JP5347367B2 - Toner, developer, image forming method, image forming apparatus, process cartridge, toner container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner that reconciles excellent low-temperature fixability with excellent offset resistant performance. <P>SOLUTION: This toner containing an acetic acid ethyl insoluble polyester component obtained by preparing toner solution by dissolving or dispersing, in an organic solvent, at least compound containing active hydrogen group, a polyester component capable of reacting with the compound containing active hydrogen group, and an acetic acid ethyl soluble polyester component, then preparing fluid dispersion by emulsifying or dispersing the toner solution in an aqueous medium, and making the compound containing active hydrogen group react with the polyester component capable of reacting with the compound containing active hydrogen group in the aqueous medium. The polyester component capable of reacting with the compound containing active hydrogen group is made of polyester resin with a weight average molecular weight of 10000-100000 obtained by condensing and polymerizing an acid component, at least one diol compound selected from aliphatic diol and cycloaliphatic diol, and aromatic diol compound under existence of catalyst. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a toner for developing an electrostatic image by electrophotography, a developer using the toner, an image forming method, an image forming apparatus, a process cartridge, and a container containing toner.

  In the image formation by electrophotography, generally, an electric latent image is formed on a photoconductor produced using a photoconductive substance by various means. Next, after developing the latent image using a developer, the image formed by the developer is transferred to paper or the like as necessary, and then fixed by heating, pressing, or solvent vapor.

  The methods for developing electrical latent images can be broadly divided into a liquid development method using a liquid developer in which various pigments and dyes are finely dispersed in an insulating organic liquid, a cascade method, a magnetic brush method, and a powder cloud. There is a dry development system using a dry developer (hereinafter sometimes referred to as “toner”) prepared by dispersing a colorant such as carbon black in a natural or synthetic resin, as in the past, etc. The dry development method is widely used.

  As a fixing method used in the dry development method, a heating heat roller method is widely used because of its energy efficiency. In recent years, in order to save energy by fixing the toner at a low temperature, the thermal energy given to the toner at the time of fixing tends to be small. In the 1999 International Energy Agency (IEA) DSM (Demand-Side Management) program, there is a technology procurement project for next-generation copiers, and the required specifications are published. For copiers of 30 cpm or more, drastically reduced energy consumption compared to conventional copiers so that the standby time is within 10 seconds and the standby power consumption is 10 to 30 watts or less (differs depending on the copying speed). Achievement is required. One method for achieving this requirement is to reduce the heat capacity of a fixing member such as a heated heat roller to improve the temperature responsiveness of the toner, but it is not fully satisfactory.

  In order to achieve the above requirement and minimize the waiting time, it is considered to be an essential technical achievement matter to lower the fixing temperature of the toner itself and lower the toner fixing temperature when it can be used. In order to cope with such low-temperature fixing, an attempt has been made to use a polyester resin having excellent low-temperature fixability and relatively good heat-resistant storage stability, instead of the styrene-acrylic resin that has been widely used conventionally (Patent Document 1). Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, and Patent Document 6). In addition, there are attempts to add a specific non-olefinic crystalline polymer in the binder for the purpose of improving low-temperature fixability (see Patent Document 7), attempts to use crystalline polyester (see Patent Document 8), and the like. It cannot be said that the molecular structure and molecular weight of the polyester resin are optimized.

Further, it is impossible to achieve the specifications of the DSM program even if these conventionally known techniques are applied, and it is necessary to establish a low-temperature fixing technique that is further advanced than the conventional technical field.
Therefore, for further low-temperature fixing, it is necessary to control the thermal characteristics of the resin itself. However, if the glass transition temperature (Tg) is lowered too much, the heat-resistant storage stability is deteriorated, and the molecular weight is reduced. If the T1 / 2 temperature is lowered too much, there are problems such as lowering the hot offset occurrence temperature. For this reason, by controlling the thermal characteristics of the resin itself, it has not been possible to obtain a toner having excellent low-temperature fixability and a high hot offset occurrence temperature.

  Next, a method for producing a toner used for developing an electrostatic image is roughly classified into a pulverization method and a polymerization method. In the pulverization method, a colorant, a charge control agent, an offset preventive agent, and the like are melt-mixed and uniformly dispersed in a thermoplastic resin, and the resulting composition is pulverized and classified to produce a toner. . According to this pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of materials. That is, the composition obtained by melt mixing must be capable of being pulverized and classified by an economically usable apparatus. From this requirement, the melt-mixed composition must be made sufficiently brittle. For this reason, when the above composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, toner weight The average particle size must be reduced, and fine powder having a particle size of 4 μm or less and coarse powder having a particle size of 15 μm or more must be removed by classification, which has a disadvantage that the toner yield becomes very low. In the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent and the like in the thermoplastic resin. As a result, the toner fluidity, developability, durability, image quality, etc. are adversely affected. There is a drawback of affecting.

In recent years, in order to overcome these problems in the pulverization method, a toner production method using a polymerization method has been proposed and implemented. For example, toner particles are obtained by a suspension polymerization method or an emulsion polymerization aggregation method (see Patent Document 9).
However, in these production methods, it has been difficult to use a polyester resin superior in low-temperature fixability as a toner.
In order to solve this problem, for example, a toner made of a polyester resin in a spherical shape using a solvent in water (see Patent Document 10), a toner using an isocyanate reaction (see Patent Document 11), and the like have been proposed. Yes. However, none of the proposals can satisfy the low-temperature fixability and the toner productivity.

  Further, Patent Document 12, Patent Document 13 and the like have been proposed as the following to solve low-temperature fixability by toner granulated in an aqueous medium, but there is still room for investigation.

(Patent Document 12)
Obtained by dissolving or dispersing a toner composition containing an active hydrogen group-containing compound (A), a polymer (B) having a site capable of reacting with an active hydrogen group, a colorant, and a release agent in an organic solvent. The organic solvent liquid is dispersed in the form of droplets in an aqueous medium, and after reacting (A) and (B) or while reacting, the organic solvent is removed, washed and dried with a toner (B ) Has a weight average molecular weight of 50,000 to 200,000 and a molecular weight exhibiting the maximum peak of 20,000 to 40,000.

(Patent Document 13)
Resin particles obtained by removing a solvent from an aqueous dispersion of an oily mixture (I) containing a resin (K) and an organic solvent and an aqueous medium (II), wherein (K) is a polyol component Polyester resin (K1) obtained by polycondensation of a polycarboxylic acid component and a fat having 2 to 6 carbon atoms having a number average molecular weight of 1000 to 9500 and a polyol component of 85 to 100 mol% in a tetrahydrofuran-soluble component of (K1) Particles consisting of a group diol or 70-100 mol% 1,2-propylene glycol.

JP 60-90344 A JP-A 64-15755 Japanese Patent Laid-Open No. 2-82267 JP-A-3-229264 JP-A-3-41470 JP-A-11-305486 JP 62-63940 A Japanese Patent No. 2931899 Japanese Patent No. 2537503 JP-A-9-34167 JP-A-11-149180 JP 2007-264619 A JP 2007-238954 A

  The present invention has been made in view of the above-described conventional problems, and can achieve both excellent low-temperature fixability and anti-offset performance, and can form a good high-definition image, and It is an object to provide a developer, an image forming method, an image forming apparatus, a process cartridge, and a toner-containing container using the toner.

In order to solve the above problems, the invention according to claim 1 is soluble in an organic solvent, at least an active hydrogen group-containing compound, a polyester component capable of reacting with the active hydrogen group-containing compound, and the organic solvent. A polyester solution is dissolved or dispersed to prepare a toner solution, and then the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion. In the aqueous medium, the active hydrogen group-containing compound and A toner comprising a polyester component insoluble in the organic solvent produced by a reaction between the active hydrogen group-containing compound and a reactive polyester component;
The polyester component capable of reacting with the active hydrogen group-containing compound comprises a polyester obtained by condensation polymerization of an aliphatic diol and an acid component in the presence of a catalyst, an aromatic diol and an acid component in the presence of a catalyst. It is characterized by comprising a polyester resin having a weight average molecular weight of 10,000 to 100,000, which is obtained by reacting (polymerizing) the polyester obtained by condensation polymerization .

  According to a second aspect of the present invention, in the toner of the first aspect, the polyester component insoluble in the organic solvent includes a gel component having an increased molecular weight due to an extension reaction.

  According to a third aspect of the present invention, in the toner according to the first or second aspect, the polyester component capable of reacting with the active hydrogen group-containing compound contains an isocyanate group.

  The invention according to claim 4 is the toner according to claim 3, wherein the content of free isocyanate groups in the polyester component capable of reacting with the active hydrogen group-containing compound is 1.5% by mass or less. And

  According to a fifth aspect of the present invention, in the toner according to any one of the first to fourth aspects, the organic solvent is ethyl acetate, and the polyester component soluble in the organic solvent is an ethyl acetate soluble polyester component. The polyester component insoluble in the organic solvent is an ethyl acetate insoluble polyester component.

Invention according to claim 6, in the toner according to any one of claims 1 to 5, wherein the aliphatic Jio Le is, 1,4-butanediol, propylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol and 1 , 6-hexanediol.

  The invention according to claim 7 is the toner according to any one of claims 1 to 6, wherein the aromatic diol compound is an ethylene oxide 2 mol adduct of bisphenol A or a propylene oxide 2 mol adduct. To do.

The invention according to claim 8, The toner according to any one of claims 1 to 7, mol ratios of the aliphatic Jio Le said aromatic diol compound is 9.5 / 0.5-6 / 4 It is characterized by being.

  The invention according to claim 9 is the toner according to any one of claims 1 to 8, wherein the acid component is terephthalic acid or isophthalic acid.

  According to a tenth aspect of the present invention, in the toner according to any one of the first to ninth aspects, the catalyst is a Ti-based catalyst.

  According to an eleventh aspect of the present invention, in the toner according to any one of the first to tenth aspects, the toner has a volume average particle diameter (Dv) of 3 to 8 μm.

  According to a twelfth aspect of the present invention, in the toner according to any one of the first to eleventh aspects, the volume average particle diameter (Dv) / number average particle diameter (Dn) of the toner is 1.25 or less. It is characterized by.

  A thirteenth aspect of the present invention is a developer containing the toner according to any one of the first to twelfth aspects.

  According to a fourteenth aspect of the present invention, there is provided an electrostatic latent image forming step for forming an electrostatic latent image on an electrostatic latent image carrier, and the toner according to any one of the first to twelfth aspects of the present invention. An image forming method comprising at least a developing step for developing a visible image by using a toner, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium It is characterized by being.

  According to a fifteenth aspect of the present invention, there is provided an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image. To 12 to develop a visible image by developing with the toner according to any one of claims 1 to 12, a transfer means for transferring the visible image to a recording medium, and fixing the transferred image transferred to the recording medium. An image forming apparatus having at least a fixing unit.

  According to a sixteenth aspect of the present invention, an electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of the first to twelfth aspects. It is a process cartridge having at least developing means for forming a visible image.

  The invention described in claim 17 is a toner-containing container filled with the toner according to any one of claims 1-12.

  According to the present invention, it is possible to obtain a toner that can achieve both excellent low-temperature fixability and anti-offset performance and can form a good high-definition image.

Hereinafter, the present invention will be described in detail.
(toner)
The present invention prepares a toner solution by dissolving or dispersing at least an active hydrogen group-containing compound, a polyester component capable of reacting with the active hydrogen group-containing compound, and a polyester component soluble in the organic solvent in an organic solvent. Thereafter, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and the polyester component capable of reacting with the active hydrogen group-containing compound in the aqueous medium. A toner containing a polyester component insoluble in the organic solvent produced by reaction,
The active hydrogen group-containing compound capable of reacting a Poriesu ether component in the presence of a catalyst and a polyester obtained by an aliphatic diol and an acid component to a condensation polymerization in the presence of a catalyst, an aromatic diol and an acid component It is possible to achieve both excellent low-temperature fixability and anti-offset performance by comprising a polyester resin having a weight average molecular weight of 10,000 to 100,000 obtained by reacting (polymerizing) the polyester obtained by condensation polymerization with A toner capable of forming a high-definition image is obtained.

Here, in the polyester component soluble in the organic solvent and the polyester component insoluble in the organic solvent, soluble or insoluble in the organic solvent means that 30 parts by weight of the organic solvent and 70 parts by weight of the polyester component are stirred and dissolved. It is judged by the presence or absence of insoluble components by visual inspection.
As described later, since ethyl acetate is preferably used as the organic solvent in the present invention, in this case, the “polyester component soluble in an organic solvent” is an “ethyl acetate-soluble polyester component”. “Polyester component insoluble in organic solvent” is “ethyl acetate insoluble polyester component”. In the following, the description will proceed mainly assuming that ethyl acetate is used as the organic solvent.

In the present invention, the polyester component capable of reacting with the active hydrogen group-containing compound is, as described above, a polyester obtained by condensation polymerization of an aliphatic diol and an acid component in the presence of a catalyst, an aromatic diol and an acid. It consists of a polyester resin having a weight average molecular weight of 10,000 to 100,000, which is obtained by reacting (polymerizing) a polyester obtained by subjecting components to condensation polymerization in the presence of a catalyst .

  Examples of at least one diol compound selected from the above aliphatic diols and alicyclic diols include 1,4-butanediol, propylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol, and 1,6-hexanediol. 1 type may be used individually and may use 2 or more types together.

  In addition, the aromatic diol compound is at least one selected from an ethylene oxide 2 mol adduct and a propylene oxide 2 mol adduct of bisphenol A, and may be used alone or in combination of two types. May be.

The molar ratio of the aliphatic diol and the aromatic diol compound is 9.5 / 0.5 to 6/4.

  As the acid component, either terephthalic acid or isophthalic acid is suitable.

  Moreover, as said catalyst, Ti type catalyst is preferable, for example, titanium tetrabutoxide etc. are mentioned.

  The weight average molecular weight of the produced polyester resin (hereinafter referred to as precursor polyester resin) is preferably 10,000 to 100,000, more preferably 15,000 to 50,000. When the weight average molecular weight is less than 10,000, the low-temperature fixability is not exhibited, and when it exceeds 100,000, it may be difficult to produce particles.

Gel permeation chromatography (GPC) is used for the measurement of molecular weight. Measurement of molecular weight distribution by GPC can be performed, for example, as follows.
That is, first, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent is allowed to flow at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 mass% is injected and measured. 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 created by several monodisperse polystyrene standard samples and the count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Or the molecular weights made by Toyo Soda Industry Co., Ltd. are 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8. It is preferable to use 6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. As the detector, an RI (refractive index) detector can be used.

As a glass transition temperature of the said precursor polyester resin, 30-60 degreeC is preferable and 40-50 degreeC is more preferable. Moreover, as a hydroxyl value of this precursor polyester resin, 10 mgKOH / g or more is preferable, and 20-40 mgKOH / g is more preferable. Moreover, as an acid value of this precursor polyester resin, 0-10 mgKOH / g is preferable and 0-5 mgKOH / g is more preferable.
Here, the acid value can be measured by a method specified in JIS K0070, and the hydroxyl value can be measured by a method specified in JIS K0070.

The precursor polyester resin is, for example, put a diol compound, an acid component, and a titanium-based catalyst in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and allowed to react at 230 ° C. for 8 hours under normal pressure. Then, it is obtained by reacting at a reduced pressure of 10 to 15 mmHg for 5 hours. The obtained precursor polyester resin becomes a precursor polyester of an ethyl acetate insoluble polyester component by reacting with an isocyanate group-containing compound.
The isocyanate group content in the precursor polyester of the ethyl acetate insoluble polyester component is preferably 1.5% by mass or less, and more preferably 0.8 to 1.5% by mass. When the content of the free isocyanate group exceeds 1.5% by mass, the reaction between the polyester resin and the isocyanate group is insufficient, so that the ethyl acetate insoluble polyester component may not be formed.

  Here, the said free isocyanate group content (NCO%) can be measured by the method based on JISK1603, for example.

The ethyl acetate-insoluble polyester component preferably includes a gel component having an increased molecular weight due to an extension reaction in terms of hot offset.
The gel component was calculated from the Soxhlet extraction residue. Details are shown below.
a) Weigh accurately 0.5 g of toner into a Soxhlet extraction cylindrical filter paper whose exact weight was measured.
b) Put 200 g of ethyl acetate into a flat bottom flask (300 ml).
c) Install the cylindrical filter paper of (a) in the Soxhlet extraction tube.
d) Connect the flat bottom flask-Soxhlet extraction tube-cooling tube and heat the flat bottom flask with a mantle heater.
e) Extraction of cetyl acetate in the flask is performed for 7 hours from the start of boiling.
f) The extracted cylindrical filter paper is thoroughly washed with ethyl acetate and then dried until a constant weight is obtained.
g) The gel amount is calculated from the sample weight measured in (a), the weight of the cylindrical filter paper, and the weight measured in (f).

  As the precursor polyester component of the ethyl acetate insoluble polyester component, an isocyanate group-containing polyester prepolymer is particularly preferable.

  There is no restriction | limiting in particular as polyisocyanate (PIC) used for an isocyanate group containing polyester prepolymer, Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate , Araliphatic diisocyanates, isocyanurates, those phenol derivatives, oximes, caprolactams and the like blocked. Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate. These can be used alone or in combination of two or more.

  The mixing ratio when the polyisocyanate (PIC) and the precursor polyester component are reacted is a mixing equivalent of the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group [OH] in the precursor polyester component. The ratio ([NCO] / [OH]) is usually preferably 5/1 to 2/1, more preferably 4/1 to 2.5 / 1, and 3/1 to 2.1. / 1 is particularly preferred. When the isocyanate group [NCO] exceeds 5, offset resistance may be deteriorated, and when it is less than 2, low-temperature fixability may be deteriorated.

  Next, as the toner material, in addition to the polyester component, active hydrogen group-containing compound, ethyl acetate-soluble polyester component, release agent, colorant, and other resin fine particles, charge control agent, etc. Contains the ingredients.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an extender, a crosslinking agent, and the like for producing an ethyl acetate-insoluble polyester component by reaction with a polyester component capable of reacting with the active hydrogen group-containing compound in the aqueous medium.
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. For example, an ethyl acetate insoluble polyester capable of reacting with the active hydrogen group-containing compound When the precursor polyester of the component is composed of the above-mentioned isocyanate group-containing polyester prepolymer, amines are preferred because they can be polymerized with the isocyanate group-containing polyester prepolymer by a reaction such as elongation reaction or crosslinking reaction.

  There is no restriction | limiting in particular as said amines, Although it can select suitably according to the objective, For example, diamine, a trivalent or more polyamine, amino alcohol, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, diamine and a mixture of diamine and a small amount of trivalent or higher polyamine are particularly preferable.

  Examples of the diamine include aromatic diamines, alicyclic diamines, aliphatic diamines, and the like. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine. Examples of the trivalent or higher polyamine include diethylenetriamine, triethylenetetramine, and the like. Examples of the amino alcohol include ethanolamine and hydroxyethylaniline.

  As a mixing ratio of the amines and the isocyanate group-containing polyester prepolymer, a mixing equivalent of an isocyanate group [NCO] in the isocyanate group-containing prepolymer and an amino group [NHx] in the amines (B) is used. The ratio ([NCO] / [NHx]) is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, and 1 / 1.5 to 1.5 / 1. Is particularly preferred. If the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may decrease. If it exceeds 3/1, the molecular weight of the urea-modified polyester resin will be low. The hot offset resistance may be deteriorated.

-Ethyl acetate soluble polyester component-
There is no restriction | limiting in particular as said ethyl acetate soluble polyester component, According to the objective, it can select suitably, The polycondensate of a polyol (PO) and polycarboxylic acid (PC), etc. are mentioned. The ethyl acetate-soluble polyester component is partially compatible with the ethyl acetate-insoluble polyester component, that is, has a similar structure compatible with each other, such as low-temperature fixability and hot offset resistance. This is preferable.

  The weight average molecular weight (Mw) of the ethyl acetate-soluble polyester component is preferably 1000 to 30000, more preferably 1500 to 15000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). When the weight average molecular weight (Mw) is less than 1000, the heat resistant storage stability is deteriorated. On the other hand, when the weight average molecular weight (Mw) exceeds 30000, the low-temperature fixability may be deteriorated.

As a glass transition temperature of the said ethyl acetate soluble polyester component, it is 30-70 degreeC normally, 35-70 degreeC is more preferable, and 35-50 degreeC is still more preferable. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be deteriorated, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient.
The hydroxyl value of the ethyl acetate-soluble polyester component is preferably 5 mgKOH / g, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
As an acid value of the said ethyl acetate soluble polyester component, 1.0-50.0 mgKOH / g is preferable, 1.0-45.0 mgKOH / g is more preferable, 15.0-45.0 mgKOH / g is still more preferable. . Generally, it becomes easy to be negatively charged by giving the toner an acid value. When the ethyl acetate-soluble polyester component is contained in the toner, the mixing mass ratio between the ethyl acetate-insoluble polyester component and the ethyl acetate-soluble polyester component is preferably 5/95 to 75/25. ~ 25/75 is more preferred. When the mixing mass ratio of the ethyl acetate-soluble polyester component exceeds 95, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. May get worse.

-Other ingredients-
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a coloring agent, a mold release agent, a charge control agent, an inorganic fine particle, a fluidity improver, a cleaning property improver, a magnetic material , Metal soap, and the like.

  The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon. These may be used individually by 1 type and may use 2 or more types together.

  The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.

  When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor pigment dispersion in the toner occurs, the coloring power decreases, The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. 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. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

  There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably. Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, long chain hydrocarbons, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable. Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred. Examples of the polyolefin wax include polyethylene wax and polypropylene wax. Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

  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, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable. If the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and if it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature. The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

  There is no restriction | limiting in particular in content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable. When the content exceeds 40% by mass, toner fluidity may be deteriorated.

  The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material is preferable. For example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone Or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like. These may be used individually by 1 type and may use 2 or more types together. Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of a quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), Fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (manufactured by Nippon Carlit Co., Ltd.), quinacridone, azo pigment, other sulfonic acid groups, Carboxyl group, polymer compounds having a functional group such as quaternary ammonium salts, and the like. The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with the toner components when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed on the toner surface after production.

  The content of the charge control agent in the toner differs depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, etc., and cannot be generally defined. For example, for 100 parts by mass of the binder resin 0.1-10 mass parts is preferable, and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced. The electrostatic attractive force with the developing roller may increase, resulting in a decrease in developer fluidity and a decrease in image density.

-Resin fine particles-
The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate. Examples of the resin include vinyl resins. Of these, vinyl resins are particularly preferable.
These may be used alone or in combination of two or more. Among these, at least one selected from vinyl resins, polyurethane resins, epoxy resins, and polyester resins is preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained. The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like. Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used.

  The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles. The method for preparing the aqueous dispersion of the resin fine particles is, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material and is selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Or the like, or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (3) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it may be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). (4) Preliminary polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) After the resin prepared by any polymerization reaction mode such as condensation and condensation polymerization is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles , A method of dispersing in water in the presence of an appropriate dispersant, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) (6) A polymerization reaction (addition polymerization) in advance, in which resin fine particles are obtained by spraying a resin solution in which the resin is dissolved in a solvent to obtain resin fine particles and then dispersing the resin fine particles in water in the presence of an appropriate dispersant. , Ring-opening polymerization, polyaddition, addition condensation The resin fine particles can be obtained by adding a poor solvent to a resin solution obtained by dissolving a resin prepared in a solvent by a polymerization reaction method such as condensation polymerization or by cooling a resin solution previously dissolved in a solvent by heating. And then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) in advance (Any polymerization reaction mode such as addition, addition condensation, and condensation polymerization may be used.) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated or heated. (8) A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation or condensation polymerization) is used as a solvent. In the dissolved resin solution A method of dissolving a suitable emulsifier and then adding water to carry out phase inversion emulsification is preferable.

  Examples of the toner include toners produced by a known suspension polymerization method, emulsion aggregation method, emulsion dispersion method, etc., and can react with an active hydrogen group-containing compound and the active hydrogen group-containing compound. A toner solution containing a precursor polyester component of an ethyl acetate insoluble polyester component is dissolved in an organic solvent to prepare a toner solution, and then the toner solution is dispersed in an aqueous medium to prepare a dispersion liquid. And reacting the active hydrogen group-containing compound with a precursor polyester component of an ethyl acetate insoluble polyester component capable of reacting with the active hydrogen group-containing compound to form an adhesive substrate in the form of particles, and removing the organic solvent. The toner obtained in this way is preferred.

-Toner solution-
The toner solution is prepared by dissolving the toner material in the organic solvent.

-Organic solvent-
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. in terms of ease of removal. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples thereof include ethyl, methyl ethyl ketone, and methyl isobutyl ketone. Among these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used alone or in combination of two or more. There is no restriction | limiting in particular as usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner materials, and 60-140 mass parts is more. 80 to 120 parts by mass are more preferable.

-Dispersion-
The dispersion is prepared by dispersing the toner solution in an aqueous medium. When the toner solution is dispersed in the aqueous medium, a dispersion (oil droplets) made of the toner solution is formed in the aqueous medium.

-Aqueous medium-
There is no restriction | limiting in particular as said aqueous medium, It can select suitably from well-known things, For example, water, a solvent miscible with this water, a mixture thereof etc. are mentioned, Among these, water is especially preferable. The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone. These may be used alone or in combination of two or more.

  The toner solution is preferably dispersed in the aqueous medium with stirring. The dispersion method is not particularly limited and can be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction disperser. High pressure jet disperser, ultrasonic disperser, and the like. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion (oil droplets) can be controlled to 2 to 20 μm. When the high-speed shearing disperser is used, conditions such as the number of revolutions, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the number of revolutions is 1000 -30000 rpm is preferable, 5000-20000 rpm is more preferable, the dispersion time is preferably 0.1-5 minutes in the case of a batch system, and the dispersion temperature is preferably 0-150 ° C. under pressure, -98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

  The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.

  The toner solution is prepared in the organic solvent by using the active hydrogen group-containing compound, a precursor polyester component of an ethyl acetate insoluble polyester component that can react with the active hydrogen group-containing compound, the colorant, the release agent, It can be performed by dissolving or dispersing a toner material such as a charge control agent and the unmodified polyester resin.

  In the toner material, components other than the precursor polyester component (prepolymer) of the ethyl acetate-insoluble polyester component capable of reacting with the active hydrogen group-containing compound are used in the preparation of the aqueous medium phase. When dispersed in the medium, it may be added to and mixed with the aqueous medium, or when the toner solution is added to the aqueous medium phase, it may be added to the aqueous medium phase together with the toner solution.

  The dispersion can be prepared by emulsifying and dispersing the previously prepared toner solution in the previously prepared aqueous medium phase. In the emulsification / dispersion, the active hydrogen group-containing compound and the precursor polyester of the ethyl acetate insoluble polyester component capable of reacting with the active hydrogen group-containing compound are subjected to an elongation reaction or a crosslinking reaction. The insoluble polyester (for example, the urea-modified polyester resin) includes, for example, the toner solution containing an ethyl acetate insoluble polyester precursor polyester component (for example, the isocyanate group-containing polyester prepolymer) that can react with the active hydrogen group-containing compound. It is formed by emulsifying and dispersing in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines) to form a dispersion and subjecting both to an extension reaction or a crosslinking reaction in the aqueous medium phase. The toner solution may be emulsified and dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form a dispersion, and the two are subjected to an extension reaction or a crosslinking reaction in the aqueous medium phase. Or after the toner solution is added and mixed in the aqueous medium, Was added sex hydrogen group-containing compound, to form a dispersion, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the above case, the modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  The reaction conditions for producing the adhesive substrate by the emulsification / dispersion are not particularly limited, and the ethyl acetate insoluble polyester precursor polyester component and the active hydrogen group-containing compound capable of reacting with the active hydrogen group-containing compound are not limited. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours, the reaction temperature is preferably 0 to 150 ° C., and 40 to 98 ° C is more preferred.

  In the aqueous medium phase, as a method for stably forming the dispersion containing an ethyl acetate insoluble polyester precursor polyester component (for example, the isocyanate group-containing polyester prepolymer) that can react with the active hydrogen group-containing compound, for example, In the aqueous medium phase, an ethyl acetate insoluble polyester precursor polyester component (for example, the isocyanate group-containing polyester prepolymer) that can react with the active hydrogen group-containing compound, the colorant, the release agent, the charge control agent, Examples include a method in which the toner solution prepared by dissolving or dispersing the toner material such as the unmodified polyester resin in the organic solvent is added and dispersed by shearing force. The details of the dispersion method are as described above.

  In the preparation of the dispersion, if necessary, a dispersant may be used from the viewpoint of stabilizing the dispersion (oil droplets composed of the toner solution) and sharpening the particle size distribution while obtaining a desired shape. preferable. There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a sparingly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (above, manufactured by Asahi Glass Co., Ltd.); Florad FC-93, FC-95, FC-98. FC-129 (above, manufactured by Sumitomo 3M Co., Ltd.); Unidyne DS-101, DS-102 (above, manufactured by Daikin Industries, Ltd.); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (above, manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (above, To- Chem Products, Inc.); Footage F-100, F150 (above, Neos) and the like.

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

  Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.

  Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.

  Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite. Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers of compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, celluloses, and the like. Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin monoacrylate, Examples include glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinylpyridine, vinylpyrrolidone, vinylimidazole, and ethyleneimine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

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

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

  The organic solvent is removed from the obtained dispersion (emulsified slurry). The organic solvent is removed by (1) a method of gradually raising the temperature of the entire reaction system to completely evaporate and remove the organic solvent in the oil droplets, and (2) spraying the emulsified dispersion in a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying.

  Thus, the obtained toner particles are mixed with particles of the colorant, the release agent, the charge control agent, and the like, or further, a mechanical impact force is applied to the release particles from the surface of the toner particles. It is possible to prevent the particles such as the agent from being detached. As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board, etc. are mentioned. As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverization air pressure, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

  The toner preferably has the following volume average particle diameter (Dv), volume average particle diameter (Dv) / number average particle diameter (Dn), glass transition temperature (Tg), and the like.

The volume average particle diameter (Dv) of the toner is, for example, preferably 3 to 8 μm, more preferably 4 to 7 μm, and still more preferably 5 to 6 μm. Here, the volume average particle size is defined as Dv = (Σ (nD ³ ) / Σn) ^1/3 (where n is the number of particles and D is the particle size). When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing unit, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. When the thickness exceeds 8 μm, the resolution is high and high. It becomes difficult to obtain an image of an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

  The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner is preferably 1.25 or less, more preferably 1.05 to 1.25. In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, leading to a decrease in the charging ability of the carrier, When used as a developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur. Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention. On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high resolution and high quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large. It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25. On the other hand, when the volume average particle size / number average particle size is smaller than 1.05, there are some preferable aspects from the viewpoint of stabilizing the behavior of the toner and uniformizing the charge amount, but the toner is not sufficiently charged. In some cases, it was also found that the cleaning property may be deteriorated.

  The volume average particle diameter and the ratio (Dv / Dn) between the volume average particle diameter and the number average particle diameter are measured using, for example, a particle size measuring device “Multisizer II” manufactured by Beckman Coulter, Inc. Can do.

  The glass transition temperature of the toner is preferably 40 to 70 ° C. When the glass transition temperature is less than 40 ° C, the heat-resistant storage stability is insufficient, and when it exceeds 70 ° C, the low-temperature fixability may be adversely affected. Here, the glass transition temperature of the toner can be measured using, for example, a TG-DSC system TAS-100 manufactured by Rigaku Corporation.

  The coloring of the toner is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. Although it can be obtained by appropriately selecting the type of the colorant, it is preferably a color toner.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected appropriately. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable. In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developer, Good and stable developability can be obtained.

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

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

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D ₅₀ )) of 10 to 200 μm, and more preferably 40 to 100 μm. When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur. In particular, in the case of a full color having many solid portions, the reproduction of the solid portions may be deteriorated.

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

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

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

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

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

  When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93 to 97% is more preferable.

  Since the developer of the present invention contains the toner of the present invention, it is possible to achieve both excellent low-temperature fixability and offset resistance, and to form a good high-definition image. The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

(Image forming method)
Next, an image forming method using the toner of the present invention will be described.
The image forming method of the present invention has at least an electrostatic charge image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, a recycling step, You may have a control process etc. further.

  The electrostatic charge image forming step is a step of forming an electrostatic charge image on the electrostatic charge image carrier (photosensitive member). The electrostatic charge image can be formed, for example, by charging the surface of the photosensitive member uniformly by applying a voltage using a charging device and then performing imagewise exposure using an exposure device. it can.

  The material, shape, structure, size and the like of the photoreceptor are not particularly limited and can be appropriately selected from known ones, but the shape is preferably a drum shape. Examples of the photoreceptor include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors (OPC) such as polysilane and phthalopolymethine. Amorphous silicon photoreceptors are preferable in terms of long life. .

The charging device is not particularly limited and can be appropriately selected depending on the purpose. For example, a known contact charger including a conductive or semiconductive roll, brush, film, rubber blade, Examples thereof include a non-contact charger using corona discharge such as corotron and scorotron. The charging device is preferably arranged in contact or non-contact with the photoreceptor, and charges the surface of the photoreceptor by applying a DC voltage and an AC voltage in a superimposed manner.
The charging device is a charging roller that is disposed in close proximity to the photoconductor via a gap tape, and charges the surface of the photoconductor by applying a DC voltage and an AC voltage superimposed on the charging roller. Those that do are preferred.

  The exposure apparatus is not particularly limited as long as it can image-wise expose the surface of the photoreceptor charged by the charging apparatus, and can be appropriately selected according to the purpose. Examples thereof include a rod lens array system, a laser optical system, and a liquid crystal shutter optical system. In the case of a photoconductor using a transparent support, an optical backside system that performs imagewise exposure from the backside of the photoconductor may be employed.

  The developing step is a step of forming a visible image by developing the electrostatic image with the toner of the present invention using a developing device.

  The developing device is not particularly limited as long as it can be developed using the toner of the present invention, and can be appropriately selected from known ones. For example, the developing device contains a developer composed of the toner of the present invention, Examples include those having at least a developer carrying member capable of bringing a developer into contact or non-contact with an electrostatic charge image, and preferably including a developer-containing container in a detachable manner. The developing device may be either a single-color developing device or a multi-color developing device, and examples thereof include a stirrer that charges a developer by frictional stirring and a rotatable magnet roller. In the developing device, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. Since the magnet roller is disposed in the vicinity of the photoconductor, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the photoconductor by an electric attractive force. As a result, the electrostatic charge image is developed with toner, and a visible image is formed on the surface of the photoreceptor. Note that an alternating electric field is preferably applied when the toner is moved to the surface of the photoreceptor.

  The transfer process is a process in which a visible image is transferred to a transfer target using a transfer device. After the primary transfer of the visible image onto the intermediate transfer member using the intermediate transfer member, the visible image is transferred to the transfer target. A mode in which secondary transfer is performed on a transfer body is preferred. Further, a full-color toner is preferably used as the toner, and a primary transfer step in which a visible image is transferred onto an intermediate transfer member to form a composite transfer image, and a second transfer in which the composite transfer image is transferred onto a transfer target. An embodiment having a next transfer step is preferable. The visible image can be transferred by charging the photoconductor using, for example, a transfer charger.

  The transfer device preferably has a primary transfer device that transfers a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer device that transfers the composite transfer image onto a transfer target. The transfer device (primary transfer device, secondary transfer device) preferably has at least a transfer device that peels and charges the visible image formed on the photosensitive member toward the transfer target. There may be one transfer device or two or more transfer devices. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

  The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. Examples thereof include a transfer belt.

  The transfer target is not particularly limited and can be appropriately selected from known recording media.

  The fixing step is a step of fixing the visible image transferred to the transfer target using a fixing device, and may be fixed for each color toner each time it is transferred to the transfer target. The toners may be fixed simultaneously at the same time in a state where the toners are laminated.

  The fixing device is not particularly limited and may be appropriately selected according to the purpose. However, a fixing device that is heat-pressed and fixed using a known fixing member is preferable. The fixing member is preferably in the form of a roller or a belt, and examples thereof include a combination of a heating roller and a pressure roller, and a combination of a heating roller, a pressure roller and an endless belt. At this time, it is preferable that heating temperature is 80-200 degreeC normally.

  In the present invention, the fixing device includes a heating body having a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film. It is possible to use means for heating and press-fixing by passing the transfer body on which the received image is formed.

  Depending on the purpose, for example, a known optical fixing device may be used together with the fixing device or instead of the fixing device.

  The neutralization step is a step of performing neutralization by applying a neutralization bias to the photoconductor using a neutralization device.

  The neutralization device is not particularly limited, and may be any one as long as it can apply a neutralization bias to the photosensitive member, and can be appropriately selected from known neutralization devices. Examples thereof include a neutralization lamp.

  The cleaning step is a step of removing toner remaining on the photoreceptor using a cleaning device.

  The cleaning device is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected from known cleaners. For example, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller A cleaner, a blade cleaner, a brush cleaner, a web cleaner, etc. are mentioned.

  The recycling process is a process in which the toner removed in the cleaning process is recycled to the developing device using a recycling apparatus.

  There is no restriction | limiting in particular in a recycling apparatus, For example, a well-known conveyance means etc. are mentioned.

  A control process is a process of controlling each process using a control device.

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

  Next, the image forming method of the present invention will be described with reference to FIG. The image forming apparatus shown in FIG. 1 includes a photosensitive member 10, a charging device 20, an exposure device 30, a developing device 40, an intermediate transfer member 50, a cleaning device 60 having a cleaning blade, a charge eliminating device 70, a transfer device. A device 80 is provided. Note that a charging roller is used as the charging device 20, a static elimination lamp as the static elimination device 70, and a transfer roller as the transfer device 80.

The intermediate transfer member 50 is an endless belt, and is designed to be stretched by three support rollers 51 arranged on the inner side thereof so as to be movable in the arrow direction. A part of the three support rollers 51 also functions as a transfer bias roller capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer member 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof. Further, a transfer device 80 capable of applying a secondary transfer bias for transferring a visible image (secondary transfer) to the transfer target 95 is disposed opposite to the transfer device 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the visible image on the intermediate transfer member 50 is in contact with the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. And the contact portion between the intermediate transfer body 50 and the transfer body 95.
Note that transfer paper is used as the transfer target 95.

  The developing device 40 includes a developing belt 41 as a developer carrier, 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. ing. The developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K, and the developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The developing unit 45M includes a developer accommodating portion 42M, a developer supply roller 43M, and a developing roller 44M. The developing unit 45C includes a developer accommodating portion 42C, the developer supplying roller 43C, and the developing roller 44C. Yes. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

In this image forming apparatus, after the charging device 20 uniformly charges the photoconductor 10, the exposure device 30 exposes the photoconductor 10 imagewise to form an electrostatic image. Next, the developing device 40 supplies the developer to develop the electrostatic charge image formed on the photoconductor 10 to form a visible image.
The visible image is transferred (primary transfer) onto the intermediate transfer body 50 by the voltage applied from the support roller 51 and further transferred (secondary transfer) onto the transfer body 95. As a result, a transfer image is formed on the transfer target 95. The toner remaining on the photoconductor 10 is removed by the cleaning device 60, and the charge of the photoconductor 10 is removed by the charge eliminating lamp 70.

Next, another aspect of the image forming method of the present invention will be described with reference to FIG. The image forming apparatus shown in FIG. 2 has a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan around the photosensitive member 10, instead of the developing device 40 in the image forming apparatus shown in FIG. The developing unit 45C has the same configuration as that of the image forming apparatus shown in FIG.
In FIG. 2, the same components as those in the image forming apparatus shown in FIG. The same applies to FIGS. 3 and 4 described later.

  Next, another aspect of the image forming method of the present invention will be described with reference to FIG. The image forming apparatus shown in FIG. 3 is a tandem type color image forming apparatus. The image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

  The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15, and 16 and can rotate clockwise in FIG. 3. A cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. On the intermediate transfer member 50 stretched by the support roller 14 and the support roller 15, four image forming units 18 of yellow, cyan, magenta, and black are arranged opposite to each other along the conveying direction. A means 120 is arranged. An exposure device 21 is disposed in the vicinity of the image forming unit 120. The secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the image forming unit 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of support rollers 23, and the recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 are mutually connected. It is possible to touch. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt and a pressure roller 27 that is pressed against the fixing belt 26. A reversing device 28 for reversing the recording paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25 in order to form images on both sides of the recording paper.

  Next, formation of a full-color image (color copy) using the image forming unit 120 will be described. First, an original document is set on the document table 130 of the automatic document feeder (ADF) 400 or the automatic document feeder 400 is opened, and the original document is set on the contact glass 32 of the scanner 300. Close.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. When this happens, the scanner 300 is immediately driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33, and reflected light from the document surface is reflected by a mirror in the second traveling body 34. Further, the image is received by the reading sensor 36 through the imaging lens 35, and the original is read to obtain image information of black, yellow, magenta and cyan. Next, each image information is transmitted to each image forming unit 18 in the image forming means 120, and a visible image of each color of black, yellow, magenta and cyan is formed.

  As shown in FIG. 4, the image forming unit 18 includes a photoconductor 10, a charging device (no reference) for uniformly charging the photoconductor 10, and an exposure device 21, based on each image information. A developing device that develops an electrostatic charge image formed by exposing the photoconductor 10 to each other using each toner (black toner, yellow toner, magenta toner, and cyan toner) to form a visible image using each toner. (No code), a transfer charger (no code) for transferring a visible image onto the intermediate transfer member 50, a cleaning device (no code), and a charge eliminating device (no code) are provided, based on each image information Thus, a visible image of each color can be formed. Next, the visible images of the respective colors are sequentially transferred (primary transfer) onto the intermediate transfer body 50 that is rotated and moved by the support rollers 14, 15 and 16, and the visible images of the respective colors are superimposed to form a composite transfer image. It is formed.

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed the recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and 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 142 is rotated to feed out the recording paper on the manual feed tray 54, separated one by one by the separation roller 52, put into 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 to remove paper dust from the recording paper. Then, the registration roller 49 is rotated in synchronization with the composite transfer image formed on the intermediate transfer member 50, and the recording paper is sent between the intermediate transfer member 50 and the secondary transfer device 22, so that the secondary transfer device. By transferring the composite transfer image onto the recording paper (secondary transfer) by 22, a color image is formed on the recording paper. The toner remaining on the intermediate transfer member 50 is removed by the cleaning device 17.

  The recording paper on which the color image is formed is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the composite transfer image is heated and pressed and fixed on the recording paper. Thereafter, the recording paper is switched by the switching claw 55 and discharged by the discharge roller 56 and is stacked on the discharge tray 57. Alternatively, it is switched by the switching claw 55 and reversed by the reversing device 28 and led to the transfer position again. After an image is formed also on the back surface, the sheet is discharged by the discharge roller 56 and stacked on the discharge tray 57.

(Process cartridge)
The process cartridge of the present invention includes an electrostatic charge image carrier on which an electrostatic charge image is formed, and a developing device that develops the electrostatic image formed on the electrostatic charge image carrier using the toner of the present invention. It is integrally supported and is detachable from the image forming apparatus main body. The process cartridge of the present invention may further support other means appropriately selected as needed.

  FIG. 5 shows an example of the process cartridge of the present invention. The process cartridge includes a photosensitive member 101 and includes a charging unit 102, an exposure unit 103, a developing unit 104, a cleaning unit 107, and a transfer unit 108. These members can be the same as those used in the image forming apparatus described above.

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

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples, “part” and “%” are based on mass unless otherwise specified. In the following examples and comparative examples, the volume average particle size (Dv) and particle size distribution (Dv / Dn), NCO%, acid value, hydroxyl value, and glass transition temperature (Tg) of the toner are measured as follows. went.

<Volume Average Particle Size (Dv) and Particle Size Distribution (Dv / Dn)>
The volume average particle size and particle size distribution of the toner were measured using a particle size measuring device (“Coulter Counter TAII”; manufactured by Coulter Electronics Co., Ltd.) under the condition of an aperture diameter of 100 μm. From these results, (volume average particle diameter / number average particle diameter) was calculated.

<Measurement of free isocyanate group content (NCO%)>
NCO% was measured by a method based on JIS K1603.

<Method for measuring acid value>
The acid value is measured by the method specified in JIS K0070. However, when the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.

<Method for measuring hydroxyl value>
The method for measuring the hydroxyl value is according to the method specified in JIS K0070. However, when the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.

<Glass transition temperature (Tg)>
A TG-DSC system TAS-100 manufactured by Rigaku Corporation was used as an apparatus for measuring the glass transition temperature (Tg). First, 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, and the sample was cooled to room temperature and allowed to stand for 10 minutes. DSC measurement was carried out by heating at / min. Tg was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

<Gel content of ethyl acetate insoluble polyester component>
Calculation was performed by the method using the Soxhlet.

[Example 1]
-Synthesis of organic fine particle emulsion-
In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 83 parts of styrene, methacrylic acid When 83 parts of acid, 110 parts of butyl acrylate, and 1 part of ammonium persulfate were charged and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. This was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to give a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). An aqueous dispersion was obtained. This is designated as [fine particle dispersion 1]. The volume average particle diameter of the fine particles contained in the obtained [fine particle dispersion 1] was measured with a particle size distribution measuring apparatus (“LA-920”, manufactured by Horiba, Ltd.) using a laser light scattering method. there were. Further, a part of [Fine Particle Dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 59 ° C., and the weight average molecular weight (Mw) was 150,000.

-Preparation of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries Ltd.), and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

-Synthesis of low molecular weight polyester-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid, and 2 parts of dibutyltin oxide was charged and reacted at 230 ° C. under normal pressure for 8 hours. Subsequently, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain [Low molecular weight polyester 1].
The obtained [low molecular weight polyester 1] had a glass transition temperature (Tg) of 43 ° C., a weight average molecular weight (Mw) of 6700, a number average molecular weight of 2500, and an acid value of 25.

-Preparation of masterbatch (MB)-
1200 parts of water, 540 parts of carbon black (Printtex 35, manufactured by Degussa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], 1200 parts of a polyester resin (manufactured by Sanyo Chemical Industries, Ltd., RS801) are added, and a Henschel mixer is added. (Mitsui Mining Co., Ltd.) The obtained mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized with a pulverizer to obtain a carbon black masterbatch. This is designated as [Masterbatch 1].

-Synthesis of Prepolymer 1-
(1) 152 parts of propylene glycol, 166 parts of terephthalic acid, and 0.5 parts of titanium tetrabutoxide are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and are heated at 230 ° C under normal pressure. The mixture was reacted for 1 hour, and then reacted at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Intermediate polyester precursor 1].
(2) 316 parts of bisphenol A ethylene oxide 2 mol adduct, 332 parts of terephthalic acid, and 0.5 part of titanium tetrabutoxide are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. The mixture was reacted at 230 ° C. for 8 hours and then reacted at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Intermediate polyester precursor 2].
(3) 317.3 parts of the [intermediate polyester precursor 1] and 76.5 parts of the [intermediate polyester precursor 2] are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. The mixture was reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate polyester 1]. The obtained [Intermediate polyester 1] had a weight average molecular weight of 23,000, a glass transition temperature (Tg) of 42 ° C., an acid value of 0.3, and a hydroxyl value of 16.5.
(4) In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 250 parts of the [intermediate polyester 1], 18 parts of isophorone diisocyanate, and 250 parts of ethyl acetate are placed and reacted at 100 ° C. for 5 hours. [Prepolymer 1] was obtained.
The isocyanate mass% of the obtained [Prepolymer 1] was 0.61%.

-Preparation of oil phase-
In a reaction vessel equipped with a stir bar and a thermometer, 378 parts of [low molecular polyester 1], 110 parts of carnauba wax, 22 parts of CCA (salicylic acid metal complex E-84, manufactured by Orient Chemical Industries), and ethyl 947 The temperature was raised to 80 ° C. with stirring and held at 80 ° C. for an hour, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a reaction vessel and mixed for 1 hour to obtain a dissolved product. This is referred to as [Raw material solution 1].
Next, 1324 parts of [Raw Material Solution 1] was transferred to a reaction vessel, and using a bead mill (Ultra Visco Mill, manufactured by IMEX), liquid feeding speed: 1 kg / hr, disk peripheral speed: 6 m / sec, 0.5 mm Carbon black and wax were dispersed under the conditions of zirconia bead filling amount: 80% by volume and pass number: 3 times. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and a dispersion was obtained by using a bead mill under the same conditions as described above, with the number of passes being one time. This is designated as [Pigment and Wax Dispersion 1]. The obtained [Pigment and Wax Dispersion 1] had a solid content concentration (130 ° C., 30 minutes) of 50%.

-Emulsification-
[Pigment and wax dispersion 1] 749 parts, [Prepolymer 1] 115 parts, and isophorone diamine 1.3 parts were put in a container and mixed for 1 minute at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika). . Thereafter, 1200 parts of [Aqueous Phase 1] was added to the container and mixed for 20 minutes at a TK homomixer and 13,000 rpm to obtain an aqueous medium dispersion. This is designated as [Emulsified slurry 1].

-Deorganic solvent-
[Emulsion slurry 1] was put into a vessel equipped with a stirrer and a thermometer, and after removing the solvent for 8 hours at 30 ° C, aging was performed for 4 hours at 45 ° C, and the organic solvent was distilled off. A dispersion was obtained. This is designated as [Dispersion Slurry 1]. The obtained [Dispersion Slurry 1] had a volume average particle size of 5.15 μm and a number average particle size of 4.51 μm (measured with Multisizer II).

-Washing and drying-
[Dispersion Slurry 1] 100 parts were filtered under reduced pressure, and then washed and dried as follows.
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (12000 rpm for 10 minutes), and then filtered.
(2) 100 parts of ion-exchanged water was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12000 rpm), and then filtered under reduced pressure.
(3) 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (12000 rpm for 10 minutes) and then filtered.
(4) 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (at 12000 rpm for 10 minutes), and then filtered twice to obtain a filter cake.
This filter cake was dried at 45 ° C. for 48 hours with a circulating drier and sieved with a mesh having an opening of 75 μm to obtain a toner. This is referred to as [Toner 1].

[Example 2]
[Toner 2] was produced in the same manner as in Example 1 except that [Prepolymer 2] synthesized as follows was used instead of [Prepolymer 1] in Example 1.

-Synthesis of Prepolymer 2-
(1) 152 parts of propylene glycol, 166 parts of terephthalic acid, and 0.5 parts of titanium tetrabutoxide are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and are heated at 230 ° C. under normal pressure. The mixture was reacted for 1 hour and then at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Intermediate polyester precursor 1].
(2) 316 parts of bisphenol A ethylene oxide 2 mol adduct, 332 parts of terephthalic acid, and 0.5 part of titanium tetrabutoxide are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. The mixture was reacted at 230 ° C. for 8 hours and then reacted at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Intermediate polyester precursor 2].
(3) 170.0 parts of the [intermediate polyester precursor 1] and 245 parts of the [intermediate polyester precursor 2] are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. The mixture was reacted at 230 ° C. for 8 hours under reduced pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 2]. The obtained [Intermediate polyester 2] had a weight average molecular weight of 22000, a glass transition temperature (Tg) of 48 ° C., an acid value of 0.4, and a hydroxyl value of 16.8.
(4) In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 250 parts of the above [intermediate polyester 2], 18 parts of isophorone diisocyanate and 250 parts of ethyl acetate are placed and reacted at 100 ° C. for 5 hours. [Prepolymer 2] was obtained.
The isocyanate mass% of the obtained [Prepolymer 2] was 0.63%.

Example 3
[Toner 3] was produced in the same manner as in Example 1 except that [Prepolymer 3] synthesized as follows was used instead of [Prepolymer 1] in Example 1.

-Synthesis of Prepolymer 3-
(1) 176.3 parts of neopentyl glycol, 166 parts of terephthalic acid, and 0.5 part of titanium tetrabutoxide are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and 230 ° C. under normal pressure. And then reacted for 1 hour at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester Precursor 3].
(2) 316 parts of bisphenol A ethylene oxide 2 mol adduct, 332 parts of terephthalic acid, and 0.5 part of titanium tetrabutoxide are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. The mixture was reacted at 230 ° C. for 8 hours, and then reacted at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Intermediate polyester precursor 2].
(3) In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 344.0 parts of the [intermediate polyester precursor 3] and 76.5 parts of the [intermediate polyester precursor 2] are placed. The mixture was reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 3]. The obtained [Intermediate polyester 3] had a weight average molecular weight of 23,000, a glass transition temperature (Tg) of 40 ° C., an acid value of 0.4, and a hydroxyl value of 16.4.
(4) In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 250 parts of the above [intermediate polyester 3], 18 parts of isophorone diisocyanate and 250 parts of ethyl acetate are placed and reacted at 100 ° C. for 5 hours. [Prepolymer 3] was obtained.
The [Prepolymer 3] obtained had an isocyanate mass% of 0.62%.

Example 4
[Toner 4] was produced in the same manner as in Example 1 except that [Prepolymer 4] synthesized as follows was used instead of [Prepolymer 1] in Example 1.

-Synthesis of Prepolymer 4-
(1) In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introducing pipe, 180 parts of 1,4-butanediol, 166 parts of terephthalic acid, and 0.5 part of titanium tetrabutoxide are placed under normal pressure, 230 The mixture was reacted at 0 ° C. for 8 hours, and then reacted at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Intermediate polyester precursor 4].
(2) 316 parts of bisphenol A ethylene oxide 2 mol adduct, 332 parts of terephthalic acid, and 0.5 part of titanium tetrabutoxide are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. The mixture was reacted at 230 ° C. for 8 hours and then reacted at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Intermediate polyester precursor 2].
(3) In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 349 parts of the [intermediate polyester precursor 4] and 76.5 parts of the [intermediate polyester precursor 2] are placed under normal pressure. The mixture was reacted at 230 ° C. for 8 hours, and further reacted at 10 to 15 mmHg reduced pressure for 5 hours to obtain [Intermediate Polyester 4]. The obtained [Intermediate polyester 4] had a weight average molecular weight of 23,000, a glass transition temperature (Tg) of 38 ° C., an acid value of 0.4, and a hydroxyl value of 16.5.
(4) In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 250 parts of the above [intermediate polyester 4], 18 parts of isophorone diisocyanate and 250 parts of ethyl acetate are placed and reacted at 100 ° C. for 5 hours. [Prepolymer 4] was obtained.
The isocyanate mass% of the obtained [Prepolymer 4] was 0.60%.

Example 5
[Toner 5] was produced in the same manner as in Example 1 except that [Prepolymer 5] synthesized as follows was used instead of [Prepolymer 1] in Example 1.

-Synthesis of Prepolymer 5-
(1) 236 parts of 1,6-hexanediol, 166 parts of terephthalic acid, and 0.5 part of titanium tetrabutoxide are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and 230 ° C. under normal pressure. And then reacted for 1 hour at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester Precursor 5].
(2) 316 parts of bisphenol A ethylene oxide 2 mol adduct, 332 parts of terephthalic acid, and 0.5 part of titanium tetrabutoxide are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. The mixture was reacted at 230 ° C. for 8 hours and then reacted at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Intermediate polyester precursor 2].
(3) In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 538.2 parts of the [intermediate polyester precursor 5] and 61.3 parts of the [intermediate polyester precursor 2] are placed. The mixture was reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 5]. The obtained [Intermediate polyester 5] had a weight average molecular weight of 23,000, a glass transition temperature (Tg) of 39 ° C., an acid value of 0.4, and a hydroxyl value of 16.5.
(4) In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 250 parts of the above [intermediate polyester 5], 18 parts of isophorone diisocyanate and 250 parts of ethyl acetate are placed and reacted at 100 ° C. for 5 hours. [Prepolymer 5] was obtained.
The isocyanate mass% of the obtained [Prepolymer 5] was 0.62%.

Example 6
[Toner 6] was produced in the same manner as in Example 1 except that [Prepolymer 6] synthesized as follows was used instead of [Prepolymer 1] in Example 1.
-Synthesis of Prepolymer 6-
(1) 152 parts of propylene glycol, 166 parts of terephthalic acid, and 0.5 parts of titanium tetrabutoxide are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and are heated at 230 ° C under normal pressure. The mixture was reacted for 1 hour, and then reacted at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Intermediate polyester precursor 1].
(2) 316 parts of bisphenol A ethylene oxide 2 mol adduct, 332 parts of terephthalic acid, and 0.5 part of titanium tetrabutoxide are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. The mixture was reacted at 0 ° C. for 8 hours, and then reacted at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Intermediate polyester precursor 2].
(3) 317.3 parts of the [intermediate polyester precursor 1] and 76.5 parts of the [intermediate polyester precursor 2] are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. The mixture was reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 10 hours to obtain [Intermediate polyester 6]. The obtained [Intermediate polyester 6] had a weight average molecular weight of 52,000, a glass transition temperature (Tg) of 44 ° C., an acid value of 0.1, and a hydroxyl value of 12.5.
(4) In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 250 parts of the above [intermediate polyester 6], 14 parts of isophorone diisocyanate and 250 parts of ethyl acetate are allowed to react at 100 ° C. for 5 hours. Prepolymer 6] was obtained.
The [Prepolymer 6] obtained had an isocyanate mass% of 0.51%.

[Comparative Example 1]
In Example 1, instead of [Prepolymer 1], [Prepolymer 7] synthesized as follows was used, and the same as Example 1 except that 1.3 parts of isophoronediamine was changed to 3.2 parts. Thus, [Toner 7] was produced.

-Synthesis of Prepolymer 7-
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 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 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 7]. [Intermediate Polyester 7] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51. Next, 410 parts of [Intermediate Polyester 7], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 7] was obtained. The [Prepolymer 7] obtained had an isocyanate mass% of 1.53%.

[Comparative Example 2]
[Toner 8] was produced in the same manner as in Example 1 except that [Prepolymer 8] synthesized as follows was used instead of [Prepolymer 1] in Example 1.

-Synthesis of Prepolymer 8-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 463 parts of propylene glycol, 657 parts of terephthalic acid, 96 parts of trimellitic anhydride, and 2 parts of titanium tetrabutoxide are placed at 230 ° C. under normal pressure. Then, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 8]. The obtained [Intermediate polyester 8] had a weight average molecular weight of 28,000, a glass transition temperature (Tg) of 36 ° C., an acid value of 0.5, and a hydroxyl value of 16.5. Next, 250 parts of [intermediate polyester 8], 18 parts of isophorone diisocyanate, and 250 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. [Prepolymer 8] was obtained. The isocyanate mass% of the obtained [Prepolymer 8] was 0.61%.

  Next, each of the toners of Examples 1 to 6 and Comparative Examples 1 and 2 thus obtained was evaluated for heat resistant storage stability, fixability, charging characteristics, and stability over time. The results are shown in Table 1.

<Heat resistant storage stability>
Each toner was stored at 50 ° C. for 8 hours, and then sieved with a 42 mesh sieve for 2 minutes. A toner having better heat-resistant storage stability has a lower residual ratio. The following four levels were evaluated.
〔Evaluation criteria〕
×: 30% or more △: 20% or more and less than 30% ○: 10% or more and less than 20% ◎: Less than 10%

<Fixability>
Using an image forming apparatus (Imagio Neo 450, manufactured by Ricoh Co., Ltd.), a solid image and a transfer sheet of thick paper (made by Ricoh Co., Ltd., type 6200, manufactured by NBS Ricoh Co., copy printing paper <135>), Adjustment is made so that each toner of 1.0 ± 0.1 mg / cm ² is developed, and adjustment is made so that the temperature of the fixing belt is variable. The minimum fixing temperature was measured. The minimum fixing temperature was determined as the fixing minimum temperature at which the remaining ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.

<Charging characteristics>
(1) 15 seconds stirring Q / M
Silicone resin-coated ferrite carrier (average particle size 50 μm) ... 100 parts by weight Each toner: 4 parts by weight are placed in a stainless steel pot up to 30% of the internal volume, stirred for 15 seconds at a stirring speed of 100 rpm, blow-off method I asked more.
(2) 10 minutes stirring Q / M
The amount of charge when stirring for 10 minutes was obtained in the same manner as in (1) above.

<Stability over time>
Evaluation of stability over time was made by outputting a thin line evaluation image in an environment of 30 ° C. and 90% humidity after running 100,000 sheets, and judging based on the degree of reproduction of the thin line. (5 parts by mass of the prepared toner and 95 parts by mass of a silicone resin-coated ferrite carrier having an average particle size of 50 μm are mixed for 10 minutes with a blender to prepare a developer, which is then placed in a commercially available color copier (PRETER 550; manufactured by Ricoh). Evaluation was performed.)
・ Thin wires overlap each other and cannot be separated and separated.
・ Thin lines overlap, but can be identified separately ・ ・ ・ ・ △
・ Thin lines can be distinguished from each other, but slight blurring of the lines is noticed.
・ Thin lines can be separated and identified, and no blurring or blurring can be seen. ・ ◎

Note) “Bisphenol AEO adduct” in the table represents an ethylene oxide 2 mol adduct of bisphenol A. “Bisphenol APO adduct” represents a propylene oxide 2 mol adduct of bisphenol A.

  From the above table, the polyester component capable of reacting with the active hydrogen group-containing compound of the example is an acid component, at least one diol compound selected from an aliphatic diol and an alicyclic diol, and an aromatic diol compound. It is clear that when the toner is subjected to condensation polymerization in the presence of a catalyst, a toner having a low fixing minimum temperature and good heat-resistant storage stability can be obtained. In contrast, when only at least one diol compound selected from an aliphatic diol and an alicyclic diol was used in the comparative example, the heat-resistant storage stability was good, but the fixing minimum temperature was high, and the aromatic When only the group diol compound is used, it can be seen that although the minimum fixing temperature is good, the heat resistant storage stability is not good, and not only the stability over time is good.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus in which a toner of the present invention is used. It is a schematic block diagram which shows the other example of the image forming apparatus in which the toner of this invention is used. 1 is a schematic configuration diagram illustrating an example of a tandem type image forming apparatus in which a toner of the present invention is used. FIG. 5 is a partially enlarged view of the tandem type image forming apparatus of FIG. 4. FIG. 3 is a schematic configuration diagram illustrating an example of a process cartridge in which the toner of the present invention is used.

Explanation of symbols

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 discharge tray 58 corona charger 60 cleaning device 61 developing device 62 transfer charger 63 photoconductor cleaning device 64 discharger 70 discharger lamp 80 transfer roller 90 cleaning device 95 transfer paper 100 image forming device 101 photoconductor 102 charging means 103 exposure 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 14 Feeding path 147 transport rollers 148 feed path 150 copier main body 200 feeder table 300 Scanner 400 automatic document feeder (ADF)

Claims (17)

A toner solution is prepared by dissolving or dispersing at least an active hydrogen group-containing compound, a polyester component capable of reacting with the active hydrogen group-containing compound, and a polyester component soluble in the organic solvent in an organic solvent, A toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound reacts with the polyester component capable of reacting with the active hydrogen group-containing compound in the aqueous medium. A toner containing a polyester component insoluble in the organic solvent,
The polyester component capable of reacting with the active hydrogen group-containing compound comprises a polyester obtained by condensation polymerization of an aliphatic diol and an acid component in the presence of a catalyst, an aromatic diol and an acid component in the presence of a catalyst. A toner comprising a polyester resin having a weight average molecular weight of 10,000 to 100,000 obtained by reacting with a polyester obtained by condensation polymerization .   The toner according to claim 1, wherein the polyester component insoluble in the organic solvent includes a gel component having an increased molecular weight due to an elongation reaction.   The toner according to claim 1, wherein the polyester component capable of reacting with the active hydrogen group-containing compound contains an isocyanate group.   The toner according to claim 3, wherein the content of free isocyanate groups in the polyester component capable of reacting with the active hydrogen group-containing compound is 1.5% by mass or less.   The organic solvent is ethyl acetate, the polyester component soluble in the organic solvent is an ethyl acetate soluble polyester component, and the polyester component insoluble in the organic solvent is an ethyl acetate insoluble polyester component. Item 5. The toner according to any one of Items 1 to 4. Wherein the aliphatic Jio Le is, 1,4-butanediol, propylene glycol, ethylene glycol, diethylene glycol, either one of claims 1 to 5, characterized in that either neopentyl glycol and 1,6-hexanediol The toner described in 1.   The toner according to claim 1, wherein the aromatic diol compound is a 2 mol adduct of bisphenol A or 2 mol adduct of propylene oxide. The toner according to any one of claims 1 to 7 mol ratio of the aliphatic Jio Le said aromatic diol compound is characterized by a 9.5 / 0.5-6 / 4.   The toner according to claim 1, wherein the acid component is terephthalic acid or isophthalic acid.   The toner according to claim 1, wherein the catalyst is a Ti-based catalyst.   11. The toner according to claim 1, wherein the toner has a volume average particle diameter (Dv) of 3 to 8 μm.   The toner according to claim 1, wherein the toner has a volume average particle diameter (Dv) / number average particle diameter (Dn) of 1.25 or less.   A developer comprising the toner according to claim 1.   An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to any one of claims 1 to 12 to form a visible image An image forming method comprising at least a developing step for forming, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium.   An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the toner according to any one of claims 1 to 12 A developing means for forming a visible image by developing the toner, a transferring means for transferring the visible image to a recording medium, and a fixing means for fixing the transferred image transferred to the recording medium. An image forming apparatus.   An electrostatic latent image carrier and development means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner according to any one of claims 1 to 12 into a visible image. A process cartridge comprising at least a process cartridge.   A toner-filled container filled with the toner according to claim 1.

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