JP2007248558A - Toner and developer for electrostatic charge image development - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner that maintains cleaning property and high image quality, as well as low-temperature fixing property and shows proper charging properties and can form proper visible images over a long period of time. <P>SOLUTION: The toner is obtained by mixing a polymerized toner (A) obtained by a polymerization method and a pulverized toner (B) obtained by a pulverization method, wherein the ratio of a binder resin r to a colorant ca in the pulverized toner (B) is in the range of r:ca=97:3 to 100:0, with respect to the total 100 of the binder resin r and the colorant ca in the pulverized toner (B), and the weight average particle size DvB of the pulverized toner (B) is within the range of DvA×2 to DvA×10, with respect to the weight average particle size DvA of the polymerized toner (A). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner for developing an electrostatic charge image formed on the surface of a photoreceptor in electrophotography and electrostatic recording, and a developer using the toner.

Conventionally, in an electrophotographic apparatus, an electrostatic recording apparatus, or the like, an electric or magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a transfer material such as paper and then fixed by a method such as heating. Toner used for electrostatic image development is generally colored particles in which a binder, a colorant, a charge control agent, and other additives are contained in a binder resin. There is a suspension 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 the pulverization method, a toner having some excellent characteristics can be produced. However, in order to obtain a small particle size toner which has been desired in recent years from the principle of the method, more kinetic energy is required. Therefore, productivity is inferior, and it is not preferable from the viewpoint of energy saving.

In recent years, in order to overcome these problems in the pulverization method, a toner production method by a suspension polymerization method has been proposed and implemented. A technique for producing a toner for developing an electrostatic latent image by a polymerization method is known. For example, toner particles are obtained by a suspension polymerization method.
The closer the toner is to a spherical shape, the better the image quality and the better the chargeability due to improved toner fluidity.
However, a toner close to a spherical shape has a drawback of poor cleaning properties.

  For this reason, there have been proposals to make the toner shape potato-like or indefinite, or a function as a cleaning aid by additives, but the former has a charging property due to inferior toner fluidity compared to spherical toner. Inhomogeneity is likely to occur, and the latter has problems such as low temperature fixability being liable to be disturbed and also being liable to cause photoconductor contamination due to detachment from the toner, and no means for satisfying these has yet been reported.

  In addition, a toner in which a spherical toner obtained by a polymerization method and a toner obtained by a pulverization / kneading method are mixed has been proposed (Patent Document 1). It tends to cause a drop and is not practical.

JP 2003-107953 A

The object of the present invention is to interpolate each other's disadvantages while taking advantage of the advantages of the polymerized toner and the advantages of the kneaded and pulverized toner.
Therefore, the first object of the present invention is to achieve both low temperature fixability while maintaining cleanability and high image quality. A second object is to provide a toner having good chargeability and capable of forming a good visible image over a long period of time.

As a result of extensive studies by the present inventors, it has been found that the above problems are effective in achieving (1) to (7) of the present invention.
(1) In the toner obtained by mixing the polymerized toner A obtained by the polymerization method and the pulverized toner B obtained by the pulverization method, when the total of the binder resin r and the colorant ca of the pulverized toner B is 100, pulverization The ratio of the binder resin r of toner B to the colorant ca is
r: ca = 97: 3 to 100: 0,
A toner for developing an electrostatic charge image, wherein the weight average particle diameter DvB of the pulverized toner B is in the range of DvA × 2 to DvA × 10 with respect to the weight average particle diameter DvA of the polymerization toner A.
(2) The staticity described in (1) above, wherein the circularity of the polymerized toner A is in the range of 0.93 to 0.99 and the circularity of the ground toner B is in the range of 0.90 to 0.75. Toner for charge image development.
(3) The electrostatic charge image developing toner according to (1) or (2) above, wherein the difference in 1/2 outflow start temperature between the polymerized toner A and the pulverized toner B is within a range of ± 3 ° C. .
(4) The electrostatic charge according to any one of (1) to (3) above, wherein the acid values of the binder resins of the polymerized toner A and the pulverized toner B are in the range of 1 to 35 KOH mg / g, respectively. Toner for image development.
(5) The electrostatic image development according to any one of (1) to (4) above, wherein the amount of the external additive used for the pulverized toner B is in the range of 0.5 to 0.1%. Toner.
(6) The binder resin of polymerized toner A contains unmodified polyester (ii) together with polyester (i) obtained by extending and / or cross-linking modified polyester, and the binder of pulverized toner B is at least polyester. The electrostatic image developing toner according to any one of the above (1) to (5), wherein:
(7) A developing method using the electrostatic image developing toner according to any one of (1) to (6) above in a developing device having a toner recycling mechanism.

  As will be apparent from the following detailed and specific description, the present invention is compatible with low-temperature fixability while maintaining cleaning properties and high image quality, has good chargeability, and provides a good visible image over a long period of time. Thus, it is possible to provide a toner that can be formed over a wide range.

The present invention is described in detail below.
Conventionally, a polymerized toner generally has a smooth toner surface and often has a high degree of circularity.
When the degree of circularity is high or the surface of the toner particles is smooth, the contact area between the toner particles and / or the toner particles and the photosensitive member is small, so that there is an advantage of excellent transferability. Since the performance tends to be inferior to that of the pulverized toner, it has been proposed to use an inorganic fine particle cleaning aid such as silica or titanina. However, in order to realize a desired cleaning effect, these toners have a toner weight average particle diameter. In many cases, the size of about 0.1 to 1% is necessary, or it is necessary to add a large amount to the toner, and there is a problem that it easily causes photoconductor contamination or carrier contamination due to detachment from the toner base particles. It was. In recent years, low-temperature fixing toners have been desired as energy-saving measures. However, since the cleaning aid is mainly composed of inorganic fine particles, it tends to hinder low-temperature fixing, making it difficult to achieve both cleaning performance and low-temperature fixing performance. ing.
Therefore, the present invention mainly aims at achieving both cleaning performance and low-temperature fixing performance.

In general, the polymer toner tends to easily pass through the cleaning blade at the cleaning portion. Although no established theory has been established for this mechanism, a high pressure is always applied by the pressure from the cleaning blade immediately before the polymerization toner A is immediately before the nip portion of the cleaning blade (the portion where the photosensitive member and the cleaning blade are always in contact). Therefore, it is considered that the polymerized toner has a round shape compared to the pulverized toner and has an acute angle on the surface, so that it easily aggregates, adheres strongly to the photoreceptor, and easily passes through the cleaning blade.
That is, the purpose of the pulverized toner B is to suppress the aggregation of the polymerized toner due to the pressure from the cleaning blade.

  By making the ratio of the colorant ca to the binder resin r as small as possible or not added, the pulverized toner B can function as a “cleaning aid that is highly transparent and does not impair fixing properties”, not as a toner. In the image on paper after fixing, it is difficult to visually confirm the influence of the pulverized toner on the image quality deterioration, and a fine image derived from the polymerized toner is provided, while it functions as a cleaning aid for the polymerized toner A. . Furthermore, by aligning the fixing performance of the polymerized toner A and the pulverized toner B, both cleaning performance and low-temperature fixing performance can be achieved.

Specifically, in the toner obtained by mixing the polymerized toner A obtained by the polymerization method and the pulverized toner B obtained by the pulverization method, the total of the binder resin r and the colorant ca of the pulverized toner B was set to 100. If
The ratio of the binder resin r and the colorant ca of the pulverized toner B is in the range of r: ca = 97: 3 to 100: 0, more preferably in the range of r: ca = 99: 1 to 100: 0. There is a point.
In the present invention, it is important that the pulverized toner B on the image cannot be visually identified.
Therefore, when ca exceeds 3 with respect to the range r: ca = 97: 3 defined by the present invention, that is, when the ratio of the colorant ca of the pulverized toner B is high, the cleaning performance which is one of the aims of the present invention is Although it can function satisfactorily, the presence of the pulverized toner B can be visually recognized on the image, and the high image quality that is a feature of the present invention is not obtained.
The ca ratio is preferably blended to such an extent that the pulverized toner B cannot be recognized on the image, and in this respect, ca: 3 or less is necessarily preferable.
In consideration of the resistance and chargeability of the toner, the pulverized toner B can be used without a colorant.

The weight average particle diameter DvB of the pulverized toner B is DvA × 2 to DvA × 10 with respect to the weight average particle diameter DvA of the polymerization toner A, and more preferably within the range of DvA × 4 to DvA × 6. It is desirable.
Here, the most important is the ratio of DvB of pulverized toner B to DvA of polymerized toner A. By realizing the above ratio, the aggregation of the polymerized toner A immediately before the cleaning nip is alleviated, and the cleaning property is improved.
The smaller the weight average particle diameter DvA of the polymerized toner A is, the smaller the particle diameter, the better the dot reproducibility because the toner particles have a sufficiently small particle diameter with respect to the minute latent image dots.
However, since it is necessary to set the balance with the weight average particle diameter DvB of the pulverized toner B, it is desirable to set within the above range.
If the DvB of the pulverized toner B is less than DvA × 2, cleaning defects are likely to occur, and if it exceeds DvA × 10, the weight average particle diameter of the polymerized toner A is too large. Cannot be improved, and this is also undesirable because it tends to cause cleaning defects.

The circularity of the polymerized toner A is in the range of 0.93 to 0.99, and more preferably in the range of 0.96 to 0.99.
When the circularity of the polymerized toner A is less than 0.93, the high fluidity unique to the polymerized toner is hindered, and it becomes difficult to obtain a uniform and high quality image such as dot reproducibility. In addition, when the circularity exceeds 0.99, it is difficult to avoid poor cleaning even when the pulverized toner B is combined.

The circularity of the pulverized toner B is desirably 0.90 to 0.75. The function of the pulverized toner B is a cleaning aid effect. By setting the function within this range, the effect of reducing toner aggregation immediately before the cleaning nip is exhibited.
If it exceeds 0.90, the toner aggregation relaxation effect is low, and if it is less than 0.75, an excessively distorted shape is liable to cause frictional charging failure, which is not preferable.

The difference between the 1/2 outflow start temperature of the polymer toner A and the pulverized toner B is preferably within a range of ± 3 ° C.
In order to realize a low-temperature fixing toner, it is necessary to approximate the fixing performance of the polymerized toner A and the pulverized toner B. It is important to align toner viscoelasticity as much as possible so that toner dissolution at the time of fixing is uniform, so that the difference in anchor effect on paper does not occur locally.
In the characteristics shown here, the 1/2 outflow start temperature refers to the outflow start temperature and 1/2 outflow start temperature obtained with a flow characteristic evaluation device Flow Tester CFT-500D manufactured by SHIMADZU.

By setting the acid values of the resins used for the polymerization toner A and the pulverized toner B to be in the range of 1 to 35 KOH mg / g, more preferably in the range of 1 to 15 KOH mg / g, the charging performance under high temperature and high humidity conditions The saturation charge level approximates, and a better image can be obtained.
If both or one of the acid values is out of the above range, the toner charge distribution tends to be broad, and background staining and toner scattering are likely to be induced in image formation, which is not preferable.

The external additive amount of the pulverized toner B is preferably 0.5 to 0.1%, and more preferably 0.3 to 0.1.
When the amount of the external additive of the pulverized toner B exceeds 0.5%, the external additive is easily detached from the pulverized toner base particles, and the photosensitive member is easily contaminated. If it is less than 0.1%, the fluidity of the pulverized toner B is deteriorated, the charging characteristics are lowered, and internal contamination is likely to occur.

  The glass transition point (Tg) of the binders of the polymerized toner A and the pulverized toner B is preferably 50 to 70 ° C., more preferably 55 to 65 ° C. By setting both toners within this range, low-temperature fixing performance and toner blocking due to high-temperature storage can be satisfied, and a practical low-temperature fixing toner can be realized.

The binder resin of the polymerized toner A preferably contains unmodified polyester together with the modified polyester, and the binder of the pulverized toner B is preferably at least polyester.
By using these resins in combination, the polymerized toner and the pulverized toner are preferable because compatibility at the time of fixing is improved and desired toner transparency is obtained.

Further, in the present invention, cleaning performance, which is not good for polymerized toner, is improved by pulverized toner, so that the efficiency of toner collected by the cleaning unit is high, and application to a developing device having a toner recycling mechanism is also effective.
The toner recycling mechanism and layout are not particularly defined in the present invention, but the present invention is particularly effective in a system that uses toner after cleaning of the photoreceptor.

  Incidentally, the mixing ratio of the polymerized toner A and the pulverized toner B needs to be selected according to the volume specific resistance and the volume average particle diameter defined above, and is not particularly defined in the present invention. If A: pulverized toner B is in the range of 50:50 to 90:10, it is more preferable that the functional separation described above is easily achieved.

Hereinafter, measurement items described in the present invention will be described.
(Roundness)
For example, the average circularity can be determined by a flow type particle image analyzer FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.).
Measurement condition
Dispersion medium used: Cell sheath Measurement mode: LPF → HPF
Analysis conditions
Particle diameter cumulative frequency: Upper (predetermined value No. 12)% diameter
Lower (predetermined value No. 13)% diameter
Dilution factor: 1.00 times As a specific measurement method, a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant in 100 to 150 ml of water from which impure solids have been removed in advance. Add 0.5 ml and add about 0.1 to 0.5 g of the sample to be measured. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

(Volume average particle diameter)
As an apparatus for measuring the particle size distribution of toner particles by the Coulter counter method, there are Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the weight and number of toner particles or toner using a 100 μm aperture as an aperture. Calculate weight distribution and number distribution. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter (D1) of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 .35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

(1/2 outflow start temperature)
It can be measured using a flow tester.
As a flow tester, for example, there is an elevated flow tester CFT500D type of SHIMADZU. The flow curve of this flow tester becomes the data shown in FIGS. 1A and 1B, from which each temperature can be read. In the figure, Tfb is the outflow start temperature, and the melting temperature in the 1/2 method is the T1 / 2 temperature.
・ Load: 5 kg / cm ²
-Temperature rising rate: 3.0 ° C / min,
・ Die diameter: 1.00mm,
・ Die length: 10.0mm

(Tg)
Differential scanning calorimeter DSC
The Tg of the toner can be obtained by the following DSC apparatus, and the so-called 2nd peak glass transition temperature measured from room temperature after the sample was heated from room temperature to 150 ° C. was used.
・ Measurement device: DSC device (DSC60; manufactured by Shimadzu Corporation)
-Sample amount: about 5mg
-Temperature rising temperature: 10 ° C / min
Measurement range: room temperature to 150 ° C
Measurement environment: In nitrogen gas atmosphere

(Acid value)
The acid value represents the total amount of the acid component at the end, and the acid value is measured according to JIS K007.
According to 0 method. However, when the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.

Hereinafter, the toner manufacturing method will be described.
In the present invention, any means may be used for the production method of the polymerized toner A and the pulverized toner B, but the polymerized toner A is a prepolymer composed of at least a modified polyester resin in an organic solvent. A method obtained by dissolving or dispersing a crosslinking compound and / or a colorant, causing the dissolution or dispersion to undergo a crosslinking reaction and / or elongation reaction in an aqueous medium, and removing the solvent from the obtained dispersion. preferable.

Hereinafter, an example of a manufacturing method of the polymerization toner A will be described.
(Urea-modified polyester)
Examples of the polyester (i) modified with a urea bond include a reaction product of a polyester prepolymer (A) having an isocyanate group and an amine (B). Examples of the polyester prepolymer (A) having an isocyanate group include a product obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate (3), which is a polycondensate of polyol (1) and polycarboxylic acid (2). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol; bisphenol And alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol (1) and the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactams, etc. And a combination of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. As (B6) which blocked the amino group of (B1) to (B5), ketimine compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of (B1) to (B5), Examples include oxazoline compounds. Among these amines (B), preferred are (B1) and a mixture of (B1) and a small amount of (B2).

  Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low, and the hot offset resistance deteriorates. In the present invention, the polyester (i) modified with a urea bond may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

The residual monomer amount in the toner shown in the present invention may be adjusted by any method.
For example, it can also be controlled by the temperature and time during condensation polymerization of urea-modified polyester and / or unmodified polyester.
The urea-modified polyester (i) of the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the urea-modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester is not particularly limited when the unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. (I) When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

(Unmodified polyester)
In the present invention, not only the polyester (i) modified with a urea bond but also the polyester (ii) not modified can be included as a toner binder component together with the (i). By using (ii) in combination, the low-temperature fixability and glossiness when used in a full-color apparatus are improved, which is preferable to single use. Examples of (ii) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (i) above, and preferred ones are also the same as (i). (Ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (i) and (ii) preferably have similar compositions. When (ii) is contained, the weight ratio of (i) and (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. When the weight ratio of (i) is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (ii) is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (ii) is usually 1-30, preferably 5-20. By having an acid value, it tends to be negatively charged.

  In the present invention, the glass transition point (Tg) of the toner binder is usually 50 to 70 ° C., preferably 55 to 65 ° C. If it is less than 50 ° C., the heat resistant storage stability of the toner is deteriorated, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the urea-modified polyester resin, the dry toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester-based toners. As the storage elastic modulus of the toner binder, the temperature (TG ′) at which 10000 dyne / cm 2 is obtained at a measurement frequency of 20 Hz is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the toner binder, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or lower, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or more. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.

(Coloring agent)
As the coloring agent of the present invention, known dyes and pigments can be used, such as carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G) , R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fayce Red, Parachlor Ortoni Roaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo Red, Chrome Vermillion, 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, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Fu Talocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

  The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
Further, a wax may be contained together with the toner binder and the colorant. Known waxes can be used as the wax of the present invention, such as polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. It is done. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecandiol diol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax 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. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of 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-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they can be added directly when dissolved and dispersed in an organic solvent. May be.

(Resin fine particles)
The resin fine particles used in the present invention can be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resins, polyurethane resins, epoxy resins, Examples thereof include polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, and polycarbonate resin. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.

  The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, such as a styrene- (meth) acrylate resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylate polymer, Examples include styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.

(External additive)
As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
Moreover, you may use together the fluororesin fine particle described in Claims 1-2.
Other polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resins Examples include polymer particles.
Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

(Toner production method in aqueous medium)
The aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.
The toner particles may be formed by reacting a dispersion composed of a prepolymer (A) having an isocyanate group in an aqueous medium with (B), or using a urea-modified polyester (i) produced in advance. good. As a method for stably forming a dispersion comprising urea-modified polyester (i) or prepolymer (A) in an aqueous medium, a toner raw material comprising urea-modified polyester (i) or prepolymer (A) in an aqueous medium is used. And a method of dispersing by shearing force. The prepolymer (A) and other toner compositions (hereinafter referred to as toner raw materials), a colorant masterbatch, a release agent, a charge control agent, an unmodified polyester resin, etc. are dispersed in an aqueous medium. It may be mixed at the time of formation, but it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.
The fluororesin fine particles of the present invention may be added to either the aqueous medium or the oily phase in which the toner composition is dispersed, but is preferable from the viewpoint that the reaction in the aqueous medium is difficult to inhibit.

The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferable in that the dispersion of the urea-modified polyester (i) or prepolymer (A) has a low viscosity and is easily dispersed.
The amount of the aqueous medium used relative to 100 parts of the toner composition containing the urea-modified polyester (i) and the prepolymer (A) is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.
In the step of synthesizing the urea-modified polyester (i) from the prepolymer (A), the amine (B) may be added and reacted before the toner composition is dispersed in the aqueous medium, or may be dispersed in the aqueous medium. An amine (B) may be added later to cause a reaction from the particle interface. In this case, urea-modified polyester is preferentially produced on the surface of the manufactured toner, and a concentration gradient can be provided inside the particles.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphates, alkylamines as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in a liquid containing water Amine salts such as salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl N, amphoteric surfactants such as N- dimethyl ammonium betaine and the like.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkyl carboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-ll0, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF- 102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  Examples of cationic surfactants include aliphatic primary, secondary or secondary amine acids having fluoroalkyl groups, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, and benzas. Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) , Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.

  Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant which is hardly soluble in water.

  Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride or other (meth) acrylic monomer containing a hydroxyl group, For example, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-acrylate -Hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Pinyl acetate, pinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinylviridine, vinylpyrrolidone, vinylimidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having nitrogen atoms or heterocyclic rings thereof, polyoxyethylene, polyoxypropylene, polymers Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

Furthermore, in order to lower the viscosity of the toner composition, a solvent in which the urea-modified polyester (i) or the prepolymer (A) is soluble can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are preferred. The usage-amount of the solvent with respect to 100 parts of prepolymers (A) is 0-300 parts normally, Preferably it is 0-100 parts, More preferably, it is 25-70 parts. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after elongation and / or crosslinking reaction.
The elongation and / or cross-linking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.
When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.
By mixing the resulting dried toner powder with dissimilar particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by giving mechanical impact force to the mixed powder By immobilizing and fusing on the surface, it is possible to prevent detachment of the foreign particles from the surface of the resulting composite particle.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron Examples include a system (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic mortar.

Hereinafter, the pulverized toner B will be described.
A known resin may be used as the binder resin, but polyester is particularly preferable.
The raw material monomer for polyester is not particularly limited, and a known polyhydric alcohol component and a polyvalent carboxylic acid component such as carboxylic acid, carboxylic acid anhydride, or carboxylic acid ester are used.
Examples of the polyhydric alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane. Bisphenol A alkylene oxide (addition mole number 1 to 10) adduct such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol, or etherified polyhydroxyl compounds thereof And those containing one or more of these are preferred. Further, from the viewpoint of improving the durability of the toner, it is preferable that an alkylene oxide adduct of bisphenol A is used in an amount of 5 mol% or more in the alcohol component.
Examples of the polyvalent carboxylic acid component include dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, and maleic acid, alkyl groups having 1 to 20 carbon atoms such as dodecenyl succinic acid, octyl succinic acid, and the like. Examples thereof include succinic acid, trimellitic acid, pyromellitic acid substituted with 2 to 20 alkenyl groups, anhydrides of these acids, and alkyl (carbon number 1 to 8) esters of these acids, and one of these. What contains the above is preferable.

The polyester can be produced by polycondensation of a polyhydric alcohol component and a polycarboxylic acid component in an inert gas atmosphere, if necessary, using an esterification catalyst at a temperature of 180 to 250 ° C. it can.
The acid value of the polyester is preferably 35 (KOH mg / g) or less from the viewpoint of environmental stability. In the present invention, the acid value of the polyester can be controlled within the above range by adjusting the ratio of the starting alcohol and carboxylic acid, adjusting the reaction conditions, or using the corresponding ester as the acid component.

As the charge control agent, colorant, master batch, and external additive used for the pulverized toner B, the materials described in the explanation of the polymerized toner A can be used.
Examples of the wax that can be used in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketone, fatty acid metal salt wax, fatty acid ester wax, and partial wax. Examples thereof include saponified fatty acid ester waxes, silicone varnishes, higher alcohols, and carnauba wax. Also, polyolefins such as low molecular weight polyethylene and polypropylene can be used.

The pulverized toner B of the present invention includes a step of mechanically mixing raw materials including at least a binder resin, a charge control agent, and a colorant as required, a step of melt-kneading, a step of pulverizing, and a step of classifying A method for producing a toner having the following can be applied. Further, in order to improve the dispersibility of the colorant, the colorant may be mixed with other raw materials after the masterbatch treatment and processed to the next step.
The mixing step for mechanical mixing may be performed under normal conditions using a normal mixer using rotating wings, and is not particularly limited. When the above mixing process is completed, the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. Specific examples of the apparatus for kneading the toner include a batch type two roll, a Banbury mixer and a continuous type twin screw extruder, such as a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type twin screw manufactured by Toshiba Machine Co., Ltd. Extruder, KCK twin screw extruder, Ikekai Iron Works PCM type twin screw extruder, Kurimoto Iron Works KEX type twin screw extruder, continuous single screw kneader, for example Bush Co. kneader Etc. are preferably used. The melt-kneaded material obtained as described above is cooled and then pulverized. For example, the pulverization is roughly pulverized using a hammer mill, a funnel plex, etc. A machine can be used. Next, the external additive is externally added to the toner particles, and the toner particles are coated on the surface of the toner particles while being pulverized by mixing and stirring the toner particles and the external additive using a mixer.
The circularity adjustment of the pulverized toner is preferably set according to the toner pulverization conditions. For example, in a fine pulverizer using a jet stream, it is preferable to adjust the compression air pressure and the collision plate shape used during pulverization.

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 weights of toner with respect to 100 parts by weight of carrier. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited only to these examples. In the following examples, parts and% are based on weight unless otherwise specified.

A. Production Example of Polymerized Toner 1) Production of Polymerized Toner A1 <Synthesis of Organic Fine Particle Emulsion 1>
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 14 parts of a sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 137 parts of styrene, 138 parts of methacrylic acid, When 1.2 parts of ammonium persulfate was charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 71 ° C. for 6 hours, and an aqueous dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-methacrylic acid etherene oxide adduct sulfate sodium salt) [ A fine particle dispersion 1] was obtained. The volume average particle diameter of the [fine particle dispersion 1] measured by LA-920 was 0.18 μm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The resin content Tg was 150 ° C.

<Adjustment of aqueous phase 1>
990 parts of water, 80 parts of [fine particle dispersion 1], 38 parts of a 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries), 90 parts of ethyl acetate, 0.6 A tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer having a primary particle number average particle size of 0.15 μm in a proportion by weight was mixed and stirred to obtain a milky white liquid. This is designated as [Aqueous Phase 1].

<Synthesis of low molecular weight polyester 1>
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 224 parts of bisphenol A ethylene oxide 2-mole adduct, 561 parts of bisphenol A propylene oxide 3-mole adduct, 217 parts terephthalic acid, 46 parts adipic acid and dibutyl 3 parts of tin oxide was added, reacted at 230 ° C. under normal pressure for 7 hours, and further reacted for 5 hours under reduced pressure of 10-15 mmHg. Then, 42 parts of trimellitic anhydride was added into the reaction vessel, and 5 parts at 180 ° C. under normal pressure. By reacting for a time, [low molecular weight polyester 1] was obtained. [Low molecular polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 6600, Tg of 41 ° C., and an acid value of 35 KOH mg / g.

<Synthesis of Prepolymer 1>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 685 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 281 parts of terephthalic acid, 24 parts of trimellitic anhydride And 3 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 10 hours, and further reacted for 8 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9400, Tg of 53 ° C., and an acid value of 35 KOH mg / g.
Next, 414 parts of [Intermediate polyester 1], 86 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 8 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

<Synthesis of ketimine 1>
176 parts of isophoronediamine and 73 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stirrer and a thermometer, and reacted at 50 ° C. for 8 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 410.

<Combination of master batch 1>
Pigment: Carbon black (Cabot Company Legal 400R) 42 parts Binder: Polyester resin 63 parts
(Sanyo Kasei RS-801 Acid value 10, Mw 20000 Tg, 64 ° C)
30 parts of water The above raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 70 minutes with two rolls set at a roll surface temperature of 135 ° C. and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 1]. Next, using this master batch pigment, a toner was prepared by the following method.

<Creation of oil phase 1>
In a container equipped with a stirrer and a thermometer, 375 parts of [Low molecular weight polyester 1], 110 parts of Carnauba WAX, 20 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Co., Ltd.), 949 parts of ethyl acetate, and 80 parts under stirring were added. The temperature was raised to 0 ° C., kept at 80 ° C. for 10 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 510 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

<Emulsification / desolvation>
[Pigment / WAX Dispersion 1] 648 parts, [Prepolymer 1] 152 parts, [Ketimine Compound 1] 7.6 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 5 minutes After mixing, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at 14,000 rpm for 40 minutes to obtain [Emulsion slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 10 hours, aging was carried out at 45 ° C. for 6 hours to obtain [Dispersion slurry 1]. [Dispersion Slurry 1] had a volume average particle size of 5.75 μm and a number average particle size of 5.2 μm (measured with Multisizer II).

<Washing and drying>
[Emulsified slurry 1] After 100 parts were filtered under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 13,000 rpm for 10 minutes), and then filtered.
(2): 100 parts of 10% sodium hydroxide aqueous solution was added to the filter cake of (1), ultrasonic vibration was applied and mixed with a TK homomixer (30 minutes at 13,000 rpm), and then filtered under reduced pressure. . This ultrasonic alkali cleaning was performed again (two ultrasonic alkali cleanings).
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (10 minutes at 13,000 rpm) and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 13,000 rpm) and then filter twice to obtain [Filter cake 1]. It was.
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, sieved with a mesh opening of 75 μm, and 0.8% of Nippon Aerosil R-972 was added to the toner base 100 with a Henschel mixer (Henschel mixer). 20B), and sieved with a mesh of 250 mesh to obtain [Polymerized toner A1] having a weight average particle diameter DvA of 4.90 μm, a circularity of 0.99, a flow tester T1 / 2 of 115 ° C., and a Tg of 51 ° C.

2) Production of polymerized toner A2 The same procedure as in “1) Production of polymerized toner A1” except that the ultrasonic alkaline cleaning in “1) Production of polymerized toner A1” was performed once and the R972 formulation was 1.4%. [Polymerized toner A2] having a weight average particle diameter DvA of 5.10 μm, a circularity of 0.93, a flow tester T1 / 2 of 114 ° C. and a Tg of 51 ° C. was obtained.

3) Production of Polymerized Toner A3 In the above-mentioned “Production of Polymerized Toner A1,” [Emulsion Slurry 1] was added, the solvent was removed at 30 ° C. for 1 hour, and then aged at 39 ° C. for 2 hours. The weight average particle diameter DvA is 4.80 μm, the circularity is 0.97, the flow tester T1 / 2 is 113 ° C., and the Tg is 50 ° C. [polymerized toner A3], except that the content is 3%. ] Was obtained.

4) Production of Polymerized Toner A4 <Synthesis of Low Molecular Polyester 2>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 262 parts of bisphenol A ethylene oxide 2 mol adduct, 212 parts of bisphenol A propylene oxide 2 mol adduct, 214 parts of bisphenol A propylene oxide 3 mol adduct, 264 parts of terephthalic acid, 50 parts of adipic acid and 4 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 12 hours, further reacted at reduced pressure of 10-15 mmHg for 5 hours, and then added to the reaction vessel with 33 parts of trimellitic anhydride. And reacted at 180 ° C. and normal pressure for 4 hours to obtain [Low molecular weight polyester 2]. [Low molecular polyester 2] had a number average molecular weight of 2490, a weight average molecular weight of 8150, a Tg of 69 ° C., and an acid value of 1.0 KOH mg / g.

<Synthesis of Prepolymer 2>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 685 parts of bisphenol A ethylene oxide 2-mole adduct, 75 parts of bisphenol A propylene oxide 2-mole adduct, 266 parts of terephthalic acid, 30 parts of trimellitic anhydride And 4 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 23 hours, and further reacted for 15 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 2]. [Intermediate polyester 2] had a number average molecular weight of 4,300, a weight average molecular weight of 8,100, a Tg of 54 ° C., and an acid value of 1.0 KOH mg / g.
It is the same except that the low molecular weight polyester 2 is used instead of the low molecular weight polyester 1 used in the preparation of the oil phase 1 and the intermediate polyester 2 is used instead of the intermediate polyester 1, and the above except that the R972 formulation is 0.5%. In the same manner as in “1) Production of polymerized toner A1,” [polymerized toner A4] having a weight average particle diameter DvA of 4.80 μm, a circularity of 0.98, a flow tester T1 / 2 of 115 ° C., and a Tg of 56 ° C. was obtained.

5) Production of polymerized toner AR4 <Synthesis of low molecular weight polyester 3>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 246 parts of bisphenol A ethylene oxide 2-mole adduct, 599 parts of bisphenol A propylene oxide 3-mole adduct, 242 parts of terephthalic acid, 50 parts of adipic acid and dibutyl After adding 4.4 parts of tin oxide and reacting at normal pressure of 230 ° C. for 8 hours and further reacting for 7 hours at a reduced pressure of 10 to 15 mmHg, 44 parts of trimellitic anhydride was added to the reaction vessel at 180 ° C. and normal pressure. For 5 hours to obtain [Low molecular weight polyester 3]. [Low molecular weight polyester 3] had a number average molecular weight of 4600, a weight average molecular weight of 8600, Tg of 44 ° C., and an acid value of 40 KOH mg / g.

<Synthesis of Prepolymer 3>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 694 parts of bisphenol A ethylene oxide 2-mole adduct, 79 parts of bisphenol A propylene oxide 2-mole adduct, 269 parts terephthalic acid, 23 parts trimellitic anhydride Then, 3.5 parts of dibutyltin oxide was added, reacted at 230 ° C. under normal pressure for 10 hours, and further reacted for 7 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 3]. [Intermediate Polyester 1] had a number average molecular weight of 4500, a weight average molecular weight of 10400, Tg of 55 ° C., and an acid value of 40 KOH mg / g.
The same applies except that the low molecular weight polyester 3 is used in place of the low molecular weight polyester 1 used in the preparation of the oil phase 1, and the intermediate polyester 3 is used in place of the intermediate polyester 1. 1) Production of Polymerized Toner A1 [polymerized toner AR4] having a weight average particle diameter DvA of 5.20 μm, a circularity of 0.98, a flow tester T1 / 2 of 115 ° C., and a Tg of 56 ° C. was obtained.

B. Production example of pulverized toner B

1) Production of pulverized toner B1 935 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 340 g of fumaric acid and 11 g of dibutyltin oxide as an esterification catalyst at 200 ° C. under a nitrogen stream. The reaction was carried out with stirring. The obtained resin is designated as polyester A. Polyester A had a glass transition point (Tg) of 60 ° C., a flow tester T1 / 2 of 116 ° C., and an acid value of 15.0 (KOH mg / g).
Polyester A 100 parts Charge control agent (TN-105 manufactured by Hodogaya Chemical Co., Ltd.) 0.5 part Carnauba WAX (Carnauba WAX1) 5.0 parts The above materials are mixed with a mixer, melted and kneaded with a two-roll mill, Rolled and cooled.
Thereafter, a turbo counter jet mill pulverizer (turbo rotating speed: 7500 rpm, feed amount 1.2 Kg / hr) of turbo industry, and a wind classifier (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) by swirling flow The toner base was mixed with 0.4% of R-972 with a Henschel mixer, sieved with an opening of 250 mesh, weight average particle diameter Dvb 9.8 μm, circularity 0.85, flow tester T1 / 2 [Crushed toner B1] having a temperature of 116 ° C. was obtained.

2) Production of pulverized toner B2 A pulverized toner B2 was obtained in the same manner as in “1) Production of pulverized toner B1” except that Dvb was changed by changing the apparatus conditions of the turbo counter jet mill pulverizer.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

3) Manufacture of pulverized toner B3 The pulverized toner B3 and pulverized toner B4 were obtained in the same manner as in “1) Manufacture of pulverized toner B1” except that the circularity was changed by changing the apparatus conditions of the turbo counter jet mill pulverizer. .
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

4) Production of pulverized toner B5 900 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 302 g of fumaric acid and 16 g of dibutyltin oxide as an esterification catalyst at 200 ° C. under a nitrogen stream. The reaction was carried out with stirring. The obtained resin is designated as polyester B. A pulverized toner B5 having a glass transition point (Tg) of Polyester B of 66 ° C. and a flow tester T1 / 2 of 118 ° C. was obtained.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

5) Production of pulverized toner B6 Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 895 g, fumaric acid 340 g and dibutyltin oxide 15 g as an esterification catalyst at 220 ° C. under a nitrogen stream. The reaction was carried out with stirring. The obtained resin is designated as polyester A. Polyester A had a glass transition point (Tg) of 61 ° C., a flow tester T1 / 2 of 116 ° C., and an acid value of 35.0 (KOH mg / g).
0.4% of R-972 was mixed with this toner base with a Henschel mixer, and sieved with an opening of 250 mesh to obtain [Crushed toner B6].
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

6) Production of ground toner B7 2450 g of polyoxypropylene (2.2) -2,2- (4-hydroxyphenyl) propane, 975 g of polyoxyethylene (2.0) -2,2- (4-hydroxyphenyl) propane Then, 830 g of terephthalic acid, 670 g of alkenyl succinic acid, 480 g of trimellitic acid and 15 g of dibutyltin oxide were stirred at 230 ° C. in a nitrogen atmosphere to obtain polyester C. Polyester C had a glass transition point (Tg) of 58 ° C., a flow tester T1 / 2 of 116 ° C., and an acid value of 1.0 (KOH mg / g).
0.4% of R-972 was mixed with this toner base with a Henschel mixer, and sieved with an opening of 250 mesh to obtain [Crushed toner B7].
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

7) Production of pulverized toner B8 A pulverized toner B8 was obtained in the same manner as in “1) Production of pulverized toner B1, except that the amount of R-972 added was 0.5%.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

8) Production of pulverized toner B9 A polymerizable monomer mixture of 140 parts of styrene, 37 parts of methyl methacrylate and 17 parts of n-butyl acrylate was charged into a reactor equipped with a thermometer, a stirrer, a gas introduction tube and a cooling tube. . The system was purged with nitrogen and then kept under a nitrogen atmosphere. While stirring, the temperature was raised to 150 ° C., and the temperature of the post-thermal polymerization system was adjusted to 205 ° C. by polymerization exotherm. A polymerizable monomer mixture of 576 parts of styrene, 152 parts of methyl methacrylate and 72 parts of n-butyl acrylate was dropped to obtain a polymerization rate of 99.8%. Unreacted polymerizable monomer was removed by heating under reduced pressure to obtain a styrene resin.
A pulverized toner B9 was obtained in the same manner as "1) Production of pulverized toner B1" except that the styrene resin was used instead of polyester A.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

9) Production of pulverized toner B10 Using 97 parts of polyester A and 3 parts of carbon black (Mitsubishi Chemical # C-44), pulverized toner B10 was obtained in the same manner as in “1) Production of pulverized toner B1”.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

10) Production of pulverized toner B11 A pulverized toner B11 was obtained in the same manner as in "1) Production of pulverized toner B1" except that Dvb was changed by changing the apparatus conditions of the turbo counter jet mill pulverizer.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

11) Production of pulverized toner B12 A pulverized toner B12 was obtained in the same manner as in “1) Production of pulverized toner B1” except that the amount of R-972 added was 0.1%.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

12) Production of pulverized toner BR1 Using 96 parts of polyester A and 4 parts of carbon black (Mitsubishi Chemical # C-44), pulverized toner BR1 was obtained in the same manner as in “1) Production of pulverized toner B1”.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

13) Production of pulverized toner BR2 A pulverized toner BR2 was obtained in the same manner as in "1) Production of pulverized toner B1" except that Dvb was changed by changing the apparatus conditions of the turbo counter jet mill pulverizer.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

14) Manufacture of pulverized toners BR3 and BR4 The pulverized toner BR3 and pulverized toner BR4 are prepared in the same manner as in “1) Manufacture of pulverized toner B1” except that the circularity is changed by changing the apparatus conditions of the turbo counter jet mill pulverizer. Obtained.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

15) Production of ground toner BR5 205 g of polyoxypropylene (2.2) -2,2- (4-hydroxyphenyl) propane, 935 g of polyoxyethylene (2.0) -2,2- (4-hydroxyphenyl) propane Then, 810 g of terephthalic acid, 870 g of alkenyl succinic acid, 420 g of trimellitic acid and 11 g of dibutyltin oxide were stirred at 190 ° C. in a nitrogen atmosphere to obtain polyester D.
The flow tester T1 / 2 of polyester D was 120 ° C.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

16) Production of pulverized toner BR6 865 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 311 g of fumaric acid and 9 g of dibutyltin oxide as an esterification catalyst in a nitrogen stream at 190 ° C. The reaction was carried out with stirring. The obtained resin is designated as polyester E. The acid value of Polyester E was 40.0 (KOH mg / g).

17) Production of pulverized toner BR7 A pulverized toner BR7 was obtained in the same manner as in “1) Production of pulverized toner B1” except that the amount of R-972 added was 0.6%.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

18) Production of pulverized toner BR8 Using 95 parts of polyester A and 5 parts of carbon black (Mitsubishi Chemical # C-44), pulverized toner BR8 was obtained in the same manner as in “1) Production of pulverized toner B1”.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

19) Production of pulverized toner BR9 A pulverized toner BR9 was obtained in the same manner as in "1) Production of pulverized toner B1" except that Dvb was changed by changing the apparatus conditions of the turbo counter jet mill pulverizer.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

20) Production of pulverized toner BR10 A pulverized toner BR10 was obtained in the same manner as in “1) Production of pulverized toner B1” except that the amount of R-972 added was changed to 0.05%.
Details of the physical properties of the toner are described in the physical properties table of pulverized toner B in Table 2 below.

[Examples 1 to 19], [Comparative Examples 1 to 4]
Each polymerized toner obtained in “A. Production Example of Polymerized Toner” and each crushed toner obtained in “B. Production Example of Crushed Toner” are mixed as shown in Table 3, and each mixed toner is mixed. The performance of was evaluated. The results are shown in Table 4 (Example) and Table 5 (Comparative example), respectively.
In the present invention, the means for mixing the polymerized toner A and the pulverized toner B is not particularly specified, but it is desirable to mix them under appropriate mixing conditions using a mixer such as a Henschel mixer.
In both the examples and comparative examples of the present invention, a Henschel mixer 20B (manufactured by Mitsui Mining Co., Ltd.) was used, and the polymerization toner A and the pulverized toner B were mixed at a blade rotation speed of 500 rpm and used for evaluation.

It is a figure showing the flow curve of the flow tester measurement of this invention.

Claims (7)

In the toner obtained by mixing the polymerized toner A obtained by the polymerization method and the pulverized toner B obtained by the pulverization method, when the total of the binder resin r and the colorant ca of the pulverized toner B is 100, The ratio of binder resin r and colorant ca is
r: ca = 97: 3 to 100: 0,
A toner for developing an electrostatic charge image, wherein the weight average particle diameter DvB of the pulverized toner B is in the range of DvA × 2 to DvA × 10 with respect to the weight average particle diameter DvA of the polymerization toner A. 2. The electrostatic charge image developing device according to claim 1, wherein the circularity of the polymerized toner A is 0.93 to 0.99, and the circularity of the pulverized toner B is 0.90 to 0.75. toner. 3. The electrostatic charge image developing toner according to claim 1, wherein the difference between the ½ outflow start temperatures of the polymerization toner A and the pulverized toner B is within a range of ± 3 ° C. 3. The electrostatic charge image developing toner according to any one of claims 1 to 3, wherein the acid values of the binder resins of the polymerized toner A and the pulverized toner B are in the range of 1 to 35 KOH mg / g, respectively. 5. The electrostatic charge image developing toner according to claim 1, wherein the amount of the external additive used in the pulverized toner B is in the range of 0.5 to 0.1%. The binder resin of the polymerized toner A contains unmodified polyester (ii) together with the polyester (i) obtained by extending and / or cross-linking the modified polyester, and the binder of the pulverized toner B is at least polyester. The toner for developing an electrostatic charge image according to any one of claims 1 to 5. A developing method using the electrostatic image developing toner according to claim 1 in a developing device having a toner recycling mechanism.

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