JP4966061B2 - Toner and image forming apparatus - Google Patents

Description

  The present invention relates to a toner used as a developer and an image forming apparatus using the toner when developing an electrostatic image formed by electrophotography, electrostatic recording, or the like.

  The image forming apparatus includes a charging step for uniformly charging an image forming area on the surface of the image carrier, an exposure step for writing on the image carrier, a developing step for forming an image with toner frictionally charged on the image carrier, The image is fixed on the printing paper after a transfer process in which the image on the image carrier is transferred directly to the printing paper or indirectly via an intermediate transfer body. Further, the untransferred toner remaining without being transferred onto the image carrier is scraped off from the image carrier by the cleaning process, and enters the next image forming process.

As the developer used, there are a two-component developer composed of a toner and a carrier and a one-component developer composed of only a magnetic or non-magnetic toner. These toners are generally produced by kneading and pulverizing a resin, a pigment, a charge control agent and a release agent by melting and kneading and then cooling and pulverizing and classifying them. It is difficult to control.
Under such circumstances, recently, there has been an attempt to control the particle size of toner particles intentionally to solve the above-mentioned problems, and polymerized toner methods such as emulsion polymerization method and dissolution suspension method as aqueous granulation. Became popular.

  In recent years, there has been an increasing demand for higher image quality, and in particular, in order to realize high-definition images in color image formation, there has also been an increasing demand for toner diameter reduction and particle size uniformity. When an image is formed using a toner having a wide particle size distribution, the problem that the fine powder toner contaminates the developing roller, charging roller, charging blade, photoconductor, carrier, etc., and the toner scatters increases. And it was difficult to achieve high reliability at the same time. On the other hand, when the particle size is uniform and the particle size distribution is sharp, the development behavior of the individual toner particles is uniform, and the reproducibility of minute dots is greatly improved.

  However, a toner having a small particle size and a uniform particle size has a problem with respect to cleaning properties. In particular, it is impossible to stably clean a toner having a uniform and small particle diameter by blade cleaning. In view of this, various methods have been proposed for improving the cleaning property by devising the toner. One of them is a method in which the toner is deformed from a spherical shape to cope with it. By changing the shape of the toner, the powder fluidity of the toner is lowered and the toner is easily blocked by blade cleaning. However, if the degree of toner deformation is excessively large, the behavior of the toner becomes unstable during development and the like, and the fine dot reproducibility deteriorates. As described above, characteristics such as toner transfer quality, transfer efficiency, and cleaning performance are affected by the toner shape. Therefore, in order to obtain a toner having the above characteristics, an optimum design of the toner shape distribution is required.

  Therefore, for example, in Patent Document 1, the average value of the toner shape factor SF-1 is 110 or more, and the number distribution of SF-1 is 2.0 ≦ A / B ≦ 7.0 [A is the maximum value of the number distribution. Means the number of toner particles / total number of toner particles (number%) falling within the range of the value of the shape factor SF-1 ± 5, and B is the number of toner particles / total toner within the range where the shape factor SF-1 is 150 or more. It means the number of particles (number%). A toner satisfying the above requirements is proposed. However, this proposal does not consider toners in the small range of SF-1, and there remains a problem that they affect the cleaning performance.

In Patent Document 2, the average value of the shape factor SF-1 is in the range of 125 to 140, and (the number of particles having a shape factor SF-1 of 120 or less) ≦ 20% by number, and (the shape factor SF-1 is Toners satisfying the number of particles of 150 or more) ≦ 20% by number have been proposed. However, when SF-1 is defined for a small range (the number of particles having a shape factor SF-1 of 120 or less) ≦ 20% by number, particles within a small range of SF-1 are not sufficiently eliminated. The fine powder mixed in the toner contaminates the inside of the developing machine, the photosensitive member, the intermediate transfer member, and the like.
JP 2005-215298 A JP 2000-267331 A

The subject of this invention is as follows.
(1) To provide an image forming apparatus and a toner capable of obtaining a high image quality excellent in fine dot reproducibility.
(2) To provide a toner and an image forming apparatus capable of obtaining high reliability and corresponding to spherical toner cleaning without causing abrasion of the cleaning blade.

The present inventors have completed the present invention to solve the above-described problems.
Adjustment of the degree of deforming of the water-based granulated toner changes the viscosity state of the oil phase and changes the level of deforming depending on the amount of the deforming agent, the pigment, and the like. Further, the goodness of the water-based granulation includes sharpness of the particle size distribution, but it is said that the shape distribution state is large and affects the cleaning on the photoreceptor.
The present invention suppresses the distribution of the shape within a specific range in a relatively circular toner (not a toner having a pulverization interface such as a pulverized toner) that is granulated in an aqueous system. It was possible to ensure cleaning performance while alive.
That is, according to the present invention, a toner and an image forming apparatus having the following characteristics are provided.

(1) An image carrier, a charging step for charging the surface of the image carrier, an exposure step for writing a latent image by exposing the image carrier, and developing a toner on the latent image written on the image carrier Development step for forming a visible image, a transfer step for transferring the visible image to a recording medium, a fixing step for fixing the transferred image transferred to the recording medium, and an image carrier that has not been transferred completely In the image forming apparatus having at least a cleaning step for cleaning the transfer residual toner , at least the binder resin, the colorant, and the interlayer ions in the layered inorganic mineral produced by water-based granulation are used for image formation. some of a toner containing a modified layered inorganic mineral modified with an organic ion, the average value of shape factor SF-1 is in the range of 130 to 160, and a shape factor SF-1 of 1 Image forming apparatus characterized by contained particles number ≦ 2% by number in the range 0-115.

(2) The toner is characterized in that the average value of the shape factor SF-1 is in the range of 130 to 150, and the number of particles in the range of the shape factor SF-1 in the range of 100 to 115 is ≦ 2% by number. The image forming apparatus according to (1).

(3) The toner includes at least a prepolymer comprising a binder resin and a modified polyester resin in an organic solvent, a compound that extends or crosslinks with the prepolymer, a colorant, a release agent, and interlayer ions in the layered inorganic mineral. A modified layered inorganic mineral partially modified with organic ions is dissolved or dispersed, the Casson yield value at 25 ° C. of the solution or dispersion is 1 to 100 Pa, and the solution or dispersion is crosslinked in an aqueous medium. The image forming apparatus according to (1) or (2), wherein the image forming apparatus is a toner obtained by a reaction and / or elongation reaction and removing the solvent from the obtained dispersion.

(4) The modified layered inorganic mineral obtained by modifying at least a part of interlayer ions in the layered inorganic mineral with organic ions is contained in an amount of 0.05 to 10 wt% in the solid content in the solution or dispersion. The image forming apparatus according to (3).
(5) The toner has a volume average particle diameter of 3 to 8 μm and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the range of 1.00 to 1.30. The image forming apparatus according to any one of (1) to (4), wherein:

(6) The image forming apparatus according to any one of (1) to (5), wherein the toner has 1 to 10% by number of particles having a particle size of 2 μm or less.
(7) The toner is a toner obtained by externally adding fine particles having an average primary particle diameter of 50 to 500 nm and a bulk density of 0.3 g / cm ³ or more to the surface of the toner base particles. The image forming apparatus according to any one of (1) to (6).

(8) Modification in which at least part of interlayer ions in the binder resin, colorant and layered inorganic mineral used in the image forming apparatus described in (1) is modified with organic ions. A toner containing a layered inorganic mineral, wherein the average value of the shape factor SF-1 is in the range of 130 to 160, and the number of particles in the range of the shape factor SF-1 in the range of 100 to 115 is ≦ 2% by number. Toner.
(9) The average value of the shape factor SF-1 is in the range of 130 to 150, and the number of particles in the range of the shape factor SF-1 in the range of 100 to 115 is ≦ 2% by number (8) ) Toner described.

(10) At least part of interlayer ions in a prepolymer composed of a binder resin and a modified polyester resin in at least an organic solvent, a compound that extends or crosslinks with the prepolymer, a colorant, a release agent, and a layered inorganic mineral is an organic substance. The modified layered inorganic mineral modified with ions is dissolved or dispersed, the Casson yield value at 25 ° C. of the solution or dispersion is 1 to 100 Pa, and the solution or dispersion is subjected to a crosslinking reaction and / or in an aqueous medium. The toner according to (8) or (9), wherein the toner is obtained by performing an elongation reaction and removing the solvent from the obtained dispersion.
(11) The modified layered inorganic mineral obtained by modifying at least part of interlayer ions in the layered inorganic mineral with organic ions is contained in an amount of 0.05 to 10 wt% in the solid content of the solution or dispersion. The toner according to (10).

(12) The toner has a volume average particle diameter of 3 to 8 μm and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the range of 1.00 to 1.30. The toner according to any one of (8) to (11), wherein
(13) The toner according to any one of (8) to (12), wherein the toner has 1 to 10% by number of particles having a particle diameter of 2 μm or less.

(14) The toner is a toner obtained by externally adding fine particles having an average primary particle diameter of 50 to 500 nm and a bulk density of 0.3 g / cm ³ or more to the surface of the toner base particles. The toner according to any one of (8) to (13).

(15) A process cartridge that integrally supports an image carrier and at least one unit selected from a charging unit, a developing unit, and a cleaning unit, and is detachable from an image forming apparatus main body. (7) A process cartridge for use in the image forming apparatus according to any one of (7).

  According to the present invention, it is possible to ensure the cleaning performance while making good use of the water-based granulation by suppressing the distribution of the shape within a specific range in the substantially spherical toner that is granulated in the water-based. A toner and an image forming apparatus that can obtain high image quality with excellent dot reproducibility and high reliability can be obtained.

  The present invention relates to an image carrier, a charging step for charging the surface of the image carrier, an exposure step for writing a latent image by exposing the image carrier, and a toner to the latent image written on the image carrier. A developing process for developing a visible image by developing, a transferring process for transferring the visible image to a recording medium, a fixing process for fixing the transferred image transferred to the recording medium, and an image carrier that has not been completely transferred In the image forming apparatus having at least a cleaning process for cleaning the upper transfer residual toner, the toner used for image formation is a toner produced by aqueous granulation, and the average value of the shape factor SF-1 is 130 to 160. And the number of particles in the range of 100 to 115 in the shape factor SF-1 ≦ 2% by number is included.

When the average value of the toner shape factor SF-1 is smaller than 130, a cleaning failure that passes through the cleaning means occurs. When the value is larger than 160, the degree of toner irregularity is excessively deformed, and a defect at the time of transfer is induced. For example, there is a high possibility that a worm-eaten image is generated as a defective transfer. The average value of the toner shape factor SF-1 is preferably 130 to 150.
When the value of the shape factor SF-1 exceeds the number of particles in the range of 100 to 115 ≦ 2% by number, cleaning failure may occur, which may cause mechanical contamination and decrease in reliability. By keeping it within the range, the cleaning property can be greatly improved. More preferably, it is 0.5 number% or less.
By using such a toner, it is possible to ensure cleaning performance even when a cleaning blade is used as a cleaning means.

<Description of shape factor>
FIG. 1 is a diagram schematically showing the shape of the toner in order to explain the shape factor SF-1. The shape factor SF-1 indicates the ratio of the roundness of the toner shape and is represented by the following formula (1). This is a value obtained by dividing the square of the maximum length MXLNG of the shape formed by projecting the toner on a two-dimensional plane by the figure area AREA and multiplying by 100π / 4.
SF-1 = {(MXLNG) ² / AREA} × (100π / 4) (1)
When the value of SF-1 is 100, the shape of the toner becomes a true sphere, and becomes larger as the value of SF-1 increases.

Specifically, the shape factor is measured by randomly sampling 300 SEM images of toner obtained by FE-SEM (S-4200) manufactured by Hitachi, Ltd., and using the image information via the interface. The sample was introduced into an image analysis apparatus (Luzex AP) manufactured by Nireco Corporation and analyzed, and the value obtained from the above equation was defined as SF-1. The value of SF-1 is preferably a value obtained by the above Luzex, but is not particularly limited to the FE-SEM device and the image analysis device as long as the same analysis result can be obtained.
When the shape of the toner is close to a spherical shape, the contact state between the toner and the toner or the toner and the photosensitive member becomes a point contact, so that the adsorbing force between the toners becomes weak, and thus the fluidity becomes high. The attracting power with the body also becomes weaker, and the transfer rate becomes higher. When the shape factor SF-1 exceeds 180, the transfer rate decreases, which is not preferable.

  The toner produced by the water-based granulation of the present invention includes at least a binder resin, a prepolymer composed of a modified polyester resin in an organic solvent, a compound that extends or crosslinks with the prepolymer, a colorant, a release agent, A modified layered inorganic mineral (hereinafter referred to as a modified layered inorganic mineral) in which at least a part of interlayer ions in the layered inorganic mineral is modified with organic ions is dissolved or dispersed, and the Casson yield value at 25 ° C. of the solution or dispersion is It is preferably 1 to 100 Pa, and is preferably a toner obtained by subjecting the solution or dispersion to a crosslinking reaction and / or elongation reaction in an aqueous medium and removing the solvent from the obtained dispersion.

  The toner further suitably used in the image forming apparatus of the present invention includes at least polyester in an organic solvent, a polyester prepolymer having a functional group containing a nitrogen atom, a compound that extends or crosslinks with the prepolymer, a colorant, and a release agent. The dispersion and the modified layered inorganic mineral are dispersed, the Casson yield value at 25 ° C. of the dispersion is 1 to 100 Pa, the dispersion is crosslinked and / or elongated in an aqueous solvent, and the solvent is removed from the resulting dispersion. This toner is obtained by removing the toner. Hereinafter, the constituent material and the manufacturing method of the toner will be described.

<Polyester>
As the binder resin, polyester is preferable, and the polyester is obtained by a polycondensation reaction between a polyhydric alcohol compound and a polycarboxylic acid compound.
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.
The polycondensation reaction between a polyhydric alcohol (PO) and a polycarboxylic acid (PC) is carried out in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and heated to 150 to 280 ° C. while reducing the pressure as necessary. The produced water is distilled off to obtain a polyester having a hydroxyl group. The hydroxyl value of the polyester is preferably 5 or more, and the acid value of the polyester is usually 1 to 30, preferably 5 to 20. By giving an acid value, it tends to be negatively charged, and furthermore, when fixing to a recording paper, the affinity between the recording paper and the toner is good and the low-temperature fixability is improved. However, when the acid value exceeds 30, there is a tendency to deteriorate with respect to the stability of charging, particularly environmental fluctuation.

  The weight average molecular weight is 10,000 to 400,000, preferably 20,000 to 200,000. A weight average molecular weight of less than 10,000 is not preferable because offset resistance deteriorates. On the other hand, if it exceeds 400,000, the low-temperature fixability is deteriorated.

  As the prepolymer comprising the modified polyester resin, a polyester prepolymer having a functional group containing a nitrogen atom is preferable, and as the polyester prepolymer having a functional group containing a nitrogen atom, the terminal of the polyester obtained by the above polycondensation reaction is used. A polyester prepolymer (A) having an isocyanate group obtained by reacting a carboxyl group, a hydroxyl group or the like with a polyvalent isocyanate compound (PIC) is preferable. In this case, examples of the compound that extends or crosslinks with the prepolymer include amines. By reacting the polyester prepolymer (A) having an isocyanate group with amines, the molecular chain is cross-linked and / or elongated to obtain a urea-modified polyester.

  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 is lowered, and the hot offset resistance is deteriorated.

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. Examples of B1 to B5 blocked amino groups (B6) include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). 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 urea-modified polyester is produced by a one-shot method or the like. Polyhydric alcohol (PO) and polyvalent carboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc., and water generated while reducing the pressure as necessary. Distill off to obtain a polyester having a hydroxyl group. Subsequently, at 40-140 degreeC, this is made to react with polyvalent isocyanate (PIC), and the polyester prepolymer (A) which has an isocyanate group is obtained. Further, this (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a urea-modified polyester.

  When reacting (PIC) and when reacting (A) and (B), a solvent may be used if necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to isocyanates (PIC), such as tetrahydrofuran (such as tetrahydrofuran).

  In addition, in the crosslinking and / or extension reaction between the polyester prepolymer (A) and the amines (B), a reaction terminator can be used as necessary to adjust the molecular weight of the resulting urea-modified polyester. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The weight average molecular weight of the urea-modified polyester is usually 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester or the like is not particularly limited when the above-mentioned unmodified polyester is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. When the urea-modified polyester is used alone, its number average molecular weight is usually 2000-15000, preferably 2000-10000, more preferably 2000-8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

By using the unmodified polyester and the urea-modified polyester in combination, the low-temperature fixability and the glossiness when used in a full-color image forming apparatus are improved. Therefore, it is preferable to use the urea-modified polyester alone. The unmodified polyester may include a polyester modified with a chemical bond other than a urea bond.
The unmodified polyester and the urea-modified polyester are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, it is preferable that the unmodified polyester and the urea-modified polyester have a similar composition.

  The weight ratio of unmodified polyester to urea-modified polyester is usually 20/80 to 95/5, preferably 70/30 to 95/5, more preferably 75/25 to 95/5, and particularly preferably 80 /. 20-93 / 7. When the weight ratio of the urea-modified polyester 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 glass transition point (Tg) of the binder resin containing unmodified polyester and urea-modified polyester is usually 45 to 65 ° C, preferably 45 to 60 ° C. If it is less than 45 ° C., the heat resistance of the toner deteriorates, and if it exceeds 65 ° C., the low-temperature fixability becomes insufficient.
In addition, since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the heat-resistant storage stability tends to be good even when the glass transition point is low as compared with known polyester-based toners.

<Colorant>
As the colorant, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher , Yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sayred, Parachlor Ortonito Aniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thio Indigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red Polyazo 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, Lid Russian nin green, anthraquinone green, titanium oxide, zinc white, litbon 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 together 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, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. 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, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.

  The amount of 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 developer fluidity 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.

<Modified layered inorganic mineral>
The modified layered inorganic mineral used in the toner of the present invention comprises at least a binder resin, a prepolymer composed of a modified polyester resin in an organic solvent, a compound that extends or crosslinks with the prepolymer, a colorant, a release agent, and a modified layered inorganic. In a solution or dispersion in which mineral is dissolved or dispersed, the Casson yield value at 25 ° C. must be 1 to 100 Pa.
If the Casson yield value is less than 1 Pa, it is difficult to obtain the target shape, and if it exceeds 100 Pa, the productivity deteriorates.
The Casson yield value is a value obtained by measuring the viscosity of an oil phase (the solution or dispersion) alone when emulsified in an aqueous medium.

Further, the modified layered inorganic mineral is preferably contained in an amount of 0.05 to 10 wt% in the solid content in the solution or dispersion. If it is less than 0.05 wt%, the target Casson yield value cannot be obtained, and if it exceeds 10 wt%, the fixing performance deteriorates.
The modified layered inorganic mineral is a layered inorganic mineral obtained by converting at least part of ions between layers in the layered inorganic mineral with organic ions, for example, one obtained by converting at least part of metal cations between layers with quaternary ammonium ions. Examples thereof include organically modified montmorillonite and organically modified smectite.

<Casson yield measurement method>
The Casson yield value can be measured using a high shear viscometer or the like.
The measurement conditions are as follows.
Device: AR2000 (TA Instruments)
Shear stress: 120 Pa / 5 min Geometry: 40 mm steel plate Geometry gap: 1 mm
Analysis software: TA DATA ANALYSIS (TA Instruments)

<Manufacturing method>
Next, a method for producing the toner will be described. Here, although a preferable manufacturing method is shown, it is not limited to this.
1) Unmodified polyester, polyester prepolymer having an isocyanate group, compounds that extend or crosslink with the prepolymer (amines), colorant, release agent, and at least part of interlayer ions in layered inorganic minerals are modified with organic ions The modified inorganic mineral is dispersed in an organic solvent to prepare a toner material liquid.
The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of an organic solvent is 0-300 weight part normally with respect to 100 weight part of polyester prepolymers, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part.

2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.
The amount of the aqueous medium used relative to 100 parts by weight of the toner material liquid is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner material liquid is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical.

Further, in order to improve the dispersion in the aqueous medium, a dispersant such as a surfactant and resin fine particles is appropriately added.
As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, fatty acid amide derivatives, polyhydric alcohols Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-Hydroxyethyl) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt , Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries, Ltd.) Manufactured), MegaFuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products), Footgent F-300 (Neos), and the like.

  The resin fine particles are added to stabilize the toner base particles formed in the aqueous medium. For this reason, it is preferable to add so that the coverage existing on the surface of the toner base particles is in the range of 10 to 90%. For example, polymethyl methacrylate fine particles 1 μm and 3 μm, polystyrene fine particles 0.5 μm and 2 μm, poly (styrene-acrylonitrile) fine particles 1 μm, trade names are PB-200H (manufactured by Kao), SGP (manufactured by Soken), Techno Examples include polymer SB (manufactured by Sekisui Chemical Co., Ltd.), SGP-3G (manufactured by Sokensha), and micropearl (manufactured by Sekisui Fine Chemical Co., Ltd.).

  In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.

  As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxy Propyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl Nitrogen compounds such as imidazole and ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, poly Xoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

3) Simultaneously with the preparation of the emulsion, the reaction with the polyester prepolymer (A) having an isocyanate group is carried out.
This reaction involves molecular chain crosslinking and / or elongation. The reaction time is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent base is removed to produce spindle-shaped toner base particles. . Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.

5) A charge control agent is injected into the toner base particles obtained above, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are externally added to obtain a toner.
The injection of the charge control agent and the external addition of the inorganic fine particles are performed by a known method using a mixer or the like.
Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained. Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between the true spherical shape and the rugby ball shape can be controlled, and the surface morphology is also controlled between the smooth shape and the umeboshi shape. be able to.

Further, as a method for producing the toner of the present invention by aqueous granulation, it may be produced by an emulsion polymerization aggregation fusion method.
The emulsified and agglomerated toner changes from the SF-1 (average value) state in which the degree of deforming is high while only agglomerated to a shape close to a sphere by heat fusion. In the case of a normal emulsion aggregation toner, since the fusion between primary particles is actively promoted from a highly deformed state with only aggregation, the degree of deformation becomes close to a sphere, exceeding the scope of the present invention. The effect of the invention cannot be obtained. If the heating time for the fusing is too short, the fusing between the aggregated primary particles is not sufficient, and the toner particles are weak against cracking and the like, producing fine powder components and causing problems. In the case of the emulsion aggregation toner, a balance is required to ensure sufficient fusion between the aggregated primary particles while maintaining the deformed state of the present invention.
The toner of the present invention is produced by an emulsion polymerization aggregation fusion method in which a resin is prepared by emulsion polymerization, heteroaggregated with a dispersion of pigment, release agent, etc., and then fused and fused. can do.

The emulsion polymerization agglomeration fusion method is a modified layered inorganic mineral in which a resin particle dispersion prepared by an emulsion polymerization method, a separately prepared colorant dispersion, and a release agent dispersion, if necessary, are at least partially modified with organic ions. Etc., and aggregating at least the resin particles and the colorant to form an aggregated particle dispersion step (hereinafter sometimes referred to as “aggregation step”), and the aggregated particles are heated and fused. A step of forming toner particles (hereinafter sometimes referred to as a “fusion step”).
In the aggregation step, the resin particle dispersion, the colorant dispersion, and if necessary, the release agent dispersion and the modified layered inorganic mineral are mixed with each other to aggregate the resin particles and form aggregated particles. Aggregated particles are formed by hetero-aggregation, etc., and at that time, for the purpose of stabilizing the aggregated particles and controlling the particle size / particle size distribution, the ionic surfactant having a polarity different from that of the aggregated particles or monovalent or more such as metal salt A compound having the following charge can be added. In the fusion step, the resin is melted by heating to a temperature equal to or higher than the glass transition point of the resin in the aggregated particles.

  In the previous stage of the fusing step, there can be provided an attaching step in which other fine particle dispersion is added to and mixed with the aggregated particle dispersion to uniformly attach the fine particles to the surface of the aggregated particles to form adhered particles. Furthermore, an adhesion step can be provided in which the modified layered inorganic mineral dispersion is added to and mixed with the aggregated particle dispersion to uniformly adhere the modified layered inorganic mineral to the surface of the aggregated particles to form adhered particles. In order to strengthen the adhesion of the modified layered inorganic mineral, after attaching the modified layered inorganic mineral, other fine particle dispersions are added and mixed to uniformly adhere the fine particles to the surface of the aggregated particles. An attachment step for forming particles can be provided. These adhered particles are formed by heteroaggregation or the like. This adhered particle dispersion is also fused by heating to a temperature equal to or higher than the glass transition point of the resin particles to form fused particles.

  The fused particles fused in the fusion step exist as a colored fused particle dispersion in the aqueous medium, and at the same time the fused particles are taken out of the aqueous medium in the washing step, the impurities mixed in the respective steps are removed. The toner is removed and dried to obtain toner as powder.

  In the washing step, acidic and possibly basic water is added in several times the amount to the fused particles and stirred, followed by filtration to obtain a solid content. The pure water is added several times to the solid content and stirred, followed by filtration. This is repeated several times until the pH of the filtrate after filtration reaches about 7, and colored toner particles are obtained. In the drying step, the toner particles obtained in the washing step are dried at a temperature below the glass transition point. At this time, it is possible to circulate dry air or heat under vacuum as necessary.

In the present invention, an alicyclic compound of an organic acid metal salt as an emulsifier can be used as it is for stabilizing the dispersibility of the resin particle dispersion, the colorant dispersion, and the release agent dispersion. However, if the colorant dispersion or release agent dispersion is not stable due to the stability due to pH, or if the resin particle dispersion is stable over time, a certain amount of surfactant may be added. Can be used.
Examples of such surfactants include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type And nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable. In the toner of the present invention, an anionic surfactant generally has a strong dispersing power and is excellent in the dispersibility of resin particles and a colorant. Therefore, a cationic agent is used as a surfactant for dispersing a release agent. Surfactants are advantageous. The nonionic surfactant is preferably used in combination with an anionic surfactant or a cationic surfactant. Surfactant may be used individually by 1 type and may use 2 or more types together.

  Specific examples of anionic surfactants include fatty acid soaps such as potassium laurate, sodium oleate, and castor oil sodium; sulfate esters such as octyl sulfate, lauryl sulfate, lauryl ether sulfate, and nonyl phenyl ether sulfate; lauryl sulfonate , Dodecylbenzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate, etc. Sulfonates: lauryl phosphate, isopropyl phosphate, nonylphenyl ether phosphate Phosphoric acid esters such as Feto; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate, sulfosuccinic acid salts, such as sodium lauryl sulfosuccinate 2; and the like.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dihydroxyethyl methyl ammonium chloride, oleyl bispolyoxyethylene methyl ammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzene dimethyl Ammonium chloride, alkyltri And quaternary ammonium salts such as chill ammonium chloride.

  Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxy Alkyl phenyl ethers such as ethylene nonyl phenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene Alkylamines such as oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as ethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid Alkanolamides such as diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate Etc.

  The content of the surfactant in each dispersion may be a level that does not impair the characteristics of the present invention, and is generally a small amount. Specifically, in the case of a resin particle dispersion, 0.01 to 1 wt. %, Preferably 0.02 to 0.5% by weight, more preferably 0.1 to 0.2% by weight. When the content is less than 0.01% by weight, aggregation may occur particularly when the pH of the resin particle dispersion is not sufficiently basic. The content in the case of the colorant dispersion and the release agent dispersion is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 0.2% by weight. If the content is less than 0.01% by weight, the stability between the particles is different at the time of agglomeration, which causes problems such as the release of specific particles. If the content exceeds 10% by weight, the particle size distribution of the particles becomes wider. In addition, there are problems such as difficulty in controlling the particle diameter, which is not preferable.

In addition to the resin, colorant, and release agent, the toner of the present invention includes other components such as an internal additive, a charge control agent, inorganic particles, organic particles, a lubricant, and an abrasive depending on the purpose. It is possible to add the fine particles.
As an internal additive, it is used to such an extent that it does not hinder the chargeability as a toner characteristic. For example, a metal such as ferrite, magnetite, reduced iron, cobalt, manganese, nickel, an alloy, or a magnetic compound such as a compound containing these metals. The body is used.

The charge control agent is not particularly limited, but in particular for color toners, colorless or light-colored ones are preferably used. For example, quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments are used.
Examples of the inorganic particles include all particles usually used as an external additive on the toner surface, such as silica, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, and cerium oxide. Examples of the organic particles include all particles usually used as external additives on the toner surface, such as vinyl resins, polyester resins, and silicone resins. In addition, these inorganic particles and organic particles, fluidity aids, cleaning aids and the like can be used. Examples of the lubricant include fatty acid amides such as ethylene bis stearic acid amide and oleic acid amide, and fatty acid metal salts such as zinc stearate and calcium stearate. As an abrasive | polishing agent, the above-mentioned silica, alumina, cerium oxide etc. are mentioned, for example.

  As described above, when the resin particle dispersion, the layered inorganic mineral dispersion modified at least partially with organic ions, the colorant dispersion, and the release agent dispersion are mixed, the content of the colorant is 50% by weight. The following is sufficient, and the range of 2 to 40% by weight is preferable. The content of the layered inorganic mineral at least partially modified with organic ions is preferably in the range of 0.05 to 10% by weight. Further, the content of the other components only needs to be a level that does not hinder the object of the present invention, and is generally extremely small, specifically in the range of 0.01 to 5% by weight, 0.5 A range of ˜2% by weight is preferred.

  In the present invention, as a dispersion medium for the resin particle dispersion, a layered inorganic mineral dispersion at least partially modified with organic ions, a colorant dispersion, a release agent dispersion, and a dispersion of other components, for example, an aqueous medium Is used. Specific examples of the aqueous medium include water such as distilled water and ion exchange water, alcohol, and the like. These may be used individually by 1 type and may use 2 or more types together.

  In the step of preparing the aggregated particle dispersion of the present invention, the aggregated particles can be adjusted by adjusting the emulsifying power of the emulsifier with pH to generate aggregation. At the same time, an aggregating agent may be added in order to stably and rapidly aggregate the particles to obtain aggregated particles having a narrower particle size distribution. As the flocculant, a compound having a monovalent or higher charge is preferable. Specifically, water-soluble surfactants such as the above-mentioned ionic surfactants and nonionic surfactants, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, Acids such as oxalic acid, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate and other inorganic acid metal salts, sodium acetate, potassium formate, sodium oxalate, phthalic acid Aliphatic acids such as sodium and potassium salicylates, metal salts of aromatic acids, metal salts of phenols such as sodium phenolate, metal salts of amino acids, triethanolamine hydrochloride, aniline hydrochloride and other aliphatic and aromatic amines Inorganic acid salts and the like. When considering the stability of the aggregated particles, the stability of the aggregating agent with respect to heat and time, and the removal during washing, a metal salt of an inorganic acid is preferable in terms of performance and use.

  The amount of these flocculants to be added varies depending on the valence of the charge, but all of them are small amounts. It is about 5% by weight or less. A smaller amount of the flocculant is preferable, and a compound having a higher valence is preferable because the amount added can be reduced.

<Description of particle size distribution>
The toner used in the present invention has a volume average particle diameter of 3 to 8 μm and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of 1.00 to 1.30. It is preferable to be in the range.
The volume average particle diameter Dv is more preferably 3.0 to 7.0 μm. In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. When the volume average particle diameter is smaller than the above range, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced. When it is used, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.

  A toner having high resolution and high image quality can be obtained when the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner is in the range of 1.00 to 1.30. Make it possible. Furthermore, in the case of a two-component developer, even if a long-term balance of the toner is performed, fluctuations in the particle size of the toner in the developer are reduced, and good and stable developability even with long-term stirring in the developing device. Is possible. If Dv / Dn exceeds 1.30, the variation in particle size of individual toner particles is large, and the behavior of the toner varies during development and the like, and the reproducibility of minute dots is impaired. Therefore, a high-quality image cannot be obtained. More preferably, Dv / Dn is in the range of 1.00 to 1.20, and a better image can be obtained.

  In order to reproduce minute dots of 600 dpi or more, the toner preferably has a volume average particle diameter of 3 to 8 μm. The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is preferably in the range of 1.00 to 1.30. The closer (Dv / Dn) is to 1.00, the sharper the particle size distribution. With such a toner having a small particle size and a narrow particle size distribution, the toner charge amount distribution is uniform, a high-quality image with little background fogging can be obtained, and the electrostatic transfer method has a high transfer rate. can do.

As an apparatus for measuring the particle size distribution of toner particles by the Coulter counter method, there are Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner can be obtained.

  As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

The toner used in the present invention preferably contains 1 to 10% by number of particles having a particle size of 2 μm or less.
The phenomenon of defects due to the above-mentioned particle size is greatly related to the content of fine powder, and in particular, when the number of particles having a particle size of 2 μm or less exceeds 10% by number, it is an obstacle to the adhesion to the carrier and the stability of charging at a high level. Become. Conversely, when the toner particle size is larger than the above range, it becomes difficult to obtain a high-resolution and high-quality image, and the toner particle size when the balance of the toner in the developer is performed. In many cases, fluctuations of It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.30.

<Measurement method of particle ratio of particle size of 2 μm or less>
The particle ratio of the particle size of 2 μm or less and the circularity of the toner of the present invention can be measured by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

The toner according to the present invention preferably satisfies the following shape rule.
FIG. 2 is a diagram schematically showing the shape of the toner of the present invention. In FIG. 2, when a substantially spherical toner is defined by a major axis r1, a minor axis r2, and a thickness r3 (where r1 ≧ r2 ≧ r3), the toner of the present invention has a major axis and a minor axis. Ratio (r2 / r1) (see FIG. 2B) is 0.5 to 1.0, and the ratio of thickness to short axis (r3 / r2) (see FIG. 2C) is 0.7 to 1.0. It is preferable to be in the range of 1.0. When the ratio of the major axis to the minor axis (r2 / r1) is less than 0.5, the dot reproducibility and transfer efficiency are inferior because of being away from the true spherical shape, and high-quality image quality cannot be obtained. On the other hand, if the ratio of thickness to minor axis (r3 / r2) is less than 0.7, the shape is close to a flat shape, and a high transfer rate like a spherical toner cannot be obtained.
In addition, r1, r2, r3 can be measured by the following method, for example. That is, the toner is uniformly dispersed and adhered on a smooth measurement surface, and 100 particles of the toner are magnified 500 times by a color laser microscope “VK-8500” (manufactured by Keyence Corporation). The major axis r1 (μm), the minor axis r2 (μm), and the thickness r3 (μm) of the particles can be measured and obtained from their arithmetic average values.

The toner used in the present invention is obtained by externally adding fine particles (hereinafter also simply referred to as fine particles) having an average primary particle size of 50 to 500 nm and a bulk density of 0.3 g / cm ³ or more to the surface of the toner base particles. It is preferable to use a toner.
By using fine particles having an average primary particle size of 50 to 500 nm and a bulk density of 0.3 g / cm ³ or more as an external additive, a small particle size toner having good cleaning properties and particularly achieving high image quality. When used, improvement in developability and transferability is improved.
In addition, although silica etc. are often used for a normal fluid improvement agent, for example, the average primary particle diameter of this silica is 10-30 nm normally, and a bulk density is 0.1-0.2 g / cm < ³ >.

  In the present invention, since fine particles having appropriate characteristics are present on the surface of the toner, an appropriate gap is formed between the toner particles and the object. Further, the fine particles have a very small contact area with the toner particles, the photoconductor, and the charge imparting member and are evenly contacted with each other. Furthermore, since it plays the role of a roller, it is difficult to be buried in toner particles even during cleaning under high stress (high load, high speed, etc.) between the cleaning blade and the photoconductor without wearing or damaging the photoconductor. Or, even if it is buried a little, it can be detached and returned, so that stable characteristics can be obtained over a long period of time. Further, the toner is moderately detached from the surface of the toner and accumulated at the tip of the cleaning blade, and the so-called dam effect has an effect of preventing a phenomenon that the toner passes from the blade. Since these characteristics have an effect of reducing the share received by the toner particles, the filming effect of the toner itself due to the low rheological component contained in the toner is exhibited for high-speed fixing (low energy fixing). In addition, when fine particles having an average primary particle size in the range of 50 to 500 μm are used, the excellent cleaning performance can be fully utilized, and since the particle size is extremely small, the powder fluidity of the toner is improved. There is no reduction. Further, although the details are not clear, even if the surface-treated fine particles are externally added to the toner or the carrier is contaminated, the degree of developer deterioration is small.

The average primary particle size (hereinafter referred to as the average particle size) of the fine particles is 50 to 500 nm, and particularly preferably 100 to 400 nm. If the thickness is less than 50 nm, the fine particles may be buried in the concave and convex portions on the toner surface to lower the role of the rollers. On the other hand, when the particle size is larger than 500 μm, when the fine particles are located between the blade and the surface of the photosensitive member, the order is the same level as the contact area of the toner itself, and the toner particles to be cleaned pass, that is, defective cleaning occurs. It becomes easy.
When the bulk density is less than 0.3 g / cm ³ , although there is a contribution to improving fluidity, the scattering and adhesion of the toner and fine particles are increased, so that the toner and roller effect and the cleaning part accumulate. As a result, the so-called dam effect that prevents toner cleaning failure is reduced.

In fine particles of the present invention, as the inorganic _{compound, SiO 2, TiO 2, Al} 2 O 3, MgO, CuO, ZnO, SnO 2, CeO 2, Fe 2 O 3, BaO, CaO, K 2 O, Na 2 O ZrO ₂ , CaO · SiO ₂ , K ₂ O (TiO ₂ ) n, Al ₂ O ₃ · 2SiO ₂ , CaCO ₃ , MgCO ₃ , BaSO ₄ , MgSO ₄ , SrTiO _{3 and the} like, preferably _{, SiO 2, TiO 2, Al} 2 O 3 and the like. In particular, these inorganic compounds may be hydrophobized with various coupling agents, hexamethyldisilazane, dimethyldichlorosilane, octyltrimethoxysilane, and the like.

  The organic compound fine particles may be thermoplastic resins or thermosetting resins, such as vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, Examples include urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.

  Specific examples of vinyl resins include polymers obtained by homopolymerization or copolymerization of vinyl monomers, such as styrene- (meth) acrylic acid ester copolymers, styrene-butadiene copolymers, (meth) acrylic acid. -Acrylic ester copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

The bulk density of the fine particles was measured by the following method. Using a 100 ml graduated cylinder, fine particles were gradually added to make 100 ml.
At that time, no vibration was applied. The bulk density was measured by the difference in weight before and after placing the fine particles of the graduated cylinder.
Bulk density (g / cm ³ ) = fine particle amount (g / 100 ml) ÷ 100

  The fine particles of the present invention can be externally added and adhered to the toner surface by mechanically mixing and adhering the toner base particles and fine particles using various known mixing devices, or in the liquid phase. There is a method in which the base particles and the fine particles are uniformly dispersed with a surfactant or the like, and are dried after the adhesion treatment.

  The image forming apparatus of the present invention includes an electrostatic latent image forming process (charging process and exposure process), a developing process, a transfer process, a fixing process, and a cleaning process. You may further have processes, such as a process and a control process.

  The electrostatic latent image forming step is a step of forming an electrostatic latent image on the image carrier. The material, shape, structure, size and the like of the image carrier can be appropriately selected from known ones. Examples of the material include inorganic substances such as amorphous silicon and selenium, and organic substances such as polysilane and phthalopolymethine. Amorphous silicon is preferable because of its long life. Further, the shape is preferably a drum shape. The electrostatic latent image can be formed by uniformly charging the surface of the image carrier and then exposing it imagewise, and can be performed by an electrostatic latent image forming unit. The electrostatic latent image forming means preferably has a charger that uniformly charges the surface of the image carrier and an exposure device that exposes the surface of the image carrier.

  Charging can be performed by applying a voltage to the surface of the image carrier using a charger. The charger can be appropriately selected according to the purpose, but a known contact charger equipped with a conductive or semiconductive roll, brush, film, rubber blade, etc., or corona discharge such as corotron or scorotron is used. Non-contact chargers and the like.

  The exposure can be performed by exposing the surface of the image carrier using an exposure device. The exposure device can be appropriately selected according to the purpose, but 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 can be used. It should be noted that an optical back side system in which exposure is performed from the back side of the image carrier may be adopted.

  The development step is a step of forming a visible image by developing the electrostatic latent image using the toner of the present invention. The visible image can be formed using a developing unit. The developing means can be appropriately selected from known ones, and preferably has a developing unit that accommodates the toner of the present invention and can apply the toner to the electrostatic latent image in a contact or non-contact manner. As the developing device, it is preferable to use a developing device provided with the toner container of the present invention. The developing device may be a dry development system or a wet development system. Further, it may be a single color developer or a multicolor developer. Specifically, a stirrer for charging the developer by friction stirring and a developer having a rotatable magnet roller can be used. The developer accommodated in the developing device is a developer using the toner of the present invention, but may be a one-component developer or a two-component developer.

  In a developing device having a two-component developer, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the image carrier by an electric attractive force. As a result, the electrostatic latent image is developed with toner, and a visible image is formed with toner on the surface of the image carrier.

  The transfer step is a step of transferring a visible image to a recording medium. The intermediate transfer member is used to primarily transfer the visible image onto the intermediate transfer member, and then the secondary transfer of the visible image onto the recording medium. It is preferable. At this time, the toner used is usually two or more colors, and it is preferable to use a full-color toner. For this reason, it is more preferable to have a primary transfer process in which a visible image is transferred onto an intermediate transfer member to form a composite transfer image, and a secondary transfer process in which the composite transfer image is transferred onto a recording medium.

  The transfer can be performed by charging the image carrier using a transfer unit. The transfer means preferably has a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. The intermediate transfer member can be appropriately selected from known transfer members according to the purpose, and a transfer belt or the like can be used.

  The transfer means preferably has a transfer device that peels and charges the visible image formed on the image carrier to the recording medium side. There may be one transfer means or a plurality of transfer means. Specific examples of the transfer device 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 medium can be appropriately selected from known recording media, and recording paper or the like can be used.

  The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit, and may be fixed each time the toner of each color is transferred to the recording medium, or each color toner is laminated. You may fix at once in the state. The fixing unit can be appropriately selected according to the purpose, but a known heating and pressing unit can be used. 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. The heating in the heating and pressurizing means is usually preferably 80 ° C to 200 ° C. 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 neutralizing by applying a neutralization bias to the image carrier, and can be performed using a neutralization unit. The neutralization means can be appropriately selected from known neutralizers, and a neutralization lamp or the like can be used.

  The cleaning step is a step of removing toner remaining on the image carrier, and can be performed using a cleaning unit. The cleaning means can be appropriately selected from known cleaners, and a magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, web cleaner, or the like can be used. It is preferable to use a blade cleaner.

  The recycling process is a process in which the toner removed in the cleaning process is recycled by the developing unit, and can be performed using the recycling unit. The recycling means can be appropriately selected according to the purpose, and a known conveying means or the like can be used.

  The control means is a process for controlling each process, and can be performed using the control means. The control means can be appropriately selected according to the purpose, and devices such as a sequencer and a computer can be used.

  FIG. 3 shows an example of an image forming apparatus used in the present invention. The image forming apparatus 100A includes a drum-shaped photosensitive member 10 as an image carrier, a charging roller 20 as a charging unit, an exposure device 30 as an exposure unit, a developing device 40 as a developing unit, and an intermediate transfer member 50. And a cleaning device 60 as a cleaning means and a static elimination lamp 70 as a static elimination means.

  The intermediate transfer member 50 is an endless belt, and is stretched by three rollers 51 so as to be movable in the direction of the arrow. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. A cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50. In addition, a transfer roller 80 serving as a transfer unit capable of applying a transfer bias for transferring (secondary transfer) a visible image (toner image) to a recording sheet 95 serving as a recording medium is disposed to face the recording paper 95. . Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is in contact with the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. And the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as a developer carrying member, and a black developing device 45K, a yellow developing device 45Y, a magenta developing device 45M, and a cyan developing device 45C provided around the developing belt 41. The black developing device 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing device 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developer 45M includes a developer container 42M, a developer supply roller 43M, and a developer roller 44M. The cyan developer 45C includes a developer container 42C, the developer supply roller 43C, and a developer. A roller 44C is provided. The developing belt 41 is an endless belt, is stretched by a plurality of belt rollers so as to be movable in the direction of the arrow, and a part of the developing belt 41 is in contact with the photoreceptor 10.

  In the image forming apparatus 100A, the charging roller 20 uniformly charges the photoconductor 10, and then exposes the photoconductor 10 using the exposure device 30 to form an electrostatic latent image. Next, the electrostatic latent image formed on the photoreceptor 10 is developed by supplying a developer from the developing device 40 to form a toner image. Further, the toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied by the roller 51, and further transferred (secondary transfer) onto the recording paper 95. As a result, a transfer image is formed on the recording paper 95. The toner remaining on the photoconductor 10 is removed by a cleaning device 60 having a cleaning blade, and the charged charge on the photoconductor 10 is removed by a static elimination lamp 70.

  FIG. 4 shows another example of the image forming apparatus used in the present invention. The image forming apparatus 100B does not include the developing belt 41, except that a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C are arranged around the photoconductor 10 so as to face each other. It has the same configuration as that of the image forming apparatus 100A and exhibits the same function and effect. In FIG. 4, the same components as those in FIG. 3 are denoted by the same reference numerals.

  FIG. 5 shows another example of the image forming apparatus used in the present invention. The image forming apparatus 100C is a tandem color image forming apparatus. The image forming apparatus 100 </ b> C includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder 400. The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16 so as to be able to move clockwise in the drawing. An intermediate transfer body cleaning device 17 for removing toner remaining on the intermediate transfer body 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched by the support rollers 14 and 15 is provided with a tandem developing device in which image forming means 18 of four colors of yellow, cyan, magenta, and black are opposed to each other along the conveying direction. 120 is arranged. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 can contact each other. It is. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.

  In the image forming apparatus 100C, a sheet reversing device 28 for reversing the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Thereby, images can be formed on both sides of the recording paper.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. First, a document is set on the document table 130 of the automatic document feeder 400, or the automatic document feeder 400 is opened to set a document on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed.

  When a start switch (not shown) is pressed, when an original is set on the automatic document feeder 400, after the original is conveyed onto the contact glass 32, on the other hand, when an original is set on the contact glass 32, Immediately, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, the reflected light from the original surface of the light irradiated by the first traveling body 33 is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35. As a result, a color original (color image) is read and used as image information for each color of black, yellow, magenta, and cyan. The image information of each color is transmitted to the image forming means 18 of each color in the tandem developing device 120, and a toner image of each color is formed.

  The toner image on the black photoconductor 10K, the toner image on the yellow photoconductor 10Y, the toner image on the magenta photoconductor 10M, and the toner image on the cyan photoconductor 10C are sequentially transferred onto the intermediate transfer member 50. (Primary transfer). Then, the toner images of the respective colors are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  As shown in FIG. 6, the image forming means 18 for each color in the tandem type developing device 120 includes a photoconductor 10, a charger 59 for uniformly charging the photoconductor 10, and a photosensor based on image information for each color. By exposing the body 10 (L in the figure), an exposure device 21 that forms an electrostatic latent image on the photoreceptor 10, and developing the electrostatic latent image using toner of each color, the photoreceptor 10 A developing unit 61 that forms toner images of the respective colors, a transfer charger 62 that transfers the toner images of the respective colors onto the intermediate transfer member 50, a photoconductor cleaning device 63, and a static eliminator 64 are provided.

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142a is selectively rotated to feed recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145a. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the paper feed roller 142b is rotated to feed out the recording paper on the manual feed tray 52, separated one by one by the separation roller 145b, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.

  Then, the registration roller 49 is rotated in time with the color transfer image formed on the intermediate transfer member 50, and the recording paper is fed between the intermediate transfer member 50 and the secondary transfer device 22, thereby being recorded on the recording paper. A color transfer image is formed. The toner remaining on the intermediate transfer member 50 after the transfer is cleaned by the intermediate transfer member cleaning device 17.

  The recording paper on which the color transfer image is formed is conveyed to the fixing device 25 by the secondary transfer device 22, and the color transfer image is fixed on the recording paper by heat and pressure. Thereafter, the recording paper is switched by the switching claw 55 and discharged by the discharge roller 56 and is stacked on the discharge tray 57. Alternatively, the sheet is switched by the switching claw 55, reversed by the sheet reversing device 28, led to the transfer position again, and after the image is formed on the back surface, the sheet is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  The process cartridge of the present invention is used in the image forming apparatus of the present invention, and integrally supports an image carrier and at least one means selected from a charging device, a developing device, and a cleaning device, and is attached to the image forming apparatus main body. It is detachable.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.
Example 1
(Synthesis of unmodified polyester resin)
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 to obtain an unmodified polyester resin (1). Was synthesized.
The obtained unmodified polyester resin 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.

(Master batch manufacturing method)
1200 parts of water, 540 parts of carbon black Printex 35 (manufactured by Dexa; DBP oil absorption = 42 ml / 100 mg, pH = 9.5) and 1200 parts of unmodified polyester resin were mixed using a Henschel mixer (manufactured by Mitsui Mining). . 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 a master batch (1).

(Preparation of wax dispersion)
In a reaction vessel equipped with a stirring bar and a thermometer, 378 parts of unmodified polyester resin (1), 110 parts of carnauba wax, 22 parts of salicylic acid metal complex E-84 (manufactured by Orient Chemical Co., Ltd.) and 947 parts of ethyl acetate are charged. The mixture was heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of master batch (1) and 500 parts of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain a raw material solution (1).
1324 parts of the obtained raw material solution (1) was transferred to a reaction vessel, filled with 80% by volume of 0.5 mm zirconia beads using an ultra visco mill (manufactured by Imex Co., Ltd.), a bead mill, and the liquid feeding speed was 1 kg / hour. , Three passes under the condition that the disk peripheral speed is 6 m / sec. I. Pigment Red and carnauba wax were dispersed to obtain a wax dispersion (1).

(Preparation of toner material dispersion)
Next, 1324 parts of a 65 wt% ethyl acetate solution of the unmodified polyester resin (1) was added to the wax dispersion (1). A layered inorganic mineral montmorillonite (Clayton APA Southern Clay modified at least partly with a quaternary ammonium salt having a benzyl group) was added to 200 parts of a dispersion obtained by one pass using Ultraviscomyl under the same conditions as above. 1.7 parts) (manufactured by Products) are added. K. Using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred for 30 minutes to obtain a toner material dispersion (1).

The viscosity of the obtained dispersion of toner material was measured as follows.
Using a parallel plate type rheometer AR2000 (made by D.A. Instruments Japan Co., Ltd.) equipped with a parallel plate with a diameter of 20 mm, the gap was set to 30 μm, and the toner material dispersion was at 25 ° C. After applying a shear force for 30 seconds at a shear rate of 30000 sec- ¹ , viscosity (viscosity A) was measured when the shear rate was changed from 0 sec- ¹ to 70 sec- ^{1 in} 20 seconds. Further, using a parallel plate rheometer AR2000, the viscosity (viscosity B) when a shearing force was applied to the dispersion of the toner material at 25 ° C. for 30 seconds at a shear rate of 30000 seconds ⁻¹ was measured.

(Synthesis of intermediate polyester resin)
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.

(Prepolymer synthesis)
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. (1) was synthesized. The free isocyanate content of the obtained prepolymer was 1.53% by weight.

(Preparation of oil phase mixture)
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 container, 749 parts of a dispersion of toner material (1), 115 parts of prepolymer (1) and 2.9 parts of a ketimine compound are charged, and using a TK homomixer (manufactured by Tokushu Kika) for 1 minute at 5000 rpm. By mixing, an oil phase liquid mixture (1) was obtained.

(Polymerization of resin particle dispersion)
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.

(Preparation of emulsified slurry)
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 (1) is charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging is performed at 45 ° C. for 4 hours to obtain a dispersed slurry (1). It was.

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.
To the obtained filter cake, 10 wt% hydrochloric acid was added to adjust the pH to 2.8, and the mixture was mixed at 12000 rpm for 10 minutes using a TK homomixer, followed by filtration.
Furthermore, 300 parts of ion-exchanged water was added to the obtained filter cake, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice to obtain a final filter cake.
The obtained final filter cake was dried at 45 ° C. for 48 hours using a circulating dryer, and sieved with a mesh having a mesh size of 75 μm to obtain toner mother particles.
To 100 parts of the obtained toner base particles, 1.0 part of hydrophobic silica as an external additive and 0.5 part of hydrophobized titanium oxide are added and mixed using a Henschel mixer (Mitsui Mining Co., Ltd.). The toner was manufactured.

Example 2
A toner was produced in the same manner as in Example 1 except that the amount of the modified layered inorganic mineral (trade name Kraton APA) was changed from 1.7 parts to 1.3 parts.
Example 3
A toner was produced in the same manner as in Example 1, except that the amount of the modified layered inorganic mineral (trade name Kraton APA) was changed from 1.7 parts to 1.0 part.

Example 4
(Preparation of resin emulsion)
The following monomers were uniformly mixed to prepare a monomer mixture.
Styrene monomer 71 parts n-butyl acrylate 25 parts acrylic acid 4 parts The following aqueous solution mixture is placed in a reactor and heated to 70 ° C under stirring. While stirring the liquid temperature at 70 ° C., 5 parts of the monomer mixture and 1% aqueous solution of potassium persulfate were added dropwise simultaneously over 4 hours, and further polymerized at 70 ° C. for 2 hours to obtain a solid content of 50%. A resin emulsion was obtained.
Water 100 parts Nonionic emulsifier (Emulgen 950) 1 part Anionic emulsifier (Neogen R) 1.5 parts (adjustment of toner particles)
The following mixture was stirred for 2 hours at 25 ° C. using a disper.
Pigment 20 parts Charge control agent (E-84, manufactured by Orient Chemical Co., Ltd.) 1 part Anionic emulsifier (Neogen R) 0.5 part Water 310 parts Next, 188 parts of the above emulsion was added to this dispersion and stirred for about 2 hours. After heating to 60 ° C., this was adjusted to pH 7.0 with ammonia. Further, this dispersion was heated to 90 ° C., and this temperature was maintained for 2 hours to obtain dispersion slurry 1.
[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 (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(2): 10% hydrochloric acid was added to the filter cake of (1) to adjust the pH to 2.8, mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(3): 300 parts of ion-exchanged water was added to the filter cake of (2), mixed with a TK homomixer (rotation speed 12000 rpm for 10 minutes), and then filtered twice to obtain [Filter cake 1].
[Filter cake 1] was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with an opening of 75 μm mesh to obtain a toner having a weight average particle diameter of 5.9 μm. Further, a toner was manufactured by externally adding R972 (silica manufactured by Nippon Aerosil Co., Ltd., average primary particle size: 0.016 μm) as a fluidity imparting agent at a ratio of 0.5 part to 100 parts of the toner.

Comparative Example 1
In Example 1 (preparation of dispersion of toner material), a layered inorganic mineral montmorillonite (manufactured by Kraton APA Southern Clay Products) at least partially modified with a quaternary ammonium salt having a benzyl group was not added, In the preparation of the emulsified slurry), the emulsified slurry (1) was desolvated at 30 ° C., and the amount of residual ethyl acetate in the emulsified slurry was adjusted to 6% by weight. 100 parts of the emulsified slurry from which the solvent has been removed is placed in a 0.7 part container of carboxymethylcellulose (CMC Daicel-1280: manufactured by Daicel Chemical Industries), and a peripheral speed of 1.8 m / s with a paddle type stirring blade. A toner was manufactured in the same manner as in Example 1 except that the mixture was mixed for 1 hour.

Comparative Example 2
A toner was produced in the same manner as in Comparative Example 1 except that 0.7 part of carboxymethylcellulose of Comparative Example 1 (CMC Daicel-1280: manufactured by Daicel Chemical Industries, Ltd.) was changed to 1 part.
Comparative Example 3
The modified layered inorganic mineral (trade name Kraton APA) was changed to organosilica sol (MEK-ST-UP, solid content concentration 20%, average primary particle size 15 nm, manufactured by Nissan Chemical Industries, Ltd.), and the amount added was changed to 20 parts. A toner was manufactured in the same manner as in Example 1 except that.

Comparative Example 4
Toner as in Comparative Example 3 except that the addition amount of organosilica sol (MEK-ST-UP, solid content concentration 20%, average primary particle size 15 nm, manufactured by Nissan Chemical Industries, Ltd.) was changed from 20 parts to 15 parts. Manufactured.
Comparative Example 5
Toner as in Comparative Example 3 except that the addition amount of organosilica sol (MEK-ST-UP, solid content concentration 20%, average primary particle size 15 nm, manufactured by Nissan Chemical Industries) was changed from 20 parts to 10 parts. Manufactured.
Comparative Example 6
A toner was prepared in the same manner as in Example 4 except that the heating time at 90 ° C. was changed to 5 hours when the dispersion slurry 1 was obtained in (preparation of resin emulsion) in Example 4.

The average value of SF-1 of the obtained toner and the content ratio of SF-1 in the range of 110 to 115 are shown in Table 1.
Further, using the obtained toner, the cleaning plate slippage amount (g) was measured as follows to evaluate the cleaning property. The results are shown in Table 1.
Evaluation of cleaning performance All toners and devices used for evaluation are left in an environment room at 25 ° C. and 50% for one day.
2. All toner on the Imageo neo C600 commercial product PCU is removed, leaving only the carrier in the development apparatus.
3. 28 g of black toner serving as a sample is put into a developing device having only a carrier, and 400 g of a developer having a toner concentration of 7% is produced.
4). A developing device is attached to the main body of Imagio neo C600, and only the developing device is idled for 5 minutes at a developing sleeve linear velocity of 300 mm / s.
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 is adjusted so that the transfer rate is 96 ± 2%.
8). A fibrous tape was attached in front of the charging roller so that the toner after the cleaning process (toner that passed through the cleaning blade) could be collected.
9. Using the above set values, 1000 charts (FIG. 7) with a band of 4 cm in the paper passing direction and 25 cm in the paper passing width direction were output.
10.8. The weight of the toner adhering to the tape attached in (1) was measured, and the amount of slipping through the cleaning blade was evaluated. The cleaning property is good when the weight of the slipped toner is less than 0.25 g.

Further, FIG. 8 shows the relationship between the cleaning blade slipping amount (g) and the content ratio of SF-1 of 100 to 115.
The horizontal axis represents the toner content rate in which the shape factor SF-1 is in the range of 100 to 115 for each toner, and the vertical axis represents the amount of slipping of the cleaning blade in each toner.
In the figure, “◯” indicates a toner having a slip-through amount of less than 0.25 g, and “×” indicates a toner of more than that.
From this result, if the average value of the shape factor SF-1 is in the range of 130 to 160 and the shape factor SF-1 is included in the range of 100 to 115 ≦ 2%, cleaning is possible. Became clear.

It is a figure which shows SF-1 calculation method. It is a figure for demonstrating prescription | regulation of a substantially spherical shape. It is a schematic explanatory drawing which shows an example of the image forming apparatus used by this invention. It is a schematic explanatory drawing which shows the other example of the image forming apparatus used by this invention. It is a schematic explanatory drawing which shows the other example of the image forming apparatus used by this invention. FIG. 4 is a schematic explanatory view showing a part of the image forming apparatus shown in FIG. 3. It is a figure which shows the chart used in the Example. It is a graph which shows the relationship between the cleaning property of an Example and a comparative example, and SF-1 content rate of 100-115.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Photoconductor 10K Black photoconductor 10Y Yellow photoconductor 10M Magenta photoconductor 10C Cyan photoconductor 14, 15, 16 Support roller 17 Intermediate transfer body cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer Device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing Belt 42K, 42Y, 42M, 42C Developer container 43K, 43Y, 43M, 43C Developer supply roller 44K, 44Y, 44M, 44C Developer roller 45K Black developer 45Y Yellow developer 45M Magenta developer 45C Cyan Present Device 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Manual feed tray 53 Manual feed path 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona charger 59 Charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Static eliminator 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Recording paper 100A, 100B, 100C Image forming device 110 Belt type fixing device 120 Tandem type developer 130 Document table 142a, 142b Paper feed roller 143 Paper bank 144 Paper feed cassette 145a, 145b Separating roller 146 Feeding path 147 Conveying roller 148 Feeding path 150 Copier main body 200 Feeding table 300 Scanner 400 Automatic document feeder

Claims (15)

An image carrier, a charging step for charging the surface of the image carrier, an exposure step for writing a latent image by exposure on the image carrier, and developing the latent image written on the image carrier by developing toner. A developing step for forming a visual image, a transferring step for transferring the visible image to a recording medium, a fixing step for fixing the transferred image transferred to the recording medium, and a transfer residue on the image carrier that has not been transferred completely. In the image forming apparatus having at least a cleaning step for cleaning the toner, the toner used for image formation is at least part of interlayer ions in the binder resin, the colorant, and the layered inorganic mineral produced by aqueous granulation. a toner comprising a modified modified layered inorganic mineral with an organic ion, the average value of shape factor SF-1 is in the range of 130 to 160, and 100 to the shape factor SF-1 Image forming apparatus characterized by contained particles number ≦ 2% by number in the range of 15.   2. The toner according to claim 1, wherein an average value of the shape factor SF-1 is in the range of 130 to 150 and the number of particles in the range of the shape factor SF-1 in the range of 100 to 115 is ≦ 2% by number. The image forming apparatus described in 1.   The toner contains at least a part of interlayer ions in a prepolymer composed of a binder resin and a modified polyester resin in an organic solvent, a compound that extends or crosslinks with the prepolymer, a colorant, a release agent, and a layered inorganic mineral. The modified layered inorganic mineral modified with organic ions is dissolved or dispersed, and the solution or dispersion has a Casson yield value at 25 ° C. of 1 to 100 Pa. The solution or dispersion is subjected to a crosslinking reaction and / or in an aqueous medium. The image forming apparatus according to claim 1, wherein the toner is a toner obtained by an extension reaction and removing the solvent from the obtained dispersion.   The modified layered inorganic mineral obtained by modifying at least a part of interlayer ions in the layered inorganic mineral with organic ions is contained in a solid content in a solution or dispersion in an amount of 0.05 to 10 wt%. The image forming apparatus according to 3.   The toner has a volume average particle diameter of 3 to 8 μm and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is in the range of 1.00 to 1.30. The image forming apparatus according to claim 1, wherein:   6. The image forming apparatus according to claim 1, wherein the toner has 1 to 10% by number of particles having a particle diameter of 2 [mu] m or less. 2. The toner according to claim 1, wherein the toner is obtained by externally adding fine particles having an average primary particle size of 50 to 500 nm and a bulk density of 0.3 g / cm ³ or more on the surface of the toner base particles. The image forming apparatus according to any one of? The modified layered inorganic mineral produced by aqueous granulation and used in the image forming apparatus according to claim 1 , wherein at least a part of interlayer ions in the binder resin, the colorant, and the layered inorganic mineral are modified with organic ions. A toner having an average value of shape factor SF-1 in the range of 130 to 160 and a number of particles in the range of shape factor SF-1 in the range of 100 to 115 ≦ 2% by number. .   9. The toner according to claim 8, wherein the average value of the shape factor SF-1 is in the range of 130 to 150, and the number of particles in the range of the shape factor SF-1 in the range of 100 to 115 is ≦ 2% by number. .   At least a part of interlayer ions in a prepolymer composed of a binder resin or a modified polyester resin in an organic solvent, a compound that extends or crosslinks with the prepolymer, a colorant, a release agent, or a layered inorganic mineral is modified with organic ions. The modified layered inorganic mineral is dissolved or dispersed, the Casson yield value at 25 ° C. of the solution or dispersion is 1 to 100 Pa, and the solution or dispersion is subjected to a crosslinking reaction and / or an extension reaction in an aqueous medium. The toner according to claim 8, wherein the toner is obtained by removing a solvent from the obtained dispersion.   The modified layered inorganic mineral obtained by modifying at least a part of interlayer ions in the layered inorganic mineral with organic ions is contained in a solid content in a solution or dispersion in an amount of 0.05 to 10 wt%. The toner according to 10.   The toner has a volume average particle diameter of 3 to 8 μm and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is in the range of 1.00 to 1.30. The toner according to claim 8.   The toner according to claim 8, wherein the toner has 1 to 10% by number of particles having a particle diameter of 2 μm or less. 9. The toner according to claim 8, wherein the toner is obtained by externally adding fine particles having an average primary particle size of 50 to 500 nm and a bulk density of 0.3 g / cm ³ or more on the surface of toner base particles. The toner according to any one of -13.   8. A process cartridge that integrally supports an image carrier and at least one unit selected from a charging unit, a developing unit, and a cleaning unit, and is detachable from an image forming apparatus main body. A process cartridge for use in the image forming apparatus described in 1.

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