JP7447525B2 - Toner, toner storage unit, developer, image forming device, and image forming method - Google Patents

Description

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

In recent years, there has been an increasing demand for higher definition and higher image quality of electrostatic images in electrophotographic equipment such as copying machines and printers. In order to achieve these, charging performance and fluidity that can respond to environmental changes such as temperature and humidity are required, so we aim to provide toner with charging performance and fluidity and further improve cleaning performance. External addition of inorganic fine particles such as silica and titanium oxide has been carried out.

For example, Patent Document 1 discloses a toner containing toner particles containing a binder resin and a colorant, and inorganic fine particles, wherein the inorganic fine particles are silica particles containing aluminum, and the inorganic fine particles are silica particles containing aluminum. The present invention discloses a toner having an aluminum content of 0.2 ppm or more and 200 ppm or less. According to the technology disclosed in Patent Document 1, the charging stability is excellent even when used under high temperature and high humidity conditions, normal temperature and normal humidity conditions, or when used for a long period of time, and fogging (background staining) in output images is prevented. It is said that it can suppress the occurrence of This is because the aluminum present in the silica particles has a positive charge, so when the silica particles come into contact with the surface of the toner particles, which have a negative charge, the silica particles become a dielectric and polarize the charge. It is presumed that this causes the toner to have improved charging properties.
Further, Patent Document 2 discloses that in a toner containing toner particles containing at least a binder resin, wax, and inorganic fine particles A, at least the inorganic fine particles A are fixed to the surface of the toner particles by surface treatment with hot air. The inorganic fine particles A have a number average particle diameter (D1) of 0.060 μm or more and 0.300 μm or less, and a BET specific surface area (BET1) of 10.0 m ² /g or more and 50.0 m ² /g or less. A toner in which the number average particle diameter (D1) and the BET specific surface area (BET1) have a specific relationship is disclosed.

Generally, although silica has excellent fluidity, there is a problem in that the environmental stability of charging performance is insufficient. Here, the low environmental stability of charging performance, which is a problem when using silica, is due to the high volume resistivity of silica. This physical property causes a so-called charge-up phenomenon in which the amount of charge becomes excessively high when the toner is charged, resulting in a problem that image quality deteriorates when development is repeated.
With the techniques disclosed in Patent Documents 1 and 2, a toner with excellent charging stability and excellent fogging (background smearing) can be obtained, but a new problem has been discovered in that the cleaning performance is insufficient.

Therefore, an object of the present invention is to provide a toner having excellent charging stability and excellent cleaning properties.

The above problem is solved by the following configuration 1).
1) A toner containing a binder resin, a colorant, a release agent, and inorganic fine particles,
The inorganic fine particles include at least inorganic fine particles 1 which are silica treated with aluminum, and inorganic fine particles 2 which are aluminum compounds treated with a fluorine compound,
A toner characterized in that a total release rate of the inorganic fine particles 1 and the inorganic fine particles 2 from the toner is 10% or more and 70% or less.

According to the present invention, it is possible to provide a toner that has excellent charging stability and excellent cleaning properties.

1 is a diagram for explaining an embodiment of an image forming apparatus of the present invention. FIG. 3 is a diagram for explaining another embodiment of the image forming apparatus of the present invention. FIG. 3 is a diagram for explaining another embodiment of the image forming apparatus of the present invention. FIG. 3 is a diagram for explaining an image forming unit.

The present invention is not limited to the embodiments shown below, and may be modified within the scope of those skilled in the art, such as other embodiments, additions, modifications, deletions, etc., and in any aspect. As long as it exhibits the functions and effects of the present invention, it is included within the scope of the present invention.

The toner of the present invention includes a binder resin, a colorant, a release agent, and inorganic fine particles, and the inorganic fine particles are at least inorganic fine particles 1 that are silica treated with aluminum and aluminum compounds treated with a fluorine compound. and inorganic fine particles 2, and the total release rate of the inorganic fine particles 1 and the inorganic fine particles 2 from the toner is 10% or more and 70% or less.

When either one of the inorganic fine particles 1 and the inorganic fine particles 2 is used, although it is excellent in scumming, the cleaning performance is insufficient. The present invention is characterized in that the inorganic fine particles 1 and the inorganic fine particles 2 are used together.

When the inorganic fine particles 1 and the inorganic fine particles 2 in the present invention are released from the toner, they aggregate due to electrostatic adhesive force to form aggregates. Since the surface of the inorganic fine particles 1 is weakly positively charged aluminum and the surface of the inorganic fine particles 2 is a strongly negatively charged fluorine compound, the liberated inorganic fine particles 1 and 2 are aggregated by electrostatic adhesion force. It is thought that the presence of these aggregates in the cleaning blade section exerts a dam effect and improves cleaning performance. Note that when the toner of the present invention is a two-component developer, strong stress is generally applied to the toner from the magnetic carrier, so that inorganic fine particles are likely to be released from the surface of the toner, and the above-mentioned cleaning performance improvement effect is further enhanced.

The toner of the present invention can improve poor cleaning caused by spherical toner. Even a spherical toner with an average circularity of 0.980 or more can provide a toner with excellent cleaning properties, and a toner with an average circularity of less than 0.980 can provide a toner with excellent cleaning properties over a long period of time. became.
From the viewpoint of improving cleaning performance over a long period of time, the average circularity of the toner of the present invention is preferably less than 0.980, more preferably less than 0.960, as described above. The average circularity is measured by the method described in the Examples below.

In the present invention, the total release rate of the inorganic fine particles 1 and the inorganic fine particles 2 from the toner is 10% or more and 70% or less, as described above.
When the total release rate exceeds 70%, the amount of released inorganic fine particles 1 and inorganic fine particles 2 increases significantly. Therefore, the number of aggregates formed by the electrostatic adhesive force between the inorganic fine particles 1 and the inorganic fine particles 2 increases. On the other hand, inorganic fine particles 1 and inorganic fine particles 2 that do not form aggregates slip through the cleaning blade, resulting in poor cleaning. In addition, the liberated excess inorganic fine particles 1 and inorganic fine particles 2 contaminate members such as the charging member, resulting in uneven resistance of the charging roller, for example, and image defects such as uneven image density.
When the total release rate is less than 10%, inorganic fine particles 1 and inorganic fine particles 2 are likely to be buried in toner base particles, and the amount of liberated inorganic fine particles 1 and inorganic fine particles 2 is significantly reduced. Therefore, the number of aggregates formed by the electrostatic adhesion force between the inorganic fine particles 1 and the inorganic fine particles 2 decreases, resulting in poor cleaning. Furthermore, the toner charging property deteriorates, resulting in image defects such as scumming.

The total release rate is more preferably 20% or more and less than 60%.
In addition, in order to adjust the total release rate to 10% or more and 70% or less, when mixing toner base particles and inorganic fine particles 1 and inorganic fine particles 2 with a mixer, for example, when using a Henschel mixer, the circumferential speed of the mixer and There are methods such as adjusting the mixing time as appropriate.

<Method for measuring total release rate>
(0) Weigh 5 g of Neugen (ET-165, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) into a 500 ml beaker. Add 300ml of distilled water and dissolve using ultrasound. Transfer to a 1000ml volumetric flask and make up to volume. (If it foams, leave it for a while.) Apply ultrasound to blend it, and prepare a 0.5% dispersion of Neugen (ET-165, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).
(1) Add 50 ml of Neugen (ET-165, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 0.5% dispersion and 3.75 g of toner to a 100 ml screw vial, and mix with a ball mill for 30 minutes.
(2) Next, using an ultrasonic homogenizer (product name: homogenizer, model VCX750, CV33, manufactured by SONICS & MATERIALS Co., Ltd.), set the dial to 50% output and apply ultrasonic energy for 1 minute under the following conditions. and disperse.
(Ultrasonic conditions)
・Vibration time: 60 seconds continuous ・Amplitude: 40W (50%)
・25℃
(3) The obtained dispersion was suction-filtered using filter paper (trade name: No. 5C, manufactured by Advantech Toyo Co., Ltd.), washed twice with ion-exchanged water again, filtered, and released inorganic fine particles 1 and inorganic fine particles 2. After removing, dry the toner.
(4) Inorganic fine particles 1 and inorganic fine particles 2 amounts (mass %) of the toner before and after dispersion of inorganic fine particles 1 and inorganic fine particles 2 were measured using a fluorescent X-ray analyzer (manufactured by Rigaku Co., Ltd., ZSX Primus IV) to measure the intensity using a calibration curve. (or the intensity difference before and after dispersion of inorganic fine particles 1 and inorganic fine particles 2) to determine the total release rate.
From the values of the amounts of inorganic fine particles 1 and inorganic fine particles 2 of the toner before and after dispersion measured by the methods (1) to (4) above, the total release rate (mass %) can be calculated using the following formula 1. can.
[Formula 1]
Release rate (%) = [(mass of inorganic fine particles 1 and inorganic fine particles 2 before dispersion - mass of residual inorganic fine particles 1 and inorganic fine particles 2 after dispersion) / mass of inorganic fine particles 1 and inorganic fine particles 2 before dispersion] x 100

<Measurement method of fluorescent X-rays>
Silica and aluminum in the toner can be determined by the fluorescent X-ray analysis.
In the present invention, the silica and aluminum contents (wt%) are determined using the following equipment and conditions. 3.00 g of toner is formed into pellets with a diameter of 3 mm and a thickness of 2 mm, and used as a measurement sample toner.
Next, the content of Si element and Al element in the pellet sample is measured by quantitative analysis using a fluorescent X-ray analyzer. At the time of measurement, correction is performed using silica and aluminum standardized samples (manufactured by Rigaku Co., Ltd.), and the content is calculated.
Measuring device: ZSX Primus IV manufactured by Rigaku Co., Ltd.
X-ray tube: Rh
X-ray tube voltage: 50kV
X-ray tube current: 10mA

Further, the ratio of the inorganic fine particles 1 to the inorganic fine particles 2 is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, as a mass ratio of the former to the latter. According to the above ratio, the number of aggregates formed by the electrostatic adhesion force between the inorganic fine particles 1 and the inorganic fine particles 2 becomes appropriate, and the cleaning performance can be further improved.

Further, in the present invention, the coverage of the inorganic fine particles 1 and the inorganic fine particles 2 is preferably 30% or more and 90% or less, and more preferably 50% or more and 80% or less.
<How to measure coverage>
If the ratio of inorganic fine particles 1 calculated by the qualitative determination method of inorganic fine particles 1 and 2 as described above is S, and the ratio of inorganic fine particles 2 is A, then the ratio of inorganic fine particles 1 to the toner (typically to the toner surface) is calculated by the following formula. , the coverage of the inorganic fine particles 1 and the inorganic fine particles 2 is determined.
Coverage rate (%)=S+A
When the coverage is 90% or less, the number of aggregates formed by the electrostatic adhesion between inorganic fine particles 1 and inorganic fine particles 2 becomes appropriate, improving cleaning performance and preventing contamination of members such as charging members. It is possible to prevent image defects such as uneven resistance of the charging roller and uneven density of the image.
Further, when the coverage is 30% or more, the number of aggregates formed by the electrostatic adhesion between the inorganic fine particles 1 and the inorganic fine particles 2 becomes appropriate, and the cleaning performance is further improved.

Further, in the present invention, the number average particle diameter of the inorganic fine particles 1 and/or the inorganic fine particles 2 is preferably 50 nm or more and 200 nm or less, and more preferably 70 nm or more and 180 nm or less.
By having a number average particle diameter of 50 nm or more, excessive embedding of inorganic fine particles on the toner particle surface is suppressed, and the number of aggregates formed by the electrostatic adhesion force between inorganic fine particles 1 and inorganic fine particles 2 becomes appropriate. Cleaning performance is further improved.
In addition, since the number average particle diameter is 200 nm or less, the number of inorganic fine particles present on the toner surface is appropriate, and the number of aggregates formed by the electrostatic adhesion between inorganic fine particles 1 and inorganic fine particles 2 is also appropriate, and cleaning Sexuality further improves. Further, it is possible to prevent contamination of members such as the charging member, and it is possible to prevent image defects such as uneven resistance of the charging roller and uneven density of the image. This may contaminate members such as the charging member, resulting in uneven resistance in the charging roller, and image defects such as uneven image density.
In the present invention, it is particularly preferable that the number average particle diameters of the inorganic fine particles 1 and the inorganic fine particles 2 are both 50 nm or more and 200 nm or less.
Note that the number average particle diameter is measured by the method described in the Examples below.

The inorganic fine particles 1 are silica treated with at least aluminum.
In the inorganic fine particles 1, the method for treating silica with aluminum is not particularly limited, but for example, there are methods such as adding an aqueous aluminum chloride solution to the silica, hydrolyzing it, and coating the surface of the silica with aluminum hydroxide.
The amount of aluminum deposited on silica is, for example, 5 to 95% by mass as Al ₂ O ₃ , preferably 10 to 75% by mass.

The inorganic fine particles 2 are aluminum compounds treated with a fluorine compound.
In the inorganic fine particles 2, the method of treating the aluminum compound with the fluorine compound is not particularly limited, but for example, there is a method of applying a fluorine-containing silane coupling agent to alumina. The fluorine-containing silane coupling agent is not particularly limited, but includes trifluoropropyltrimethoxysilane, triethoxytridecafluoro-n-octylsilane, triethoxyperfluorohexylsilane, triethoxyperfluorodecylsilane, and trimethoxyperfluorodecylsilane. , trimethoxyperfluorohexylsilane and the like.
The amount of the fluorine compound attached to the aluminum compound is, for example, 1 to 90% by mass, preferably 2 to 80% by mass.

Furthermore, in the present invention, the surfaces of the inorganic fine particles 1 and/or the inorganic fine particles 2 can be further coated with a fatty acid. According to this form, it is possible to obtain a toner external additive that has excellent fluidity, low volume resistivity, high hydrophobicity, and excellent various kinds of stability (stress resistance, environmental stability).
As the fatty acid, it is preferable to use a compound having a total number of carbon atoms of 8 to 26. Note that the hydrocarbon group may have an unsaturated bond, and may be linear or branched. Examples of such fatty acids include caprylic acid (octanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), and arachidic acid (eicosanoic acid). , behenic acid (docosanoic acid), lignoceric acid (tetracosanoic acid), myristoleic acid, sapienoic acid, oleic acid, erucic acid, isostearic acid, and the like. Among these, it is preferable to use a compound having 10 or more carbon atoms because it has an excellent hydrophobicity imparting effect. Specifically, compounds coated with lauric acid, stearic acid, oleic acid, isostearic acid, and behenic acid are used. It is preferable to do so.

The toner of the present invention further contains a binder resin, a colorant, and a release agent. These constituent components will be explained below.
<Toner raw materials>
In the toner, toner base particles containing at least a binder resin, a colorant, and a release agent may contain other components as necessary. Further, inorganic fine particles 1 and inorganic fine particles 2 are used as external additives in the toner base particles.

The toner of the present invention preferably uses a crystalline polyester resin and/or an amorphous polyester resin as the binder 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 properties that exhibit rapid viscosity near the fixing start temperature. By using the crystalline polyester resin C having such characteristics together with the amorphous polyester resin, it has good heat-resistant storage stability due to its crystallinity until just before the melting start temperature, and at the melting start temperature, the crystalline polyester resin C melts. It causes a sudden viscosity drop (sharp melt property), and as a result, it becomes compatible with the amorphous polyester resin B described later, and the viscosity of both drops sharply, resulting in fixing, so it has good heat-resistant storage stability and low-temperature fixing properties. It is possible to obtain a toner that has the following properties. In addition, good results are also shown regarding the mold release width (difference between the lower limit fixing temperature and the high temperature resistance offset generation temperature).
The crystalline polyester resin C is obtained using a polyhydric alcohol and a polyhydric carboxylic acid such as a polyhydric carboxylic acid, a polycarboxylic anhydride, a polycarboxylic acid ester, or a derivative thereof.
In addition, in the present invention, the crystalline polyester resin C refers to a polyhydric alcohol and a polyhydric carboxylic acid such as a polyhydric carboxylic acid, a polycarboxylic acid anhydride, a polyhydric carboxylic acid ester, or a derivative thereof. Modified polyester resins, such as the prepolymers described below, and resins obtained by crosslinking and/or elongating the prepolymers, 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, and includes, for example, 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 preferred. Group diols are more preferred. If the saturated aliphatic diol is a branched type, the crystallinity of the crystalline polyester resin C may decrease and the melting point may decrease. Moreover, when the carbon number of the saturated aliphatic diol exceeds 12, it becomes difficult to obtain a material for practical use. The number of carbon atoms is more preferably 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, Examples include 18-octadecanediol and 1,14-eicosandecanediol. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1, 10-decanediol and 1,12-dodecanediol are preferred.
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.

-Polyhydric carboxylic acid-
The polyvalent carboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include divalent carboxylic acids and trivalent or higher carboxylic acids.
Examples of the divalent carboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, superric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, Saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, Examples include aromatic dicarboxylic acids such as dibasic acids such as mesaconic acid; further examples include anhydrides thereof and lower (1 to 3 carbon atoms) alkyl esters thereof.
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 their anhydrides and and lower (1 to 3 carbon atoms) alkyl esters.
In addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, the polycarboxylic acid may include a dicarboxylic acid having a sulfonic acid group. Furthermore, in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, it may contain a dicarboxylic acid having a double bond.
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 may have a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a saturated aliphatic diol having 2 to 12 carbon atoms. preferable. By doing so, it is preferable in that it has high crystallinity and excellent sharp melting properties, so that it can exhibit excellent low-temperature fixing properties.

The melting point of the crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably 60°C or more and 80°C or less. If the melting point is less than 60°C, the crystalline polyester resin C tends to melt at low temperatures, and the heat-resistant storage stability of the toner may deteriorate; if it exceeds 80°C, the crystalline polyester resin C will melt due to heating during fixing. Melting of C may be insufficient, resulting in poor low-temperature fixability.

The molecular weight of the crystalline polyester resin C is not particularly limited and can be selected as appropriate depending on the purpose. From the viewpoint that if the amount is too large, the heat-resistant storage stability will deteriorate, so that the soluble content of orthodichlorobenzene in the crystalline polyester resin C has a weight average molecular weight (Mw) of 3,000 to 30,000 and a number average molecular weight ( Mn) is preferably 1,000 to 10,000, and Mw/Mn is preferably 1.0 to 10.
Furthermore, it is preferable that 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.

The acid value of the crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of affinity between the paper and the resin, it is necessary to is preferably 5 mgKOH/g or more, 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; however, in order to achieve the desired low-temperature fixability and good charging characteristics, 0 mgKOH/g to 50 mgKOH/g is preferable, and 5 mgKOH/g to 50 mgKOH/g is more preferable.

The molecular structure of the crystalline polyester resin C can be confirmed by X-ray diffraction, GC/MS, LC/MS, IR measurement, etc. in addition to NMR measurement using a solution or solid. A convenient method is to detect as crystalline polyester resin C a resin having an absorption based on δCH (out-of-plane bending vibration) of an olefin 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 it is preferably 3 parts by mass to 20 parts by mass, and 5 parts by mass, based on 100 parts by mass of the toner. Parts to 15 parts by mass are more preferred. If the content is less than 3 parts by mass, sharp melting by the crystalline polyester resin C may be insufficient, resulting in poor low-temperature fixing properties, and if it exceeds 20 parts by mass, heat-resistant storage stability may deteriorate. , and image fogging may occur more easily. When the content is within the more preferable range, it is advantageous in terms of both high image quality and low-temperature fixability.

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

<<Amorphous polyester resin A>>
The amorphous polyester resin A is not particularly limited and can be appropriately selected depending on the purpose, but preferably has a glass transition temperature (Tg) of -40°C or more and 20°C or less.
The amorphous polyester resin A is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably obtained by a reaction between a non-linear reactive precursor and a curing agent.
Further, it is preferable that the amorphous polyester resin A has at least one of a urethane bond and a urea bond, since it has better adhesion to a recording medium such as paper. Because the amorphous polyester resin A has either a urethane bond or a urea bond, the urethane bond or urea bond behaves like a pseudo-crosslinking point, and the rubbery properties of the amorphous polyester resin A become stronger. , the toner has better heat-resistant storage stability and high-temperature offset resistance.

-Nonlinear reactive precursor-
The non-linear reactive precursor is not particularly limited as long as it is a polyester resin (hereinafter sometimes referred to as "prepolymer") having a group capable of reacting with the curing agent, and may be used depending on the purpose. can be selected as appropriate.
Examples of the group capable of reacting with the curing agent in the prepolymer include a group capable of reacting with an active hydrogen group. Examples of the group capable of reacting with the active hydrogen group include an isocyanate group, an epoxy group, a carboxylic acid group, and an acid chloride group. Among these, isocyanate groups are preferred since they can introduce urethane bonds or urea bonds into the amorphous polyester resin.
The prepolymer is non-linear. The term "non-linear" means having a branched structure provided by at least one of a trihydric or higher alcohol and a trivalent or higher carboxylic acid.
Moreover, as the prepolymer, a polyester resin containing an isocyanate group is preferable.

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

---Diol---
The diol is not particularly limited and can be appropriately selected depending on the purpose, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl - Aliphatic diols such as 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol; diethylene glycol, triethylene glycol, dipropylene glycol , diols having oxyalkylene groups such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols such as ethylene oxide, propylene oxide, Alkylene oxides of bisphenols such as those with alkylene oxides such as butylene oxide added; bisphenols such as bisphenol A, bisphenol F, and bisphenol S; alkylene oxides of bisphenols such as those with alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide added to bisphenols. Examples include additives. Among these, aliphatic diols having 4 or more and 12 or less 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 include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Further, anhydrides of these may be used, lower alkyl esters (having 1 to 3 carbon atoms), or halides may be used.

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

---Trivalent or higher alcohol ---
The trihydric or higher alcohol is not particularly limited and can be selected as appropriate depending on the purpose, such as trivalent or higher aliphatic alcohols, trivalent or higher polyphenols, trivalent or higher polyphenols alkylene. Examples include oxide adducts.
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 novolak.
Examples of the alkylene oxide adducts of trivalent or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc. 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 trivalent or higher aliphatic alcohol as a constituent component, it has a branched structure in the molecular skeleton and the molecular chains form a three-dimensional network structure, so it deforms at low temperatures. However, it has a rubbery property of not flowing. Therefore, it is possible to maintain the heat-resistant storage stability and high-temperature offset resistance of the toner.
In the amorphous polyester resin A, trivalent or higher carboxylic acid, epoxy, etc. can be used as a crosslinking component, but in the case of carboxylic acid, it is often an aromatic compound and the ester bond in the crosslinking part Due to the high density, a fixed image created by heat-fixing the toner may not have sufficient gloss. When using a crosslinking agent such as epoxy, a crosslinking reaction must be carried out after the polymerization of polyester, making it difficult to control the distance between crosslinking points, making it impossible to obtain the desired viscoelasticity, and It reacts with oligomers during formation and tends to form areas with high crosslinking density, which may cause unevenness in the fixed image, resulting in poor gloss and image density.

--- Trivalent or higher carboxylic acid ---
The carboxylic acid having a valence of 3 or more is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include aromatic carboxylic acids having a valence of 3 or more. Further, anhydrides of these may be used, lower alkyl esters (having 1 to 3 carbon atoms), or halides 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 can be appropriately selected depending on the purpose, and includes, for example, diisocyanate, trivalent or higher valent isocyanate, and the like.
Examples of the diisocyanates include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and those blocked with phenol derivatives, oximes, caprolactam, and the like.
The aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene. Examples include 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, and examples include isophorone diisocyanate and cyclohexylmethane diisocyanate.
The aromatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose, for example, tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4'-diisocyanate. Examples include diphenyl, 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, and examples thereof include α, α, α', α'-tetramethylxylylene diisocyanate.
The isocyanurates are not particularly limited and can be appropriately selected depending on the purpose, and include, for example, tris(isocyanatoalkyl)isocyanurate, tris(isocyanatocycloalkyl)isocyanurate, and the like.
These polyisocyanates may be used alone or in combination of two or more.

-Hardening agent-
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. Examples include active hydrogen group-containing compounds.

--Compound containing active hydrogen group--
The active hydrogen group in the active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the purpose, such as hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), amino group, carboxyl group, mercapto group. Examples include. 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 since they can form urea bonds.

The amines are not particularly limited and can be selected as appropriate depending on the purpose, such as diamines, trivalent or higher amines, amino alcohols, aminomercaptans, amino acids, and those with blocked amino groups of these. Can be mentioned. These may be used alone or in combination of two or more.
Among these, diamines and mixtures of diamines and 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 includes, for example, aromatic diamine, alicyclic diamine, aliphatic diamine, and the like. The aromatic diamine is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include phenylene diamine, 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, and isophorone diamine. It will be done. The aliphatic diamine is not particularly limited and can be appropriately selected depending on the purpose, such as ethylene diamine, tetramethylene diamine, hexamethylene diamine, and the like.

The amine having a valence of 3 or more is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include diethylenetriamine, triethylenetetramine, and the like.

The amino alcohol is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include ethanolamine, hydroxyethylaniline, and the like.

The aminomercaptan is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include aminoethylmercaptan, aminopropylmercaptan, and the like.

The amino acid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include aminopropionic acid, aminocaproic acid, and the like.

The amino group blocked is not particularly limited and can be appropriately selected depending on the purpose, for example, it can be obtained by blocking the amino group with ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Examples include ketimine compounds and oxazoline compounds.

In order to lower the Tg of the amorphous polyester resin A and easily impart the property of deformation at low temperatures, the amorphous polyester resin A contains a diol component as a constituent component, and the diol component has a carbon number It is preferable to contain 50% by mass or more of aliphatic diols of 4 or more and 12 or less.
In addition, in order to lower the Tg of the amorphous polyester resin A and easily impart the property of deforming at low temperatures, the amorphous polyester resin A contains a fat having 4 to 12 carbon atoms in the total alcohol component. It is preferable to contain the group diol in an amount of 50% by mass or more.
In order to lower the Tg of the amorphous polyester resin A and easily impart the property of deforming at low temperatures, the amorphous polyester resin A contains a dicarboxylic acid component as a constituent component, and the dicarboxylic acid component is It is preferable to contain 50% by mass or more of aliphatic dicarboxylic acid having 4 or more and 12 or less carbon atoms.

The weight average molecular weight of the amorphous polyester resin A is not particularly limited and can be appropriately selected depending on the purpose; The following is preferable, 50,000 or more and 300,000 or less is more preferable, and 100,000 or more and 200,000 or less is particularly preferable. When the weight average molecular weight is less than 20,000, the toner tends to flow at low temperatures and may have poor heat-resistant storage stability. In addition, the viscosity during melting may be lowered, and high-temperature offset properties may be lowered.

The molecular structure of the amorphous polyester resin A can be confirmed by X-ray diffraction, GC/MS, LC/MS, IR measurement, etc. in addition to NMR measurement using a solution or solid. A convenient method is to detect amorphous polyester resin that does not have absorption based on δCH (out-of-plane bending vibration) of olefin 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 from 5 parts by mass to 25 parts by mass, and 10 parts by mass, based on 100 parts by mass of the toner. Parts by weight to 20 parts by weight are more preferable. If the content is less than 5 parts by mass, low-temperature fixing properties and high-temperature offset resistance may deteriorate; if it exceeds 25 parts by mass, heat-resistant storage properties may deteriorate and the gloss of the image obtained after fixing may deteriorate. The level may decrease. When the content is within the more preferable range, it is advantageous in that low-temperature fixability, high-temperature offset resistance, and heat-resistant storage stability are all excellent.

<<<Amorphous polyester resin B>>>
The amorphous polyester resin B preferably has a glass transition temperature (Tg) of 40°C or more and 80°C or less.
The amorphous polyester resin B is preferably a linear polyester resin.
The amorphous polyester resin B is preferably an unmodified polyester resin. The unmodified polyester resin is a polyester resin obtained using a polyhydric alcohol and a polyhydric carboxylic acid such as a polyhydric carboxylic acid, a polycarboxylic acid anhydride, a polyhydric carboxylic acid ester, or a derivative thereof. , a polyester resin that has not been modified with isocyanate compounds or the like.
It is preferable that the amorphous polyester resin B does not have urethane bonds or urea bonds.
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. By doing so, it is advantageous in terms of heat-resistant storage stability.

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

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

Further, 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 its 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, trimethylolpropane, and the like.

The molecular weight of the amorphous polyester resin B is not particularly limited and can be selected appropriately depending on the purpose. However, if the molecular weight is too low, the toner's heat-resistant storage stability and stress resistance such as stirring in the developing machine may be affected. Durability may be poor, and if the molecular weight is too high, the viscoelasticity when melting the toner may be high and low-temperature fixing properties may be poor. ) 3,000 to 10,000. Further, the number average molecular weight (Mn) is preferably 1,000 to 4,000. Further, Mw/Mn is preferably 1.0 to 4.0.
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, but is preferably 1 mgKOH/g to 50 mgKOH/g, 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 furthermore, when fixing to paper, the affinity between the paper and the toner improves, and low-temperature fixing properties can be improved. . If the acid value exceeds 50 mgKOH/g, charging stability, particularly charging stability against environmental changes, may decrease.

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

The glass transition temperature (Tg) of the amorphous polyester resin B is preferably 40°C or more and 80°C or less, more preferably 50°C or more and 70°C or less. 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 undergoes sufficient deformation due to heating and pressure during fixing, resulting in good low-temperature fixability.

The molecular structure of the amorphous polyester resin B can be confirmed by X-ray diffraction, GC/MS, LC/MS, IR measurement, etc. in addition to NMR measurement using a solution or solid. A convenient method is to detect amorphous polyester resin that does not have absorption based on δCH (out-of-plane bending vibration) of olefin 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 60 parts by mass based on 100 parts by mass of the toner. Parts by weight to 80 parts by weight are more preferred. If the content is less than 50 parts by mass, the dispersibility of pigments and release agents in the toner may deteriorate, causing image fogging and disorder. If it exceeds 90 parts by mass, crystallinity Since the contents of polyester resin C and amorphous polyester resin A are reduced, low-temperature fixability may be poor. When the content is within the more preferable range, it is advantageous in terms of both high image quality and low-temperature fixability.

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 together. In order to achieve both low-temperature fixability and high-temperature, high-humidity storage stability, the amorphous polyester resin A preferably has a very low glass transition temperature. Since the glass transition temperature is very low, it has the property of being deformed at low temperatures, deforming in response to heat and pressure during fixing, and having the property of easily adhering to recording media such as paper at lower temperatures. Further, in one embodiment of the amorphous polyester resin A, since the reactive precursor is non-linear, it has a branched structure in the molecular skeleton, and the molecular chains form a three-dimensional network structure. It has rubber-like properties that deforms at low temperatures but does not flow. Therefore, it is possible to maintain the heat-resistant storage stability and high-temperature offset resistance of the toner.

Note that when the amorphous polyester resin A has a urethane bond or urea bond with high cohesive energy, it has better adhesion to a recording medium such as paper. Further, since the urethane bond or urea bond behaves like a pseudo-crosslinking point, the rubbery properties become stronger, and as a result, the toner has better heat-resistant storage stability and high-temperature offset resistance.

That is, in the toner of the present invention, when the amorphous polyester resin A, the crystalline polyester resin C, and, if necessary, other amorphous polyester resin B are used in combination, the toner has excellent low-temperature fixing properties. Become something. Furthermore, by using amorphous polyester resin A that 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. By lowering the glass transition temperature of the toner, it has excellent low-temperature fixing properties.

<Colorant>
The coloring agent is not particularly limited and can be appropriately selected depending on the purpose, such as carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, Yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Red Red Red, Lead Red, Lead Vermilion, Cadmium Red, Cadmium Mercury Red, Antimony Vermilion, Permanent Red 4R, Para Red, Phise Red, Parachlororthonitroaniline Red, Lysol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Lysol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazole Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkali Blue Lake , Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Deep 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, oxidation Examples include titanium, zinc white, and lithobon.
The content of the colorant is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably 1 part by mass to 15 parts by mass, and 3 parts by mass to 10 parts by mass, based on 100 parts by mass of the toner. Parts by mass are more preferred.

The coloring agent can also be used as a masterbatch composited with a resin. Examples of resins to be used in the production of the masterbatch or kneaded together with the masterbatch include, in addition to the amorphous polyester resin, polymers of styrene or its substituted products such as polystyrene, polyp-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, styrene-α-chloromethacrylate Methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer Styrenic copolymers such as styrene-maleic ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide , polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used alone or in combination of two or more.

The masterbatch can be obtained by mixing a masterbatch resin and a colorant under high shear force and kneading the mixture. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. In addition, there is also the so-called flushing method, in which an aqueous paste containing colorant water is mixed and kneaded with a resin and an organic solvent, the colorant is transferred to the resin side, and the water and organic solvent components are removed. Since the cake can be used as it is, there is no need to dry it, so it is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

<Release agent>
The mold release agent is not particularly limited and can be appropriately selected from known ones.
Examples of waxes and mold release agents for waxes include vegetable waxes such as carnauba wax, cotton wax, and wood wax and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; and paraffin. Natural waxes such as petroleum waxes such as , 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.
Furthermore, fatty acid amide compounds such as 12-hydroxystearamide, stearamide, phthalic anhydride, and chlorinated hydrocarbons; poly-n-stearyl methacrylate, poly-n, which are low molecular weight crystalline polymer resins; - A homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.); a crystalline polymer having a long alkyl group in the side chain, etc. may also be used. good.
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 mold 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. When the melting point is less than 60°C, the mold release agent tends to melt at low temperatures, and the heat-resistant storage stability may be poor. If the melting point exceeds 80° C., even if the resin is melted and in the fixing temperature range, the release agent will not melt sufficiently and fixing offset may occur, resulting in image defects.

The content of the release agent is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably 2 parts by mass to 10 parts by mass, and 3 parts by mass to 10 parts by mass, based on 100 parts by mass of the toner. 8 parts by mass is more preferred. If the content is less than 2 parts by mass, high-temperature offset resistance and low-temperature fixing properties during fixing may be poor; if it exceeds 10 parts by mass, heat-resistant storage stability may be reduced and image fogging may occur. etc. may be more likely to occur. When the content is within the more preferable range, it is advantageous in terms of improving image quality and fixing stability.

<<Other ingredients>>
Examples of the other components contained in the toner of the present invention include a charge control agent, a fluidity improver, a cleaning performance improver, a magnetic material, and other external additives.

<<<Charge control agent>>>
The charge control agent is not particularly limited and can be appropriately selected depending on the purpose, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, Alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus elements or compounds, tungsten elements or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives, etc. can be mentioned.

Specifically, Bontron 03 is a nigrosine-based dye, Bontron P-51 is a quaternary ammonium salt, Bontron S-34 is a metal-containing azo dye, E-82 is an oxynaphthoic acid-based metal complex, and E- is a salicylic acid-based metal complex. 84, phenolic condensate E-89 (manufactured by Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), LRA- 901, 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. can be mentioned.

The content of the charge control agent is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably 0.1 parts by mass to 10 parts by mass, and 0.1 parts by mass to 10 parts by mass, based on 100 parts by mass of the toner. More preferably 2 parts by mass to 5 parts by mass. If the content exceeds 10 parts by mass, the chargeability of the toner will be too large, reducing the effect of the main charge control agent, increasing the electrostatic attraction force with the developing roller, and reducing the fluidity of the developer. , which may lead to a decrease in image density. These charge control agents can be melted and kneaded together with the masterbatch 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 toner particles are prepared. It's okay.

<<<Flowability improver>>>
The fluidity improver is not particularly limited as long as it can be surface-treated to increase hydrophobicity and prevent deterioration of fluidity and charging characteristics even under high humidity, and can be selected as appropriate depending on the purpose. For example, silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, etc. It will be done. It is particularly preferable that the silica and titanium oxide are surface-treated with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

<<<Cleanability improver>>>
The cleaning performance improving agent is not particularly limited as long as it is added to the toner in order to remove the developer remaining on the photoreceptor or primary transfer medium after transfer, and may be selected as appropriate depending on the purpose. For example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. can be mentioned. The polymer fine particles preferably have a relatively narrow particle size distribution, and preferably have a volume average particle size of 0.01 μm to 1 μm.

<<<Magnetic material>>>
The magnetic material is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include iron powder, magnetite, ferrite, and the like. Among these, white ones are preferred in terms of color tone.

<<<Other external additives>>>
The toner of the present invention may also contain other external additives other than the inorganic fine particles 1 and the inorganic fine particles 2.

Note that the total proportion of inorganic fine particles 1 and inorganic fine particles 2 to the entire external additive (including the above-mentioned inorganic fine particles 1 and 2) in the toner of the present invention is preferably 40 to 100% by mass, and 60 to 60% by mass. 100% by mass is more preferred.

The other external additives include, but are not particularly limited to, fine particles other than the inorganic fine particles 1 and the inorganic fine particles 2, and can be appropriately selected depending on the purpose.
Examples of the shape of the other fine particles include a spherical shape, a needle shape, and a non-spherical shape obtained by combining several spherical particles.
Examples of the other fine particles 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.), Examples include fluoropolymers. Among these, hydrophobized inorganic fine particles are preferred.
Hydrophobized silica particles, hydrophobized titania particles, and hydrophobized alumina particles are, for example, hydrophilic particles in a silane cup such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. It can be obtained by treatment with a ring agent. Also suitable are silicone oil-treated oxide fine particles obtained by processing silicone oil into inorganic fine particles by applying heat if necessary.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorphenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino Examples include modified silicone oil, epoxy-modified silicone oil, epoxy/polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, methacrylic-modified silicone oil, α-methylstyrene-modified silicone oil, and the like.
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, Examples include 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.

<Toner manufacturing method>
The method for producing the toner is not particularly limited and can be appropriately selected depending on the purpose, but the toner base particles and the external additives (including the inorganic fine particles 1 and the inorganic fine particles 2; the same applies hereinafter) It is preferable to include a mixing step of mixing.
The toner base particles contain the amorphous polyester resin A, the amorphous polyester resin B, and the crystalline polyester resin C, and further contain an oil phase containing the release agent, the colorant, etc. in an aqueous medium. It is preferable that the particles be granulated by dispersing them.

An example of a method for manufacturing such toner base particles is a known dissolution/suspension method. As an example of the method for producing the toner base particles, a method of forming toner base particles while stretching the amorphous polyester resin A through a stretching 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 material is prepared, the toner material is emulsified or dispersed, and the organic solvent is removed. Thereafter, the toner is obtained by mixing the obtained toner base particles and 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, and includes, for example, water, water-miscible solvents, and mixtures thereof. These may be used alone or in combination of two or more. Among these, water is preferred.
The water-miscible solvent is not particularly limited and can be appropriately selected depending on the purpose, and includes, for example, alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. The alcohol is not particularly limited and can be appropriately selected depending on the purpose, and includes, for example, methanol, isopropanol, ethylene glycol, and the like. The lower ketones are not particularly limited and can be appropriately selected depending on the purpose, and include, for example, acetone, methyl ethyl ketone, and the like.

<<Preparation of oil phase>>
The preparation of the oil phase containing the toner material includes at least the non-linear reactive precursor, the amorphous polyester resin B, and the crystalline polyester resin C, and if necessary, the curing. This can be carried out by dissolving or dispersing a toner material containing an agent, the releasing agent, the coloring agent, etc. in an organic solvent.
The organic solvent is not particularly limited and can be appropriately selected depending on the purpose, but organic solvents with a boiling point of less than 150° C. are preferred because they can be easily removed.
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. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1 , 1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like. 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 and the like are preferred, and ethyl acetate is more preferred.

<<Emulsification or dispersion>>
The toner material can be emulsified or dispersed by dispersing an oil phase containing the toner material in the aqueous medium. Then, when the toner material is emulsified or dispersed, the amorphous polyester resin A is produced by subjecting the curing agent and the non-linear reactive precursor to an elongation reaction and/or a crosslinking reaction.

The amorphous polyester resin A can be produced, for example, by the following methods (1) to (3).
(1) Emulsifying or dispersing an oil phase containing the non-linear reactive precursor and the curing agent in an aqueous medium, and combining the curing agent and the non-linear reactive precursor in the aqueous medium. A method of producing the amorphous polyester resin A by subjecting it to an elongation reaction and/or a crosslinking reaction.
(2) The 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 mixed in the aqueous medium. A method of producing the amorphous polyester resin A by elongating and/or crosslinking the polyester resin A.
(3) After emulsifying or dispersing the oil phase containing the non-linear reactive precursor in an aqueous medium, the curing agent is added to the aqueous medium, and the curing agent is introduced from the particle interface in the aqueous medium. A method of producing the amorphous polyester resin A by subjecting the non-linear reactive precursor to an elongation reaction and/or a crosslinking reaction.

Note that when the curing agent and the non-linear reactive precursor are caused to undergo 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 generated toner, It is also possible to provide a concentration gradient of the amorphous polyester resin A in the toner.

The reaction conditions (reaction time, reaction temperature) for producing the amorphous polyester resin A are not particularly limited, and depend on the combination of the curing agent and the non-linear reactive precursor. It can be selected as appropriate.

The reaction time is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 minutes to 40 hours, 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, more preferably 40°C to 98°C.

The method for stably forming the dispersion containing the non-linear reactive precursor in the aqueous medium is not particularly limited and can be appropriately selected depending on the purpose. Examples include a method in which an oil phase prepared by dissolving or dispersing toner material in a solvent is added and the mixture is dispersed by shearing force.

The dispersing machine for the dispersion is not particularly limited and can be appropriately selected depending on the purpose, for example, a low-speed shear type disperser, a high-speed shear type disperser, a friction type disperser, a high-pressure jet type disperser. , ultrasonic disperser, etc.
Among these, a high-speed shearing type dispersion machine is preferable since the particle size of the dispersion (oil droplets) can be controlled to 2 μm to 20 μm.

When using the high-speed shear type disperser, conditions such as rotation speed, dispersion time, and dispersion 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, 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 minute to 5 minutes.
The dispersion temperature is not particularly limited and can be appropriately selected depending on the purpose, but under pressure, it is preferably 0°C to 150°C, more preferably 40°C to 98°C. In general, the higher the dispersion temperature, the easier the dispersion.

The amount of the aqueous medium to be used when emulsifying or dispersing the toner material is not particularly limited and can be appropriately selected depending on the purpose, but it is from 50 parts by mass to 2 parts by mass based on 100 parts by mass of the toner material. ,000 parts by weight is preferable, and 100 parts by weight to 1,000 parts by weight is more preferable.
If the amount of the aqueous medium used is less than 50 parts by mass, the dispersion state of the toner material may deteriorate and toner base particles with a predetermined particle size may not be obtained; This can lead to higher production costs.

When emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets, shaping them into 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 include surfactants, poorly water-soluble inorganic compound dispersants, and polymeric protective colloids. 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. are used. be able to.

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

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

<<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 selected as appropriate depending on the purpose. Examples include a method of evaporating the organic solvent, and a method of spraying a dispersion liquid into a dry atmosphere to remove the organic solvent in the oil droplets.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, and further classified. The classification may be performed by removing particulates in a liquid using a cyclone, a decanter, centrifugation, etc., or the classification may be performed after drying.

<<Mixing process>>
The obtained toner base particles are mixed with the external additive. A general powder mixer is used to mix the additives, but it is preferably equipped with a jacket or the like so that the internal temperature can be adjusted. In addition, in order to change the history of the load applied to the additive, the additive may be added midway or gradually. In this case, the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. Alternatively, a strong load may be applied first and then a relatively weak load, or vice versa. Examples of mixing equipment that can be used include a V-type mixer, rocking mixer, Loedige mixer, Nauta mixer, Henschel mixer, Nobilta, and the like. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and agglomerated particles.

<Developer>
The developer of the present invention contains at least the above-mentioned toner and, if necessary, other appropriately selected components such as a carrier.
Therefore, it is possible to stably form a high-quality image with excellent transferability, charging property, etc. Note that the developer may be a one-component developer or a two-component developer, but when used in high-speed printers that are compatible with recent improvements in information processing speed, the lifespan may be limited. A two-component developer is preferred because of its improved performance.
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% by mass to 98% by mass, and 93% by mass to 97% by mass. More preferred.

<Career>
The carrier is not particularly limited and can be appropriately selected depending on the purpose, but preferably has a core material and a resin layer covering the core material.
＜＜Core material＞＞
The material of the core material is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include manganese-strontium-based materials, manganese-magnesium-based materials, etc. of 50 emu/g to 90 emu/g. . Further, in order to ensure image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu/g or more and magnetite of 75 emu/g to 120 emu/g. In addition, it is recommended to use a low magnetization material such as a copper-zinc type material with a strength of 30 emu/g to 80 emu/g because it can reduce the impact of the developer in a spiked state on the photoconductor and is advantageous for improving image quality. is preferred.
These may be used alone or in combination of two or more.

<<Resin layer>>
The resin layer may contain a resin and other components as necessary.
As the resin used for the resin layer, known materials that can provide the necessary chargeability can be used. Specifically, it is preferable to use a silicone resin, an acrylic resin, or a combination thereof. Moreover, it is preferable that the composition for forming the resin layer contains a silane coupling agent.
The average thickness of the resin layer is preferably 0.05 to 0.50 μm.

(toner storage unit)
The toner storage unit in the present invention refers to a unit that has a function of storing toner and stores toner therein. Here, examples of the toner storage unit include a toner storage container, a developing device, a process cartridge, and the like.
The toner storage container refers to a container that stores toner.
A developing device has means for storing and developing toner.
A process cartridge is a cartridge that integrates at least an image carrier and a developing means, stores toner, and is removably attached to an image forming apparatus. The process cartridge may further include at least one selected from charging means, exposure means, and cleaning means.
The toner storage unit according to the present invention stores the toner according to the present invention.
By attaching the toner storage unit of the present invention to an image forming apparatus and forming an image, the image formation is performed using the toner of the present invention, so that it has excellent charging stability and excellent cleaning performance.

<Process cartridge>
A process cartridge according to the present invention includes an electrostatic latent image carrier that carries an electrostatic latent image, and a visible image is formed by developing the electrostatic latent image carried on the electrostatic latent image carrier using toner. The image forming apparatus has at least a developing means, and further includes other means appropriately selected as necessary, such as a charging means, an exposure means, a developing means, a transfer means, a cleaning means, and a static eliminating means.
The developing means includes a developer container that stores the toner or developer of the present invention, and a developer carrier that supports and transports the toner or developer contained in the developer container. , and may further include a layer thickness regulating member for regulating the thickness of the supported toner layer.
The process cartridge according to the present invention can be removably installed in various electrophotographic apparatuses, facsimiles, and printers, and is preferably removably installed in an image forming apparatus of the invention described later.

(Image forming method and image forming apparatus)
The image forming apparatus of the present invention includes an electrostatic latent image carrier, an electrostatic latent image forming means, and a developing means, and further includes a static eliminating means, a cleaning means, a recycling means, a control means, etc. as necessary. have other means.
The image forming method according to the present invention includes an electrostatic latent image forming step and a developing step, and further includes other steps such as a static elimination step, a cleaning step, a recycling step, a control step, etc., as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be suitably performed by the electrostatic latent image forming means, and the developing step can be suitably performed by the developing means. The above-mentioned other steps can be suitably carried out by the above-mentioned other means.

-Electrostatic latent image forming process and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image carrier (hereinafter sometimes referred to as "electrophotographic photoreceptor" or "photoreceptor") is not particularly limited in its material, shape, structure, size, etc., and may be selected from among known ones. Although it can be selected as appropriate, the shape is preferably a drum shape, and the material includes, for example, an inorganic photoreceptor such as amorphous silicon or selenium, or an organic photoreceptor (OPC) such as polysilane or phthalopolymethine. can be mentioned. Among these, organic photoreceptors (OPCs) are preferable because they provide higher definition images.

Formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then imagewise exposing it to light, and may be performed by an electrostatic latent image forming means. Can be done.

The electrostatic latent image forming means includes, for example, a charging means (charger) that uniformly charges the surface of the electrostatic latent image carrier, and an exposure device that imagewise exposes the surface of the electrostatic latent image carrier. means (exposure device).
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and can be appropriately selected depending on the purpose, for example, a contact charger that is known per se and equipped with a conductive or semiconductive roll, brush, film, rubber blade, etc. , corotron, scorotron, and other non-contact chargers that utilize corona discharge.
The charger is preferably one that is disposed in contact with or in a non-contact state with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying DC and AC voltages in a superimposed manner.
Further, the charger is a charging roller disposed close to the electrostatic latent image carrier through a gap tape in a non-contact manner, and the electrostatic latent image is transferred by superimposing direct current and alternating current voltages to the charging roller. One that charges the body surface is preferable.
The exposure can be performed, for example, by imagewise exposing the surface of the electrostatic latent image carrier using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger in the form of an image to be formed, and may be selected as appropriate depending on the purpose. Examples of exposure devices include copying optical systems, rod lens array systems, laser optical systems, liquid crystal shutter optical systems, and the like.
In the present invention, a back-light method may be adopted in which exposure is performed imagewise from the back side of the electrostatic latent image carrier.

-Developing process and developing means-
The developing step is a step of developing the electrostatic latent image using the toner to form a visible image.
Formation of the visible image can be performed, for example, by developing the electrostatic latent image using the toner, and can be performed by the developing means.
The developing means preferably includes at least a developing device that accommodates the toner and can apply the toner to the electrostatic latent image in a contact or non-contact manner, and the developing device includes a container containing toner. etc. are more preferable.
The developing device may be a single-color developing device or a multi-color developing device, and includes, for example, a stirrer that frictionally stirs the toner to charge it and a rotatable magnetic roller. Preferred examples include:

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image to a recording medium, using an intermediate transfer body, and after first transferring the visible image onto the intermediate transfer body, transferring the visible image onto the recording medium. It is preferable to use two or more color toners, preferably full-color toners, and to transfer a visible image onto an intermediate transfer body to form a composite transfer image. A more preferred embodiment includes a second transfer step of transferring the transferred image onto a recording medium.
The transfer means (the first transfer means, the second transfer means) transfers the visible image formed on the electrostatic latent image carrier (photoreceptor) to the recording medium by peeling and charging it. It is preferable to have at least a container. The number of the transfer means may be one, or two or more.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
Note that the recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

-Fixing process and fixing means-
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the visible image is transferred to the recording medium for each color developer, or may be performed for each color developer. However, this may be done simultaneously in a laminated state.
The fixing device is not particularly limited and can be appropriately selected depending on the purpose, but known heating and pressing means are suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt, and the like.

The static elimination step is a process of applying a static elimination bias to the electrostatic latent image carrier to eliminate static electricity, and can be suitably performed by a static elimination means.
The static eliminating means is not particularly limited as long as it can apply a static eliminating bias to the electrostatic latent image carrier, and can be appropriately selected from known static eliminators, such as a static eliminating lamp, etc. Preferred examples include:

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier, and can be suitably carried out by a cleaning means.
The cleaning means is not particularly limited as long as it can remove the toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners, such as a magnetic brush cleaner. Preferred examples include electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step in which the toner removed in the cleaning step is recycled by the developing means, and can be suitably carried out by a recycling means. The recycling means is not particularly limited, and includes known conveyance means and the like.

The control step is a step of controlling each of the steps, and each step can be suitably performed by a control means.
The control means is not particularly limited as long as it can control the movement of each of the means, and can be appropriately selected depending on the purpose, and examples thereof include equipment such as a sequencer and a computer.

FIG. 1 is a schematic explanatory diagram showing an example of an image forming apparatus of the present invention.
The image forming apparatus 100A includes a photosensitive drum 10, a charging roller 20, an exposure device, a developing device 40, an intermediate transfer belt 50, a cleaning device 60 having a cleaning blade, and a static elimination lamp 70.
The intermediate transfer belt 50 is an endless belt stretched between three rollers 51 disposed inside, and can move in the direction of the arrow in FIG. Some of the three rollers 51 also function as transfer bias rollers capable of applying a transfer bias (primary transfer bias) to the intermediate transfer belt 50. Further, a cleaning device 90 having a cleaning blade is arranged near the intermediate transfer belt 50. Further, a transfer roller 80 to which a transfer bias (secondary transfer bias) for transferring the toner image onto the transfer paper 95 can be applied is arranged facing the intermediate transfer belt 50 .
Further, a corona charging device 58 for applying an electric charge to the toner image transferred to the intermediate transfer belt 50 is installed around the intermediate transfer belt 50 in a direction opposite to the photoreceptor drum 10 with respect to the rotational direction of the intermediate transfer belt 50. It is arranged between the contact portion of the intermediate transfer belt 50 and the contact portion between the intermediate transfer belt 50 and the transfer paper 95 .

The developing device 40 includes a developing belt 41, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C, which are provided around the developing belt 41. Note that the developing unit 45 for each color includes a developer storage section 42, a developer supply roller 43, and a developing roller (developer carrier) 44. Further, the developing belt 41 is an endless belt stretched between a plurality of belt rollers, and can move in the direction of the arrow in FIG. Further, a portion of the developing belt 41 is in contact with the photosensitive drum 10.

Next, a method of forming an image using the image forming apparatus 100A will be described. First, the surface of the photoreceptor drum 10 is uniformly charged using the charging roller 20, and then the photoreceptor drum 10 is exposed to exposure light L using an exposure device (not shown) to form an electrostatic latent image. form. Next, the electrostatic latent image formed on the photoreceptor drum 10 is developed with toner supplied from the developing device 40 to form a toner image. Furthermore, after the toner image formed on the photosensitive drum 10 is transferred (primary transfer) onto the intermediate transfer belt 50 by the transfer bias applied from the roller 51, the toner image is transferred by the transfer bias applied from the transfer roller 80. , are transferred onto the transfer paper 95 (secondary transfer). On the other hand, after the toner remaining on the surface of the photosensitive drum 10, on which the toner image has been transferred to the intermediate transfer belt 50, is removed by the cleaning device 60, the charge is removed by the charge removal lamp 70.

FIG. 2 shows a second example of the image forming apparatus used in the present invention. In the image forming apparatus 100B, a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C are arranged directly opposite to each other around the photoreceptor drum 10 without providing a developing belt 41. Other than that, it has the same configuration as the image forming apparatus 100A.

FIG. 3 shows a third example of the image forming apparatus used in the present invention. The image forming apparatus 100C is a tandem color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

The intermediate transfer belt 50 provided in the center of the copying apparatus main body 150 is an endless belt stretched around three rollers 14, 15, and 16, and can move in the direction of the arrow in FIG. . A cleaning device 17 having a cleaning blade for removing toner remaining on the intermediate transfer belt 50 on which the toner image has been transferred to the recording paper is arranged near the roller 15. Yellow, cyan, magenta, and black image forming units 120Y, 120C, 120M, and 120K are juxtaposed along the conveying direction and facing the intermediate transfer belt 50 stretched by rollers 14 and 15.

Further, an exposure device 21 is arranged near the image forming unit 120. Furthermore, a secondary transfer belt 24 is arranged on the side of the intermediate transfer belt 50 opposite to the side on which the image forming unit 120 is arranged. The secondary transfer belt 24 is an endless belt stretched between a pair of rollers 23, and the recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer belt 50 are transported between the rollers 16 and 23. can be contacted.

Further, in the vicinity of the secondary transfer belt 24, a fixing device 25 includes a fixing belt 26, which is an endless belt stretched between a pair of rollers, and a pressure roller 27 placed under pressure against the fixing belt 26. is located. Note that a sheet reversing device 28 is arranged near the secondary transfer belt 24 and the fixing device 25 for reversing the recording paper when forming images on both sides of the recording paper.

Next, a method for forming a full-color image using the image forming apparatus 100C will be described. First, set a color original on the document table 130 of the automatic document feeder (ADF) 400, or open the automatic document feeder 400 and set the color original on the contact glass 32 of the scanner 300. Close the device 400.
When the start switch is pressed, if the original is set on the automatic document feeder 400, the original is transported and moved onto the contact glass 32; on the other hand, if the original is set on the contact glass 32, Immediately, the scanner 300 is driven, and the first traveling body 33 equipped with a light source and the second traveling body 34 equipped with a mirror travel. At this time, the reflected light from the document surface of the light irradiated from the first traveling body 33 is reflected by the second traveling body 34, and then received by the reading sensor 36 via the imaging lens 35, so that the original is The image information is read and black, yellow, magenta, and cyan image information is obtained.

The image information of each color is transmitted to each image forming means 18 in the image forming unit 120 of each color, and a toner image of each color is formed. As shown in FIG. 4, each color image forming unit 120 includes a photoreceptor drum 10, a charging roller 160 that uniformly charges the photoreceptor drum 10, and a charge roller 160 that charges the photoreceptor drum 10 uniformly based on the image information of each color. an exposure device that exposes with exposure light L to form an electrostatic latent image of each color; a developing device 61 that develops the electrostatic latent image with a developer of each color to form a toner image of each color; It includes a transfer roller 62 for transferring onto the transfer belt 50, a cleaning device 63 having a cleaning blade, and a discharge lamp 64.
The toner images of each color formed by the image forming units 120 of each color are sequentially transferred (primary transfer) onto an intermediate transfer belt 50 that moves while being stretched across rollers 14, 15, and 16, and are superimposed to form a composite toner image. It is formed.

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed the recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and the recording paper is fed out one by one by the separation roller 145. The paper is separated and sent to a paper feed path 146, conveyed by conveyance rollers 147, guided to a paper feed path 148 in the copying apparatus main body 150, and stopped against registration rollers 49. Alternatively, the recording paper on the manual feed tray 54 is fed out by rotating the paper feed roller, separated one by one by the separation roller 52, guided to the manual paper feed path 53, and stopped against 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 recording paper.

Next, by rotating the registration roller 49 in synchronization with the composite toner image formed on the intermediate transfer belt 50, the recording paper is sent between the intermediate transfer belt 50 and the secondary transfer belt 24, and the composite toner image is formed on the intermediate transfer belt 50. Transfer the toner image onto recording paper (secondary transfer). Note that the toner remaining on the intermediate transfer belt 50 to which the composite toner image has been transferred is removed by the cleaning device 17.

The recording paper onto which the composite toner image has been transferred is conveyed by a secondary transfer belt 24, and then the composite toner image is fixed by a fixing device 25. Next, the conveyance path of the recording paper is switched by a switching claw 55, and the recording paper is discharged onto a paper discharge tray 57 by a discharge roller 56. Alternatively, the conveyance path of the recording paper is switched by the switching claw 55, the sheet is reversed by the sheet reversing device 28, an image is similarly formed on the back side, and then the recording paper is discharged onto the paper discharge tray 57 by the discharge roller 56. .

The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, parts mean parts by mass, and % means mass %.

(Synthesis of ketimine 1)
170 parts of isophorone diamine and 75 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stirring rod and a thermometer, and the mixture was reacted at 50° C. for 5 hours to obtain ketimine 1. Ketimine 1 had an amine value of 418 mgKOH/g.

(Synthesis of amorphous polyester A)
3-methyl-1,5-pentanediol, adipic acid, and trimellitic anhydride were charged into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. At this time, the molar ratio of hydroxyl groups to carboxyl groups was 1.5, the content of trimellitic anhydride in all monomers was 1 mol %, and 1000 ppm of titanium tetraisopropoxide was added to all monomers. Next, the temperature was raised to 200°C in about 4 hours, and then to 230°C in 2 hours, and the reaction was carried out until water no longer flowed out. After that, the reaction was carried out for 5 hours under reduced pressure of 10 to 15 mmHg, and the hydroxyl group An amorphous polyester having the following properties was obtained.
Amorphous polyester having a hydroxyl group and isophorone diisocyanate were charged into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. At this time, the molar ratio of isocyanate groups to hydroxyl groups was set to 2.0. Next, after diluting with ethyl acetate, the mixture was reacted at 100° C. for 5 hours to obtain a 50% ethyl acetate solution of amorphous polyester prepolymer A-1.

A 50% ethyl acetate solution of amorphous polyester prepolymer A-1 was charged into a reaction vessel equipped with a heating device, a stirrer, and a nitrogen inlet tube, and after stirring, ketimine 1 was added dropwise. At this time, the molar ratio of amino groups to isocyanate groups was set to 1. Next, after stirring at 45° C. for 10 hours, the mixture was dried under reduced pressure at 50° C. until the remaining amount of ethyl acetate became 100 ppm or less to obtain amorphous polyester A. Amorphous polyester A had a glass transition temperature of -55°C and a weight average molecular weight of 130,000.

(Synthesis of amorphous polyester B)
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, add 2 moles of ethylene oxide adduct of bisphenol A (BisA-EO), 3 moles of propylene oxide adduct of bisphenol A (BisA-PO), and terephthal. Acid and adipic acid were charged. At this time, the molar ratio of BisA-EO to BisA-PO was 40/60, the molar ratio of terephthalic acid to adipic acid was 93/7, the molar ratio of hydroxyl group to carboxyl group was 1.2, and Then, 500 ppm of titanium tetraisopropoxide was added. Next, the mixture was reacted for 8 hours at 230°C, and then for 4 hours under reduced pressure of 10 to 15 mmHg. Further, 1 mol% of trimellitic anhydride was added to all the monomers, and then reacted at 180° C. for 3 hours to obtain amorphous polyester B. Amorphous polyester B had a glass transition temperature of 67° C. and a weight average molecular weight of 10,000.

<Melting point and glass transition temperature>
The melting point and glass transition temperature were measured using a differential scanning calorimeter Q-200 (manufactured by TA Instruments). Specifically, about 5.0 mg of the target sample was placed in an aluminum sample container, and then the sample container was placed on a holder unit and set in an electric furnace. Next, the temperature was raised from -80°C to 150°C at a temperature increase rate of 10°C/min in a nitrogen atmosphere.
From the obtained DSC curve, the glass transition temperature of the target sample was determined using an analysis program in the differential scanning calorimeter.
Further, from the obtained DSC curve, the endothermic peak top temperature of the target sample was determined as the melting point using an analysis program in the differential scanning calorimeter.

<Weight average molecular weight>
The weight average molecular weight was measured using a GPC measurement device HLC-8220GPC (manufactured by Tosoh Corporation) and a column TSKgel SuperHZM-H 15 cm triplicate (manufactured by Tosoh Corporation). Specifically, the column was stabilized in a 40°C heat chamber. Next, tetrahydrofuran (THF) was flowed through the column at a flow rate of 1 mL/min, and 50 to 200 μL of a 0.05 to 0.6 mass % THF solution of the sample was injected to measure the weight average molecular weight of the sample. At this time, the number average molecular weight of the sample was calculated from the relationship between the logarithm value of a calibration curve prepared using several types of monodisperse polystyrene standard samples and the count number.
Note that the standard polystyrene samples have weight average molecular weights of 6 x 10 ² , 2.1 x 10 ³ , 4 x 10 ³ , 1.75 x 10 ⁴ , 5.1 x 10 ⁴ , 1.1 x 10 ⁵ , Samples of 3.9×10 ⁵ , 8.6×10 ⁵ , 2×10 ⁶ , and 4.48×10 ⁶ (manufactured by Pressure Chemical or Tosoh) were used.
Further, as a detector, an RI (refractive index) detector was used.

(Example 1)
<Preparation of masterbatch 1>
Using a Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd.), 1200 parts of water, 500 parts of carbon black Printex 35 (manufactured by Dexa Corporation) with a DBP oil absorption of 42 mL/100 mg and a pH of 9.5, and 500 parts of amorphous polyester B were added. After mixing, the mixture was kneaded at 150° C. for 30 minutes using two rolls. Next, after rolling and cooling, it was pulverized using a pulperizer to obtain masterbatch 1.

<Synthesis of wax dispersant 1>
Into an autoclave reaction tank equipped with a thermometer and a stirrer, 480 parts of xylene and 100 parts of Sunwax 151P (manufactured by Sanyo Chemical Industries, Ltd.), which is polyethylene with a melting point of 108°C and a weight average molecular weight of 1000, were charged, and then the polyethylene was dissolved. , nitrogen was replaced. Next, a mixed solution of 805 parts of styrene, 50 parts of acrylonitrile, 45 parts of butyl acrylate, 36 parts of di-t-butyl peroxide, and 100 parts of xylene was added dropwise over 3 hours to polymerize at 170°C and held for 30 minutes. did. Furthermore, the wax dispersant 1 was obtained by removing the solvent. Wax dispersant 1 had a glass transition temperature of 65° C. and a weight average molecular weight of 18,000.

<Preparation of wax dispersion 1>
A container equipped with a stirring rod and a thermometer was charged with 300 parts of paraffin wax HNP-9 (manufactured by Nippon Seirin Co., Ltd.) having a melting point of 75°C, 150 parts of wax dispersant 1, and 1,800 parts of ethyl acetate. Next, while stirring, the temperature was raised to 80°C, maintained for 5 hours, and then cooled to 30°C over 1 hour. Furthermore, zirconia beads having a diameter of 0.5 mm were filled in an amount of 80% by volume using a bead mill, Ultra Visco Mill (manufactured by Imex), and dispersed under three pass conditions to obtain a wax dispersion liquid 1. At this time, the liquid feeding speed was 1 kg/h, and the circumferential speed of the disk was 6 m/s.

<Preparation of oil phase 1>
After charging 225 parts of wax dispersion 1, 40 parts of a 50% ethyl acetate solution of amorphous polyester A, 390 parts of amorphous polyester B, 60 parts of masterbatch 1 and 285 parts of ethyl acetate into a container, TK The mixture was mixed for 60 minutes at 7000 rpm using a homo mixer (manufactured by Primix) to obtain oil phase 1.

<Synthesis of vinyl resin dispersion 1>
In a reaction vessel equipped with a stirring rod and a thermometer, 683 parts of water, 11 parts of sodium salt Eleminol RS-30 (manufactured by Sanyo Chemical Industries, Ltd.) of the sulfuric ester of the ethylene oxide adduct of methacrylic acid, 138 parts of styrene, and 138 parts of methacrylic acid. After adding 1 part of ammonium persulfate and 1 part of ammonium persulfate, the mixture was stirred at 400 rpm for 15 minutes to obtain a white emulsion. Next, the temperature in the system was raised to 75°C and reacted for 5 hours, then 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75°C for 5 hours to obtain vinyl resin dispersion 1. Ta. Vinyl resin dispersion 1 had a volume average particle diameter of 0.14 μm.
The volume average particle diameter of the vinyl resin dispersion 1 was measured using a laser diffraction/scattering particle size distribution analyzer LA-920 (manufactured by HORIBA).

<Preparation of aqueous phase 1>
990 parts of water, 83 parts of vinyl resin dispersion 1, 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate Eleminol MON-7 (manufactured by Sanyo Chemical Industries, Ltd.) and 90 parts of ethyl acetate were mixed and stirred, and a milky white mixture was obtained. Aqueous phase 1 was obtained.

<Emulsification/Desolvent>
After adding 0.2 parts of ketimine 1 and 1200 parts of water phase 1 to a container containing oil phase 1, they were mixed for 20 minutes at 13,000 rpm using a TK homo mixer to obtain emulsified slurry 1.
Emulsified slurry 1 was charged into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30° C. for 8 hours, and then aged at 45° C. for 4 hours to obtain dispersion slurry 1.

<Cleaning/heat treatment/drying>
100 parts of dispersion slurry 1 was filtered under reduced pressure. Next, 100 parts of ion-exchanged water was added to the filter cake, mixed for 10 minutes at 12,000 rpm using a TK homo mixer, and then filtered (hereinafter referred to as washing step (1)). Further, 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake, mixed for 30 minutes at 12,000 rpm using a TK homomixer, and then filtered under reduced pressure (hereinafter referred to as washing step (2)). Next, 100 parts of 10% hydrochloric acid was added to the filter cake, mixed for 10 minutes at 12,000 rpm using a TK homo mixer, and then filtered (hereinafter referred to as washing step (3)). Furthermore, 300 parts of ion-exchanged water was added to the filter cake, mixed for 10 minutes at 12,000 rpm using a TK homo mixer, and then filtered (hereinafter referred to as washing step (4)). At this time, the operations of washing steps (1) to (4) were repeated twice.
100 parts of ion-exchanged water was added to the filter cake, mixed for 10 minutes at 12,000 rpm using a TK homomixer, heated at 50° C. for 4 hours, and then filtered.
The filter cake was dried at 45° C. for 48 hours using a circulating air dryer, and then sieved through a mesh having an opening of 75 μm to obtain toner base particles 1 (base 1). The average circularity was 0.980 and the volume average particle diameter was 5.5 μm.

<Measurement of number average particle diameter>
A SEM image of the external additive was obtained using a field emission scanning electron microscope SU8230 (manufactured by Hitachi High-Technologies Corporation), and the number average particle diameter was measured by image analysis. First, an external additive was dispersed in tetrahydrofuran, and then the solvent was removed and dried on the substrate. This sample was observed using the SEM described above to obtain an image, and the longest length of the secondary particles of each particle was measured. The average value of 200 particles was calculated and used as the number average particle diameter. An example of SEM measurement conditions is shown below.
[SEM measurement conditions]
Acceleration voltage: 2.0kV
WD (Working Distance): 10.0mm
Observation magnification: 50000x

<Measurement of volume average particle diameter>
In the present invention, the volume average particle diameter of the toner was measured using Coulter Multisizer III (manufactured by Beckman Coulter). At this time, the aperture diameter was set to 100 μm, and Beckman Coulter Multisizer 3 version 3.51 (manufactured by Beckman Coulter) was used as analysis software. Specifically, 10 mg of toner was added to 5 mL of 10% by mass surfactant (alkylbenzene sulfonate) Neogen SC-A (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and after being dispersed for 1 minute using an ultrasonic disperser, 25 mL of Isoton III (manufactured by Beckman Coulter) was added and dispersed for 1 minute using an ultrasonic disperser. Next, after putting 100 mL of the electrolyte and the dispersion into a beaker, the particle size of 30,000 particles was measured at a concentration that would allow the particle size of 30,000 particles to be measured in 20 seconds, and from the particle size distribution, the volume The average particle size was determined.

<Average circularity>
The average circularity of the toner was measured using a wet flow type particle size/shape analyzer FPIA-3000 and analysis software FPIA-3000 Data Processing Program for FPIA version 00-10 (manufactured by Sysmex Corporation). Specifically, in a 100 mL glass beaker, 0.1 to 0.5 mL of a 10% aqueous solution of Neogen SC-A (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), an alkylbenzene sulfonate, and 0.1 to 0.5 g of toner were added. After the addition, the mixture was stirred using a micro spatula, and 80 mL of ion-exchanged water was added. Next, using an ultrasonic dispersion machine UH-50 (manufactured by SMT), the mixture was dispersed for 1 minute at 20 kHz and 50 W/10 cm ³ , and then for a total of 5 minutes to obtain a measurement sample. Here, the average circularity of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm was measured using a measurement sample with a particle concentration of 4000 to 8000 particles/10 ⁻³ cm ³ .

<External additive treatment process>
100 parts of base particles, 1.7 parts of silica 1, and 0.3 parts of alumina 1 were added to a 20L Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), and mixed at a circumferential speed of 40 m/s for 15 minutes to form a 500-mesh mixer. Passed through a sieve to obtain toner.

Silica 1 was obtained as follows. 100 g of silica particles produced by a liquid phase method (Nip Seal SP-200 manufactured by Tosoh Silica, BET, specific surface area 200 m ² /g) were dispersed in 2 L of water and heated to 85°C. Next, an aluminum chloride aqueous solution was added in an amount of 10% by mass in terms of Al ₂ O ₃ based on the silica particles, the pH was adjusted to 5.5 with a sodium hydroxide aqueous solution, and the mixture was maintained while stirring for 30 minutes. Aluminum chloride was hydrolyzed to coat the surfaces of silica particles with aluminum hydroxide. Next, sodium stearate was added in an amount of 10% by mass in terms of stearic acid based on the silica particles, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution, and the mixture was stirred and maintained for 1 hour. was hydrolyzed to obtain a silica slurry in which the surface of aluminum hydroxide was coated with stearic acid. Next, the obtained slurry was filtered to obtain a cake. Next, the obtained cake was again dispersed in 2 L of water, heated to 80°C, adjusted to pH 5.0 with hydrochloric acid, and kept under stirring for 1 hour, filtered and the residue on the filter medium was washed with water. A washed cake was obtained by. Finally, this washed cake was dried at 120° C. and then pulverized using a media type pulverizer to obtain Silica 1. The number average particle size of Silica 1 was 15 nm.

For alumina 1, alumina (manufactured by Degussa, aluminum oxide C) with a BET specific surface area of 100 m ² /g was placed in a reaction tank, and heptadecafluorodecyltrimethoxy was added to 100 g of alumina powder while stirring in a nitrogen atmosphere. A mixed solution of 10 g of silane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-7803) and 2 g of hexamethyldisilazane was sprayed, heated and stirred at 200° C. for 120 minutes, and then cooled to obtain alumina 1. The number average particle diameter of Alumina 1 was 17 nm.

Further, the total release rate and coverage of Silica 1 and Alumina 1 were measured as described above, and the results are shown in the table below.

(Examples 2 to 18, Comparative Examples 1 to 5 )
In Example 1, a toner was produced in the same manner as the toner described in Example 1, except that the formulation and mixing conditions were changed according to the following tables.

Alumina 2 used in Examples 10 and 12 was obtained as follows. Alumina (manufactured by Daimei Kagaku Kogyo Co., Ltd., TM-5D) with a BET specific surface area of 14.5 m ² /g was placed in a reaction tank, and while stirring in a nitrogen atmosphere, heptadecafluorodecyltrimethoxy was added to 100 g of alumina powder. A mixed solution of 10 g of silane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-7803) and 2 g of hexamethyldisilazane was sprayed, heated and stirred at 200° C. for 120 minutes, and then cooled to obtain alumina 2.

Silica 2 used in Examples 11 and 12 was obtained as follows. 100 g of silica particles (manufactured by Cabot Specialty Chemicals, Inc., TG-C110) were dispersed in 2 L of water and heated to 85°C. Next, an aluminum chloride aqueous solution was added in an amount of 10% by mass in terms of Al ₂ O ₃ based on the silica particles, the pH was adjusted to 5.5 with a sodium hydroxide aqueous solution, and the mixture was maintained while stirring for 30 minutes. Aluminum chloride was hydrolyzed to coat the surfaces of silica particles with aluminum hydroxide. Next, sodium stearate was added in an amount of 10% by mass in terms of stearic acid based on the silica particles, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution, and the mixture was stirred and maintained for 1 hour. was hydrolyzed to obtain a silica slurry in which the surface of aluminum hydroxide was coated with stearic acid. Next, the obtained slurry was filtered to obtain a cake. Next, the obtained cake was again dispersed in 2 L of water, heated to 80°C, adjusted to pH 5.0 with hydrochloric acid, and kept under stirring for 1 hour, filtered and the residue on the filter medium was washed with water. A washed cake was obtained by. Finally, this washed cake was dried at 120° C. and then pulverized with a media type pulverizer to obtain Silica 2.

Toner base particles 2 (base 2), which are pulverized toner, used in Example 13 are produced as follows.

<Synthesis of polyester resin A1>
The monomer species shown in Table 1 below and tetrabutoxy titanate as a condensation catalyst were placed in a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and while distilling off the water produced under a nitrogen stream, 230 The reaction was carried out at ℃ for 6 hours. Next, a reaction was carried out for 1 hour under reduced pressure of 5 mmHg to 20 mmHg to obtain amorphous polyester resin A1.
"25 mol%" in Table 1 indicates the proportion in the alcohol component when the acid component is 50 mol% and the alcohol component is 50 mol%.

<Synthesis of polyester resin B2>
Amorphous polyester resin B2 was obtained in the same manner as <Synthesis of polyester resin A1> except that the carboxylic acid component and alcohol component were changed to those shown in Table 1 below.

<Synthesis of polyester resin C1>
The carboxylic acid components and alcohol components shown in Table 1 below were charged into a 5L four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer, and thermocouple so that the OH/COOH ratio was 0.9, and titanium tetraisomer was added. After reacting with propoxide (500 ppm based on the resin component) at 180°C for 10 hours, increasing the temperature to 200°C and reacting for 3 hours, and further reacting at a pressure of 8.3 kPa for 2 hours, Example An easily compatible latent crystalline polyester resin C1 was obtained.

<Preparation of crushed toner>
<<Toner 1 prescription>>
Polyester resin A1: 24.2 parts by mass Polyester resin B2: 60.0 parts by mass Polyester resin C1: 3.2 parts by mass Mold release agent (synthetic ester wax): 4.8 parts by mass Coloring agent (phthalocyanine blue): 6. 8 parts by mass Charge control agent (monoazo metal complex): 1.0 parts by mass

The toner raw materials were premixed according to the above recipe using a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd., FM20B), and then heated to 120°C using a twin-screw kneader (manufactured by Ikegai Co., Ltd., PCM-30). It was melted and kneaded. The obtained kneaded material was rolled to a thickness of 2.7 mm using rollers, cooled to room temperature using a belt cooler, and coarsely ground to 200 μm to 300 μm using a hammer mill. Next, after finely pulverizing using a supersonic jet pulverizer Labojet (manufactured by Nippon Pneumatic Industries Co., Ltd.), the weight average particle size was reduced to 5.5 mm using an air classifier (manufactured by Nippon Pneumatic Industries Co., Ltd., MDS-I). The toner base particles 2 were obtained by classifying the particles while appropriately adjusting the louver opening so that the particle size was 8±0.2 μm. The average circularity was 0.935 and the volume average particle diameter was 5.8 μm.
In Example 1, a toner was produced in the same manner as the toner described in Example 1, except that the formulation and mixing conditions were changed according to the table below.

Note that NX90G used in Comparative Example 1 is a silica manufactured by Nippon Aerosil Co., Ltd. with a number average particle diameter of 20 nm.

<Preparation of developer>
5% by mass of the produced toner and 95% by mass of the coated ferrite carrier were uniformly mixed at 48 rpm for 5 minutes using a Turbler mixer (manufactured by Willy & Bacchofen (WAB)) to produce a toner developer. .

<Screen stain evaluation>
After filling a digital full-color multifunction machine Imagio MP C5000 (manufactured by Ricoh) with developer, an A4 size solid image with a toner adhesion amount of 0.5 mg/cm ² was copied.
Next, the initial stage is when 1,000 copies have been made, and the elapsed time is when 100,000 copies have been made.The blank image is stopped during development, and the developer on the photoreceptor after development is transferred to a tape, and the untransferred image on the tape is The difference in density was measured using a 938 spectrodensitometer (manufactured by X-RITE) to evaluate fogging.
In addition, if this difference is less than 0.005, ◎,
○ if it is 0.005 or more and less than 0.010;
△ if it is 0.010 or more and less than 0.030;
The case where it was 0.030 or more was judged as ×.
It can be said that an evaluation of △ or above is passed in practical terms.

<Cleanability>
After filling a digital full color multifunction device Imagio MP C5000 (manufactured by Ricoh) with developer, an A4 size solid image with a toner adhesion amount of 0.5 mg/cm ² was copied.
Next, the toner remaining on the photoreceptor that passed through the cleaning process was transferred to a blank sheet of paper using Scotch tape (manufactured by Sumitomo 3M), with the initial stage being when 1,000 copies were made and the aging time being when 100,000 copies had been copied. The reflection density was measured using a reflection densitometer RD514 (manufactured by Gretag Macbeth), and the cleaning performance was evaluated.
In addition, the case where the difference between the reflection density over time and the initial reflection density is less than 0.01 is ◎,
○ if the value is 0.01 or more and less than 0.15;
△ if it is 0.015 or more and less than 0.02;
The case where it was 0.02 or more was judged as ×.
An evaluation of △ or above can be said to be a pass in practical terms.

The table below shows the evaluation results of the toners of Examples and Comparative Examples.

As described above, it has been found that according to the present invention, it is possible to provide a toner that has extremely excellent cleaning properties and can form high-quality images over a long period of time.

10 Electrostatic latent image carrier (photosensitive drum)
14 Roller 15 Roller 16 Roller 17 Cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 32 Contact glass 33 1st running body 34 2nd running body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer storage section 42Y Developer storage section 42M Developer storage section 42C Developer storage section 43K Developer supply roller 43Y Developer supply Roller 43M Developer supply roller 43C Developer supply roller 44K Developing roller 44Y Developing roller 44M Developing roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer belt 51 Roller 52 Separation Roller 53 Manual feed path 54 Manual tray 55 Switching claw 56 Ejection roller 57 Ejection tray 58 Corona charging device 60 Cleaning device 61 Developing device 62 Transfer roller 63 Photoreceptor cleaning device 64 Static elimination lamp 70 Static eliminator lamp 80 Transfer roller 90 Cleaning device 95 Transfer Paper 100A, 100B, 100C Image forming apparatus 120 Image forming unit 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Conveyance roller 148 Paper feed path 150 Copying device main body 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)

Japanese Patent Application Publication No. 2017-116570 JP2012-163623A

Claims (10)

A toner containing a binder resin, a colorant, a release agent, and inorganic fine particles,
The inorganic fine particles include at least inorganic fine particles 1 which are silica treated with aluminum, and inorganic fine particles 2 which are aluminum compounds treated with a fluorine compound,
A toner characterized in that a total release rate of the inorganic fine particles 1 and the inorganic fine particles 2 from the toner is 10% or more and 70% or less. The toner according to claim 1 , wherein the mass ratio of the non-liberated inorganic fine particles 1 to the non-liberated inorganic fine particles 2 is from 10:90 to 90:10. The toner according to claim 1 or 2, wherein the coverage of the inorganic fine particles 1 and the inorganic fine particles 2 is 30% or more and 90% or less. The toner according to claim 1, wherein the inorganic fine particles 1 and/or the inorganic fine particles 2 have a number average particle diameter of 50 nm or more and 200 nm or less. The toner according to any one of claims 1 to 3, wherein the number average particle diameter of the inorganic fine particles 1 and the inorganic fine particles 2 is 50 nm or more and 200 nm or less. The toner according to claim 1, wherein the toner has an average circularity of less than 0.980. A toner storage unit containing the toner according to any one of claims 1 to 6. A developer comprising the toner according to any one of claims 1 to 6. an electrostatic latent image carrier;
an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
An image forming apparatus comprising: a developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier with the developer according to claim 8 to form a visible image. . an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier;
An image forming method comprising the step of developing the electrostatic latent image formed on the electrostatic latent image carrier with the developer according to claim 8 to form a visible image. .

Images