JP2017156698A - Toner, toner storage unit, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that shows a stable amount of charge for a long period to exhibit low-temperature fixability and heat-resistant stability, while suppressing scattering of the toner.SOLUTION: There is provided a toner containing at least a binder resin and a mold release agent, the toner containing Fe and Al, where the ratio of atomic concentration% of Fe to Al (Fe/Al) measured by X-ray fluorescence analysis (XRF) is 1.23 to 1.48, and the atomic concentration% of Al in the toner is 0.45% to 0.60%.SELECTED DRAWING: None

Description

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

  In electrophotographic image formation, the toner used in the ultra-high-speed printing system is constant even under severe conditions such as fluctuations in the operating environment temperature and humidity of the image forming apparatus and continuous output of a large number of images. In order to continue outputting high quality images, it is important to have heat resistance storage stability and stable charging characteristics to prevent toner scattering. Therefore, many inventions related to the types of external additives, various physical properties, and the number of prescriptions have been proposed. In addition, in a heat fixing type image forming apparatus, since a large amount of electric power is required in the process of fusing toner and fixing it on a recording medium such as paper, the toner is fixed at a low temperature from the viewpoint of energy saving. Sex is another important characteristic.

In view of this, there has been proposed a toner in which charging stability is improved by setting the atomic concentration% of Al element in the X-ray photoelectron spectroscopy (XPS) of the toner to 0.5 atomic% or more (for example, Patent Document 1). reference).
Further, when the atomic concentration% of the specific element when the toner is measured by XPS is A and the atomic concentration% of the specific element is B when the toner is measured by XPS after melt-kneading, A> A toner having improved charging stability by setting B is proposed (for example, see Patent Document 2). A toner having excellent charging characteristics by specifying the ratio of the amount of surface elements of Si and Fe as external additives has also been proposed (see, for example, Patent Document 3).

  An object of the present invention is to provide a toner that exhibits a low-temperature fixability and heat-resistant stability while suppressing toner scattering by exhibiting a stable charge amount over a long period of time.

Means for solving the above-described problems are the following toners. That is,
A toner containing at least a binder resin and a release agent,
The toner contains Fe and Al, and the ratio of the atomic concentration% of Fe and Al (Fe / Al) measured by X-ray fluorescence elemental analysis (XRF) is 1.23 to 1.48. In addition, the atomic concentration% of Al in the toner is 0.45% to 0.60%.

  According to the present invention, it is possible to provide a toner that exhibits low-temperature fixability and heat-resistant stability while suppressing toner scattering by exhibiting a stable charge amount over a long period of time.

FIG. 1 is a schematic configuration diagram showing an example of an image forming apparatus of the present invention. FIG. 2 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention. FIG. 3 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention. FIG. 4 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention.

(toner)
The toner of the present invention contains at least a binder resin and a release agent.
The toner of the present invention contains Fe and Al, and the ratio of the atomic concentration% of Fe and Al (Fe / Al) measured by fluorescent X-ray elemental analysis (XRF) is 1.23-1.48. In addition, the atomic concentration% of Al in the toner is 0.45% to 0.60%.
In Patent Documents 1 and 2, there is a description regarding the amount of the specific metal element in the toner, but there is no description regarding the ratio of the constituent elements. Even if only the amount of the specific element is described, the condition may be satisfied by the input amount of the material. In addition, Patent Document 3 only describes the element ratio of only the external additive. In this case, when the external additive is peeled off from the toner at the time of mixing with the carrier in the previous stage of transfer, there is no external additive. Insufficient charge difference between the toner in the state and the toner with the external additive is insufficient to prevent uneven charging in the apparatus, and insufficient to suppress toner scattering. .
As defined in the present invention, in addition to defining the amount of the specific element, by defining the ratio of the specific element present in the toner particles within a certain range, it has advantageous charging stability against toner scattering. A toner can be produced.
The toner of the present invention having the above-described configuration can exhibit low-temperature fixability and heat resistance stability while suppressing toner scattering by exhibiting a stable charge amount for a long period of time.

  As a cause of the occurrence of toner scattering, the present inventors cause unevenness in charging due to mixing with newly replenished toner when toner and carrier are mixed in the pre-transfer stage, and therefore toner scattering occurs. I found. In order to prevent this, when the Fe and Al in the toner are measured by X-ray fluorescence elemental analysis (XRF), the ratio of the atomic concentration% of Fe and Al (Fe / Al) is 1.23-1.48. It was confirmed that the range was effective.

As a method for increasing the charge amount, it is important to improve the dispersion of the metal element in the toner. As a result of intensive studies by the present inventors, the ratio of Fe to Al atomic concentration% (Fe / Al) measured by X-ray fluorescence elemental analysis (XRF) is in the range of 1.23-1.48. The inventors have found that the metal element is well dispersed in the toner. In controlling the value of Fe / Al, it is preferable to use a layered inorganic compound (particularly a modified layered inorganic compound), and a method of controlling Fe / Al by means of blending a plurality of types of bentonite is conceivable. Further, in order to improve the dispersion in the toner, a technique such as a masterbatch in which the modified layered inorganic compound is previously dispersed in the resin is also included.
Since the total amount of the modified layered inorganic compound contained in the toner itself also affects the charge amount, it is also important to define the atomic concentration% of Al in the toner. It has been found that the content is preferably in the range of 0.45% to 0.60%.

In the X-ray fluorescence analysis (XRF), the atomic concentration% of Al in the toner is 0.45% to 0.60%.
When the atomic concentration% of Al is larger than 0.60%, the toner is not sufficiently reduced in viscosity and the low-temperature fixability tends to be hindered. In addition, when the atomic concentration% of Al is smaller than 0.45%, the charge amount of the toner base particles decreases, and the toner and the carrier newly mixed when the toner and the carrier are mixed in the pre-transfer stage are mixed. Uneven charging occurs and toner scattering occurs. Also, the toner surface becomes too soft and the external additive is buried in the toner, so that the heat resistant storage stability tends to deteriorate.

  In the present invention, the ratio of the atomic concentration% of Fe and Al (Fe / Al) is more preferably 1.23-1.39. The atomic concentration% of Al in the toner is more preferably 0.50% to 0.60%.

<Fluorescent X-ray elemental analysis (XRF)>
The measurement of the X-ray fluorescence elemental analysis (XRF) in the present invention can be performed, for example, as follows.
The amount of metal elements (Al, Fe, etc.) in the toner is quantified by fluorescent X-ray analysis (ZSX 100e: automatic fluorescent X-ray analyzer manufactured by Rigaku Corporation), and the amount of metal elements (Al, Fe) present in the entire toner. ) Is calculated. In the measurement, a sample of 3.0 ± 0.1 g of toner is pressurized at 6 (t / cm ² ) for 30 seconds to produce a 40 mmφ circular pellet.

  The toner of the present invention contains at least a binder resin and a release agent, and further contains a layered inorganic compound in order to obtain a toner containing Fe and Al, and further, if necessary, a colorant and a charge control agent. Contains other ingredients such as. Moreover, you may add an external additive as needed.

<Binder resin>
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably. For example, polyester resin, silicone resin, styrene / acrylic resin, styrene resin, acrylic resin, epoxy resin, diene resin, phenol resin, terpene resin, coumarin resin, amidoimide resin, butyral resin, urethane resin, ethylene vinyl acetate resin, etc. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, polyester resins and resins obtained by combining polyester resins with the above other binder resins are preferable because they are excellent in low-temperature fixability and have sufficient flexibility even when the molecular weight is reduced.

-Polyester resin-
There is no restriction | limiting in particular as said polyester resin, Although it can select suitably according to the objective, An unmodified polyester resin and a modified polyester resin are preferable. These may be used individually by 1 type and may use 2 or more types together.

--Unmodified polyester resin--
There is no restriction | limiting in particular as said unmodified polyester resin, According to the objective, it can select suitably. Examples thereof include resins obtained by polyesterification of a polyol represented by the following general formula (1) and a polycarboxylic acid represented by the following general formula (2), a crystalline polyester resin, and the like.

However, in the said General formula (1), A represents the aromatic group or heterocyclic aromatic group which may have a C1-C20 alkyl group, an alkylene group, and a substituent, m is 2- Represents an integer of 4.
In the general formula (2), B represents an alkyl group having 1 to 20 carbon atoms, an alkylene group, an aromatic group that may have a substituent, or a heterocyclic aromatic group, and n represents 2 to 2 Represents an integer of 4.

  There is no restriction | limiting in particular as a polyol represented by the said General formula (1), According to the objective, it can select suitably. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, Pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2, -Butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A oxidation Examples include ethylene adducts, hydrogenated bisphenol A propylene oxide adducts, and the like. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as polycarboxylic acid represented by the said General formula (2), According to the objective, it can select suitably. For example, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isooctyl succinic acid , Isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, 1,2,4-benzenetricarboxylic acid, 2, , 5,7-Naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl- 2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, te La (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, etc., cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, And ethylene glycol bis (trimellitic acid). These may be used alone or in combination of two or more.

--Modified polyester resin--
There is no restriction | limiting in particular as said modified polyester resin, According to the objective, it can select suitably. For example, an active hydrogen group-containing compound, a resin obtained by subjecting a polyester capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “polyester prepolymer”) to an extension reaction and / or a crosslinking reaction, etc. Can be mentioned. The extension reaction and / or the cross-linking reaction may be stopped by a reaction terminator (blocked monoamine such as diethylamine, dibutylamine, butylamine, laurylamine, ketimine compound, etc.) as necessary.

--- Active hydrogen group-containing compound ---
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent or the like when the polyester prepolymer undergoes an elongation reaction, a crosslinking reaction, or the like in an aqueous phase.

  The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. Especially, when the said polyester prepolymer is an isocyanate group containing polyester prepolymer mentioned later, amines are preferable at the point from which high molecular weight is attained.

  There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably. For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, etc. are mentioned. These may be contained singly or in combination of two or more.

  There is no restriction | limiting in particular as said amines which are the said active hydrogen group containing compound, According to the objective, it can select suitably. Examples thereof include diamine, trivalent or higher polyamine, amino alcohol, amino mercaptan, amino acid, and those obtained by blocking the amino group of these amines.

Examples of the diamine include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine, etc.); aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.
Examples of the trivalent or higher polyamine include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid include aminopropionic acid and aminocaproic acid.
Examples of the blocked amino groups of these amines include, for example, any of these amines (diamine, trivalent or higher polyamine, amino alcohol, amino mercaptan, amino acid, etc.) and ketones (acetone, methyl ethyl ketone, And ketimine compounds and oxazolyzone compounds obtained from methyl isobutyl ketone and the like.

  These may be used individually by 1 type and may use 2 or more types together. Among these, the amines are particularly preferably diamine and a mixture of a diamine and a small amount of a trivalent or higher polyamine.

--- Polymer capable of reacting with active hydrogen group-containing compound ---
The polymer that can react with the active hydrogen group-containing compound is not particularly limited as long as it is a polymer having at least a group that can react with the active hydrogen group-containing compound, and can be appropriately selected according to the purpose. Above all, it has excellent fluidity and transparency when melted, it is easy to adjust the molecular weight of the polymer component, and it is excellent in oil-less low-temperature fixability and releasability in dry toners. Is preferred, and an isocyanate group-containing polyester prepolymer is more preferred.

  There is no restriction | limiting in particular as said isocyanate group containing polyester prepolymer, According to the objective, it can select suitably. Examples thereof include polycondensates of polyols and polycarboxylic acids, and those obtained by reacting active hydrogen group-containing polyester resins with polyisocyanates.

  There is no restriction | limiting in particular as said polyol, According to the objective, it can select suitably. For example, alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.), alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene) Glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.), Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol, alkylene oxide of the bisphenol Diols such as adducts (ethylene oxide, propylene oxide, butylene oxide, etc.); polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.), trivalent or higher phenols (phenol novolac) , Cresol novolac, etc.) trihydric or higher polyols such as alkylene oxide adducts of trihydric or higher polyphenols; mixtures of diols and trihydric or higher polyols.

  These may be used individually by 1 type and may use 2 or more types together. Among these, the polyol is preferably the diol alone or a mixture of the diol and a small amount of the trivalent or higher polyol.

  Examples of the diol include alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols (bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, etc.) Is preferred.

  There is no restriction | limiting in particular as content in the isocyanate group containing polyester prepolymer of the said polyol, According to the objective, it can select suitably. For example, 0.5 mass%-40 mass% are preferable, 1 mass%-30 mass% are more preferable, and 2 mass%-20 mass% are especially preferable. When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both the storage stability of the toner and the low-temperature fixability. Fixability may deteriorate.

  There is no restriction | limiting in particular as said polycarboxylic acid, According to the objective, it can select suitably. For example, alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.); Examples thereof include polycarboxylic acids (such as aromatic polycarboxylic acids having 9 to 20 carbon atoms such as trimellitic acid and pyromellitic acid). These may be used individually by 1 type and may use 2 or more types together.

  Among these, the polycarboxylic acid is preferably an alkenylene dicarboxylic acid having 4 to 20 carbon atoms and an aromatic dicarboxylic acid having 8 to 20 carbon atoms. In place of the polycarboxylic acid, an anhydride of polycarboxylic acid, a lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) may be used.

  There is no restriction | limiting in particular as a mixing ratio of the said polyol and the said polycarboxylic acid, According to the objective, it can select suitably. The equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] of the polyol and the carboxyl group [COOH] of the polycarboxylic acid is preferably 2/1 to 1/1, and 1.5 / 1 to 1/1. Is more preferable, and 1.3 / 1 to 1.02 / 1 is particularly preferable.

  There is no restriction | limiting in particular as said polyisocyanate, According to the objective, it can select suitably. For example, aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane Diisocyanates, etc.); cycloaliphatic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4 '-Diisocyanato-3,3'-dimethyldiphenyl, 3-methyl Diphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate, etc.); araliphatic diisocyanate (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates (Tris-isocyanate) Natoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, etc.); these phenol derivatives; those blocked with oxime, caprolactam and the like. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as a mixing ratio of the said polyisocyanate and the said active hydrogen group containing polyester resin (hydroxyl group containing polyester resin), According to the objective, it can select suitably. The equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] of the polyisocyanate and the hydroxyl group [OH] of the hydroxyl group-containing polyester resin is preferably 5/1 to 1/1, and 4/1 to 1.2. / 1 is more preferable, and 3/1 to 1.5 / 1 is particularly preferable. When the equivalent ratio [NCO] / [OH] is less than 1/1, the offset resistance may be deteriorated, and when it exceeds 5/1, the low-temperature fixability may be deteriorated.

  There is no restriction | limiting in particular as content of the said polyisocyanate in the said isocyanate group containing polyester prepolymer, According to the objective, it can select suitably. 0.5 mass%-40 mass% are preferable, 1 mass%-30 mass% are more preferable, 2 mass%-20 mass% are especially preferable. When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both storage stability and low-temperature fixability. May get worse.

  The average number of isocyanate groups contained in one molecule of the isocyanate group-containing polyester prepolymer is preferably 1 or more, more preferably 1.2 to 5, and more preferably 1.5 to 4. When the average number is less than 1, the molecular weight of the polyester resin (RMPE) modified with a urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  There is no restriction | limiting in particular as a mixing ratio of the said isocyanate group containing polyester prepolymer and the said amines, According to the objective, it can select suitably. The mixing equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] in the isocyanate group-containing polyester prepolymer and the amino group [NHx] in the amines is preferably 1/3 to 3/1. / 2 to 2/1 is more preferable, and 1 / 1.5 to 1.5 / 1 is particularly preferable. If the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be reduced. If it exceeds 3/1, the molecular weight of the urea-modified polyester resin is reduced. Hot offset resistance may deteriorate.

--- Method for synthesizing polymer capable of reacting with active hydrogen group-containing compound ---
There is no restriction | limiting in particular as a synthesis method of the polymer which can react with the said active hydrogen group containing compound, According to the objective, it can select suitably. For example, in the case of the isocyanate group-containing polyester prepolymer, the polyol and the polycarboxylic acid are heated to 150 ° C. to 280 ° C. in the presence of a known esterification catalyst (titanium tetrabutoxide, dibutyltin oxide, etc.). And a method of synthesizing by reacting the polyisocyanate with the hydroxyl group-containing polyester at 40 ° C. to 140 ° C. after the water is distilled off to obtain the hydroxyl group-containing polyester. .

  There is no restriction | limiting in particular as a weight average molecular weight (Mw) of the polymer which can react with the said active hydrogen group containing compound, According to the objective, it can select suitably. The molecular weight distribution by GPC (gel permeation chromatography) of the soluble portion of tetrahydrofuran (THF) is preferably 3,000 to 40,000, more preferably 4,000 to 30,000. When the weight average molecular weight (Mw) is less than 3,000, the storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated.

  The weight average molecular weight (Mw) can be measured, for example, as follows. First, the column was stabilized in a 40 ° C. heat chamber, and at this temperature, tetrahydrofuran (THF) as a column solvent was flowed at a flow rate of 1 mL / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. Measurement is performed by injecting 50 μL to 200 μL of a tetrahydrofuran sample solution. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared by several monodisperse polystyrene standard samples and the number of counts.

As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co. Or the molecular weight made by Toyo Soda Industry Co., Ltd. is 6 × 10, 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × It is preferable to use 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector can be used as the detector.

<Release agent>
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably. For example, plant wax (carnauba wax, cotton wax, wood wax, rice wax, etc.), animal wax (beeswax, lanolin, etc.), mineral wax (ozokerite, cercin etc.), petroleum wax (paraffin, microcrystalline, petrolatum, etc.) ) Waxes and waxes; synthetic hydrocarbon waxes (Fischer-Tropsch wax, polyethylene wax, etc.), synthetic waxes other than natural waxes (esters, ketones, ethers, etc.); 1,2-hydroxystearic acid amide, Fatty acid amides such as stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; homopolymers or copolymers of polyacrylates such as poly (n-stearyl methacrylate) and poly (n-lauryl methacrylate) which are low molecular weight crystalline polymers ( Acrylic acid n- Crystalline polymer having a stearyl over long chain alkyl group in the side chain of ethyl methacrylate copolymer, etc.) and the like; and the like.

  Among these, Fischer-Tropsch wax, paraffin wax, microcrystalline wax, monoester wax, and rice wax are preferable because less unnecessary volatile organic compounds are generated during fixing.

  A commercial item can be used for the mold release agent. Examples of the microcrystalline wax include “HI-MIC-1045”, “HI-MIC-1070”, “HI-MIC-1080”, “HI-MIC-1090” manufactured by Nippon Seiki Co., Ltd. “Bsquare 180 White”, “Bsquare 195” manufactured by WAX Petrolife, “CAREVALAC WN-1442” manufactured by Cray Valley, and the like.

  There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 60 to 100 degreeC is preferable and 65 to 90 degreeC is more preferable. When the melting point is 60 ° C. or more, even when stored at a high temperature of about 30 to 50 ° C., it is possible to suppress the exudation of the release agent from the toner base material and maintain good heat-resistant storage stability. When the temperature is 100 ° C. or lower, it is preferable because cold offset hardly occurs during fixing at a low temperature.

The melting point is measured by DSC. For example, it can be measured under the following measurement conditions using TA-60WS and DSC-60 manufactured by Shimadzu Corporation.
(Measurement condition)
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 mL / min)
Temperature conditions 1st. Temperature rise Start temperature: 20 ° C., Temperature rise rate: 10 ° C./min, End temperature: 150 ° C., Holding time: None 1st. Temperature drop Temperature drop: 10 ° C./min, end temperature: 20 ° C., retention time: none 2nd. Temperature rise Temperature rise rate: 10 ° C / min, end temperature: 150 ° C
The measurement results are analyzed using data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation.
The melting point is 2nd. The temperature at the top of the endothermic peak measured at elevated temperature is used.

  The release agent is preferably present in a dispersed state in the toner base particles, and for this purpose, the release agent and the binder resin are preferably incompatible with each other. The method for finely dispersing the release agent in the toner base particles is not particularly limited and may be appropriately selected depending on the purpose. For example, the release agent is dispersed by applying a kneading shear force during toner production. The method etc. are mentioned.

  The dispersion state of the release agent can be confirmed by observing a thin film slice of toner particles with a transmission electron microscope (TEM). The dispersion diameter of the release agent is preferably small, but if it is too small, there are cases where bleeding during fixing is insufficient. Therefore, if the release agent can be confirmed at a magnification of 10,000, the release agent is present in a dispersed state. When the release agent cannot be confirmed at 10,000 times, even when finely dispersed, the dyeing at the time of fixing becomes insufficient.

  There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 3 mass%-15 mass% are preferable, and 5 mass%-10 mass% are more preferable. . When the content is less than 3% by mass, the hot offset resistance may be deteriorated, which is not preferable. When the content exceeds 15% by mass, the exudation amount of the release agent during fixing tends to be excessive. This is not preferable because the heat-resistant storage stability tends to deteriorate.

<Layered inorganic compound>
The layered inorganic compound may be a modified layered inorganic compound.
The modified layered inorganic compound refers to, for example, an inorganic mineral formed by superposing layers having a thickness of several nm. “Denature” means introducing organic ions into ions existing between the layers. Specifically, it is described in JP-T-2003-515795, JP-T-2006-500605, and JP-T-2006-503313. This is called intercalation in a broad sense.
Known modified layered inorganic compounds include smectites (montmorillonite, saponite, etc.), kaolin groups (kaolinite, etc.), magadiite, and kanemite. The modified layered inorganic compound is highly hydrophilic due to its modified modified layered structure. Therefore, when used in a toner that is dispersed and granulated in an aqueous medium without modifying the modified layered inorganic compound, the layered inorganic mineral migrates into the aqueous medium and the toner cannot be deformed. By modifying, the hydrophilicity becomes high, and it is easily deformed during granulation, dispersed and refined, and fully exhibits the charge adjusting function.
Commercially available products of the above modified layered inorganic compounds include Quentium 18 such as Bentone 3, Bentone 38, Bentone 38V (manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 40 (manufactured by Big Chemie Japan), and the like. Bentonite: Stearalkonium bentonite such as Bentone 27 (manufactured by Leox), Thixogel LG (manufactured by United catalyst), Clayton AF, Clayton APA (above, manufactured by Big Chemie Japan), etc .; Clayton HT (manufactured by Big Chemie Japan), etc. Quaternium 18 / benzalkonium bentonite. In order to prevent toner scattering, it is also preferable that the toner contains Si and Mg having an effect of improving the charge amount, and the modified layered inorganic compound is preferably a viscosity mineral containing Si and Mg. Si and Mg are present in illite, chlorite, montmorillonite, and the like, but a modified layered inorganic compound derived from montmorillonite is more preferable from the viewpoint of dispersibility. Examples of the modified layered inorganic compound derived from montmorillonite include Clayton APA, Clayton HT, (manufactured by Big Chemie Japan).

  It is desirable to use a quaternary alkyl ammonium salt as the organic cation modifier of the layered inorganic compound (modified layered inorganic compound) obtained by modifying at least part of the ions of the modified layered inorganic compound with an organic cation. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.

When the modified layered inorganic compound is masterbatched and contained in the toner, the Fe / Al value may be controlled to a desired value at the kneading temperature in the masterbatching step. In that case, when Fe / Al is larger than 1.49, the ratio of the element of Fe in the aluminosilicate contained in a layered inorganic compound is large. In this case, since the electronegativity of Fe is larger than that of Mg and Al, the overall electronegativity is increased, the electric attractive force between the aluminosilicate layers between layers is increased, and the dispersion in the toner becomes difficult. Also, the metal elements are arranged in an aggregated state. As a result, it is assumed that sufficient charging characteristics cannot be exhibited because the metal element is not sufficiently dispersed. Further, when Fe / Al is less than 1.23, the toner base particles are charged too much, so that the gap of the charge amount becomes large depending on the presence or absence of the external additive, causing toner scattering.
Further, when Fe / Al is 1.23 to 1.39, the electric attractive force between the aluminosilicate layers is weakened and overdispersed, and charging due to the presence or absence of an external additive due to high charge of the toner base particles. The effect of quantity difference is reduced. Therefore, in this invention, it is more preferable that the ratio (Fe / Al) of atomic concentration% of Fe and Al is in the range of 1.23 to 1.39.

  When the toner is prepared by the dissolution suspension method, in order to more sufficiently disperse the modified layered inorganic compound, the number of rotations when dispersing the oil phase by a homomixer is sufficiently increased in addition to the above-described means by master batch. There is also a means. In that case, care should be taken that the temperature of the oil phase itself does not rise too much or the oil phase jumps in the container.

<Colorant>
There is no restriction | limiting in particular as a coloring agent used for the said toner, According to the objective, it can select suitably from a well-known coloring agent.
There is no restriction | limiting in particular as a color of the colorant of the said toner, According to the objective, it can select suitably. The toner can be at least one selected from black toner, cyan toner, magenta toner, and yellow toner, and each color toner can be obtained by appropriately selecting the type of colorant. preferable.

  Examples of black products include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), titanium oxide, and the like. And organic pigments such as aniline black (CI Pigment Black 1).

  Examples of the magenta color pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 163, 177, 179, 184, 202, 206, 207, 209, 211, 269; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45 and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, Green 7, Green 36, and the like.

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 139, 151, 154, 155, 180, 185; I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content is less than 1% by mass, the coloring power of the toner may be reduced. When the content is more than 15% by mass, poor dispersion of the pigment in the toner may occur. The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. Such a resin is not particularly limited, but it is preferable to use a binder resin or a resin having a structure similar to the binder resin from the viewpoint of compatibility with the binder resin.

  The masterbatch can be produced by applying a high shear force and mixing or kneading the resin and the colorant. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. The flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove water and the organic solvent. For mixing or kneading, for example, a high shear dispersion device such as a three-roll mill can be used.

<Charge control agent>
Further, in order to impart an appropriate charging ability to the toner, a charge control agent can be contained in the toner as necessary.
Any known charge control agent can be used as the charge control agent. Since the color tone may change when a colored material is used, a colorless or nearly white material is preferable. For example, a triphenylmethane dye, a molybdate chelate pigment, a rhodamine dye, an alkoxyamine, a quaternary ammonium salt (fluorine) Modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine-based activators, metal salts of salicylic acid, metal salts of salicylic acid derivatives, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The content of the charge control agent is determined by the toner production method including the type of the binder resin and the dispersion method, and is not uniquely limited. 01 mass%-5 mass% are preferable, and 0.02 mass%-2 mass% are more preferable. When the addition amount exceeds 5% by mass, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the developer fluidity is reduced, and the image The density may be lowered, and if it is less than 0.01% by mass, the charge start-up property and the charge amount are not sufficient, and the toner image may be easily affected.

<External additive>
There is no restriction | limiting in particular as said external additive, According to the objective, it can select suitably from well-known things.
For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (eg, zinc stearate, aluminum stearate, etc.); metal oxides (eg, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoro Examples thereof include polymers. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

  Examples of the hydrophobized silica fine particles include HDK H2000T, HDK H2000 / 4, HDK H2050EP, HVK21, HDK H1303VP (all manufactured by Clariant Japan); R972, R974, RX200, RY200, R202, R805, R812, NX90G (all manufactured by Nippon Aerosil Co., Ltd.) and the like.

  Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); MT-150W. , MT-500B, MT-600B, MT-150A (all of which are manufactured by Teica).

  Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T (any Also, manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both manufactured by Teika); IT-S (produced by Ishihara Sangyo Co., Ltd.).

There is no restriction | limiting in particular as content of the said external additive, Although it can select suitably according to the objective, 0.3 mass part-3.0 mass parts are preferable with respect to 100 mass parts of toner base particles. 0.5 parts by mass to 2.0 parts by mass is more preferable.
The total coverage of the external additive with respect to the toner base particles is not particularly limited, but is preferably 50% to 90%, and more preferably 60% to 80%.

<Toner production method>
As the toner production method and materials in the present invention, all known ones can be used as long as the conditions are satisfied, and the toner production method and materials are not particularly limited. There is a chemical method.

Examples of the chemical method include a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, a dispersion polymerization method, etc., in which a monomer is used as a starting material; a resin or a resin precursor is dissolved in an organic solvent and the like in an aqueous medium. Dispersing or emulsifying dissolution suspension method; in the dissolution suspension method, an oil phase composition containing a resin precursor (reactive group-containing prepolymer) having a functional group capable of reacting with an active hydrogen group is contained in resin fine particles. A method of emulsifying or dispersing in an aqueous medium and reacting an active hydrogen group-containing compound and the reactive group-containing prepolymer in the aqueous medium (ester elongation method); from a resin or resin precursor and an appropriate emulsifier Phase inversion emulsification method in which water is added to the resulting solution for phase inversion; aggregation in which resin particles obtained by these methods are dispersed in an aqueous medium and granulated into particles of a desired size by heating and melting And the like. Among these, the toner obtained by the dissolution suspension method, the ester elongation method, and the aggregation method is preferable from the viewpoint of granulation properties (particle size distribution control, particle shape control, etc.), and the toner obtained by the ester elongation method is preferable. More preferred.
In the following, detailed description of these production methods will be given.

  In the dissolution suspension method, for example, an oil phase composition in which a toner composition containing at least a binder resin or a resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent is used. This is a method for producing toner base particles by dispersing or emulsifying in a medium.

The organic solvent used for dissolving or dispersing the toner composition is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later.
Examples of the organic solvent include ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl. Ether solvents such as ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2 -Alcohol solvents, such as ethylhexyl alcohol and benzyl alcohol, and these 2 or more types of mixed solvents are mentioned.

In the dissolution suspension method, when the oil phase composition is dispersed or emulsified in an aqueous medium, an emulsifier or a dispersant may be used as necessary.
As the emulsifier or dispersant, known surfactants, water-soluble polymers and the like can be used. The surfactant is not particularly limited, and is an anionic surfactant (alkyl benzene sulfonic acid, phosphate ester, etc.), a cationic surfactant (quaternary ammonium salt type, amine salt type, etc.), an amphoteric surfactant (carbon carboxyl). Acid salt type, sulfate ester type, sulfonate salt type, phosphate ester salt type, etc.), nonionic surfactants (AO addition type, polyhydric alcohol type, etc.) and the like. One surfactant may be used alone, or two or more surfactants may be used in combination.

Examples of the water-soluble polymer include cellulose compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin, chitosan. , Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, partially neutralized sodium hydroxide of polyacrylic acid) , Sodium acrylate-acrylic acid ester copolymer), sodium hydroxide of styrene-maleic anhydride copolymer ( Min) neutralized product water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.
Moreover, said organic solvent, a plasticizer, etc. can also be used together as an auxiliary | assistant of emulsification or dispersion | distribution.

  The toner according to the present invention includes at least a binder resin, a binder resin precursor having a functional group capable of reacting with an active hydrogen group (reactive group-containing prepolymer), a colorant, and a release agent in a dissolution suspension method. An active phase group-containing prepolymer and an active hydrogen group-containing compound contained in the oil phase composition and / or the aqueous medium are dispersed or emulsified in an aqueous medium containing resin fine particles. It is preferable to obtain the toner base particles by a method of reacting with (the ester elongation method).

The resin fine particles can be formed using a known polymerization method, but is preferably obtained as an aqueous dispersion of resin fine particles. Examples of the method for preparing an aqueous dispersion of resin fine particles include the methods shown in the following (a) to (h).
(A) A method in which an aqueous dispersion of resin fine particles is directly prepared from a vinyl monomer as a starting material by any one of a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method.
(B) After dispersing a precursor of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin (monomer, oligomer, etc.) or a solvent solution thereof in an aqueous medium in an aqueous medium, A method of preparing an aqueous dispersion of resin fine particles by heating or adding a curing agent to cure.
(C) Polyaddition or condensation resin precursors (monomers, oligomers, etc.) such as polyester resins, polyurethane resins, and epoxy resins, or solvent solutions thereof (preferably liquids, which may be liquefied by heating). A method for preparing an aqueous dispersion of resin fine particles by dissolving a suitable emulsifier in the mixture and then adding water to effect phase inversion emulsification.
(D) A resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is pulverized and classified using a mechanical rotary type or jet type fine pulverizer. A method of preparing an aqueous dispersion of resin fine particles by obtaining resin fine particles and then dispersing in water in the presence of an appropriate dispersant.
(E) Fine resin particles are formed by spraying a resin solution in which a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Then, resin fine particles are dispersed in water in the presence of a suitable dispersant to prepare an aqueous dispersion of resin fine particles.
(F) A poor solvent is added to a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, or heated to a solvent in advance. By cooling the dissolved resin solution, the resin fine particles are precipitated, the solvent is removed to form the resin fine particles, and then the resin fine particles are dispersed in water in the presence of an appropriate dispersant to disperse the resin fine particles in water. A method for preparing a liquid.
(G) A resin solution obtained by dissolving a resin previously synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent in the presence of an appropriate dispersant. A method of preparing an aqueous dispersion of resin fine particles by dispersing in a solvent and then removing the solvent by heating, decompression or the like.
(H) A suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, and then water To prepare an aqueous dispersion of resin fine particles by phase inversion emulsification.

  The volume average particle diameter of the resin fine particles is preferably 10 nm or more and 300 nm or less, and more preferably 30 nm or more and 120 nm or less. When the volume average particle size of the resin fine particles is less than 10 nm or more than 300 nm, the particle size distribution of the toner may be deteriorated.

  The solid content concentration of the oil phase is preferably about 40 to 80%. If the concentration is too high, dissolution or dispersion becomes difficult, and the viscosity becomes high and difficult to handle. If the concentration is too low, the productivity of the toner decreases.

  The toner composition other than the binder resin such as the colorant and the release agent, and the masterbatch thereof are individually dissolved or dispersed in an organic solvent, and then mixed with the binder resin solution or dispersion. May be.

  As the aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The dispersion or emulsification method in the aqueous medium is not particularly limited, and known equipment such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable from the viewpoint of reducing the particle size of the particles. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

  In order to remove the organic solvent from the obtained emulsified dispersion, there is no particular limitation, and a known method can be used. For example, the whole system is gradually raised while stirring the whole system under normal pressure or reduced pressure. A method of warming and completely evaporating and removing the organic solvent in the droplets can be employed.

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

  In the agglomeration method, for example, a toner base particle is produced by mixing and aggregating a resin fine particle dispersion comprising at least a binder resin, a colorant particle dispersion, and a release agent particle dispersion as necessary. is there. The resin fine particle dispersion is obtained by a known method such as emulsion polymerization, seed polymerization, phase inversion emulsification, and the like. The colorant particle dispersion and the release agent particle dispersion are obtained by a known wet dispersion method. It can be obtained by dispersing a colorant or a release agent in an aqueous medium.

For the control of the aggregation state, methods such as applying heat, adding a metal salt, and adjusting pH are preferably used.
There is no restriction | limiting in particular as said metal salt, The monovalent metal which comprises salts, such as sodium and potassium; The bivalent metal which comprises salts, such as calcium and magnesium; The trivalent metal which comprises salts, such as aluminum, etc. Is mentioned.
Examples of the anion constituting the salt include chloride ion, bromide ion, iodide ion, carbonate ion, and sulfate ion. Among these, magnesium chloride, aluminum chloride, and complexes and multimers thereof are preferable. .
Also, heating between the agglomeration and after completion of the agglomeration can promote fusion between the resin fine particles, which is preferable from the viewpoint of toner uniformity. Furthermore, the shape of the toner can be controlled by heating. Normally, the toner becomes more spherical when heated further.

  As the method for washing and drying the toner base particles dispersed in the aqueous medium, the above-described method and the like can be used.

Further, in order to improve the fluidity, storage stability, developability, and transferability of the toner, the external additive may be added to and mixed with the toner base particles produced as described above.
For mixing external additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

(Developer)
The developer of the present invention contains at least the toner and contains other components such as a carrier selected as appropriate. The developer may be a one-component developer or a two-component developer.

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

<< Core particle >>
The core particles are not particularly limited as long as they are magnetic core particles, and can be appropriately selected according to the purpose. For example, ferromagnetic metals such as iron and cobalt; oxidation of magnetite, hematite, ferrite, and the like Iron; resin particles in which magnetic materials such as various alloys and compounds are dispersed in a resin. Among these, Mn-based ferrite, Mn-Mg-based ferrite, Mn-Mg-Sr-based ferrite and the like are preferable from the viewpoint of environmental considerations.

<< Coating layer >>
The coating layer contains at least a resin, and may contain other components such as a filler as necessary.
-Resin-
There is no restriction | limiting in particular as resin for forming the coating layer of a carrier, According to the objective, it can select suitably. For example, a crosslinkable copolymer containing polyolefin (for example, polyethylene, polypropylene, etc.) or a modified product thereof, polystyrene, acrylic resin, acrylonitrile, vinyl acetate, vinyl alcohol, vinyl chloride, vinyl carbazole, vinyl ether, etc .; consisting of an organosiloxane bond Silicone resins or modified products thereof (for example, modified products by alkyd resin, polyester resin, epoxy resin, polyurethane, polyimide, etc.); polyamide; polyester; polyurethane; polycarbonate; urea resin; melamine resin; benzoguanamine resin; Examples thereof include polyimide resins and derivatives thereof. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is preferable.

(Toner storage unit)
The toner storage unit in the present invention refers to a unit in which toner is stored in a unit having a function of storing toner. Here, examples of the toner storage unit include a toner storage container, a developing device, and a process cartridge.
The toner container is a container that contains toner.
The developing device is a unit having a means for containing and developing toner.
The process cartridge is a cartridge in which at least an electrostatic latent image carrier (also referred to as an image carrier) and a developing unit are integrated, accommodates toner, and is detachable from the image forming apparatus. The process cartridge may further include at least one selected from a charging unit, an exposure unit, and a cleaning unit.
By mounting the toner containing unit of the present invention on an image forming apparatus and forming an image, the toner can be prevented from being scattered while exhibiting low-temperature fixability and heat-resistant stability by exhibiting a stable charge amount over the long term. The characteristics of the toner can be utilized.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, and a developing unit, and further includes other units as necessary.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The other steps can be preferably performed by the other means.
More preferably, the image forming apparatus of the present invention is an electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image carrier. The electrostatic latent image formed on the body is developed with toner to form a toner image, and a developing means including toner, and the toner image formed on the electrostatic latent image carrier are transferred to a recording medium Transfer means for transferring to the surface, and fixing means for fixing the toner image transferred to the surface of the recording medium.
In the image forming method of the present invention, more preferably, an electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier and the electrostatic latent image carrier formed on the electrostatic latent image carrier. A developing process for developing the electrostatic latent image with toner to form a toner image, a transfer process for transferring the toner image formed on the electrostatic latent image carrier onto the surface of the recording medium, and the recording A fixing step of fixing the toner image transferred onto the surface of the medium.
The toner is used in the developing unit and the developing step. Preferably, the toner image may be formed by using a developer containing the toner and further containing other components such as a carrier as necessary.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and may be appropriately selected from known materials. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium. And organic photoreceptors such as polysilane and phthalopolymethine.

<Electrostatic latent image forming means>
The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Examples thereof include at least a charging member that charges the surface of the electrostatic latent image carrier and an exposure member that exposes the surface of the electrostatic latent image carrier imagewise.

<Developing means>
The developing unit is not particularly limited as long as it is a developing unit equipped with toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image, depending on the purpose. Can be selected as appropriate.

<Other means>
Examples of the other means include a transfer means, a fixing means, a cleaning means, a static elimination means, a recycling means, and a control means.

Next, one mode for carrying out a method of forming an image by the image forming apparatus of the present invention will be described below with reference to the drawings.
FIG. 1 shows a first example of an image forming apparatus of the present invention. The image forming apparatus 100 </ b> A 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 by three rollers 51 arranged on the inner side, and can move in the direction of the arrow in the figure. A part of the three rollers 51 also functions as a transfer bias roller that can apply a transfer bias (primary transfer bias) to the intermediate transfer belt 50. Further, a cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer belt 50. Further, a transfer roller 80 capable of applying a transfer bias (secondary transfer bias) for transferring the toner image to the transfer paper 95 is disposed to face the intermediate transfer belt 50.

  Further, around the intermediate transfer belt 50, a corona charging device 58 for applying a charge to the toner image transferred to the intermediate transfer belt 50 is connected to the photosensitive drum 10 with respect to the rotation direction of the intermediate transfer belt 50. It is disposed between the contact portion of the intermediate transfer belt 50 and the contact portion of 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 provided around the developing belt 41. Each color developing unit 45 includes a developer container 42, a developer supply roller 43, and a developing roller (developer carrier) 44. The developing belt 41 is an endless belt stretched by a plurality of belt rollers, and can move in the direction of the arrow in the figure. Further, a part of the developing belt 41 is in contact with the photosensitive drum 10.

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

  FIG. 2 shows a second example of the image forming apparatus used in the present invention. In the image forming apparatus 100B, the black developing unit 45K, the yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are arranged directly facing each other around the photosensitive drum 10 without providing the developing belt 41. Other than that, the configuration is the same as that of 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 100 </ b> C is a tandem type 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 at 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 the figure. In the vicinity of the roller 15, 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 onto the recording paper is disposed. The image forming units 120Y, 120C, 120M, and 120K for yellow, cyan, magenta, and black are juxtaposed along the conveyance direction while facing the intermediate transfer belt 50 stretched by the rollers 14 and 15.

  An exposure device 21 is disposed in the vicinity of the image forming unit 120. Further, the secondary transfer belt 24 is disposed on the side of the intermediate transfer belt 50 opposite to the side on which the image forming unit 120 is disposed. The secondary transfer belt 24 is an endless belt stretched around a pair of rollers 23, and the recording paper and the intermediate transfer belt 50 conveyed on the secondary transfer belt 24 are between the rollers 16 and 23. Can touch.

  Further, in the vicinity of the secondary transfer belt 24, a fixing device 25 is provided with a fixing belt 26 that is an endless belt stretched between a pair of rollers, and a pressure roller 27 that is arranged to be pressed against the fixing belt 26. Is arranged. A sheet reversing device 28 for reversing the recording paper when an image is formed on both sides of the recording paper is disposed in the vicinity of the secondary transfer belt 24 and the fixing device 25.

  Next, a method for forming a full-color image using the image forming apparatus 100C will be described. First, a color document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a color document is set on the contact glass 32 of the scanner 300 to automatically convey the document. The device 400 is closed. When the start switch is pressed, when an original is set on the automatic document feeder 400, after the original is conveyed and moved onto the contact glass 32, on the other hand, when the original is set on the contact glass 32, Immediately, the scanner 300 is driven, and the first traveling body 33 including the light source and the second traveling body 34 including the mirror travel. At this time, the reflected light from the original 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, whereby the original is received. It is read and image information of black, yellow, magenta and cyan is obtained.

  The image information for each color is transmitted to the image forming unit 120 for each color, and a toner image for each color is formed. As shown in FIG. 4, each color image forming unit 120 includes a photosensitive drum 10, a charging roller 160 that uniformly charges the photosensitive drum 10, and the image information of each color, respectively. An exposure device that exposes the 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; A transfer roller 62 for transferring onto the transfer belt 50, a cleaning device 63 having a cleaning blade, and a static elimination lamp 64 are provided.

  The toner images of the respective colors formed by the image forming units 120 of the respective colors are sequentially transferred (primary transfer) onto the intermediate transfer body 50 that is stretched and moved by the rollers 14, 15, and 16, and 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 recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the paper feed roller is rotated to feed out the recording paper on the manual feed tray 54, separated one by one by the separation roller 52, guided to the manual paper feed path 53, and abutted against the registration roller 49 and stopped.

  The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied in order 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 sent. The toner image is transferred onto the recording paper (secondary transfer). 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 on which the composite toner image has been transferred is conveyed by the secondary transfer belt 24 and then the composite toner image is fixed by the fixing device 25. Next, the conveyance path of the recording paper is switched by the switching claw 55, and the recording paper is discharged onto the paper discharge tray 57 by the discharge roller 56. Alternatively, the recording path of the recording paper is switched by the switching claw 55, reversed by the sheet reversing device 28, an image is similarly formed on the back side, and then discharged onto the discharge tray 57 by the discharge roller 56. .

  According to the image forming method and the image forming apparatus of the present invention, high-quality images can be provided over a long period of time.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples. “Part” represents “part by mass” unless otherwise specified. “%” Represents “% by mass” unless otherwise specified.

(Synthesis of polyester resin A)
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A propylene oxide 2 mol adduct and bisphenol A propylene oxide 3 mol adduct in a molar ratio of 80/20, isophthalic acid and adipine The acid was adjusted to a molar ratio of 70/30, OH / COOH = 1.33, and reacted with 500 ppm of titanium tetraisopropoxide at 230 ° C. for 10 hours at normal pressure. Next, after reaction for 5 hours at a reduced pressure of 10 mmHg to 15 mmHg, 11 parts of trimellitic anhydride was added to the reaction vessel and reacted for 3 hours at 180 ° C. and normal pressure to obtain [Polyester Resin A].

(Preparation of masterbatch 1)
Yellow pigment C.I. I. Pigment yellow 185 (manufactured by BASF) 18 parts, 82 parts of polyester resin A and 15 parts of ion-exchanged water were mixed, and then kneaded using an open roll kneader Needex (manufactured by Mitsui Mining Co., Ltd.). Got a batch. Specifically, kneading started from 100 ° C., and the mixture was gradually cooled to 50 ° C.

(Preparation of masterbatch 2)
After mixing 55 parts of modified layered inorganic compound (Clayton APA (manufactured by Big Chemie Japan)), 45 parts of polyester resin A and 15 parts of ion-exchanged water, an open roll kneader Kneadex (manufactured by Mitsui Mining Co., Ltd.) was used. And kneaded at 160 ° C. to obtain a master batch of the modified layered inorganic compound.
The modified layered inorganic compound contains Al, Fe, Si, and Mg, which were confirmed by measurement by fluorescent X-ray elemental analysis (XRF).

(Synthesis of polyester prepolymer 1)
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 Part and 2 parts of dibutyltin oxide were allowed to react at 230 ° C. for 8 hours under normal pressure. Furthermore, [intermediate polyester] was synthesized by reacting under reduced pressure of 10 mmHg to 15 mmHg for 5 hours. Next, 410 parts of the synthesized [intermediate polyester], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Thus, [Polyester Prepolymer 1] was synthesized.

Example 1
<Preparation of toner>
-Preparation of release agent dispersion-
70 parts of Carnauba wax (WA-05, manufactured by Celerica Noda), 140 parts of [Polyester resin A] and 290 parts of ethyl acetate are placed in a container equipped with a stirring bar and a thermometer, and the temperature is raised to 75 ° C. with stirring. , Kept at 75 ° C. for 1.5 hours, cooled to 30 ° C. in 1 hour, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 5 kg / hr, a disk peripheral speed of 6 m / sec, Filled with 80% by volume of 0.5 mm zirconia beads and dispersed under the conditions of 3 passes to obtain a [release agent dispersion].

-Production of oil phase 1-
In a container equipped with a thermometer and a stirrer, 139 parts of [Polyester resin A], 88 parts of [Mold release agent dispersion], 29 parts of [Masterbatch 1], 2.5 parts of [Masterbatch 2], and ethyl acetate 86 parts were added and pre-dispersed with a stirrer, and then stirred with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a rotational speed of 5,000 rpm to uniformly dissolve and disperse [oil phase 1]. Got.

-Production of dispersion of resin fine particles-
In a reaction vessel equipped with a stirrer and a thermometer, 600 parts of water, 120 parts of styrene, 100 parts of methacrylic acid, 45 parts of butyl acrylate, sodium salt of alkylallylsulfosuccinate (Eleminol JS-2, manufactured by Sanyo Chemical Industries) 10 And 1 part of ammonium persulfate were added and stirred at 400 rpm for 20 minutes to obtain a white emulsion. This emulsion was heated to raise the temperature in the system to 75 ° C. and reacted for 6 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours to obtain [resin fine particle dispersion]. The volume average particle diameter of the particles contained in this [resin fine particle dispersion] was 60 nm, the weight average molecular weight of the resin was 140,000, and Tg was 73 ° C.

-Preparation of aqueous phase-
990 parts of water, 89 parts of [resin fine particle dispersion], 37 parts of a 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. [Aqueous phase] was obtained.

-Emulsification or dispersion-
To 338 parts of the [oil phase 1], 54 parts of an ethyl acetate solution of the [polyester prepolymer 1] and 2.3 parts of a 50% ethyl acetate solution of isophoronediamine are added, and a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) is added. ) At 5,000 rpm, and uniformly dissolved and dispersed to obtain [Oil Phase 1 ′]. Next, 608 parts of [Aqueous phase] is put in another container in which a stirrer and a thermometer are set, and while stirring at 11,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), [oil phase 1 '] Was added and emulsified for 1 minute to obtain [Emulsified slurry 1].

-Solvent removal-Washing-Drying-
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Slurry 1]. The obtained [Slurry 1] was kept at 40 ° C. for 4 hours, then filtered under reduced pressure, and the following washing treatment was performed.
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered.
(2) Add 100 parts of ion-exchanged water to the filter cake of (1) above, mix with TK homomixer (rotation speed: 6,000 rpm for 5 minutes), and then stir 1% hydrochloric acid to a pH of about 3.3. In this state, stirring was continued for 1 hour, followed by filtration.
(3) N, N, N, -trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium, iodide (product), which is a fluorine-containing compound of the general formula (1), in the filter cake of (2) Name: 1% aqueous solution of Footent 310 (manufactured by Neos Co., Ltd., fluorine-containing compound) so as to be 0.10% by mass with respect to the amount of toner composition material (the mass finally contained in the non-magnetic one-component toner) Slowly added with stirring. Thereafter, the mixture was stirred at room temperature for 1 hour and then separated by filtration to obtain a filter cake 1.

  The obtained filter cake 1 was dried at 40 ° C. for 48 hours in a circulating dryer. Thereafter, the mixture was sieved with a mesh having an opening of 75 μm to prepare [Toner Base Particles 1].

  Next, commercially available silica fine powder NAX50 [manufactured by Nippon Aerosil Co., Ltd .; average primary particle size 30 nm] 2.8 parts and H20TM [manufactured by Clariant Co .; average primary particle size 20 nm] with respect to 100 parts of the toner base particles. 0.9 parts were mixed with a Henschel mixer. Next, this was passed through a sieve having an opening of 60 μm to remove coarse particles and aggregates, thereby obtaining [Toner 1].

For [Toner 1], the atomic concentration% of Al in the toner and the ratio (Fe / Al) of the atomic concentration% of Fe and Al in the toner were determined by the following X-ray fluorescence elemental analysis (XRF) measurement. The measurement results are shown in Table 1.
[Measurement by X-ray fluorescence analysis (XRF)]
The amount of metal elements (Al, Fe, etc.) in the toner is quantified by fluorescent X-ray analysis (ZSX 100e: automatic fluorescent X-ray analyzer manufactured by Rigaku Corporation), and the amount of metal elements (Al, Fe) present in the entire toner. ) Was calculated. For the measurement, a sample of 3.0 ± 0.1 g of toner was pressurized at 6 (t / cm ² ) for 30 seconds to produce a 40 mmφ circular pellet.

<Production of developer>
4 parts of the obtained toner 1 and 96.0 parts of a magnetic carrier described below were mixed by a ball mill to prepare a developer.
-Fabrication of carrier-
Silicone resin (organostraight silicone) 100 parts by mass Toluene 100 parts by mass γ- (2-aminoethyl) aminopropyltrimethoxysilane 5 parts by mass Carbon black 10 parts by mass The above mixture is dispersed with a homomixer for 20 minutes to form a coating layer forming solution. Was prepared. This coating layer forming liquid was coated on the surface of 1000 parts by mass of spherical magnetite having a particle diameter of 50 μm using a fluid bed type coating apparatus to obtain a magnetic carrier.
Using an image forming apparatus using a developer containing [Toner 1], toner scattering, low-temperature fixability, and heat-resistant storage stability were evaluated by the evaluation methods described below. The results are shown in Table 1.

<Low temperature fixability>
The image is obtained by using an evaluation machine that has been tuned by modifying the image forming apparatus (“IPSIO Color 8100”; manufactured by Ricoh Co., Ltd.) into an oilless fixing method, and using cardboard (“copy printing paper <135>”; NBS Ricoh Company, Ltd.) The toner was adjusted so that 1.0 ± 0.1 mg / cm ² of toner was developed with a solid image. The fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more was determined as the minimum fixing temperature. Evaluation was made according to the following evaluation criteria.
[Evaluation criteria]
A: Fixing lower limit is less than 120 ° C. ○: Fixing lower limit is from 120 ° C. to less than 135 ° C. Δ: Fixing lower limit is from 135 ° C. to less than 150 ° C. ×: Fixing lower limit is 150 ° C. or more

<Toner scattering property>
Visually check the degree of toner contamination in the machine when 80,000 sheets of 20% image area chart are output continuously using a commercially available digital full color printer (image MPC6000, A4 horizontal color 50 sheets / minute, manufactured by Ricoh Co., Ltd.) The evaluation was made in four stages according to the following criteria. “Δ” or more is practical.
[Evaluation criteria]
◎: Toner stains are not observed at all and are in a good state. ○: Slightly stains are not a problem. △: Slight stains are observed. There is a problem

<Heat resistant storage stability>
Shake 10.0 g of toner into a 30 mL bottle, shake it for more than 10 minutes, and tap it 150 times using a tapping device (KRS-409, manufactured by Kuramotsu Scientific Instruments) with a constant temperature of 50 ° C. Leave in a bath for 24 hours. Thereafter, a needle was set on the upper surface of the sample using testing apparatus for penetration (manufactured by Nikka Engineering Co., Ltd.), and the depth of penetration of the needle into the sample was used as an index for heat resistant storage stability. The heat resistant storage stability was evaluated in the following four stages.
“◎” and “◯” are levels that have no problem at all, “Δ” is a level that is slightly poor in storability, but has no practical problem, and “×” is a level that has a problem in practical use.
[Evaluation criteria]
◎: 29 mm or more ○: 24 mm or more and less than 29 mm △: 19.5 mm or more and less than 24 mm ×: less than 19.5 mm

<Comprehensive judgment>
Comprehensive judgment was performed according to the following evaluation criteria.
[Evaluation criteria]
A (very good): Among the three evaluation items, ◎ is one or more, and Δ and X are none. B (very good): Among the three evaluation items, all items are good.
C (Good): Among the three evaluation items, Δ is one and × None D (Permitted): Among the three evaluation items, Δ is two or more and × None E (Difficult to use): Three evaluations Among the items, one or more x was used, and A, B, C, and D were accepted and E was rejected.

(Example 2)
In Example 1, [Toner 2] was obtained in the same manner as in Example 1 except that the kneading temperature was changed from 160 ° C. to 170 ° C. in “Adjustment of Masterbatch 2” in Example 1.
A toner and a developer were obtained by the same method as in Example 1, and the same measurement and evaluation as in Example 1 were performed. The results are shown in Table 1.

Example 3
In Example 1, [Toner 3] was obtained in the same manner as in Example 1 except that the kneading temperature was changed from 160 ° C. to 150 ° C. in “Preparation of Masterbatch 2” in Example 1.
A toner and a developer were obtained by the same method as in Example 1, and the same measurement and evaluation as in Example 1 were performed. The results are shown in Table 1.

Example 4
In Example 1, [Toner] was prepared in the same manner as in Example 1 except that the amount of input of master batch 2 was changed from 2.5 parts to 2.25 parts in “Preparation of oil phase 1” in Example 1. 4] was obtained.
A toner and a developer were obtained by the same method as in Example 1, and the same measurement and evaluation as in Example 1 were performed. The results are shown in Table 1.

(Example 5)
In Example 1, [Toner] was prepared in the same manner as in Example 1 except that, in “Preparation of oil phase 1” in Example 1, the input amount of master batch 2 was changed from 2.5 parts to 3.0 parts. 5] was obtained.
A toner and a developer were obtained by the same method as in Example 1, and the same measurement and evaluation as in Example 1 were performed. The results are shown in Table 1.

Example 6
In Example 1, in “Preparation of oil phase 1” in Example 1, the input amount of Masterbatch 2 was changed from 2.5 parts to 2.25 parts, and in Example 1, “Masterbatch 2” in Example 1 was changed. [Toner 6] was obtained in the same manner as in Example 1 except that the kneading temperature was changed from 160 ° C. to 170 ° C.
A toner and a developer were obtained by the same method as in Example 1, and the same measurement and evaluation as in Example 1 were performed. The results are shown in Table 1.

(Example 7)
In Example 1, in “Production of Oil Phase 1” in Example 1, 1.4 parts were added in the state of the modified layered inorganic compound instead of masterbatch 2, and [Polyester Resin A] was changed from 139 parts to 142 parts. Except for the change, [Toner 7] was obtained in the same manner as in Example 1.
A toner and a developer were obtained by the same method as in Example 1, and the same measurement and evaluation as in Example 1 were performed. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, [Toner 8] was obtained in the same manner as in Example 1 except that the kneading temperature was changed from 160 ° C. to 175 ° C. in “Adjustment of Masterbatch 2” in Example 1.
A toner and a developer were obtained by the same method as in Example 1, and the same measurement and evaluation as in Example 1 were performed. The results are shown in Table 1.

(Comparative Example 2)
In Example 1, [Toner 9] was obtained in the same manner as in Example 1 except that the kneading temperature was changed from 160 ° C. to 145 ° C. in “Adjustment of Masterbatch 2” in Example 1.
A toner and a developer were obtained by the same method as in Example 1, and the same measurement and evaluation as in Example 1 were performed. The results are shown in Table 1.

(Comparative Example 3)
In Example 1, [Toner] was prepared in the same manner as in Example 1 except that the amount of input of master batch 2 was changed from 2.5 parts to 2.1 parts in “Preparation of oil phase 1” in Example 1. 10] was obtained.
A toner and a developer were obtained by the same method as in Example 1, and the same measurement and evaluation as in Example 1 were performed. The results are shown in Table 1.

(Comparative Example 4)
In Example 1, [Toner] was prepared in the same manner as in Example 1 except that, in “Preparation of oil phase 1” in Example 1, the input amount of master batch 2 was changed from 2.5 parts to 3.0 parts. 11] was obtained.
A toner and a developer were obtained by the same method as in Example 1, and the same measurement and evaluation as in Example 1 were performed. The results are shown in Table 1.

  As is apparent from the evaluation results in Table 1, the toners of Examples 1 to 7 have sufficiently excellent toner scattering properties, low-temperature fixability, and heat-resistant storage stability. In particular, the toners of Examples 1 and 3 show particularly excellent results. On the other hand, the toners of Comparative Examples 1 to 4 have practically problematic results in at least one of toner scattering property, low temperature fixing property, and heat resistant storage property.

Aspects of the present invention are as follows, for example.
<1> A toner containing at least a binder resin and a release agent,
The toner contains Fe and Al, and the ratio of the atomic concentration% of Fe and Al (Fe / Al) measured by X-ray fluorescence elemental analysis (XRF) is 1.23 to 1.48. The toner is characterized in that the atomic concentration% of Al in the toner is 0.45% to 0.60%.
<2> The ratio of the atomic concentration% of Fe and Al (Fe / Al) is 1.23 to 1.39, and the atomic concentration% of Al in the toner is 0.50% to 0.60%. The toner according to <1>.
<3> The toner according to any one of <1> to <2>, wherein the toner contains Si and Mg.
<4> The toner according to any one of <1> to <3>, wherein the toner contains a modified layered inorganic compound.
<5> The toner according to any one of <1> to <4>, wherein the modified layered inorganic compound is obtained by modifying montmorillonite.
<6> A toner storage unit that stores the toner according to any one of <1> to <5>.
<7> an electrostatic latent image carrier, and electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means comprising toner for developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a toner image;
Transfer means for transferring the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium,
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <5>.
<8> an electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
A developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a toner image;
A transfer step of transferring a toner image formed on the electrostatic latent image carrier onto the surface of a recording medium;
Fixing the toner image transferred to the surface of the recording medium,
The toner is the toner according to any one of <1> to <5>.

  According to the toner according to any one of <1> to <5>, the toner storage unit according to <6>, the image forming apparatus according to <7>, and the image forming method according to <8>. Thus, the above-described problems can be solved and the object of the present invention can be achieved.

JP 2008-233163 A JP 2007-279707 A JP 2004-117963 A

Claims (8)

A toner containing at least a binder resin and a release agent,
The toner contains Fe and Al, and the ratio of the atomic concentration% of Fe and Al (Fe / Al) measured by X-ray fluorescence elemental analysis (XRF) is 1.23 to 1.48. The toner is characterized in that the atomic concentration% of Al in the toner is 0.45% to 0.60%.   The ratio of the atomic concentration% of Fe and Al (Fe / Al) is 1.23 to 1.39, and the atomic concentration% of Al in the toner is 0.50% to 0.60%. The toner according to 1.   The toner according to claim 1, wherein the toner contains Si and Mg.   The toner according to claim 1, wherein the toner contains a modified layered inorganic compound.   The toner according to claim 1, wherein the modified layered inorganic compound is obtained by modifying montmorillonite.   A toner containing unit containing the toner according to claim 1. An electrostatic latent image carrier, and electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means comprising toner for developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a toner image;
Transfer means for transferring the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium,
An image forming apparatus according to claim 1, wherein the toner is the toner according to claim 1. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
A developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a toner image;
A transfer step of transferring a toner image formed on the electrostatic latent image carrier onto the surface of a recording medium;
Fixing the toner image transferred to the surface of the recording medium,
6. The image forming method according to claim 1, wherein the toner is the toner according to claim 1.