JP2012013859A - Toner, developer, toner container, process cartridge, image forming method, image forming apparatus and method for producing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner having excellent heat-resistant storage property and fixing releasing property and high transfer efficiency and giving high-quality image for an OHP (overhead projector) sheet, and to provide a developer using the toner, a toner container, a process cartridge, an image forming apparatus and a method for producing the toner.SOLUTION: The method for producing a toner includes a core particle granulating step of dispersing a release agent in a binder resin to form core particles; a blooming step of annealing the particles in an atmosphere of temperature of 45°C or higher and lower by 3°C or more than the glass transition temperature of the binder resin, so as to deposit the release agent on the surfaces of the core particles; and an encapsulating step of covering surfaces of the core particles with shells. The toner produced by the method realizes an object of the invention.

Description

  The present invention relates to a toner for developing an electrostatic charge image in an OHP sheet, electrophotography, electrostatic recording, electrostatic printing, and the like, a developer using the toner, a container containing the toner, a process cartridge, an image forming apparatus, The present invention relates to an image forming method and a toner manufacturing method.

  Conventionally, a contact heating fixing method such as a heat roll fixing method has been widely adopted as a toner fixing method. A fixing device used for a heat roll fixing method includes a heating roll and a pressure roll, and passes a recording sheet carrying a toner image through a pressure contact portion (nip portion) between the heating roll and the pressure roll. As a result, the toner image is melted and fixed on the recording sheet.

  In the contact heating fixing method represented by the heat roll fixing method, the toner image on the recording sheet is fixed by bringing the surface of a heating member (for example, a heating roll) of the contact heating fixing device into contact with the toner image. It is necessary to prevent an offset phenomenon in which a part of an image adheres and is transferred to the next recording sheet and becomes dirty.

  In the case of the contact heat fixing method, the heating temperature is preferably as low as possible in order to save energy. However, if the thermal properties of the binder resin constituting the toner are too low, the heat-resistant storage property (heat storage property) As a result, there was a problem that blocking and the like occurred.

  In order to solve such a problem, for example, a toner in which a spherical wax is fixed on the surface of the toner has been proposed (Patent Document 1).

  However, the spherical wax present on the surface of the toner according to this proposal has a problem that the developability and transferability are lowered because the fluidity of the toner is lowered. In addition, there is a problem that the chargeability, durability, and heat-resistant storage properties are liable to be adversely affected.

  For example, a toner having a core-shell structure in which the content of the release agent (wax) contained in the shell is higher than the content of the release agent contained in the core has been proposed (Patent Document 2).

  However, it is clear that the toner according to this proposal inevitably exposes the release agent to the toner surface layer, and the release agent exposed on the surface lowers the fluidity of the toner. There was a problem that decreased. In addition, there is a problem that the chargeability, durability, and heat-resistant storage properties are liable to be adversely affected.

  For example, a toner having a core-shell structure, in which a release agent is encapsulated in a core binder resin (low Tg resin) covered with a shell made of a binder resin having a high glass transition temperature (Tg) is proposed. (Patent Document 3).

  However, since there is a release agent in the center of the core, the releasability at fixing is insufficient, and if there is too much release agent, the printed matter on the OHP sheet is projected and the stain of the release agent There is a problem that the projection is projected and the quality of the projected image is inferior.

  As described above, there is a strong demand for the rapid development of a toner having excellent heat resistance, fixing releasability (fixing separation property), transfer efficiency, and image quality of the OHP sheet.

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention is a toner having excellent heat-resistant storage property and fixing releasability, high transfer efficiency, and good image quality of an OHP sheet, and a developer, a container containing toner, a process cartridge, and image formation using the toner. It is an object of the present invention to provide an apparatus and a toner manufacturing method.

Means for solving the problems are as follows. That is,
<1> In a transmission electron microscope (TEM) image in a cross-section of an ultrathin section of a toner having a core-shell structure including a toner material containing at least a binder resin, a colorant, and a release agent in the core , Showing a sea-island structure in which the release agent exists in an island shape in the continuous phase of the binder resin, the volume average particle diameter of the toner is D, and 0.025 D (μm) on the inner side from the peripheral edge of the TEM image. (A1), the peripheral area excluding the peripheral area (A1) from the inner 0.05D (μm) area from the peripheral edge of the TEM image is (A2), and the peripheral edge of the TEM image The intermediate region excluding the peripheral region (A1) and the peripheral region (A2) from the region 0.2D (μm) inside from the part is defined as (B), the peripheral region (A1) of the TEM image, the peripheral Region (A2) and When the internal region excluding the intermediate region (B) is (C), the core is composed of the intermediate region (B) and the internal region (C), and the shell is the peripheral region (A1) and The peripheral area (A2) is composed of the area occupied by the island in the peripheral area (A1) IA1 (%), the area occupied by the island in the peripheral area (A2) is IA2 (%), When the ratio of the area occupied by the island in the intermediate region (B) is IB (%) and the ratio of the area occupied by the island in the inner region (C) is IC (%), the following formula (1) The toner includes the island satisfying the relationship of 3) and existing across the peripheral area (A2) and the intermediate area (B).
IA2> IA1 (1)
IB> IA2 (2)
IB> IC (3)
<2> The toner according to <1>, wherein the release agent is a pentaerythritol ester wax.
<3> The toner according to any one of <1> to <2>, wherein IA1 (%), IA2 (%), IB (%), and IC (%) satisfy the following formulas (i) to (v): It is.
0 ≦ IA1 ≦ 5 (i)
3 ≦ IA2 ≦ 20 (ii)
3 ≦ IB ≦ 70 (iii)
0 ≦ IC ≦ 5 (iv)
IC> IA1 (v)
<4> The toner according to any one of <1> to <3>, wherein the toner has an average circularity of 0.930 to 0.995.
<5> The toner according to any one of <1> to <4>, wherein the toner has at least one endothermic peak measured by a differential scanning calorimeter (DSC) in a range of 60 ° C to 90 ° C. is there.
<6> The toner according to <5>, wherein the half value width of the endothermic peak is 8 ° C. or less.
<7> The toner according to any one of <1> to <6>, wherein the content of the release agent is 3 parts by mass to 15 parts by mass with respect to 100 parts by mass of the binder resin.
<8> The toner according to any one of <1> to <7>, wherein a 1/2 outflow temperature (T1 / 2) measured by a flow tester in the toner is 110 ° C. to 140 ° C.
<9> The binder resin of the core contains at least a resin having a polyester skeleton, and the shell is made of resin fine particles made of a vinyl copolymer resin, and the total mass (B) and internal region (C) ( <8> to <8> in which the mass ratio ((A1 + A2) / (B + C)) of the total mass (A1 + A2) of the peripheral area (A1) and the peripheral area (A2) to B + C) is 0.05 to 0.5. The toner according to any one of the above.
<10> The toner according to any one of <1> to <9>, wherein the resin fine particles of the shell are at least one obtained by aggregation and fusion of fine particles of a vinyl copolymer resin.
<11> The toner according to any one of <1> to <10>, wherein the resin fine particles of the shell have a mass average molecular weight of 50,000 or less and a glass transition temperature of 40 ° C. to 80 ° C.
<12> The toner according to any one of <1> to <11>, wherein the binder resin of the core contains a modified polyester resin having at least one of urethane and urea groups.
<13> The above <1> to <12>, wherein the core binder resin contains at least one modified polyester resin that is chain-extended and cross-linked by a reaction between a modified polyester resin having an isocyanate group at a terminal and amines. The toner according to any one of the above.
<14> A developer comprising the toner according to any one of <1> to <13>.
<15> A toner-containing container filled with the toner according to any one of <1> to <13>.
<16> An image forming apparatus comprising at least an electrostatic latent image carrier and a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier using a toner to form a visible image A process cartridge that is detachable from a main body, wherein the toner is the toner according to any one of <1> to <13>.
<17> An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to make it visible In the image forming apparatus having at least a developing unit that forms an image, a transfer unit that transfers the visible image to a recording medium, and a fixing unit that fixes the transfer image transferred to the recording medium by a fixing member, the toner is An image forming apparatus comprising the toner according to any one of <1> to <13>.
<18> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, In the image forming method including at least a transfer step of transferring a visible image to a recording medium and a fixing step of fixing the transferred image transferred to the recording medium by a fixing member, the toner is the above <1> to <13>. An image forming method, wherein the toner is any one of the above.
<19> A core particle granulation step in which a release agent is dispersed in the binder resin to form core particles, and the temperature range is 45 ° C. or higher and 3 ° C. or lower than the glass transition temperature of the binder resin. A toner manufacturing method comprising: a blooming step of annealing in a temperature atmosphere to deposit the release agent on the surface of the core particle; and an encapsulation step of covering the surface of the core particle with a shell. is there.
<20> The method for producing a toner according to <19>, wherein the release agent is a pentaerythritol ester wax.

  According to the present invention, a conventional problem can be solved, a toner having excellent heat-resistant storage property and fixing releasability, high transfer efficiency, and good image quality of an OHP sheet, and a developer using the toner , A toner container, a process cartridge, an image forming apparatus, and a toner manufacturing method.

FIG. 1 is a schematic configuration diagram showing an example of a process cartridge of the present invention. FIG. 2 is a schematic configuration diagram showing an example of the image forming apparatus of the present invention. FIG. 3 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention. FIG. 4 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention. FIG. 5 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention. FIG. 6 is a schematic configuration diagram showing another example of the tandem type image forming apparatus of the present invention. FIG. 7 is a partially enlarged view of FIG. FIG. 8 is a schematic configuration diagram illustrating an example of a cross-sectional shape of the toner. FIG. 9 is a schematic configuration diagram illustrating an example of a cross-sectional shape of the core particle after the core particle forming step. FIG. 10 is a schematic configuration diagram illustrating an example of a cross-sectional shape of the core particle after the blooming process. FIG. 11 is a schematic configuration diagram illustrating an example of a cross-sectional shape of the toner after the encapsulation process. FIG. 12 is an enlarged view of the fixing device.

(toner)
The toner of the present invention has a core-shell structure having a core and a shell on the surface of the core.

The toner of the present invention shows a sea-island structure in which the release agent exists in an island shape in the continuous phase of the binder resin in a transmission electron microscope (TEM) image in a cross section of an ultrathin section.
In the sea-island structure, a matrix composed of a continuous phase of a binder resin is expressed as “sea”, and a state where a release agent exists as a domain in the matrix is expressed as “island”.
Here, the method of cross-sectional TEM observation of the ultra-thin section of the toner is, specifically, after embedding the toner in an epoxy resin, taking out a section using a cryomicrotome, and staining with ruthenium trioxide. Ultrathin sections are made to 100 μm. The ultrathin section is observed with a transmission electron microscope (TEM) at a magnification of 10,000 times for the cross section of the toner. Take 20 photographs of toner cross sections whose major axis is 0.9 to 1.2 times the toner volume average particle diameter, and evaluate these photographs (20 toners). Thus, the dispersion state of the release agent was observed. In the dyed TEM image, the part of the release agent close to the interface with the resin is dyed and observed, and the inside of the wax domain is lightly dyed or rarely dyed, and occasionally a lamellar phase is observed. This is because the interface of the release agent is in an amorphous state and the inside is in a crystalline state. The area ratio of the island region of the release agent was an arithmetic average of 20 toners.

  By adopting such a sea-island structure for the toner of the present invention, the release agent present in the island region at the time of fixing is melted when the part of the island region reaches the melting point, so that the inside of the island region melts. When the same amount of the mold is added, it is considered that the sea-island structure can increase the amount of elution to the toner surface layer and is excellent in fixing releasability. As a result, since it is not necessary to add an excessive amount of the release agent to the toner, it is considered that the heat-resistant storage property and the transfer efficiency are high, and the image quality of the OHP sheet is improved.

As the toner of the present invention, when the volume average particle diameter of the toner is D, as shown in an example in FIG. ), And a peripheral region excluding the peripheral region (A1) from a region 0.05D (μm) inside from the peripheral portion of the TEM image is defined as (A2), and 0.2D (inside from the peripheral portion of the TEM image) μm), an intermediate region excluding the peripheral region (A1) and the peripheral region (A2) is defined as (B), and the peripheral region (A1), the peripheral region (A2), and the intermediate region of the TEM image The internal area excluding the area (B) is defined as (C).
The core includes the intermediate region (B) and the internal region (C), and the shell includes the peripheral region (A1) and the peripheral region (A2).

As an example of the toner, as shown in FIG. 11, the toner A of the present invention comprises at least a colorant B, a release agent C, and a binder resin containing them, but in the continuous phase of the binder resin. The (matrix) shows a sea-island structure in which the release agent C exists in an island shape (domain shape), and the release agent C (island region) is contained in a large amount in the intermediate region (B). It preferably exists over the intermediate region (B).
The proportion of the islands that exists across the peripheral region (A2) and the intermediate region (B) is preferably 5% to 15% with respect to the total release agent present in the toner, and 5% to 12%. % Is more preferable, and 5% to 10% is particularly preferable.
When the ratio is less than 5%, there is not enough release agent to ooze out during fixing, and particularly when applied to an oilless fixing process, fixing releasability may be insufficient, and 15% If this value is exceeded, the toner surface will be affected, resulting in a decrease in toner fluidity, non-uniform chargeability, and deterioration in heat-resistant storage, resulting in deterioration in image quality and toner spillage. It can be a cause.

  The release agent C exists as a domain (island) in the toner, and is observed in an island shape in a transmission electron microscope (TEM) image in a cross section of an ultrathin section of the toner. Even if the release agent is present in the intermediate region (B), it is not preferable in the case where it is present as a continuous layer, because the toner becomes mechanically brittle and the like. It is important to be distributed (domain state).

Proportion of area occupied by the island (release agent) in the outer peripheral area (A1) (IA1 (%)), Proportion of area occupied by the island (release agent) in the inner peripheral area (A2) (IA2 ( %)), The ratio of the area occupied by the island (release agent) in the intermediate area (B) (IB (%)), and the ratio of the area occupied by the island (release agent) in the inner area (C) As (IC (%)), the following formulas (1) to (3) are satisfied.

IA2> IA1 (1)
IB> IA2 (2)
IB> IC (3)

The IA1 (%), the IA2 (%), the IB (%), and the IC (%) more preferably satisfy the relationships of the following formulas (i) to (v).

0 ≦ IA1 ≦ 5 (i)
3 ≦ IA2 ≦ 20 (ii)
3 ≦ IB ≦ 70 (iii)
0 ≦ IC ≦ 5 (iv)
IC> IA1 (v)

As a ratio (IA1 (%)) of the area (IA1 (%)) occupied by the island (release agent) in the peripheral area outside (A1), 0% to 5% is preferable, 0% to 2% is more preferable, and 0% is particularly preferable. preferable.
When the IA1 exceeds 5%, the toner surface is affected, so that the fluidity of the toner, the nonuniformity of the charging property, and the deterioration of the heat-resistant storage property are manifested, and the image quality is deteriorated and in the apparatus. It causes quality deterioration such as toner spillage.

The ratio (IA2 (%)) of the area occupied by the island (release agent) in the peripheral region inner side (A2) is preferably 3% to 20%, more preferably 3% to 15%, and more preferably 3% to 10%. % Is particularly preferred.
When the IA2 is less than 3%, the effect of forming an island is not seen, and there is not enough release agent to ooze out at the time of fixing. Therefore, particularly when applied to an oilless fixing process, the fixing release property is satisfactory. If it exceeds 20%, the surface of the toner is affected, so that the fluidity of the toner, the non-uniformity of the charging property, and the deterioration of the heat-resistant storage property become obvious, and the image quality is deteriorated and the apparatus This may cause quality deterioration such as toner spillage.

The area ratio (IB (%)) occupied by the island (release agent) in the intermediate region (B) is preferably 3% to 70%, and more preferably 5% to 50%.
When the IB is less than 3%, there are not enough release agents to ooze out during fixing, and particularly when applied to an oil-less fixing process, fixing release properties may not be obtained satisfactorily. If it exceeds the upper limit, the mechanical strength of the intermediate region (B) is lowered, so that the toner is cracked or chipped due to the stress of each electrophotography, and the toner chargeability may be lowered or non-uniform. On the other hand, if the IB exceeds 70%, fine powder generated due to lack of toner adheres to and contaminates the regulating member, the photoconductor, etc., and the chargeability is lowered. Further, when printing is performed on an OHP sheet, an excessive mold release agent oozes out to the outside of the printed portion, which may cause hazy image noise even when projected with OHP.

The area ratio (IC (%)) occupied by the island (release agent) in the internal region (C) is preferably 0% to 5%, more preferably 0% to 2%, and particularly preferably 0%. .
When the IC exceeds 5%, the area occupied by the binder resin and the colorant is relatively reduced, so that the pigment dispersibility is lowered, leading to a reduction in image density and a narrow color reproduction range. Furthermore, excessive release agent can cause image noise during OHP projection.

<Core particles>
The core particles contain a binder resin and a colorant, and further contain other components as necessary.

<< Binder resin >>
The binder resin preferably contains at least a polyester resin. This is more preferable because the design range of the thermal characteristics and viscoelastic characteristics of the binder resin is expanded.
The core particles preferably contain at least a modified polyester resin. This further increases the design range of the thermal characteristics and viscoelastic characteristics of the binder resin, which is more preferable. In addition, these adhere to the surface of the core material as monomers, macromonomers, and polymers having reactive groups, and then cause radical polymerization and condensation polymerization reactions by heating, a crosslinking agent, a polymerization initiator, etc. It may be a binder resin precursor that forms a binder resin having characteristics.

The core particles are preferably composed of particles formed by extending or cross-linking an organic solvent oil droplet in which a toner composition containing at least a prepolymer is dispersed in an aqueous medium. This makes it possible to form a toner having a core-shell structure.
As the core particle, a toner composition including at least a polymer having a site capable of reacting with a compound having an active hydrogen group, a polyester resin, a colorant, and a release agent is contained in an aqueous medium in the presence of resin fine particles. It is preferable to carry out crosslinking or elongation reaction. Similarly, a toner having the core-shell structure can be formed, and a toner having appropriate softening characteristics can be formed inside the shell and the core particles, which is more preferable.

-Polyester resin-
As the polyester resin, there are a modified polyester resin and an unmodified polyester resin. However, it is easy to crosslink and extend, and the modified polyester resin may be contained in that it is suitable for adjustment of viscoelasticity for the purpose of preventing offset. More preferred.

--Modified polyester resin--
As the modified polyester resin, for example, a polyester prepolymer having an isocyanate group can be used. Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group, which is further reacted with a polyisocyanate (3). Is mentioned. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1- The mixture of 2) is preferred.
Examples of the diol (1-1) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide of alicyclic diol, bisphenols, alkylene oxide of bisphenols, and the like.
Examples of the alkylene glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like.
Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol.
Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.
Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S.
Examples of the alkylene oxide of the alicyclic diol include ethylene oxide, propylene oxide, butylene oxide, and the like.
Examples of the alkylene oxides of the bisphenols include ethylene oxide, propylene oxide, butylene oxide, and the like.
Among these, 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.
Examples of the trihydric or higher polyol (1-2) include 3 to 8 or higher polyhydric aliphatic alcohols, trihydric or higher phenols, and alkylene oxide adducts of trihydric or higher polyphenols. Can be mentioned.
Examples of the trivalent to octavalent or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.
Examples of the trivalent or higher phenols include trisphenol PA, phenol novolac, and cresol novolak.

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

  The ratio of the polyol (1) to the polycarboxylic acid (2) is usually preferably 2/1 to 1/1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1.5 / 1 to 1/1 are more preferable, and 1.3 / 1 to 1.02 / 1 are particularly preferable.

Examples of the polyisocyanate (3) include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and polyisocyanates blocked with phenol derivatives, oximes, caprolactams, and the like. Etc. These may be used alone or in combination of two or more.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,6-diisocyanatomethyl caproate.
Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate.
Examples of the aromatic diisocyanate include tolylene diisocyanate and diphenylmethane diisocyanate.
Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate.

The ratio of the polyisocyanate (3) is preferably 5/1 to 1/1 as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. / 1 to 1.2 / 1 is more preferable, and 2.5 / 1 to 1.5 / 1 is particularly preferable.
When the [NCO] / [OH] is less than 1, the urea content in the modified polyester is lowered, and the hot offset resistance may be deteriorated. When it exceeds 5, the low-temperature fixability may be deteriorated. is there.
The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is preferably 0.5% by mass to 40% by mass, more preferably 1% by mass to 30% by mass. A mass% to 20 mass% is particularly preferred.
When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. May get worse.

The number of isocyanate groups contained per molecule in the prepolymer (A) having the isocyanate group is preferably 1 or more, more preferably 1.5 to 3 on average, and particularly preferably 1.8 to 2.5 on average. preferable.
When the number of isocyanate groups contained per molecule is less than one, the molecular weight of any modified polyester after crosslinking and elongation is lowered, and hot offset resistance may be deteriorated.

In the present invention, amines can be used as at least one of the crosslinking agent and the extender. Examples of the amines (B) include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), or amino acids (B1) to (B5). What blocked the group (B6) etc. are mentioned.
Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines.
Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, and the like.
Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine.
Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine).
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of (B6) obtained by blocking the amino group of (B1) to (B5) include ketimine compounds and oxazolines obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Compound etc. are mentioned. Among these amines (B), preferred are (B1) and a mixture of (B1) and a small amount of (B2).

Furthermore, if necessary, the molecular weight of the modified polyester after completion of the reaction can be adjusted by using a terminator for at least one of crosslinking and elongation.
Examples of the terminator include monoamines or those blocked (ketimine compounds).
Examples of the monoamine include diethylamine, dibutylamine, butylamine, and laurylamine.
The ratio of the amines (B) is the equivalent ratio [NCO] / [NHx of the isocyanate group [NCO] in the prepolymer (A) having an isocyanate group and the amino group [NHx] in the amine (B). ] Is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and particularly 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 (i) is lowered, and the hot offset resistance may be deteriorated.

The binder resin preferably contains a modified polyester resin having either a urethane group or a urea group in order to adjust viscoelasticity for the purpose of preventing offset. The content of the modified polyester resin having either a urethane group or a urea group is preferably 20% or less, more preferably 15% or less, and particularly preferably 10% or less in the binder resin.
If the content exceeds 20%, the low-temperature fixability may deteriorate.

  As the modified polyester resin having either the urethane group or the urea group, it may be directly mixed with the binder resin, but from the viewpoint of productivity, a relatively low molecular weight modified polyester resin having an isocyanate group at the terminal ( (Hereinafter sometimes referred to as prepolymer) and amines that react with the binder resin are mixed with the binder resin, and have either urethane groups or urea groups by chain extension or crosslinking reaction during or after granulation. It is preferable to use a modified polyester resin.

--Unmodified polyester resin--
In the present invention, it is important not only to use the modified polyester alone, but also to contain a polyester not modified with the modified polyester as a toner binder component. By using the unmodified polyester resin in combination, the low temperature fixability and the glossiness and gloss uniformity when used in a full color apparatus are improved. Examples of the unmodified polyester resin include polycondensates of polyol (1) and polycarboxylic acid (2) similar to the polyester component of the modified polyester resin, and preferred ones are the same as the modified polyester resin. The unmodified polyester resin is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, such as a urethane bond. The modified polyester resin and the unmodified polyester resin are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component of the modified polyester resin and the unmodified polyester resin preferably have similar compositions. The mass ratio [(A) / (C)] of the modified polyester resin (A) and the unmodified polyester resin (C) when the modified polyester resin is contained is preferably 5/95 to 75/25, 10/90 to 25/75 is more preferable, 12/88 to 25/75 is still more preferable, and 12/88 to 22/78 is particularly preferable.
When the mass ratio [(A) / (C)] is less than 5/95, the hot offset resistance is deteriorated, and it may be disadvantageous in terms of both heat-resistant storage properties and low-temperature fixability.

The peak molecular weight of the unmodified polyester resin (C) is preferably 1,000 to 30,000, more preferably 1,500 to 10,000, and particularly preferably 2,000 to 8,000.
When the peak molecular weight is less than 1,000, the heat-resistant storage property may be deteriorated, and when it exceeds 10,000, the low-temperature fixability may be deteriorated.

The hydroxyl value of the unmodified polyester resin (C) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g to 120 mgKOH / g, and particularly preferably 20 mgKOH / g to 80 mgKOH / g.
If the hydroxyl value is less than 5 mgKOH / g, it may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The hydroxyl value is measured under the following conditions based on the measurement method described in JIS K0070-1966.
Weigh accurately 0.5 g of sample into a 100 mL volumetric flask, and accurately add 5 mL of acetylating reagent. Then, it is immersed in a 100 ° C. ± 5 ° C. flask bath and heated. After 1 to 2 hours, the flask is taken out of the bath, allowed to cool, added with water and shaken to decompose acetic anhydride. Further, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with a (1/2) N potassium hydroxide ethyl alcohol solution using a potentiometric automatic hand titrator (DL-53 Titrator, manufactured by METTLER TOLEDO) to determine the OH value.

The acid value of (C) is preferably 0.5 mgKOH / g to 40 mgKOH / g, and more preferably 5 mgKOH / g to 35 mgKOH / g. By giving the acid value, it tends to be negatively charged. In addition, those having an acid value and a hydroxyl value exceeding these ranges are easily affected by the environment under high temperature and high humidity and low temperature and low humidity, and are liable to cause image deterioration.
The acid value is measured under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of polyester (0.3 g for ethyl acetate-soluble component) is added to 120 mL of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 mL of ethanol is added to prepare a sample solution.
The measurement can be performed by a potentiometric automatic hand titrator (DL-53 Titrator, manufactured by METTLER TOLEDO). Specifically, the measurement is performed as follows.
Titrate with a pre-standardized (1/10) N caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (mL number) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

The glass transition temperature (Tg) of the binder resin is preferably 40 ° C to 80 ° C, more preferably 40 ° C to 70 ° C, and particularly preferably 40 ° C to 60 ° C.
When the glass transition temperature is less than 40 ° C., the heat-resistant storage property of the toner deteriorates, and when it exceeds 80 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the crosslinked and elongated polyester resin, the toner of the present invention exhibits good heat-resistant storage stability even when the glass transition temperature is low, as compared with known polyester-based toners.

The glass transition temperature (Tg) can be measured using, for example, a TG-DSC system TAS-100 manufactured by Rigaku Corporation.
First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. Next, after heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample is allowed to stand at 150 ° C. for 10 minutes, and then the sample is cooled to room temperature and left for 10 minutes. Furthermore, the DSC measurement is performed by heating again to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. Tg is calculated from the contact point between the tangent line and the base line of the endothermic curve near Tg, using the analysis system in the TAS-100 system.

<< Colorant >>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, 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, Lead Red, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faisa Red, Lachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone , Pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, Indanthrene blue (RS, BC), indigo, ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, 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 Examples include green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and litbon.

The content of the colorant is preferably 1% by mass to 15% by mass and more preferably 3% by mass to 10% by mass with respect to the toner.
If the content is less than 1% by mass, the desired hue may not be reached, and if it exceeds 15% by mass, charging failure or fixing property may be caused.

The colorant can also be used as a master batch combined with a resin. As the binder resin kneaded together with the production of the master batch or the master batch, in addition to the above-mentioned modified or unmodified polyester resin, a polymer of styrene or a substituted product thereof, a styrene copolymer, 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, aliphatic or alicyclic hydrocarbon resin , Aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. These may be used alone or in combination of two or more.
Examples of the polymer of the styrene or a substituted product thereof include polystyrene, poly p-chlorostyrene, and polyvinyl toluene.
Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - like maleic acid ester copolymer.

  As the master batch, a master batch resin and a colorant can be mixed under high shearing force and kneaded to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. In addition, the so-called flushing method, which is a wet method of colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Since the cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

<< Releasing agent >>
Examples of the release agent (wax) include pentaerythritol esters.
The pentaerythritol ester is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include pentaerythritol tetrabehenate and pentaerythritol diacetate dibehenate. Among these, pentaerythritol tetrabehenate is preferable.

The melting point of the release agent is preferably 40 ° C to 160 ° C, more preferably 50 ° C to 120 ° C, and particularly preferably 60 ° C to 90 ° C.
When the melting point is less than 40 ° C., the heat-resistant storage property is adversely affected.

The average length of the major axis of the release agent is preferably 0.1 μm to 2.5 μm, more preferably 0.2 μm to 1.8 μm, and particularly preferably 0.3 μm to 1.5 μm.
When the average length is less than 0.1 μm, the exudation of the release agent from the toner particles is delayed, and the releasing effect at the time of fixing may be significantly reduced. Since the state of dispersion of the release agent and the resin in the particles becomes non-uniform, the charging uniformity may be poor and the heat-resistant storage stability may be deteriorated.
The average length is determined by, for example, observing the cross section of the toner at a magnification of 10,000 with a transmission electron microscope (TEM). It can be determined by taking 20 photographs of the 1.2 times magnification, measuring the major axis of the release agent by image evaluation, and taking the arithmetic average value as the average length.

The aspect ratio of the release agent is preferably 3 or more, more preferably 3.5 or more, and particularly preferably 4 or more.
When the aspect ratio is less than 3, bleeding of the release agent from the toner particles is delayed, and the release effect at the time of fixing may be significantly reduced.

The average distance between the boundaries of the release agent domains present in the shell, which will be described later, and the toner surface is preferably 0.025 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.075 μm or more.
When the average distance is less than 0.025 μm, the rigidity of the toner is lowered, and the chargeability and fluidity may be lowered due to toner cracking or toner missing.

The island part height of the release agent is preferably 60% or less, more preferably 55% or less, and particularly preferably 50% or less of the thickness of the shell.
If the height of the island portion exceeds 60% of the thickness of the shell, it affects the toner surface closest to each domain of the release agent that is further dispersed. Non-uniformity and deterioration of heat-resistant storage properties become obvious, which may cause deterioration of image quality and quality deterioration such as toner spillage in the apparatus.

The melt viscosity of the release agent is preferably 5 cps to 1,000 cps, more preferably 10 cps to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point.
When the melt viscosity exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability is poor.

As content of the said mold release agent, 3 mass parts-15 mass parts are preferable with respect to 100 mass parts of binder resin, 3 mass parts-12 mass parts are more preferable, and 3 mass parts-10 mass parts are especially. preferable.
When the content is less than 3 parts by mass, the release effect due to the release agent is lost, and there is a possibility that the margin for preventing offset may be lost. When the content exceeds 15 parts by mass, the release agent melts at a low temperature. The release agent is likely to be affected by heat energy and mechanical energy, and the release agent oozes out from the toner during stirring in the developing unit and adheres to the toner regulating member and the photoconductor, thereby generating image noise. Further, when printing is performed on the OHP sheet, the release agent may spread outside the printing area and appear as image noise in the projected image.

The range of a preferable endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the release agent is preferably 60 to 90 ° C, and more preferably 65 to 80 ° C.
If the range of the endothermic peak is less than 60 ° C., fluidity and heat-resistant storage properties may be deteriorated, and if it exceeds 90 ° C., fixability tends to be deteriorated.
Moreover, the preferable half value width of the endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) is preferably 8 ° C. or less, and more preferably 6 ° C. or less. In the case where the so-called endothermic peak is broader than the half width of more than 8 ° C., the fluidity and heat resistant storage stability are deteriorated.
The endothermic peak can be measured using a differential scanning calorimeter (DSC6200 manufactured by Seiko Instruments Inc.). Specifically, a release agent or toner is weighed in a 5 mg aluminum pan, set in a differential scanning calorimeter, heated from room temperature to 200 ° C., and cooled from that temperature to 0 ° C. at a cooling rate of 10 ° C./min. The measured samples were measured at a heating rate of 10 ° C./min. The result at this time was plotted by temperature and calorific value, and the temperature at which the calorific value was the minimum value was defined as the endothermic peak. In addition, a line segment is drawn perpendicularly to the baseline from the endothermic peak, and the temperature difference between the two points where the line passing through the center of the line segment and parallel to the baseline intersects the temperature-calorie plot is the half-value width of the endothermic peak. It was. Further, the glass transition temperature can be obtained from a base line below the glass transition point and a curved line portion corresponding to a half height of the base line above the glass transition point.

The weight average molecular weight of the release agent is preferably 300 to 3,000, more preferably 350 to 2,800, and particularly preferably 400 to 2,500.
When the mass average molecular weight is less than 300, the heat-resistant storage property of the toner is deteriorated, and blocking may occur during storage and in the developing machine. When it exceeds 3,000, the release agent is released. In some cases, the sexual effect cannot be obtained and the occurrence of an offset is observed.

<Shell>
The toner having a core-shell structure of the present invention is preferably formed by forming a shell whose core surface is coated with at least resin fine particles. This makes it possible to stably provide a toner having a stable and uniform core-shell structure, that is, a structure having different softening temperatures between the shell and the core particles.

<< Resin fine particles >>
The glass transition temperature (Tg) of the resin fine particles is preferably 40 ° C to 80 ° C, and more preferably 50 ° C to 70 ° C.
If the glass transition temperature exceeds 80 ° C, the low-temperature fixability may be deteriorated, and if it is less than 40 ° C, the heat-resistant storage property may be deteriorated.
The glass transition temperature can be measured using, for example, a TG-DSC system TAS-100 manufactured by Rigaku Corporation.

The mass average molecular weight of the resin fine particles is preferably 50,000 or less, and more preferably 30,000 or less.
When the mass average molecular weight exceeds 50,000, the low-temperature fixability may be deteriorated.
The mass average molecular weight can be measured, for example, by gel permeation chromatography (GPC). The molecular weight measurement by GPC is carried out with a THF solvent using a GPC / HLC-8120 manufactured by Tosoh Corporation as a measuring apparatus and a column / TSKgel SuperHM-M (15 cm) manufactured by Tosoh Corporation. The mass average molecular weight is calculated from the measurement result using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.

The residual ratio of the resin fine particles to the toner of the present invention is preferably 0.5% by mass to 5.0% by mass.
When the residual ratio is less than 0.5% by mass, the heat-resistant storage property of the toner deteriorates, and blocking occurs during storage and in the developing machine. When the residual rate exceeds 5.0% by mass, the resin fine particles Inhibits the exudation of the release agent, the release effect of the release agent cannot be obtained, and the occurrence of offset may be observed.
The residual ratio of the resin fine particles can be measured by, for example, analyzing a substance caused by the resin fine particles not by toner particles by a pyrolysis gas chromatograph mass spectrometer and calculating from the peak area. As the detector, a mass spectrometer is preferable.

  The resin fine particles are not particularly limited, and any resin can be used as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resin, polyurethane resin, epoxy Examples include resins, crystalline polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. These may be used alone or in combination of two or more. Among these, a plurality of types of monomers can be mixed and polymerized, and the degree of freedom in selecting monomer types is high. For example, it is easy to introduce a polar group such as carboxylic acid sulfonic acid, and for example, emulsion polymerization or In suspension polymerization, a vinyl copolymer resin is preferable in that it can be structured in the polymer particle depending on the polarity of the monomer, and a functional group derived from a desired monomer species can be efficiently distributed on the particle surface.

  Examples of the vinyl copolymer resin include styrene-butadiene copolymer, (meth) acrylic acid-acrylic ester polymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic. An acid copolymer etc. are mentioned.

The crystalline polyester resin refers to a polyester resin in which a crystalline region in which long chain molecules are regularly arranged in a molecular structure and an amorphous region that is not regularly arranged are mixed.
The crystalline polyester resin means a polymer (copolymer) obtained by polymerizing a component constituting polyester and another component in addition to a polymer having a 100% polyester structure as a constituent component. However, in the latter case, the other component other than the polyester constituting the polymer (copolymer) is 50% by mass or less.
Further, the degree of crystallinity is not necessarily 100%, and if it has a slight crystallinity, the function is exhibited, preferably 10% to 100%, more preferably 30% to 100%.

  The crystalline polyester resin is synthesized from, for example, a polyvalent carboxylic acid component and a polyhydric alcohol component. As said crystalline polyester resin, a commercial item may be used and what was synthesize | combined may be used.

The polyvalent carboxylic acid component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic dicarboxylic acids, dibasic acids and other aromatic dicarboxylic acids, trivalent or higher carboxylic acids, and the like. Examples thereof include anhydrides and lower alkyl esters thereof.
Examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12 -Dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid and the like.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, mesaconic acid, and the like.
Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like. These may be used individually by 1 type and may use 2 or more types together.
In addition, as an acid component, the dicarboxylic acid component which has a sulfonic acid group other than the said aliphatic dicarboxylic acid and aromatic dicarboxylic acid may be contained. Further, in addition to the aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid component having a double bond may be contained.

  The polyhydric alcohol component is preferably an aliphatic diol, and more preferably a linear aliphatic diol having a main chain portion having 7 to 20 carbon atoms. If the aliphatic diol is branched, the crystallinity of the polyester resin is lowered, and the melting point may be lowered. Further, when the main chain portion has less than 7 carbon atoms, when polycondensation with an aromatic dicarboxylic acid, the melting temperature becomes high and fixing at low temperature may be difficult, while the main chain portion has 20 carbon atoms. Exceeding the above range makes it difficult to obtain practical materials. The number of carbon atoms in the main chain portion is more preferably 14 or less.

  The aliphatic diol suitably used for the synthesis of the crystalline polyester is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol, 1,3-propanediol, 1,4-butane Diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, and the like. Among these, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are particularly preferable from the viewpoint of availability.

Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used alone or in combination of two or more.
Among the polyhydric alcohol components, the content of the aliphatic diol is preferably 80 mol% or more, and more preferably 90% or more.
If the content of the aliphatic diol is less than 80 mol%, the crystallinity of the polyester resin is lowered and the melting temperature is lowered, so that the toner blocking resistance, the image storage stability, and the low temperature fixability are deteriorated. May end up.

If necessary, a polycarboxylic acid or a polyhydric alcohol may be added at the final stage of the synthesis for the purpose of adjusting the acid value or the hydroxyl value.
Examples of the polyvalent carboxylic acid include aromatic carboxylic acids, aliphatic carboxylic acids, and alicyclic carboxylic acids.
Examples of the aromatic carboxylic acids include terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid, and the like.
Examples of the aliphatic carboxylic acids include maleic anhydride, fumaric acid, succinic acid, alkenyl succinic anhydride, and adipic acid.
Examples of the alicyclic carboxylic acids include cyclohexanedicarboxylic acid.

Examples of the polyhydric alcohol include aliphatic diols, alicyclic diols, and aromatic diols.
Examples of the aliphatic diols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, and glycerin.
Examples of the alicyclic diols include cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, and the like.
Examples of the aromatic diols include bisphenol A ethylene oxide adducts and bisphenol A propylene oxide adducts.

The crystalline polyester resin can be produced at a polymerization temperature of 180 ° C. to 230 ° C., and the reaction system is reacted under reduced pressure as necessary to remove water and alcohol generated during condensation.
When the polymerizable monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. If there is a polymerizable monomer having poor compatibility in the copolymerization reaction, the polymerizable monomer having poor compatibility and the polymerizable monomer and the acid or alcohol to be polycondensed are condensed in advance. And then polycondensation with the main component.

Examples of the catalyst that can be used in the production of the polyester resin include alkali metal compounds, alkaline earth metal compounds, metal compounds, phosphorous acid compounds, phosphoric acid compounds, and amine compounds.
Examples of the alkali metal compound include sodium and lithium.
Examples of the alkaline earth metal compound include magnesium and calcium.
Examples of the metal compound include zinc, manganese, antimony, titanium, tin, zirconium, germanium, and the like.

  Examples of the catalyst include sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, and titanium. Tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, Zirconium tetrabutoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, oxidized germanium Um, triphenyl phosphite, tris (2,4-di -t- butyl-phenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, triphenyl amine.

The acid value of the crystalline polyester resin (mg of KOH necessary for neutralizing 1 g of resin) is preferably 3.0 mgKOH / g to 30.0 mgKOH / g, and 6.0 mgKOH / g to 25.0 mgKOH / g is more preferable, and 8.0 mgKOH / g to 20.0 mgKOH / g is particularly preferable.
When the acid value is less than 3.0 mgKOH / g, dispersibility in water is lowered, and thus it may be very difficult to produce particles by a wet process. In addition, since the stability as the polymer particles during aggregation is significantly reduced, it may be difficult to produce an efficient toner. On the other hand, when the acid value exceeds 30.0 mgKOH / g, the hygroscopicity as a toner increases and the toner may be easily affected by the environment.
The acid value is measured under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of polyester (0.3 g for ethyl acetate-soluble component) is added to 120 mL of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 mL of ethanol is added to prepare a sample solution.
The measurement can be performed with a potentiometric automatic hand titrator (DL-53 Titrator, manufactured by METTLER TREND). Specifically, the measurement is performed as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (mL number) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

  The crystalline resin containing the above crystalline polyester resin is mainly composed of a crystalline polyester resin synthesized from an aliphatic polymerizable monomer (hereinafter sometimes referred to as “crystalline aliphatic polyester resin”). 50 mass% or more). Furthermore, in this case, the constituent ratio of the aliphatic polymerizable monomer constituting the crystalline aliphatic polyester resin is preferably 60 mol% or more, and more preferably 90 mol% or more. As the aliphatic polymerizable monomer, the above-mentioned aliphatic diols and dicarboxylic acids can be suitably used.

The following emulsification step is preferable as a method for producing the resin fine particles containing at least the crystalline polyester resin. When used in the toner shell, it is more preferably used in the state of an emulsified dispersion.
In the emulsification step, one or more crystalline resins and, if necessary, one or more amorphous polyester resins are used at a temperature higher than the melting point of the resin or the glass transition temperature and lower than the boiling point of the organic solvent used. After heating and dissolving at a temperature of 5% to obtain a uniform solution, a basic aqueous solution is added as a neutralizing agent, followed by adding pure water and maintaining the pH at 7 to 9 to give a stirring shear to cause phase inversion. An O / W type emulsion (emulsion) is obtained. Next, the obtained emulsion is distilled under reduced pressure to remove the solvent, thereby obtaining a resin particle emulsion.
The pH after neutralization is preferably 7-9, more preferably 7-8. When the pH is less than 7, there is a problem that coarse particles are likely to be generated in the emulsion, and when it exceeds 9, there is a problem that the aggregate particle size is expanded by aggregation in the next step. As the basic aqueous solution, for example, an alkali metal hydroxide such as an aqueous ammonium solution, sodium hydroxide, or potassium hydroxide may be used.

  By using particles in which the crystalline polyester resin and the non-crystalline polyester resin are compatible as described above, the resin particle portion having a lower acid value is likely to agglomerate, so that the core-shell structure of the present invention is obtained. A toner having the same can be obtained.

The average particle diameter of the resin fine particles is preferably 1,000 nm or less, more preferably 10 nm to 1,000 nm, still more preferably 10 nm to 800 nm, and particularly preferably 100 nm to 500 nm. When the average particle size exceeds 1,000 nm, the particle size distribution of the finally obtained toner cannot be stably controlled, the generation of free particles may occur, and the performance and reliability may be reduced. If it is less than 10 nm, toner may not be formed.
Here, the said average particle diameter can be measured with a dispersion body, using measuring apparatuses, such as LA-920 (Horiba Seisakusho) or UPA-EX150 (Nikkiso), for example.
As the average particle diameter, MV (volume average value) measured by UPA-EX150 was used. The specific measurement method is as follows. First, the measurement part is filled with a solvent, and zero point measurement is performed. Next, a dispersion of resin fine particles is added to the measurement unit, and the loading index is adjusted to fall within the range of 1 to 1.5, and measurement is performed. Note that pure water was used as the solvent, and the analysis conditions were set as follows.
Particle refractive index 1.59
Particle permeability Transparent particle shape True spherical particle density 1
Solvent refractive index 1.333
Solvent viscosity 0.797 mPa · s at 30 ° C, 1.002 mPa · s at 20 ° C
Filter Standard
Sensitivity Standard
Measurement time 60 seconds Zero Set 30 seconds

Examples of the dispersion medium in the dispersion include an aqueous medium and an organic solvent. Examples of the aqueous medium include water such as distilled water and ion-exchanged water, alcohols, acetate esters, ketones, and mixtures thereof. These may be used alone or in combination of two or more.
A surfactant may be added to and mixed with the aqueous medium.
There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, etc. are mentioned. Among these, anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together.

Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium alkylnaphthalenesulfonate, and sodium dialkylsulfosuccinate.
Examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.
Examples of the nonionic surfactant include polyethylene glycol, alkylphenol ethylene oxide adduct, polyhydric alcohol, and the like.
As the organic solvent, for example, an alcohol such as ethyl acetate, methyl ethyl ketone, acetone, toluene, and isopropyl alcohol can be used, and the organic solvent is appropriately selected according to the binder resin.

When the resin fine particle is a crystalline polyester or an amorphous polyester resin, it has a self-water dispersibility containing a functional group that can be anionic by neutralization, and a part or all of the functional group that can be hydrophilic is a base. A stable aqueous dispersion can be formed under the action of an aqueous medium neutralized with. In the crystalline polyester and the amorphous polyester resin, the functional group that can become a hydrophilic group by neutralization is an acidic group such as a carboxyl group or a sulfone group, and examples of the neutralizing agent include sodium hydroxide, potassium hydroxide, Examples thereof include inorganic bases such as lithium hydroxide, calcium hydroxide, sodium carbonate and ammonia, and organic bases such as diethylamine, triethylamine and isopropylamine.
Further, when using a polyester resin that does not disperse in water as a binder resin, that is, does not have self-water dispersibility, it is ionic in the resin solution and / or an aqueous medium mixed therewith as in the case of the release agent described later. Disperse with a polyelectrolyte such as surfactant, polymer acid, polymer base, etc., heat above melting point, and process with a homogenizer or pressure discharge type disperser that can apply a strong shearing force. Of particles. When this ionic surfactant or polymer electrolyte is used, the concentration in the aqueous medium can be about 0.5% by mass to 5% by mass.

The volume average particle size of the resin fine particles is preferably 120 nm to 670 nm, and more preferably 200 nm to 600 nm.
When the volume average particle size is less than 120 nm, a sufficient core-shell structure may not be formed. When the volume average particle size exceeds 670 nm, the thickness of the shell becomes too thick, and the original low-temperature fixability cannot be exhibited sufficiently. There is.
The volume average particle diameter can be measured by, for example, a particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.).

The average thickness of the shell is preferably 0.10 μm to 0.55 μm, more preferably 0.15 μm to 0.50 μm, and particularly preferably 0.15 μm to 0.45 μm.
When the average thickness is less than 0.10 μm, a sufficient core-shell structure may not be formed, and when it exceeds 0.55 μm, the original low-temperature fixability may not be sufficiently exhibited. As the average thickness of the shell, the shell thickness of 10 toners was randomly measured with a transmission electron microscope, and the average value was defined as the average thickness.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, inorganic fine particles, charge control agents, external additives, fluidity improvers, cleaning improvers, magnetic materials, metals For example, soap.

<< Inorganic fine particles >>
The inorganic fine particles are used as an external additive for imparting fluidity, developability, chargeability and the like to toner particles.
The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples thereof include silicon and silicon nitride. These may be used alone or in combination of two or more. Among these, silica, titania, titanium oxide, alumina and the like can be mentioned. These may be subjected to a hydrophobic treatment.
Examples of commercially available products of the silica include HDK H2000, HDK H2000 / 4, HDK H2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all , Manufactured by Nippon Aerosil Co., Ltd.).
Examples of commercially available titania include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.). ), MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation).
Examples of commercially available titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Industry Co., Ltd.), TAF-500T, and TAF-1500T (all , Manufactured by Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (all manufactured by Teika Co., Ltd.), IT-S (produced by Ishihara Sangyo Co., Ltd.), and the like.

  In order to obtain the silica, the titania, and the alumina, hydrophilic fine particles can be obtained by treating with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Further, silicone oil-treated oxide fine particles or inorganic fine particles obtained by treating silicon oil with heat if necessary to treat it with inorganic fine particles are also suitable.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino acid. Modified silicone oil, epoxy modified silicone oil, epoxy / polyether modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, acrylic, methacryl modified silicone oil, α-methylstyrene modified silicone oil, etc. .

The average particle size of primary particles of the inorganic fine particles is preferably 100 nm or less, and more preferably 3 nm or more and 70 nm or less.
If the average particle size of the primary particles is less than 3 nm, the inorganic fine particles may be buried in the toner, and the function thereof may not be effectively exhibited. If the average particle size exceeds 100 nm, the surface of the photoreceptor is unevenly damaged. It is not preferable.

The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm.
Further, the content of the inorganic fine particles in the toner is preferably 0.01% by mass to 5.0% by mass, and more preferably 0.01% by mass to 2.0% by mass.
As the specific surface area by BET method of the inorganic fine ^particles, 20m ² / ^g~500m 2 / g are preferred.

<< Charge Control Agent >>
The toner of the present invention may contain a charge control agent as necessary.
The charge control agent is not particularly limited and may be appropriately selected from known ones. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes , Alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and salicylic acid derivative metal salts Etc. Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84, phenol-condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), No. Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, boron complex LR-147 (manufactured by Nippon Carlit), copper phthalocyanine, perylene Quinacridone, azo pigment, a sulfonic acid group, a carboxyl group, and the like and polymeric compounds having a functional group such as quaternary ammonium salts.

The content of the charge control agent is determined by the toner production method including the type of binder resin, the presence / absence of additives used as necessary, and the dispersion method, and is not uniquely limited. However, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of said binder resins, and 0.2 mass part-5 mass parts are more preferable.
When the content exceeds 10 parts by mass, the chargeability of the toner is too large, the effect of the main charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, and the flowability of the developer is reduced. The image density may be reduced. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, or of course, may be added when directly dissolving or dispersing in an organic solvent, or may be fixed on the toner surface after preparation of toner particles. May be.

  The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having a fluoroalkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. It is particularly preferable that the silica and the titanium oxide are surface-treated with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photosensitive member or the primary transfer medium. For example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, Examples include polymer fine particles produced by soap-free emulsion polymerization such as methyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 μm to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite etc. are mentioned. Among these, white is preferable in terms of color tone.

(Toner production method)
The toner production method of the present invention includes a core particle granulation step, a resin fine particle adhesion step, a desolvation step, and an encapsulation step.

<Core particle granulation process>
In the core particle granulation step, at least a binder resin, a colorant and a release agent are dissolved or dispersed in an organic solvent to form a dissolved product, and then the dissolved product is dispersed in an aqueous medium to granulate the core particles. It is a process.

-Organic solvent-
Examples of the organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, and ethyl acetate. , Methyl ethyl ketone, methyl isobutyl ketone and the like. These may be used alone or in combination of two or more. Among these, ester solvents such as methyl acetate and ethyl acetate, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable.

The amount of the organic solvent used is preferably 50 parts by weight to 150 parts by weight, more preferably 60 parts by weight to 140 parts by weight, and particularly preferably 80 parts by weight to 120 parts by weight with respect to 100 parts by weight of the toner composition. .
When the amount used is less than 50 parts by mass, the binder resin and the colorant are poorly dissolved, and core particles having a predetermined particle size may not be obtained. When the amount used exceeds 150 parts by mass, it is not economical. .

The binder resin, the colorant, and the release agent may be simultaneously dissolved or dispersed in an organic solvent, or may be dissolved or dispersed individually.
When the release agent is dissolved or dispersed, an organic solvent that does not dissolve the release agent is used as a dispersion, but the dispersion is produced by a general method. That is, an organic solvent and a release agent may be mixed and dispersed with a disperser such as a bead mill. Also, after mixing the organic solvent and the release agent, once heated to the melting point of the release agent, cooled with stirring, and then dispersed with a disperser such as a bead mill, the dispersion time may be shorter. . Moreover, a mold release agent may mix and use multiple types, and may add a dispersion | distribution adjuvant and a polyester resin.

-Aqueous medium-
As the aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the water-miscible solvent include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, and ethylene glycol.
Examples of the cell solves include methyl cell solve.
Examples of the lower ketones include acetone and methyl ethyl ketone.
The amount of the aqueous medium used is preferably 50 to 2,000 parts by mass, and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner composition.
When the amount used is less than 50 parts by mass, the dispersion state of the binder resin and the colorant is poor, and core particles having a predetermined particle size may not be obtained. Not right.

A method for dispersing the dissolved material in the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. The known equipment can be applied.
In order to make the particle diameter of the core particles 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is preferably 1,000 to 30,000 rpm, more preferably 5,000 to 20,000 rpm.
Although there is no limitation in particular as a dispersion time, in the case of a batch system, it is 0.1 to 5 minutes normally. The temperature during dispersion is preferably 0 ° C. to 150 ° C. (under pressure), more preferably 40 ° C. to 98 ° C. In addition, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a slightly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used alone or in combination of two or more. Among these, surfactants are preferable.

--Surfactant--
Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Florad FC-93, FC-95, FC-98, FC -129 (manufactured by 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 & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); 100, F150 (manufactured by Neos) and the like.

Examples of the cationic surfactant include amine salt type surfactants, quaternary ammonium salt type cationic surfactants, and cationic surfactants having a fluoroalkyl group.
Examples of the amine salt type surfactant include alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like.
Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. .
Examples of the cationic surfactant having a fluoroalkyl group include aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.
Examples of the aliphatic quaternary ammonium salts include aliphatic primary, secondary or tertiary amino acids having a fluoroalkyl group, and perfluoroalkyl (carbon number 6 to 10) sulfonamidopropyltrimethylammonium salts. .
Examples of commercially available cationic surfactants include Surflon S-121 (Asahi Glass Co., Ltd.), Florad FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries Co., Ltd.), Mega Facks F-150, F-824 (manufactured by Dainippon Ink & Chemicals, Inc.), Xtop EF-132 (manufactured by Tochem Products Co., Ltd.), Footgent F-300 (manufactured by Neos), and the like.

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the fatty acid amide derivative include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.

  Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.

Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like.
Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylate, N-methylolacrylamide, N-methylolmethacrylamide and the like.
Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like.
Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate.
Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds.
Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In the preparation of the dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method in which the calcium phosphate salt is dissolved with an acid such as hydrochloric acid and then washed with water or decomposed with an enzyme.

  In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

<Desolvation step>
The said solvent removal process is a process of removing an organic solvent from the obtained dispersion liquid (emulsion slurry).

  The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed into a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the water-based dispersant together.

When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed by removing the fine particle portion in a liquid by, for example, a cyclone, a decanter, or centrifugation, and the classification operation may be performed after obtaining a powder after drying.
Thereafter, a further ripening step is more preferable because the hollow state inside the toner can be controlled. The aging temperature is preferably 30 ° C to 55 ° C, more preferably 40 ° C to 50 ° C.
The aging time is preferably 5 hours to 36 hours, and more preferably 10 hours to 24 hours.
When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder after drying, but it is preferably performed in a liquid in terms of efficiency. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.

<Blooming process>
The blooming step is a step of forming a convex portion (island region) on the toner surface with the release agent segregated on the surface of the core due to the blooming phenomenon. Blooming refers to a phenomenon in which a release agent thermally expands in a solid state.

  FIG. 9 is a schematic cross-sectional view showing an example of a core cross-section. When blooming and aging the core as shown in FIG. 9, the island region of the release agent exposed on the surface of the core is thermally expanded as shown in FIG. 10, and the release agent is deposited on the toner surface. .

In the blooming step, when the core is heated at a temperature below the melting temperature for a long time (hereinafter also referred to as annealing), the release agent present on the core surface is thermally expanded, and the core in the state shown in FIG. 10 is obtained. .
When annealing is performed, when the release agent molecular chain slightly moves, the portion where the polar group is present in the vicinity repels and tries to stabilize. This is because when the island shape is completely covered with the sea area material (binder resin), the deformation force of the release agent is inferior to the surrounding pressure, so only in the island area of the release agent molecule. This occurs because the volume change does not occur, but when the island region of the release agent is exposed on the surface of the binder resin, it appears in the opening direction.
The surface exposed domain diameter (exposed width of islands) of the release agent is preferably 0.2 μm or more, and more than half of the release agent domain particles extracted and separated from the toner by thermal expansion have an aspect ratio of 3 or more. It becomes a spindle-shaped and cylindrical shape.

As a minimum of the temperature of the said heating, 45 degreeC or more is preferable, 50 degreeC or more is more preferable, and 55 degreeC or more is especially preferable.
The upper limit of the heating temperature is preferably 3 ° C. or more, more preferably 4 ° C. or more, and more preferably 5 ° C. or more lower than the glass transition temperature of the core particles.
If the lower limit of the temperature is less than 45 ° C., the convex state of the release agent may not be sufficiently formed. If the upper limit of the temperature is lower than the glass transition temperature of the core particles by less than 3 ° C., it is not preferable because coalescence between the core particles occurs.

The aging time is preferably 24 hours to 48 hours, more preferably 27 hours to 45 hours, and particularly preferably 30 hours to 42 hours.
If the aging time is less than 24 hours, the mold release agent may be insufficiently expanded and precipitated. If it exceeds 48 hours, after the capsule process (shelling), the shell layer surface vicinity or the shell The release agent may be deposited on the surface, which may impair the shell function.

<Encapsulation process>
The encapsulation step is a step of covering the surface of the core particle with a shell.
By attaching the shell to the core, a release agent is present in the core side portion of the shell. Since the part of the release agent present in the shell is small, the release agent can be eluted in a short time when receiving heat energy during fixing. Further, since the release agent present in an island shape in the intermediate region (B) is changed in shape, this release agent exists in a spindle shape with respect to the toner depth direction. Therefore, when elution starts, it can be an elution route for the release agent existing in the intermediate region (B), so that a large amount of release agent that can contribute to fixing can be supplied in a shorter time. It becomes.
In addition, after the encapsulation step, all the release agents present in the peripheral region (A2) are those in which the release agent present in the intermediate region (B) is thermally expanded by blooming. As for the mold release agent which exists in (A2), all the ends of an island area | region will exist in an intermediate | middle area | region (B).
Thus, by performing the encapsulation step after the blooming step, the toner has excellent heat storage stability and fixing releasability, high transfer efficiency, excellent durability for an electrophotographic process, and good image quality of an OHP sheet. Can be provided.

  As the encapsulation step, it is preferable to use an aqueous dispersion in which resin fine particles are dispersed. This dispersion can be easily produced by a conventional emulsion polymerization method and may be used as it is in the encapsulation step. In order to stabilize the dispersion of the core and resin fine particles to some extent, for example, a surfactant or the like may be added. The timing of adding the resin fine particles is preferably after the organic solvent is removed.

  In the encapsulation step, the pH may be adjusted with sodium hydroxide, hydrochloric acid or the like in order to adhere more efficiently. A monovalent to trivalent metal salt may be added as a flocculant. Examples of the monovalent metal constituting the salt include lithium, potassium, and sodium. Examples of the divalent metal include calcium and magnesium. Examples of the trivalent metal include aluminum. Examples of the anion constituting the salt include chloride ion, bromide ion, iodide ion, carbonate ion and sulfate ion. In addition, the adhesion may be promoted by heating, but the adhesion may be performed at or below the glass transition temperature of the fine particles, or may be performed at or above the glass transition temperature. However, when adhered at a temperature near or below the glass transition temperature, at least one of aggregation and fusion between the fine particles may hardly proceed, so that the aggregation and It is preferable to promote at least one of the fusion bonding, promote the coating of the core particles, and make the surface of the shell portion uniform. However, from the viewpoint of adjusting the degree of surface uniformity and adjusting the sphericity as toner particles, the heating temperature and the heating time are appropriately adjusted.

<Extension, cross-linking reaction>
In order to introduce a modified polyester resin having at least one of urethane and urea groups, when adding a modified polyester resin having an isocyanate group at the terminal and amines capable of reacting with this, a toner composition in an aqueous medium Before dispersing the product, the amines may be mixed in the oil phase, or the amines may be added to the aqueous medium.
The time required for the reaction is selected depending on the isocyanate group structure of the polyester prepolymer and the reactivity between the added amines, and is usually 1 minute to 40 hours, preferably 1 hour to 24 hours.
The reaction temperature is usually 0 to 150 ° C., preferably 20 to 98 ° C. This reaction may be performed before the encapsulation step, or may be allowed to proceed simultaneously during the encapsulation step. Further, it may be after the encapsulation step is completed. Moreover, a well-known catalyst can be used as needed.

<Washing and drying process>
A known technique is used for washing and drying the toner particles dispersed in the aqueous medium. That is, after solid-liquid separation with a centrifuge, a filter press, etc., the obtained toner cake is redispersed in ion exchange water at about room temperature to about 40 ° C., and after adjusting the pH with acid or alkali as necessary, After removing the impurities and surfactants by repeating the process of solid-liquid separation again and again, the toner powder is obtained by drying with an air dryer, circulating dryer, vacuum dryer, vibration fluid dryer, etc. . At this time, the fine particle component of the toner may be removed by centrifugation or the like, and after drying, a desired particle size distribution can be obtained using a known classifier as necessary.

<External processing>
The resulting toner particles are mixed with the charge control agent particles or by applying a mechanical impact force to prevent the charge control agent particles from detaching from the surface of the toner particles. can do.

  As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board is mentioned. As an apparatus used in this method, for example, an Ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverization air pressure, a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

  The shape and size of the toner of the present invention are not particularly limited and can be appropriately selected according to the purpose. The average circularity, shape factors SF-1 and SF-2 are as follows. And a weight average particle diameter, and a ratio of the weight average particle diameter to the number average particle diameter (weight average particle diameter / number average particle diameter).

The average circularity of the toner is preferably 0.930 to 0.995, and more preferably 0.955 to 0.995.
If the average circularity is less than 0.930, toner transferability may be significantly reduced. When the average circularity is 0.930 to 0.995, a core-shell structure can be secured with a shape close to a sphere appropriately.
The average circularity is defined as (peripheral length of circle having the same area as the projected particle area / perimeter length of projected particle image) × 100%.
The average circularity is measured using, for example, a flow particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation), and analyzed using analysis software (FPIA-2100, Data Processing Program for FPIA version 00-10). Went. As a specific measurement method, 0.1 to 0.5 mL of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant in 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 subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the shape and distribution of the toner are measured by the above apparatus with the dispersion concentration being 3,000 to 10,000 / μL. can get.
Specifically, 0.5 mL of 10% alkylbenzene sulfonate aqueous solution is added as a dispersant to 100 mL of water from which impure solids have been removed in advance, and about 0.3 g of a measurement sample is further added. The suspension in which the sample was dispersed was subjected to a dispersion treatment with an ultrasonic disperser for 3 minutes, and the shape and distribution of the toner were measured with the above apparatus with a dispersion concentration of about 5,000 particles / μL.

When the toner has a shape factor SF-1 of 100 to 150 and a shape factor SF-2 of 100 to 140, it is more preferable that the core-shell structure can be secured in an appropriately spherical shape.
The toner shape factors SF-1 and SF-2 are measured by, for example, FE-SEM (ULTRA55) manufactured by Carl Zeiss, and 300 FE-SEM images of the obtained toner are randomly sampled. Image information was introduced into an image analysis apparatus (LMEYE, manufactured by Lasertec Co., Ltd.) through an interface, analyzed, and values obtained from the following equations were defined as shape factors SF-1 and SF-2. The values of SF-1 and SF-2 are preferably values obtained by Luzex, but are not particularly limited to the FE-SEM device and the image analysis device as long as similar analysis results can be obtained.
SF-1 = (L ² / A) × (π / 4) × 100
SF-2 = (P2 / A) × (1 / 4π) × 100
Here, the absolute maximum length of the toner is L, the projected area of the toner is A, and the maximum peripheral length of the toner is P. In the case of a true sphere, all become 100, and from a spherical shape to an indefinite shape as the value becomes larger than 100. In particular, SF-1 represents the shape of the entire toner (such as an ellipse or a sphere), and SF-2 is a shape factor indicating the degree of unevenness on the surface.

The toner has a weight average particle diameter D4 of preferably 2 μm to 7 μm, and more preferably 2 μm to ₅ μm.
The ratio (D ₄ / Dn) between the weight average particle diameter D ₄ and the number average particle diameter Dn is preferably 1.25 or less, and more preferably 1.15 or less. Accordingly, it is more preferable that toner particles having a uniform core-shell structure can be formed while securing the charge developing property, transfer property, and fixing property of the toner.

The weight average particle diameter (D ₄ ) and number average particle diameter (Dn) of the toner, and the ratio (D ₄ / Dn) thereof are, for example, Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter Inc.), etc. Can be measured.
Specifically, first, 0.1 to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) is added as a dispersant to 100 to 150 mL of the electrolytic aqueous solution. Here, the electrolytic solution is prepared by preparing a 1% by mass NaCl aqueous solution using first grade sodium chloride, and 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 mass and number of toner particles or toner using a 100 μm aperture as an aperture. Calculate mass distribution and number distribution. From the obtained distribution, the weight average particle diameter (D ₄ ) and number average particle diameter of the toner can be obtained.
As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted.

At least one endothermic peak measured by a differential scanning calorimeter (DSC) in the toner is preferably present in the range of 60 ° C. to 90 ° C., and more preferably two or more.
If the endothermic peak is less than one, the releasing effect of the releasing agent cannot be obtained, and offset may be generated.
In addition, the half width of the endothermic peak is preferably 8 ° C. or less, more preferably 7 ° C. or less, and particularly preferably 6 ° C. or less.
When the half width exceeds 8 ° C., a so-called endothermic peak becomes broad, and toner fluidity and heat-resistant storage stability may be deteriorated.
The endothermic peak can be measured using a differential scanning calorimeter (DSC6200 manufactured by Seiko Instruments Inc.). Specifically, a release agent or toner is weighed in a 5 mg aluminum pan, set in a differential scanning calorimeter, heated from room temperature to 200 ° C., and cooled from that temperature to 0 ° C. at a cooling rate of 10 ° C./min. The measured samples were measured at a heating rate of 10 ° C./min. The result at this time was plotted by temperature and calorific value, and the temperature at which the calorific value was the minimum value was defined as the endothermic peak. In addition, a line segment is drawn perpendicularly to the baseline from the endothermic peak, and the temperature difference between the two points where the line passing through the center of the line segment and parallel to the baseline intersects the temperature-calorie plot is the half-value width of the endothermic peak. It was. Further, the glass transition temperature can be obtained from a base line below the glass transition point and a curved line portion corresponding to a half height of the base line above the glass transition point.

The ½ outflow temperature (T1 / 2) measured by the flow tester in the toner is preferably 110 ° C. to 140 ° C., more preferably 120 ° C. to 135 ° C., and particularly preferably 125 ° C. to 135 ° C.
When the ½ outflow temperature is less than 110 ° C., the smoothness of the printed surface after fixing is lowered, so that a so-called hot offset phenomenon in which the image gloss is extremely lowered is likely to occur. A so-called cold offset phenomenon occurs in which the toner is not sufficiently fixed on the fixing member and toner remains on the fixing member.
The 1/2 outflow temperature can be measured as follows. Using a flow tester (CFT-500 / manufactured by Shimadzu Corporation), 1.5 g of a measurement sample was weighed, and using a die having a height of 1.0 mm and a diameter of 1.0 mm, the temperature rising rate was 3.0 ° C./min. Measurement was performed under the conditions of a preheating time of 180 seconds, a load of 30 kg, and a measurement temperature range of 80 to 140 ° C., and the temperature at which the above sample flowed out 1/2 was defined as a 1/2 outflow temperature.

As the storage elastic modulus of the toner of the present invention, the temperature (TG ′) at which the measurement frequency is 20 Hz is 10,000 dyne / cm ² is usually 100 ° C. or higher and more preferably 110 ° C. to 200 ° C.
When the temperature (TG ′) is less than 100 ° C., the hot offset resistance may be deteriorated.

As the viscosity of the toner of the present invention, the temperature (Tη) at which the poise is 1,000 poise at a measurement frequency of 20 Hz is preferably 180 ° C. or less, more preferably 90 ° C. to 160 ° C.
When the temperature (Tη) exceeds 180 ° C., the low-temperature fixability may be deteriorated. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and particularly preferably 20 ° C. or higher. The upper limit of the difference between TG ′ and Tη is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage properties and low-temperature fixability, the difference between Tη and Tg is preferably 0 ° C to 100 ° C, more preferably 10 ° C to 90 ° C, and particularly preferably 20 ° C to 80 ° C.

Mass ratio ((A1 + A2) / (B + C) of the total mass (A1 + A2) of the peripheral area (A1) and the peripheral area (A2) to the total mass (B + C) of the intermediate area (B) and the internal area (C) ) Is preferably 0.05 to 0.5, more preferably 0.07 to 0.4, and particularly preferably 0.1 to 0.3.
When the mass ratio is less than 0.05, the effect of the resin fine particles of the shell cannot be sufficiently exerted, and when it exceeds 0.5, the content of the binder resin becomes too small and the fixing characteristics are deteriorated. There are things to do.

The volume average particle diameter D of the toner is preferably 3 μm to 9 μm, more preferably 4.5 μm to 8.5 μm, and particularly preferably 4 μm to 8 μm.
If the volume average particle size is less than 3 μm, the image forming process may be hindered, and if it exceeds 9 μm, the resolution of the image may be deteriorated.

The particle size distribution and the volume average particle size can be measured by, for example, Coulter Counter TA-II or Coulter Multisizer II (both manufactured by Coulter). As a measuring method, first, 0.1 to 5 mL of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 mL of the electrolytic aqueous 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 the measurement sample is further added as a solid content. 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. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dp) of the toner can be obtained.
Specifically, 0.5 mL of a 10% alkylbenzene sulfonate aqueous solution is added as a dispersant to 100 mL of an electrolytic aqueous solution ISOTON-II (manufactured by Coulter). Here, 10 mg of the measurement sample is further added as a solid content. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser, and the volume and number of toner particles or toner are measured with the measuring device using a 100 μm aperture as the aperture. The particle diameter (Dv) and the number average particle diameter (Dp) were determined.
As a channel, for example, less than 2.00 to 2.52 μm; less than 2.52 to 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; 6.35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Less than .40 μm; 25.40 to less than 32.00 μm; 13 channels of 32.00 to less than 40.30 μm are used, and particles having a particle size of 2.00 μm to less than 40.30 μm can be targeted.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected appropriately. The developer may be a one-component developer or a two-component developer.
In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and image can be obtained even when the developing device is used (stirred) for a long time.

  There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, a manganese-strontium (Mn-Sr) type material of 50 emu / g-90 emu / g, manganese-magnesium ( A Mn—Mg) -based material is preferable, and from the viewpoint of securing image density, highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 emu / g to 120 emu / g) are preferable. In addition, the weakness of the copper-zinc (Cu-Zn) system (30 emu / g to 80 emu / g) is advantageous in that the contact with the photoconductor in which the toner is in a flashing state can be weakened, which is advantageous for improving the image quality. Magnetized materials are preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably 10 μm to 200 μm, and more preferably 40 μm to 100 μm, in terms of average particle diameter (mass average particle diameter (D ₅₀ )).
When the average particle size (mass average particle size (D ₅₀ )) is less than 10 μm, in the distribution of carrier particles, the number of fine powder systems increases, and the magnetization per particle may be lowered to cause carrier scattering. If the thickness exceeds 200 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, fluorine Examples thereof include a copolymer of vinylidene fluoride and vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, polyacrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene-acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

The resin layer is prepared by, for example, dissolving the silicone resin in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the coating method include a dipping method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate etc. are mentioned.
The baking is not particularly limited, and may be an external heating system or an internal heating system. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

  The amount of the resin layer in the carrier is preferably 0.01% by mass to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

Since the developer of the present invention contains the toner of the present invention, it is possible to achieve both excellent low-temperature fixability and anti-offset performance and form a good high-definition image.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be used suitably. Further, it can be particularly suitably used for the following toner-containing container, process cartridge, image forming apparatus and image forming method.

(Toner container)
The toner-containing container of the present invention comprises the toner or the developer of the present invention contained in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, the thing etc. which have a toner container main body and a cap are mentioned suitably.
The size, shape, structure, material and the like of the toner container body are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably a cylindrical shape, In particular, a spiral unevenness is formed on the surface, the toner as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function, etc. preferable.
The material of the toner container main body is not particularly limited and may be appropriately selected depending on the intended purpose. However, a material having good dimensional accuracy is preferable, for example, a resin is preferable. Among these, for example, polyester Preferred examples include resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic resin, polycarbonate resin, ABS resin, polyacetal resin and the like.
The container containing toner is easy to store and transport, has excellent handleability, and can be suitably used for replenishing toner by being detachably attached to a process cartridge and an image forming apparatus of the present invention described later. .

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using toner to produce a visible image. And at least developing means to be formed, and other means appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably mounted on various electrophotographic image forming apparatuses, and is preferably detachably mounted on the image forming apparatus of the present invention described later.

Here, as shown in FIG. 1, the process cartridge includes a photosensitive member 101, and at least one of a charging unit 102, a developing unit 104, a transfer unit 108, a cleaning unit 107, and a charge eliminating unit (not shown). And an apparatus (part) that can be attached to and detached from the image forming apparatus main body.
Here, the image forming process using the process cartridge shown in FIG. 1 will be described. The photosensitive member 101 is exposed to the surface by rotating by the charging unit 102 and exposing 103 by the exposing unit (not shown) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the image is formed. The electrostatic latent image is developed with toner by the developing unit 104, and the toner development is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by the cleaning unit 107 and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step. , Recycling process, control process, etc.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

The image forming apparatus is preferably a tandem type developing system in which at least four developing units of different developing colors are arranged in series, the system speed is 500 mm / sec to 2,500 mm / sec, and the pressing surface pressure of the fixing member it is preferred but is ^{5N / cm 2 ~90N / cm 2} . This makes it possible to meet the demand for low-temperature fixing in high-speed printing, and an image having a sufficiently strong fixing strength can be obtained even in a situation where the amount of heat supplied and fixed is insufficient.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image carrier (sometimes referred to as “photoconductive insulator”, “electrophotographic photoreceptor”, or “photoreceptor”) is particularly limited in terms of material, shape, structure, size, and the like. However, it can be appropriately selected from known ones, and as its shape, a drum shape is preferably mentioned, and examples of the material thereof include inorganic photoreceptors such as amorphous silicon and selenium, polysilane, phthalopolymethine, and the like. Organic photoreceptors and the like can be mentioned. Among these, amorphous silicon is preferable from the viewpoint of long life.

  As the amorphous silicon photoreceptor, for example, a support is heated to 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method is applied on the support. A photoconductor having a photoconductive layer made of a-Si (hereinafter sometimes referred to as “a-Si-based photoconductor”) can be used by a film forming method such as the above. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferable.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. Can do.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and can be appropriately selected according to the purpose. Non-contact charger using corona discharge such as a charger, corotron, and scorotron.

The shape of the charger may take any form, such as a magnetic brush or a fur brush, in addition to a roller, and can be selected according to the specifications and form of the image forming apparatus. When the magnetic brush is used, the magnetic brush is composed of various ferrite particles such as Zn-Cu ferrite as a charger, a non-magnetic conductive sleeve for supporting it, and a magnet roll included therein. Or, when using a brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound or attached to a metal or other conductive core. To make a charger.
The charger is not limited to the contact charger as described above. However, since an image forming apparatus in which ozone generated from the charger is reduced is obtained, a contact charger is used. preferable.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. Examples thereof include various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferred examples include a developer containing at least a developer, and at least a developing device capable of contacting or non-contacting the toner or the developer with the electrostatic latent image. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, 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 electrostatic latent image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrostatically attracted by the static force. It moves to the surface of the electrostatic latent image carrier. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier.

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the visible latent image using a transfer charger and charging the electrostatic latent image carrier, and can be performed by the transfer unit. The transfer means includes 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. Embodiments are preferred.
The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The intermediate transfer member preferably has a static friction coefficient of 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably from several Ωcm to 10 ³ Ωcm. By setting the volume resistance to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means is less likely to remain on the intermediate transfer member. Transfer unevenness can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

  The material of the intermediate transfer member is not particularly limited and can be appropriately selected from known materials according to the purpose. For example, (1) a material having a high Young's modulus (tensile elastic modulus) is used as a single-layer belt. PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) / PAT (polyalkylene terephthalate) blend material, ETFE (ethylene tetrafluoroethylene copolymer) / PC, ETFE / PAT, PC / PAT blend material, carbon black dispersed thermosetting polyimide, and the like. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and registration is not likely to occur particularly during color image formation. (2) A belt having a two- to three-layer structure in which a belt having a high Young's modulus is used as a base layer and a surface layer or an intermediate layer is provided on the outer periphery of the belt. Therefore, the line image has a performance capable of preventing the line image from being lost. (3) Belts having a relatively low Young's modulus using rubber and elastomer, and these belts have an advantage that line images are hardly lost due to their softness. In addition, the belt width is made larger than that of the drive roll and the tension roll, and the elasticity of the belt ear protruding from the roll is used to prevent meandering, so that a low cost can be realized without the need for ribs or meandering prevention devices. .

Conventionally, fluorine-based resin, polycarbonate resin, polyimide resin, and the like have been used for the intermediate transfer belt. However, in recent years, an elastic belt having an elastic member made of the entire belt layer or a part of the belt has been used. . The transfer of a color image using a resin belt has the following problems.
A color image is usually formed with four colored toners. On one color image, toner layers of 1 to 4 layers are formed. The toner layer receives pressure by passing through the primary transfer (transfer from the photoreceptor to the intermediate transfer belt) and the secondary transfer (transfer from the intermediate transfer belt to the sheet), and the cohesive force between the toners increases. When the cohesive force between the toners increases, the phenomenon of missing characters in the characters and missing edges in the solid portion image tends to occur. Since the resin belt has a high hardness and does not deform according to the toner layer, the toner layer is easily compressed, and the character dropout phenomenon is likely to occur.
Recently, there is an increasing demand for forming full-color images on various papers, for example, Japanese paper, intentionally irregularities, and forming images on paper. However, a paper with poor smoothness is liable to generate toner and voids at the time of transfer, and transfer loss is likely to occur. If the transfer pressure at the secondary transfer portion is increased to improve the adhesion, the condensing power of the toner layer is increased, and the above-described character void is generated.
The elastic belt is used for the following purposes. The elastic belt is deformed corresponding to the toner layer and the paper having poor smoothness at the transfer portion. In other words, since the elastic belt deforms following local irregularities, it is possible to obtain a good adhesion without excessively increasing the transfer pressure with respect to the toner layer, and a paper with poor flatness that has no void in characters. In contrast, a transfer image with excellent uniformity can be obtained.

  Examples of the resin for the elastic belt include polycarbonate, fluororesin (ETFE, PVDF), polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene- Vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (for example, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer) Styrene-octyl acrylate copolymer and styrene-phenyl acrylate copolymer), styrene-methacrylic acid ester copolymer (for example, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer) Styrene-phenyl methacrylate Styrene resin (monopolymer or copolymer containing styrene or a styrene substitution product), methacrylic acid, such as styrene-α-chloroacrylic acid methyl copolymer, styrene-acrylonitrile-acrylic acid ester copolymer Methyl resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (for example, silicone-modified acrylic resin, vinyl chloride resin-modified acrylic resin, acrylic / urethane resin, etc.), vinyl chloride resin, styrene-acetic acid Vinyl copolymer, vinyl chloride-vinyl acetate copolymer, rosin modified maleic acid resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene, polyvinylidene chloride, ionomer resin, polymer Use one or a combination of two or more selected from the group consisting of urethane resin, silicone resin, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin and polyvinyl butyral resin, polyamide resin, modified polyphenylene oxide resin, etc. Can do. However, it is a matter of course that the material is not limited to the above materials.

  The elastic rubber or elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, butyl rubber, fluorine rubber, acrylic rubber, EPDM, NBR, acrylonitrile-butadiene-styrene rubber natural rubber, isoprene Rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin series Rubber, Ricone rubber, Fluoro rubber, Polysulfide rubber, Polynorbornene rubber, Hydrogenated nitrile rubber, Thermoplastic elastomer (eg polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide) , It can be used polyurea, polyester, one kind or two kinds or more combinations selected from the group consisting of a fluorine resin).

The conductive material for adjusting the resistance value is not particularly limited and can be appropriately selected depending on the purpose. For example, carbon black, graphite, metal powder such as aluminum or nickel, tin oxide, titanium oxide, antimony oxide, oxidation Conductive metal oxides such as indium, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), indium oxide-tin oxide composite oxide (ITO), conductive metal oxides are barium sulfate, magnesium silicate In addition, it may be coated with insulating fine particles such as calcium carbonate. Of course, the conductive agent is not limited thereto.
Surface layer materials and surface layers are required to prevent contamination of the photoreceptor with elastic materials, reduce surface friction resistance to the surface of the transfer belt, reduce toner adhesion, and improve cleaning and secondary transfer properties. . For example, materials that use one or a combination of two or more of polyurethane, polyester, epoxy resin, etc. to reduce surface energy and increase lubricity, such as fluororesin, fluorine compound, fluorocarbon, titanium dioxide, silicon carbide, etc. These powders and particles can be used by dispersing one type, two or more types, or a combination of particles having different particle sizes. Further, it is also possible to use a material having a reduced surface energy by forming a fluorine-rich layer on the surface by heat treatment, such as a fluorine-based rubber material.
The manufacturing method of the belt is not limited. For example, a centrifugal molding method in which a material is poured into a rotating cylindrical mold to form a belt, a spray coating method in which a liquid paint is sprayed to form a film, a cylindrical mold is used. Examples include, but are not limited to, a dipping method in which the material is soaked in a solution, a casting method in which the material is poured into an inner mold or an outer mold, a method in which a compound is wound around a cylindrical mold and vulcanized and polished. In general, a belt is manufactured by combining a plurality of manufacturing methods.

As a method for preventing elongation as an elastic belt, there are a method of forming a rubber layer in a core resin layer with little elongation, a method of putting a material for preventing elongation into a core layer, and the like, but the method is limited to a specific manufacturing method is not.
There is no restriction | limiting in particular as a material which comprises the core body layer which prevents elongation, According to the objective, it can select suitably, For example, natural fibers, such as cotton and silk; Polyester fiber, Nylon fiber, Acrylic fiber, Polyolefin Synthetic fibers such as fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyurethane fibers, polyacetal fibers, polyfluoroethylene fibers, phenol fibers; inorganic fibers such as carbon fibers, glass fibers, boron fibers; iron fibers, A woven fabric or a thread-like material using a metal fiber such as copper fiber is also used.
The yarn may be twisted in any manner, such as one or a plurality of filaments twisted, one-twisted yarn, various twisted yarns, twin yarn. Further, for example, fibers of a material selected from the above material group may be blended. Further, the yarn can be used after an appropriate conductive treatment. On the other hand, as the woven fabric, any woven fabric such as knitted fabric can be used. Interwoven woven fabric can also be used and naturally conductive treatment can be performed.
The production method for providing the core layer is not particularly limited and can be appropriately selected according to the purpose.For example, a method of providing a coating layer on a woven fabric woven in a cylindrical shape on a mold or the like, A method of providing a coating layer on one or both sides of a core layer by immersing a woven cloth woven in a cylindrical shape into liquid rubber, a method of winding a thread around a mold or the like, and providing a coating layer thereon Can be mentioned.
The thickness of the elastic layer depends on the hardness of the elastic layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur in the surface layer. Also, it is not preferable that the thickness is too thick (about 1 mm or more) because the amount of expansion and contraction becomes large and the image is stretched.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means. 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 is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing member, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, and a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, and web cleaners.

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

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

  Next, one mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter also referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and the exposure. An exposure device 30 as a means, a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. 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. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) onto a transfer sheet 95 as a final recording medium. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. 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 arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion 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 the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 3 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 2, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

In the tandem type electrophotographic apparatus in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention, the image on each photoconductor 1 is transferred by the transfer device 2 by the sheet conveying belt 3 as shown in FIG. As shown in FIG. 5, the image on each photoconductor 1 is sequentially transferred to the intermediate transfer body 4 by the primary transfer device 2 as shown in FIG. There is an indirect transfer type in which an image on the transfer body 4 is collectively transferred to a sheet s by a secondary transfer device 5. The transfer device 5 is a transfer conveyance belt, but may be a roller shape.
Comparing the direct transfer type and the indirect transfer type, the former arranges the sheet feeding device 6 on the upstream side of the tandem image forming apparatus T on which the photoconductors 1 are arranged, and the fixing device 7 on the downstream side. There is a drawback in that the size increases in the sheet conveying direction. On the other hand, the latter can set the secondary transfer position relatively freely. The sheet feeding device 6 and the fixing device 7 can be arranged so as to overlap with the tandem image forming apparatus T, and there is an advantage that downsizing is possible.
In the former, in order not to increase the size in the sheet conveying direction, the fixing device 7 is disposed close to the tandem type image forming apparatus T. For this reason, the fixing device 7 cannot be disposed with a sufficient margin that allows the sheet s to bend, and an impact when the leading edge of the sheet s enters the fixing device 7 (particularly with a thick sheet) or fixing. Due to the difference in speed between the sheet conveyance speed when passing through the apparatus 7 and the sheet conveyance speed by the transfer conveyance belt, there is a drawback that the fixing device 7 tends to affect image formation on the upstream side. On the other hand, in the latter case, the fixing device 7 can be disposed with a sufficient margin that the sheet s can be bent, so that the fixing device 7 hardly affects the image formation.
In view of the above, recently, an indirect transfer type of tandem type electrophotographic apparatus has attracted attention.
In this type of color electrophotographic apparatus, as shown in FIG. 5, the transfer residual toner remaining on the photoreceptor 1 after the primary transfer is removed by the photoreceptor cleaning device 8 to clean the surface of the photoreceptor 1. In preparation for another image formation. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.

A tandem image forming apparatus 100 shown in FIG. 6 is a tandem color image forming apparatus. The tandem image forming apparatus 120 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 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, and can be rotated clockwise in FIG. 6. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. 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 transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. 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 tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. .

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

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The electrostatic latent image carrier 10 is uniformly charged, and the electrostatic latent image carrier is exposed (L in FIG. 7) for each color image corresponding to each color image information. An exposure device that forms an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and each color toner (black toner, yellow toner, magenta toner, and cyan toner) Develop with A developing device 61 for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, and a static eliminator 64 are provided. Each single color image (black image, yellow image, magenta image, and cyan image) can be formed based on the color image information. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet 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 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 145, 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 synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming method and the image forming apparatus of the present invention, the toner of the present invention having the ultimate low-temperature fixing property, anti-fixing wrapping prevention property, heat-resistant storage property, pressure-resistant storage property, development stability, and high-speed printing compatibility. Since it is used, a high-quality image can be formed efficiently.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Synthesis Example 1)
<Synthesis of polyester 1>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 233 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 525 parts by mass of bisphenol A propylene oxide 3-mole adduct, 206 parts by mass of terephthalic acid, 47 adipic acid 47 Part by mass and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 46 parts by weight of trimellitic anhydride was added to the reaction vessel, and reacted at 180 ° C. for 2 hours under normal pressure to obtain “Polyester 1”. Synthesized.
The number average molecular weight of the obtained “Polyester 1” was 2,600, and the mass average molecular weight was 6,900. It was 44 degreeC when the glass transition temperature was measured with the differential scanning calorimeter DSC6200 (made by Seiko Instruments Inc.). The acid value was 26 mgKOH / g.
-Measurement of number average molecular weight and mass average molecular weight-
The number average molecular weight and the mass average molecular weight were measured as follows. Hereinafter, the number average molecular weight and the mass average molecular weight in all synthesis examples were also measured under the same conditions.
Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel
SuperHZM-M x 3
Temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 0.35 mL / min Sample: 0.01 mL injection of a sample with a concentration of 0.05 to 0.6% Use a molecular weight calibration curve created from a monodisperse polystyrene standard sample from the molecular weight distribution of the toner resin measured under the above conditions And calculated. As a monodisperse polystyrene standard sample, 10 samples in the range of 5.8 × 100 to 7.5 × 1,000,000 were used.
-Measurement of acid value-
The acid value was measured as follows. Hereinafter, the acid values in all synthesis examples were also measured under the same conditions.
1-1.5 g of a sample was precisely weighed in an Erlenmeyer flask, 20 mL of xylene was added thereto, and then dissolved by heating. After dissolution, 20 mL of dioxane was added, and the solution was titrated as soon as possible with a 1% phenolphthalein solution as an indicator with a N / 10 potassium hydroxide standard methanol solution while the solution did not become cloudy or hazy. At the same time, a blank test was performed.

Acid value = [5.61 × (AB) × f] / S
However,
A: mL number of N / 10 potassium hydroxide standard methanol solution required for this test B: mL number of N / 10 potassium hydroxide standard methanol solution required for blank test f: N / 10 potassium hydroxide standard methanol solution Factor S: Sample (g)

(Synthesis Example 2)
<Synthesis of polyester 2>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 180 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 595 parts by mass of bisphenol A propylene oxide 3-mole adduct, 192 parts by mass of terephthalic acid, 50 adipic acid Part by mass and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 63 parts by weight of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 3 hours under normal pressure to obtain “Polyester 2”. Synthesized. The number average molecular weight and mass average molecular weight of the obtained “Polyester 2” were measured with a GPC apparatus (HLC-8220 GPC, manufactured by Tosoh Corporation). The number average molecular weight was 2,800, the mass average molecular weight was 7,200, and the glass transition. It was 44 degreeC when temperature was measured with the differential scanning calorimeter DSC6200 (made by Seiko Instruments Inc.). It was 33 mgKOH / g when the acid value was measured.

(Synthesis Example 3)
<Synthesis of polyester 3>
550 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 201 parts by mass of bisphenol A propylene oxide 2-mole adduct, 215 parts by mass of terephthalic acid, 48 parts by mass of adipic acid in a reaction vessel equipped with a condenser and a nitrogen introducing tube Part and 2 parts by mass of dibutyltin oxide were allowed to react at 230 ° C. for 8 hours under normal pressure. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 25 parts by weight of trimellitic anhydride was added to the reaction vessel, and reacted at 180 ° C. for 2 hours under normal pressure to obtain “Polyester 3”. Synthesized. The obtained “Polyester 3” had a number average molecular weight of 2,300 and a weight average molecular weight of 5,800, and the glass transition temperature was measured with a differential scanning calorimeter DSC6200 (manufactured by Seiko Instruments Inc.). Met. The acid value was measured and found to be 12 mgKOH / g.

(Synthesis Example 4)
<Synthesis of polyester 4>
Into a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 785 parts by mass of a bisphenol A propylene oxide 3 mol adduct, 258 parts by mass of terephthalic acid, 47 parts by mass of adipic acid, and 2 parts by mass of dibutyltin oxide were prepared. The reaction was carried out at 230 ° C. for 8 hours under normal pressure. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 20 parts by mass of trimellitic anhydride was added to the reaction vessel, and reacted at 180 ° C. for 2 hours under normal pressure to obtain “Polyester 4”. Synthesized.
The obtained “Polyester 4” had a number average molecular weight of 2,200, a weight average molecular weight of 4,800, a glass transition temperature of 45 ° C., and an acid value of 24 mgKOH / g.

(Synthesis Example 5)
<Synthesis of polyester 5>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 550 parts of bisphenol A ethylene oxide 2-mole adduct, 201 parts by mass of bisphenol A propylene oxide 3-mole adduct, 258 parts by mass of terephthalic acid, 48 parts by mass of adipic acid Part and 2 parts by mass of dibutyltin oxide were allowed to react at 230 ° C. for 8 hours under normal pressure. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 60 parts by mass of trimellitic anhydride was added to the reaction vessel, and reacted at 180 ° C. under normal pressure for 3 hours to obtain “Polyester 5”. Synthesized.
The obtained “Polyester 5” had a number average molecular weight of 2,800, a weight average molecular weight of 8,000, a glass transition temperature of 46 ° C., and an acid value of 28 mgKOH / g.

(Synthesis Example 6)
<Manufacture of vinyl resin fine particle dispersion 1>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 1.6 parts by mass of sodium dodecyl sulfate and 492 parts by mass of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution obtained by dissolving 2.5 parts by mass of potassium sulfate in 100 parts by mass of ion-exchanged water was added, and 15 minutes later, 153 parts by mass of styrene monomer, 38 parts by mass of butyl acrylate, 9 parts by mass of methacrylic acid, n-octyl mercaptan 3 0.5 parts by mass of the mixed solution was dropped over 90 minutes, and then kept at 80 ° C. for 60 minutes.
Then, it cooled and the "vinyl resin fine particle dispersion 1" was obtained. The obtained dispersion was placed in a 2 mL petri dish and the solid obtained by evaporating the dispersion medium had a number average molecular weight of 11,000 and a mass average molecular weight of 19,000. It was 63 degreeC when the glass transition temperature was measured with the differential scanning calorimeter DSC6200 (made by Seiko Instruments Inc.).
The average particle size of “Vinyl resin fine particle dispersion 1” was measured using a particle size measuring device (manufactured by Nikkiso Co., Ltd., UPA-EX150) and found to be 51 nm.
The average particle size was measured by filling the solvent in the measuring part and measuring the zero point. Next, a dispersion of “vinyl resin fine particle dispersion 1” was added to the measurement section, and the measurement was performed by adjusting the loading index to be in the range of 1 to 1.5. In this case, pure water was used as a solvent, and the analysis conditions were set as follows.
Particle refractive index 1.59
Particle permeability Transparent particle shape True spherical particle density 1
Solvent refractive index 1.333
Solvent viscosity 0.797 mPa · s at 30 ° C, 1.002 mPa · s at 20 ° C
Filter Standard
Sensitivity Standard
Measurement time 60 seconds Zero Set 30 seconds

(Synthesis Example 7)
<Manufacture of vinyl resin fine particle dispersion 2>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1.2 parts by weight of sodium dodecyl sulfate and 492 parts by weight of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution prepared by dissolving 2.5 parts by mass of potassium sulfate in 100 parts by mass of ion-exchanged water was added, and 15 minutes later, 148 parts by mass of styrene monomer, 33 parts by mass of butyl acrylate, 19 parts by mass of methacrylic acid, n-octyl mercaptan 3 A part by mass of the mixed solution was dropped over 90 minutes, and then kept at 80 ° C. for 60 minutes.
Thereafter, it was cooled to obtain “Vinyl resin fine particle dispersion 2”. The obtained dispersion was placed in a 2 mL petri dish, and the solid obtained by evaporating the dispersion medium had a number average molecular weight of 14,000 and a mass average molecular weight of 28,000. It was 68 degreeC when the glass transition temperature was measured with the differential scanning calorimeter DSC6200 (made by Seiko Instruments Inc.). When the average particle size was measured in the same manner as in “Vinyl resin fine particle dispersion 1”, it was 80 nm.

(Synthesis Example 8)
<Manufacture of vinyl resin fine particle dispersion 3>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1.2 parts by weight of sodium dodecyl sulfate and 492 parts by weight of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution prepared by dissolving 2.5 parts by mass of potassium sulfate in 100 parts by mass of ion-exchanged water was added, and 15 minutes later, 156 parts by mass of styrene monomer, 29 parts by mass of butyl acrylate, 15 parts by mass of methacrylic acid, n-octyl mercaptan 3 4 parts by mass of the mixed solution was dropped over 90 minutes, and then kept at 80 ° C. for 60 minutes.
Then, it cooled and the "vinyl resin fine particle dispersion 3" was obtained. The obtained dispersion was placed in a 2 mL petri dish and the solid obtained by evaporating the dispersion medium had a number average molecular weight of 12,000 and a mass average molecular weight of 23,000. It was 68 degreeC when the glass transition temperature was measured with the differential scanning calorimeter DSC6200 (made by Seiko Instruments Inc.). When the average particle size was measured in the same manner as in “Vinyl resin fine particle dispersion 1”, it was 88 nm.

(Synthesis Example 9)
<Manufacture of vinyl resin fine particle dispersion 4>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 2.0 parts by mass of sodium dodecyl sulfate and 492 parts by mass of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution prepared by dissolving 2.5 parts by mass of potassium sulfate in 100 parts by mass of ion-exchanged water was added, and 15 minutes later, 132 parts by mass of styrene monomer, 12 parts by mass of butyl acrylate, 33 parts by mass of methacrylic acid, n-octyl mercaptan 3 0.5 parts by mass of the mixed solution was dropped over 90 minutes, and then kept at 80 ° C. for 60 minutes.
Then, it cooled and the "vinyl resin fine particle dispersion 4" was obtained. The obtained dispersion is placed in a 2 mL petri dish, and the solid obtained by evaporating the dispersion medium has a number average molecular weight of 28,000, a mass average molecular weight of 70,500, a glass transition temperature of 37 ° C., and an average particle size of “vinyl”. It was 82 nm when it measured similarly to the "system resin fine particle dispersion 1".

(Synthesis Example 10)
<Manufacture of vinyl resin fine particle dispersion 5>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1.2 parts by weight of sodium dodecyl sulfate and 492 parts by weight of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution obtained by dissolving 2.5 parts by mass of potassium sulfate in 100 parts by mass of ion-exchanged water was added, and 15 minutes later, 116 parts by mass of styrene monomer, 25 parts by mass of butyl acrylate, 50 parts by mass of methoxydiethylene glycol methacrylate, n-octyl mercaptan 2.0 parts by mass of the mixed solution was dropped over 90 minutes, and then kept at 80 ° C. for 60 minutes.
Then, it cooled and the "vinyl resin fine particle dispersion 5" was obtained. The obtained dispersion is placed in a 2 mL petri dish, and the solid obtained by evaporating the dispersion medium has a number average molecular weight of 15,800, a mass average molecular weight of 55,000, a glass transition temperature of 81 ° C., and an average particle size of “vinyl”. It was 110 nm when it measured similarly to the "system resin fine particle dispersion 1".

(Synthesis Example 11)
<Production of polyester resin fine particle dispersion 1>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 36 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 3,782 parts by mass of bisphenol A propylene oxide 2-mole adduct, 724 parts by mass of terephthalic acid and dibutyl After adding 15 parts by mass of tin oxide and reacting at 230 ° C. under normal pressure for 8 hours and further reacting at 10 to 15 mmHg under reduced pressure for 5 hours, 760 parts by mass of fumaric acid and 3.5 parts by mass of hydroquinone were added to the reaction vessel. After reacting at 5 ° C. and normal pressure for 5 hours, it was further reacted under reduced pressure to obtain “Polyester 6”.
Next, 1,500 parts by mass of “Polyester 6”, anionic surfactant (Neopelex G-15, manufactured by Kao Corporation), 100 parts by mass of sodium dodecylbenzenesulfonate (solid content: 15% by weight), nonionic interface An activator (Emulgen 430, manufactured by Kao Corporation), 15 parts by mass of polyoxyethylene (26 mol) oleyl ether (HLB: 16.2), and 689 parts by mass of a 5% by mass potassium hydroxide aqueous solution were heated to 95 ° C. with stirring. Then, after maintaining at 95 ° C. for 2 hours, 15 g / min of deionized water was added dropwise over 190 minutes, and then maintained at 95 ° C. for 60 minutes.
Then, it was cooled to obtain “Polyester resin fine particle dispersion 1”. The obtained dispersion is placed in a 2 mL petri dish, and the solid obtained by evaporating the dispersion medium has a number average molecular weight of 3,760, a mass average molecular weight of 8,240, a glass transition temperature of 66 ° C., and an average particle size of “ It was 140 nm when measured similarly to "Vinyl resin fine particle dispersion 1".

(Synthesis Example 12)
<Production of Prepolymer 1>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, 22 parts by mass of merit acid and 2 parts by mass of dibutyltin oxide were added, reacted for 8 hours at 230 ° C. under normal pressure, and further reacted for 5 hours under reduced pressure of 10 to 15 mmHg to obtain “Intermediate Polyester 1”. “Intermediate polyester 1” had a number average molecular weight of 2,100 and a weight average molecular weight of 9,500. It was 55 degreeC when the glass transition temperature was measured with the differential scanning calorimeter DSC6200 (made by Seiko Instruments Inc.). The acid value was 0.5 mgKOH / g and the hydroxyl value was 49 mgKOH / g.
Next, 411 parts by mass of “Intermediate Polyester 1”, 89 parts by mass of isophorone diisocyanate, 300 parts by mass of ethyl acetate, and 200 parts by mass of methyl ethyl ketone are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. To give “Prepolymer 1”. “Prepolymer 1” had a free isocyanate weight percentage of 1.53%.

The hydroxyl value was measured as follows. Hereinafter, the hydroxyl values in all synthesis examples were also measured under the same conditions.
Measurement was performed under the following conditions in accordance with the measurement method described in JIS K0070-1966.
0.5 g of intermediate polyester 1 was precisely weighed into a 100 mL volumetric flask, and 5 mL of an acetylating reagent was correctly added thereto. Then, it was heated by being immersed in a bath at 100 ° C. ± 5 ° C. After 1 to 2 hours, the flask was taken out of the bath, allowed to cool, then added with water and shaken to decompose acetic anhydride. Further, in order to complete the decomposition, the flask was again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask was thoroughly washed with an organic solvent. This solution was subjected to potentiometric titration with a N / 2 potassium hydroxide ethyl alcohol solution using a potentiometric automatic hand titrator (DL-53 Titrator, manufactured by METTLER TOLEDO) to determine the hydroxyl value.

Example 1
<Preparation of Toner 1>
-Preparation of aqueous phase-
970 parts by weight of ion-exchanged water, 40 parts by weight of a 25% by weight aqueous dispersion of a sodium salt of styrene, methacrylic acid, butyl acrylate and ethylene oxide adduct sulfate, 48 parts of sodium dodecyl diphenyl ether disulfonate. 140 mass parts of 5 mass% aqueous solution (the Sanyo Chemical Industries make, Eleminol MON-7) and 90 mass parts of ethyl acetate and methyl ethyl ketone mixed solution (60 mass% / 40 mass%) were mixed and stirred, and the milky white liquid was obtained. . This is designated as “aqueous phase 1”.

-Production of master batch (MB) 1-
30 parts by mass of water, 40 parts by mass of carbon black (manufactured by Cabot, Regal 400R), and polyester resin (manufactured by Sanyo Chemical Co., Ltd., RS-801 acid value 10, mass average molecular weight: 20,000, glass transition temperature: 64 ° C.) Add 60 parts by mass, mix with a Henschel mixer (Mitsui Mining Co., Ltd.), knead the mixture for 45 minutes at 130 ° C. using two rolls, roll cool, crush to 1 mm size with a pulverizer, A master batch 1 ”was prepared.

-Preparation of oil phase-
In a container in which a stir bar and a thermometer are set, 545 parts by weight of “polyester 1”, ester wax 1 (manufactured by NOF Corporation, product number WEP-5, mass average molecular weight 750, endothermic peak 82. 2 ° C., half-width 5.2 ° C.) was charged with 181 parts by mass, and 1,450 parts by mass of ethyl acetate and methyl ethyl ketone mixed solution (60% by mass / 40% by mass). This was maintained for 5 hours and then cooled to 30 ° C. in 1 hour. Next, 500 parts by mass of “Masterbatch 1” and 100 parts by mass of a mixed solution of ethyl acetate and methyl ethyl ketone (60% by mass / 40% by mass) were charged into the container and mixed for 1 hour to obtain “raw material solution 1”. .
1,500 parts by mass of the obtained “raw material solution 1” was transferred into a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, Filled with 80% by volume of 5 mm zirconia beads, carbon black and wax were dispersed under conditions of 3 passes. Next, 425 parts by mass of “Polyester 1” and 230 parts by mass of a mixed solution of ethyl acetate and methyl ethyl ketone (60% by mass / 40% by mass) were added and passed once with a bead mill under the above conditions to obtain “Pigment and wax dispersion 1”. It was. Ethyl acetate and methyl ethyl ketone mixed solution (60 mass% / 40 mass%) was added and adjusted so that the solid content concentration of the obtained “Pigment and Wax Dispersion 1” was 50 mass%. This is designated as “oil phase 1”.

-Core particle granulation process-
975 parts by weight of the obtained “Oil Phase 1” and 2.6 parts by weight of isophoronediamine as an amine are mixed, 88 parts by weight of “Prepolymer 1” is added, and TK homomixer (manufactured by Tokushu Kika Co., Ltd.) After mixing for 1 minute at 000 rpm, 1,200 parts by mass of “Aqueous Phase 1” was added and mixed for 20 minutes while adjusting at 8,000 to 13,000 rpm with a TK homomixer to obtain “Emulsion Slurry 1”.

-Desolvation step-
“Emulsified slurry 1” was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain “dispersed core slurry 1”.

-Blooming process-
100 parts by weight of “dispersed core slurry 1” was filtered under reduced pressure, dried at 40 ° C. for 8 hours in a circulating drier, sieved with a mesh of 75 μm, and further aged at 55 ° C. for 32 hours. Particle 1 "was obtained.

-Encapsulation process-
After adding 100 parts by mass of ion-exchanged water to “core particle 1” and mixing with TK homomixer (rotation speed: 12,000 rpm for 10 minutes), “vinyl resin fine particle dispersion 1” is 1: 0 in solid content ratio. 3 and heated to 74 ° C. over 30 minutes. A solution obtained by dissolving 100 parts by mass of magnesium chloride hexahydrate in 100 parts by mass of ion-exchanged water was kept at 74 ° C. while being added little by little. After 4 hours, an aqueous hydrochloric acid solution was added to adjust to pH 5 and then heated to 80 ° C. After 2 hours, it was cooled to obtain “Dispersion Slurry 1”.

-Cleaning and drying-
After 100 parts by mass of “Dispersion Slurry 1” was filtered under reduced pressure, washing and drying were performed as follows.
(1) 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2) 100 parts by mass of 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3) 100 parts by mass of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(4) Add 300 parts by mass of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm), and then filter twice. Obtained.
The obtained “filter cake 1” was dried at 42 ° C. for 48 hours in a circulating drier. Thereafter, the mixture was sieved with a mesh having an opening of 75 μm to obtain “toner base particles 1”.
Thereafter, 100 parts by mass of the obtained “toner base particles 1”, 0.5 parts by mass of hydrophobic silica having a particle size of 10 nm and 0.5 parts by mass of hydrophobic titanium oxide having a particle size of 13 nm were mixed with a Henschel mixer. Thus, “Toner 1” was produced.

(Example 2)
<Preparation of Toner 2>
In Example 1, a toner 2 was produced in the same manner as in Example 1 except that the encapsulation step was performed as follows.
-Encapsulation process-
After adding 100 parts by mass of ion-exchanged water to “core particle 1” and mixing with TK homomixer (rotation speed: 12,000 rpm for 10 minutes), “vinyl resin fine particle dispersion 1” is 1: 0 in solid content ratio. .15 and heated to 74 ° C. over 30 minutes. A solution obtained by dissolving 100 parts by mass of magnesium chloride hexahydrate in 100 parts by mass of ion-exchanged water was kept at 74 ° C. while being added little by little. After 4 hours, an aqueous hydrochloric acid solution was added to adjust to pH 5 and then heated to 80 ° C. After 2 hours, cooling was performed to obtain “Dispersion Slurry 2”.

(Example 3)
<Preparation of Toner 3>
In Example 1, a toner 3 was produced in the same manner as in Example 1 except that the encapsulation step was performed as follows.
-Encapsulation process-
After adding 100 parts by mass of ion-exchanged water to “core particle 1” and mixing with TK homomixer (rotation speed: 12,000 rpm for 10 minutes), “vinyl resin fine particle dispersion 1” is 1: 0 in solid content ratio. 4 and heated to 74 ° C. over 30 minutes. A solution obtained by dissolving 100 parts by mass of magnesium chloride hexahydrate in 100 parts by mass of ion-exchanged water was kept at 74 ° C. while being added little by little. After 4 hours, an aqueous hydrochloric acid solution was added to adjust to pH 5 and then heated to 80 ° C. After 2 hours, cooling was performed to obtain “Dispersion Slurry 3”.

Example 4
<Preparation of Toner 4>
In Example 1, a toner 4 was produced in the same manner as in Example 1 except that the encapsulation step was performed as follows.
-Encapsulation process-
After adding 100 parts by mass of ion-exchanged water to “core particle 1” and mixing with TK homomixer (rotation speed: 12,000 rpm for 10 minutes), “vinyl resin fine particle dispersion 2” is 1: 0 in solid content ratio. 3 and heated to 74 ° C. over 30 minutes. A solution obtained by dissolving 100 parts by mass of magnesium chloride hexahydrate in 100 parts by mass of ion-exchanged water was kept at 74 ° C. while being added little by little. After 4 hours, an aqueous hydrochloric acid solution was added to adjust to pH 5 and then heated to 80 ° C. After 2 hours, cooling was performed to obtain “Dispersion Slurry 4”.

(Example 5)
<Preparation of Toner 5>
In Example 1, a toner 5 was produced in the same manner as in Example 1 except that the encapsulation step was performed as follows.
-Encapsulation process-
After adding 100 parts by mass of ion-exchanged water to “core particle 1” and mixing with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), “vinyl resin fine particle dispersion 3” was added at a solid content ratio of 1: 0. 3 and heated to 74 ° C. over 30 minutes. A solution obtained by dissolving 100 parts by mass of magnesium chloride hexahydrate in 100 parts by mass of ion-exchanged water was kept at 74 ° C. while being added little by little. After 4 hours, an aqueous hydrochloric acid solution was added to adjust to pH 5 and then heated to 80 ° C. After 2 hours, cooling was performed to obtain “Dispersion Slurry 5”.

(Example 6)
<Preparation of Toner 6>
In Example 1, a toner 6 was produced in the same manner as in Example 1 except that the oil phase was prepared as follows.
-Preparation of oil phase-
In a container in which a stir bar and a thermometer are set, 545 parts by weight of “polyester 1”, ester wax 1 (manufactured by NOF Corporation, product number WEP-5, mass average molecular weight 750, endothermic peak 82. 72 parts by mass of 2 ° C. and half-value width 5.2 ° C.) and 1,450 parts by mass of a mixed solution of ethyl acetate and methyl ethyl ketone (60% by mass / 40% by mass) were heated to 80 ° C. with stirring, and then heated to 80 ° C. This was maintained for 5 hours and then cooled to 30 ° C. in 1 hour. Next, 500 parts by mass of “Masterbatch 1” and 100 parts by mass of a mixed solution of ethyl acetate and methyl ethyl ketone (60% by mass / 40% by mass) were charged into the container and mixed for 1 hour to obtain “raw material solution 2”. .
1,500 parts by mass of the obtained “raw material solution 2” was transferred into a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, Filled with 80% by volume of 5 mm zirconia beads, carbon black and wax were dispersed under conditions of 3 passes. Next, 425 parts by mass of “Polyester 1” and 230 parts by mass of a mixed solution of ethyl acetate and methyl ethyl ketone (60% by mass / 40% by mass) are added and passed once with a bead mill under the above conditions to obtain “Pigment and wax dispersion 2”. It was. The resulting “Pigment and Wax Dispersion 2” was adjusted by adding ethyl acetate and methyl ethyl ketone mixed solution (60% by mass / 40% by mass) so that the solid content concentration became 50% by mass. This is designated as “oil phase 2”.

(Example 7)
<Preparation of Toner 7>
In Example 1, a toner 7 was produced in the same manner as in Example 1 except that the oil phase was prepared as follows.
-Preparation of oil phase-
In a container in which a stir bar and a thermometer are set, 545 parts by weight of “polyester 1”, ester wax 1 (manufactured by NOF Corporation, product number WEP-5, mass average molecular weight 750, endothermic peak 82. 2 ° C., full width at half maximum (5.2 ° C.) of 300 parts by mass, and ethyl acetate / methyl ethyl ketone mixed solution (60% by mass / 40% by mass) of 1,450 parts by mass were heated to 80 ° C. with stirring. This was maintained for 5 hours and then cooled to 30 ° C. in 1 hour. Next, 500 parts by mass of “Masterbatch 1” and 100 parts by mass of a mixed solution of ethyl acetate and methyl ethyl ketone (60% by mass / 40% by mass) were charged into the container and mixed for 1 hour to obtain “raw material solution 3”. .
1,500 parts by mass of the obtained “raw material solution 3” was transferred into a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, Filled with 80% by volume of 5 mm zirconia beads, carbon black and wax were dispersed under conditions of 3 passes. Next, 425 parts by weight of “Polyester 1” and 230 parts by weight of a mixed solution of ethyl acetate and methyl ethyl ketone (60% by weight / 40% by weight) were added and passed once with a bead mill under the above conditions to obtain “Pigment and Wax Dispersion 3”. It was. Ethyl acetate and methyl ethyl ketone mixed solution (60 mass% / 40 mass%) was added and adjusted so that the solid content concentration of the obtained “Pigment and Wax Dispersion 3” was 50 mass%. This is designated as “oil phase 3”.

(Example 8)
<Preparation of Toner 8>
In Example 1, Toner 8 was produced in the same manner as in Example 1 except that the oil phase was prepared as follows.
-Preparation of oil phase-
In a container in which a stirring bar and a thermometer are set, 516 parts by weight of “polyester 2”, ester wax 1 (manufactured by NOF Corporation, product number WEP-5, mass average molecular weight 750, endothermic peak 82.2 ° C., 181 parts by mass (full width at half maximum of 5.2 ° C.), 1,300 parts by mass of ethyl acetate and methyl ethyl ketone mixed solution (60% by mass / 40% by mass), heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours After holding, it was cooled to 30 ° C. in 1 hour. Next, 500 parts by mass of “Masterbatch 1” and 100 parts by mass of a mixed solution of ethyl acetate and methyl ethyl ketone (60% by mass / 40% by mass) were charged into the container and mixed for 1 hour to obtain “raw material solution 4”.
1,500 parts by mass of the obtained “raw material solution 4” was transferred into a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, Filled with 80% by volume of 5 mm zirconia beads, the carbon black and the release agent were dispersed under conditions of 3 passes. Next, 425 parts by mass of “Polyester 2” and 230 parts by mass of a mixed solution of ethyl acetate and methyl ethyl ketone (60% by mass / 40% by mass) are added and passed once with a bead mill under the above conditions to obtain “Pigment and wax dispersion 4”. It was. The resulting “pigment and wax dispersion 4” was adjusted by adding a mixed solution of ethyl acetate and methyl ethyl ketone (60% by mass / 40% by mass) so that the solid content concentration became 50% by mass. This is designated as “oil phase 4”.

Example 9
<Preparation of Toner 9>
In Example 1, a toner 9 was produced in the same manner as in Example 1 except that the oil phase was prepared as follows.
-Preparation of oil phase-
In a container in which a stirring bar and a thermometer are set, 516 parts by weight of “polyester 3”, ester wax 1 (manufactured by NOF Corporation, product number WEP-5, mass average molecular weight 750, endothermic peak 82.2 ° C., 181 parts by mass (full width at half maximum of 5.2 ° C.), 1,300 parts by mass of ethyl acetate and methyl ethyl ketone mixed solution (60% by mass / 40% by mass), heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours After holding, it was cooled to 30 ° C. in 1 hour. Next, 500 parts by mass of “Masterbatch 1” and 100 parts by mass of a mixed solution of ethyl acetate and methyl ethyl ketone (60% by mass / 40% by mass) were charged into the container and mixed for 1 hour to obtain “raw material solution 5”.
1,500 parts by mass of the obtained “raw material solution 5” was transferred into a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, Filled with 80% by volume of 5 mm zirconia beads, the carbon black and the release agent were dispersed under conditions of 3 passes. Next, 425 parts by weight of “Polyester 3” and 230 parts by weight of a mixed solution of ethyl acetate and methyl ethyl ketone (60% by weight / 40% by weight) were added, followed by one pass with a bead mill under the above conditions to obtain “Pigment and wax dispersion 5”. It was. The resulting “pigment and wax dispersion 5” was adjusted by adding a mixed solution of ethyl acetate and methyl ethyl ketone (60% by mass / 40% by mass) so that the solid content concentration became 50% by mass. This is designated as “oil phase 5”.

(Example 10)
<Preparation of Toner 10>
In Example 1, a toner 10 was produced in the same manner as in Example 1 except that the master batch (MB) 1 was replaced with the master batch (MB) 2 prepared as follows when the oil phase was prepared. .
-Production of master batch (MB) 2-
30 parts by weight of water, C.I. I. Pigment Blue 15: 3 (manufactured by Dainichi Seika Co., Ltd., ECB-301), 50 parts by mass of polyester resin (manufactured by Sanyo Chemical Co., Ltd., RS-801 acid value 10, Mw 20,000, Tg 64 ° C.), pigment dispersant ( Avecia, Solsperse S24000sc) was added, mixed with a Henschel mixer (Mitsui Mining Co., Ltd.), the mixture was kneaded at 130 ° C. for 45 minutes using two rolls, cooled by cooling, and pulverized to a size of 1 mm with a pulverizer. Thus, “master batch 2” was produced.

(Example 11)
<Preparation of Toner 11>
In Example 1, during the preparation of the oil phase, ester wax 1 (manufactured by NOF Corporation, product number WEP-5, mass average molecular weight 750, endothermic peak 82.2 ° C., half-value width 5.2 ° C.) was used as a release agent. ) Was replaced with ester wax 2 (manufactured by NOF Corporation, product number WEP-2, mass average molecular weight 700, endothermic peak 61.0 ° C., half-value width 3.8 ° C.). 11 was produced.

(Example 12)
<Preparation of Toner 12>
In Example 1, during the preparation of the oil phase, ester wax 1 (manufactured by NOF Corporation, product number WEP-5, mass average molecular weight 750, endothermic peak 82.2 ° C., half-value width 5.2 ° C.) was used as a release agent. ) Was replaced with ester wax 3 (manufactured by NOF Corporation, product number WEP-8, mass average molecular weight 780, endothermic peak 81.0 ° C., half-value width 8.8 ° C.). 12 was produced.

(Example 13)
<Preparation of Toner 13>
In Example 1, a toner 13 was produced in the same manner as in Example 1 except that the oil phase was prepared as follows.
-Preparation of oil phase-
In a container in which a stir bar and a thermometer are set, 545 parts by weight of “polyester 1”, ester wax 1 (manufactured by NOF Corporation, product number WEP-5, mass average molecular weight 750, endothermic peak 82. 2 ° C., half-width 5.2 ° C.) and 50 parts by mass, and 1,450 masses of a mixed solution of ethyl acetate and methyl ethyl ketone (60% by mass / 40% by mass) were heated to 80 ° C. with stirring. This was maintained for 5 hours and then cooled to 30 ° C. in 1 hour. Next, 500 parts by mass of “Masterbatch 1” and 100 parts by mass of a mixed solution of ethyl acetate and methyl ethyl ketone (60% by mass / 40% by mass) were charged into the container and mixed for 1 hour to obtain “raw material solution 6”. .
1,500 parts by mass of the obtained “raw material solution 6” was transferred into a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, Filled with 80% by volume of 5 mm zirconia beads, carbon black and wax were dispersed under conditions of 3 passes. Next, 425 parts by weight of “Polyester 1” and 230 parts by weight of a mixed solution of ethyl acetate and methyl ethyl ketone (60% by weight / 40% by weight) are added, and one pass is performed with a bead mill under the above conditions to obtain “Pigment and wax dispersion 6”. It was. The resulting “pigment and wax dispersion 6” was adjusted by adding a mixed solution of ethyl acetate and methyl ethyl ketone (60% by mass / 40% by mass) so that the solid content concentration became 50% by mass. This is designated as “oil phase 6”.

(Example 14)
<Preparation of Toner 14>
In Example 1, a toner 14 was prepared in the same manner as in Example 1 except that “Polyester 1” was replaced with “Polyester 4” when the oil phase was prepared.

(Example 15)
<Preparation of Toner 15>
In Example 1, a toner 15 was produced in the same manner as in Example 1 except that “Polyester 1” was replaced with “Polyester 5” when the oil phase was prepared.

(Example 16)
<Preparation of Toner 16>
In Example 1, a toner 16 was produced in the same manner as in Example 1 except that the encapsulation step was performed as follows.
-Encapsulation process-
After adding 100 parts by mass of ion-exchanged water to “core particle 1” and mixing with TK homomixer (rotation speed: 12,000 rpm for 10 minutes), “vinyl resin fine particle dispersion 1” is 1: 0 in solid content ratio. 0.04 and heated to 74 ° C. over 30 minutes. A solution obtained by dissolving 100 parts by mass of magnesium chloride hexahydrate in 100 parts by mass of ion-exchanged water was kept at 74 ° C. while being added little by little. After 4 hours, an aqueous hydrochloric acid solution was added to adjust to pH 5 and then heated to 80 ° C. After 2 hours, cooling was performed to obtain “Dispersion Slurry 16”.

(Example 17)
<Preparation of Toner 17>
In Example 1, a toner 17 was produced in the same manner as in Example 1 except that the encapsulation step was performed as follows.
-Encapsulation process-
After adding 100 parts by mass of ion-exchanged water to “core particle 1” and mixing with TK homomixer (rotation speed: 12,000 rpm for 10 minutes), “vinyl resin fine particle dispersion 1” is 1: 0 in solid content ratio. 6 and heated to 74 ° C. over 30 minutes. A solution obtained by dissolving 100 parts by mass of magnesium chloride hexahydrate in 100 parts by mass of ion-exchanged water was kept at 74 ° C. while being added little by little. After 4 hours, an aqueous hydrochloric acid solution was added to adjust to pH 5 and then heated to 80 ° C. After 2 hours, cooling was performed to obtain “Dispersion Slurry 17”.

(Example 18)
<Preparation of Toner 18>
In Example 1, a toner 18 was prepared in the same manner as in Example 1 except that the “vinyl resin fine particle dispersion 1” was replaced with “vinyl resin fine particle dispersion 4” during the encapsulation step.

(Example 19)
<Preparation of Toner 19>
In Example 1, a toner 19 was produced in the same manner as in Example 1 except that the “vinyl resin fine particle dispersion 1” was replaced with “vinyl resin fine particle dispersion 5” during the encapsulation step.

(Example 20)
<Preparation of Toner 20>
In Example 1, a toner 20 was produced in the same manner as in Example 1 except that isophoronediamine and “prepolymer 1” were not added during the core particle granulation step.

(Example 21)
<Preparation of Toner 21>
In Example 1, a toner 21 was produced in the same manner as in Example 1 except that isophoronediamine was not added during the core particle granulation step.

(Example 22)
<Preparation of Toner 22>
In Example 1, a toner 22 was prepared in the same manner as in Example 1 except that “vinyl resin fine particle dispersion 1” was replaced with “polyester resin fine particle dispersion 1” during the core particle granulation step. did.

(Example 23)
<Preparation of Toner 23>
In Example 1, toner 23 was produced in the same manner as in Example 1 except that the aging time in the blooming process was changed from 32 hours to 42 hours.

(Comparative Example 1)
<Preparation of Toner 24>
In Example 1, a toner 24 was produced in the same manner as in Example 1 except that the blooming process was not performed.

(Comparative Example 2)
<Preparation of Toner 25>
In Example 2, a toner 25 was produced in the same manner as in Example 2 except that the blooming process was not performed.

(Comparative Example 3)
<Preparation of Toner 26>
In Example 3, a toner 26 was produced in the same manner as in Example 3 except that the blooming process was not performed.

(Comparative Example 4)
<Preparation of Toner 27>
In Example 4, toner 27 was produced in the same manner as in Example 4 except that the blooming process was not performed.

(Comparative Example 5)
<Preparation of Toner 28>
In Example 5, Toner 28 was produced in the same manner as Example 5 except that the blooming process was not performed.

(Comparative Example 6)
<Preparation of Toner 29>
In Example 6, a toner 29 was produced in the same manner as in Example 6 except that the blooming process was not performed.

(Comparative Example 7)
<Preparation of Toner 30>
In Example 7, Toner 30 was produced in the same manner as Example 7 except that the blooming process was not performed.

(Comparative Example 8)
<Preparation of Toner 31>
In Example 8, a toner 31 was produced in the same manner as in Example 8 except that the blooming process was not performed.

(Comparative Example 9)
<Preparation of Toner 32>
In Example 9, a toner 32 was produced in the same manner as in Example 9 except that the blooming process was not performed.

(Comparative Example 10)
<Preparation of Toner 33>
In Example 1, during the preparation of the oil phase, ester wax 1 (manufactured by NOF Corporation, product number WEP-5, mass average molecular weight 750, endothermic peak 82.2 ° C., half-value width 5.2 ° C.) was used as a release agent. ) Was replaced with polyethylene wax 1 (manufactured by Toyo Atre Co., Ltd., product number polywax 500, mass average molecular weight 500, half-value width 7.5 ° C.), toner 33 was prepared in the same manner as in Example 1.

(Comparative Example 11)
<Preparation of Toner 34>
In Example 2, toner 34 was produced in the same manner as in Example 1 except that the aging time in the blooming process was changed from 32 hours to 60 hours.

(Comparative Example 12)
<Preparation of Toner 35>
In Example 6, a toner 35 was produced in the same manner as in Example 1 except that the aging time in the blooming process was changed from 32 hours to 60 hours.

(Comparative Example 13)
<Preparation of Toner 36>
In Example 1, during the preparation of the oil phase, the amount of ester wax 1 added was changed from 181 parts by mass to 120 parts by mass, and carnauba wax 1 (manufactured by Noda Celalica, product number WA-03, mass average). A toner 36 was produced in the same manner as in Example 1 except that 120 parts by mass of a molecular weight of 800 and a half-value width of 6.6 ° C. were added.

(Comparative Example 14)
<Preparation of Toner 37>
In Example 1, a toner 37 was produced in the same manner as in Example 1 except that the encapsulation step was not performed.

(Physical properties)
For the obtained toner 1 to toner 37, volume average particle diameter (Dv), ratio of area occupied by island (distribution of release agent), average circularity, endothermic peak, 1/2 outflow temperature, ratio of release agent The ratio of the total mass (B + C) of the intermediate region (B) and the internal region (C) to the total mass (A1 + A2) of the peripheral region (A1) and the peripheral region (A2) ((A1 + A2) / (B + C)) Was measured. The results are shown in Table 1.

<Ratio of area occupied by island (distribution of mold release agent)>
After embedding the toner in an epoxy resin, a section was taken out using a cryomicrotome, stained with ruthenium trioxide, and then cut into ultrathin sections of about 100 μm. This ultrathin section was observed with a transmission electron microscope (TEM) at a magnification of 10,000 times for the cross section of the toner. During toner cross-sectional observation, 20 points of photographs in which the major axis of the toner cross-section is 0.9 to 1.2 times the toner volume average particle diameter are photographed, and these photographs (20 toners) are image-evaluated. The dispersion state of the release agent was observed.
In addition, it was confirmed by observation with the transmission electron microscope (TEM) that the toners of Examples 1 to 23 include islands of a release agent that exist across the peripheral area (A2) and the intermediate area (B). . The release agent present in the peripheral region (A2) is considered to be due to the thermal expansion of the release agent particles existing in the intermediate region (B).

<Average circularity>
Measurement was performed using a flow type particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation), and analysis was performed using analysis software (FPIA-2100, Data Processing Program for FPIA version 00-10).
0.5 mL of 10% alkylbenzene sulfonate aqueous solution as a dispersant was added to 100 mL of water from which impure solids in the container were removed, and about 0.3 g of a measurement sample was further added. The suspension in which the toner was dispersed was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser, and the shape and distribution of the toner were measured with the above apparatus at a dispersion concentration of about 5,000 particles / μL.

<Endothermic peak>
The toner is weighed in a 5 mg aluminum pan, set in a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.), heated from room temperature to 200 ° C., and cooled from that temperature to 0 ° C. at a cooling rate of 10 ° C./min. The measured toner was measured at a heating rate of 10 ° C./min. The result at this time was plotted by temperature and calorific value, and the temperature at which the calorific value was the minimum value was defined as the endothermic peak. In addition, a line segment is drawn perpendicularly to the baseline from the endothermic peak, and the temperature difference between the two points where the line passing through the center of the line segment and parallel to the baseline intersects the temperature-calorie plot is the half-value width of the endothermic peak. It was.

<1/2 outflow temperature (T1 / 2)>
Using a flow tester (CFT-500 / manufactured by Shimadzu Corporation), 1.5 g of a measurement sample was weighed, and using a die having a height of 1.0 mm and a diameter of 1.0 mm, the temperature rising rate was 3.0 ° C./min. Measurement was performed under the conditions of a preheating time of 180 seconds, a load of 30 kg, and a measurement temperature range of 80 ° C. to 140 ° C., and the temperature at which the above sample flowed out by 1/2 was defined as a 1/2 outflow temperature.

<Volume average particle diameter>
0.5 mL of 10% alkylbenzene sulfonate aqueous solution was added as a dispersing agent to 100 mL of electrolytic aqueous solution ISOTON-II (manufactured by Coulter). Further, 10 mg of toner was added as a solid content. The electrolytic solution in which the toner is suspended is dispersed for 3 minutes with an ultrasonic disperser, and the volume and number of toner particles or toner are determined using a 100 μm aperture as an aperture with a Coulter Counter TA-II (manufactured by Coulter). The volume average particle diameter (Dv) of the toner was measured.

<(A1 + A2) / (B + C)>
The total mass part of the material used in the granulation of the core particles was “B + C”, and the total mass part of the material used in the production of the resin fine particles was “A1 + A2”.

<Ratio of release agent>
From the ratio of the total amount of the resin components contained in the water phase, oil phase, and resin fine particles and the amount of the release agent added during the preparation of the oil phase, the ratio to 100 parts by mass of the binder resin is obtained as the ratio of the release agent. It was.

(Evaluation)
The obtained toner 1 to toner 37 were evaluated for heat-resistant storage property, transfer property (whiteout), charging durability, fixing releasability (fixing separation property), low-temperature fixing property, and OHP projection quality. The results are shown in Table 2.

<Heat resistant storage>
The toner 1 was stored at 50 ° C. for 8 hours, and then sieved with a 42 mesh sieve for 2 minutes. The residual rate on the wire mesh was used as an index of heat resistant storage stability (thermal storage stability). The heat-resistant storage property was evaluated in the following four stages. The same evaluation was performed for toner 2 to toner 37.
[Evaluation criteria]
×: 30% or more Δ: 20 to less than 30% ○: less than 10 to 20% ◎: less than 10%

<Transferability>
130 g of toner 1 was put in a process cartridge of Ricoh's ipsio CX 2500, and 20 lattice print patterns were printed in an N / N (23 ° C., 45%) environment. The 20th lattice pattern was visually evaluated. The same evaluation was performed for toner 2 to toner 37.
[Evaluation criteria]
A: Printed without problems.
○: Slight white spots are seen in the lattice lines, but there is no practical problem.
Δ: Clear white spots are observed in the lattice lines, which is problematic in practical use.
X: Lattice lines appear to be two lines, and there is a problem in practical use.

<Charging durability>
Toner 1 was put in a process cartridge of Ricoh ipsio CX 2500, and a predetermined print pattern having a B / W ratio of 3% was continuously printed in an N / N (23 ° C., 45%) environment. After continuous printing of 50 and 1,500 sheets in an N / N environment, the toner on the developing roller during blank paper pattern printing is sucked and the amount of charge is measured with an electrometer. After printing 50 sheets and printing 1,500 sheets The subsequent charge amount difference was evaluated. The same evaluation was performed for toner 2 to toner 37.
[Evaluation criteria]
A: Absolute value of difference in charge amount is less than 5 μC / g ○: Absolute value of difference in charge amount is 5 μC / g or more and less than 10 μC / g Δ: Absolute value of difference in charge amount is 10 μC / g or more and less than 15 μC / g ×: Charging Absolute value of quantity difference is 15μC / g or more

<Fixing separation>
An unfixed image in which a solid band image (adhesion amount 10 g / m ² ) having a width of 3 mm was printed on the tip 3 mm with A4 longitudinal paper using Ricoh's ipsio CX2500 was produced. This unfixed image was fixed at a fixing temperature in increments of 10 ° C. in the range of 130 ° C. to 190 ° C. using the following fixing device, a separable / non-offset temperature range was determined, and evaluated according to the following evaluation criteria. The temperature range refers to a fixing temperature range in which the paper is satisfactorily separated from the heating roller, no offset phenomenon occurs, and image peeling does not easily occur. The paper used and the paper passing direction were 45 g / m ² of Y-long vertical paper that is disadvantageous in separability. The peripheral speed of the fixing device was 120 mm / sec.
The fixing device is of a soft roller type having a fluorine surface layer composition as shown in FIG. Specifically, the heating roller 71 has an outer diameter of 40 mm, an aluminum core 73 and a 1.5 mm-thick elastic body layer 74 made of silicone rubber, and a PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) surface layer. 75, and a heater 76 is provided inside the aluminum cored bar. The pressure roller 72 has an outer diameter of 40 mm, and has an elastic body layer 78 and a PFA surface layer 79 made of silicone rubber and having a thickness of 1.5 mm on an aluminum cored bar 77. The paper P on which the unfixed image Q is printed is passed as shown in FIG.
[Evaluation criteria]
A: Separable / non-offset in all temperature ranges.
A: Separable / non-offset temperature range was 50 ° C. or higher and lower than 70 ° C.
Δ: Separable / non-offset temperature range was 30 ° C. or higher and lower than 50 ° C.
X: The separable / non-offset temperature range was less than 30 ° C.

<Low temperature fixability>
Using a non-magnetic one-component development type full color printer Ipsio CX3000 (manufactured by Ricoh), an unfixed image is created so that the adhesion amount becomes 1.0 ± 0.1 mg / cm ^2, and only the fixing portion of Ricoh's Ipsio CX2500 Using the fixing test device modified so that the fixing belt temperature and the belt linear velocity become desired values, the fixing temperature is fixed in the range of 120 ° C. to 200 ° C. A smear property test was conducted to evaluate the temperature that satisfies the smear property.
[Evaluation criteria]
(Double-circle): It was less than 135 degreeC.
A: 135 ° C. or higher and lower than 145 ° C.
X: It was 145 degreeC or more.

<OHP projection quality>
The toner 1 was printed on the OHP sheet using Ripoh's ipsio CX2500 under the N / N environment (23 ° C., 45%), and then projected by OHP. The image was visually evaluated for bleeding of the release agent. Judgment criteria are as follows. The same evaluation was performed for toner 2 to toner 37.
[Evaluation criteria]
(Double-circle): The bleeding of a mold release agent is not seen at all.
○: Slight blurring is observed at the peripheral edge of the character, but there is no practical problem.
X: Bleeding is observed at the peripheral edge of the character, and the character is difficult to read.

  The toner of the present invention is suitably used for high-quality electrophotographic image formation. The developer of the present invention using the toner of the present invention and the image forming method can be widely used for full-color copiers, full-color laser printers, full-color plain paper fax machines using direct or indirect electrophotographic multicolor image development systems, and the like. .

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Transfer device 3 Sheet conveyance belt 4 Intermediate transfer body 5 Secondary transfer device 6 Paper feed device 7 Fixing device 8 Photoconductor cleaning device 9 Intermediate transfer body cleaning device 10 Photoconductor (photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer 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 Developer 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Development roller Roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Ejection Roller 57 Discharge tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Static eliminator 70 Static elimination lamp 71 Heating roller 72 Pressure roller 73 Aluminum core metal 74 Elastic body layer 75 PFA surface layer 76 Heater 77 Aluminum core metal 78 Elastic layer 79 PFA surface layer 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 101 Photoconductor 102 Charging unit 103 Exposure by exposure unit 104 Development unit 105 Recording medium 107 Clear Ninging means 108 Transfer means 110 Belt-type image fixing device 120 Tandem type developing device 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Conveying roller 148 Paper feed path 150 Copying apparatus main body 200 Feeding Paper table 210 Image fixing device 220 Heating roller 230 Pressure roller 300 Scanner 400 Automatic document feeder (ADF)
A Toner B Colorant C Release Agent D Core (Internal Region C)
E Intermediate area B
F shell (peripheral region A1, peripheral region A2)
Q Unfixed image P Paper

JP-T-2006-503313 Special table 2006-500605 gazette JP 2003-202708 A JP 2006-285188 A JP 2008-70530 A

Claims (20)

A core-shell structure toner including a toner material containing at least a binder resin, a colorant, and a release agent in a core,
In a transmission electron microscope (TEM) image in a cross section of the ultra-thin section of the toner, a sea-island structure in which the release agent exists in an island shape in the continuous phase of the binder resin is shown.
The volume average particle diameter of the toner is D,
The peripheral region from the peripheral part of the TEM image to the inner side 0.025D (μm) is (A1),
The peripheral region excluding the peripheral region (A1) from the region 0.05D (μm) inside from the peripheral portion of the TEM image is (A2),
An intermediate region excluding the peripheral region (A1) and the peripheral region (A2) from the region 0.2D (μm) inside from the peripheral portion of the TEM image is (B),
When the inner region excluding the peripheral region (A1), the peripheral region (A2) and the intermediate region (B) of the TEM image is (C),
The core is composed of the intermediate region (B) and the internal region (C), and the shell is composed of the peripheral region (A1) and the peripheral region (A2),
The ratio of the area occupied by the island in the peripheral area (A1) is IA1 (%), the ratio of the area occupied by the island in the peripheral area (A2) is IA2 (%), and the ratio of the island in the intermediate area (B) When the proportion of the area occupied is IB (%) and the proportion of the area occupied by the island in the internal region (C) is IC (%), the following formulas (1) to (3) are satisfied, and A toner comprising the island that exists across the peripheral area (A2) and the intermediate area (B).
IA2> IA1 (1)
IB> IA2 (2)
IB> IC (3)   The toner according to claim 1, wherein the release agent is a pentaerythritol ester wax. The toner according to claim 1, wherein IA1 (%), IA2 (%), IB (%), and IC (%) satisfy the following formulas (i) to (v).
0 ≦ IA1 ≦ 5 (i)
3 ≦ IA2 ≦ 20 (ii)
3 ≦ IB ≦ 70 (iii)
0 ≦ IC ≦ 5 (iv)
IC> IA1 (v)   The toner according to claim 1, wherein the toner has an average circularity of 0.930 to 0.995.   The toner according to claim 1, wherein at least one endothermic peak measured by a differential scanning calorimeter (DSC) in the toner exists in a range of 60 ° C. to 90 ° C. 6.   The toner according to claim 5, wherein the half-value width of the endothermic peak is 8 ° C. or less.   The toner according to claim 1, wherein the content of the release agent is 3 to 15 parts by mass with respect to 100 parts by mass of the binder resin.   The toner according to any one of claims 1 to 7, wherein a 1/2 outflow temperature (T1 / 2) measured by a flow tester in the toner is 110 ° C to 140 ° C. The core binder resin contains at least a resin having a polyester skeleton,
The shell is made of resin fine particles made of vinyl copolymer resin,
The mass ratio ((A1 + A2) / (B + C)) of the total mass (A1 + A2) of the peripheral area (A1) and the peripheral area (A2) to the total mass (B + C) of the intermediate area (B) and the internal area (C) is 0. The toner according to any one of claims 1 to 8, which is from 05 to 0.5.   The toner according to claim 1, wherein the resin fine particles of the shell are at least one obtained by agglomeration and fusion of fine particles of a vinyl copolymer resin.   11. The toner according to claim 1, wherein the resin fine particles of the shell have a mass average molecular weight of 50,000 or less and a glass transition temperature of 40 ° C. to 80 ° C. 11.   The toner according to claim 1, wherein the core binder resin contains a modified polyester resin having at least one of urethane and urea groups.   The binder resin according to any one of claims 1 to 12, wherein the binder resin of the core contains at least one modified polyester resin that is chain-extended and cross-linked by a reaction between a modified polyester resin having an isocyanate group at a terminal and amines. toner.   A developer comprising the toner according to claim 1.   A toner-filled container filled with the toner according to claim 1. The image forming apparatus main body includes at least an electrostatic latent image carrier and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image. A possible process cartridge,
The process cartridge according to claim 1, wherein the toner is the toner according to claim 1. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image An image forming apparatus having at least developing means for transferring, a transferring means for transferring the visible image to a recording medium, and a fixing means for fixing the transferred image transferred to the recording medium by a fixing member.
The image forming apparatus according to claim 1, wherein the toner is the toner according to claim 1. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, and the visible image In an image forming method including at least a transfer step of transferring the image to a recording medium and a fixing step of fixing the transferred image transferred to the recording medium by a fixing member,
An image forming method, wherein the toner is the toner according to claim 1. A core particle granulation step in which a release agent is dispersed in a binder resin to form core particles;
A blooming step of annealing in a temperature atmosphere having a temperature range of 45 ° C. or more and 3 ° C. or less lower than the glass transition temperature of the binder resin, and depositing the release agent on the surface of the core particles;
And a step of encapsulating the surface of the core particles with a shell.   The method for producing a toner according to claim 19, wherein the release agent is a pentaerythritol ester wax.