JP7494542B2 - Toner, developer, toner storage unit and image forming apparatus - Google Patents

Description

The present invention relates to a toner, a developer, a toner storage unit, and an image forming device.

The toner used in electrophotography, electrostatic recording, electrostatic printing, etc. is first attached to an image carrier such as an electrostatic latent image carrier on which an electrostatic charge image is formed in the development process, then transferred from the electrostatic latent image carrier to a transfer medium such as transfer paper in the transfer process, and then fixed to the paper surface in the fixing process.

At that time, toner that was not transferred remains on the latent image holding surface, and it is necessary to clean the remaining toner so as not to interfere with the formation of the next electrostatic image. To clean the remaining toner, blade cleaning is often used, which is a simple device with good cleaning properties, and it is known that the more the toner shape is deformed, the better the cleaning properties. It is also known that the more uniform the particle size distribution and shape, the better the cleaning properties (see Patent Document 1).

Since polymerized toner basically produces spherical toner, a method is known in which, in the suspension polymerization method, a deforming agent such as an inorganic filler or layered inorganic mineral is unevenly distributed on the toner surface to make the toner non-spherical (deformed) (see Patent Document 2).

However, the resulting toner has a shape close to spherical when the particle size is small, and the larger the particle size, the more irregular the shape becomes, with a wider circularity distribution. As a result, cleaning and transfer properties deteriorate.

Meanwhile, Patent Document 3 proposes a toner in which, under the following analytical conditions, the measurement results of the toner using a flow-type particle image analyzer are: average circularity Rave. 0.960≦Rave.≦0.980; most frequent particle diameter θmax 4.0 μm≦θmax≦6.0 μm; and the number of particles with a particle diameter of 0.75×θmax or less and a circularity of 0.980 or more is 1.0% or less of the limited particle number. Patent Document 6 claims that it is possible to provide a toner with excellent cleaning and transfer properties, in which the toner particle size is not too small, the shape is not too spherical, the particle size distribution and circularity distribution are narrow, and the toner has an extremely uniform particle size distribution and an extremely uniform circularity distribution.

However, in conventional techniques, there are cases where it is not possible to simultaneously achieve both cleaning and transferability, and further improvements are required to achieve both.

Therefore, the present invention aims to provide a toner that can achieve both cleaning and transferability.

In order to achieve the above object, the toner of the present invention is a toner containing a binder resin and a release agent, the standard deviation of circularity measured using a flow type particle image analyzer is 0.020 or more, and in the average particle size and circularity measured using the flow type particle image analyzer, when the average circularity of particles having a particle size equal to or smaller than the average particle size is defined as average circularity (A) and the average circularity of particles having a particle size larger than the average particle size is defined as average circularity (B),
A-B≦0.004
the toner has a glass transition temperature Tg1st in a first temperature rise measured by differential scanning calorimetry (DSC) of 20° C. or more and 50° C. or less, the toner has a glass transition temperature Tg2nd in a second temperature rise measured by differential scanning calorimetry (DSC) of −40° C. or more and 30° C. or less, the toner has a storage modulus at 40° C. of the toner insoluble in THF is G'(40), and the toner has a storage modulus at 100° C. of the toner insoluble in THF is G'(100),
1×105 ^≦ G′(100)≦1× ¹⁰⁷
G'(40)/G'(100)≦3.5×10
The present invention is characterized in that:
However, the particle diameter is the circle-equivalent diameter, the average particle diameter is determined based on the circle-equivalent diameter (number basis), and the analysis conditions for the flow-type particle image analyzer are as follows:
Particle size limit: 0.5 μm≦circle equivalent diameter (number basis)≦200.0 μm
Particle shape limit: 0.93<circularity≦1.00

The present invention provides a toner that has both good cleaning properties and good transfer properties.

FIG. 2 is a diagram illustrating a spindle shape of toner. FIG. 2 is a diagram illustrating a spindle shape of toner. FIG. 2 is a diagram illustrating a spindle shape of toner. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an embodiment of the present invention. FIG. 2 is a schematic configuration diagram illustrating another example of an image forming apparatus according to an embodiment of the present invention. FIG. 2 is a schematic configuration diagram illustrating another example of an image forming apparatus according to an embodiment of the present invention. FIG. 5 is a partially enlarged view of FIG. 4 . FIG. 2 is a schematic diagram illustrating an example of a process cartridge.

The toner, developer, toner storage unit, and image forming apparatus according to the present invention will be described below with reference to the drawings. Note that the present invention is not limited to the embodiments shown below, and can be modified within the scope of what a person skilled in the art can imagine, including other embodiments, additions, modifications, deletions, etc., and any aspect is within the scope of the present invention as long as it achieves the functions and effects of the present invention.

(toner)
The toner of the present invention is a toner containing a binder resin and a release agent, and has a standard deviation of circularity determined using a flow type particle image analyzer of 0.020 or more, and when, in the average particle size and circularity determined using the flow type particle image analyzer, the average circularity of particles having a particle size equal to or smaller than the average particle size is defined as average circularity (A) and the average circularity of particles having a particle size larger than the average particle size is defined as average circularity (B),
A-B≦0.004
The present invention is characterized in that:
The particle diameter is the equivalent circle diameter, the average particle diameter is determined based on the equivalent circle diameter (number basis), and the analysis conditions for the flow type particle image analyzer are as follows:
Particle size limit: 0.5 μm≦circle equivalent diameter (number basis)≦200.0 μm
Particle shape limit: 0.93<circularity≦1.00

According to the present invention, it is possible to provide a toner that can achieve both cleaning and transferability. Furthermore, according to a preferred embodiment of the present invention, it is possible to improve low-temperature fixability, heat-resistant storage stability, and high-temperature and high-humidity storage stability while achieving both cleaning and transferability.

The toner of this embodiment contains a binder resin and a release agent. Below, we will explain an example of the composition of the toner of this embodiment that contains toner base particles and external additives.

<Toner Base Particles>
The toner base particles contain a binder resin and a release agent, and preferably contain a crystalline polyester resin. In addition, the toner base particles preferably contain a colorant, an amorphous polyester resin, and the like, and further contain other components as necessary.

<<Binding resin>>
Examples of the binder resin include crystalline polyester resin and amorphous polyester resin.

<<<Crystalline polyester resin>>>
The crystalline polyester resin (hereinafter, sometimes referred to as "crystalline polyester resin C") has high crystallinity and therefore exhibits heat melting characteristics that show a rapid viscosity change near the fixing start temperature.

By using the crystalline polyester resin C having such characteristics together with the amorphous polyester resin, a toner having both good heat-resistant storage stability and low-temperature fixability can be obtained. For example, by using both together, the heat-resistant storage stability is good due to the crystallinity up to just before the melting start temperature, and at the melting start temperature, a sudden viscosity drop (sharp melt property) occurs due to the melting of the crystalline polyester resin C, which is accompanied by compatibility with the amorphous polyester resin B described later, and the viscosity of both is suddenly reduced, allowing good fixation.
Also, good results are shown with respect to the release width (the difference between the minimum fixing temperature and the temperature at which high-temperature offset occurs).

The crystalline polyester resin C is obtained by using a polyhydric alcohol and a polycarboxylic acid or a derivative thereof, such as a polycarboxylic acid, a polycarboxylic anhydride, or a polycarboxylic ester.

In the present invention, the crystalline polyester resin C refers to a resin obtained by using a polyhydric alcohol and a polycarboxylic acid or a derivative thereof, such as a polycarboxylic acid, a polycarboxylic anhydride, or a polycarboxylic acid ester, as described above. Modified polyester resins, such as the prepolymers described below, and resins obtained by subjecting the prepolymers to a crosslinking and/or elongation reaction, do not belong to the crystalline polyester resin C.

-Polyhydric alcohol-
The polyhydric alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples of the polyhydric alcohol include diols and trihydric or higher alcohols.
Examples of the diol include saturated aliphatic diols. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferred, and linear saturated aliphatic diols having 2 to 12 carbon atoms are more preferred. If the saturated aliphatic diol is a branched type, the crystallinity of the crystalline polyester resin C may decrease, resulting in a decrease in melting point. If the carbon number of the saturated aliphatic diol exceeds 12, it becomes difficult to obtain a practical material. It is more preferred that the carbon number is 12 or less.

Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 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, and 1,14-eicosanedecanediol. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol are preferred in terms of the high crystallinity and excellent sharp melt properties of the crystalline polyester resin C.

Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
These may be used alone or in combination of two or more.

-Polycarboxylic acid-
The polyvalent carboxylic acid is not particularly limited and may be appropriately selected depending on the purpose. Examples of the polyvalent carboxylic acid include divalent carboxylic acids and trivalent or higher carboxylic acids.

Examples of the divalent carboxylic acid include saturated aliphatic dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, and 1,18-octadecanedicarboxylic acid; aromatic dicarboxylic acids such as dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, and mesaconic acid; and further, anhydrides and lower (1 to 3 carbon atoms) alkyl esters of these.

Examples of the trivalent or higher carboxylic acids include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, as well as their anhydrides and lower (carbon number 1 to 3) alkyl esters.

The polycarboxylic acid may include a dicarboxylic acid having a sulfonic acid group in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, and may further include a dicarboxylic acid having a double bond in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid.
These may be used alone or in combination of two or more.

The crystalline polyester resin C is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. That is, the crystalline polyester resin C preferably has a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. This is preferable in that it has high crystallinity and excellent sharp melt properties, and therefore can exhibit excellent low-temperature fixability.

The melting point of the crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 60°C or higher and 80°C or lower. If the melting point is 60°C or higher, the crystalline polyester resin C can be prevented from melting at low temperatures, which would otherwise cause the heat-resistant storage stability of the toner to decrease. If the melting point is 80°C or lower, the melting of the crystalline polyester resin C due to heating during fixing can be improved, and a decrease in low-temperature fixability can be prevented.

The molecular weight of the crystalline polyester resin C is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint that a resin having a sharp molecular weight distribution and a low molecular weight has excellent low-temperature fixability, and that a large amount of low-molecular weight components reduces heat-resistant storage stability, it is preferable that the crystalline polyester resin C has an orthodichlorobenzene-soluble content of 3,000 to 30,000 in weight average molecular weight (Mw), 1,000 to 10,000 in number average molecular weight (Mn), and Mw/Mn of 1.0 to 10, as measured by GPC.
More preferably, the weight average molecular weight (Mw) is 5,000 to 15,000, the number average molecular weight (Mn) is 2,000 to 10,000, and the Mw/Mn is 1.0 to 5.0.

There is no particular restriction on the acid value of the crystalline polyester resin C, and it can be appropriately selected according to the purpose. From the viewpoint of affinity between paper and resin, in order to achieve the desired low-temperature fixability, it is preferably 5 mgKOH/g or more, and more preferably 10 mgKOH/g or more. On the other hand, in order to improve high-temperature offset resistance, it is preferably 45 mgKOH/g or less.

The hydroxyl value of the crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the purpose. In order to achieve the desired low-temperature fixability and good charging characteristics, it is preferably 0 mgKOH/g to 50 mgKOH/g, and more preferably 5 mgKOH/g to 50 mgKOH/g.

The molecular structure of the crystalline polyester resin C can be confirmed by NMR measurement of a solution or solid, as well as X-ray diffraction, GC/MS, LC/MS, IR measurement, etc. A simple method includes a method of detecting, as the crystalline polyester resin C, a resin having an absorption due to olefin δCH (out-of-plane bending vibration) at 965±10 cm ⁻¹ or 990±10 cm ⁻¹ in an infrared absorption spectrum.

The content of the crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3 to 20 parts by mass, and more preferably 5 to 15 parts by mass, relative to 100 parts by mass of the toner. When the content is 3 parts by mass or more, the sharp melting caused by the crystalline polyester resin C can be improved, and low-temperature fixability can be improved. When the content is 20 parts by mass or less, deterioration of heat-resistant storage stability can be suppressed, and the occurrence of image fogging can be suppressed. When the content is within the above more preferred range, it is advantageous in that both high image quality and low-temperature fixability are excellent.

<<<Amorphous polyester resin>>>
The amorphous polyester resin is not particularly limited and may be appropriately selected depending on the purpose, but it is preferable that the amorphous polyester resin contains an amorphous polyester resin A and an amorphous polyester resin B described below.

--Amorphous polyester resin A--
The amorphous polyester resin A is not particularly limited and may be appropriately selected depending on the purpose. The glass transition temperature (Tg) of the amorphous polyester resin A is preferably from −60° C. to 20° C., and more preferably from −40° C. to 20° C.

The amorphous polyester resin A is not particularly limited and can be selected appropriately depending on the purpose, but it is preferably obtained by reacting a non-linear reactive precursor with a curing agent.

In addition, since the amorphous polyester resin A has better adhesion to recording media such as paper, it is preferable that the amorphous polyester resin A has at least one of a urethane bond and a urea bond. When the amorphous polyester resin A has either a urethane bond or a urea bond, the urethane bond or the urea bond behaves like a pseudo-crosslinking point, the rubber-like properties of the amorphous polyester resin A are strengthened, and the toner has better heat resistance storage stability and high-temperature offset resistance.

--Nonlinear reactive precursors--
The non-linear reactive precursor is not particularly limited as long as it is a polyester resin (hereinafter, sometimes referred to as a "prepolymer") having a group capable of reacting with the curing agent, and can be appropriately selected depending on the purpose.
Examples of the group in the prepolymer that can react with the curing agent include a group that can react with an active hydrogen group. Examples of the group that can react with the active hydrogen group include an isocyanate group, an epoxy group, a carboxylic acid, and an acid chloride group. Among these, an isocyanate group is preferred because it can introduce a urethane bond or a urea bond into the amorphous polyester resin.

The prepolymer is preferably non-linear, which means that the prepolymer has a branched structure imparted by at least one of a tri- or higher hydric alcohol and a tri- or higher hydric carboxylic acid.
The prepolymer is preferably a polyester resin containing an isocyanate group.

---Polyester resin containing isocyanate groups---
The polyester resin containing an isocyanate group is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a reaction product of a polyester resin having an active hydrogen group and a polyisocyanate. The polyester resin having an active hydrogen group can be obtained, for example, by polycondensation of a diol, a dicarboxylic acid, and at least one of a trivalent or higher alcohol and a trivalent or higher carboxylic acid. The trivalent or higher alcohol and the trivalent or higher carboxylic acid impart a branched structure to the polyester resin containing an isocyanate group.

---Diol---
The diol is not particularly limited and can be appropriately selected depending on the purpose. Examples of the diol include aliphatic diols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol; diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene Examples of the diol include diols having an oxyalkylene group such as glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols to which alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide have been added; bisphenols such as bisphenol A, bisphenol F and bisphenol S; and alkylene oxide adducts of bisphenols such as bisphenols to which alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide have been added. Among these, aliphatic diols having 4 to 12 carbon atoms are preferred. These diols may be used alone or in combination of two or more.

---Dicarboxylic acid---
The dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, etc. Furthermore, anhydrides, lower (1 to 3 carbon atoms) alkyl esters, or halides of these may be used.

The aliphatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid.

The aromatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, but is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms. The aromatic dicarboxylic acid having 8 to 20 carbon atoms is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid.
Among these, aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferred.
These dicarboxylic acids may be used alone or in combination of two or more.

---Trihydric or higher alcohols---
The trihydric or higher alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples of the trihydric or higher alcohol include aliphatic alcohols of trihydric or higher hydricity, polyphenols of trihydric or higher hydricity, and alkylene oxide adducts of polyphenols of trihydric or higher hydricity.

Examples of the trivalent or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.
Examples of the trivalent or higher polyphenols include trisphenol PA, phenol novolac, and cresol novolac.
Examples of the alkylene oxide adducts of trivalent or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to trivalent or higher polyphenols.

The amorphous polyester resin A preferably contains a trivalent or higher aliphatic alcohol as a constituent component.
Since the amorphous polyester resin A contains a trivalent or higher aliphatic alcohol as a constituent, it has a branched structure in the molecular skeleton and the molecular chain has a three-dimensional network structure, so that it has rubber-like properties of deforming at low temperatures but not flowing, and therefore the toner can maintain its heat-resistant storage stability and high-temperature offset resistance.

The amorphous polyester resin A can use trivalent or higher carboxylic acids or epoxy as crosslinking components, but in the case of carboxylic acids, they are often aromatic compounds and the ester bond density of the crosslinked parts is high, so the gloss of the fixed image created by heating and fixing the toner may not be fully expressed. When using a crosslinking agent such as epoxy, the crosslinking reaction must be carried out after polymerization of the polyester, making it difficult to control the distance between crosslinking points and making it impossible to obtain the desired viscoelasticity. In addition, it is easy for the crosslinked parts to react with the oligomers during polyester production and form parts with high crosslinking density, which can cause unevenness in the fixed image and poor gloss and image density.

---Trivalent or higher carboxylic acid---
The trivalent or higher carboxylic acid is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include trivalent or higher aromatic carboxylic acids, etc. Furthermore, anhydrides, lower (1 to 3 carbon atoms) alkyl esters, or halides of these may be used.

The trivalent or higher aromatic carboxylic acid is preferably a trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms. Examples of the trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms include trimellitic acid and pyromellitic acid.

---Polyisocyanate---
The polyisocyanate is not particularly limited and may be appropriately selected depending on the purpose. Examples of the polyisocyanate include diisocyanates and tri- or higher valent isocyanates.

Examples of the diisocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and those blocked with phenol derivatives, oximes, caprolactam, etc.

The aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate.

The alicyclic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples include isophorone diisocyanate and cyclohexylmethane diisocyanate.

The aromatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4'-diisocyanatodiphenyl, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 4,4'-diisocyanato-3-methyldiphenylmethane, and 4,4'-diisocyanato-diphenyl ether.

The aromatic aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. For example, α,α,α',α'-tetramethylxylylene diisocyanate can be used.

The isocyanurates are not particularly limited and may be appropriately selected depending on the purpose. Examples of the isocyanurates include tris(isocyanatoalkyl)isocyanurate and tris(isocyanatocycloalkyl)isocyanurate.
These polyisocyanates may be used alone or in combination of two or more.

-- Hardener --
The curing agent is not particularly limited as long as it is a curing agent that can react with the non-linear reactive precursor to produce the amorphous polyester resin A, and can be appropriately selected depending on the purpose. For example, an active hydrogen group-containing compound can be used.

---Active hydrogen group-containing compound---
The active hydrogen group in the active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, etc. These may be used alone or in combination of two or more.
The active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the purpose, but amines are preferred because they are capable of forming a urea bond.

The amines are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, blocked amino groups of these, etc. These may be used alone or in combination of two or more.
Among these, diamines and mixtures of diamines with small amounts of trivalent or higher amines are preferred.

The diamine is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include aromatic diamines, alicyclic diamines, and aliphatic diamines. The aromatic diamine is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include phenylenediamine, diethyltoluenediamine, and 4,4'-diaminodiphenylmethane.

The alicyclic diamine is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminocyclohexane, isophoronediamine, etc. The aliphatic diamine is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.

The trivalent or higher amine is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include diethylenetriamine and triethylenetetramine.
The amino alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples of the amino alcohol include ethanolamine and hydroxyethylaniline.
The amino mercaptan is not particularly limited and can be appropriately selected depending on the purpose. Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan.
The amino acid is not particularly limited and can be appropriately selected depending on the purpose. Examples of the amino acid include aminopropionic acid and aminocaproic acid.
The blocked amino group is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include ketimine compounds obtained by blocking the amino group with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and oxazoline compounds.

In order to lower the Tg of the amorphous polyester resin A and to easily impart the property of deformation at low temperatures, the amorphous polyester resin A preferably contains a diol component as a constituent component, and the diol component preferably contains 50% by mass or more of an aliphatic diol having 4 to 12 carbon atoms.

The amorphous polyester resin A preferably contains 50% by mass or more of an aliphatic diol having 4 to 12 carbon atoms in the total alcohol component. In this case, the Tg of the amorphous polyester resin A can be lowered, making it easier to impart the property of deformation at low temperatures.

The amorphous polyester resin A preferably contains a dicarboxylic acid component as a constituent component, and the dicarboxylic acid component preferably contains 50% by mass or more of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms. In this case, the Tg of the amorphous polyester resin A can be lowered, making it easier to impart the property of deformation at low temperatures.

The weight average molecular weight of the amorphous polyester resin A is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10,000 to 1,000,000, more preferably 10,000 to 300,000, and particularly preferably 10,000 to 200,000, as measured by GPC (gel permeation chromatography). When the weight average molecular weight is 10,000 or more, the toner can be prevented from flowing at low temperatures, improving the heat-resistant storage stability. It can also prevent the viscosity at the time of melting from decreasing, and prevent the high-temperature offset property from decreasing.

The molecular structure of the amorphous polyester resin A can be confirmed by NMR measurement of a solution or solid, as well as X-ray diffraction, GC/MS, LC/MS, IR measurement, etc. A simple method includes a method of detecting an amorphous polyester resin that does not have absorption due to olefin δCH (out-of-plane bending vibration) at 965±10 cm ⁻¹ and 990±10 cm ⁻¹ in an infrared absorption spectrum.

The content of the amorphous polyester resin A is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 5 parts by mass to 25 parts by mass, and more preferably 10 parts by mass to 20 parts by mass, relative to 100 parts by mass of the toner. When the content is 5 parts by mass or more, deterioration of low-temperature fixing property and high-temperature offset resistance can be suppressed. When the content is 25 parts by mass or less, deterioration of heat-resistant storage property and decrease in gloss of the image obtained after fixing can be suppressed. When the content is within the above-mentioned more preferred range, it is advantageous in that all of low-temperature fixing property, high-temperature offset resistance, and heat-resistant storage property are excellent.

--Amorphous polyester resin B--
The amorphous polyester resin B is preferably a linear polyester resin, and more preferably an unmodified polyester resin.
The unmodified polyester resin is a polyester resin obtained using a polyhydric alcohol and a polycarboxylic acid or a derivative thereof, such as a polycarboxylic acid, a polycarboxylic anhydride, or a polycarboxylic ester, and is not modified with an isocyanate compound or the like.
The amorphous polyester resin B preferably does not have a urethane bond or a urea bond.

The amorphous polyester resin B preferably contains a dicarboxylic acid component as a constituent, and the dicarboxylic acid component preferably contains 50 mol% or more of terephthalic acid. This is advantageous in terms of heat resistance storage stability.

Examples of the polyhydric alcohol include diols.
Examples of the diol include alkylene (carbon number 2 to 3) oxide (average number of moles added: 1 to 10) adducts of bisphenol A such as polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane and polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane; ethylene glycol, propylene glycol; hydrogenated bisphenol A, and alkylene (carbon number 2 to 3) oxide (average number of moles added: 1 to 10) adducts of hydrogenated bisphenol A.
These may be used alone or in combination of two or more.

Examples of the polycarboxylic acid include dicarboxylic acids.
Examples of the dicarboxylic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid; and succinic acids substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, such as dodecenylsuccinic acid and octylsuccinic acid.
These may be used alone or in combination of two or more.

For the purpose of adjusting the acid value and hydroxyl value, the amorphous polyester resin B may contain at least one of a trivalent or higher carboxylic acid and a trivalent or higher alcohol at the end of the resin chain.
Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, and acid anhydrides thereof.
Examples of the trihydric or higher alcohol include glycerin, pentaerythritol, and trimethylolpropane.

The molecular weight of the amorphous polyester resin B is not particularly limited and can be appropriately selected depending on the purpose. In GPC (gel permeation chromatography) measurement, the weight average molecular weight (Mw) is preferably 3,000 to 10,000. The number average molecular weight (Mn) is preferably 1,000 to 4,000. The Mw/Mn ratio is preferably 1.0 to 4.0.

When the molecular weight is equal to or greater than the lower limit, it is possible to prevent the toner's heat-resistant storage stability and durability against stress such as stirring in a developing machine from decreasing. When the molecular weight is equal to or less than the upper limit, it is possible to prevent the toner's viscoelasticity from increasing when melted, and to prevent the low-temperature fixability from decreasing.

The weight average molecular weight (Mw) is more preferably 4,000 to 7,000. The number average molecular weight (Mn) is more preferably 1,500 to 3,000. The Mw/Mn is more preferably 1.0 to 3.5.

The acid value of the amorphous polyester resin B is not particularly limited and can be appropriately selected depending on the purpose. It is preferably 1 mgKOH/g to 50 mgKOH/g, and more preferably 5 mgKOH/g to 30 mgKOH/g. When the acid value is 1 mgKOH/g or more, the toner tends to be negatively charged, and further, when fixed to paper, the affinity between the paper and the toner is improved, and low-temperature fixing properties can be improved. When the acid value is 50 mgKOH/g or less, it is possible to suppress a decrease in charging stability, particularly charging stability against environmental changes.

The hydroxyl value of the amorphous polyester resin B is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 5 mgKOH/g or more.

The glass transition temperature (Tg) of the amorphous polyester resin B is preferably 40°C or higher and 80°C or lower, and more preferably 50°C or higher and 70°C or lower. When the glass transition temperature is 40°C or higher, the toner has sufficient heat-resistant storage stability and durability against stress such as stirring in a developing machine, and also has good filming resistance. When the glass transition temperature is 80°C or lower, the toner is sufficiently resistant to deformation due to heating and pressure during fixing, and has good low-temperature fixing properties.

The molecular structure of the amorphous polyester resin B can be confirmed by NMR measurement of a solution or solid, as well as X-ray diffraction, GC/MS, LC/MS, IR measurement, etc. A simple method includes a method of detecting an amorphous polyester resin that does not have absorption due to olefin δCH (out-of-plane bending vibration) at 965±10 cm ⁻¹ and 990±10 cm ⁻¹ in an infrared absorption spectrum.

The content of the amorphous polyester resin B is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 50 parts by mass to 90 parts by mass, and more preferably 60 parts by mass to 80 parts by mass, relative to 100 parts by mass of the toner. When the content is 50 parts by mass or more, the dispersibility of the pigment and release agent in the toner can be suppressed from deteriorating, and the occurrence of fogging and distortion of the image can be suppressed. When the content is 90 parts by mass or less, the contents of the crystalline polyester resin C and the amorphous polyester resin A can be prevented from decreasing, and the low-temperature fixability can be suppressed from decreasing. When the content is in the above-mentioned more preferred range, it is advantageous in that both high image quality and low-temperature fixability are excellent.

In order to further improve the low-temperature fixability, it is preferable to use the amorphous polyester resin A and the crystalline polyester resin C in combination. In order to achieve both low-temperature fixability and high-temperature and high-humidity storage stability, it is preferable that the amorphous polyester resin A has a very low glass transition temperature. Since the glass transition temperature is very low, it has the property of deforming at low temperatures, and deforms in response to heating and pressure during fixing, and has the property of being easily adhered to recording media such as paper at lower temperatures. In addition, in one embodiment of the amorphous polyester resin A, since the reactive precursor is nonlinear, it has a branched structure in the molecular skeleton and the molecular chain has a three-dimensional network structure, so it has a rubber-like property of deforming at low temperatures but not flowing. Therefore, it is possible to maintain the heat-resistant storage stability and high-temperature offset resistance of the toner.

When the amorphous polyester resin A has a urethane bond or urea bond with high cohesive energy, the adhesion to recording media such as paper is superior. In addition, since the urethane bond or urea bond behaves like a pseudo-crosslinking point, the rubber-like properties are stronger, resulting in superior heat-resistant storage stability and high-temperature offset resistance of the toner.

That is, in the toner of the present invention, when the amorphous polyester resin A and the crystalline polyester resin C are used in combination, and if necessary, other amorphous polyester resin B, the toner has excellent low-temperature fixing properties. Furthermore, by using the amorphous polyester resin A, which has a glass transition temperature in the ultra-low temperature range, it is possible to maintain heat-resistant storage stability and high-temperature offset resistance even if the glass transition temperature of the toner is set lower than before, and by lowering the glass transition temperature of the toner, the toner has excellent low-temperature fixing properties.

<<Coloring Agent>>
The colorant is not particularly limited and can be appropriately selected depending on the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, yellow ochre, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Balkan fast yellow (5G, R), tartrazine lake, quinoline yellow lake, anthrazan yellow BGL, isoindolinone yellow, red iron oxide, red lead, vermilion, cadmium red, cadmium mercury ... Curie Red, Antimony Vermilion, Permanent Red 4R, Para Red, Phaysee Red, Parachlor Orthonitroaniline Red, Lithol 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, Lithol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux Ludo F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine Blue, Examples of the pigments include fast sky blue, indanthrene blue (RS, BC), indigo, ultramarine, Prussian blue, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc oxide, and lithopone.

The content of the colorant is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 part by mass to 15 parts by mass, and more preferably 3 parts by mass to 10 parts by mass, per 100 parts by mass of the toner.

The colorant can also be used as a masterbatch composited with a resin. Examples of resins to be used in the manufacture of the masterbatch or to be kneaded with the masterbatch include, in addition to the amorphous polyester resin, polymers of styrene or its substitutes such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, and styrene-α-chloromethyl methacrylate copolymer. Examples of such styrene copolymers include styrene-acrylonitrile copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, and styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resins, epoxy polyol resins, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resins, rosin, modified rosin, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffin, and paraffin wax. These may be used alone or in combination of two or more.

The master batch can be obtained by mixing and kneading the resin and colorant for the master batch under high shear force. In this case, an organic solvent can be used to enhance the interaction between the colorant and the resin. In addition, a method called the flushing method, in which an aqueous paste containing water for the colorant is mixed and kneaded with the resin and organic solvent, the colorant is transferred to the resin side, and the water and organic solvent components are removed, is also preferably used because it does not require drying since the wet cake of the colorant can be used as is. A high shear dispersion device such as a three-roll mill is preferably used for mixing and kneading.

<<Release Agent>>
The release agent is not particularly limited and can be appropriately selected from known agents.
Examples of waxes and wax release agents include natural waxes such as vegetable waxes such as carnauba wax, cotton wax, and wood wax rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cerusin; and petroleum waxes such as paraffin, microcrystalline, and petrolatum.
In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene, and polypropylene; synthetic waxes such as esters, ketones, and ethers; and the like can also be used.

Furthermore, fatty acid amide compounds such as 12-hydroxystearic acid amide, stearic acid amide, phthalimide anhydride, and chlorinated hydrocarbons; homopolymers or copolymers of polyacrylates such as poly-n-stearyl methacrylate and poly-n-lauryl methacrylate, which are low molecular weight crystalline polymer resins (for example, copolymers of n-stearyl acrylate and ethyl methacrylate); crystalline polymers with long alkyl groups on the side chains, etc. may also be used.

Among these, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax are preferred.

The melting point of the release agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 60°C or higher and 80°C or lower. If the melting point is 60°C or higher, the release agent can be prevented from melting at low temperatures, and the heat-resistant storage stability can be prevented from decreasing. If the melting point is 80°C or higher, when the resin melts and is in the fixing temperature range, the release agent can be prevented from melting sufficiently, causing fixing offset, and preventing image defects.

The content of the release agent is not particularly limited and can be appropriately selected depending on the purpose. It is preferably 2 to 10 parts by mass, and more preferably 3 to 8 parts by mass, relative to 100 parts by mass of the toner. When the content is 2 parts by mass or more, it is possible to suppress a decrease in high-temperature offset resistance and low-temperature fixability during fixing, and when it is 10 parts by mass or less, it is possible to suppress a decrease in heat-resistant storage stability and to suppress the occurrence of image fogging. When the content is within the above-mentioned more preferred range, it is advantageous in terms of improving image quality and fixing stability.

<<Other ingredients>>
Examples of the other components contained in the toner base particles include a charge control agent, a deforming agent, a flowability improving agent, a cleaning property improving agent, and a magnetic material.

<<<Charge control agent>>>
The charge control agent is not particularly limited and can be appropriately selected according to the purpose. For example, Nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdic acid chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substance or compounds, tungsten simple substance or compounds, fluorine-based activators, salicylic acid metal salts, and salicylic acid derivative metal salts can be mentioned.

Specific examples include the nigrosine dye Bontron 03, the quaternary ammonium salt Bontron P-51, the metal-containing azo dye Bontron S-34, the oxynaphthoic acid metal complex E-82, the salicylic acid metal complex E-84, and the phenol condensate E-89 (all manufactured by Orient Chemical Industry Co., Ltd.), the quaternary ammonium salt molybdenum complexes TP-302 and TP-415 (both manufactured by Hodogaya Chemical Co., Ltd.), LRA-901, the boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymeric compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

The content of the charge control agent is not particularly limited and can be appropriately selected according to the purpose. It is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, relative to 100 parts by mass of the toner. When the content is 10 parts by mass or less, the chargeability of the toner is prevented from becoming too high, the effect of the main charge control agent can be maintained, the electrostatic attraction force with the developing roller is prevented from increasing, and a decrease in the fluidity of the developer and a decrease in image density can be suppressed. These charge control agents can be melt-kneaded together with the master batch and resin and then dissolved and dispersed, or of course they can be added when directly dissolved and dispersed in an organic solvent, or they can be fixed on the toner surface after the toner particles are produced.

<<<<Deformation Agent>>>
In the present embodiment, a deforming agent may be contained for the purpose of deforming the shape of the color toner. The deforming agent may be appropriately selected depending on the purpose as long as it can achieve this purpose, but it is preferable to contain a layered inorganic mineral in which at least a part of the interlayer ions of the layered inorganic mineral are modified with an organic ion.

There are no particular limitations on the layered inorganic mineral that can be used as a deforming agent in which at least a portion of the interlayer ions of the layered inorganic mineral are modified with organic ions, and it can be appropriately selected according to the purpose. For example, a layered inorganic mineral having a basic smectite crystal structure modified with an organic cation is preferable. In addition, metal anions can be introduced by replacing a portion of the divalent metal of the layered inorganic mineral with a trivalent metal. However, since the introduction of metal anions results in high hydrophilicity, layered inorganic compounds in which at least a portion of the metal anions are modified with organic anions are preferable.

The organic cation modifier for layered inorganic minerals in which at least a portion of the ions of the layered inorganic minerals are modified with organic ions is not particularly limited as long as it can be modified in this way with organic ions, and examples of such modifiers include quaternary alkyl ammonium salts, phosphonium salts, and imidazolium salts. Among these, quaternary alkyl ammonium salts are preferable. Examples of such quaternary alkyl ammonium include trimethylstearyl ammonium, dimethylstearyl benzyl ammonium, and oleyl bis(2-hydroxyethyl)methyl ammonium.

The organic anion modifier for layered inorganic minerals in which at least a portion of the ions of the layered inorganic minerals are modified with organic ions is not particularly limited as long as it can be modified with organic ions as described above, but examples of such modifiers include sulfates, sulfonates, carboxylates, or phosphates having branched, unbranched, or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, etc. Carboxylic acids with an ethylene oxide skeleton are preferred.

By modifying at least a portion of the layered inorganic mineral with organic ions, the toner has a suitable degree of hydrophobicity, the oil phase (described below) containing the toner composition has non-Newtonian viscosity, and the toner can be deformed. In this case, the content of the layered inorganic mineral, part of which has been modified with organic ions in the toner material, is preferably 0.05% to 10% by mass, and more preferably 0.05% to 5% by mass in the toner.

In addition, layered inorganic minerals partially modified with organic ions can be appropriately selected, such as montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferred, since it does not affect the toner properties, allows easy viscosity adjustment, and allows the amount added to be small.

Commercially available layered inorganic minerals partially modified with organic cations include quaternium-18 bentonites such as Bentone 3, Bentone 38, Bentone 38V (all manufactured by Rheox Corporation), Thixogel VP (manufactured by United Catalyst), Clayton 34, Clayton 40, and Clayton XL (all manufactured by Southern Clay Corporation); stearalkonium bentonites such as Bentone 27 (manufactured by Rheox Corporation), Thixogel LG (manufactured by United Catalyst), Clayton AF, and Clayton APA (all manufactured by Southern Clay Corporation); and quaternium-18/benzalkonium bentonites such as Clayton HT and Clayton PS (all manufactured by Southern Clay Corporation). Clayton AF and Clayton APA are preferred.

As a layered inorganic mineral partially modified with an organic anion, DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) modified with an organic anion represented by the following general formula (III) is more preferable. An example of the following general formula (III) is Hitenol 330T (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

R ₁ (OR ₂ ) _n OSO ₃ M General formula (III)

[In the general formula, R ₁ represents an alkyl group having 13 carbon atoms, R ₂ represents an alkylene group having 2 to 6 carbon atoms, n represents an integer from 2 to 10, and M represents a monovalent metal element]

The content of the deforming agent is preferably 0.05% to 10% by mass in the toner, and more preferably 0.05% to 5% by mass, similar to the content of the layered inorganic mineral.

<<<Flow improver>>>
The flowability improver is not particularly limited, and can be appropriately selected according to purpose, as long as it can be surface-treated to increase hydrophobicity and prevent the deterioration of flowability and charging properties even under high humidity.For example, silane coupling agent, silylating agent, silane coupling agent with fluorinated alkyl group, organic titanate coupling agent, aluminum coupling agent, silicone oil, modified silicone oil, etc. can be mentioned.The silica and titanium oxide are particularly preferably surface-treated with such flowability improver and used as hydrophobic silica and hydrophobic titanium oxide.

<<<Cleaning improver>>>
The cleaning property improver is not particularly limited as long as it is added to the toner to remove the developer remaining on the photoconductor or primary transfer medium after transfer, and can be appropriately selected according to the purpose. For example, it may be a fatty acid metal salt such as zinc stearate, calcium stearate, or stearic acid, or a polymer fine particle produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles or polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and are preferably ones having a volume average particle size of 0.01 μm to 1 μm.

<<<Magnetic materials>>>
The magnetic material is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include iron powder, magnetite, ferrite, etc. Among these, those that are white in color are preferred.

<External Additives>
As the external additive, inorganic fine particles and hydrophobized inorganic fine particles can be used in combination with the oxide fine particles. The average particle size of the hydrophobized primary particles is preferably 1 nm to 100 nm, and more preferably 5 nm to 70 nm.

It is preferable that the hydrophobized inorganic particles contain at least one type of inorganic particles having an average primary particle size of 20 nm or less and at least one type of inorganic particles having an average primary particle size of 30 nm or more, and that the specific surface area measured by the BET method is 20 m ² /g to 500 m ² /g.

The external additive is not particularly limited and can be appropriately selected depending on the purpose. Examples include silica fine particles, hydrophobic silica, fatty acid metal salts (e.g., zinc stearate, aluminum stearate, etc.), metal oxides (e.g., titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymers, etc.

Suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles.
Examples of silica fine particles include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.).
Examples of titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Kogyo Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Kogyo Co., Ltd.), MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation).

Examples of hydrophobically treated titanium oxide particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Kogyo Co., Ltd.), TAF-500T, TAF-1500T (all manufactured by Fuji Titanium Kogyo Co., Ltd.), MT-100S, MT-100T (all manufactured by Teika Corporation), and IT-S (manufactured by Ishihara Sangyo Co., Ltd.).

Hydrophobized oxide particles, hydrophobized silica particles, hydrophobized titania particles, and hydrophobized alumina particles can be obtained, for example, by treating hydrophilic particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Silicone oil-treated oxide particles and inorganic particles, which are treated with silicone oil by heating if necessary, are also suitable.

Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, methacryl-modified silicone oil, and α-methylstyrene-modified silicone oil.

Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferred.

The content of the external additive is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.1 parts by weight to 5 parts by weight, and more preferably 0.3 parts by weight to 3 parts by weight, per 100 parts by weight of the toner.

The average particle size of the primary particles of the inorganic fine particles is not particularly limited and can be appropriately selected depending on the purpose. It is preferably 100 nm or less, and more preferably 3 nm to 70 nm. If it is 3 nm or more, it is possible to prevent the inorganic fine particles from being buried in the toner and not effectively performing their functions. Also, if it is 100 nm or less, it is possible to prevent uneven damage to the photoreceptor surface.

<Glass transition temperature>
<<Tg1st (toner)>>
The glass transition temperature of the toner at the first temperature rise in differential scanning calorimetry (DSC) [Tg1st (toner)] is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of low-temperature fixability, it is preferably 20° C. or more and 50° C. or less, and more preferably 35° C. or more and 45° C. or less.

With conventional toners, when the Tg is around 50°C or less, the toner is prone to coagulation due to temperature changes during transportation and storage in summer and tropical regions. As a result, the toner solidifies in the toner bottle and adheres to the developing machine. In addition, toner clogging in the toner bottle can lead to poor refilling, and toner adherence in the developing machine can easily lead to image abnormalities.

Even if the toner has a lower Tg than conventional toners, if the amorphous polyester resin A, which is the low Tg component in the toner, is non-linear, the toner can maintain heat-resistant storage stability. In particular, if the amorphous polyester resin A has urethane bonds or urea bonds with high cohesive force, the effect of maintaining heat-resistant storage stability becomes more pronounced.

When the Tg1st (toner) is 20°C or higher, it is possible to suppress the deterioration of heat-resistant storage stability, blocking in the developing machine, and filming on the photoreceptor. When the Tg1st is 50°C or lower, it is possible to suppress the deterioration of the low-temperature fixing property of the toner.

<<[Tg2nd (toner)]>>
The glass transition temperature [Tg2nd (toner)] at the second temperature rise in differential scanning calorimetry (DSC) of the toner is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0° C. or higher and 30° C. or lower, and more preferably 0° C. or higher and 15° C. or lower. When [Tg2nd (toner)] is 0° C. or higher, it is possible to suppress a decrease in blocking resistance of the fixed image (printed matter), and when it is 30° C. or lower, it is possible to suppress a decrease in low-temperature fixability and glossiness.

The value of [Tg2nd (toner)] can be adjusted, for example, by the Tg of the crystalline polyester resin and the amount of the resin.

<<[[Tg1st (toner)] - [Tg2nd (toner)]]>>
The difference [[Tg1st(toner)]-[Tg2nd(toner)]] between the glass transition temperature [Tg1st(toner)] at the first heating stage and the glass transition temperature [Tg2nd(toner)] at the second heating stage in differential scanning calorimetry (DSC) of the toner is not particularly limited and may be appropriately selected depending on the purpose, but is more preferably 10° C. or more. The upper limit of the difference is not particularly limited and may be appropriately selected depending on the purpose, but the difference [[Tg1st(toner)]-[Tg2nd(toner)]] is preferably 50° C. or less.

If the difference [[Tg1st (toner)] - [Tg2nd (toner)]] is 10°C or more, it is advantageous in terms of excellent low-temperature fixing properties. The difference [[Tg1st (toner)] - [Tg2nd (toner)]] being 10°C or more means that the crystalline polyester resin C, the amorphous polyester resin A, and the amorphous polyester resin B, which were in an incompatible state before heating (before the first temperature rise), become compatible after heating (after the first temperature rise). Note that the compatible state after heating does not need to be a completely compatible state.

<<Tg2nd (THF insoluble matter)>>
The glass transition temperature [Tg2nd (THF insoluble)] of the tetrahydrofuran (THF) insoluble portion of the toner at the second temperature rise in differential scanning calorimetry (DSC) is not particularly limited and can be appropriately selected depending on the purpose. For example, it is preferably −40° C. or higher and 30° C. or lower, and more preferably 0° C. or higher and 20° C. or lower. When the [Tg2nd (THF insoluble)] is −40° C. or higher, it is advantageous in that the blocking resistance of the fixed image (printed matter) can be suppressed from decreasing, and when it is 30° C. or lower, it is advantageous in that the low-temperature fixability and glossiness can be suppressed from decreasing.

The value of [Tg2nd (THF insoluble)] can be adjusted, for example, by changing the number of carbon atoms in the diol and dicarboxylic acid of the amorphous polyester resin A.

<Storage modulus>
<<[G'(100) (THF insoluble portion)] and [[G'(40) (THF insoluble portion)]/[G'(100) (THF insoluble portion)]]>>
The storage modulus [G'(100) (THF insoluble matter)] of the tetrahydrofuran (THF) insoluble matter of the toner at 100° C. is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 1.0×10 ⁵ Pa to 1.0×10 ⁷ Pa, and more preferably 5.0×10 ⁵ Pa to 5.0×10 ⁶ Pa. When the storage modulus [G'(100) (THF insoluble matter)] is within the more preferred range, it is advantageous in that low-temperature fixing property is more excellent.

The ratio [G'(40)(THF insoluble)]/[G'(100)(THF insoluble)] of the storage modulus at 40°C [G'(40)(THF insoluble)] to the storage modulus at 100°C [G'(100)(THF insoluble)] of the THF insoluble portion of the toner is not particularly limited and can be appropriately selected according to the purpose, but is preferably 3.5 x 10 or less. When the ratio [G'(40)(THF insoluble)]/[G'(100)(THF insoluble)] is 3.5 x 10 or less, the deterioration of low-temperature fixability can be suppressed.

In the toner, the [G'(100) (THF insoluble content)] is 1.0×10 ⁵ Pa to 1.0×10 ⁷ Pa, and the ratio [[G'(40) (THF insoluble content)]/[G'(100) (THF insoluble content)]] is 3.5×10 or less, thereby promoting compatibility between the crystalline polyester resin and the amorphous polyester resin, which is a high Tg component, lowering the 1/2 outflow temperature measured by a thermal flow evaluation device (flow tester), and improving the image gloss.

The values of [G'(100) (THF insolubles)] and [G'(40) (THF insolubles)] can be adjusted, for example, by the resin composition (difunctional or higher polyol, difunctional or higher acid component).

Specifically, for example, it can be adjusted by doing the following: To increase G', shorten the distance of the ester bonds in the resin. Use a resin composition with aromatic rings. To decrease G', use a linear polyester resin. Use a polyol with alkyl groups on the side chains as a resin component.

<<THF insoluble matter>>
The THF insoluble matter of the toner can be obtained as follows.
One part of toner is added to 100 parts of tetrahydrofuran (THF) and refluxed for 6 hours, after which the insoluble components are precipitated using a centrifuge to separate the insoluble components from the supernatant.
The insoluble component is dried at 40° C. for 20 hours to obtain a THF insoluble component.

<<Method for measuring storage modulus G'>>
The storage modulus (G') under various conditions can be measured, for example, using a dynamic viscoelasticity measuring device (ARES, manufactured by TA Instruments Co., Ltd.) The frequency during measurement is 1 Hz.
Specifically, the measurement sample is molded into a pellet having a diameter of 8 mm and a thickness of 1 to 2 mm, and fixed to a parallel plate having a diameter of 8 mm. The pellet is then stabilized at 40°C, and heated to 200°C at a heating rate of 2.0°C/min at a frequency of 1 Hz (6.28 rad/s) and a strain of 0.1% (strain control mode), to measure the storage modulus.

In this specification, the storage modulus at 40°C may be expressed as G'(40°C) and the storage modulus at 100°C as G'(100°C).

<Melting Point>
The melting point of the toner is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 60° C. or more and 80° C. or less.

<Volume average particle size>
The volume average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 3 μm to 7 μm. The ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. The toner preferably contains 1 number % to 10 number % of components having a volume average particle diameter of 2 μm or less.

<Methods of calculating and analyzing various properties of toner and toner components>
The Tg, acid value, hydroxyl value, molecular weight, and melting point of the amorphous polyester resin A, the amorphous polyester resin B, the crystalline polyester resin C, and the release agent may be measured for each of them. Alternatively, the Tg, molecular weight, melting point, and mass ratio of the constituent components may be calculated by separating the components from an actual toner by gel permeation chromatography (GPC) or the like and subjecting each of the separated components to an analytical method described later.

Separation of each component by GPC can be carried out, for example, by the following method.
In the GPC measurement using THF (tetrahydrofuran) as the mobile phase, the eluate is fractionated using a fraction collector or the like, and fractions corresponding to the desired molecular weight portion are collected from the full integral of the elution curve.

After concentrating and drying the combined eluate using an evaporator or similar, the solids are dissolved in a heavy solvent such as deuterated chloroform or deuterated THF, and 1H-NMR measurements are performed. The ratio of constituent monomers of the resin in the eluted components is calculated from the integral ratio of each element.

Another method is to concentrate the eluate, hydrolyze it with sodium hydroxide or the like, and then calculate the constituent monomer ratio by qualitatively and quantitatively analyzing the decomposition products using high performance liquid chromatography (HPLC) or the like.

In the case where the toner manufacturing method forms toner base particles while generating amorphous polyester resin A by an elongation reaction and/or crosslinking reaction between the non-linear reactive precursor and the curing agent, the amorphous polyester resin A may be separated from the actual toner by GPC or the like to determine the Tg and other properties of the amorphous polyester resin A. In addition, amorphous polyester resin A may be synthesized separately by an elongation reaction and/or crosslinking reaction between the non-linear reactive precursor and the curing agent, and the Tg and other properties of the synthesized amorphous polyester resin A may be measured.

<<Means for separating toner components>>
An example of a means for separating each component when analyzing the toner will be described in detail below.
First, 1 g of the toner is put into 100 mL of THF, and a solution in which the soluble matter is dissolved is obtained while stirring for 30 minutes under a condition of 25° C. This is filtered through a membrane filter having an opening of 0.2 μm to obtain the THF-soluble matter in the toner.
Next, this is dissolved in THF to prepare a sample for GPC measurement, and the sample is injected into the GPC used for measuring the molecular weight of each of the above-mentioned resins.
Meanwhile, a fraction collector is placed at the eluate outlet of the GPC to collect the eluate at predetermined counts, and the eluate is obtained at 5% area ratios from the start of elution (the rise of the curve) of the elution curve.
Next, for each elution, 30 mg of a sample is dissolved in 1 mL of deuterated chloroform, and 0.05% by volume of tetramethylsilane (TMS) is added as a standard substance.
The solution is filled into a 5 mm diameter glass tube for NMR measurement, and a spectrum is obtained by 128 accumulations at 23° C. to 25° C. using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.).
The monomer composition and the constituent ratio of the amorphous polyester resin A, the amorphous polyester resin B, the crystalline polyester resin C, and the like contained in the toner can be determined from the peak integral ratio of the obtained spectrum.

For example, the peaks are assigned as follows, and the component ratio of the constituent monomers is determined from the integral ratio of each peak.
Peak assignments can be done, for example,
Around 8.25 ppm: From the benzene ring of trimellitic acid (one hydrogen)
Around 8.07 ppm to 8.10 ppm: From the benzene ring of terephthalic acid (4 hydrogen atoms)
Around 7.1 ppm to 7.25 ppm: From the benzene ring of bisphenol A (4 hydrogen atoms)
Around 6.8 ppm: From the benzene ring of bisphenol A (4 hydrogens) and from the double bond of fumaric acid (2 hydrogens)
Around 5.2 ppm to 5.4 ppm: derived from methine of bisphenol A propylene oxide adduct (one hydrogen)
Around 3.7 ppm to 4.7 ppm: derived from methylene of bisphenol A propylene oxide adduct (2 hydrogens) and derived from methylene of bisphenol A ethylene oxide adduct (4 hydrogens)
Around 1.6 ppm: This can be attributed to the methyl group of bisphenol A (6 hydrogen atoms).

From these results, for example, the extract recovered in the fraction in which the amorphous polyester resin A accounts for 90% or more can be treated as the amorphous polyester resin A. Similarly, the extract recovered in the fraction in which the amorphous polyester resin B accounts for 90% or more can be treated as the amorphous polyester resin B. The extract recovered in the fraction in which the crystalline polyester resin C accounts for 90% or more can be treated as the crystalline polyester resin C.

<<Measuring method of melting point and glass transition temperature (Tg)>>
The melting point and glass transition temperature (Tg) in the present invention can be measured, for example, by using a DSC system (differential scanning calorimeter) ("Q-200", manufactured by TA Instruments).
Specifically, the melting point and glass transition temperature of a sample can be measured by the following procedure.
First, about 5.0 mg of the target sample is placed in an aluminum sample container, the sample container is placed on a holder unit, and set in an electric furnace. Next, in a nitrogen atmosphere, the sample is heated from -80°C to 150°C at a heating rate of 10°C/min (first heating). After that, the sample is cooled from 150°C to -80°C at a temperature drop rate of 10°C/min, and further heated to 150°C at a heating rate of 10°C/min (second heating). In each of the first and second heating, a DSC curve is measured using a differential scanning calorimeter ("Q-200", manufactured by TA Instruments).

From the obtained DSC curves, the analysis program in the Q-200 system can be used to select the DSC curve at the first heating step and determine the glass transition temperature of the target sample at the first heating step. Similarly, the DSC curve at the second heating step can be selected and the glass transition temperature of the target sample at the second heating step can be determined.

Furthermore, using the analysis program in the Q-200 system, the DSC curve at the first heating step can be selected from the obtained DSC curves, and the endothermic peak top temperature at the first heating step of the target sample can be determined as the melting point. Similarly, the DSC curve at the second heating step can be selected, and the endothermic peak top temperature at the second heating step of the target sample can be determined as the melting point.

In this specification, when a toner is used as a target sample, the glass transition temperature during the first temperature increase is designated as Tg1st, and the glass transition temperature during the second temperature increase is designated as Tg2nd.
In this specification, the glass transition temperatures and melting points of the amorphous polyester resin A, the amorphous polyester resin B, and the crystalline polyester resin C, as well as other components such as the release agent, are defined as the endothermic peak top temperature, Tg, during the second heating, unless otherwise specified.

<<Method of measuring particle size distribution>>
The volume average particle diameter (D4) and number average particle diameter (Dn) of the toner, and the ratio thereof (D4/Dn) can be measured using, for example, a Coulter Counter TA-II or a Coulter Multisizer II (both manufactured by Coulter Corporation). In the present invention, a Coulter Multisizer II was used. The measurement method will be described below.

First, 0.1 mL to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) is added as a dispersant to 100 mL to 150 mL of the electrolytic solution. Here, the electrolytic solution is a 1% by mass NaCl aqueous solution prepared using first-class sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Then, 2 mg to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion process for about 1 minute to 3 minutes using an ultrasonic disperser, and the volume and number of toner particles or toner are measured using the measuring device with a 100 μm aperture as an aperture, and the volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle size (D4) and number average particle size (Dn) of the toner can be obtained.

Thirteen channels are used, with diameters of 2.00 μm or more and less than 2.52 μm; 2.52 μm or more and less than 3.17 μm; 3.17 μm or more and less than 4.00 μm; 4.00 μm or more and less than 5.04 μm; 5.04 μm or more and less than 6.35 μm; 6.35 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; 20.20 μm or more and less than 25.40 μm; 25.40 μm or more and less than 32.00 μm; and 32.00 μm or more and less than 40.30 μm, and particles with diameters of 2.00 μm or more and less than 40.30 μm are targeted.

<<Average particle size, average circularity, standard deviation of circularity>>
In this embodiment, the average particle size, the average circularity, and the standard deviation of the circularity are measured using, for example, a flow type particle image analyzer FPIA-3000 (manufactured by Sysmex Corporation).

Specific measurement methods include adding 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, as a dispersant to 100 to 150 ml of water from which solid impurities have been removed in advance in a container, and then adding approximately 0.1 to 0.5 g of the measurement sample. The suspension in which the sample has been dispersed is subjected to a dispersion treatment for approximately 1 to 3 minutes using an ultrasonic disperser, and the average particle size, average circularity, and standard deviation (SD) of the circularity are measured using the above device with a dispersion concentration of 3,000 to 10,000 particles/μl.

The particle diameter is the equivalent circle diameter, the average particle diameter is determined based on the equivalent circle diameter (number basis), and the analysis conditions for the flow type particle image analyzer are as follows:
Particle size limit: 0.5 μm≦circle equivalent diameter (number basis)≦200.0 μm
Particle shape limit: 0.93<circularity≦1.00

In the present embodiment, the average circularity is defined as follows.
(Average circularity) = (perimeter of a circle equal to the projected area) / (perimeter of the projected image)

In this embodiment, the standard deviation of the circularity determined using a flow-type particle image analyzer is 0.020 or more. If the standard deviation of the circularity is less than 0.020, good cleaning properties cannot be obtained.

In this embodiment, in the average particle size and circularity obtained using a flow-type particle image analyzer, the average circularity of particles whose particle size is equal to or smaller than the average particle size is defined as average circularity (A), and the average circularity of particles whose particle size is larger than the average particle size is defined as average circularity (B).

In other words, it can be expressed as follows:
The average circularity of particles when the particle size is limited to 0.5 μm≦circle equivalent diameter (by number)≦average particle size is defined as the average circularity (A).
The average circularity of particles when the particle size is limited to average particle size<circle equivalent diameter (number basis)≦200.0 μm is defined as the average circularity (B).

In this embodiment, A-B≦0.004, and preferably A-B≦0.002. If A-B exceeds 0.004, the chargeability of each toner particle becomes non-uniform, resulting in poor transfer and reduced image quality.

When the standard deviation of circularity is 0.020 or more and A-B≦0.004, the toner has excellent cleaning and transfer properties.

In order to make the standard deviation of the circularity determined using a flow type particle image analyzer 0.020 or more, for example, the standard deviation can be adjusted by using a device (described later) that applies shear force to an emulsion dispersion containing a toner composition, by adjusting the amount of a thickener (described later), by adjusting the viscosity of an oil phase (described later) containing a toner composition by adjusting the content of a deformable agent, or by adjusting the residual concentration of an organic solvent in a desolvated slurry (described later).
In order to make A-B≦0.004, for example, a method of adjusting the amount of a thickener or a device that applies a shear force to the emulsion dispersion containing the toner composition can be used.

<<Measurement of SF2>>
The toner shape factor SF2 can be obtained by randomly sampling 100 toner images enlarged at 500 times using a scanning electron microscope (SU-8230: manufactured by Hitachi High-Technologies Corporation) and analyzing the image information using an image analyzer (LuzexIII) manufactured by Nicolet via an interface.

The shape factor SF2 indicates the proportion of projections and recesses in the shape of the toner, and is expressed by the following formula (1). It is the square of the perimeter PERI of the figure created by projecting the toner onto a two-dimensional plane, divided by the area AREA of the figure, and multiplied by 100π/4.

SF2={(PERI) ² /AREA}×(100π/4) Equation (1)

In the above formula (1), AREA is the toner projection area, MXLNG is the absolute maximum length, and PERI is the circumference.

When the SF2 value is 100, there are no irregularities on the toner surface, and the larger the SF2 value, the more pronounced the irregularities on the toner surface become. SF2 is preferably 110 to 130, and more preferably 110 to 120. When SF2 is 110 or more, it is possible to prevent the toner surface from becoming uneven, which would make it easier for the toner to roll, and to improve cleaning properties. When SF2 is 130 or less, it is possible to prevent the toner surface from becoming too uneven, making it easier to uniformly charge the toner surface, and suppressing transfer defects and deterioration of image quality.

In order to make the SF2 be 110 to 130, for example, a method of adjusting the amount of a thickener (described later) or the like that applies shear force to the emulsion dispersion containing the toner composition, adjusting the viscosity of the oil phase (described later) that contains the toner composition by adjusting the content of a deforming agent, or adjusting the residual concentration of an organic solvent in the solvent-removed slurry (described later), can be mentioned.

<<Measurement of molecular weight>>
The molecular weight of each of the components of the toner can be measured, for example, by the following method.

Gel permeation chromatography (GPC) measuring device: GPC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel Super HZM-H 15 cm triple column (Tosoh Corporation)
Temperature: 40°C
Solvent: THF
Flow rate: 0.35 mL / min
Sample: 100 μL of 0.15% by mass sample is injected. Sample pretreatment: Toner is dissolved in tetrahydrofuran (THF) (containing stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.) at 0.15% by mass, then filtered through a 0.2 μm filter, and the filtrate is used as the sample. 100 μL of the THF sample solution is injected and measured.

When measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithm of a calibration curve created using several types of monodisperse polystyrene standard samples and the count number. The standard polystyrene samples used to create the calibration curve are Showdex STANDARD Std. Nos. S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, and S-0.580 manufactured by Showa Denko K.K. The detector used is a refractive index (RI) detector.

<Toner Manufacturing Method>
The method for producing the toner is not particularly limited and may be appropriately selected depending on the purpose, but it is preferable that the method includes a mixing step of mixing the toner base particles with the external additive.

The toner base particles preferably contain the amorphous polyester resin A, the amorphous polyester resin B, and the crystalline polyester resin C, and are preferably granulated by dispersing an oil phase containing the release agent, the colorant, etc., in an aqueous medium, as necessary.

The toner base particles preferably contain the nonlinear reactive precursor, the amorphous polyester resin B, and the crystalline polyester resin C, and further, if necessary, are preferably granulated by dispersing an oil phase containing the curing agent, the release agent, the colorant, etc., in an aqueous medium.

An example of a method for producing such toner base particles is a known dissolution suspension method. As an example of a method for producing the toner base particles, a method of forming toner base particles while elongating the amorphous polyester resin A by an elongation reaction and/or crosslinking reaction between the prepolymer and the curing agent is shown below. In such a method, an aqueous medium is prepared, an oil phase containing the toner materials is prepared, the toner materials are emulsified or dispersed, and the organic solvent is removed. The toner is then obtained by mixing the obtained toner base particles with the external additive.

<<Preparation of aqueous medium (aqueous phase)>>
The aqueous medium can be prepared, for example, by dispersing resin particles in the aqueous medium. The amount of the resin particles added to the aqueous medium is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the aqueous medium.

The aqueous medium is not particularly limited and can be appropriately selected depending on the purpose. Examples of the aqueous medium include water, solvents miscible with water, and mixtures of these. These may be used alone or in combination of two or more. Of these, water is preferred.

The water-miscible solvent is not particularly limited and can be appropriately selected depending on the purpose. Examples of the water-miscible solvent include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
The alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples of the alcohol include methanol, isopropanol, and ethylene glycol.
The lower ketones are not particularly limited and can be appropriately selected depending on the purpose. Examples of the lower ketones include acetone and methyl ethyl ketone.

<<Preparation of oil phase>>
The oil phase containing the toner materials can be prepared by dissolving or dispersing the toner materials, which include, for example, the nonlinear reactive precursor, the amorphous polyester resin B, and the crystalline polyester resin C, and further include, as necessary, the curing agent, the releasing agent, the colorant, etc., in an organic solvent. The oil phase may also include a profile-forming agent.

The organic solvent is not particularly limited and can be appropriately selected depending on the purpose, but an organic solvent having a boiling point of less than 150° C. is preferred in terms of ease of removal.
The organic solvent having a boiling point of less than 150° C. is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. These may be used alone or in combination of two or more.
Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, etc. are preferable, and ethyl acetate is more preferable.

<<Emulsification or Dispersion>>
The toner materials can be emulsified or dispersed by dispersing an oil phase containing the toner materials in the aqueous medium. When the toner materials are emulsified or dispersed, the curing agent and the non-linear reactive precursor undergo an elongation reaction and/or a crosslinking reaction to produce the amorphous polyester resin A.

The amorphous polyester resin A can be produced, for example, by the following methods (1) to (3).
(1) A method of producing the amorphous polyester resin A by emulsifying or dispersing an oil phase containing the non-linear reactive precursor and the curing agent in an aqueous medium, and carrying out an elongation reaction and/or a crosslinking reaction between the curing agent and the non-linear reactive precursor in the aqueous medium.
(2) A method in which an oil phase containing the non-linear reactive precursor is emulsified or dispersed in an aqueous medium to which the curing agent has been added in advance, and the curing agent and the non-linear reactive precursor are subjected to an elongation reaction and/or a crosslinking reaction in the aqueous medium to produce the amorphous polyester resin A.
(3) A method in which an oil phase containing the non-linear reactive precursor is emulsified or dispersed in an aqueous medium, the curing agent is added to the aqueous medium, and the curing agent and the non-linear reactive precursor undergo an elongation reaction and/or a crosslinking reaction at the particle interface in the aqueous medium, thereby producing the amorphous polyester resin A.

In addition, when the curing agent and the non-linear reactive precursor are subjected to an elongation reaction and/or a crosslinking reaction from the particle interface, the amorphous polyester resin A is preferentially formed on the surface of the toner produced, and a concentration gradient of the amorphous polyester resin A can be provided in the toner.

The reaction conditions (reaction time, reaction temperature) for producing the amorphous polyester resin A are not particularly limited, and can be appropriately selected depending on the combination of the curing agent and the non-linear reactive precursor.
The reaction time is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 minutes to 40 hours, and more preferably 2 hours to 24 hours.
The reaction temperature is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0°C to 150°C, and more preferably 40°C to 98°C.

The method for stably forming a dispersion liquid containing the nonlinear reactive precursor in the aqueous medium is not particularly limited and can be appropriately selected depending on the purpose. For example, an oil phase prepared by dissolving or dispersing the toner materials in a solvent is added to the aqueous medium phase, and the mixture is dispersed by shear force.

The dispersing machine for the dispersion is not particularly limited and can be appropriately selected depending on the purpose. Examples of the dispersing machine include a low-speed shear type dispersing machine, a high-speed shear type dispersing machine, a friction type dispersing machine, a high-pressure jet type dispersing machine, and an ultrasonic dispersing machine.
Among these, the high-speed shear type disperser is preferred because it is capable of controlling the particle size of the dispersion (oil droplets) to 2 μm to 20 μm.

When the high-speed shear type dispersing machine is used, the conditions such as the rotation speed, dispersing time, and dispersing temperature can be appropriately selected depending on the purpose.
The rotation speed is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1,000 rpm to 30,000 rpm, and more preferably 5,000 rpm to 20,000 rpm.
The dispersion time is not particularly limited and can be appropriately selected depending on the purpose, but in the case of a batch method, it is preferably 0.1 to 5 minutes.
The dispersion temperature is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0° C. to 150° C. under pressure, and more preferably 40° C. to 98° C. In general, the higher the dispersion temperature, the easier the dispersion.

The amount of the aqueous medium used when emulsifying or dispersing the toner materials is not particularly limited and can be appropriately selected depending on the purpose. The amount of the aqueous medium used is preferably 50 parts by mass to 2,000 parts by mass, more preferably 100 parts by mass to 1,000 parts by mass, based on 100 parts by mass of the toner materials.
When the amount of the aqueous medium used is 50 parts by mass or more, the dispersion state of the toner materials can be prevented from becoming poor, and the toner base particles having a predetermined particle size can be prevented from not being obtained. When the amount of the aqueous medium used is 2,000 parts by mass or less, the production cost can be prevented from increasing.

When the oil phase containing the toner materials is emulsified or dispersed, it is preferable to use a dispersant from the viewpoints of stabilizing the dispersion such as oil droplets, forming a desired shape, and sharpening the particle size distribution.
The dispersant is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include surfactants, poorly water-soluble inorganic compound dispersants, polymer-based protective colloids, etc. These may be used alone or in combination of two or more. Among these, surfactants are preferred.

The surfactant is not particularly limited and can be appropriately selected depending on the purpose. For example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc. can be used.

The anionic surfactant is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include alkylbenzene sulfonate, α-olefin sulfonate, phosphate, etc. Among these, those having a fluoroalkyl group are preferred.

In the elongation reaction and/or crosslinking reaction in producing the amorphous polyester resin A, a catalyst can be used.
The catalyst is not particularly limited and can be appropriately selected depending on the purpose. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

<<Removal of organic solvent>>
The method for removing the organic solvent from the dispersion liquid such as the emulsified slurry is not particularly limited and can be appropriately selected depending on the purpose. For example, a method of gradually increasing the temperature of the entire reaction system to evaporate the organic solvent in the oil droplets, a method of spraying the dispersion liquid in a dry atmosphere to remove the organic solvent in the oil droplets, etc. can be mentioned.

Although there are no particular limitations, the residual concentration of the organic solvent in the desolvated slurry is preferably, for example, 5 to 15 mass %, and more preferably 8 to 12 mass %.

When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, and further classified. The classification can be performed by removing fine particles in a liquid using a cyclone, decanter, or centrifugation, or the classification can be performed after drying.

<<Deformation process>>
In this embodiment, the following can be mentioned as an example of how to obtain irregularly shaped particles. A highly viscous aqueous solution containing a thickener is mixed with the emulsion dispersion, and the mixed solution is passed through a device that applies shear force using a homomixer, a helical ribbon type agitator, a paddle type agitator, or the like, to make it possible to deform the emulsion particles by utilizing the difference in viscosity between the oil phase and the water phase in the mixed solution. Thereafter, a process is provided in which the solvent is removed from the dispersion at or below the Tg of the binder resin, thereby fixing the particles and making it possible to produce a toner with a desired shape.

The conditions for deforming the shape can be adjusted by adjusting the viscosity difference between the oil and water phases by adjusting the concentration of the organic solvent, temperature, the thickener in the water phase, the activator, and the temperature, in addition to the rotation speed of the device that applies the shear force.

As the organic solvent, any of the conventionally known organic solvents can be used, but ethyl acetate is particularly preferred.

The thickener is not particularly limited, and examples thereof include polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, polyacrylates (alkali metal salts, organic amine salts, quaternary ammonium salts, etc.; weight average molecular weight 3,000 to 3,000,000), carboxymethyl cellulose, polyethylene glycol (weight average molecular weight 2,000 to 200,000), and guar gum.

Organic solvent concentration is measured using gas chromatography under the following conditions.

[Measurement of organic solvent concentration]
Equipment: Shimadzu Gas Chromatograph SIMAZU GC-14A
Column: PEG 20M 20%
Chromasorb W MESH 60-80
Column temperature: 100 ° C.
Injection temperature: 180°C
N2 gas flow rate: 40 ml/min Sample solution: 5% dimethylformamide solution Solvent injection amount: 1 μl
Detector: FID
A calibration curve was prepared using n-hexane as a standard substance to determine the organic solvent concentration.

Methods for adjusting the shear force include the processing time and number of processing times of the device, the temperature and viscosity of the dispersion liquid, and the concentration of the organic solvent in the particles. In addition, the degree of deformation caused by shear force also differs depending on the coverage rate of the organic fine particles on the particle surface, the degree of elongation and/or crosslinking reaction, etc., resulting in differences in the resulting shape.

In this embodiment, it is important that the concentration of the organic solvent when applying shear force to the mixed solution is 5 to 15% by weight, preferably 10 to 13% by weight.

To remove the organic solvent from the resulting emulsion dispersion, a method can be used in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely evaporated and removed. Alternatively, the emulsion dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner particles, and the aqueous dispersant can also be evaporated and removed at the same time.

The drying atmosphere into which the emulsified dispersion is sprayed generally includes air, nitrogen, carbon dioxide, heated combustion gas, etc., and in particular various air streams heated to a temperature equal to or higher than the boiling point of the highest boiling point solvent used. The desired quality can be obtained by short-term processing using a spray dryer, belt dryer, rotary kiln, etc.

The toner of the present invention preferably has a spindle shape.
When the toner has a spindle shape, the powder fluidity is appropriately adjusted, so that frictional charging is performed smoothly and background smearing does not occur, and minute latent image dots are developed in an orderly manner, and then transferred efficiently, resulting in excellent dot reproducibility. Furthermore, the powder fluidity appropriately brakes the scattering during this process, preventing scattering. Compared to spherical toner, spindle-shaped toner has a limited axis of rotation, so cleaning failures such as slipping under the cleaning means are less likely to occur.

When the toner shape is irregular or flat, the powder fluidity may be poor, which may cause the following problems: Frictional charging may not be performed smoothly, which may cause problems such as background smearing. When developing tiny latent image dots, it is difficult to achieve a dense and uniform toner arrangement, which may result in poor dot reproducibility. In electrostatic transfer methods, the toner is less susceptible to the effects of electric field lines, which may result in poor transfer efficiency. When the toner is close to a perfect sphere, the powder fluidity is too good and it reacts excessively to external forces, which may cause problems such as toner particles scattering outside the dots during development and transfer. In addition, spherical toner tends to roll on the photoconductor, so it may slip between the photoconductor and the cleaning means, resulting in poor cleaning.

The toner shape will be described with reference to Fig. 1A, Fig. 1B, and Fig. 1C. Fig. 1A is an example of the shape expressed by the xyz axes, Fig. 1B is an example of the shape expressed by the xz axes, and Fig. 1C is an example of the shape expressed by the yz axes. Fig. 1B and Fig. 1C illustrate _r1 , _r2 , and _r3 .

In this embodiment, it is preferable that the ratio _{r2 / r1} of the toner's major axis _r1 to its minor axis r2 is 0.5 to 0.8, and the ratio _r3 / _r2 of the toner's thickness _r3 to its minor axis _r2 is 0.5 to 1.0. In this case, a more preferable spindle shape can be obtained.
It is more preferable that r ₃ /r ₂ is 0.7 to 1.0.

When _r2 / _r1 is 0.5 or more, dot reproducibility and transfer efficiency can be improved, and high-quality image quality can be easily obtained. When _r2 / _r1 is 0.8 or less, a shape other than a sphere can be easily formed, and cleaning failure can be suppressed even in a low-temperature and low-humidity environment.

In addition, when _r3 / _r2 is 0.5 or more, it is possible to prevent the toner from becoming flat and suppress the transfer rate from decreasing. In particular, when _r3 / _r2 is 1.0, the toner becomes a rotating body with the long axis as the rotation axis. Therefore, by forming the toner into a spindle shape close to this, it is possible to obtain a toner that is neither amorphous/flat nor spherical, and has improved triboelectric charging properties, dot reproducibility, transfer efficiency, anti-scattering properties, and cleanability that both shapes have.

Here, the long axis length _r1 , the short axis length _r2 , and the thickness _r3 of the toner can be measured by taking pictures at different viewing angles and observing them with, for example, a scanning electron microscope (SU8230: manufactured by Hitachi High-Technologies Corporation). It is preferable to take average values of _r1 , _r2 , and _r3 for, for example, 30 or more particles.

In order to set _r2 / _r1 and _r3 / _r2 within the above ranges, for example, methods can be used such as adjusting the amount of thickener or using a device that applies shear force to the emulsion dispersion containing the toner composition, adjusting the viscosity of the oil phase containing the toner composition by adjusting the content of a deforming agent, or adjusting the residual concentration of the organic solvent in the solvent-removed slurry.

<<Mixing process>>
The obtained toner base particles are mixed with the external additive. At this time, by applying a mechanical impact force, it is possible to suppress the particles of the external additive from being detached from the surfaces of the toner base particles.

The method of applying the mechanical impact force is not particularly limited and can be appropriately selected depending on the purpose. For example, there is a method of applying an impact force to the mixture using a blade rotating at high speed, or a method of introducing the mixture into a high-speed air stream and accelerating it to cause the particles to collide with each other or with an appropriate collision plate.

The equipment used in the above method is not particularly limited and can be appropriately selected depending on the purpose. Examples include an Ang Mill (manufactured by Hosokawa Micron Corporation), an equipment modified from an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the grinding air pressure, a Hybridization System (manufactured by Nara Machinery Works), a Cryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), an automatic mortar, etc.

(Developer)
The developer of the present invention contains at least the toner, and optionally contains other components such as a carrier that are appropriately selected.
For this reason, it is possible to stably form high-quality images with excellent transferability, charging property, etc. The developer may be a one-component developer or a two-component developer, but when used in a high-speed printer corresponding to the recent improvement in information processing speed, a two-component developer is preferable because of its improved life.

When the developer is used as a one-component developer, there is little variation in the particle size of the toner even when the toner is balanced, there is little filming of the toner on the developing roller, and there is little melting of the toner on components such as blades that thin the toner layer, and good, stable developability and images can be obtained even with long-term stirring in the developing device.

When the developer is used as a two-component developer, there is little fluctuation in the particle size of the toner even when the toner is balanced over a long period of time, and good and stable developability and images can be obtained even with long-term stirring in the developing device.

<Career>
The carrier is not particularly limited and can be appropriately selected depending on the purpose, but is preferably one having a core material and a resin layer covering the core material.

<<Core material>>
The material for the core material is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include manganese-strontium-based materials of 50 emu/g to 90 emu/g and manganese-magnesium-based materials of 50 emu/g to 90 emu/g. In order to ensure image density, it is preferable to use high magnetization materials such as iron powder of 100 emu/g or more and magnetite of 75 emu/g to 120 emu/g. In addition, it is preferable to use low magnetization materials such as copper-zinc-based materials of 30 emu/g to 80 emu/g, because this can reduce the impact of the developer in a standing state on the photoconductor and is advantageous for improving image quality.
These may be used alone or in combination of two or more.

The volume average particle diameter of the core material is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 μm to 150 μm, and more preferably 40 μm to 100 μm. If the volume average particle diameter is 10 μm or more, it is possible to prevent the carrier from containing a large amount of fine powder and to suppress the occurrence of carrier scattering due to a decrease in magnetization per particle. If it is 150 μm or less, it is possible to prevent a decrease in the specific surface area and to suppress the occurrence of toner scattering, and in full color with many solid areas, it is possible to suppress deterioration of the reproduction of the solid areas in particular.

When the toner is used in a two-component developer, it may be mixed with the carrier. The content of the carrier in the two-component developer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 90 parts by weight to 98 parts by weight, more preferably 93 parts by weight to 97 parts by weight, relative to 100 parts by weight of the two-component developer.

The developer of the present invention can be suitably used for image formation by various known electrophotographic methods, such as magnetic one-component development method, non-magnetic one-component development method, and two-component development method.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention comprises at least an electrostatic latent image carrier, an electrostatic latent image forming means, and a developing means, and further comprises other means as necessary.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a development step, and further includes other steps as necessary.
The image forming method can be suitably performed by the image forming apparatus, the electrostatic latent image forming process can be suitably performed by the electrostatic latent image forming means, the developing process can be suitably performed by the developing means, and the other processes can be suitably performed by the other means.

<Electrostatic Latent Image Bearing Member>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and can be appropriately selected from known materials. Examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferred in terms of long life.

The amorphous silicon photoreceptor may be, for example, a photoreceptor having a photoconductive layer made of a-Si formed on the support by heating the support to 50°C to 400°C and forming a film on the support by a deposition method such as vacuum deposition, sputtering, ion plating, thermal CVD (Chemical Vapor Deposition), photo-CVD, or plasma CVD. Among these, the plasma CVD method, that is, the method of decomposing a raw material gas by direct current, high frequency, or microwave glow discharge to form an a-Si deposition film on the support, is preferred.

The shape of the electrostatic latent image carrier is not particularly limited and can be appropriately selected depending on the purpose, but a cylindrical shape is preferable. The outer diameter of the cylindrical electrostatic latent image carrier is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3 mm to 100 mm, more preferably 5 mm to 50 mm, and particularly preferably 10 mm to 30 mm.

<Electrostatic latent image forming unit and electrostatic latent image forming process>
The electrostatic latent image forming unit is not particularly limited as long as it is a unit that forms an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected depending on the purpose. For example, it may be a unit having at least a charging member that charges the surface of the electrostatic latent image carrier and an exposure member that exposes the surface of the electrostatic latent image carrier to light in an imagewise manner.
The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image bearing member, and can be appropriately selected depending on the purpose. For example, it can be performed by charging the surface of the electrostatic latent image bearing member and then exposing it imagewise, and can be performed by using the electrostatic latent image forming unit.

<<Charging member and charging>>
The charging member is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a contact charger having a conductive or semiconductive roller, brush, film, rubber blade, etc., which is known per se, and a non-contact charger using corona discharge such as a corotron or scorotron.
The charging can be carried out, for example, by applying a voltage to the surface of the electrostatic latent image bearing member using the charging member.

The shape of the charging member may be any shape, such as a roller, a magnetic brush, a fur brush, etc., and can be selected according to the specifications and shape of the image forming apparatus.
The charging member is not limited to the contact-type charging member, but it is preferable to use a contact-type charging member because it allows an image forming apparatus in which the amount of ozone generated from the charging member is reduced.

<<Exposure member and exposure>>
The exposing member is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charging member in the form of an image to be formed, and can be appropriately selected depending on the purpose. Examples of the exposing member include various exposing members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
The light source used in the exposure member is not particularly limited and can be appropriately selected depending on the purpose. For example, fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light-emitting diodes (LEDs), semiconductor lasers (LDs), electroluminescence (EL), and other light-emitting materials in general can be mentioned.

In order to irradiate only light in a desired wavelength range, various filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used.
The exposure can be carried out, for example, by exposing the surface of the electrostatic latent image bearing member imagewise using the exposure member.
In the present invention, a backlight system may be adopted in which exposure is performed imagewise from the back side of the electrostatic latent image bearing member.

<Developing means and developing process>
The developing unit is not particularly limited as long as it is a developing unit having a toner for developing the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image, and can be appropriately selected depending on the purpose.
The developing step is not particularly limited as long as it is a step of developing the electrostatic latent image formed on the electrostatic latent image carrier with a toner to form a visible image, and can be appropriately selected depending on the purpose. For example, the developing step can be performed by the developing unit.

The developing means may be of a dry developing type or a wet developing type, and may be a single-color developing means or a multi-color developing means.
The developing means is preferably a developing device having an agitator that frictionally agitates the toner to charge it, a magnetic field generating means fixed inside, and a developer carrier that can rotate and carries a developer containing the toner on its surface.
In the developing means, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction during this process and held in a standing state on the surface of a rotating magnet roller to form a magnetic brush. The magnet roller is disposed in the vicinity of the electrostatic latent image carrier. Therefore, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the electrostatic latent image carrier by electrical attraction. As a result, the electrostatic latent image is developed by the toner, and a visible image by the toner is formed on the surface of the electrostatic latent image carrier.

<Other Means and Other Steps>
Examples of the other means include a transfer means, a fixing means, a cleaning means, a discharging means, a recycling means, and a control means.
Examples of the other steps include a transfer step, a fixing step, a cleaning step, a discharging step, a recycling step, and a control step.

<<Transfer means and transfer process>>
The transfer means is not particularly limited as long as it is a means for transferring a visible image onto a recording medium, and can be appropriately selected according to the purpose. Among them, a preferred embodiment has a primary transfer means for transferring a visible image onto an intermediate transfer body to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium.
The transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and can be appropriately selected depending on the purpose. Among them, an intermediate transfer body is used, and a visible image is primarily transferred onto the intermediate transfer body, and then the visible image is secondarily transferred onto the recording medium.

The transfer step can be carried out, for example, by charging the visible image on the photoconductor using a transfer charger, and can be carried out by the transfer unit.
Here, when the image to be secondarily transferred onto the recording medium is a color image made up of toners of multiple colors, the transfer means can be configured to sequentially overlay toners of each color on the intermediate transfer body to form an image on the intermediate transfer body, and the intermediate transfer means can be configured to secondarily transfer the image on the intermediate transfer body onto the recording medium all at once.
The intermediate transfer body is not particularly limited and can be appropriately selected from known transfer bodies depending on the purpose. For example, a transfer belt is preferably used.

The transfer means (the primary transfer means and the secondary transfer means) preferably includes at least a transfer device that peels and charges the visible image formed on the photoreceptor onto the recording medium. Examples of the transfer device include a corona transfer device that uses 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 is capable of transferring an unfixed image after development, and can be appropriately selected depending on the purpose. A PET base for overhead projectors can also be used.

<<Fixing means and fixing process>>
The fixing means is not particularly limited as long as it is a means for fixing the transferred image transferred to the recording medium, and can be appropriately selected depending on the purpose, but is preferably a known heating and pressing member. Examples of the heating and pressing member include a combination of a heating roller and a pressing roller, and a combination of a heating roller, a pressing roller, and an endless belt.
The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected according to the purpose. For example, the fixing step may be performed for each color toner every time it is transferred to the recording medium, or may be performed simultaneously for each color toner in a laminated state.

The fixing step can be carried out by the fixing means.
The heating temperature in the heating and pressing member is usually preferably 80°C to 200°C.
In the present invention, depending on the purpose, for example, a known optical fixing device may be used together with or instead of the fixing means.
The surface pressure in the fixing step is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 N/cm ² to 80 N/cm ² .

<<Cleaning means and cleaning process>>
The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected depending on the purpose, for example, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, a web cleaner, etc.
The cleaning step is not particularly limited as long as it is a step that can remove the toner remaining on the photoreceptor, and can be appropriately selected depending on the purpose. For example, the cleaning step can be performed by the cleaning unit.

<<Static Charge Elimination Means and Static Charge Elimination Process>>
The charge removing means is not particularly limited as long as it is a means for removing charge by applying a charge removing bias to the photoconductor, and may be appropriately selected depending on the purpose. For example, a charge removing lamp may be used.
The charge removal step is not particularly limited as long as it is a step of removing electricity by applying a charge removal bias to the photoconductor, and may be appropriately selected depending on the purpose. For example, the charge removal step may be performed by the charge removal unit.

<<Recycling methods and recycling processes>>
The recycling means is not particularly limited as long as it is a means for recycling the toner removed in the cleaning step back to the developing device, and may be appropriately selected depending on the purpose. For example, a known transport means may be used.
The recycling process is not particularly limited as long as it is a process for recycling the toner removed by the cleaning process back into the developing device, and can be appropriately selected depending on the purpose. For example, the recycling process can be performed by the recycling means.

<<Control means and control process>>
The control means is not particularly limited as long as it is a means capable of controlling the movement of each of the means, and can be appropriately selected depending on the purpose. For example, devices such as a sequencer and a computer can be mentioned.
The control step is not particularly limited as long as it is a step that can control the movement of each step, and can be appropriately selected depending on the purpose. For example, it can be performed by the control means.

Next, one embodiment of a method for forming an image by the image forming apparatus of the present invention will be described with reference to Fig. 2. The color image forming apparatus 100A shown in Fig. 2 includes a photoconductor drum 10 (hereinafter sometimes referred to as "photoconductor 10") as the electrostatic latent image carrier, a charging roller 20 as the charging means, an exposure device 30 as the exposure means, a developing unit 40 as the developing means, an intermediate transfer body 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 body 50 is an endless belt, and is designed to be movable in the direction of the arrow by three rollers 51 arranged inside and stretching it. Some of the three rollers 51 also function as transfer bias rollers that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer body 50. A cleaning device 90 having a cleaning blade is arranged near the intermediate transfer body 50. In addition, a transfer roller 80 as the transfer means that can apply a transfer bias for transferring (secondary transfer) the developed image (toner image) to a transfer paper 95 as a recording medium is arranged near the intermediate transfer body 50, facing the intermediate transfer body 50. Around the intermediate transfer body 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer body 50 is arranged between the contact portion between the photoconductor 10 and the intermediate transfer body 50 and the contact portion between the intermediate transfer body 50 and the transfer paper 95 in the rotation direction of the intermediate transfer body 50.

The developing device 40 is composed of a developing belt 41 as the developer carrier, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C arranged around the developing belt 41. The black developing unit 45K includes a developer container 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. The developing belt 41 is an endless belt that is rotatably stretched around multiple belt rollers, and a portion of it is in contact with the electrostatic latent image carrier 10.

In the color image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 uniformly charges the photoconductor drum 10. The exposure device 30 exposes the photoconductor drum 10 imagewise to light to form an electrostatic latent image. The electrostatic latent image formed on the photoconductor 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 body 50 by the voltage applied from the roller 51, and is further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The remaining toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the discharge lamp 70.

Figure 3 shows another example of an image forming apparatus of the present invention. Image forming apparatus 100B has the same configuration as image forming apparatus 100A shown in Figure 2, except that it does not have a developing belt 41 and has a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C arranged directly opposite each other around the photoconductor drum 10.

Another example of the image forming apparatus of the present invention is shown in Fig. 4. The image forming apparatus shown in Fig. 4 comprises a copying machine main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
An endless belt-like intermediate transfer member 50 is provided in the center of the copying machine main body 150 .
The intermediate transfer body 50 is stretched around support rollers 14, 15, and 16, and can rotate clockwise in FIG. 4. An intermediate transfer body cleaning device 17 for removing residual toner on the intermediate transfer body 50 is disposed near the support roller 15. A tandem type developing device 120 is disposed on the intermediate transfer body 50 stretched around the support rollers 14 and 15 along the conveying direction of the intermediate transfer body 50, in which four image forming means 18 for yellow, cyan, magenta, and black are arranged in a row facing each other. An exposure device 21, which is the exposure member, is disposed near the tandem type developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer body 50 opposite to the side where the tandem type 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 can come into contact with each other. A fixing device 25, which is the fixing means, is disposed near the secondary transfer device 22. The fixing device 25 includes a fixing belt 26, which is an endless belt, and a pressure roller 27 disposed so as to be pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 is disposed near the secondary transfer device 22 and the fixing device 25 for reversing the transfer paper in order to form images on both sides of the transfer paper.

Next, we will explain how to form a full-color image (color copy) using the tandem developing device 120. That is, first, set the document on the document table 130 of the automatic document feeder (ADF) 400, or open the automatic document feeder 400 and set the document on the contact glass 32 of the scanner 300, and then close the automatic document feeder 400.

When the start switch is pressed, the scanner 300 starts after the document is transported and moved onto the contact glass 32 when the document is set on the automatic document feeder 400, or immediately when the document is set on the contact glass 32. Then, the first travelling body 33 and the second travelling body 34 start to travel. At this time, light from the light source is irradiated by the first travelling body 33, and the reflected light from the document surface is reflected by the mirror in the second travelling body 34, and is received by the reading sensor 36 through the imaging lens 35 to read the color document (color image), which is converted into image information in black, yellow, magenta and cyan.

Then, the image information for black, yellow, magenta, and cyan is transmitted to 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 developing device 120. Then, in each image forming means, a toner image for black, yellow, magenta, and cyan is formed.

That is, as shown in FIG. 5, 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 includes 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), a charging device 160 which is the charging means for uniformly charging the electrostatic latent image carrier 10, and a charging device 160 which is a charging device for charging the electrostatic latent image carrier 10 based on each color image information. The device is equipped with an exposure device that exposes the electrostatic latent image carrier to light (L in FIG. 5) in the form of an image corresponding to each color image, forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, a developing device 61 that is the developing means that develops the electrostatic latent image with each color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer body 50, a cleaning device 63, and a charge remover 64.

Each image forming means 18 can form a single-color image (black image, yellow image, magenta image, and cyan image) based on the image information of each color. The black image, yellow image, magenta image, and cyan image thus formed are sequentially transferred (primary transfer) onto the intermediate transfer body 50 which is rotated and moved by the support rollers 14, 15, and 16, respectively, as follows: the black image formed on the black electrostatic latent image carrier 10K, the yellow image formed on the yellow electrostatic latent image carrier 10Y, the magenta image formed on the magenta electrostatic latent image carrier 10M, and the cyan image formed on the cyan electrostatic latent image carrier 10C. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer body 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 a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. The sheets are separated one by one by the separation roller 145 and sent to the paper feed path 146, transported by the transport roller 147 and guided to the paper feed path 148 in the copying machine main body 150, where they are stopped by hitting the registration roller 49. Alternatively, the paper feed roller 142 is rotated to feed a sheet (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, and placed in the manual feed path 53, where they are also stopped by hitting the registration roller 49. The registration roller 49 is generally used while being grounded, but may be used with a bias applied to remove paper dust from the sheets.

Then, the registration roller 49 rotates in time with the composite color image (color transfer image) composited on the intermediate transfer body 50, and a sheet (recording paper) is sent between the intermediate transfer body 50 and the secondary transfer device 22, and the composite color image (color transfer image) is transferred (secondary transfer) onto the sheet (recording paper) by the secondary transfer device 22. In this way, a color image is transferred and formed on the sheet (recording paper). Note that any residual toner remaining on the intermediate transfer body 50 after the image transfer is cleaned by the intermediate transfer body cleaning device 17.

The sheet (recording paper) on which the color image has been transferred and formed is transported by the secondary transfer device 22 and sent to the fixing device 25, where the composite color image (color transfer image) is fixed onto the sheet (recording paper) by heat and pressure. The sheet (recording paper) is then switched by the switching claw 55 and discharged by the discharge rollers 56, and stacked on the paper output tray 57. Alternatively, the sheet is switched by the switching claw 55 and inverted by the sheet inverting device 28, and led back to the transfer position, an image is also recorded on the back side, and then discharged by the discharge rollers 56 and stacked on the paper output tray 57.

(Toner storage unit)
The toner storage unit in the present invention refers to a unit having a function of storing toner and storing the toner. Examples of the toner storage unit include a toner storage container, a developing unit, and a process cartridge.
The toner storage container refers to a container that stores toner.
The developing device has a means for containing toner and developing the toner.
The process cartridge is a cartridge which integrates at least an image carrier and a developing means, contains toner, and is detachably mountable to an image forming apparatus. The process cartridge may further include at least one selected from a charging means, an exposure means, and a cleaning means.

By mounting the toner storage unit of the present invention on an image forming device and forming an image, the toner of the present invention is used to form an image, so that both cleaning properties and transfer properties can be achieved.

The toner storage container is not particularly limited and can be appropriately selected from known containers. For example, it can be one that has a container body and a cap.

Furthermore, the size, shape, structure, material, etc. of the container body are not particularly limited and can be changed as appropriate.
The shape is preferably cylindrical or the like, and a spiral unevenness is formed on the inner peripheral surface, and by rotating the developer, which is the content, it is possible to move to the discharge port side. It is particularly preferable that a part or all of the spiral unevenness has a bellows function.

Furthermore, although there are no particular limitations on the material, it is preferable that the material has good dimensional accuracy. Examples of the material include resin materials such as polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, and polyacetal resin.

The toner storage container is easy to store, transport, and handle, and can be detachably attached to a process cartridge, image forming device, etc., and used to replenish toner.

One example of a process cartridge according to the present invention is molded so as to be detachable from various image forming devices, and has at least an electrostatic latent image carrier that carries an electrostatic latent image, and a developing means that develops the electrostatic latent image carried on the electrostatic latent image carrier with the developer of the present invention to form a toner image. The process cartridge of the present invention may further have other means as necessary.

The developing means includes at least a developer container that contains the developer of the present invention, and a developer carrier that carries and transports the developer contained in the developer container. The developing means may further include a regulating member or the like for regulating the thickness of the developer carried.

Figure 6 shows an example of a process cartridge according to the present invention. The process cartridge 110 has a photosensitive drum 10, a corona charger 52, a developing device 40, a transfer roller 80, and a cleaning device 90.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. "Parts" refers to "parts by mass" unless otherwise specified. "%" refers to "% by mass" unless otherwise specified. Example 15 refers to Reference Example 15, which is not included in the present invention.

The measured values in the following examples were measured by the methods described in this specification. The Tg and molecular weight of amorphous polyester resin A, amorphous polyester resin B, crystalline polyester resin C, etc. were measured from each resin obtained in the manufacturing examples.

(Production Example 1)
<Synthesis of ketimines>
In a reaction vessel equipped with a stirring bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50° C. for 5 hours to obtain [Ketimine Compound 1]. [Ketimine Compound 1] had an amine value of 418.

(Production Example A-1)
<Synthesis of amorphous polyester resin A-1>
-Synthesis of Prepolymer A-1-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, 3-methyl-1,5-pentanediol, isophthalic acid and adipic acid were added together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) so that the molar ratio of hydroxyl groups to carboxyl groups, OH/COOH, was 1.1, the composition of the diol component was 100 mol% of 3-methyl-1,5-pentanediol, the composition of the dicarboxylic acid component was 45 mol% of isophthalic acid and 55 mol% of adipic acid, and the amount of trimethylolpropane in the total monomers was 1.5 mol%. After that, the temperature was raised to 200°C in about 4 hours, and then raised to 230°C over 2 hours, and the reaction was carried out until no water was discharged. After that, the reaction was further carried out for 5 hours under a reduced pressure of 10 mmHg to 15 mmHg to obtain [Intermediate Polyester A-1].

Next, the obtained [Intermediate Polyester A-1] and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of IPDI/hydroxyl groups of intermediate polyester) of 2.0, diluted with ethyl acetate to make a 50% ethyl acetate solution, and reacted at 100°C for 5 hours to obtain [Prepolymer A-1].

-Synthesis of amorphous polyester resin A-1-
The obtained [Prepolymer A-1] was stirred in a reaction vessel equipped with a heater, a stirrer, and a nitrogen inlet tube, and further, [Ketimine Compound 1] was added dropwise to the reaction vessel in an amount such that the amount of amine in [Ketimine Compound 1] was equimolar to the amount of isocyanate in [Prepolymer A-1], and the prepolymer extension product was taken out after stirring for 10 hours at 45° C. The obtained prepolymer extension product was dried under reduced pressure at 50° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain [Amorphous Polyester Resin A-1]. The physical properties of this resin are shown in Table 1.

(Production Example A-2)
<Synthesis of amorphous polyester resin A-2>
-Synthesis of Prepolymer A-2-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, 3-methyl-1,5-pentanediol and adipic acid were added together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) so that the molar ratio of hydroxyl groups to carboxyl groups, OH/COOH, was 1.1, the diol component was 100 mol% of 3-methyl-1,5-pentanediol, the dicarboxylic acid component was 100 mol% of adipic acid, and the amount of trimethylolpropane in the total monomers was 1.5 mol%. After that, the temperature was raised to 200°C in about 4 hours, and then raised to 230°C in 2 hours, and the reaction was carried out until no water was discharged. After that, the reaction was further carried out for 5 hours under a reduced pressure of 10 mmHg to 15 mmHg to obtain [Intermediate Polyester A-2].

Next, the obtained [Intermediate Polyester A-2] and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of IPDI/hydroxyl groups of intermediate polyester) of 2.0, diluted with ethyl acetate to make a 50% ethyl acetate solution, and reacted at 100°C for 5 hours to obtain [Prepolymer A-2].

-Synthesis of amorphous polyester resin A-2-
The obtained [Prepolymer A-2] was stirred in a reaction vessel equipped with a heater, a stirrer, and a nitrogen inlet tube, and further, [Ketimine Compound 1] was added dropwise to the reaction vessel in an amount such that the amount of amine in [Ketimine Compound 1] was equimolar to the amount of isocyanate in [Prepolymer A-2], and the prepolymer extension product was taken out after stirring at 45° C. for 10 hours. The obtained prepolymer extension product was dried under reduced pressure at 50° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain [Amorphous Polyester Resin A-2]. The physical properties of this resin are shown in Table 1.

(Production Example A-3)
<Synthesis of amorphous polyester resin A-3>
-Synthesis of prepolymer A-3-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, bisphenol A ethylene oxide 2 mole adduct, bisphenol A propylene oxide 2 mole adduct, terephthalic acid and trimellitic anhydride were added together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) so that the OH/COOH molar ratio of hydroxyl groups to carboxyl groups was 1.3, the diol component was 90 mol% bisphenol A ethylene oxide 2 mole adduct and 10 mol% bisphenol A propylene oxide 2 mole adduct, and the carboxylic acid component was 90 mol% terephthalic acid and 10 mol% trimellitic anhydride. After that, the temperature was raised to 200°C in about 4 hours, and then raised to 230°C over 2 hours, and the reaction was carried out until no water was discharged. After that, the reaction was further carried out for 5 hours under a reduced pressure of 10 mmHg to 15 mmHg to obtain [Intermediate Polyester A-3].

Next, the obtained [Intermediate Polyester A-3] and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of IPDI/hydroxyl groups of intermediate polyester) of 2.0, diluted with ethyl acetate to make a 50% ethyl acetate solution, and reacted at 100°C for 5 hours to obtain [Prepolymer A-3].

-Synthesis of amorphous polyester resin A-3-
The obtained [Prepolymer A-3] was stirred in a reaction vessel equipped with a heater, a stirrer, and a nitrogen inlet tube, and further, [Ketimine Compound 1] was added dropwise to the reaction vessel in an amount such that the amount of amine in [Ketimine Compound 1] was equimolar to the amount of isocyanate in [Prepolymer A-3], and the prepolymer extension product was taken out after stirring at 45° C. for 10 hours. The obtained prepolymer extension product was dried under reduced pressure at 50° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain [Amorphous Polyester Resin A-3]. The physical properties of this resin are shown in Table 1.

(Production Example A-4)
<Synthesis of amorphous polyester resin A-4>
-Synthesis of Prepolymer A-4-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, 1,2-propylene glycol, terephthalic acid, adipic acid and trimellitic anhydride were added together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) so that the molar ratio of hydroxyl groups to carboxyl groups, OH/COOH, was 1.3, the composition of the diol component was 1,2-propylene glycol 100 mol%, the composition of the dicarboxylic acid component was terephthalic acid 80 mol% and adipic acid 20 mol%, and the amount of trimellitic anhydride in the total monomer was 2.5 mol%. After that, the temperature was raised to 200°C in about 4 hours, and then raised to 230°C over 2 hours, and the reaction was carried out until no water was discharged. After that, the reaction was further carried out for 5 hours under a reduced pressure of 10 mmHg to 15 mmHg to obtain [Intermediate Polyester A-4].

Next, the obtained [Intermediate Polyester A-4] and isophorone diisocyanate were added to a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of IPDI/hydroxyl groups of intermediate polyester) of 2.0, diluted with ethyl acetate to make a 50% ethyl acetate solution, and reacted at 100°C for 5 hours to obtain [Prepolymer A-4].

-Synthesis of amorphous polyester resin A-4-
The obtained [Prepolymer A-4] was stirred in a reaction vessel equipped with a heater, a stirrer, and a nitrogen inlet tube, and further, [Ketimine Compound 1] was added dropwise to the reaction vessel in an amount such that the amount of amine in [Ketimine Compound 1] was equimolar to the amount of isocyanate in [Prepolymer A-4], and the prepolymer extension product was taken out after stirring at 45° C. for 10 hours. The obtained prepolymer extension product was dried under reduced pressure at 50° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain [Amorphous Polyester Resin A-4]. The physical properties of this resin are shown in Table 1.

(Production Example B-1)
<Synthesis of amorphous polyester resin B-1>
In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A ethylene oxide 2 mole adduct, bisphenol A propylene oxide 2 mole adduct, terephthalic acid, and adipic acid were added to obtain a mixture of bisphenol A propylene oxide 2 mole adduct and bisphenol A ethylene oxide 2 mole adduct in a molar ratio (bisphenol A propylene oxide 2 mole adduct/bisphenol A ethylene oxide 2 mole adduct) of 60/40, and terephthalic acid and adipic acid. The mixture was charged with terephthalic acid and adipic acid in a molar ratio (terephthalic acid/adipic acid) of 97/3, and the molar ratio of hydroxyl groups to carboxyl groups, OH/COOH, was 1.3, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at normal pressure and 230°C for 8 hours, and then reacted at a reduced pressure of 10 mmHg to 15 mmHg for 4 hours. Then, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% relative to the total resin components, and reacted at 180°C, normal pressure, for 3 hours to obtain [Amorphous Polyester Resin B-1]. The physical properties of this resin are shown in Table 2.

(Production Example B-2)
<Synthesis of amorphous polyester resin B-2>
In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A propylene oxide 2-mol adduct, 1,3-propylene glycol, terephthalic acid, and adipic acid were added in a molar ratio of 90/10 between the bisphenol A propylene oxide 2-mol adduct and 1,3-propylene glycol (bisphenol A propylene oxide 2-mol adduct/1,3-propylene glycol) and 90/10 between the terephthalic acid and adipic acid (terephthalic acid). The mixture was charged with a 80/20 mixture of hydroxyl and carboxyl groups (acid/adipic acid) and a molar ratio of OH/COOH of 1.4, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at normal pressure and 230°C for 8 hours, and then reacted for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg. Then, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% relative to the total resin components, and reacted at 180°C, normal pressure, and for 3 hours to obtain [Amorphous Polyester Resin B-2]. The physical properties of this resin are shown in Table 2.

(Production Example B-3)
<Synthesis of amorphous polyester resin B-3>
In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A propylene oxide 2 mole adduct, bisphenol A ethylene oxide 2 mole adduct, isophthalic acid, and adipic acid were added to obtain a mixture of bisphenol A propylene oxide 2 mole adduct and bisphenol A ethylene oxide 2 mole adduct in a molar ratio (bisphenol A propylene oxide 2 mole adduct/bisphenol A ethylene oxide 2 mole adduct) of 30/70, and isophthalic acid and adipic acid. The mixture was charged with isophthalic acid and adipic acid in a molar ratio of 80/20 (isophthalic acid/adipic acid), and the molar ratio of hydroxyl groups to carboxyl groups, OH/COOH, was 1.2, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at normal pressure and 230°C for 8 hours, and then reacted at a reduced pressure of 10 mmHg to 15 mmHg for 4 hours. Then, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% relative to the total resin components, and reacted at 180°C, normal pressure, for 3 hours to obtain [Amorphous Polyester Resin B-3]. The physical properties of this resin are shown in Table 2.

(Production Example C-1)
<Synthesis of Crystalline Polyester Resin C-1>
Sebacic acid and 1,6-hexanediol were charged into a 5 L four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple so that the molar ratio of hydroxyl groups to carboxyl groups, OH/COOH, was 0.9, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at 180°C for 10 hours, then heated to 200°C and reacted for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to obtain [Crystalline polyester resin C-1]. The physical properties of this resin are shown in Table 3.

(Production Example C-2)
<Synthesis of Crystalline Polyester Resin C-2>
[Crystalline polyester resin C-2] was obtained in the same manner as in the synthesis of [Crystalline polyester resin C-1], except that the dicarboxylic acid was changed to dodecanedioic acid. The physical properties are shown in Table 3.

Example 1
<Preparation of Masterbatch (MB)>
1,200 parts of water, 500 parts of carbon black (Printex 35, manufactured by Dexa) [DBP oil absorption = 42 mL/100 mg, pH = 9.5], and 500 parts of [amorphous polyester resin B-1] were added and mixed in a Henschel mixer (manufactured by Nippon Coke and Engineering Co., Ltd.). The mixture was kneaded using two rolls at 150°C for 30 minutes, then cooled by rolling, and pulverized with a pulverizer to obtain [Master batch 1].

<Preparation of wax dispersion>
In a container equipped with a stirring rod and a thermometer, 50 parts of paraffin wax (manufactured by Nippon Seiro Co., Ltd., HNP-9, hydrocarbon wax, melting point 75°C, SP value 8.8) as [release agent 1] and 450 parts of ethyl acetate were charged, and the temperature was raised to 80°C while stirring. The temperature was kept at 80°C for 5 hours, and then the mixture was cooled to 30°C in 1 hour. Dispersion was performed using a bead mill (Ultraviscomill, manufactured by Imex Co., Ltd.) under conditions of a liquid delivery rate of 1 kg/hr, a disk peripheral speed of 6 m/sec, 80% by volume of zirconia beads with a diameter of 0.5 mm, and 3 passes to obtain [wax dispersion 1].

<Preparation of Crystalline Polyester Resin Dispersion>
A vessel equipped with a stirring rod and a thermometer was charged with 50 parts of [Crystalline polyester resin C-1] and 450 parts of ethyl acetate, and the temperature was raised to 80°C with stirring. The temperature was maintained at 80°C for 5 hours, and then the mixture was cooled to 30°C in 1 hour. Dispersion was carried out using a bead mill (Ultraviscomill, manufactured by Imex) under conditions of a liquid delivery rate of 1 kg/hr, a disk peripheral speed of 6 m/sec, a filling rate of 80% by volume of zirconia beads with a diameter of 0.5 mm, and 3 passes to obtain [Crystalline polyester resin dispersion 1].

<Preparation of Oil Phase>
50 parts of [WAX dispersion 1], 150 parts of [Amorphous polyester resin A-1], 50 parts of [Crystalline polyester resin dispersion 1], 750 parts of [Amorphous polyester resin B-1], 50 parts of [Master batch 1] (pigment), and 2 parts of [Ketimine compound 1] were placed in a container and mixed with a TK homomixer (manufactured by Primix Corporation) at 5,000 rpm for 60 minutes to obtain [Oil phase 1].
The above blending amounts indicate the blending amounts of solid content in each raw material.

<Synthesis of organic fine particle emulsion (fine particle dispersion)>
A reaction vessel equipped with a stirring rod and a thermometer was charged with 683 parts of water, 11 parts of sodium salt of methacrylic acid ethylene oxide adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries, Ltd.), 138 parts of styrene, 138 parts of methacrylic acid, and 1 part of ammonium persulfate, and stirred at 400 rpm for 15 minutes, yielding a white emulsion. The mixture was heated to a system temperature of 75°C and reacted for 5 hours. Further, 30 parts of a 1% aqueous ammonium persulfate solution was added, and the mixture was aged at 75°C for 5 hours to obtain an aqueous dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-sodium salt of methacrylic acid ethylene oxide adduct sulfate) [fine particle dispersion 1].
The volume average particle diameter of [fine particle dispersion 1] was measured with an LA-920 (manufactured by HORIBA Co., Ltd.) and was found to be 0.14 μm. A part of [fine particle dispersion 1] was dried to isolate the resin content.

<Preparation of aqueous phase>
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyldiphenyletherdisulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate were mixed and stirred to obtain a milky white liquid. This was designated as [aqueous phase 1].

<Emulsification and desolvation 1>
To the vessel containing the [oil phase 1], 1,200 parts of [water phase 1] was added and mixed for 20 minutes at 8,000 rpm using a TK homomixer to obtain [emulsified slurry 1].
[Emulsified slurry 1] was placed in a container equipped with a stirrer and a thermometer, and the solvent was removed at 30° C. for 30 minutes to obtain [Desolvated slurry 1]. The residual ethyl acetate concentration in [Desolvated slurry 1] is shown in Table 4.

＜Deformation＞
To [solvulant-removed slurry 1], 30 parts of carboxymethylcellulose (Cellogen HH, Daiichi Kogyo Seiyaku Co., Ltd.) was added as a thickener, and the mixture was stirred at 150 rpm for 1 hour using a helical ribbon stirrer to obtain [irregularly shaped slurry 1].

<Solvent removal 2, maturation>
The solvent was removed from [irregularized slurry 1] at 30° C. for 8 hours, and then the slurry was aged at 45° C. for 4 hours to obtain [dispersed slurry 1].

<Washing and drying>
[Dispersion Slurry 1] 100 parts was filtered under reduced pressure, and then
(1): 100 parts of ion-exchanged water was added to the filter cake, and the mixture was mixed with a TK homomixer (at 12,000 rpm for 10 minutes) and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), and the mixture was mixed with a TK homomixer (at 12,000 rpm for 30 minutes), followed by filtration under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), and the mixture was mixed with a TK homomixer (at 12,000 rpm for 10 minutes) and then filtered.
(4): 300 parts of ion-exchanged water is added to the filter cake of (3), mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered.
The above steps (1) to (4) were repeated twice to obtain [Filter Cake 1].
The filtered cake 1 was dried in a circulating air dryer at 45° C. for 48 hours, and sieved through a 75 μm mesh to obtain toner base particles 1.

<External additive treatment step>
100 parts of [toner base particles 1] and 2.0 parts of hydrophobic silica (HDK-2000, manufactured by Clariant Co., Ltd.) as an external additive were mixed in a Henschel mixer, and the mixture was passed through a sieve with 500 mesh openings to obtain [toner 1].

Example 2
[Toner 2] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, the blending amount of [Amorphous polyester resin A-1] was changed to 120 parts, the blending amount of [Amorphous polyester resin B-1] was changed to 780 parts, and in <Deformation>, the rotation speed of the device for applying shear force was changed to 300 rpm.

Example 3
[Toner 3] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, the blending amount of [Amorphous polyester resin A-1] was changed to 180 parts, the blending amount of [Amorphous polyester resin B-1] was changed to 720 parts, and in <Deformation>, the blending amount of the thickener was changed to 5 parts.

Example 4
[Toner 4] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was changed to [Amorphous polyester resin A-2], [Amorphous polyester resin B-1] was changed to [Amorphous polyester resin B-3], the blending amount of [Crystalline polyester resin C-1] was changed to 150 parts, in <Emulsification and solvent removal 1> the residual ethyl acetate concentration was changed to 8 wt %, and in <Deformation> the blending amount of thickener was changed to 50 parts.

Example 5
[Toner 5] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, the amount of [Amorphous Polyester Resin A-1] was changed to 120 parts, the amount of [Amorphous Polyester Resin B-1] was changed to 820 parts, and the amount of [Crystalline Polyester Resin C-1] was changed to 200 parts, and in <Deformation>, the amount of the thickener was changed to 5 parts, the device for applying shear force was changed to a homomixer, and the rotation speed was changed to 8000 rpm.

Example 6
[Toner 6] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, the amount of [Amorphous Polyester Resin A-1] was changed to 180 parts, [Amorphous Polyester Resin B-1] was changed to [Amorphous Polyester Resin B-3], and the amount of [Crystalline Polyester Resin C-1] was changed to 0 parts, and in <Deformation>, the device for applying shear force was changed to a homomixer and the rotation speed was changed to 8000 rpm.

(Example 7)
[Toner 7] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was changed to [Amorphous polyester resin A-2] and the blending amount was changed to 180 parts, [Amorphous polyester resin B-1] was changed to [Amorphous polyester resin B-3] and the blending amount was changed to 720 parts, [Crystalline polyester resin C-1] was changed to [Crystalline polyester resin C-2], and in <Deformation>, the device for applying shear force was changed to a homomixer and the rotation speed was changed to 4000 rpm.

(Example 8)
[Toner 8] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, the amount of [Amorphous Polyester Resin A-1] was changed to 120 parts, [Amorphous Polyester Resin B-1] was changed to [Amorphous Polyester Resin B-2], the amount was changed to 780 parts, and 2 parts of Clayton APA (manufactured by BYK Japan KK) was added as a deformation agent.

Example 9
[Toner 9] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was changed to [Amorphous polyester resin A-2], 2 parts of Clayton APA (manufactured by BYK Japan KK) was added as a deformation agent, and in <Deformation>, the device for applying shear force was changed to a paddle type and the rotation speed was changed to 400 rpm.

Example 10
[Toner 10] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin B-1] was changed to [Amorphous polyester resin B-2], 5 parts of MEK-ST-UP (manufactured by Nissan Chemical Industries, Ltd.) was added as a deformation agent, and in <Emulsification and desolvation 1>, the residual ethyl acetate concentration was changed to 15 wt %.

(Example 11)
[Toner 11] was obtained in the same manner as in Example 7, except that the blending amount of [Crystalline Polyester Resin C-2] in Example 7 was changed to 0 part.

Example 12
Toner 12 was obtained in the same manner as in Example 11, except that the rotation speed of the device for applying shear force was changed to 2000 rpm.

(Example 13)
Toner 13 was obtained in the same manner as in Example 2, except that the rotation speed of the device for applying shear force was changed to 400 rpm.

(Example 14)
[Toner 14] was obtained in the same manner as in Example 5, except that 2 parts of Clayton APA (manufactured by BYK Japan KK) was added as the deforming agent.

(Example 15)
[Toner 15] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was changed to [Amorphous polyester resin A-3], the blending amount was changed to 50 parts, and [Amorphous polyester resin B-1] was changed to [Amorphous polyester resin B-2].

(Comparative Example 1)
[Toner 16] was obtained in the same manner as in Example 1, except that in the <Deformation of the shaping> of Example 1, the blending amount of the thickener was changed to 0 part.

(Comparative Example 2)
Toner 17 was obtained in the same manner as in Example 1, except that in the <irregularization> of Example 1, the rotation speed of the device for applying shear force was changed to 600 rpm.

(Comparative Example 3)
[Toner 18] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was changed to [Amorphous polyester resin A-3], [Amorphous polyester resin B-1] was changed to [Amorphous polyester resin B-2], in <Emulsification and solvent removal 1>, the residual ethyl acetate concentration was changed to 0 wt %, and in <Deformation>, the device for applying shear force was changed to a homomixer and the rotation speed was changed to 12,000 rpm.

(Comparative Example 4)
[Toner 19] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was changed to [Amorphous polyester resin A-4], [Amorphous polyester resin B-1] was changed to [Amorphous polyester resin B-3], 5 parts of Clayton APA (manufactured by BYK Japan KK) was added as a deformation agent, and the residual ethyl acetate concentration in <Emulsification and desolvation 1> was changed to 0 wt %.

(Comparative Example 5)
[Toner 20] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, 10 parts of Clayton APA (manufactured by BYK Japan) was added as a deformation agent, in <Emulsification and desolvation 1>, the residual ethyl acetate concentration was changed to 0 wt %, and the <Deformation process> was omitted.

(Comparative Example 6)
[Toner 21] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, the amount of [Amorphous Polyester Resin A-1] was changed to 750 parts, the amount of [Amorphous Polyester Resin B-1] was changed to 150 parts, 5 parts of Clayton APA (manufactured by BYK Japan KK) was added as a deformation agent, and in <Emulsification and Solvent Removal 1>, the residual ethyl acetate concentration was changed to 20 wt %.

(Comparative Example 7)
[Toner 22] was obtained in the same manner as in Example 3, except that the residual ethyl acetate concentration in Example 3 was changed to 4 wt %.

(Comparative Example 8)
[Toner 23] was obtained in the same manner as in Example 1, except that 11 parts of Clayton APA (manufactured by BYK Japan KK) was added as the deforming agent.

The combinations of polyester resin, deforming agent, residual ethyl acetate concentration in the desolvated slurry, amount of thickener, shearing device, and rotation speed for each toner are shown in Table 4.

The average circularity, standard deviation of circularity, average circularity (A), average circularity (B), A-B, major axis _r1 , minor axis _r2 , thickness _r3 , _r2 / _r1 , _r3 / _r2 , and SF2 of the obtained toner are shown in Table 5.

<Methods for measuring average particle size, average circularity, and standard deviation of circularity>
The average particle size, average circularity, and standard deviation of circularity were measured using a flow type particle image analyzer FPIA-3000 (manufactured by Sysmex Corporation).
0.5 ml of alkylbenzenesulfonate was added as a dispersant to 100-150 ml of water from which solid impurities had been removed in advance in a container, and 0.1 g of the measurement sample was further added. The suspension in which the sample was dispersed was subjected to a dispersion treatment for about 1 minute using an ultrasonic disperser, and the average particle size, average circularity, and standard deviation (SD) of the circularity were measured using the above-mentioned device with a dispersion concentration of 3,000-10,000 particles/μl.
The particle diameter was determined as the equivalent circle diameter, and the average particle diameter was determined based on the equivalent circle diameter (number basis). The analysis conditions for the flow type particle image analyzer were as follows:
Particle size limit: 0.5 μm≦circle equivalent diameter (number basis)≦200.0 μm
Particle shape limit: 0.93<circularity≦1.00

The average circularity is defined as follows.
(Average circularity) = (perimeter of a circle equal to the projected area) / (perimeter of the projected image)

<Method of measuring average circularity (A) and average circularity (B)>
The average circularity of particles when the particle diameter is limited to 0.5 μm≦circle equivalent diameter (number basis)≦average particle diameter is defined as the average circularity (A).
The average circularity of the particles when the particle size was limited to average particle size<circle equivalent diameter (number basis)≦200.0 μm was defined as the average circularity (B).

<Method of measuring major axis _r1 , minor axis _r2 , thickness _r3 , _r2 / _r1 , and _r3 / _r2 >
The major axis _r1 , minor axis _r2 , and thickness _r3 of the toner were measured by taking photographs at different viewing angles using a scanning electron microscope SU8230 (manufactured by Hitachi High-Technologies Corporation). _r1 , _r2 , and _r3 were average values for 30 or more particles.

<Measurement method for SF2>
The toner shape factor SF2 was obtained by randomly sampling 100 toner images enlarged at a magnification of 500 times using a scanning electron microscope (SU-8230: manufactured by Hitachi High-Technologies Corporation) and analyzing the image information using an image analyzer (LuzexIII: manufactured by Nicolet) via an interface.
The shape factor SF2 indicates the ratio of projections and recesses in the shape of the toner, and is expressed by the following formula (1): SF2 is the square of the perimeter PERI of the figure formed by projecting the toner onto a two-dimensional plane, divided by the area AREA of the figure, and multiplied by 100π/4.

SF2={(PERI) ² /AREA}×(100π/4) Equation (1)

In the above formula (1), AREA is the toner projection area, MXLNG is the absolute maximum length, and PERI is the circumference.

<Soxhlet extraction>
One part of the toner was added to 100 parts of tetrahydrofuran (THF), and the mixture was refluxed for 6 hours. The insoluble components were then precipitated using a centrifuge, and the insoluble components were separated from the supernatant.
The insoluble matter was dried at 40° C. for 20 hours to obtain a THF insoluble matter.

The Tg1st (toner), Tg2nd (THF insoluble), G'(100) (THF insoluble), and G'(40) (THF insoluble)/G'(100) (THF insoluble) ratios of the obtained toner are shown in Table 6.

<Evaluation>
The obtained toner was subjected to the following evaluations, and the results are shown in Table 7.

<<Offset resistance>>
The carrier used in imageo MP C5503 (manufactured by Ricoh Company, Ltd.) and the toner obtained above were mixed so that the toner concentration was 5% by mass, thereby obtaining [Developer 1].
After putting [Developer 1] into a unit of imageo MP C5503 (manufactured by Ricoh Co., Ltd.), a rectangular solid image of 2 cm x 15 cm was formed on PPC paper type 6000 <70W> A4 T (manufactured by Ricoh Co., Ltd.) so that the toner adhesion amount was 0.40 mg/cm ^2. At this time, the surface temperature of the fixing roller was changed, and it was observed whether or not cold offset occurred, in which the development residual image of the solid image was fixed in a place other than the desired place, and the offset resistance was evaluated.

〔Evaluation criteria〕
◎: Less than 110°C ○: 110°C or more and less than 120°C △: 120°C or more and less than 130°C ×: 130°C or more

<<Heat resistance storage stability>>
The toner was filled into a 50 mL glass container and left in a thermostatic chamber at 50° C. for 24 hours, and then cooled to 24° C. Next, the penetration [mm] was measured by a penetration test (JIS K2235-1991) to evaluate the heat resistance storage stability.

〔Evaluation criteria〕
◎: Penetration of 20 mm or more ○: Penetration of 15 mm or more and less than 20 mm △: Penetration of 10 mm or more and less than 15 mm ×: Penetration of less than 10 mm

<<High temperature and humidity storage stability>>
5 g of the toner was stored for 2 weeks in an environment of 40° C. and 70% relative humidity, and then sieved for 5 minutes through a sieve with 106 μm mesh openings, and the amount of the toner remaining on the wire mesh was weighed and evaluated according to the following evaluation criteria.

〔Evaluation criteria〕
◎: Amount of toner on the wire net is 0 mg
◯: Amount of toner on the wire net is more than 0 mg and less than 2 mg △: Amount of toner on the wire net is 2 mg or more and less than 50 mg ×: Amount of toner on the wire net is 50 mg or more

<Cleaning performance evaluation>
The carrier used in imageo MP C5503 (manufactured by Ricoh Co., Ltd.) and the toner obtained above were mixed so that the toner concentration was 5% by mass to obtain a developer. After the developer was put into the unit of imageo MP C5503 (manufactured by Ricoh Co., Ltd.), an image with an image area ratio of 30% was developed, and after transferring to a transfer paper, the copier was stopped while the transfer residual toner remaining on the photoreceptor was being cleaned with a cleaning blade, and the transfer residual toner on the photoreceptor that had passed through the cleaning process was transferred to a blank paper with Scotch tape (manufactured by Sumitomo 3M Co., Ltd.), which was measured at 10 points with a Macbeth reflection densitometer RD514 type, and the difference between the average value and the measurement result when the tape was simply attached to a blank paper was obtained, and the evaluation was performed according to the following criteria.
The cleaning blade used had been used after cleaning 20,000 sheets.

〔Evaluation criteria〕
◎: Difference is 0.010 or less. ○: Difference is more than 0.010 and 0.012 or less. △: Difference is more than 0.012 and 0.015 or less. ×: Difference is more than 0.015.

<Transferability Evaluation>
A running test was carried out for the [Developer 1] using an imageo MP C5503 (manufactured by Ricoh Co., Ltd.) tuned to a linear velocity of 162 mm/sec and a transfer time of 40 msec, in which a solid pattern of A4 size with a toner adhesion amount of 0.6 mg/ ^cm2 was output as a test image. At the beginning of the test image and after outputting 100,000 sheets, the transfer efficiency in the primary transfer was calculated using the following (Equation 2), and the transfer efficiency in the secondary transfer was calculated using the following (Equation 3). The evaluation criteria are as follows.

Primary transfer efficiency (%)=(amount of toner transferred onto intermediate transfer member/amount of toner developed onto electrophotographic photosensitive member)×100 (Equation 2)
Secondary transfer efficiency (%)=(amount of toner transferred onto intermediate transfer body−amount of transfer remaining toner on intermediate transfer body/amount of toner transferred onto intermediate transfer body)×100 (Equation 3)

〔Evaluation criteria〕
The evaluation criteria were as follows: the average value of the primary transfer rate and the secondary transfer rate was calculated, and the evaluation was performed according to the following criteria.
◎: 90% or more ○: 85% or more but less than 90% △: 80% or more but less than 85% ×: Less than 80%

The results are shown in Table 7.

10 Photoconductor drum 20 Charging roller 30 Exposure device 40 Developing device 50 Intermediate transfer body 60 Cleaning device 70 Discharging lamp 150 Copying device main body 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)

JP 2005-049858 A JP 2008-233406 A JP 2015-179252 A

Claims (8)

A toner containing a binder resin and a release agent,
The standard deviation of the circularity measured using a flow particle image analyzer is 0.020 or more,
In the average particle size and circularity determined using the flow-type particle image analyzer, when the average circularity of particles having a particle size equal to or smaller than the average particle size is defined as average circularity (A) and the average circularity of particles having a particle size larger than the average particle size is defined as average circularity (B),
A-B≦0.004
The filling,
the toner has a glass transition temperature Tg1st in a first temperature rise measured by differential scanning calorimetry (DSC) of 20° C. or more and 50° C. or less;
the THF-insoluble portion of the toner has a glass transition temperature Tg2nd measured at the second temperature rise in differential scanning calorimetry (DSC) of -40°C or more and 30°C or less;
When the storage modulus of the THF-insoluble matter of the toner at 40° C. is G′(40) and the storage modulus of the THF-insoluble matter of the toner at 100° C. is G′(100),
1×105 ^≦ G′(100)≦1× ¹⁰⁷
G'(40)/G'(100)≦3.5×10
A toner characterized by satisfying the above requirements.
However, the particle diameter is the circle-equivalent diameter, the average particle diameter is determined based on the circle-equivalent diameter (number basis), and the analysis conditions for the flow-type particle image analyzer are as follows:
Particle size limit: 0.5 μm≦circle equivalent diameter (number basis)≦200.0 μm
Particle shape limit: 0.93<circularity≦1.00 the ratio _r2 / _r1 of the major axis _r1 to the minor axis _r2 of the toner is 0.5 to 0.8;
_{2. The toner according to claim 1, wherein the ratio r 3 /} r 2 of the thickness r ₃ of the toner to the minor axis r ₂ is 0.5 to 1.0. The toner according to claim 1 or 2, characterized in that the shape factor SF2 of the toner is 110 to 130. 4. The toner according to claim 1 , wherein the binder resin contains a crystalline polyester resin. 5. The toner according to claim 1 , wherein the binder resin contains an amorphous polyester resin. A developer comprising the toner according to any one of claims 1 to 5 . A toner storage unit containing the toner according to any one of claims 1 to 5 . an electrostatic latent image carrier; and an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
a developing unit having a toner for developing the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image,
6. An image forming apparatus, comprising the toner according to claim 1 .

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