity) after sieving 100 g of pulverized toner with a 500 mesh sieve is limited to 10 mg or less. As disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 2002-162772) disclosing such air classification technology, and further disclosed in Japanese Patent Laid-Open No. 4-121112 of Patent Document 3, vibration is applied using a ball, and the powder As in the case of pulverized toner, coarse powder is removed using a known classifier as in the case of pulverized toner. However, the strainer has a minimum particle size of 100 μm, which is at least 100 μm from the viewpoint of productivity. It was very coarse, 10 times or more, and sufficient coarse particles could not be taken.
Furthermore, classification with a decanter or the like, and after drying, a classification process similar to the pulverization method may be performed to remove coarse powder (removal of the fine powder process), but classification is an unnecessary process. This is undesirable because it causes a decrease in productivity. In addition, these processes are simply air classification based on the mass difference (pneumatic classification), or wind power classification in which the mass difference is expanded by applying acceleration (typically angular acceleration due to rotational force). Therefore, as described above, the entrainment of coarse powder of several times the target particle size cannot be completely cut, leaving a trace amount of coarse powder, which causes clogging in the gap portion in the developing machine and cannot be developed. Was generated.
For these problems, for example, in Patent Document 2 (Japanese Patent Laid-Open No. 6-19201) and the like, the shape and openings of the screen are defined, coarse powder in the sieving step, prevention of fusion due to mechanical heat generation, Although it is supposed to prevent re-aggregation due to van der Waal force, the opening of the sieve is considerably larger than the target particle size, and the coarse powder that has passed through development is low in charge due to insufficient removal of the coarse powder. Therefore, the toner was not transferred and hit the cleaning blade when the cleaning blade was removed, resulting in chipping of the cleaning blade. In addition, the developed image also has poor transferability, so that a phenomenon that the image is formed at a position different from the target image area (transfer dust), or the image that has not been transferred destroys the cleaning blade in the cleaning section. It had an adverse effect such as.

An object of the present invention is to provide a toner manufacturing method that enables coarse particles to be removed by a simple process at a stage different from the conventional one.
That is, an object of the present invention is to provide a toner manufacturing method that enables sieving on a finer screen and removes coarse powder that is slightly larger than the target particle size, thereby reliably preventing the coarse powder from entering. There is.

Above problems, (1) "least also the present invention, a granulation step of granulating the toner base particles in an aqueous medium, and a particle size distribution adjustment step of adjusting the particle size distribution of the particle size of the toner base particles In the toner production method, the particle size distribution adjusting step includes a step of centrifuging the aqueous medium slurry containing the toner base particles based on a rotating spiral blade provided inside the screen from a cylindrically fixed screen. The screen is made to collide with the screen by force to remove coarse particles in the toner base particles , and the opening diameter W (μm) of the screen is expressed as Dv (μm). And the following relationship

を満たすものであることを特徴とするトナーの製造方法」、
（２）「前記トナー粒子の体積平均粒径Ｄｖ＝３〜７μｍであることを特徴とする前記第（１）項に記載のトナーの製造方法」、
（３）「前記トナー粒子の体積平均粒径Ｄｖと、個数平均粒径Ｄｎの比（Ｄｖ/Ｄｎ）が１．０５〜１．２５であることを特徴とする前記第（１）項または第（２）項に記載のトナーの製造方法」、
（４）「前記円筒状のスクリーンを傾斜させて固定することを特徴とする前記第（１）項乃至第（３）項のいずれかに記載のトナーの製造方法」、
（５）「前記粒度分布調整工程に投入するスラリーの固形分濃度を１０〜４０ｗｔ％にすることを特徴とする前記第（１）項乃至第（４）項のいずれかに記載のトナーの製造方法」、
（６）「前記粒度分布調整工程に投入するスラリーの粘度を５ｃｐｓ〜３００ｃｐｓとすることを特徴とする前記第（１）項乃至第（５）項のいずれかに記載のトナーの製造方法」、
（７）「スクリーンの開口径が３〜２８μｍであることを特徴とする前記第（１）項乃至第（６）項のいずれかに記載のトナーの製造方法」、
（８）「前記粒度分布調整工程は、前記スラリーを前記スクリーンに間歇的に衝突させるものであることを特徴とする前記第（１）項乃至第（７）項のいずれかに記載のトナーの製造方法」、
（９）「前記粒度分布調整工程は、前記スラリーを前記スクリーンに衝突させることにより、該スクリーンを振動させ粗粒子を除去する工程であることを特徴とする前記第（１）項乃至第（８）項のいずれかに記載のトナーの製造方法」、により達成される。

A toner production method characterized by satisfying "
(2) “The toner production method according to (1) above, wherein the volume average particle diameter Dv of the toner particles is 3 to 7 μm”,
(3) “The ratio of the volume average particle diameter Dv of the toner particles to the number average particle diameter Dn ( Dv / Dn ) is 1.05 to 1.25”, The method for producing the toner according to (2) ”,
( 4 ) "The method for producing toner according to any one of (1) to ( 3 ) above, wherein the cylindrical screen is fixed while being inclined",
( 5 ) “Production of toner according to any one of items (1) to ( 4 ), wherein the solid content concentration of the slurry to be added to the particle size distribution adjusting step is 10 to 40 wt%. Method",
( 6 ) "The method for producing a toner according to any one of (1) to ( 5 ) above, wherein the viscosity of the slurry to be added to the particle size distribution adjusting step is 5 cps to 300 cps",
( 7 ) "The method for producing a toner according to any one of (1) to ( 6 ) above, wherein the opening diameter of the screen is 3 to 28 µm",
( 8 ) The toner according to any one of (1) to ( 7 ), wherein the particle size distribution adjusting step causes the slurry to intermittently collide with the screen. Production method",
( 9 ) "The particle size distribution adjusting step is a step of vibrating the screen to remove coarse particles by causing the slurry to collide with the screen. ( 9 ) to ( 8 ) The method for producing a toner according to any one of the items).

  As will be apparent from the following detailed and specific description, the present invention enables sieving with a finer screen and enables removal of coarse powder slightly larger than the target particle size, thus ensuring the entry of coarse powder. An extremely excellent effect is provided that a method for producing a toner for preventing the above is provided.

  FIG. 1 is a schematic cross-sectional view of an example of a wet classifier used in the particle size distribution adjusting step (sieving step) of the present invention. In the classifying device of this example, the blade (12) rotates at a high speed inside the cylindrical screen (11). The blade (12) is fixed to the rotating shaft (12a), and the rotating shaft (12a) is disposed in the axial direction at the center of the inside of the cylindrical screen (11). It is supported by a non-bearing and is given rotational force by power means. The rotating shaft (12a) in the apparatus of this example is provided with a slurry supply port (13) for supplying the material to be classified into the cylindrical screen (11). In the wet classifier of this example, the classified toner is discharged from the toner collecting section (14), and the coarse particles are discharged from the coarse particle outlet (15). The cylindrical screen (11) of the classifying device of this example is not horizontally disposed, but is slightly inclined so that the slurry supply port (13) side is high and becomes lower toward the opposite end. Yes. However, it is needless to say that the classifying device according to the present invention is not essential to be arranged in such an inclination, and even if it is a horizontal type (horizontal direction arrangement type), it is a vertical type (upright with a rotating axis direction standing up). Type).

  In the present invention, a screen having an opening diameter of 3 to 100 μm can be used as the mesh size (mesh opening diameter) of the cylindrical screen (11), and the viscosity of the slurry, the solid content in the slurry, etc. Although it depends on conditions, it is preferably 3 to 36 μm, and more preferably 3 to 28 μm.

  According to the classifying device of such a configuration example, intermittent vibration is given to the screen (11) as the blades (12) rotate, and the slurry is completely discharged into the screen surface. In combination, it is understood that vibration is sufficient and separation is promoted, and the period of vibration is the number of rotations of the rotating shaft (12a), the angle and height of the rotating blade (12), the gradient, etc. It is understood that it depends on.

Further, in the present invention, the blade (12) and the slurry supply port (13) are not necessarily limited to those shown in FIG.
2 to 4 show photographs of still another apparatus according to the present invention. In the apparatus of FIG. 2, in FIG. 2, the slurry supply port is arranged horizontally, and the wing shape is spiral. However, it does not deny other shapes and structures of the blades. 3 and 4 are photographs of a state in which the periphery of the spiral portion located at the center of FIG. 2 is surrounded by a mesh. A screen that looks like a white cylinder is a screen. A slurry (an aqueous dispersion of base particles) is placed inside the screen, and the slurry that has passed through the opening of the screen is collected by sieving and used as a toner.

  The slurry supplied from the slurry supply port (13) collides with the blade (12) to be agglomerated, collides with the screen (11) by centrifugal force, and the toner having a particle size below the mesh passes to the outside. The coarse particles are collected by the toner collecting part (14) and move inside the screen to be discharged from the coarse particle discharge port (15). Further, the screen (11) is clogged due to the vibration of the blade (12), which causes the slurry to collide with the screen irregularly due to the centrifugal force, so that the screen (11) strikes and vibrates with the rotation of the blade. Can be prevented.

  The characteristic of the classifier used in the present invention is that, first of all, classification can be performed in a slurry state. When used in the form of a slurry, it does not occur due to agglomeration due to charging, or agglomeration due to charging, so that agglomeration due to electrification does not occur. Aggregation can be loosened, and the toner can be sufficiently deaggregated by the rotating blades. Therefore, productivity reduction and clogging hardly occur due to aggregation.

  Another feature is that a strong centrifugal force is applied to a slurry containing mother particles (also referred to as mother particles, hereinafter the same) to pass through a screen. In the conventional apparatus, toner is passed through the screen only by gravity in the dry type, and in the case of slurry, the productivity cannot be increased by using a screen fixed to the flow rate. I couldn't. However, in the apparatus used in the present invention, since the toner is given a stronger force to pass through the screen, it can be used on a screen having an opening that is almost the same as the toner particle size.

  The blade | wing (12) used for the classification apparatus in this invention may be attached to the rotating shaft (12a), for example, and the rotation speed is the range of about 500-2000 rpm. Any known screen may be used, but a screen made of a resin such as polyester or amide is preferable because the opening can be made very small and a minute amount of vibration can be applied.

  The classifying device according to the present invention can be used for sieving toner having a volume average particle diameter of about 3 to 15 μm, and is particularly effective for sieving toner having a small particle diameter of about 3 to 7 μm. Can demonstrate. These toners usually use a screen having an opening of about 30 to 50 μm for classification of coarse particles and are screened by a dry method. However, the classifying apparatus in the present invention is not limited to this, and the average particle diameter Dv is 5 μm. It can cope with classification enough. For this reason, it is possible to screen coarse particles that are 2 to 4 times the target particle size Dv, and it is possible to remove the coarse powder that is a little larger than the target particle size and has been a problem.

The toner in the toner production method of the present invention is preferably applied to a chemical method toner in which a liquid is used in the preparation of base particles, and in particular, a granulation step of granulating at least in an aqueous system, a toner base particle or toner powder system More preferably, the present invention is applied to the production of a toner having a particle size distribution adjusting step for adjusting the particle size distribution, and the external addition step of externally adding to the granulated toner base particles.
Although it is possible to use the particles obtained by the pulverization method, it is not preferred to bother to make a slurry and increase the number of processing steps. It is preferable to add a classification step to the toner granulated in the aqueous system.

  The toner particle diameter is preferably 3 to 7 μm in volume average particle diameter Dv. Even if the particle size exceeds 7 μm, sieving is possible with this method, but even with known sieving, the effect does not change and there is no need to stick to this method. In addition, there is a possibility that the thickness is less than 3 μm, but the influence of the coarse powder in the case of 3 μm is not known and is unknown.

  The ratio of the volume average particle diameter Dv to the number average particle diameter Dn, Dv / Dn, is preferably 1.05 to 1.25. When Dv / Dn exceeds 1.25, the amount of clogging in the sieving process increases and productivity is unfavorable.

  Furthermore, in this invention, it is preferable that the viscosity of the slurry thrown into a particle size distribution adjustment process is 5 cps-300 cps. Since the aqueous medium obtained by the granulation step of granulating the toner base particles, the slurry can be used as it is or preferably after being slightly diluted before being introduced into the particle size distribution adjustment step.

  The toner production method of the present invention is preferably applied to a chemical method toner in which a liquid is used in the preparation of base particles, and in particular, a suspension in which an oil phase is emulsified, suspended or aggregated in an aqueous medium to form toner base particles. It is preferably applied by a turbid polymerization method, an emulsion polymerization method, a polymer suspension method or the like. In particular, the toner is preferably a toner having a small particle diameter and a nearly spherical toner particle. This includes not necessarily perfectly spherical toner particles, but deformed toner base particles for some deformation from the particle size. As a method for producing such toner of toner particles, an oil phase containing a binder resin component and / or a precursor thereof is emulsified, suspended, coagulated or aggregated in an aqueous medium to form toner base particles. There are a turbid polymerization method (including partial polymerization such as polymer molecular chain extension reaction, oligomer component polymerization, crosslinking and curing reaction, the same applies hereinafter), emulsion polymerization method, polymer suspension method and the like. Hereinafter, examples of these toner production methods and materials, additives, etc. used in the production methods will be described.

(Suspension polymerization method)
A colorant, a release agent and the like are dispersed in an oil-soluble polymerization initiator and a polymerizable monomer, and then emulsified and dispersed by an emulsification method described later in an aqueous medium containing a surfactant and other solid dispersants. Thereafter, after the polymerization reaction to form particles, a wet treatment for attaching the inorganic fine particles A to the toner particle surfaces in the present invention may be performed. At that time, it is preferable to treat the toner particles from which excess surfactant and the like are removed by washing.
Polymerizable monomers such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, acrylamide, methacrylamide, diacetone Functional groups can be introduced on the surface of toner particles by using a part of acrylate or methacrylate such as acrylamide or these methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate and other amino groups. .
Further, by selecting a dispersant having an acid group or a basic group as a dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

(Emulsion polymerization aggregation method)
A water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by an ordinary emulsion polymerization technique. Separately, a dispersion in which a colorant, a release agent and the like are dispersed in an aqueous medium is prepared, and after mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. Thereafter, a wet treatment of inorganic fine particles A described later may be performed. A functional group can be introduced on the surface of the toner particles by using a latex similar to the monomer that can be used in the suspension polymerization method.

(Polymer suspension method)
As an aqueous medium used in the polymer suspension method, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.
In the oil phase of the toner composition, a colorant such as resin, prepolymer and pigment, a release agent, a charge control agent and the like are dissolved or dispersed in a volatile solvent.
An oil phase composed of a toner composition is dispersed in an aqueous medium in the presence of a surfactant, a solid dispersant and the like, and a prepolymer is reacted to form particles. Thereafter, a wet treatment of inorganic fine particles A described later may be performed.

  In order to introduce a functional group into the toner particles, a copolymer with a monomer having a functional group used in the suspension polymerization method, or a functional group of an acid group as an acid monomer in the case of a polyester resin is used. It can be obtained by using one having three or more or esterifying the terminal hydroxyl group of the obtained polyester resin with a compound having a plurality of acid groups. Further, as a dispersion stabilizer in an aqueous medium, which will be described later, an acid group-containing surfactant, polar polymer, organic or inorganic resin fine particles can be used, and an acid group can be introduced by remaining on the toner particle surface. Examples of the acid group include a carboxyl group, a sulfone group, a sulfonic acid group, and a phosphoric acid group.

  The toner of the present invention more preferably dissolves at least a compound having an active hydrogen group, a polymer having a site capable of reacting with the active hydrogen group, a polyester, a colorant, and a release agent in an organic solvent. Alternatively, it is a toner obtained by subjecting a dispersed toner material liquid to a crosslinking and / or elongation reaction in an aqueous medium. Hereinafter, the constituent material and the manufacturing method of the toner will be described.

(Modified polyester)
The toner according to the present invention contains modified polyester (I) as a binder resin. The modified polyester (I) refers to a state in which a bonding group other than an ester bond is present in the polyester resin, or resin components having different configurations are bonded to the polyester resin by a covalent bond, an ionic bond, or the like. Specifically, the polyester terminal is modified by introducing a functional group such as a carboxylic acid group or an isocyanate group that reacts with a hydroxyl group (active hydrogen group thereof) and then reacting with an active hydrogen-containing compound to modify the polyester terminal. .

  Examples of the modified polyester (I) include urea-modified polyester obtained by a reaction between a polyester prepolymer (A) having an isocyanate group and amines (B). As the polyester prepolymer (A) having an isocyanate group, a polyester having a polycondensate of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC) and having an active hydrogen group is further added to a polyvalent isocyanate compound (PIC). And those reacted with. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

The urea-modified polyester is produced as follows.
Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO) and trihydric or higher polyhydric alcohol (TO). (DIO) alone or a mixture of (DIO) and a small amount of (TO) preferable. Examples of the dihydric alcohol (DIO) 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 diols (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 bisphenol (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyhydric alcohol (TO) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC). (DIC) alone and (DIC) with a small amount of (TC) Mixtures are preferred. Divalent carboxylic acids (DIC) 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) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polyhydric carboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.). The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

Examples of the polyvalent isocyanate compound (PIC) 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.); isocyanates; Those blocked with caprolactam or the like; and combinations of two or more of these.
The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.

The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. . If it is less than 0.5 wt%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40 wt%, the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

Next, as amines (B) to be reacted with the polyester prepolymer (A), a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), an amino mercaptan (B4) ), Amino acid (B5), and amino acid block of (B1) to (B5) (B6).
Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diamine cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like. Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. As (B6) which blocked the amino group of (B1) to (B5), ketimine compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of (B1) to (B5), And oxazolidine compounds. Among these amines (B), preferred are (B1) and a mixture of (B1) and a small amount of (B2).

The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). Is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.
The urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

The modified polyester (I) used in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester (I) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. The peak molecular weight at this time is preferably 1000 to 10000. When the molecular weight is less than 1000, the elongation reaction hardly occurs, the elasticity of the toner is small, and as a result, the resistance to hot offset deteriorates. On the other hand, when it exceeds 10,000, the problem in production becomes high in the deterioration of fixability, particle formation and pulverization. The number average molecular weight of the modified polyester (I) is not particularly limited when the unmodified polyester (II) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. In the case of (I) alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.
In the crosslinking and / or extension reaction between the polyester prepolymer (A) and the amines (B) to obtain the modified polyester (I), a reaction terminator is used as necessary to adjust the molecular weight of the resulting urea-modified polyester. be able to. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

(Unmodified polyester)
In the present invention, not only the modified polyester (I) is used alone, but also the unmodified polyester (II) can be contained as a binder resin component together with the (I). By using (II) in combination, the low-temperature fixability and the glossiness when used in a full-color apparatus are improved, which is preferable to single use. Examples of (II) include polycondensates of polyhydric alcohol (PO) and polyvalent carboxylic acid (PC) similar to the polyester component of (I), and preferred ones are also the same as (I). . Further, (II) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example. It is preferable that (I) and (II) are at least partially compatible in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (I) and (II) preferably have similar compositions. When (II) is contained, the weight ratio of (I) to (II) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. When the weight ratio of (I) is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (II) is 1000-10000 normally, Preferably it is 2000-8000, More preferably, it is 2000-5000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (II) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (II) is preferably from 1 to 5, more preferably from 2 to 4. Since a high acid value wax is used as the wax, the low acid value binder leads to electrification and high volume resistance, so that it is easy to match the toner used for the two-component developer.

  The glass transition point (Tg) of the binder resin is usually 35 to 70 ° C, preferably 55 to 65 ° C. If the temperature is lower than 35 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the toner of the present invention tends to have good heat storage stability even when the glass transition point is low, as compared with known polyester-based toners. Show.

(Coloring agent)
As the colorant, known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, Yellow lead, Titanium yellow, Polyazo yellow, Oil yellow, Hansa yellow (GR, A, RN, R), Pigment yellow L, Benzidine yellow (G, GR), Permanent yellow (NCG), Vulcan fast yellow (5G, R) ), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Se Red, parachlor ortho nitroa Phosphorus Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thio Indigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Po Azo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalo Anine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant can also be used as a master batch combined with a resin. As a binder resin to be kneaded with the production of the master batch or the master batch, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene or the like, or a copolymer of these and a vinyl compound, Polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

(Charge control agent)
Known charge control agents can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus Simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, metal salt of salicylic acid derivative, and the like. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group include polymer compounds having a functional group such as a carboxyl group. Of these, substances that control the negative polarity of the toner are particularly preferably used.

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

(Release agent)
As a release agent, a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface. The effect on high temperature offset is exhibited without applying a release agent such as oil. Examples of such a wax component include the following. Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, and paraffin, microcrystalline, And petroleum waxes such as petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones, and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. .
The charge control agent and the release agent can be melt-kneaded together with the master batch and the binder resin, and of course, they may be added when dissolved and dispersed in the organic solvent.

In common with any of these toner production methods, the granulating step according to the present invention can be performed after granulation.
This step is preferably performed after the toner particles are formed and the used surfactant and the like are removed by washing.
Excess surfactant present in water is removed by solid-liquid separation operations such as filtration and centrifugation, and the resulting slurry is redispersed in an aqueous medium.
At this time, the viscosity of the aqueous phase is preferably 5 cps to 300 ps, more preferably 5 cps to 100 ps. Even if it is less than 5 cps, the fine particles can be classified, but it is considered that the solid content is low, and the productivity may be deteriorated.
Further, if it exceeds 300 cps, the viscosity of the slurry is high, and particularly when a screen with fine openings is used, it becomes difficult for the slurry to pass through the screen itself, resulting in poor productivity.
The solid content concentration of the fine particles in the slurry is preferably 10 wt% to 40 wt%. Also for the same reason as above, when 10 wt% or less, the productivity is poor, and when it is 40 wt% or more, the viscosity is increased, and further, the aggregation of fine particles seen in a dry method is not sufficiently unraveled, resulting in poor efficiency. From that.

  After these fine particles are prepared, classified and dried, an external additive may be added to the obtained fine particles.

(External additive)
As the external additive, inorganic fine particles such as a metal oxide, a metal carbide, a metal nitride, and a metal carbonate can be used. Specifically, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide Cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like.
Furthermore, organic fine particles can be used as the external additive. Specifically, polymer-based fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation systems such as silicone, benzoguanamine, and nylon, heat Polymer particles made of a curable resin may be used.

Further, the external additive used in the toner of the present invention can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents that may contain alkyl groups, fluorinated alkyl groups, titanate coupling agents, coupling agents such as aluminum coupling agents, silicone oils, higher fatty acids, fluorine compounds and the like are preferable surface treatment agents. Can be mentioned.
In particular, a silane coupling agent which is an example of a coupling agent is used for improving the degree of hydrophobicity and fluidity. Specifically, as the silane coupling agent, chlorosilane, alkoxysilane, silazane, special silylating agent and the like can be used, and alkoxysilane is more preferable. Examples of the alkoxysilane include vinyltrimethoxysilane, propyltrimethoxysilane, I-butyltrimethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, and n-dodecyltrimethoxy. A silane etc. can be mentioned.
As the silicone oil, polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane or the like can be used, and fluorine-containing siloxane or the like may be used.
The fluorine compound is preferably an organosilicon compound having a fluorine atom, such as 3,3,4,4,5,5,6,6,6-nonafluorohexyltrichlorosilane, 3,3,3-trifluoropropyl. Trimethoxysilane, methyl-3,3,3-trifluoropropyldichlorosilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,4,4,5,5,6,6,6- Nonafluorohexylmethyldichlorosilane and the like can be mentioned.
Further, examples of higher fatty acids include stearic acid, oleic acid, palmitic acid, and linoleic acid, and metal salts of these higher fatty acids may be used. Specific examples include zinc stearate, aluminum stearate, copper stearate, magnesium stearate, calcium stearate, zinc oleate, manganese oleate, zinc palmitate, zinc linoleate, and calcium linoleate.

In the toner of the present invention, the external additive is dry mixing in which inorganic / organic fine particles such as hydrophobic silica fine powder are externally added in a mixer together with a mixed medium such as glass beads. For mixing external additives, a general mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. The external additive is appropriately added at the beginning or in the middle. Examples of the mixer include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, and a Henschel mixer.
Further, wet mixing is used in which the toner is externally added in a water-based and / or alcohol-based solvent. In this wet mixing, an external additive is added to the toner dispersed in an aqueous solvent and adhered to the toner surface. Further, when this external additive has been subjected to a hydrophobic treatment, it may be dispersed after a small amount of alcohol or the like is used in combination to lower the interfacial tension to facilitate wetting. Thereafter, the solvent can be removed by heating and fixed to prevent desorption. As a result, the external additive can be uniformly dispersed on the toner surface. Further, when the toner and the external additive are dispersed in the aqueous solvent, the external additive can be uniformly dispersed on the toner surface by adding the surfactant. Further, it is preferable to use an external additive or a surfactant having a polarity opposite to that of the toner.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following, “part” means part by weight, and “%” means weight%.
Hereinafter, a specific method for producing the toner according to the present invention will be described.

<Synthesis of resin fine particle emulsion>
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 80 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate, 12 parts of butyl thioglycolate and 1 part of ammonium persulfate were added and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt) A dispersion was obtained. This is designated as [fine particle dispersion 1]. The volume average particle size of the [fine particle dispersion 1] measured by a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corp.) was 120 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 42 ° C., and the weight average molecular weight was 30,000.

<Preparation of aqueous phase>
990 parts of water, 65 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (ELEMINOL MON-7 manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred to give a milky white color Obtained liquid. This is designated as [Aqueous Phase 1].

<Synthesis of non-reactive resin>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 8 hours at normal pressure, and further react for 5 hours at 10-15 mmHg reduced pressure, then add 44 parts of trimellitic anhydride to the reaction vessel at 180 ° C at normal pressure. It reacted for 2 hours and obtained polyester (unmodified polyester resin 1) of non-reactive resin [A]. The non-reactive resin [A] had a number average molecular weight of 2500, a weight average molecular weight of 6700, Tg of 43 ° C., and an acid value of 24.

<Synthesis of intermediate polyester>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.

[Synthesis of Modified Polyester Resin (hereinafter referred to as “Prepolymer 1”) Reactive with Compounds Having Active Hydrogen Groups]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 410 parts of the above [intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate were added and reacted at 100 ° C. for 5 hours. ] Was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

<Synthesis of ketimine>
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

<Synthesis of master batch>
1200 parts of water, 40 parts of carbon black (manufactured by Cabot, Regal 400R), 60 parts of the non-reactive resin [A] and 30 parts of water are further added and mixed with a Henschel mixer (manufactured by Mitsui Mining). Was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

(Fine particle preparation example 1)
<Creation of oil phase>
In a container equipped with a stir bar and a thermometer, 400 parts of the non-reactive resin [A], 110 parts of carnauba wax, and 947 parts of ethyl acetate are charged, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. After that, it was cooled to 30 ° C. at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed is 1 kg / hr, a disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. The wax was dispersed under the conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of the non-reactive resin [A] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1]. The solid content concentration of [Pigment / Wax Dispersion 1] (130 ° C., 30 minutes) was 50%.

<Emulsification>
[Pigment / Wax Dispersion 1] 648 parts, [Prepolymer 1] 154 parts, [Ketimine Compound 1] 10.2 parts are put in a container and 1 at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika). After mixing for 1 minute, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at a rotation speed of 10,000 rpm for 20 minutes to obtain [Emulsion Slurry 1].
That is, it is dispersed in an aqueous medium containing resin fine particles and an elongation reaction is performed.

<Desolvent>
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

<Washing>
[Dispersion Slurry 1] After filtering 100 parts 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): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): 300 parts of ion exchanged water was added to the filter cake of (3), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered twice to obtain a cake ([mother A filter cake of fine particles A] was obtained.

<Sieving treatment>
(1): Add 100 parts of ion-exchanged water to the filter cake of [mother fine particles A], and mix with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes).
When the solid content concentration and the slurry viscosity were measured, the solid content concentration was 30% and the slurry viscosity was 89 cps.
When the particle size of the particles was measured by Coulter Multisizer III, the particles were Dv = 4.8 μm and Dv / Dn = 1.15 (fine particles A).
These fine particles A (slurry) were configured as shown in FIG. 1 and sieved using a wet sieving apparatus having an opening of 10 μm (material nylon) and a total screen area of 3140 cm ² .

<Drying / Mixing>
The cake obtained by filtering and separating the fine particles obtained through the sieve was dried at 45 ° C. for 48 hours using a circulating air dryer, and sieved with a mesh of 75 μm to obtain [Toner Base Particle 1].
To 100 parts of the obtained toner base particles, 1.5 parts of hydrophobic silica H2000 (manufactured by Clariant) as an external additive is added and mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). 1] was produced.

  [Toner 2] was produced in the same manner as in Example 1 except that the sieve opening was changed to 15 μm (polyester material).

  The ion-exchanged water before sieving was changed from 100 parts in Example 1 to 200 parts to obtain mother fine particles B. When the same procedure was performed as in slurry 1, the solid content concentration was 15% and the slurry viscosity was 43 cps. This was processed in the same manner as in Example 1 to obtain [Toner 3].

After introducing 5 parts by mass of Na ₃ PO ₄ into 500 parts by mass of ion-exchanged water and heating to 60 ° C., a Claremix high-speed stirrer (manufactured by MTechnic Co., Ltd., peripheral speed 22 m / s) is installed and stirred. did. To this, an aqueous solution in which ₂ parts by mass of CaCl ₂ was dissolved in 15 parts by mass of ion-exchanged water was quickly added to obtain an aqueous dispersion medium containing Ca ₃ (PO ₄ ) ₂ .
・ Polymerizable monomer Styrene 85 parts by mass
・ N-butyl acrylate 20 parts by mass
-Colorant C.I. I. Pigment Blue 15: 3 7.5 parts by mass
・ Charge control agent E-88 (manufactured by Orient Chemical Co., Ltd.) 1 part by mass
・ Polar resin Saturated polyester 5 parts by mass
(Acid value 10 mgKOH / g, peak molecular weight: 7,500)
・ Release agent Ester wax
(Maximum endothermic peak temperature in DSC 72 ° C.) 15 parts by mass
-Clayton APA (manufactured by Southern Clay Products) 15 parts by mass On the other hand, the above materials were heated to 60 ° C. and stirred to uniformly dissolve or disperse each material in the polymerizable monomer. To this was added 3 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator to prepare a polymerizable monomer composition.
The polymerizable monomer composition is introduced into the aqueous dispersion medium, and then at a temperature of 60 ° C. and N ₂ atmosphere for 15 minutes with a CLEARMIX high-speed stirrer (manufactured by M Technique, peripheral speed 22 m / s). Stirring to produce particles of the polymerizable monomer composition in the aqueous dispersion medium. After the dispersion, the stirring apparatus was stopped and introduced into a polymerization apparatus equipped with a full zone stirring blade (manufactured by Shinko Pantech Co., Ltd.). In the polymerization apparatus 11, the polymerizable monomer was reacted for 5 hours while stirring the stirring blade at the maximum peripheral speed of stirring: 3 m / s in a N ₂ atmosphere at a temperature of 60 ° C. Thereafter, the temperature was raised to 80 ° C., and the polymerizable monomer was further reacted for 5 hours. After completion of the polymerization reaction, 100 parts of the resulting slurry was filtered 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): 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered twice to obtain a cake ([mother A filter cake of fine particles C] was obtained.

<Sieving treatment>
100 parts of ion-exchanged water is added to the filter cake of [base fine particles C] and mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes).
When the solid content concentration and the slurry viscosity were measured, the solid content concentration was 30% and the slurry viscosity was 89 cps.
When the particle size of the particles was measured by Coulter Multisizer III, the particles were Dv = 4.9 μm Dv / Dn = 1.24.
The slurry of FIG. 1 was subjected to sieving using a wet sieving apparatus having an aperture of 10 μm (material nylon) and a total screen area of 3140 cm ² .

<Drying and mixing>
The cake obtained by filtering and separating the fine particles obtained through the sieve was dried at 45 ° C. for 48 hours using a circulating drier and sieved with a mesh of 75 μm to obtain [Toner Base Particle 4].
To 100 parts of the obtained toner base particles, 1.5 parts of hydrophobic silica H2000 (manufactured by Clariant) as an external additive is added and mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). 4] was produced.

  [Toner 5] was prepared in the same manner as in Example 1 except that the emulsifying conditions of Example 1 were changed from 20 minutes to 10 minutes to form mother fine particles D.

-Preparation of colorant dispersion (1)-
・ 125 parts of carbon black (Degussa: Printex35)
・ Azisper PB821 (Azinomoto Finetech) 18.8 parts
-Ethyl acetate (Wako Pure Chemical Industries, Ltd .: special grade) 356.2 parts
The above was dissolved / dispersed using Ultraviscomyl (manufactured by Imex) to prepare a colorant dispersion (1) in which a colorant (black pigment) was dispersed.

(Preparation of release agent dispersion)
-Preparation of release agent dispersion (1) (wax component A)-
Carnauba wax 30 parts (melting point: 83 ° C., acid value 8 mgKOH / g, saponification value 80 mgKOH / g)
・ 270 parts of ethyl acetate (Wako Pure Chemical Industries, Ltd .: special grade)
The above was wet pulverized using an ultra visco mill (manufactured by IMEX Co., Ltd.) to prepare a release agent dispersion (1).
-Preparation of a layered compound modified with an organic cation (a deforming agent dispersion A)-
・ Clayton APA (Southern Clay Products) 30 parts
・ 270 parts of ethyl acetate (Wako Pure Chemical Industries, Ltd .: special grade)
The above was wet pulverized using Ultra Visco Mill (manufactured by Imex Co., Ltd.) to prepare a deforming agent dispersion A.
・ Polyester (1)
350 parts of a polyester resin comprising a bisphenol A propylene oxide adduct, a bisphenol A ethylene oxide adduct, a terephthalic acid derivative (Mw 50,000 Mn 3,000, acid value 15 mg KOH / g, hydroxyl value 27 mg KOH / g Tg 55 ° C., softening point 112 ° C.) Dispersion (1) 237 parts · Release agent dispersion (1) 72 parts · Release agent dispersion (2) 304 parts · Hydrophobic silicon oxide fine particles (Aerosil R972) 17.8 parts It stirred well until it became uniform (this liquid was made into A liquid).
On the other hand, 100 parts of calcium carbonate dispersion in which 40 parts of calcium carbonate fine particles were dispersed in 60 parts of water, 200 parts of 1% aqueous solution of Serogen BS-H (Daiichi Kogyo Seiyaku Co., Ltd.), and 157 parts of water were added. K. The mixture was stirred for 3 minutes using a homodisper fmodel (manufactured by Primix) (this solution was designated as solution B). In addition, T.W. K. Using a homomixer mark2 fmodel (manufactured by Primix), 345 parts of the solution B and 250 parts of the solution A were stirred at 10,000 rpm for 2 minutes to suspend the mixed solution, and then propeller type at room temperature and normal pressure for 48 hours. The solvent was removed by stirring with a stirrer. Next, hydrochloric acid was added to remove calcium carbonate.
After filtering 100 parts of the resulting slurry 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.
Add 300 parts of ion-exchanged water to the filter cake of (1), mix with a TK homomixer (rotation speed 12,000 rpm for 10 minutes), and then filter twice. Filter cake).

<Sieving treatment>
(1): Add 100 parts of ion-exchanged water to the filter cake of [mother fine particles E], and mix with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes).
When the solid content concentration and the slurry viscosity were measured, the solid content concentration was 30% and the slurry viscosity was 89 cps.
When the particle size of the particles was measured by Coulter Multisizer III, the particles were Dv = 6.1 μm Dv / Dn = 1.17.
The slurry was sieved using a wet sieving apparatus having the configuration of FIG. 1 and a mesh opening of 15 μm (material polyester) and a total screen area of 3140 cm ² .

<Drying / Mixing>
The cake obtained by filtering and separating the fine particles obtained through the sieve was dried at 45 ° C. for 48 hours using a circulating air dryer, and sieved with a mesh of 75 μm to obtain [Toner Base Particle 6].
To 100 parts of the obtained toner base particles, 1.5 parts of hydrophobic silica H2000 (manufactured by Clariant) as an external additive is added and mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). 6] was produced.

(Creation of toner 7)
229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propion oxide 3-mole adduct, 208 parts of terephthalic acid, 46 parts of adipic acid and dibutyltin oxide 2 parts were added and reacted at 230 ° C. under normal pressure for 8 hours. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added to the reaction vessel, and reacted at 180 ° C. for 2 hours under normal pressure, [unmodified polyester resin 2] Was synthesized.
The obtained [unmodified polyester resin 2] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a glass transition temperature of 43 ° C., and an acid value of 25 mgKOH / g.
1200 parts of water, 470 parts of carbon black Printex 35 (manufactured by Dexa; DBP oil absorption = 42 ml / 100 mg, pH = 9.5) and 530 parts of [unmodified polyester resin 2] were used using a Henschel mixer (manufactured by Mitsui Mining). And mixed. The resulting mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare [Masterbatch 2].
In a reaction vessel equipped with a stirrer and a thermometer, 378 parts of [Non-modified Polyester Resin 2], 110 parts of carnauba wax, and 947 parts of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After maintaining the time, it was cooled to 30 ° C. over 1 hour. Next, 500 parts of a master batch and 500 parts of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain a raw material solution.
1324 parts of the obtained raw material solution was transferred to a reaction vessel, and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill Ultra Visco Mill (manufactured by Imex Co., Ltd.). 3 passes under the condition of 6 m / sec. I. Pigment Red and carnauba wax were dispersed to obtain a wax dispersion.

Next, 1324 parts of a 65 wt% ethyl acetate solution of unmodified polyester resin was added to the wax dispersion. 1.0 part of Kraton APA (manufactured by Southern Clay Products) is added to 200 parts of a dispersion obtained by one pass using Ultraviscomil under the same conditions as described above. K. Using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred at 7000 rpm for 60 minutes to obtain a toner material dispersion.
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester resin was synthesize | combined.
The obtained intermediate polyester resin had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition temperature of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g.

Next, 410 parts of the intermediate polyester resin, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Was synthesized. The free isocyanate content of the obtained prepolymer was 1.53% by weight.
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound. The amine value of the obtained ketimine compound was 418 mgKOH / g.
In a reaction vessel, 749 parts of a dispersion of toner material, 115 parts of a prepolymer and 2.9 parts of a ketimine compound are charged and mixed at 5,000 rpm for 1 minute using a TK homomixer (manufactured by Tokushu Kika). A mixture was obtained.

In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 11 parts of reactive emulsifier (sodium salt of sulfuric acid ester of methacrylic acid ethylene oxide adduct), Eleminol RS-30 (manufactured by Sanyo Chemical Industries), styrene 83 Parts, 83 parts of methacrylic acid, 110 parts of butyl acrylate and 1 part of ammonium persulfate were stirred at 400 rpm for 15 minutes to obtain an emulsion. The emulsion was heated, heated to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% by weight aqueous ammonium persulfate solution was added and aged at 75 ° C. for 5 hours to prepare a resin particle dispersion.
The volume average particle size of the resin particles contained in the obtained resin particle dispersion was measured using a particle size distribution measuring apparatus Microtrac Ultra Fine Particle Size Distribution Meter UPA-EX150 (manufactured by Nikkiso Co., Ltd.) using a laser Doppler method. However, it was 105 nm. Further, a part of the resin particle dispersion was dried to isolate the resin, and the glass transition temperature of the resin was measured. As a result, it was 59 ° C. and the weight average molecular weight was 150,000.

990 parts of water, 83 parts of resin particle dispersion, 37 parts of a 48.5% by weight aqueous solution of dodecyl diphenyl ether disulfonate, Eleminol MON-7 (manufactured by Sanyo Kasei Kogyo Co., Ltd.), 1% by weight aqueous solution of sodium carboxymethylcellulose polymer dispersant 135 parts of BS-H-3 (Daiichi Kogyo Seiyaku Co., Ltd.) and 90 parts of ethyl acetate were mixed and stirred to obtain an aqueous medium.
To 1200 parts of the aqueous medium, 867 parts of the oil phase mixed liquid was added and mixed for 20 minutes at 13000 rpm using a TK homomixer to prepare a dispersion (emulsified slurry).

Next, the emulsified slurry was charged into a reaction vessel in which a stirrer and a thermometer were set, and after removing the solvent at 30 ° C. for 8 hours, aging was performed at 45 ° C. for 4 hours to obtain a dispersed slurry.
When the obtained dispersion slurry was measured using Multisizer III (manufactured by Beckman Coulter, Inc.), Dv was 3.3 μm and Dv / Dn1.25.
After 100 parts by weight of the dispersion slurry was filtered under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, mixed at 12000 rpm for 10 minutes using a TK homomixer, and then filtered. The obtained filter cake was added with 10% by weight phosphoric acid to adjust the pH to 3.7, mixed at 12000 rpm for 10 minutes using a TK homomixer, and then filtered.

  Furthermore, after adding 300 parts of ion exchange water to the obtained filter cake, mixing for 10 minutes at 12000 rpm using a TK type homomixer, the operation of filtering was performed twice, and the filter cake (filtering of [mother fine particles H] was performed. Cake).

<Sieving treatment>
(1): Add 100 parts of ion-exchanged water to the filter cake of [mother fine particles H] and mix with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes).
When the solid content concentration and the slurry viscosity were measured, the solid content concentration was 30% and the slurry viscosity was 89 cps.
The slurry of FIG. 1 was subjected to sieving using a wet sieving apparatus having a mesh size of 10 μm (material polyester) and a screen total area of 3140 cm ² .

<Drying / Mixing>
The cake obtained by filtering and separating the fine particles obtained through the sieve was dried at 45 ° C. for 48 hours using a circulating air dryer, and sieved with a mesh of 75 μm to obtain [Toner Base Particle 7].
To 100 parts of the obtained toner base particles, 1.5 parts of hydrophobic silica H2000 (manufactured by Clariant) as an external additive is added and mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). 7] was produced.
[Comparative Example 1]

  [Toner 8] was produced in the same manner as in Example 1 except that the sieve opening was 25 μm (polyester material).

[Comparative Example 2]
[Toner 9] was produced in the same manner as in Example 6 except that the opening of the sieving apparatus was changed from 75 μm to 25 μm (material polyester) with the mother fine particles E used in Example 6.

[Comparative Example 3]
[Toner 10] was produced in the same manner as in Example 6 except that the mesh size of the sieving apparatus was changed from 75 μm to 10 μm (material nylon) with the mother fine particles E used in Example 6. The product was not obtained due to severe clogging.

[Comparative Example 4]
30 parts of ion-exchanged water were further added to the mother fine particles E used in Example 6, the solid content concentration was 20%, and the opening of the sieve device was changed from 75 μm to 10 μm (material nylon) as in Comparative Example 3. Was carried out in the same manner as in Example 6 to produce [Toner 11]. However, the sieve was severely clogged and no product was obtained.

Evaluation (1) Transfer dust 1. All toners and devices used for evaluation were left in an environmental room at 25 ° C. and 50% for one day.
2. All the toner of the Imageo neo C600 commercial product PCU was removed, leaving only the carrier in the developing device.
3. In a developing device having only a carrier, 28 g of black toner serving as a sample was charged, and 400 g of a developer having a toner concentration of 7% was prepared.
4). A developing device was mounted on the Imageo neo C600 main body, and only the developing device was idled for 5 minutes at a developing sleeve linear velocity of 300 mm / s.
5. Both the developing sleeve and the photosensitive member were rotated at 300 mm / s trailing, and the charging potential and the developing bias were adjusted so that the toner on the photosensitive member would be 0.6 ± 0.05 mg / cm ² .
6). The cleaning blade was only one cleaning blade mounted on a commercially available Imagio neo C600 PCU, its elastic modulus was 70%, the thickness was 2 mm, and the contact angle with the image carrier at the counter was 20 °.
7). Under the above development conditions, the transfer current was adjusted so that the transfer rate was 96 ± 2%.
8). A grid-like image (see FIG. 5) was output as an image using the above set values and a usage environment of 5 ° C. and 15%.
9. Transfer dust due to coarse powder in the printed image appears as dust at the rear end of the image because the transfer is heavy during transfer and the transfer is delayed. For this reason, the printed image was observed for the state of dust at the edge of the image with a 30 × magnifier. ○ is a sharp image of dust, and Δ is 1 to 3 on the A4 image. The case where more transfer dust was generated was marked as x.

(2) Blade chipping (cleanability evaluation)
1. All toners and devices used for evaluation were left in an environmental room at 25 ° C. and 50% for one day.
2. All the toner of the Imageo neo C600 commercial product PCU was removed, leaving only the carrier in the developing device.
3. In a developing device having only a carrier, 28 g of black toner serving as a sample was charged, and 400 g of a developer having a toner concentration of 7% was prepared.
4). A developing device was mounted on the Imageo neo C600 main body, and only the developing device was idled for 5 minutes at a developing sleeve linear velocity of 300 mm / s.
5. Both the developing sleeve and the photosensitive member were rotated at 300 mm / s trailing, and the charging potential and the developing bias were adjusted so that the toner on the photosensitive member would be 0.6 ± 0.05 mg / cm ² .
6). The cleaning blade was only one cleaning blade mounted on a commercially available Imagio neo C600 PCU, its elastic modulus was 70%, the thickness was 2 mm, and the contact angle with the image carrier at the counter was 20 °.
7). Under the above development conditions, the transfer current was adjusted so that the transfer rate was 96 ± 2%.
8). Using the above set values, 5000 band charts showing the density of the 100% density portion and the 0% density portion were output under the usage environment of 10 ° C. and 15%.
9. After passing the paper, a halftone image was output, and the image and the cleaning blade were confirmed.
At this time, the image was not affected and the blade was also problematic. The image was not affected, but the blade was applied. The case was .DELTA., And the blade was applied and the image was streaked.

(3) Particle Size Measurement The volume average particle size (Dv) and number average particle size (Dn) of the toner of the present invention are measured using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm. Measured and analyzed with analysis software (Beckman Coulter Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) was added to a glass 100 ml beaker, 0.5 g of each toner was added, and the mixture was stirred with a micropartel. Subsequently, 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.
The evaluation results are shown in the following table. In the table, ER is the solid content concentration of the slurry.

It is a schematic sectional drawing which shows an example of the classification apparatus used by this invention.

11 Screen 12 Blade 12a Rotating Shaft 13 Slurry Supply Port 14 Toner Collection Portion 15 Coarse Grain Discharge Port

Japanese Patent Laid-Open No. 2002-162772 JP-A-6-19201 JP-A-4-121112

Claims (9)

Least also, a granulation step of granulating the toner base particles in an aqueous medium, a method for producing a toner having a particle size distribution adjustment step of adjusting the particle size distribution of the particle size of the toner base particles, the particle size In the distribution adjusting step, the aqueous medium slurry containing the toner base particles is caused to collide with the screen by centrifugal force based on rotating spiral blades provided inside the screen from the inside of the screen fixed in a cylindrical shape. It is made in a sieving step for removing coarse particles in the particles, and the opening diameter W (μm) of the screen has the following relationship when the weight average particle diameter of the obtained toner particles is Dv (μm).

2. A toner production method, wherein: The toner production method according to claim 1, wherein a weight average particle diameter Dv of the toner particles is 3 to 7 μm. The toner production method according to claim 1 or 2, wherein a ratio ( Dv / Dn ) of the weight average particle diameter Dv and the number average particle diameter Dn of the toner particles is 1.05 to 1.25. . Method for producing a toner according to any one of claims 1 to 3, characterized in that fixing by inclining the cylindrical screen. Method for producing a toner according to any one of claims 1 to 4, characterized in that the solids concentration of the slurry to be introduced into the particle size distribution adjustment step to 10 to 40 wt%. Method for producing a toner according to any one of claims 1 to 5, characterized in that the 5cps~300cps the viscosity of the slurry to be introduced into the particle size distribution adjustment step. Method for producing a toner according to any one of claims 1 to 6, characterized in that the opening diameter of the screen is 3～28Myuemu. The particle size distribution adjustment step method for producing a toner according to any one of claims 1 to 7, characterized in that the slurry to the screen is intended to intermittently collision. The particle size distribution adjustment step, by impinging the slurry to the screen, the production of the toner according to any one of claims 1 to 8, characterized in that a step of removing coarse particles by vibrating the screen Method.

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