JP2010039291A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner that excels in low-temperature fixability, environmental stability, development durability and contamination prevention in members, and enabling toner images of high image quality to be formed. <P>SOLUTION: The toner for electrostatic charge image development contains toner particles, containing at least a binder resin, a colorant and wax, and a fatty acid metal salt, wherein wettability of the fatty acid metal salt with a mixture solvent of methanol and water under specified conditions, and for which the wettability of the toner with a mixture solvent of methanol and water are specified. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic image used in an image forming method such as electrophotography and electrostatic printing.

  In recent years, with the development of computers and multimedia, there has been a demand for means for outputting high-definition full-color images in a wide range of fields from offices to homes.

  Heavy users demand high durability that does not deteriorate image quality even when a large number of copies or prints are made. On the other hand, in small offices and homes, high-quality images are obtained, and from the viewpoints of space saving, energy saving and light weight, the size of the device is reduced, waste toner is reused or waste toner (cleanerless), and the fixing temperature is low. Is required.

  Considering the recent demands for miniaturization, weight reduction, energy saving and high reliability, the toner performance cannot be met without further improvement in toner performance such as low-temperature fixability, high durability, and environmental stability.

  In the case of full color, three or four color toners are superimposed to form an image. However, if the color toners of the respective colors are not developed in the same manner, color reproduction is inferior and color unevenness occurs. However, these colorings are performed with pigments and dyes, and these have a great influence on development. Further, in a full-color image, fixability and color mixing at the time of fixing are important. In order to achieve the high speed demanded in recent years, a binder resin suitable for low-temperature fixability is selected, but the influence on the developability and durability of this binder resin is also great. One of the effects is the influence of temperature and humidity on the charge amount, and there is an urgent need to develop a color toner having a stable charge amount even in a wide range of environments.

  One means for solving these problems is a method for controlling the surface properties of the toner.

  In the evaluation of toner surface properties, wettability in mixed solvents with different solubility parameters (hereinafter also referred to as SP values) of organic fine particles, inorganic fine particles, and fatty acid metal salts used for toner and toner surface treatment is an effective index. It becomes.

  As a toner in which the material present in the toner particles is uniform, a magnetic toner that defines the transmittance and molecular weight in wettability with respect to a mixed solvent of water and methanol is disclosed (see Patent Document 1).

  However, the toner has some problems as a toner excellent in low-temperature fixability, environmental stability, and durability that are currently required.

  Further, a toner having inorganic fine particles on the surface of toner particles is disclosed in which a difference between the wettability of toner particles without the inorganic fine particles and the wettability of the toner with water is defined (Patent Document 2). reference).

  However, the toner is contaminated with members such as an anti-static roller, a photosensitive drum and a developing roller due to embedding external additives in a high-speed system, and it is a little as a toner excellent in low-temperature fixability, environmental stability and development durability. Has a problem.

  Further, a toner is disclosed in which durability deterioration is suppressed by adding a fatty acid metal salt to the toner. However, many of these fatty acid metal salts have non-uniform shapes and surface states, and on the other hand, the fatty acid metal salts cause fogging and a decrease in image density, resulting in poor image quality. Thus, it has been disclosed to improve fogging while improving filming and voiding in an electrostatic latent image carrier by using a fatty acid metal salt and a titanic acid compound in combination (see Patent Document 3).

  Further, a toner containing a fatty acid metal salt having a specific volume average particle size is disclosed (for example, see Patent Documents 4 and 5).

  In addition, a toner is disclosed in which the circularity of the toner containing the fatty acid metal salt and the particle diameter ratio of the fatty acid metal salt are defined (see, for example, Patent Document 6).

  However, a toner having excellent filming, fogging and member contamination in a high-speed machine has some problems.

  Toners using these external additives are effective in improving the blade cleaning characteristics, improving the blade turnability, and suppressing the surface of the electrostatic latent image carrier. Further, uniform charging properties and the effect of suppressing drum filming can be obtained.

  However, such a toner containing a fatty acid metal salt having a different surface state is excellent in lubricity on the surface of the electrostatic latent image carrier, but the fatty acid metal salt is easily consumed selectively during the endurance. Effect is reduced. In addition, in order to obtain the effects as described above, it is necessary to add a sufficient amount of the fatty acid metal salt, but problems such as member contamination are likely to occur due to the influence of the excess fatty acid metal salt. Furthermore, since such a problem tends to become a significant problem in color toners used in high-speed image forming apparatuses, an appropriate amount of a material having a sufficient effect is used when applied to a high-speed apparatus. We have to go.

  Further, inventions have been made that pay attention to the relationship between the number average particle diameter of the toner, the ratio of 3.17 μm or less, and the number particle diameter of the fatty acid metal salt.

  According to this invention, there is obtained a toner with little friction of the photoconductor, no image fogging and no image blur even when printed at high temperature and high humidity, a uniform halftone and a small amount of toner scattering of fine dots (for example, (See Patent Document 7).

  Furthermore, a toner is disclosed in which the relationship between the toner particle diameter and the fatty acid metal salt particle diameter is defined by a one-component developer including toner particles having a melt viscosity in a certain range, a fluidity improver and a fatty acid metal salt. . According to this, a toner having a high density and less fog and excellent sharpness can be obtained (see, for example, Patent Document 8).

  However, although the toner as described above has less fog and can output a fine image, further improvement is necessary in application to a non-magnetic one-component image forming apparatus having a high process speed, and these inventions are sufficient. Performance has not been expressed.

  Therefore, the conventional techniques as described above have some problems with the high demands currently required.

  On the other hand, as a typical method for producing a fatty acid metal salt, a method of reacting a solution of an inorganic metal compound dropwise with a solution of an alkali metal salt of a fatty acid (metathesis method), or a fatty acid and an inorganic metal Examples include a method (melting method) in which a compound is kneaded at a high temperature to react.

  Further, various studies have been made on the refinement of fatty acid metal salts.

  For example, an invention has been made about a production method for forming a fatty acid metal salt into fine particles and a toner using the same (for example, see Patent Document 9).

  Such toner is refined by controlling the solvent concentration and temperature during synthesis when the fatty acid metal salt is produced by a wet method. The toner containing such a fatty acid metal salt sufficiently exhibits the performance as a lubricant and provides a high effect as a cleaning aid. Further, since the fatty acid metal salt finer than the toner particle diameter adheres firmly to the toner surface and behaves together with the toner particles in the developing container, it is not selectively consumed even in durability. Therefore, the effect as a cleaning aid can be maintained until the end of durability.

JP 2002-278147 A JP 2003-202700 A JP-A-8-272132 JP 2004-163807 A JP 2002-296829 A JP 2006-17934 A Japanese Patent No. 0347966 Japanese Patent Application Laid-Open No. 09-311499 Japanese Patent No. 0390580

  An object of the present invention is to provide a toner that solves the above problems.

  More specifically, the object is to provide a toner capable of forming a high-quality toner image excellent in low-temperature fixability, environmental stability, development durability, and member contamination by adding a fatty acid metal salt having a uniform surface state. .

  In order to achieve the above object, a first invention according to the present application is directed to a toner having at least a binder resin, a colorant, and a wax, and a toner having a fatty acid metal salt. DSme (10) −DSme (90) ≦ 7 when the wettability with respect to the mixed solvent is measured by the transmittance of light having a wavelength of 780 nm and the methanol concentration when the transmittance is A% is DSme (A) volume%. The toner wettability of the toner with respect to the mixed solvent of methanol and water is measured by the transmittance of light having a wavelength of 780 nm, and the methanol concentration when the transmittance is 50% is DTme (50) volume%. When it does, it is in the range of 15.0 <= DTme (50) <= 80.0.

  A second invention according to the present application is characterized in that the fatty acid metal salt has a volume average particle diameter (Dvs) of 0.15 μm or more and 0.65 μm or less, and a volume-based variation coefficient of 50 or less. .

  A third invention according to the present application is characterized in that the toner has a viscosity at 100 ° C. of 5,000 to 40,000 Pa · s by a flow tester heating method.

  According to a fourth aspect of the present invention, the toner contains a nonionic surfactant.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by adopting the following configuration. Specifically, the inventors have found that a toner excellent in low-temperature fixing property, environmental stability, development durability, and member contamination can be obtained, and the present invention has been completed.

  According to the first invention, a toner excellent in environmental stability, development durability, and member contamination can be obtained.

  In addition, according to the second aspect of the invention, it is possible to obtain a toner that suppresses fogging over long-term printing.

  Furthermore, according to the third invention, it is possible to obtain a toner having high gloss and excellent low-temperature fixability without impairing durability.

  Furthermore, according to the fourth aspect of the invention, it is possible to obtain a toner that is excellent in reducing member contamination, developing stability, and fog suppression.

  In order to solve the above problems, the present invention relates to a toner for electrostatic image development having toner particles containing at least a binder resin, a colorant, and a wax and a fatty acid metal salt, and mixing the fatty acid metal salt with methanol and water. DSme (10) −DSme (90) ≦ 7, where the wettability with respect to the solvent is measured by the transmittance of light having a wavelength of 780 nm and the methanol concentration when the transmittance is A% is DSme (A) volume%. The toner wettability of the toner with respect to the mixed solvent of methanol and water was measured by the transmittance of light having a wavelength of 780 nm, and the methanol concentration when the transmittance was 50% was defined as DSme (50) volume%. In this case, the present invention relates to a toner characterized by being in the range of 15.0 ≦ DSme (50) ≦ 80.0.

  According to the present invention, by specifying the wettability of a fatty acid metal salt and a toner in a mixed solvent of methanol and water, a high-quality toner image excellent in low-temperature fixability, environmental stability, development durability, and member contamination A toner capable of forming a toner can be provided.

  Hereinafter, the present invention will be described in detail. In the present invention, the wettability of the fatty acid metal salt and the toner in a mixed solvent of water and methanol is measured in the study for evaluating the surface property of the fatty acid metal salt and the toner. For example, when the fatty acid metal salt has few different shapes and surface states, the wettability (precipitation degree) of the fatty acid metal salt is uniform. Since the fatty acid metal salt and the toner have a certain wettability, the charging characteristics of the toner are stabilized, and the performance is excellent in environmental stability, development durability, and member contamination.

  A graph of the methanol concentration of the fatty acid metal salt against the transmittance of light having a wavelength of 780 nm is shown in FIG. The region where the transmittance exceeds 90% indicates that the fatty acid metal salt is almost not wetted with methanol, and the region where the transmittance is lower than 10% indicates that the fatty acid metal salt is almost completely wetted. . As shown in FIG. 1, in the fatty acid metal salt of the present invention, the wettability of the fatty acid metal salt with respect to a mixed solvent of methanol and water is measured by the transmittance of light having a wavelength of 780 nm, and the methanol when the transmittance is A%. When the concentration is DSme (A) volume%, DSme (10) −DSme (90) ≦ 7.00. By setting DSme (10) −DSme (90) ≦ 7.00, the charging characteristics of the toner are stabilized, and environmental stability, development durability, and member contamination are improved. More preferably, DSme (10) −DSme (90) ≦ 5.00. By setting DSme (10) −DSme (90) ≦ 5.00, fog after durability is improved.

  This indicates that most of the particles in the fatty acid metal salt are wet in a range where the difference in methanol concentration in the present invention is small, and this is an index indicating that the shape and surface state of the fatty acid metal salt are uniform. Yes. Since the fatty acid metal salt has a uniform shape and surface state, the charging characteristics of the toner are stabilized, and a toner excellent in environmental stability, development durability, and member contamination can be obtained.

  In the toner of the present invention, the wettability of the toner with respect to the mixed solvent of methanol and water of the toner is measured by the transmittance of light having a wavelength of 780 nm, and the methanol concentration when the transmittance is 50% is DTme (50) volume. %, It is in the range of 15.0 ≦ DTme (50) ≦ 80.0. When the wettability of the toner with respect to the mixed solvent of methanol and water is 15.0 ≦ DTme (50) ≦ 80.0, the fatty acid metal salt, the inorganic fine powder, and the toner particles have high affinity. This is because member contamination due to liberation of the body is reduced. Preferably, 15.0 ≦ DTme (50) ≦ 70.0. By setting it within the range of 15.0 ≦ DTme (50) ≦ 70.0, the change in the charge amount of the toner due to the liberation of the fatty acid metal salt and the inorganic fine powder is reduced, and the environmental stability is improved. More preferably, 30.0 ≦ DTme (50) ≦ 70.0. By making it within the range of 30.0 ≦ DTme (50) ≦ 70.0, the liberation of the fatty acid metal salt and the inorganic fine powder is reduced, and the image stability before and after the endurance and the environmental stability are improved.

  As described above, when the toner contains a fatty acid metal salt having a uniform shape and surface state to some extent, when the toner is rubbed between the toner carrier and the toner supply roller, the toner is effective due to the effect as a lubricant. It is thought that the damage of the material is reduced and the suppression of the contamination of the member is promoted. Further, since the shape and the surface state are uniform to some extent, it can be present in the toner uniformly, and the toner of reverse polarity is reduced. As a result, it is possible to reduce the fog and image stability degradation that have occurred with conventional fatty acid metal salts, and a stable and high-quality image can be obtained even in a long-term high-temperature and high-humidity environment.

  In the fatty acid metal salt in the present invention, when the wettability of the fatty acid metal salt to a mixed solvent of methanol and water is measured by the transmittance of light having a wavelength of 780 nm, the methanol concentration when the transmittance is A% is DSme (A). When the volume% is set, it is preferable that 62 ≦ DSme (50). By being 62 <= DSme (50), member contamination and environmental stability improve.

  The adjustment method of DSme (50) can be adjusted by adding silicone oil or a nonionic surfactant to the fatty acid metal salt.

  The toner in the present invention preferably contains a nonionic surfactant because fog, environmental stability and member contamination are improved.

  Examples of the nonionic surfactant will be specifically described below.

  The nonionic surfactant is a general term for substances belonging to nonionic (nonionic) surfactants classified according to the miscellaneous goods industrial quality labeling regulations by the Ministry of Economy, Trade and Industry. In addition, there are classifications of anions (anions), cations (cations), amphoteric surfactants, and other surfactants. Nonionic (nonionic) surfactants are further classified into fatty acids, higher alcohols, and alkylphenols. A preferred group as the surfactant present on the surface of the fatty acid metal salt composition is a higher alcohol type or alkylphenol type surfactant.

  There are surfactants classified other than the above, specifically cationic and anionic surfactants.

  When the cationic and anionic surfactants were examined, it was found that a fatty acid metal salt composition having a preferable particle size and charging characteristics could not be stably formed, and was not suitable for use in a fatty acid metal salt composition.

  Next, in order to confirm the suitability for electrophotography, we investigated the charging characteristics in the environment of the synthesized samples. As a result, all the fatty acid metal salt compositions synthesized with ionic surfactants had charging characteristics. It turned out that the environmental fluctuations of the Such a material having a large environmental fluctuation in the charging characteristics is not preferable because it obstructs the charging characteristics of the toner and easily causes problems such as fogging and toner leakage in a high humidity environment.

  It is estimated that the reason why such an environmental change in the charging characteristics occurs is that moisture is easily adsorbed on the polarization portion in the fatty acid metal salt composition acid, and the charge cannot be partially retained due to the influence of the adsorbed water. is doing.

  Therefore, when the further examination was performed about the nonionic surfactant, the following surfactants can be used conveniently with respect to a fatty-acid metal salt composition.

  Specific examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene lauryl ethers. Examples include ethylene alkyl ethers; alkylphenyl polyoxyethylene ethers such as polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether.

Among these, lauryl alcohol ethylene oxide addition ether, oleyl alcohol ethylene oxide addition ether, McCall alcohol ethylene oxide addition ether, and nonylphenol alcohol ethylene oxide addition ether are preferable.
The nonionic surfactant is preferably contained in an amount of 0.001 to 5.00 parts by mass, more preferably 0.02 to 1.00 parts by mass, per 100 parts by mass of the fatty acid metal salt.

  When the content of the nonionic surfactant per 100 parts by mass of the fatty acid metal salt is less than 0.001 part by mass, the particle size consumed by the toner tends to be selective. This is thought to be because the charge amount of the fine particles in the toner becomes excessive and is not consumed in development.

  As a result, the fine particles in the toner are excessively charged, and are continuously rubbed on the surface of the toner carrying member without being developed. As a result, the toner is fused to the surface of the toner carrying member. If the toner is fused to the surface of the toner carrier, the chargeability of the toner is hindered, causing problems such as image fogging and streak images.

  In addition, when the content of the nonionic surfactant per 100 parts by mass of the fatty acid metal salt exceeds 5.00 parts by mass, the charging characteristics in a high humidity environment deteriorated, and the product was left in the environment in the second half of durability. This is not preferable because it causes image fogging of time. Therefore, the surfactant used when synthesizing the fatty acid metal salt composition affects the charging characteristics of the fatty acid metal salt composition particles.

Moreover, about surfactant, the HLB value which digitized the hydrophilicity and hydrophobic balance was advocated, and is widely used in each field | area. Therefore, various surfactants were examined for the surfactants used in the synthesis of the fatty acid metal salt composition. As a result, there are groups of surfactant species and HLB values that can effectively produce the fatty acid metal salt composition. I found out. An HLB value suitable for dispersing and stabilizing the fatty acid metal salt composition is 5.0 or more and 15.0 or less. A nonionic surfactant satisfying a preferred HLB value can be achieved by controlling the alcohol component and the ethylene oxide addition component in the surfactant. More specifically,
Lauryl alcohol ethylene oxide 5 mol adduct: HLB value 10.8
Lauryl alcohol ethylene oxide 10 mol adduct: 〃 14.1
Lauryl alcohol ethylene oxide 23 mol adduct: 〃 16.9
Oleyl alcohol ethylene oxide 10 mol adduct: 〃 12.4
Oleyl alcohol ethylene oxide 20 mol adduct: １５ 15.3
McCall alcohol ethylene oxide 5 mol adduct: 〃 9.3
McCall alcohol ethylene oxide 7 mol adduct: モ ル 10.8
McCall alcohol ethylene oxide 11 mol adduct: モ ル 13.2
McCall alcohol ethylene oxide 14 mol adduct: 〃 14.2
Nonylphenol alcohol ethylene oxide 4 mol adduct: 〃 8.9
Nonylphenol alcohol ethylene oxide 6 mol adduct: １ 10.9
Nonylphenol alcohol ethylene oxide 7 mol adduct: 〃 11.7
Nonylphenol alcohol ethylene oxide 10 mol adduct: 〃 13.3
Nonylphenol alcohol ethylene oxide 12 mol adduct: 〃 14.1
Nonylphenol alcohol ethylene oxide 14 mol adduct: 〃 14.8
Is mentioned.

In addition, as a formula for calculating the HLB of the surfactant component used in the present invention, the following HLB value-number system by Griffin is used.
(1) In the case of polyhydric alcohol fatty acid ester HLB value = 20 (1-S / A)
S: Saponification value of ester A: Neutralization value of fatty acid (2) In the case of tall oil, pine resin, beeswax, lauric polyhydric alcohol derivative HLB value = (E + P) / 5
E: Ethylene oxide content (% by mass) in the constituent molecules
P: Polyhydric alcohol content (% by mass) in the constituent molecules
(3) When the hydrophilic group is ethylene oxide HLB value = E / 5
E: Ethylene oxide content (% by mass) in the constituent molecules

<Quantification method of nonionic surfactant>
The following method can be used for measuring the content of the nonionic surfactant in the fatty acid metal salt composition.

  Specifically, it can be performed by analyzing an organic volatile substance to be heat-desorbed obtained by heating a fatty acid metal salt composition using a gas chromatography with a mass spectrometer. As a preferable measuring apparatus, for example, a combination of TRACE2000GC / MS (manufactured by ThermoQuest) and a headspace sampler can be used.

The following was used as conditions.
Extraction condition 120.0 ℃
Sample amount 1.0g
Column 0.32mm capillary column

  A method of identifying an unknown substance from a chart can be performed by searching a library from a mass spectrum chart for a substance in which a peak appears. When the substance could be identified, the peak derived from the nonionic surfactant among the substances was defined as the surfactant peak. For the quantification, a calibration curve was prepared with the surfactant used at the time of synthesis and a standard reagent of the substance qualitatively determined from the mass spectrum chart, and the analyte was quantified based on the calibration curve.

  Fatty acids in the fatty acid metal salt composition include monovalent saturated fatty acids such as butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid and montanic acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacin Examples thereof include polyvalent saturated fatty acids such as acids, monovalent unsaturated fatty acids such as crotonic acid and oleic acid, and polyvalent unsaturated fatty acids such as maleic acid and citraconic acid.

  Saturated or unsaturated fatty acids having 8 to 35 carbon atoms are preferred. Among them, an acid mainly composed of stearic acid is preferable.

  Many fatty acids existing in nature exist as a mixture of acid components having different carbon numbers. Taking stearic acid obtained as a natural product as an example, stearic acid having 18 carbon atoms as a main component and further containing a trace amount of fatty acid components such as 14 carbon atoms, 16 carbon atoms, 20 carbon atoms and 22 carbon atoms. Usually, a product obtained by increasing the purity of the fatty acid component through a purification process to some extent is commercially available. Furthermore, as a high-purity product, there are Japanese Pharmacopoeia grade products and the like, but it is preferable to use these to obtain the effect. When stearic acid is used as the fatty acid, the purity of stearic acid is preferably 90.0% by mass or more, more preferably 99.9% by mass or more and 95.0% by mass or less of the whole.

  If the purity of stearic acid is less than 90.0% by mass, the heat resistance of the stearic acid metal salt particles is deteriorated, and solidification in the raw material container and handling become difficult during production, which is not preferable. Further, it is not preferable to set the purity of stearic acid to 99.9% by mass or more because of the purification cost.

  Here, the purity of the fatty acid is the purity of the stearic acid component, and fatty acids having carbon numbers other than 18 and other organic and inorganic substances are considered as impurities.

  As the main metal species forming the salt, lithium, sodium, potassium, copper, rubinium, silver, zinc, magnesium, calcium, strontium, aluminum, iron, cobalt, nickel and the like can be used. Furthermore, it is preferable to use zinc and calcium in order to keep the chargeability of the toner within an appropriate range throughout the durability.

  In addition to the main metal species, other metal species may be included. At this time, it is preferable that the element ratio of the main metal species and the other metal species group (the other metal ratio in the whole) is less than 30%.

  The most preferable fatty acid metal salt composition is zinc stearate and calcium stearate.

  In the present invention, the volume average particle diameter (Dvs) of the fatty acid metal salt is preferably 0.15 μm or more and 0.65 μm or less, and the volume-based variation coefficient is 50 or less. When the volume average particle size (Dvs) is smaller than 0.15 μm, the particle size is small, so that the function as a lubricant is reduced, and it is difficult to obtain the effect of suppressing the contamination of the toner on the toner carrier and the like. On the other hand, when the thickness exceeds 0.65 μm, the fatty acid metal salt tends to be unevenly present on the surface of the toner particles, so that charge distribution occurs in the toner particles and the toner of reverse polarity increases. For this reason, fog and image stability due to the fatty acid metal salt are likely to occur in a high temperature and high humidity environment. Further, when the particle size is increased, the release in the toner tends to occur easily. When a large number of sheets are printed, the fatty acid metal salt is released from the toner and the effect of suppressing the contamination of the member is reduced. Image defects due to contamination are likely to occur. A more preferable range of the volume average particle diameter (Dvs) is 0.30 μm or more and 0.60 μm or less, and when it is within this range, the effects of the present invention can be obtained more stably. If the coefficient of variation exceeds 50, the chargeability becomes unstable due to variations in the particle size of the fatty acid metal salt present in the toner, and the reverse polarity toner increases and fog is likely to occur. The variation coefficient is more preferably 40 or less, and if it is 40 or less, a more stable image can be obtained.

  In the present invention, the fatty acid metal salt liberation rate in the toner needs to be 1.0% or more and 25.0% or less. When the liberation rate is in the range of 1.0% or more and 25.0% or less, a certain amount of the fatty acid metal salt is present on the surface of the toner particles even after the printing of a large number of sheets. It is demonstrated continuously. When the liberation rate is less than 1.0%, it means that the mixing process is performed with an excessive force such that the fatty acid metal salt is embedded in the toner particle surface. In such a case, even if the particle size of the fatty acid metal salt at the time of addition is large, the particle size becomes small due to mechanical stress, and it is difficult to obtain the effect of suppressing member contamination on the toner carrier. Further, since stress is applied to the toner particles, the seepage of the wax and the cracking of the toner particles occur, and fog and development streaks are likely to occur in a high temperature and high humidity environment. Conversely, when the liberation rate exceeds 25.0%, fogging due to liberation of fatty acid metal increases. Further, when a large number of sheets are printed, the liberated fatty acid metal salt is consumed and the effect as a lubricant when the toner is rubbed is diminished, so that the toner carrier may be contaminated with the member. The A more preferable range of the liberation ratio is 2.0% or more and 20.0% or less, and if it is within this range, an image with higher image quality can be obtained more stably.

  The quantification of the release of the fatty acid metal salt by this method simulates the release of the fatty acid metal salt during toner deterioration when an actual image is formed. By allowing the toner to pass through the mesh, the fatty acid metal salt that is inadequately attached and easily released is either sprayed or reduced on the mesh during the mesh pass. This simulates that the fatty acid metal salt is liberated when the toner is subjected to a load in each rubbing region and deteriorates through image formation. Even in the case where a large number of printings are performed with a smaller difference in the strength of the fatty acid metal salt before and after the sieve, the lubricant effect of the fatty acid metal salt is exhibited and the suppression of filming, which is an effect of the present invention, is obtained. However, if the difference is too small, it is suggested that excessive force is applied in the mixing step as described above, and the particle size is smaller than the particle size at which the filming suppression effect is obtained.

  Since the fatty acid metal in the present invention has a smaller particle size and a uniform distribution compared to conventional ones, it can be easily attached to the toner particles to some extent. It is necessary to optimize the mixing process conditions (temperature, rotation time, etc.) in order to be within the range of the liberation rate.

  The toner of the present invention has a toner number-based variation coefficient A and a fatty acid metal salt volume-based variation coefficient B from the viewpoint of high development and high image quality, and the toner number-based variation coefficient A and fatty acid. The ratio (A / B) of the volume-based variation coefficient B of the metal salt is preferably 0.55 or more and 0.90 or less. When the ratio of the variation coefficients is within such a range, the particle size distribution of the fatty acid metal salt is balanced with respect to the particle size distribution of the toner, and a high-development high-quality image with a balance between fog and density stability is obtained. can get. When the ratio of variation coefficients is less than 0.55, the particle size distribution of the fatty acid metal salt is broader than the toner particle size distribution, so that charging becomes non-uniform and fogging is likely to occur. On the other hand, if it exceeds 0.90, the particle size distribution of the fatty acid metal salt is too sharp with respect to the particle size distribution of the toner, which is effective in suppressing fogging, but the reason is not clear but the concentration stability cannot be obtained. A decrease in density is likely to occur. Considering the balance between fog and density stability, the ratio of the coefficient of variation is more preferably 0.60 or more and 0.85 or less.

  The toner of the present invention preferably has specific wettability in a mixed solvent of a specific organic solvent and water. For example, when the wettability is evaluated with a solvent whose solubility parameter (hereinafter also referred to as SP value) of the organic solvent is close to that of water, it is easy to monitor the influence of a substance that is easily compatible with water. That is, it means that the more ionic polar groups are, the easier it is to get wet, and it is an effective index for evaluating the effects of environmental stability and developability. On the other hand, when the wettability is evaluated with a solvent having a solubility parameter of the organic solvent that is farther than that of water, it is easy to monitor the influence of a substance that is not readily compatible with water. That is, the smaller the ionic polar group, the more the organic solvent is required, and thus the less the wetness becomes.

  Therefore, a toner whose organic solvent dropping curve satisfies a specific requirement exhibits excellent charging characteristics even in a high-temperature and high-humidity environment, preventing the contamination of the toner carrier and the photosensitive drum during durability.

  Specifically, the wettability (precipitation degree) of the toner with respect to methanol or diacetone alcohol was measured by transmittance with respect to the concentration transition of the methanol or diacetone alcohol aqueous solution. Examples of the toner raw material that affects the wettability characteristics (hydrophobic characteristics and hydrophilic characteristics with respect to water) with respect to methanol or diacetone alcohol include resins, waxes, dyes and pigments, and charge control agents. Among these, particularly the hydrophilic and hydrophobic properties are influenced, and the presence of the resin component on the surface and in the vicinity of the surface, the wax and the hydrophilic group of the charge control agent greatly affects the hydrophilic properties. For example, when there are many carboxylic acid groups, carboxylic acid groups, sulfonic acid groups, sulfonic acid groups, and hydroxyl group components on and near the toner surface, the affinity for methanol, which is a solvent whose solubility parameter is close to water, is high. The wettability in water and methanol mixed solvent becomes low. On the other hand, when measured with diacetone alcohol, which is a solvent whose solubility parameter is far from that of water than methanol, when there is a lot of wax on the toner surface and in the vicinity of the surface, the affinity for diacetone alcohol is high, The wettability in water and diacetone alcohol mixed solvent becomes high.

  The above transmittance curve is a sample solution for measuring the hydrophilic and hydrophobic properties of a fatty acid metal salt or toner by adding a specific amount of the fatty acid metal salt or toner to a methanol or diacetone alcohol aqueous solution of a specific concentration. Then, it is measured by using an apparatus configured to continuously measure the change in the transmittance of the sample solution when methanol or diacetone alcohol is added thereto at a constant dropping rate. The toner having the wettability of the fatty acid metal salt and the toner with respect to the methanol or diacetone alcohol aqueous solution in which the transmittance curve thus obtained satisfies specific requirements is the toner of the present invention, and the shape of the fatty acid metal salt It also changes depending on the surface state and the exposed state of the raw materials constituting the toner. Therefore, when the toner is manufactured, the toner of the present invention can be obtained by knowing these types and properties and selecting a material and manufacturing method corresponding to the types and properties.

  As an apparatus for measuring a drop transmittance curve of methanol or diacetone alcohol of the present invention, for example, a powder wettability tester WET-101P manufactured by Reska Co., Ltd. was used, and methanol or diacetic acid was measured under the following conditions and procedures. A drop transmission curve of acetone alcohol is used.

  First, 70 ml of ion-exchanged water is placed in a 100 ml container and the bubbles are dispersed in an ultrasonic disperser for 5 minutes to remove bubbles and the like in the solution. Sieve the fatty acid metal salt or toner, which is the specimen, with a mesh of 150 μm, add 0.1 g of the fatty acid metal salt or toner that passed through the sieve, and measure the hydrophobic properties of the fatty acid metal salt or toner. Prepare a sample solution for use. As a container for preparing and measuring a sample solution, a glass flask having a circular diameter of 5 cm and a height of 88 mm can be used.

Next, while stirring the prepared sample liquid for measurement at a speed of 6.67 s ⁻¹ , methanol was added at 1.5 ml / min. The fatty acid metal salt and the toner are suspended and dispersed in the solvent. While dropping methanol, the transmitted light intensity of light having a wavelength of 780 nm of the measurement sample is measured to obtain the transmittance, and a methanol dropping transmittance curve as shown in FIG. 1 is created. Here, the stirring can be performed using a magnetic stirrer (for example, a spindle having a length of 25 mm and a maximum diameter of 8 mm and having a Teflon (registered trademark) coating).

  When the fatty acid metal salt was measured under the above conditions, the methanol concentration when the transmittance was 10% was defined as DSme (10) volume%, and the methanol concentration when the transmittance was 90% was defined as DSme (90).

  When the toner was measured under the above conditions, the methanol concentration when the transmittance was 50% was defined as DTme (50) volume%.

First, a blank measurement in a state where there is no sample is performed on the drop transmittance curve of diacetone alcohol. 70 ml of a diacetone alcohol aqueous solution having a predetermined concentration is placed in a 100 ml container and dispersed for 5 minutes with an ultrasonic disperser to remove bubbles and the like in the solution. In this liquid, while continuously adding diacetone alcohol at a drop rate of 1.5 ml / min, the photoelectric output voltage Vb (V) of the laser detector is measured with light having a wavelength of 780 nm, and the change in the concentration of diacetone alcohol is measured. Get the laser voltage relationship. The photoelectric output voltage Vbx (V) of the laser detector when x (ml) of diacetone alcohol is dropped. Next, 70 ml of the same concentration of diacetone alcohol aqueous solution used in the blank measurement is put in this into a 100 ml container and dispersed for 5 minutes with an ultrasonic disperser to remove bubbles in the solution. Sieve the sample toner in a diacetone alcohol aqueous solution with the same concentration as the blank measurement with bubbles removed, and add 0.1 g of the toner passed through the sieve. Prepare a sample solution for use. Next, while stirring the prepared measurement sample solution at a rate of 6.67 s ⁻¹ , continuously adding diacetone alcohol at a dropping rate of 1.5 ml / min to the measurement sample solution. The photoelectric output voltage Vt (V) of the laser detector is measured with light having a wavelength of 780 nm. The photoelectric output voltage of the laser detector when x (ml) of diacetone alcohol is dropped is defined as Vtx (V).

  Next, a percentage ratio of {Vtx−Vbx} (V) to initial voltage ({Vt0−Vb0} when the diacetone alcohol dropping amount is 0.0 ml) (V) is calculated. For example, when the initial voltage is 3.5V and the input signal is 1.75V, the transmittance is 50%. The percent ratio is defined as transmittance (%), and a diacetone alcohol dropping transmittance curve as shown in FIG. 2 is prepared. Here, the stirring can be performed using a magnetic stirrer (for example, a spindle having a length of 25 mm and a maximum diameter of 8 mm and having a Teflon (registered trademark) coating).

  When the toner was measured under the above conditions, the diacetone alcohol concentration when the transmittance was 50% was defined as DTdaa (50) volume%.

  An example showing a drop transmittance curve of a mixed solvent of methanol (MeOH) and water and a mixed solvent of diacetone alcohol (DAA) and water is shown in FIG.

  In the toner of the present invention, when the wettability of the toner with respect to the mixed solvent of diacetone alcohol and water is measured by the transmittance of light having a wavelength of 780 nm, the concentration of diacetone alcohol when the transmittance is 50% is DTdaa (50). A preferable DTdaa value is 16.0 to 45.0 when it is defined as volume%. When the DTdaa value is less than 16.0%, a large amount of highly hydrophilic polar resin, charge control agent and dye / pigment may be exposed, and environmental stability and image density decrease occur. On the other hand, when the Daa value is 45.0 or more, wax having high hydrophobicity may be exposed, and fusion to the developing roller and development streaks occur. More preferably, it is 18.0 to 40.0, and still more preferably 20.0 to 35.0. This is because environmental stability and durability are improved.

  In the toner of the present invention, when the wettability of the toner with respect to the mixed solvent of methanol and water of the toner is measured by the transmittance of light having a wavelength of 780 nm, the methanol concentration when the transmittance is 50% is DTme (50) volume. %, And when the wettability of the toner with respect to the mixed solvent of diacetone alcohol and water is measured by the transmittance of light having a wavelength of 780 nm, when the concentration of diacetone alcohol when the transmittance is 50% is DTdaa volume%, In the case of 15.0 ≦ DTme (50) −DTdaa (50) ≦ 60.0, the presence state of the resin, wax and charge control agent on the toner surface is appropriate, and the resin, wax and charge on the toner surface are appropriate. The environmental stability of the charge amount of the control agent is appropriate, and the developability in a high temperature and high humidity environment is good. More preferably, when the wettability of the toner with respect to the mixed solvent of methanol and water is measured by the transmittance of light having a wavelength of 780 nm, the methanol concentration when the transmittance is 50% is defined as DTme (50) volume%, When the wettability of the toner with respect to the mixed solvent of diacetone alcohol and water is measured by the transmittance of light having a wavelength of 780 nm, the concentration of diacetone alcohol when the transmittance is 50% is DTdaa (50) volume%. 22.0 ≦ DTme (50) −DTdaa (50) ≦ 50.0, more preferably 24.0 ≦ DTme (50) −DTdaa (50) ≦ 45.0. The presence of the resin component, wax and charge control agent is appropriate. As a result, the amount of charge once held under any environment can be held for a long time, and a high image density can be obtained.

  In the present invention, the value of (DTme (50) −DTdaa (50)) can be adjusted with a polar resin, an inorganic fine powder, a charge control agent, and a surfactant.

  The methanol wettability of the fatty acid metal salt and the methanol or diacetone alcohol wettability of the toner have specific values, which indicates that the fatty acid metal salt having a uniform surface state exists on the uniform toner surface. Thereby, the density fluctuation | variation before and behind durability in a high-speed machine, fog, and member contamination can be reduced.

  Further, in the toner of the present invention, in the endothermic chart measured by differential scanning calorimetry (DSC), the heat amount integral value Q represented by the endothermic area in the range of 40 to 130 ° C. is 10 to 35 J per 1 g of toner. preferable. In the present invention, the endothermic area can be adjusted by the wax species and the amount of wax.

  As described above, a toner having a specific methanol wettability under a specific condition, an endothermic main peak in a specific temperature range, and a main peak in a specific molecular weight region in measurement by GPC-RI. It is preferable to constitute. As a result, it is possible to obtain a toner having high performance in member contamination, low-temperature fixability, high-temperature offset resistance and durability. Of the configurations defined in the present invention, by setting the heat quantity integral value Q represented by the endothermic area in the range of 40 to 130 ° C. to 10 to 35 J per 1 g of toner, good releasability is exhibited even at low temperature fixing. be able to. Further, when wax is added to the toner, the intermolecular force between the polymer chains of the binder resin is moderately relaxed, and softening of the toner due to heat absorption during fixing and curing of the resin due to heat dissipation of the toner form an appropriate state. be able to. The heat quantity integral value Q represented by the endothermic area can be adjusted by appropriately selecting the type of wax, its content, and the like. A method for calculating the heat quantity integral value Q will be described later. It is more preferable that the heat quantity integral value Q expressed by the endothermic area is 15 to 35 J per 1 g of toner.

  When the heat quantity integral value Q expressed by the heat absorption area is less than 10 J per 1 g of toner, the fixing property is deteriorated, the gloss of the fixed image is lowered, and the fixing member or the like is expected to be suppressed or scratched. Absent. On the other hand, when the heat quantity integral value Q expressed by the heat absorption area exceeds 35 J per 1 g of toner, the plastic effect of the wax becomes too great, and the offset resistance deteriorates.

  The viscosity value of the toner by the flow tester temperature raising method in the present invention is determined by the following method.

As an apparatus, for example, a flow tester CFT-500D (manufactured by Shimadzu Corporation) is used, and measurement is performed under the following conditions.
Sample: About 1.0 g of toner is weighed and molded using a pressure molding machine at a load of 100 kg / cm ² for 1 minute to obtain a sample.
-Die hole diameter: 1.0 mm
-Die length: 1.0 mm
・ Cylinder pressure: 9.807 × 10 ⁵ (Pa)
・ Measurement mode: Temperature rising method ・ Temperature rising speed: 4.0 ° C./min
By the above method, the viscosity (Pa · s) of the toner at 50 to 200 ° C. is measured to obtain the viscosity (Pa · s) at 100 ° C. The value obtained here is taken as the viscosity at 100 ° C. in the toner flow tester temperature measurement method.

  By setting the viscosity at 100 ° C. by the flow tester temperature raising method to 5,000 to 40,000 Pa · s, more preferably 7500 to 40,000 Pa · s, an image having excellent low-temperature fixability and image glossiness can be obtained. If it is less than 5000 Pa · s, the gloss is lowered due to the penetration of toner into the medium, which is not preferable. Specifically, with use over a long period of time, the inorganic fine powder added as an external additive is buried in the surface of the toner particles, or the toner particles are deformed and the triboelectric charging characteristics become non-uniform. For this reason, a phenomenon in which toner adheres to the non-image area on the transfer material (hereinafter referred to as fogging) tends to occur, which is not preferable. If it is greater than 40,000 Pa · s, the toner particles cannot be sufficiently deformed during the fixing step in high-speed and low-temperature printing, and the toner image tends to be peeled off when the surface of the fixed image is rubbed. In the present invention, the viscosity at 100 ° C. determined by the flow tester temperature raising method can be adjusted by the amount of the low molecular weight resin, the monomer type at the time of producing the binder resin, the initiator amount, the reaction temperature, and the reaction time.

  The viscosity at 100 ° C. correlates with toner fixing properties (gross). By reducing the viscosity change due to the temperature change, it is possible to reduce the gloss unevenness due to the temperature change of the fixing device and the environmental change during use such as temperature and humidity.

  In the toner of the present invention, the average circularity of toner particles of 2 μm or more (particles having an equivalent circle diameter of 2 μm or more) in a number-based equivalent circle diameter-circularity scattergram measured by a flow particle image analyzer is contaminated with a member. From the viewpoint, it is preferably 0.970 or more and 1.000 or less, and the mode circularity is preferably 0.98 or more and 1.00 or less from the viewpoint of transferability. In the toner of the present invention, the average circularity can be adjusted by, for example, a hybridization system (manufactured by Nara Machinery Co., Ltd.), and the mode circularity is adjusted by, for example, a hybridization system (manufactured by Nara Machinery Co., Ltd.). be able to.

  The average circularity of the toner is measured using a flow type particle image analyzer “FPIA-2100” (trade name, manufactured by Sysmex Corporation), and is calculated using the following formula.

  Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the toner particle image. Define. The measurement uses the perimeter of the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm).

  In the present invention, the circularity is an index indicating the degree of unevenness of the toner particles, and is 1.000 when the toner particles are completely spherical. The more complicated the surface shape, the smaller the circularity.

  The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following equation, where ci is the circularity (center value) at the dividing point i of the particle size distribution and m is the number of measured particles.

  Note that “FPIA-2100”, which is a measuring apparatus used in the present invention, calculates the circularity of each particle, and then calculates the average circularity. 1.00 is divided into classes equally divided every 0.01, and the average circularity is calculated using the center value of the division points and the number of measured particles.

  As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, followed by further measurement. Add 0.02 g of sample and disperse uniformly. As a means for dispersing, an ultrasonic disperser “Tetora150 type” (trade name, manufactured by Nikka Ki Bios Co., Ltd.) is used, and dispersion treatment is performed for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more. In order to suppress variation in circularity, the installation environment of the apparatus is controlled at 23 ° C. ± 0.5 ° C. so that the temperature inside the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C. Preferably, autofocus is performed using 2 μm latex particles every 2 hours.

  To measure the degree of circularity of the toner particles, the flow type particle image analyzer is used, the concentration of the dispersion is readjusted so that the toner particle concentration at the time of measurement is 3000 to 10,000 particles / μl, and the toner particles are 1000 Measure more than one. After the measurement, using this data, data having an equivalent circle diameter of less than 2 μm is cut to determine the average circularity of the toner particles. The mode circularity of the toner of the present invention is the highest circularity value in the circularity frequency distribution.

  Furthermore, “FPIA-2100”, which is a measuring apparatus used in the present invention, improves the magnification of the processed particle image, compared with “FPIA-1000” that has been used to calculate the shape of the toner. The accuracy of toner shape measurement has been improved by improving the processing resolution of the captured image (256 × 256 → 512 × 512), thereby achieving more reliable capture of fine particles. Therefore, when it is necessary to measure the shape more accurately as in the present invention, the FPIA-2100 that can obtain information on the shape more accurately is more useful.

  The molecular weight distribution of the tetrahydrofuran (THF) soluble part of the toner in the present invention will be described below.

<GPC-RI (gel permeation chromatography-refractometer) measurement>
3 to 5 show examples of molecular weight distribution charts measured for the tetrahydrofuran (THF) soluble content of the preferred toner in the present invention.

  In the molecular weight distribution chart measured by GPC of the tetrahydrofuran (THF) soluble part of the toner, the molecular weight at the main peak p (M1) is M1, and the height at that time is h (M1) [mV]. The molecular weight distribution is shown in FIG. Here, h (4000) indicates the height at a molecular weight of 4000.

  In the molecular weight distribution chart measured by GPC of the THF soluble part of the toner shown in FIG. 3, the molecular weight distribution chart when the height is converted to h (M1) [mV] = 100 is shown in FIG. .

  In FIG. 4, the height at the main peak P (M1) is indicated by H (M1) (the molecular weight at the main peak is M1). In FIG. 4, the height at a molecular weight of 4,000 is indicated by H (4,000).

  FIG. 5 shows the same molecular weight distribution chart as in FIG. 4, where S1 is the integral value in the region of molecular weight 500 to 2,500, S2 is the integral value in the region of molecular weight 2,500 to 15,000. The integrated value in the region of 15,000 to 1,000,000 is indicated by S3.

  The toner satisfying the molecular weight distribution defined by the present invention as shown in FIGS. 3 to 5 has the effects described below.

  In the chart of molecular weight distribution measured by GPC of the THF soluble content of the toner, the toner containing a component having a molecular weight of 4,000 to 15,000 is effective for low-temperature fixability and has a low melt viscosity. A high gloss image can be obtained.

  Here, it is preferable that H (4,000) and H (M1) satisfy H (4,000): H (M1) = (0.100 to 0.950): 1.00. When H (4,000) is less than 0.100 with respect to H (M1), the low-temperature fixability is deteriorated. In particular, when H (4,000) is less than 0.100 with respect to H (M1), it means that the amount of low molecular weight components effective for improving gloss is small, and gloss is reduced. . Moreover, when H (4,000) exceeds 0.950 with respect to H (M1), offset resistance deteriorates, which is not preferable. Further, H (4,000): H (M1) = (0.200 to 0.750): 1.00 is preferable. In the present invention, the value of H (4000) and the value of H (M1) can be adjusted by the amount of low molecular weight resin, the amount of initiator at the time of producing the binder resin, the reaction temperature, and the reaction time.

  In the present invention, in the molecular weight distribution chart measured by GPC of the THF soluble content in the toner, the integrated value (S1) in the region where the molecular weight is 300 to 2,000 and the molecular weight 2,000 to 15, The ratio of the integral value (S2) in the region of 1,000 to the integral value (S3) in the region of molecular weight 15,000 to 1,000,000 is S1: S2: S3 = (0.01 to 0.95): 1. 00: (1.00 to 8.00) is preferable. Since S1: S2: S3 = (0.01 to 0.95): 1.00: (1.00 to 8.00), the components contained in the toner are contained in a well-balanced state. Further improvement in fixing property, offset resistance and high gloss of a fixed image can be achieved.

  When S2 is 1.00 and S1 is less than 0.01 or S3 exceeds 8.00, the low-temperature fixability may be deteriorated. On the contrary, S1 exceeds 0.95. When S3 is less than 1.00, the offset resistance may deteriorate.

  In the present invention, a charge control agent can be used at the time of toner production, and a known one can be used as the charge control agent. In particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous medium is particularly preferable.

  Examples of the charge control agent that control the toner to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, and monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Others include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenols. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and resin charge control agents.

  Examples of toners that are positively charged include the following. Modified products of nigrosine by nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and lake pigments thereof Triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybthenic acid, phosphotungsten molybthenic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide); higher fatty acids Metal salt of resin; charge control agent based on resin.

  The toner of the present invention can contain these charge control agents singly or in combination of two or more.

  Among these charge control agents, metal-containing salicylic acid compounds are preferable, and the metal is particularly preferably aluminum or zirconium. The most preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound.

  The addition amount of these charge control agents is preferably 0.01 to 10.00% by mass of the binder resin or polymerizable monomer.

  The toner of the present invention controls the hydrophilic and hydrophobic characteristics of the toner surface by controlling the wettability in a mixed solvent of a specific organic solvent and water, promotes dispersion of a part of the colorant and wax, and achieves good chargeability. This improves the contamination of parts.

  Furthermore, in order to fully exhibit the effects of the present invention, it is preferable to contain a sulfur element-containing polymer as a charge control agent. The dispersion of the colorant is stabilized by the polarity of the sulfur element-containing polymer, the uniformity of the toner surface state is further improved, and a stable image density can be obtained.

  Furthermore, the sulfur element-containing polymer preferably has a certain acid value. In general, in combination with a colorant often having basicity, the acid of the polymer and the base on the surface of the colorant are combined, so that the colorant is in a surface-treated state. This suppresses charge leakage using the colorant as a charge leakage point, makes the toner charge amount distribution more uniform, and maintains high transferability even when continuous image output is performed. .

  Next, the sulfur element-containing polymer used in the present invention will be described.

  The fact that the amount of triboelectric charge can be increased by incorporating a sulfur element-containing polymer into the toner is a conventionally known matter, and in the present invention, the sulfur element-containing polymer is also incorporated into the toner. Thus, a toner having a high charge amount is obtained.

  The sulfur element-containing polymer is preferably a polymer having a sulfonic acid group. By containing the sulfonic acid group in the polymer, a more stable state is obtained with metals such as magnesium, calcium, barium, zinc, aluminum and phosphorus. Further, the dispersion of the colorant in the toner particles is further promoted, and in addition, the dispersion of a part of the wax due to the dispersion of the colorant is also improved.

  Further, the glass transition point (Tg) of the sulfur element-containing polymer is preferably 50 ° C to 100 ° C. More preferably, it is higher than 70 ° C and not higher than 100 ° C, and more preferably 73 ° C to 100 ° C. When the glass transition point is less than 50 ° C., the fluidity and storage stability of the toner are inferior and the transferability is also inferior. When the glass transition point exceeds 100 ° C., the fixability at the time of an image having a high toner printing rate is deteriorated.

  As the monomer containing elemental sulfur used for producing the elemental sulfur-containing polymer, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid vinyl Examples thereof include sulfonic acid, methacrylsulfonic acid, and maleic acid amide derivatives, maleimide derivatives, and styrene derivatives having the following structures. Preferred is (meth) acrylamide containing a sulfonic acid group.

  The sulfur element-containing polymer according to the present invention may be a homopolymer of the above monomer, but is preferably a copolymer of the above monomer and another monomer. As the monomer that forms a copolymer with the above monomer, polymerizable monomers such as vinyl aromatic hydrocarbons and (meth) acrylic acid esters are preferably used. More specifically, monomers as exemplified below can be used.

  Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene derivatives such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2 -Ethylhexyl acrylate Acrylates such as methyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; , Ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n -Nonyl methacrylate, diethyl phosphate ethyl methacrylate Methacrylic acid esters such as dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl ethyl ether, vinyl And vinyl ethers such as isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, Examples include 2,2′-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylol methanetoteramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

  The sulfur element-containing polymer preferably contains 0.01 to 20.00% by mass of a unit derived from a monomer having sulfur element, more preferably 0.05 to 10.00% by mass, and still more preferably 0.00. It is preferable to contain 10 to 7.00 mass%. When the amount is less than 0.01% by mass, the effect of adding the sulfur element-containing polymer is not sufficiently obtained, and when it exceeds 20.00% by mass, the fixability is particularly deteriorated.

  There are bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, ionic polymerization, and the like as methods for producing a sulfur element-containing polymer, but solution polymerization is preferable from the viewpoint of operability.

  The sulfur element-containing polymer has a structure represented by the following formula. Counter ions are preferably hydrogen ions, sodium ions, potassium ions, calcium ions, and ammonium ions, and more preferably hydrogen ions.

X (SO ₃ ⁻ ) _n · _m Y ^{k +}
(Wherein X represents a polymer site derived from the polymerizable monomer, Y ⁺ represents a counter ion, k is a valence of the counter ion, m and n are integers, and n = k × m.)

  The acid value (mgKOH / g) of the sulfur element-containing polymer is preferably 3.0 to 80.0, more preferably 5.0 to 40.0, and still more preferably 10.0 to 30.0.

  When the acid value is less than 3.0, it is difficult to obtain a sufficient charge control action, and the environmental stability tends to be inferior. On the other hand, when the acid value exceeds 50.0, when particles are produced by suspension polymerization using a composition containing such a polymer, the toner particles have an irregular shape. Then, the circularity becomes small, and the contained release agent appears on the toner surface, which tends to cause a decrease in developability.

  The sulfur element-containing polymer is preferably contained in an amount of 0.01 to 15.00 parts by mass, more preferably 0.1 to 10.00 parts by mass, per 100 parts by mass of the binder resin.

  When the content of the sulfur element-containing monomer is less than 0.01 parts by mass, sufficient charge control action is difficult to obtain, and when it exceeds 15.00 parts by mass, the toner is produced by suspension polymerization. In carrying out, the granulation property is lowered, and developability and transferability are lowered.

  Furthermore, in the present invention, it is preferable to contain a unit derived from a monomer having 0.001 to 3.000 parts by mass of a sulfur element per 100 parts by mass of the binder resin, and further 0.005 to 2. 000 parts by mass, particularly 0.010 to 1.500 parts by mass are preferred.

  In the above binder resin, the presence of a unit derived from a monomer having a sulfur element and the molar ratio thereof can be determined by a fluorescent X-ray apparatus or a mass spectrometer.

  The content of the sulfur element-containing polymer in the toner can be measured using capillary electrophoresis or the like.

  As for the molecular weight of the sulfur element-containing polymer, the weight average molecular weight (Mw) is preferably 500 to 100,000. More preferably, it is 1,000 to 70,000, and still more preferably 5,000 to 50,000. When the weight average molecular weight (Mw) is less than 500, the fluidity of the toner tends to be inferior, and the transferability is lowered. When the weight average molecular weight (Mw) exceeds 100,000, in addition to taking time to dissolve in the monomer, the effect of improving the dispersibility of the pigment is reduced, and the coloring power of the toner is reduced. End up.

  The volatile content of the sulfur element-containing polymer is preferably 0.01% to 2.00%. In order to reduce the volatile content to less than 0.01%, the volatile content removal process becomes complicated. When the volatile content exceeds 2.00%, charging at high temperature and high humidity, especially charging after standing. It becomes inferior. The volatile matter is the proportion of mass that decreases when heated at a high temperature (135 ° C.) for 1 hour.

  When obtaining the physical properties as described above, extraction of the sulfur element-containing polymer from the toner is not particularly limited, and any method can be used.

  A production method for producing the toner of the present invention is a method for producing a toner directly in a medium (hereinafter also referred to as a polymerization method) such as a suspension polymerization method, an interfacial polymerization method and a dispersion polymerization method. preferable. The toner obtained by this polymerization method (hereinafter also referred to as “polymerized toner”) has high transferability because the shape of individual toner particles is almost spherical and the distribution of charge amount is relatively uniform. In particular, among the above polymerization methods, a suspension polymerization method is preferable as a production method for producing the toner of the present invention.

  The suspension polymerization method will be described below.

  In the present invention, the suspension polymerization method is a granulation step in which a monomer composition containing at least a polymerizable monomer and a colorant is dispersed in an aqueous medium to produce droplets of the monomer composition. And a polymerization method for producing toner particles through at least a polymerization step for polymerizing the polymerizable monomer in the droplets. As will be described later, a wax, a polar resin, and a low molecular weight resin can be added to the monomer composition as desired. Further, the weight average molecular weight (Mw) of the THF-soluble component of the low molecular weight resin determined by GPC is preferably 2,000 to 6,000 from the viewpoints of low-temperature fixability and blocking resistance.

  In the toner of the present invention, the resin component may have a reactive functional group for the purpose of improving the viscosity change of the toner at a high temperature. For example, a double bond, an isocyanate group, etc. are raised.

  In the production of the toner of the present invention, a polar resin can be added to the monomer composition for the purpose of improving the shape of the toner particles, the dispersibility and fixing properties of the material, and the image characteristics. For example, hydrophilic functions such as amino groups, carboxylic acid groups, hydroxyl groups, sulfonic acid groups, glycidyl groups, and nitrile groups cannot be used because monomers are water-soluble and dissolve in aqueous suspension to cause emulsion polymerization. When it is desired to introduce a monomer component containing a group into the toner, a random copolymer of these and a vinyl compound such as styrene or ethylene, a copolymer such as a block copolymer, and a graft copolymer, a polyester, and a polyamide Can be used in the form of polycondensates such as, or addition polymers such as polyethers and polyimines.

  In addition to the above, examples of the low molecular weight resin that can be added to the monomer composition include homopolymers of styrene and substituted products thereof such as polystyrene and polyvinyltoluene; 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- Dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl Methyl ether copolymer, styrene-vinyl ether Styrenic copolymers such as ether ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Combined; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic Alternatively, alicyclic hydrocarbon resins, aromatic petroleum resins and the like can be used alone or in combination.

  Among the low molecular weight resins, the glass transition point (Tg) of the low molecular weight resin is preferably 40 to 100 ° C. When the glass transition point is less than 40 ° C., the strength of the entire toner particles is lowered, and the transferability and development characteristics are liable to be lowered during a multi-endurance test. Further, the toner particles are aggregated in a high-temperature and high-humidity environment, resulting in a problem that storage stability is lowered. On the other hand, if the glass transition point exceeds 100 ° C., the problem of poor fixing tends to occur.

  The glass transition point of the low molecular weight resin is more preferably 40 to 70 ° C., particularly preferably 40 to 65 ° C., from the viewpoints of low temperature fixability and high gloss image.

  The addition amount of the low molecular weight resin is preferably 0.1 to 75 parts by mass in 100 parts by mass of the binder resin in the toner particles. When the amount is less than 0.1 part by mass in 100 parts by mass of the binder resin in the toner particles, the effect of adding the low molecular weight resin is small.

The toner of the present invention preferably contains an addition reactive resin having a double bond. Therefore, when the toner of the present invention is produced, it is preferable to use an addition reactive resin having a double bond. As the addition-reactive resin having a double bond, a styrene resin is preferable. For example, in a styrene resin produced by polymerization at a high temperature of 170 ° C. or higher, double bonds of 4.6 to 4.9 ppm and 5.0 to 5.2 ppm are measured in ¹ H-NMR measurement using a deuterated chloroform solvent. A peak derived from is observed. That is, the addition-reactive resin obtained as described above has double bonds, and these double bonds are crosslinked during the production of toner particles. Thus, by introducing a small amount of a crosslinked structure in the toner particles, the rate of change in the viscosity of the toner at a high temperature can be reduced more effectively. Furthermore, when the weight-average molecular weight of the addition-reactive resin is 2,000 to 6,000, the molecular weight is higher and the reactivity is gentle compared to a conventionally used low-molecular crosslinking agent such as divinylbenzene. By finely cross-linking, a toner having a thermal property with a low viscosity but a small viscosity change rate depending on temperature can be obtained.

  The number-average molecular weight of the addition-reactive resin having a double bond is preferably 500 or more and 3,000 or less. When the number average molecular weight of the addition-reactive resin is smaller than 500, there are many components having a small molecular weight, and the storage stability deteriorates due to the oozing out. On the other hand, when the number average molecular weight is larger than 3,000, the low-temperature fixability is lowered. In the present invention, the number average molecular weight of the addition-reactive resin can be measured by GPC. In the present invention, the number average molecular weight of the addition-reactive resin can be adjusted by the amount of solvent, the type of solvent, the reaction temperature, and the amount of initiator when the addition-reactive resin is produced.

  In addition to the above, addition-reactive resins that can be added to the monomer composition include the following. Homopolymers of styrene such as polystyrene and polyvinyltoluene and substituted products thereof; 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-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate Copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer , Styrene-butadi Copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene copolymer such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, Polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. It can be used alone or in combination.

  The glass transition point (Tg) of the addition-reactive resin is preferably 40 to 100 ° C. When the glass transition point is less than 40 ° C., the strength of the whole toner particles is lowered, and the transferability and development characteristics are liable to be lowered during a multi-endurance test. Further, the toner particles are aggregated in a high-temperature and high-humidity environment, resulting in a problem that storage stability is lowered. On the other hand, if the glass transition point exceeds 100 ° C., the problem of poor fixing tends to occur.

  The glass transition point of the addition-reactive resin is more preferably 40 to 70 ° C., particularly preferably 40 to 65 ° C., from the viewpoints of low temperature fixability and high gloss image.

  The addition amount of the addition reactive resin is preferably 0.1 to 75 parts by mass in 100 parts by mass of the binder resin in the toner particles. When the amount is less than 0.1 part by mass in 100 parts by mass of the binder resin in the toner particles, the effect of adding the addition reactive resin is small.

  The toner of the present invention is preferably a toner containing toner particles having at least a core portion and a shell portion and an inorganic fine powder. The toner particles have a shell portion so as to cover the core portion. By adopting such a structure, it is possible to prevent charging failure and blocking in each environment due to deposition of the core portion on the toner surface. Further, it is more preferable that a surface layer portion having a contrast different from that of the shell portion is present on the surface of the shell portion. The presence of this surface layer portion can improve environmental stability, durability, and blocking resistance.

  The material constituting the surface layer portion preferably has a molecular chain polar structure. In the present invention, the molecular chain polar structure refers to a molecular structure in which atoms in the molecule have many δ + or δ− electron density states.

  Resin molecules are composed of a plurality of types of atoms, and the constituent atoms have inherent electronegativity, and the values differ greatly depending on the atoms. Due to this difference in electronegativity, electrons are localized in the molecule. In this localization, the state changes depending on the type, number, and bonding mode of the atoms to be configured, and the polarity of the molecular chain changes.

  What is preferable as the molecular chain polar structure is, for example, a bond structure formed by condensation polymerization or addition polymerization. Specifically, ester bonds (—COO—), ether bonds (—O—), amide bonds (—CONH—), imine bonds (—NH—), urethane bonds (—NHCOO—), urea bonds ( -NHCONH-).

For example, in an ether chain (—CH ₂ —O—CH ₂ —) or the like, electrons on the carbon atom are slightly deficient (δ ⁺ ), and electrons on the oxygen atom are slightly excessive (δ ⁻ ). Furthermore, a bond angle with an oxygen atom as a vertex is in a state. Thus, if there are many polarized molecular chains, the polarity of the molecule, that is, the resin will increase, and if there are few polarized molecular chains, it will decrease. In general, molecules composed of hydrocarbons have low polarity.

  When the surface layer portion has a molecular chain polar structure, charging stability is improved. In addition, when toner particles are produced in a polar solvent such as an aqueous or hydrophilic medium, the surface layer portion having a molecular chain polar structure is more uniformly formed in the vicinity of the toner surface. Underlying charging stability and durability during high-speed printing are improved.

  From the above viewpoint, the toner of the present invention preferably contains a polyester resin.

  A particularly suitable material for the surface layer in the toner of the present invention is a polyester resin or a derivative thereof.

  The polyester resin can be constituted by a known production method from a polyhydric alcohol and a polyvalent carboxylic acid component. Among the monomers constituting the polyester resin, polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, and dipropylene glycol. , Triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2,2,4-trimethylpentane-1,3-diol, hydrogenated bisphenol A, or the following general formula (I) And diols represented by the following general formula (II). These polyhydric alcohols may be used alone or in a mixed state. However, it is not limited to these, and other trivalent or higher alcohol components can be used as the crosslinking component.

  In general formula (I), R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2-10.

  In general formula (II), R ′ represents any of the following groups. R ′ may be the same or different.

  Among the monomers constituting the polyester resin, the polyvalent carboxylic acid component includes naphthalene dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, succinic acid, adipic acid Dicarboxylic acids such as sebacic acid and azelaic acid; dicarboxylic anhydrides such as phthalic anhydride and maleic anhydride; and lower alkyl esters of dicarboxylic acids such as dimethyl terephthalate, dimethyl maleate and dimethyl adipate; Can do. In particular, the main component is preferably a lower alkyl ester of a dicarboxylic acid such as dimethyl terephthalate, dimethyl maleate, dimethyl adipate or a derivative thereof.

  The polyester resin may be cross-linked by using the following trivalent or higher acid component. Examples of crosslinking components include trimellitic acid, tri-n-ethyl 1,2,4-tricarboxylate, tri-n-butyl 1,2,4-tricarboxylate, and tri-n-hexyl 1,2,4-tricarboxylate. 1,2,4-benzenetricarboxylic acid triisobutyl, 1,2,4-benzenetricarboxylic acid tri-n-octyl, 1,2,4-benzenetricarboxylic acid tri-2-ethylhexyl and tricarboxylic acid lower alkyl ester Can be used. However, it is not limited thereto, and other trivalent or higher acid components or trivalent or higher carboxylic acid lower alkyl esters can be used as the crosslinking component.

  Moreover, you may use a monovalent | monohydric carboxylic acid component and a monovalent alcohol component to such an extent that the characteristic of the polyester resin which can be used for this invention is not impaired. For example, benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, stearic acid, etc. Monocarboxylic acid; one or more of n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, dodecyl alcohol, etc. Functional monomers and the like can be added.

  The polyester resin that can be used in the present invention can be produced by an ordinary polyester synthesis method. For example, after polyhydric carboxylic acid component and polyhydric alcohol component are subjected to esterification reaction or transesterification reaction, polycondensation reaction is carried out according to a conventional method by introducing low-boiling polyhydric alcohol component under reduced pressure or introducing nitrogen gas. A polyester resin is obtained. In the esterification or transesterification reaction, an ordinary esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, magnesium acetate, or the like can be used as necessary. Regarding polymerization, known polymerization catalysts such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, and germanium dioxide can be used.

  Further, the polymerization temperature and the amount of catalyst are not particularly limited, and may be arbitrarily selected as necessary.

  The polyester resin is particularly preferably a vinyl-modified polyester resin modified with a vinyl monomer.

  The vinyl-modified polyester resin has a structure in which a polyester and a vinyl polymer are bonded to each other, the internal protection performance is given by a polyester skeleton, and the charging stability can be improved by a vinyl polymer unit.

  In the toner of the present invention, the main component of the binder resin is usually a vinyl polymer, and the vinyl-modified polyester resin includes a vinyl polymer obtained by addition polymerization of an aromatic vinyl monomer and a (meth) acrylic acid ester monomer. It is preferable that the polyester is chemically bonded.

  Further, the vinyl-modified polyester resin is contained in the ester exchange reaction between the hydroxyl group contained in the polyester and the (meth) acrylic acid ester contained in the vinyl polymer, the hydroxyl group contained in the polyester and the vinyl polymer. It can be produced by an ester reaction with a carboxy group. The vinyl-modified polyester resin preferably contains 1 to 60% by mass of a vinyl monomer as a monomer component constituting the resin, more preferably 10 to 50% by mass, and further 15 to 40% by mass. It is preferable to contain. When the above value is less than 1% by mass, the charging performance may be inferior, and when it exceeds 60% by mass, the fixing performance may be inferior.

  As a particularly preferable polyester or vinyl-modified polyester resin, it is preferable to contain bisphenol A and / or linear alkyldiol as an alcohol component constituting the resin in an amount of less than 50 mol% with respect to 100 mol% of all alcohol components. Moreover, it is preferable that a linear aryl dicarboxylic acid and / or a linear alkyl dicarboxylic acid is used as the acid component in an amount of 50 mol% or more in 100 mol% of the total acid component. More preferred acid components include lower alkyl esters of dicarboxylic acids such as dimethyl terephthalate, dimethyl maleate, and dimethyl adipate.

  The polyester or vinyl-modified polyester resin that can be used in the present invention may use the above-described monovalent carboxylic acid component and monovalent alcohol component to the extent that the characteristics are not impaired.

  Examples of the vinyl monomer that can be used to produce the vinyl-modified polyester resin used in the present invention include vinyl polymerizable monomers copolymerizable with styrene. Examples of such vinyl polymerizable monomers include the vinyl polymerizable monomers described below.

  In the present invention, when a vinyl-modified polyester resin is produced, a reactive group to be bonded to the vinyl polymer and the polyester is a polyester resin, a vinyl polymer, a monomer constituting the polyester, and a vinyl polymerizable monomer. It is preferably contained in at least one of the body. Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

As a manufacturing method of the vinyl modified polyester resin used for this invention, the manufacturing method shown to the following (1)-(4) can be mentioned, for example.
(1) After forming a vinyl polymer, it is a method of forming a vinyl-modified polyester resin while polymerizing polyester in the presence thereof. An organic solvent can be appropriately used.
(2) A method for producing a vinyl-modified polyester resin by forming a polyester and then polymerizing a vinyl-based polymerizable monomer in the presence of the polyester.
(3) After forming a vinyl polymer and polyester, a vinyl-modified polyester resin is obtained by adding a vinyl polymerizable monomer and / or a polyester monomer (alcohol, carboxylic acid, etc.) in the presence of these polymers. It is a manufacturing method. Also in this case, an organic solvent can be appropriately used.
(4) A method in which a vinyl-modified polyester resin is produced by forming a vinyl polymer and a polyester and then bonding them together by an ester bond or an amide bond. Moreover, an organic solvent can be used suitably.

  In the production methods (1) to (4), the reaction may be performed in the presence of a low softening point compound.

  Among the production methods (1) to (4), the production method (2) is particularly preferable because the molecular weight control of the vinyl polymer unit is easy.

  Furthermore, a vinyl-modified polyester resin having a block type in which a vinyl polymer is bonded to a polyester terminal by introducing a vinyl group only at the terminal of the polyester unit in the production method of (2) above and polymerizing a vinyl monomer, This is particularly preferable from the viewpoints of low-temperature fixability and charging stability.

  The polar resin that can be used in the present invention may be purified by reprecipitation operation or washing.

  Preferred examples of the polymerizable monomer that can be used to produce the toner particles of the present invention include vinyl-based polymerizable monomers. Preferred examples of the vinyl polymerizable monomer include the following. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, ethyl Acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl Acrylic polymerizable monomers such as acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n- Propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethylphos Fate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic polymerizable monomers such as acrylate; methylene aliphatic monocarboxylic esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl Vinyl ethers such as ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  The shell portion of the toner of the present invention is preferably composed of a vinyl polymer formed from these vinyl polymerizable monomers and an added resin. Among these vinyl polymers, a styrene polymer, a styrene-acrylic copolymer, or a styrene-methacrylic copolymer is preferable from the viewpoint of efficiently covering the wax mainly forming the inside or the central portion.

  The material constituting the core of the toner of the present invention is preferably wax. The wax component usable in the toner according to the present invention includes paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof according to the Fischer-Tropsch method, polyethylene, Polyolefin waxes such as polypropylene and derivatives thereof, natural waxes such as carnauba wax and candelilla wax and derivatives thereof, and the like include oxides, block copolymers with vinyl monomers, and graft modified products. In addition, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes, and silicone resins. Can be used.

  In particular, ester waxes having at least one long-chain ester moiety having 10 or more carbon atoms represented by the following formulas (4) to (9) can improve transparency of an overhead projector transparency film (OHP film). It is preferable without inhibition.

（式中、ａ及びｂは独立して０乃至４の整数を示し、ａ＋ｂは４であり、Ｒ¹及びＲ²は独立して炭素数が１乃至４０の有機基を示し、ｎ及びｍは独立して０乃至１５の整数を示し、ｎとｍが同時に０になることはない。）

(Wherein, a and b independently represent an integer of 0 to 4, a + b is 4, R ¹ and R ² independently represent an organic group having 1 to 40 carbon atoms, and n and m are Independently represents an integer of 0 to 15, and n and m are not 0 at the same time.)

（式中、ａ及びｂは独立して１乃至３の整数を示し、ａ＋ｂは４であり、Ｒ¹は炭素数が１乃至４０の有機基を示しｎ及びｍは独立して０乃至１５の整数を示し、ｎとｍが同時に０になることはない。）

(Wherein, a and b independently represent an integer of 1 to 3, a + b is 4, R ¹ represents an organic group having 1 to 40 carbon atoms, and n and m independently represent 0 to 15) Indicates an integer, and n and m are not 0 at the same time.)

（式中、ａ及びｂは独立して０乃至３の整数を示し、ａ＋ｂは２または３であり、Ｒ¹及びＲ²は独立して炭素数が１乃至４０の有機基を示し、且つＲ¹とＲ²との炭素数差が１０以上である基を示し、Ｒ³は炭素数が１以上の有機基を示し、ｃは２または１であり、ａ＋ｂ＋ｃ＝４であり、ｎ及びｍは独立して０乃至１５の整数を示し、ｎとｍが同時に０になることはない。）

(Wherein, a and b independently represent an integer of 0 to 3, a + b is 2 or 3, R ¹ and R ² independently represent an organic group having 1 to 40 carbon atoms, and R ¹ and the number of carbon atoms difference between R ² represents a group of 10 or more, R ³ represents one or more organic groups having a carbon number, c is 2 or 1, a + b + c = a 4, n and m are Independently represents an integer of 0 to 15, and n and m are not 0 at the same time.)

（式中、Ｒ¹及びＲ²は炭素数が１乃至４０の炭化水素基を示し、且つＲ¹及びＲ²は、お互いに同じでも異なる炭素数でもよい。）

(Wherein R ¹ and R ² represent a hydrocarbon group having 1 to 40 carbon atoms, and R ¹ and R ² may be the same or different from each other.)

（式中、Ｒ¹及びＲ²は炭素数が１乃至４０の炭化水素基を示し、ｎは２乃至２０の整数であり、且つＲ¹及びＲ²は、お互いに同じでも異なる炭素数でもよい。）

(Wherein R ¹ and R ² represent a hydrocarbon group having 1 to 40 carbon atoms, n is an integer of 2 to 20, and R ¹ and R ² may be the same or different from each other) .)

（式中、Ｒ¹及びＲ²は炭素数が１乃至４０の炭化水素基を示し、ｎは２乃至２０の整数であり、且つＲ¹及びＲ²は、お互いに同じでも異なる炭素数でもよい。）

(Wherein R ¹ and R ² represent a hydrocarbon group having 1 to 40 carbon atoms, n is an integer of 2 to 20, and R ¹ and R ² may be the same or different from each other) .)

  As the molecular weight of the wax, those having a weight average molecular weight (Mw) of 300 to 1,500 are preferable. If it is less than 300, the wax is likely to be exposed to the toner particle surface, and if it exceeds 1,500, the low-temperature fixability is lowered. Particularly preferred are those in the range of 400 to 1,250. Furthermore, when the ratio of the weight average molecular weight / number average molecular weight (Mw / Mn) is 1.5 or less, the peak of the DSC endothermic curve of the wax becomes sharper, and the mechanical strength of the toner particles at room temperature is improved. Particularly excellent toner characteristics exhibiting sharp melting characteristics upon fixing can be obtained.

  Specific examples of the ester wax include compounds represented by the following formula.

  In recent years, the need for full-color double-sided images has increased, and when a double-sided image is formed, the toner image on the transfer material first formed on the front surface is also used when the next image is formed on the back surface. There is a possibility of passing again through the heating section. At that time, it is necessary to sufficiently consider the high-temperature offset resistance of the fixed image of the toner. Specifically, it is preferable to add 2 to 30% by mass of wax in the toner particles. When the content is less than 2% by mass, the high temperature offset resistance is lowered, and further, the image on the back surface may show an offset phenomenon when fixing a double-sided image. When the amount is more than 30% by mass, toner particles are likely to be coalesced during granulation in the production by the polymerization method, and those having a wide particle size distribution are likely to be generated.

  In the present invention, a polymerization initiator can be used in the polymerization of the toner particles. The following are mentioned as a polymerization initiator used when manufacturing a toner particle by a polymerization method. 2,2′-azobis- (2,4-divaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyloxycarbonate, cumene hydroperoxide, 2,4-dichloro Peroxide polymerization initiators such as benzoyl peroxide and lauroyl peroxide. These polymerization initiators are preferably added in an amount of 0.5 to 20.0% by mass relative to the polymerizable monomer, and may be used alone or in combination.

  The binder resin of the toner particles is preferably a vinyl resin. The vinyl resin is produced by polymerization of the vinyl polymerizable monomer described above.

  In order to control the molecular weight of the binder resin of the toner particles, a chain transfer agent may be added. A preferred addition amount is 0.001 to 15,000 mass% of the polymerizable monomer.

  In order to control the molecular weight of the binder resin of the toner particles, a crosslinking agent may be added. Examples of the crosslinkable monomer include the following. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and the above acrylates were changed to methacrylate The.

  The following are mentioned as a polyfunctional crosslinking monomer. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate thereof, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylphthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate. A preferred addition amount is 0.001 to 15,000 mass% of the polymerizable monomer.

  In the present invention, when the medium used in the polymerization is an aqueous dispersion medium, the following dispersion stabilizers for the monomer composition particles may be used. Tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina . Examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, starch.

  Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate.

  Further, in the present invention, when using a poorly water-soluble inorganic dispersion stabilizer and adjusting an aqueous medium, the amount of these dispersion stabilizers used is 0.2 to 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is preferable that it is 2.0 mass parts. In the present invention, it is preferable to adjust the aqueous medium using 300 to 3,000 parts by mass of water with respect to 100 parts by mass of the monomer composition.

  In the present invention, when preparing an aqueous medium in which the above poorly water-soluble inorganic dispersant is dispersed, a commercially available dispersion stabilizer may be used as it is. In order to obtain dispersion-stable particles having a fine and uniform particle size, an aqueous medium may be prepared by generating a poorly water-soluble inorganic dispersant in a liquid medium such as water under high-speed stirring. For example, when tricalcium phosphate is used as a dispersion stabilizer, a preferred dispersion stabilizer can be obtained by mixing sodium phosphate aqueous solution and calcium chloride aqueous solution under high speed stirring to form fine particles of tricalcium phosphate. Can do.

In the present invention, for the purpose of imparting various properties, the following various inorganic fine powders can be contained in the toner. The inorganic fine powder preferably has a particle size of 1/10 or less of the weight average particle size of the toner particles in view of durability when added to the toner particles. The particle size of the inorganic fine powder means the average particle size obtained by observing the surface of the toner particles with an electron microscope. As inorganic fine powders for the purpose of imparting these properties, for example, the following are used.
1) Fluidity imparting agent: metal oxide (for example, silica, alumina, titanium oxide), carbon black and carbon fluoride. Each of them is more preferably hydrophobized.
2) Abrasive: metal oxide (eg strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitride (eg silicon nitride), carbide (eg silicon carbide), metal salt (eg calcium sulfate, barium sulfate) , Calcium carbonate).
3) Lubricant: Fluorine resin powder (for example, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (for example, zinc stearate, calcium stearate).
4) Charge controllable particles: metal oxides (for example, tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.

  The inorganic fine powder treats the surface of the toner particles in order to improve the fluidity of the toner and to make the toner particles uniformly charged. By hydrophobizing the inorganic fine powder, it is possible to adjust the chargeability of the toner, improve the environmental stability, and improve the characteristics in a high-humidity environment. It is preferable to use it. When the inorganic fine powder added to the toner absorbs moisture, the chargeability as the toner is lowered, and the developability and transferability are easily lowered.

  As treatment agents for the hydrophobic treatment of inorganic fine powder, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, organotitanium Compounds. These treatment agents may be used alone or in combination.

  Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, the inorganic fine powder is treated with silicone oil simultaneously with or after the hydrophobic treatment with the coupling agent. The hydrophobized inorganic fine powder treated with silicone oil is good for maintaining a high charge amount of the toner even in a high humidity environment and reducing selective developability.

  The degree of hydrophobicity, which indicates the degree of hydrophobic treatment of the inorganic fine powder contained in the toner of the present invention, is the wettability of the inorganic fine powder with respect to a mixed solvent of methanol and water.

  The wettability of the inorganic fine powder to the mixed solvent of methanol and water was measured by the transmittance of light having a wavelength of 780 nm, a methanol dropping transmittance curve was prepared, and the methanol concentration when the transmittance was 50% was determined as the degree of hydrophobicity ( Volume%). As a measuring apparatus, for example, a powder wettability tester WET-101P manufactured by REHSCA (Resca) Co., Ltd. can be used, and specific measuring operations include the methods exemplified below.

  First, 70 ml of a hydrated methanol solution composed of 60% by volume of methanol and 40% by volume of water is placed in a container and dispersed with an ultrasonic disperser for 5 minutes to remove bubbles and the like in the solution. In this solution, 0.5 g of the inorganic fine powder as a specimen is added and suspended, and a sample solution for measuring the hydrophobic properties of the inorganic fine powder is prepared. As a container for preparing and measuring a sample solution, a glass flask having a circular diameter of 5 cm and a height of 88 mm can be used.

Next, while stirring the prepared sample liquid for measurement at a speed of 6.67 s ⁻¹ , methanol was added at 1.3 ml / min. Are continuously added at a dropping rate of 1 to disperse the suspended fine inorganic powder in the solvent. While dropping methanol, the transmitted light intensity of light having a wavelength of 780 nm of the measurement sample is measured to obtain the transmittance, and a methanol dropping transmittance curve is created. Here, the stirring can be performed using a magnetic stirrer (for example, a spindle having a length of 25 mm and a maximum diameter of 8 mm and having a Teflon (registered trademark) coating). Then, the methanol concentration when the transmittance is 50% is calculated as the degree of hydrophobicity of the hydrophobic silica.

  In the measurement of the degree of hydrophobicity, when the degree of hydrophobicity of the inorganic fine powder as a specimen is less than 60%, the specimen is added to a water-containing methanol solution composed of 60 volume% methanol and 40 volume% water. The transmittance curve cannot be obtained. Therefore, when the hydrophobicity of the inorganic fine powder as a specimen is less than 60%, the measurement was performed with the methanol concentration of the initial solution set to 0%.

  These inorganic fine powders are preferably used in an amount of 0.1 to 10 parts by weight, and more preferably 0.5 to 3.5 parts by weight with respect to 100 parts by weight of the toner particles. These inorganic fine powders may be used alone or in combination.

Here, the specific surface area BET of the inorganic fine powder can be determined by a low temperature gas adsorption method by a dynamic constant pressure method according to a BET method (preferably a BET multipoint method). For example, using a specific surface area measuring device “Gemini 2375 Ver. 5.0” (manufactured by Shimadzu Corporation), nitrogen gas is adsorbed on the surface of the sample (hydrophobic silica A or B) and measured using the BET multipoint method. By doing so, the BET specific surface area (m ² / g) can be calculated.

  The toner of the present invention preferably has a weight average particle diameter D4 of 2.0 to 12.0 μm, more preferably 4.0 to 9.0 μm, and still more preferably 5 It is preferable to have a weight average particle diameter (D4) of 0.0 to 8.0 μm.

  The glass transition point (Tg) of the toner of the present invention is 40 to 100 ° C., preferably 40 to 80 ° C. More preferably, it is 45 to 70 ° C. When the glass transition point is lower than 40 ° C., the blocking resistance of the toner is lowered. When the glass transition point exceeds 100 ° C., the low temperature offset resistance of the toner and the transparency of the transmitted image of the overhead projector film are deteriorated.

  The content of insoluble content of tetrahydrofuran (THF) in the toner of the present invention is preferably less than 16.0% by mass with respect to toner components other than the toner colorant and inorganic fine powder. More preferably, it is 0.0 mass% or more and less than 10.0 mass%, Most preferably, it is 0.0 mass% or more and less than 5.0 mass%. When it is larger than 16.0% by mass, the low-temperature fixability is lowered.

  The THF-insoluble content of the toner refers to the mass ratio of the ultra-high molecular weight polymer component (substantially crosslinked polymer) that has become insoluble in the THF solvent. The THF-insoluble content of the toner is defined by the values measured as follows.

1.0 g of toner is weighed (W1 g), placed in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Filter Paper), subjected to a Soxhlet extractor, extracted for 20 hours using 200 ml of THF as a solvent, and soluble components extracted by the solvent are extracted. After evaporation, vacuum drying is performed at 40 ° C. for several hours, and the amount of the THF-soluble resin component is weighed (W2 g). The weight of a component other than the resin component such as a pigment in the toner is (W3 g). The THF-insoluble content can be obtained from the following formula.
THF insoluble matter (mass%) = (W1− (W3 + W2)) / (W1−W3) × 100

  The THF insoluble content of the toner can be adjusted by the degree of polymerization and the degree of crosslinking of the binder resin.

  The weight average molecular weight of the toner in the present invention (hereinafter also referred to as the weight average molecular weight in gel permeation chromatography (GPC) of the soluble portion of tetrahydrofuran (THF) in the toner) (Mw) is 15000 to 80000. preferable. Such toner exhibits good environmental stability and durability stability. Further, it is preferable that the weight average molecular weight in gel permeation chromatography (GPC) of the soluble part of tetrahydrofuran (THF) in the toner is 20000 to 60000. If the weight average molecular weight in the gel permeation chromatography (GPC) of the soluble content of tetrahydrofuran (THF) in the toner is less than 15000, the blocking resistance and durability tend to be poor. And high gloss images are difficult to obtain. In the present invention, the weight average molecular weight (Mw) of the toner depends on the addition amount and weight average molecular weight of the low molecular resin, the reaction temperature at the time of toner production, the reaction time, the initiator amount, the chain transfer agent amount, and the crosslinking agent amount. Can be adjusted.

  In the present invention, the ratio Mw / Mn of the weight average molecular weight and the number average molecular weight in gel permeation chromatography (GPC) of the soluble portion of tetrahydrofuran (THF) in the toner is preferably 5 to 100. More preferably, Mw / Mn is 5 to 30. When Mw / Mn is less than 5, the fixable temperature range is narrow, and when it exceeds 100, the low-temperature fixability is deteriorated.

  As the colorant used in the present invention, a known colorant can be used.

  Examples of yellow pigments include yellow iron oxide, navel yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake. Isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specific examples include the following. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment Yellow 180.

  Examples of the orange pigment include the following. Permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK.

  Red pigments include Bengala, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eoxin Lake, Rhodamine Lake B, Alizarin Lake, etc. Examples include azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.

  Blue pigments include alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, indanthrene blue BG and other copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dyes Examples include lake compounds. Specific examples include the following. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment Blue 66.

  Examples of purple pigments include fast violet B and methyl violet lake.

  Examples of the green pigment include Pigment Green B, Malachite Green Lake, and Final Yellow Green G. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

  Examples of the black pigment include carbon black, aniline black, non-magnetic ferrite, magnetite, and those that are toned in black using the yellow colorant / red colorant / blue colorant.

  These colorants can be used alone or in combination, and further in a solid solution state.

  In the present invention, it is necessary to pay attention to the polymerization inhibitory property and dispersion medium transferability of the colorant. If necessary, the surface may be modified by subjecting the colorant to a surface treatment with a substance that does not inhibit polymerization. In particular, since dyes and carbon black often have polymerization inhibiting properties, care must be taken when using them.

  As a preferred method for treating the dye, a polymerizable monomer is previously polymerized in the presence of these dyes, and the resulting colored polymer is added to the monomer composition. Moreover, about carbon black, you may process with the substance (for example, organosiloxane etc.) which reacts with the surface functional group of carbon black besides the process similar to the said dye.

  During the toner particle production process, the temperature may be raised in the latter half of the polymerization reaction. Further, in order to remove the unreacted polymerizable monomer or by-product, it is preferable to partially distill off the dispersion medium from the reaction system in the latter half of the reaction or after the completion of the polymerization reaction. After completion of the reaction, the produced toner particles are washed, collected by filtration, and dried.

  In the suspension polymerization method, it is preferable to use 300 to 3,000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer composition.

  A method for measuring and evaluating physical properties relating to the toner of the present invention will be described below.

<Particle size and particle size distribution of fatty acid metal salt>
The particle size and particle size distribution of the fatty acid metal salt in the present invention were measured using a laser diffraction / scattering particle size distribution measuring apparatus LA-920 (manufactured by HORIBA). The attached dedicated software is used for setting the measurement conditions and analyzing the measurement data. As a specific measurement method, first, an electrolyte solution (a solution obtained by dissolving special grade sodium chloride in ion-exchanged water to a concentration of about 1% by mass, for example, “ISOTON II” Beckman Coulter, Inc.) The batch type cell containing “manufactured” is set in a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by HORIBA) to adjust the optical axis and the background. Next, about 1 mg of fatty acid metal salt in a glass 30 cc sample bottle and “Contaminone N” as a dispersing agent (for washing a pH 7 precision measuring instrument comprising a nonionic surfactant, an anionic surfactant and an organic builder) About 0.2 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent (made by Wako Pure Chemical Industries, Ltd.) about 3 times by mass with ion-exchanged water and 20 ml of an electrolytic aqueous solution are added. The sample bottle was subjected to ultrasonic dispersion for 60 seconds using an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios). The obtained fatty acid metal salt dispersion was added to the batch cell until the transmittance of the tungsten lamp reached 95% to 90%, and the particle size distribution was measured.

  Based on the obtained particle size distribution data, volume average particle size (Dvs), coefficient of variation, and (D95) / (D5) / (D50) were determined.

  The volume average particle diameter (Dvs) here is an arithmetic average diameter on a volume basis, and is obtained by the following formula using a value obtained by arithmetically averaging the frequency distribution.

  The coefficient of variation referred to here is a value obtained by dividing the arithmetic standard deviation obtained by the following equation by the volume average particle diameter (Dvs).

J: Particle size division number (1 to 80 at a fixed interval)
q (J): Frequency distribution value on a volume basis (%)
X (J): representative diameter (μm) of the J-th particle size range on a volume basis

<Rate of fatty acid metal salt>
The liberation rate of the fatty acid metal salt in the toner according to the present invention is determined using a powder tester (manufactured by Hosokawa Micron) having a digital vibrometer (Digivibro Model 1332), an X-ray fluorescence analyzer Axios (manufactured by PANallytical), and measurement condition setting and measurement. The liberation rate of the fatty acid metal salt was determined from the intensity difference of fluorescent X-rays using the attached dedicated software “SuperQ ver. 4.0F” (manufactured by PANalytical) for data analysis.

  As a specific measuring method, a sieve having a mesh size of 25 μm (635 mesh) is set on a vibrating table of a powder tester. 5 g of a sample accurately weighed is added to the sieve having a mesh size of 25 μm (635 mesh), the amplitude of the digital vibrometer is adjusted to about 0.60 mm, and vibration is applied for about 2 minutes. The above operation is further repeated twice, and the sample is passed through a 25 μm (635 mesh) sieve three times in total. Next, about 4 g of the obtained sample is placed on an aluminum ring having a diameter of 40 mm, and compressed by a press machine at 150 kN to prepare a sample. The obtained sample was measured with a fluorescent X-ray analyzer (Axios). Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).

The liberation rate of the fatty acid metal salt was determined from the following formula by measuring the Kα ray net intensity (KCPS) of the metal element of the fatty acid metal salt before and after the sieve.
{(Kα ray net intensity of metal element of fatty acid metal salt in toner before sieve) − (Kα ray net intensity of metal element of fatty acid metal salt in toner passed through sieve)} / (Fatty acid metal salt in toner before sieve) (Kα line net intensity of metallic elements)

<Measurement of molecular weight>
The molecular weight of the chromatogram obtained by GPC (gel permeation chromatography) of the present invention is measured under the following conditions.

<Molecular weight (RI) measurement>
<Measurement conditions>
Column (manufactured by Showa Denko KK): Shodex GPC KF-801, Shodex GPC KF-802, Shodex GPC KF-803, Shodex GPC KF-804, Shodex GPC KF-805, Shodex GPC KF-806, G 807 (diameter 8.0mm, length 30cm) 7 stations ・ Temperature: 40 ℃
・ Flow rate: 0.6ml / min
・ Detector: RI
Sample concentration: 10 μl of 0.1% by mass sample

  For sample preparation, a toner sample to be measured is placed in tetrahydrofuran (THF), 0.04 g of a resin for toner is dispersed in 20 ml of THF, dissolved, and allowed to stand for 24 hours, and then a 0.2 μm filter (for example, Myshori Disc H -25-2 (manufactured by Tosoh Corporation), Excro Disc 25CR Gelman (manufactured by Science Japan), etc. can be preferably used), and the filtrate is used as a sample. The calibration curve uses a molecular weight calibration curve created with a monodisperse polystyrene standard sample. As a standard polystyrene sample for preparing a calibration curve, for example, TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-40, F-20, F-10, manufactured by Tosoh Corporation, Calibration curves can be created using F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500, and at least about 10 standard polystyrene samples are used. Is appropriate. After 0.04 g of the toner resin is dispersed in 20 ml of THF and dissolved, the mixture is allowed to stand for 24 hours. The product is preferably used, and the filtrate is used as a sample.

  In general, in the measurement of the molecular weight distribution of GPC, the chromatogram rises from the baseline on the high molecular weight side and starts measurement from the starting point, and the molecular weight is measured up to about 400 on the low molecular weight side.

<DSC measurement>
In the present invention, M-DSC (trade name, manufactured by TA Instruments) was used as a differential scanning calorimeter (DSC). Weigh accurately 6 mg of the toner sample to be measured. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 1 ° C./min and normal temperature and humidity in a measurement temperature range of 20 to 200 ° C. Measurement is performed at a modulation amplitude of ± 0.5 ° C. and a frequency of 1 / min. The maximum glass transition point Tg (° C.) is calculated from the obtained reversing heat flow curve. Tg is obtained as Tg (° C.) as the center value of the intersection of the baseline before and after endotherm and the tangent of the curve due to endotherm.

  In addition, in the endothermic chart at the time of temperature rise measured by DSC, the calorific integral value Q (J / g) obtained by converting the endothermic amount (J) represented by the peak area of the endothermic main peak into the amount of heat per gram of toner is measured. did. An example of a reversing heat flow curve obtained by DSC measurement of the toner is shown in FIG. The calorie integral value Q (J / g) is obtained using the reversing heat flow curve obtained from the above measurement. For the calculation, analysis software Universal Analysis Ver. Using 2.5H (manufactured by TA Instruments) and using the function of Integral PeakLinear, the integrated value of heat Q (J / g) from the region surrounded by the straight line connecting the measurement points at 35 ° C and 135 ° C and the endothermic curve Ask for.

<Measurement of toner weight average particle diameter (D4)>
Measurement of particle size distribution of toner As a measuring device, Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter Inc.) is used. As the electrolyte, first grade sodium chloride is used to prepare an approximately 1% NaCl aqueous solution. For example, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.11 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 ml of the electrolytic aqueous solution, and 5 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 minute, and the measuring device is used to measure the volume and number of toner particles for each channel using a 100 μm aperture as the aperture. The volume distribution and the number distribution are calculated. Then, the weight-based toner weight average particle diameter (D4) obtained from the volume distribution of the toner particles (the median value of each channel is a representative value for each channel) is obtained.

  Channels are 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00 to 40.30 μm are used.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples.

  Next, production examples of fatty acid metal salts used in the present invention will be described.

<Production of fatty acid metal salt 1>
A receiving container with a stirrer was prepared, and the stirrer was rotated at 340 rpm. Into this container, 500 parts by mass of a 0.5% by mass sodium stearate aqueous solution and 0.025 parts by mass of polyoxyalkylene alkyl ether (trade name: Emulgen LS106 Kao Co., Ltd.), which is the activator (1), are charged. Adjusted to 85 ° C. Next, 525 parts by mass of a 0.2% by mass aqueous zinc sulfate solution and 0.025 parts by mass of polyoxyalkylene alkyl ether (trade name Emulgen LS106 Kao Co., Ltd.) which is the activator (1) are added to this receiving container over 15 minutes. And dripped. After the completion of charging the whole amount, the reaction was terminated by aging for 10 minutes at the temperature during the reaction.

Next, the fatty acid metal salt slurry thus obtained was washed by filtration. The obtained washed fatty acid metal salt cake was roughly crushed and then dried at 105 ° C. using a continuous instantaneous air dryer. Then, it grind | pulverized on the conditions of the air volume of 6.0 m < ³ > / min, and the process speed of 80 kg / h with the nano grinding mill [NJ-300] (made by a Sanrex company). Next, after reslurrying and removing fine particles and coarse particles using a wet centrifugal classifier, the mixture was dried at 80 ° C. using a continuous instantaneous air dryer to obtain fatty acid metal salt 1. The obtained fatty acid metal salt 1 had a volume average particle diameter (Dvs) of 0.46 μm, a coefficient of variation of 32, and a number average particle diameter (D1s) of 0.31 μm. Table 5 shows the physical properties of the fatty acid metal salt 1.

<Production of fatty acid metal salt 2>
In fatty acid metal salt 1, except that 0.5% by mass sodium stearate aqueous solution is changed to 0.25% by mass sodium stearate aqueous solution, and 0.2% by mass zinc sulfate aqueous solution is changed to 0.15% by mass zinc sulfate aqueous solution. Fatty acid metal salt 2 was obtained in the same manner as fatty acid metal salt 1. The obtained fatty acid metal salt 2 had a volume average particle diameter (Dvs) of 0.32 μm, a coefficient of variation of 28, and a number average particle diameter (D1s) of 0.25 μm. Table 5 shows the physical properties of the fatty acid metal salt 2.

<Production of fatty acid metal salt 3>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 2.0% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 1.0% by mass calcium chloride aqueous solution. The reaction was terminated by aging for 5 minutes. Other steps were carried out in the same manner as fatty acid metal salt 1 to obtain fatty acid metal salt 3. The obtained fatty acid metal salt 3 had a volume average particle diameter (Dvs) of 0.60 μm, a coefficient of variation of 41, and a number average particle diameter (D1s) of 0.41 μm. Table 5 shows the physical properties of the fatty acid metal salt 3.

<Production of fatty acid metal salt 4>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was added to 0.25% by mass sodium stearate aqueous solution, 0.2% by mass zinc sulfate aqueous solution to 0.15% by mass zinc sulfate aqueous solution, and The conditions were changed so that the air flow was 10.0 m ³ / min and the pulverization step was performed three times. The obtained fatty acid metal salt 4 had a volume average particle diameter (Dvs) of 0.18 μm, a coefficient of variation of 39, and a number average particle diameter (D1s) of 0.09 μm. Table 5 shows the physical properties of the fatty acid metal salt 4.

<Production of fatty acid metal salt 5>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 0.7% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.3% by mass zinc sulfate aqueous solution. The pulverization conditions were an air volume of 4.0 m ³ / min and a processing speed of 50 kg / h. Other steps were carried out in the same manner as fatty acid metal salt 1 to obtain fatty acid metal salt 5. The obtained fatty acid metal salt 5 had a volume average particle diameter (Dvs) of 0.64 μm, a coefficient of variation of 33, and a number average particle diameter (D1s) of 0.43 μm. Table 5 shows the physical properties of the fatty acid metal salt 5.

<Production of fatty acid metal salt 6>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 1.0% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.4% by mass zinc sulfate aqueous solution. Further, the reaction was terminated by aging for 15 minutes. The pulverization condition was an air volume of 4.0 m ³ / min. Other steps were carried out in the same manner as fatty acid metal salt 1 to obtain fatty acid metal salt 6. The obtained fatty acid metal salt 6 had a volume average particle diameter (Dvs) of 0.73 μm, a coefficient of variation of 38, and a number average particle diameter (D1s) of 0.59 μm. Table 5 shows the physical properties of the fatty acid metal salt 6.

<Production of fatty acid metal salt 7>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 0.05% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.02% by mass zinc sulfate aqueous solution. Further, the pulverization condition was set to an air volume of 10.0 m ³ / min, and the pulverization step was performed three times. Thereafter, the classification step was not performed, and coarse particles were removed by passing through a mesh to obtain a fatty acid metal salt 7. The obtained fatty acid metal salt 7 had a volume average particle diameter (Dvs) of 0.11 μm, a coefficient of variation of 56, and a number average particle diameter (D1s) of 0.07 μm. Table 5 shows the physical properties of the fatty acid metal salt 7.

<Production of fatty acid metal salt 8>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 1.0% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.4% by mass zinc sulfate aqueous solution. Moreover, the classification process after performing a grinding | pulverization process was not performed but the fatty-acid metal salt 8 was obtained. The obtained fatty acid metal salt 8 had a volume average particle diameter (Dvs) of 0.62 μm, a coefficient of variation of 58, and a number average particle diameter (D1s) of 0.42 μm. Table 5 shows the physical properties of the fatty acid metal salt 8.

<Fatty acid metal salt 9>
Commercially available zinc stearate (MZ2 manufactured by NOF Corporation) is used as fatty acid metal salt 9. The volume average particle diameter (Dvs) was 1.29 μm, and the coefficient of variation was 44. Table 5 shows the physical properties of the fatty acid metal salt 9.

<Fatty acid metal salt 10>
A commercially available zinc stearate (manufactured by SZ2000 Sakai Chemical Industry Co., Ltd.) is designated as fatty acid metal salt 10. The volume average particle diameter (Dvs) was 5.30 μm, and the coefficient of variation was 58. Table 5 shows the physical properties of the fatty acid metal salt 10.

<Fatty acid metal salt 11>
A receiving container with a stirrer was prepared, and the stirrer was rotated at 340 rpm. 500 mass parts of 0.5 mass% sodium stearate aqueous solution was thrown into this receiving container, and liquid temperature was adjusted to 85 degreeC. Next, 525 mass parts of 0.2 mass% zinc sulfate aqueous solution was dripped at this receptacle over 15 minutes. After the completion of charging the whole amount, the reaction was terminated by aging for 10 minutes at the temperature during the reaction.
Next, the fatty acid metal salt slurry thus obtained was washed by filtration. The obtained washed fatty acid metal salt cake was roughly crushed and then dried at 105 ° C. using a continuous instantaneous air dryer. Then, after pulverizing with a nano grinding mill [NJ-300] (manufactured by Sanrex) under conditions of an air volume of 6.0 m ³ / min and a processing speed of 80 kg / h, reslurry and fine particles using a wet centrifugal classifier After removal of the coarse particles, the fatty acid metal salt 11 was obtained by drying at 80 ° C. using a continuous instantaneous air flow dryer. The obtained fatty acid metal salt 11 had a volume average particle diameter (Dvs) of 0.46 μm, a coefficient of variation of 31, and a number average particle diameter (D1s) of 0.32 μm. Table 5 shows the physical properties of the fatty acid metal salt 11.

<Production of fatty acid metal salt 12>
In fatty acid metal salt 1, activator (2) polyoxyethylene alkyl ether (trade name Sannonic SS-50) whose polyoxyalkylene alkyl ether (trade name Emulgen LS106 Kao Co., Ltd.), which is activator (1), is shown in Table 4. Changed to Sanyo Chemical Co., Ltd. Other steps were carried out in the same manner as fatty acid metal salt 1 to obtain fatty acid metal salt 12. The obtained fatty acid metal salt 12 had a volume average particle diameter (Dvs) of 0.45 μm, a coefficient of variation of 31, and a number average particle diameter (D1s) of 0.30 μm. Table 5 shows the physical properties of the fatty acid metal salt 12.

<Production of fatty acid metal salt 13>
In fatty acid metal salt 1, the active agent (1) polyoxyalkylene alkyl ether (trade name: Emulgen LS106 Kao Co., Ltd.) is shown in Table 4 as active agent (3) polyoxyethylene alkyl ether (trade name: NAROACTY N- 40 Sanyo Chemical Co., Ltd.). Other steps were carried out in the same manner as fatty acid metal salt 1 to obtain fatty acid metal salt 13. The obtained fatty acid metal salt 13 had a volume average particle diameter (Dvs) of 0.48 μm, a coefficient of variation of 34, and a number average particle diameter (D1s) of 0.35 μm. Table 5 shows the physical properties of the fatty acid metal salt 13.

<Production of fatty acid metal salt 14>
In fatty acid metal salt 1, activator (4) polyoxyethylene fatty acid diester (trade name: IONET DL-200) whose polyoxyalkylene alkyl ether (trade name: Emulgen LS106 Kao Co., Ltd.), which is the active agent (1), is shown in Table 4. Changed to Sanyo Chemical Co., Ltd. The other processes were carried out in the same manner as in fatty acid metal salt 1 to obtain fatty acid metal salt 14. The obtained fatty acid metal salt 14 had a volume average particle diameter (Dvs) of 0.47 μm, a coefficient of variation of 34, and a number average particle diameter (D1s) of 0.35 μm. Table 5 shows the physical properties of the fatty acid metal salt 14.

<Production of fatty acid metal salt 15>
In fatty acid metal salt 1, activator (1) polyoxyalkylene alkyl ether (trade name: Emulgen LS106 Kao Co., Ltd.) activator (5) polyoxyalkylene alkyl ether (trade name: NAROACTY N-) 160 Sanyo Chemical Co., Ltd.)). Other steps were carried out in the same manner as the fatty acid metal salt 1 to obtain a fatty acid metal salt 15. The obtained fatty acid metal salt 15 had a volume average particle diameter (Dvs) of 0.49 μm, a coefficient of variation of 33, and a number average particle diameter (D1s) of 0.34 μm. Table 5 shows the physical properties of the fatty acid metal salt 15.

{Resin synthesis example}
(Production example of styrene resin (1))
38 mass parts of xylene was put into a pressure resistant reactor equipped with a dropping funnel, a Liebig condenser and a stirrer, and the temperature was raised to 200 ° C. The pressure at this time was 0.30 MPa. A mixture of 100 parts by mass of styrene monomer, 0.15 parts by mass of n-butyl acrylate and 3.8 parts by mass of di-tert-butyl peroxide was charged into a dropping funnel and added to xylene at 200 ° C. over 3.5 hours. It was dripped under pressure (0.30 MPa). After the dropping, the reaction was further carried out at 180 ° C. for 2 hours to complete the solution polymerization, and xylene was removed. The obtained styrene resin had a weight average molecular weight of 2,800 and Tg of 57 ° C. This is designated as styrene resin (1).

(Production example of styrene resin (2))
A reactor equipped with a dropping funnel, a Liebig cooler, a nitrogen-filled tube (nitrogen flow rate 100 ml / min) and a stirrer was charged with 610 parts by mass of xylene and heated to 140 ° C. A mixture of 100 parts by mass of styrene monomer, 0.15 parts by mass of n-butyl acrylate and 19.0 parts by mass of di-tert-butyl peroxide was charged into a dropping funnel, and xylene at 140 ° C. under atmospheric pressure over 1.5 hours. It was dripped at. Further, the reaction was carried out for 2 hours under reflux of xylene (137 ° C. to 145 ° C.) to complete solution polymerization, and xylene was removed. The resulting styrene resin had a weight average molecular weight of 3,100 and Tg of 56 ° C. This is designated as styrene resin (2).

(Production example of styrene resin (3))
700 parts by mass of xylene was placed in a reactor equipped with a dropping funnel, a Liebig cooler, a nitrogen-filled tube (nitrogen flow rate 100 ml / min) and a stirrer, and the temperature was raised to 140 ° C. A mixture of 100 parts by mass of styrene monomer and 8.0 parts by mass of di-tert-butyl peroxide was charged into the dropping funnel and dropped into xylene at 140 ° C. over 1.5 hours at normal pressure. Further, the reaction was carried out for 2 hours under reflux of xylene (137 ° C. to 145 ° C.) to complete solution polymerization, and xylene was removed. The resulting styrene resin had a weight average molecular weight of 8,100 and Tg of 60 ° C. This is designated as a styrene resin (3).

(Production example of styrene resin (4))
A mixture of 20 parts by mass of xylene, 80 parts by mass of styrene, 20 parts by mass of n-butyl acrylate and 2.1 parts by mass of di-tert-butyl peroxide as an initiator was charged into a reactor equipped with a Liebig cooler and a stirrer. Polymerization was carried out at a temperature of 100 ° C. for 24 hours. Thereafter, xylene was removed to obtain a styrene resin (4). The resulting styrene resin had a weight average molecular weight of 420,000 and a Tg of 62 ° C. This is designated as a styrene resin (4).

  Table 2 shows the physical properties of the styrene resins (1) to (4) obtained above.

(Example of production of negative charge control resin)
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 255 parts by mass of methanol, 145 parts by mass of 2-butanone and 100 parts by mass of 2-propanol, As a monomer, 88 parts by mass of styrene, 6.2 parts by mass of 2-ethylhexyl acrylate, and 5.1 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added and heated to reflux temperature while stirring. A solution prepared by diluting 1.0 part by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 5 hours. Further, a solution prepared by diluting 1.2 parts by mass of 2,2′-azobisisobutyronitrile with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and the mixture was further stirred for 5 hours to complete the polymerization.

  Next, the polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less by a cutter mill equipped with a 150 mesh screen, and further finely pulverized by a jet mill. The fine powder was classified with a 250 mesh sieve to obtain particles of 60 μm or less. Next, the particles were dissolved by adding MEK to a concentration of 10%, and the above solution was gradually poured into 20 times the amount of MEK in methanol for reprecipitation. The resulting precipitate was washed with one-half the amount of methanol used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours.

Further, MEK was added and redissolved so that the particles after the vacuum drying had a concentration of 10%, and the above solution was gradually poured into n-hexane 20 times the amount of MEK for reprecipitation. The obtained precipitate was washed with half the amount of n-hexane used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours. The polar polymer thus obtained had a Tg of about 83 ° C., a main peak molecular weight (Mp) of 21,400, Mn 11,100, Mw 33,200, and an acid value of 14.5. Further, the composition measured by ¹ H-NMR (EX-400: 400 MHz manufactured by JEOL Ltd.) was as charged. The obtained resin is referred to as negative charge control resin 1.

(Example of production of polyester resin (1))
・ Terephthalic acid: 11.1 mol
Bisphenol A-propylene oxide 2 mol adduct (PO-BPA): 10.1 mol
The polyester monomer is charged into an autoclave together with an esterification catalyst, and a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirring device are attached to the autoclave, and the pressure is reduced under a nitrogen atmosphere at 195 ° C. according to a conventional method. Reaction was performed until Tg became 68-75 degreeC, and the polyester-type resin 1 was obtained. Table 3 shows the physical properties.

(Example of production of polyester resin (2))
・ Terephthalic acid: 9.8 mol
-Bisphenol A-propylene oxide 2-mol adduct (PO-BPA): 10.0 mol
The polyester monomer is charged into an autoclave together with an esterification catalyst, and a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirring device are attached to the autoclave, and the pressure is reduced under a nitrogen atmosphere at 195 ° C. according to a conventional method. Reaction was performed until Tg became 68-75 degreeC, and the polyester-type resin A was obtained (Mw 10,600, Mw / Mn 3.13, Tg 71 degreeC).

  Next, the polyester resin A (9.8 mol of terephthalic acid, 10.0 mol of bisphenol A-propylene oxide 2-mol adduct (PO-BPA) 10.0 mol) was added to 25.0 mol of xylene, and this mixed solution was added at 135 ° C. Heated. A mixture of 15.3 mol of styrene, 1.54 mol of acrylic acid and 1.96 mol of tert-butylperoxybenzoate as a radical polymerization initiator in 10 parts by mass of xylene in a nitrogen atmosphere, It was added dropwise over a period of minutes. The mixture was held at 135 ° C. for another 5 hours to complete the radical polymerization reaction. Further, the mixed solution was depressurized while being heated to remove the solvent, thereby obtaining a polyester resin (2). Table 3 shows the physical properties.

(Production example of toner particle 1)
In a four-necked vessel, 720 parts by weight of ion-exchanged water, 920 parts by weight of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, and 15.0 parts by weight of an aqueous 1.0 mol HCl solution are added, and a high-speed stirring device TK is added. -Hold at 60 ° C with stirring at 12,000 rpm using a homomixer. To this, 75 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene monomer 64.0 parts by mass n-butyl acrylate 16.0 parts by mass Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.50 parts by mass Styrenic resin (1) 20 parts by mass (Mw = 2800, Mw / Mn = 1) .72)
Polyester resin (1) 5 parts by mass Negative charge control agent 1 (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.5 parts by weight Negatively charged control resin 1 0.5 parts by weight Wax [Fischer-Tropsch wax (1), endothermic main peak temperature 78.2 ° C.] 10 parts by weight Disperse the monomer mixture with an attritor for 3 hours Monomer composition obtained by adding 8.0 parts by mass (toluene solution 50%) of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate as a polymerization initiator to the monomer mixture 1 prepared The product was put into an aqueous dispersion medium and granulated for 5 minutes while maintaining the rotational speed of the high-speed stirring device at 12,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring. Table 1 shows the raw materials and polymerization conditions, Table 3 shows the raw materials and physical properties of the polyester resin, and Table 2 shows the physical properties and raw materials of the styrene resin.

  Next, the temperature in the container was raised to 80 ° C. and maintained for 3 hours, and then gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain slurry 1. Dilute hydrochloric acid was added to the container containing the slurry 1 to remove the dispersion stabilizer. Further, filtration, washing and drying were performed to obtain polymer particles (toner particles 1) having a weight average particle diameter of 5.8 μm.

(Production example of toner particle 2)
20 parts by mass of the styrene resin (1) of Example 1 was changed to 0 parts by mass, 8.0 parts by mass of t-butyl peroxypivalate was changed to 3.0 parts by mass, and 0.25 part by mass of divinylbenzene was added. Except for the above, toner particles 2 were obtained in the same manner as in Example 1. The raw materials and polymerization conditions are shown in Table 1.

(Production example of toner particle 3)
Toner particles 3 were obtained in the same manner as in Example 1 except that 20 parts by mass of the styrene resin (1) in Example 1 was changed to 20 parts by mass of the styrene resin (2). The raw materials and polymerization conditions are shown in Table 1.

(Production example of toner particles 4)
Styrene monomer of Example 1 64.0 parts by mass 54.0 parts by mass, polyester resin (1) 5.0 parts by mass polyester resin (2) 5.0 parts by mass, Fischer-Tropsch wax 10.0 masses Toner particles 4 were obtained in the same manner as in Example 1, except that 10.0 parts by mass of behenyl behenate and 8.0 parts by mass of t-butyl peroxypivalate were changed to 12.0 parts by mass. The raw materials and polymerization conditions are shown in Table 1.

(Production example of toner particles 5)
Toner particles 5 were obtained in the same manner as in Example 1 except that 10.0 parts by mass of Fischer-Tropsch in Example 1 was changed to 4.6 parts by mass of Fischer-Tropsch. The raw materials and polymerization conditions are shown in Table 1.

(Production Example of Toner Particle 6)
Toner particles 6 were obtained in the same manner as in Example 1 except that 10.0 parts by mass of Fischer-Tropsch of Example 1 was changed to 20.0 parts by mass of Fischer-Tropsch. The raw materials and polymerization conditions are shown in Table 1.

(Production example of toner particles 7)
Toner particles 7 were obtained in the same manner as in Example 1 except that 0.5 parts by mass of negative charge control agent 1 in Example 1 was changed to 0.0 parts by mass. The raw materials and polymerization conditions are shown in Table 1.

(Example of production of toner particles 8)
Negative charge control agent 1 of Example 1 Toner particles 8 were obtained in the same manner as in Example 1 except that 0.5 parts by mass was changed to 0.0 parts by mass. The raw materials and polymerization conditions are shown in Table 1.

(Example of production of toner particles 9)
Styrene resin (3) 60 parts by mass Styrene resin (4) 40 parts by mass Copper phthalocyanine pigment 6.5 parts by mass Negative charge control agent 1 (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.5 parts by mass Negative charge control resin 1 0.5 parts by mass Wax [Fischer-Tropsch wax (1), endothermic main peak temperature 78 ° C.]
10 parts by mass After the above materials are mixed with a Henschel mixer, melt kneading is performed at 130 ° C. with a twin-screw kneading extruder, the kneaded product is cooled, and then coarsely pulverized with a cutter mill and using a fine pulverizer using a jet stream. The toner particles 9 having a weight average particle diameter of 6.2 μm were obtained by pulverization and classification using an air classifier.

(Production Example of Toner Particle 10)
Styrene monomer of Example 1 64.0 parts by mass 37.4 parts by mass, n-butyl acrylate 16.0 parts by mass 7.6 parts by mass, styrene resin (1) 20.0 parts by mass 0.0 parts by mass Parts, Fischer-Tropsch wax 10 parts by weight behenyl behenate 12 parts by weight, polyester resin (1) 5.0 parts by weight 55 parts by weight, negative charge control resin 1 0.5 part by weight 0.0 parts by weight The toner particles 10 were obtained in the same manner as in Example 1 except that 0.12 parts by mass of divinylbenzene was added. The raw materials and polymerization conditions are shown in Table 1.

(Production Example of Toner Particle 11)
[Production of resin fine particle dispersion 1]
360 g of styrene
n-butyl acrylate 40g
Acrylic acid 7g
Dodecanethiol 23g
Carbon tetrabromide 2.5g
Non-ionic surfactant Nonipol 400 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) and anionic surfactant Neogen SC (trade name, Daiichi Kogyo Seiyaku Co., Ltd.) were prepared by mixing and dissolving the above materials. Company) was dissolved in 10.4 g ion exchange water 550.0 g, dispersed and emulsified in a flask, mixed slowly for 10 minutes, and 50 g ion exchange water dissolved with 4.2 g ammonium persulfate was added, and nitrogen was added. Replaced. After that, the flask was heated with an oil bath while stirring until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, an anionic resin fine particle dispersion 1 having a center diameter of 148 nm, a glass transition point of 54 ° C., and Mw of 12,100 was obtained.

[Production of resin fine particle dispersion 2]
280 g of styrene
n-butyl acrylate 120g
Acrylic acid 7.0g
Disperse the above-mentioned materials mixed and dissolved in a flask in 7.0 g of nonionic surfactant Nonipol 400 and 12.2 g of anionic surfactant Neogen SC dissolved in 550.0 g of ion-exchanged water, While emulsifying and slowly mixing for 10 minutes, 50 g of ion-exchanged water in which 3.2 g of ammonium persulfate was dissolved was added to perform nitrogen substitution. After that, the flask was heated with an oil bath while stirring until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, an anionic resin fine particle dispersion 2 having a center diameter of 102 nm, a glass transition point of 53 ° C., and a Mw of 510,000 was obtained.

[Production of colorant dispersion]
Copper phthalocyanine pigment PV FAST BLUE (BASF) 20g
Anionic surfactant Neogen SC 2.5g
Ion exchange water 80g
The above materials were mixed and dispersed for 10 minutes at an oscillation frequency of 28 kHz using an ultrasonic cleaner W-113 manufactured by Honda Electronics Co., Ltd. to obtain a colorant dispersion. When the particle size distribution of this sample was measured by a particle size measuring apparatus LA-700 manufactured by Horiba, Ltd., the volume average particle size was 150 nm, and coarse particles of 1 μm were not observed.

[Production of Release Agent Dispersion 1]
200 g of paraffin wax HNP0190 (melting point: 85 ° C Nippon Seiwa)
Anionic surfactant Neogen SC 10g
780 g of ion exchange water
The above material was heated to 95 ° C., emulsified with a Gaulin homogenizer at a discharge pressure of 560 × 10 ⁵ N / m ² , and then rapidly cooled to obtain a release agent dispersion. When this sample was measured with a particle size measuring apparatus LA-700 manufactured by Horiba, Ltd., the volume average particle diameter was 138 nm, and coarse particles of 0.8 μm or more were 5% or less.

[Production of Toner Particles 11]
Resin fine particle dispersion 1 225 g
Resin fine particle dispersion 2 35g
Colorant dispersion 30g
Release agent dispersion 1 30 g
SANISOL B50 (general name manufactured by Kao Corporation) 1.5g
The above materials were placed in a round stainless steel flask, mixed and dispersed with Ultra Turrax T50, and then heated to 50 ° C. while stirring the flask in an oil bath for heating. After maintaining at 50 ° C. for 1 hour, 3.2 g of Neogen SC was added, and then the stainless steel flask was sealed, heated to 105 ° C. while continuing stirring using a magnetic seal, and maintained for 3 hours. After cooling, the mixture was filtered and thoroughly washed with ion exchange water to obtain toner particles 11.

(Production example of toner particles 12)
Toner particles 12 were obtained in the same manner as in Example 1 except that 5.0 parts by mass of the polyester resin (1) was added to the raw material of the toner particles 9. The raw materials and polymerization conditions are shown in Table 1.

(Production example of toner particles 13)
<Suspension granulation method>
(Toner binder synthesis)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 660 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 100 parts by mass of bisphenol A propylene oxide 2 mol adduct, 290 parts by mass of terephthalic acid and dibutyltin oxide 2 .5 parts by mass was added, and the reaction was carried out at 220 ° C. and normal pressure for 12 hours. Furthermore, after reacting under reduced pressure of 10 to 15 mmHg for 6.5 hours, the mixture was cooled to 190 ° C., 30 parts by mass of phthalic anhydride was added thereto, and reacted for 2 hours. Subsequently, it cooled to 80 degreeC and reacted with 180 mass parts of isophorone diisocyanate in ethyl acetate for 2 hours, and the isocyanate containing prepolymer (1) was obtained.

  Next, 266 parts by mass of prepolymer (1) and 14 parts by mass of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain urea-modified polyester (1) having a weight average molecular weight of 66000. 625 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 100 parts by mass of bisphenol A propylene oxide 2-mole adduct, 139 parts by mass of terephthalic acid, and 139 parts by mass of isophthalic acid at 230 ° C. under normal pressure for 5 hours in the same manner as above. Then, the reaction was performed at a reduced pressure of 10 to 15 mmHg for 5.5 hours to obtain unmodified polyester (a) having a peak molecular weight of 6100. 250 parts by mass of the urea-modified polyester (1) and 750 parts by mass of the unmodified polyester (a) were dissolved and mixed in 2000 parts by mass of a tetrahydrofuran solvent to obtain a tetrahydrofuran solution of the toner binder (1).

  240 parts by mass of a tetrahydrofuran solution of the toner binder (1); I. Pigment Blue 15: 3 pigment 5.2 parts by weight, wax [Fischer-Tropsch wax (1), endothermic main peak temperature 78.2 ° C.] 10 parts by weight, and stirred at 12,000 rpm at 55 ° C. using a TK homomixer And uniformly dissolved and dispersed. In a beaker, 706 parts by mass of ion-exchanged water, 295 parts by mass of a hydroxyapatite 10% suspension (Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.) and 0.18 parts by mass of sodium dodecylbenzenesulfonate were uniformly dissolved. Next, the temperature was raised to 55 ° C., and the toner material solution was added and stirred for 10 minutes while stirring at 12000 rpm with a TK homomixer. Next, this mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, heated to 98 ° C. to remove the solvent, filtered, washed, dried, and then classified by air to obtain toner particles 13.

(Production example of toner 1)
100 parts by mass of toner particles 1 with a specific surface area of 200 m ² / g by BET method and 1.5 parts by mass of hydrophobic silica having a hydrophobicity of 81, a specific surface area of 100 m ² / g by BET method, and a hydrophobicity of 62 The titanium oxide 0.1 mass part and the fatty acid metal salt 1 0.2 mass part are mixed for 140 seconds with a Henschel mixer (Mitsui Mining Co., Ltd.) (mixing process 1). Thereafter, a pause process of 125 seconds is taken (pause process 1). Immediately after the pause process for 125 seconds, the mixing process is restarted and the mixing process for 160 seconds is performed (mixing process 2). Thereafter, a pause process of 125 seconds is taken (pause process 2). Immediately after 125 seconds, mixing was resumed and mixing was continued for 160 seconds (mixing step 3). Thereafter, a pause process of 125 seconds is taken (pause process 3). Immediately after 125 seconds, mixing was resumed and mixing was continued for 160 seconds (mixing step 4). By repeating the mixing step and the pause step as described above, the maximum temperature reached in the tank was about 32 ° C. The toner thus obtained is referred to as Toner 1. The physical properties of the obtained toner 1 are shown in Tables 5 and 6.

(Production example of toner 2)
Toner 2 was obtained in the same manner as in the production example of toner 1, except that fatty acid metal salt 1 was changed to fatty acid metal salt 2. Table 5 and Table 6 show the physical properties of Toner 2 thus obtained.

(Production example of toner 3)
Toner 3 was obtained in the same manner as in the production example of toner 1, except that fatty acid metal salt 1 was changed to fatty acid metal salt 3. Table 5 and Table 6 show the physical properties of Toner 2 thus obtained.

(Production example of toner 4)
Toner 4 was obtained in the same manner as in the production example of toner 1, except that fatty acid metal salt 1 was changed to fatty acid metal salt 4. Table 5 and Table 6 show the physical properties of Toner 2 thus obtained.

(Production example of toner 5)
A toner 5 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 5. The physical properties of the obtained toner 5 are shown in Tables 5 and 6.

(Production example of toner 6)
Toner 6 was obtained in the same manner as in the production example of toner 1, except that fatty acid metal salt 1 was changed to fatty acid metal salt 6. The physical properties of the obtained toner 6 are shown in Tables 5 and 6.

(Production example of toner 7)
Toner 7 was obtained in the same manner as in the production example of toner 1, except that fatty acid metal salt 1 was changed to fatty acid metal salt 7. The physical properties of the obtained toner 7 are shown in Tables 5 and 6.

(Production example of toner 8)
Toner 8 was obtained in the same manner as in the production example of toner 1 except that toner particle 1 was changed to toner particle 2. Tables 5 and 6 show the physical properties of Toner 8 thus obtained.

(Production example of toner 9)
A toner 9 was obtained in the same manner as in the production example of the toner 1 except that the toner particle 1 was changed to the toner particle 3. The physical properties of the obtained toner 9 are shown in Tables 5 and 6.

(Production example of toner 10)
A toner 10 was obtained in the same manner as in the production example of the toner 1 except that the toner particle 1 was changed to the toner particle 4. The physical properties of the obtained toner 10 are shown in Tables 5 and 6.

(Production example of toner 11)
A toner 11 was obtained in the same manner as in the production example of the toner 1 except that the toner particle 1 was changed to the toner particle 5. The physical properties of the obtained toner 11 are shown in Tables 5 and 6.

(Production example of toner 12)
A toner 12 was obtained in the same manner as in the production example of the toner 1 except that the toner particle 1 was changed to the toner particle 6. The physical properties of the obtained toner 12 are shown in Tables 5 and 6.

(Production example of toner 13)
A toner 13 was obtained in the same manner as in the production example of the toner 1 except that the toner particle 1 was changed to the toner particle 7. The physical properties of the obtained toner 13 are shown in Tables 5 and 6.

(Production example of toner 14)
A toner 14 was obtained in the same manner as in the production example of the toner 1 except that the toner particle 1 was changed to the toner particle 8. The physical properties of the obtained toner 14 are shown in Tables 5 and 6.

(Production example of toner 15)
Toner 15 was obtained in the same manner as in the production example of toner 1 except that toner particle 1 was changed to toner particle 10. The physical properties of the obtained toner 15 are shown in Tables 5 and 6.

(Production example of toner 16)
Toner 16 was obtained in the same manner as in the production example of toner 1 except that toner particle 1 was changed to toner particle 11. The physical properties of the obtained toner 16 are shown in Tables 5 and 6.

(Production example of toner 17)
A toner 17 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 11. Table 5 and Table 6 show the physical properties of Toner 17 thus obtained.

(Production example of toner 18)
A toner 18 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 8. The physical properties of the obtained toner 18 are shown in Tables 5 and 6.

(Production example of toner 19)
A toner 19 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 9. The physical properties of the obtained toner 19 are shown in Tables 5 and 6.

(Production example of toner 20)
A toner 20 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 10. The physical properties of the obtained toner 20 are shown in Tables 5 and 6.

(Production example of toner 21)
Toner 21 was obtained in the same manner as in the production example of toner 1 except that toner particle 1 was changed to toner particle 9. The physical properties of the obtained toner 21 are shown in Tables 5 and 6.

(Production example of toner 22)
A toner 22 was obtained in the same manner as in the production example of the toner 1 except that the toner particle 1 was changed to the toner particle 12. The physical properties of the obtained toner 22 are shown in Tables 5 and 6.

(Production example of toner 23)
Toner 23 was obtained in the same manner as in the production example of toner 1, except that toner particle 1 was changed to toner particle 2 and fatty acid metal salt 1 was changed to fatty acid metal salt 9. Table 5 and Table 6 show the physical properties of Toner 23 thus obtained.

(Production example of toner 24)
Toner 24 was obtained in the same manner as in the production example of toner 1, except that toner particle 1 was changed to toner particle 10 and fatty acid metal salt 1 was changed to fatty acid metal salt 10. The physical properties of the obtained toner 24 are shown in Tables 5 and 6.

(Production example of toner 25)
Toner 25 was obtained in the same manner as in the production example of toner 1, except that toner particle 1 was changed to toner particle 11 and fatty acid metal salt 1 was changed to fatty acid metal salt 9. The physical properties of the obtained toner 25 are shown in Tables 5 and 6.

(Production example of toner 26)
Toner 25 was obtained in the same manner as in the production example of toner 1 except that toner particle 1 was changed to toner particle 13. The physical properties of the obtained toner 26 are shown in Tables 5 and 6.

(Production example of toner 27)
A toner 27 was obtained in the same manner as in the production example of the toner 1 except that the toner particles 1 were changed to the toner particles 13 and the fatty acid metal salt 1 was changed to the fatty acid metal salt 9. The physical properties of the obtained toner 27 are shown in Tables 5 and 6.

(Production example of toner 28)
A toner 28 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 12. The physical properties of the obtained toner 28 are shown in Tables 5 and 6.

(Production example of toner 29)
A toner 29 was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 13. The physical properties of the obtained toner 29 are shown in Tables 5 and 6.

(Production example of toner 30)
A toner was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 14. The physical properties of the obtained toner 30 are shown in Tables 5 and 6.

(Production example of toner 31)
A toner was obtained in the same manner as in the production example of the toner 1 except that the fatty acid metal salt 1 was changed to the fatty acid metal salt 15. The physical properties of the obtained toner 31 are shown in Tables 5 and 6.

<Example 1>
A toner cartridge of a tandem Canon laser beam printer LBP5500 having the configuration as shown in FIG. 7 was used, and 240 g of toner 1 was loaded. Then, an image having a printing ratio of 2% is obtained in an environment of low temperature and low humidity (15 ° C./15% RH), normal temperature and normal humidity (25 ° C./60% RH), and high temperature and high humidity (32 ° C./80% RH). Up to 1,000 sheets were printed out, and the solid image density was evaluated at the initial stage and when 15,000 sheets were output. The results are shown in Table 7. Next, the fixing evaluation was performed, and the results are also shown in Table 7.

<Fixing test>
Unfixed toner at a fixing speed of 100 to 260 ° C at 2.5 ° C intervals at a process speed of 200 mm / sec by a modified fixing device modified so that the fixing temperature of the laser beam printer LBP5500 made by Canon can be adjusted. The image (0.5 mg / cm ² ) was heated and pressed without oil on the image receiving paper (75 g / m ² ) to form a fixed image on the image receiving paper. The gloss value of the image in the fixed image area was measured using a handy gloss meter gloss checker (trade name IG-310, manufactured by HORIBA, Ltd.).

<Image density measurement>
Regarding the image density, using a Macbeth densitometer (RD-914; manufactured by Macbeth), using an SPI auxiliary filter, low temperature and low humidity (L / L) (15 ° C./15% RH), normal temperature and normal humidity (N / N) ) (25 ° C./60% RH) and high temperature and high humidity (H / H) (32 ° C./80% RH).

<Durable image density measurement>
An example in which the toner of the present invention is applied to a laser beam printer will be described below.

A toner cartridge of a tandem Canon laser beam printer LBP5500 having the configuration as shown in FIG. 7 was used, and 240 g of toner was loaded. Then, after being left for 15 days in an environment of low temperature and low humidity (15 ° C./15% RH), normal temperature and normal humidity (25 ° C./60% RH), and high temperature and high humidity (32 ° C./80% RH), the toner cartridge is placed. Then, up to 15,000 images with a printing ratio of 2% were printed out using recording paper (75 mg / cm ² ). Then, the evaluation of the solid image density at the initial stage and at the time of outputting 15,000 sheets was performed according to the following evaluation criteria.
Rank A: 1.30 or higher Rank B: 1.29 to 1.20
Rank C: 1.19 to 1.10
Rank D: 1.09 or less

<Development streak evaluation>
The development streak was evaluated according to the following criteria from a halftone image (toner applied amount 0.25 mg / cm ² ) obtained after printing 15,000 sheets.
A: A vertical streak in the paper discharge direction, which appears as a development streak, is not seen on the developing roller or the halftone image. There is no problem in practical use.
B: Although there are 1 to 5 thin circumferential streaks at both ends of the developing roller, no vertical streak in the paper discharge direction, which appears as a developing streak, is seen on the halftone image. There is no problem in practical use.
C: There are several thin circumferential streaks at both ends of the developing roller, and several fine developing streaks can be seen on the halftone image. However, there is no practical problem at the level that can be erased by image processing.
D: Many development streaks are seen on the developing roller and the halftone image, and cannot be erased by image processing.

<Fog>
The fog density (%) is calculated from the difference between the whiteness of the white portion of the printed image and the whiteness of the transfer paper measured by “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.), and the image fog is evaluated according to the following criteria. did.
A: Very good (less than 1.5%)
B: Good (1.5% or more, less than 2.5%)
C: Practical use possible (2.5% or more, less than 4.0%)
D: Not practical (4% or more)

<Measurement of ¹ H-NMR (nuclear magnetic resonance) spectrum>
The measurement was performed under the following conditions.

Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Data points: 32768
Frequency range: 10500Hz
Integration count: 10000 times Measurement temperature: 60 ° C
Sample: 50 mg of a measurement sample is put into a sample tube having a diameter of 5 mm, CDCl ₃ is added as a solvent, and this is dissolved in a constant temperature bath at 60 ° C. to prepare.

Determination of proton abundance ratio of methine group (—CH═CH—) derived from double bond by ¹ H-NMR measurement:
Intensity ratio between 4.6 to 4.9 ppm of methine group hydrogen (corresponding to 1H each) and 5.0 to 5.2 ppm of methine group hydrogen (corresponding to 1H each) in ¹ H-NMR spectrum, S _{4.6 to 4.9} / S _{5.0 to 5.2} is obtained.

A: With peak B: Without peak

<Example 2>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 2. The results are shown in Table 7.

<Example 3>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 3. The results are shown in Table 7.

<Example 4>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 4. The results are shown in Table 7.

<Example 5>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 5. The results are shown in Table 7.

<Example 6>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 6. The results are shown in Table 7.

<Example 7>
The same operation as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 7. The results are shown in Table 7.

<Example 8>
The same operation as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 8. The results are shown in Table 7.

<Example 9>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 9. The results are shown in Table 7.

<Example 10>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 10. The results are shown in Table 7.

<Example 11>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 11. The results are shown in Table 7.

<Example 12>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 12. The results are shown in Table 7.

<Example 13>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 13. The results are shown in Table 7.

<Example 14>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 14. The results are shown in Table 7.

<Example 15>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 15. The results are shown in Table 7.

<Example 16>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 16. The results are shown in Table 7.

<Example 17>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 17. The results are shown in Table 7.

<Comparative Example 1>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 18. The results are shown in Table 7.

<Comparative example 2>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 19. The results are shown in Table 7.

<Comparative Example 3>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 20. The results are shown in Table 7.

<Comparative example 4>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 21. The results are shown in Table 7.

<Comparative Example 5>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 22. The results are shown in Table 7.

<Comparative Example 6>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 23. The results are shown in Table 7.

<Comparative Example 7>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 24. The results are shown in Table 7.

<Comparative Example 8>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 25. The results are shown in Table 7.

<Example 18>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 26. The results are shown in Table 7.

<Comparative Example 9>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 27. The results are shown in Table 7.

<Example 19>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 28. The results are shown in Table 7.

<Example 20>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 29. The results are shown in Table 7.

<Example 21>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 30. The results are shown in Table 7.

<Example 22>
The same procedure as in Example 1 was performed except that the toner 1 of Example 1 was changed to the toner 31. The results are shown in Table 7.

It is a figure which shows the methanol aqueous solution dripping transmittance | permeability curve of the fatty-acid metal salt of this invention. It is a figure which shows the methanol aqueous solution and diacetone alcohol aqueous solution dripping transmittance | permeability curve of the toner of this invention. It is a figure which shows the chart of the molecular weight distribution measured by GPC of the THF soluble part of the toner of this invention. In the chart of FIG. 1, it is a figure which shows the chart of molecular weight distribution when converting the height of a peak into h (M1) [mV] = 1.00. In the chart of FIG. 2, integrated values S1, S2, and S3 of three molecular weight regions are shown. It is a figure which shows the reversing heat flow curve measured by the differential scanning calorimeter (DSC) of the toner of this invention. 1 is a schematic configuration diagram illustrating an example of a process cartridge and an image forming apparatus of the present invention.

Explanation of symbols

5: photoreceptor 6: developing roller 7: toner supply roller 8: toner 9: regulating blade 10: developing device 11: laser beam 12: charging device 13: cleaning device 14: cleaning charging device 15: fixing device 16: driving roller 17: transfer roller 18: bias power source 19: tension roller 20: transfer conveyance belt 21: driven roller 22: paper 23: paper feed roller 24: suction roller

Claims (21)

In a toner having at least a binder resin, a colorant, and a wax, and a toner having a fatty acid metal salt,
When the wettability of the fatty acid metal salt with respect to a mixed solvent of methanol and water is measured by the transmittance of light having a wavelength of 780 nm, and the methanol concentration when the transmittance is A% is DSme (A) volume%, DSme (A 90) -DSme (10) ≦ 7.00, the wettability of the toner with respect to the mixed solvent of methanol and water is measured by the transmittance of light having a wavelength of 780 nm, and the methanol when the transmittance is 50% A toner having a density of 15.0 ≦ DTme (50) ≦ 80.0 when the density is DTme (50) volume%.   When the wettability of the fatty acid metal salt to a mixed solvent of methanol and water was measured by the transmittance of light having a wavelength of 780 nm, the DSme (A) volume% when the methanol concentration when the transmittance was A% was DSme The toner according to claim 1, wherein (90) −DSme (10) ≦ 5.0.   The toner according to claim 1, wherein the toner contains 0.5 to 3.5 parts by mass of an inorganic fine powder with respect to 100 parts by mass of toner particles.   When the wettability of the toner with respect to the mixed solvent of methanol and water of the toner is measured by the transmittance of light having a wavelength of 780 nm, when the methanol concentration when the transmittance is 50% is DTme (50) volume%, 30 The toner according to claim 1, wherein 0.0 ≦ DTme (50) ≦ 70.0.   When the wettability of the fatty acid metal salt with respect to the mixed solvent of methanol and water was measured by the transmittance of light having a wavelength of 780 nm, when the methanol concentration when the transmittance was A% was DSme (A) volume%, 62 The toner according to claim 1, wherein ≦ DSme (50).   6. The fatty acid metal salt has a volume average particle diameter (Dvs) of 0.15 μm or more and 0.65 μm or less, and a volume-based variation coefficient of 50 or less. The toner described in 1.   The toner according to claim 1, wherein a liberation rate of the fatty acid metal salt is 1.0% or more and 25.0% or less. The toner according to any one of claims 1 to 7, wherein the following equation is satisfied, where A is a coefficient of variation based on the number of toners and B is a coefficient of variation based on the volume of the fatty acid metal salt.
Formula 0.55 ≦ (A / B) ≦ 0.90   The toner according to claim 1, wherein the toner contains a nonionic surfactant.   The toner according to claim 1, wherein the nonionic surfactant is an ether type surfactant.   The toner according to claim 1, wherein the nonionic surfactant has an HLB value in a range of 5.0 to 15.0.   The nonionic surfactant is selected from the group consisting of polyoxyethylene alkyl ethers, polyalkylene alkyl ethers, and polyoxyethylene alkyl phenyl ethers. The toner described.   The toner according to claim 12, wherein the content of the polyoxyethylene alkyl ether, polyalkylene alkyl ether, and polyoxyethylene alkyl phenyl ether in the fatty acid metal salt composition is 10 to 500 ppm.   When the wettability of the toner with respect to the mixed solvent of methanol and water is measured by the transmittance of light having a wavelength of 780 nm, the methanol concentration when the transmittance is 50% is DTme (50) volume%, and diacetone alcohol is used. In addition, when the wettability of the toner with respect to the mixed solvent of water and the transmittance of light having a wavelength of 780 nm is measured, when the diacetone alcohol concentration when the transmittance is 50% is DTdaa (50) volume%, 15.0 The toner according to claim 1, wherein ≦ DTme (50) −DTdaa (50) ≦ 60.0.   In the endothermic chart measured by differential scanning calorimetry (DSC) of the toner, a heat quantity integral value Q expressed by an endothermic area in the range of 40 to 130 ° C. is 10 to 35 J per 1 g of toner. Item 15. The toner according to any one of Items 1 to 14.   The toner according to claim 1, wherein the toner has a viscosity at 100 ° C. of 5000 to 40000 Pa · s as measured by a flow tester heating method.   The average circularity of toner particles having a weight average particle diameter of 2 μm or more is 0.970 or more and 1.000 or less, and the mode circularity is 0.98 or more and 1.00 or less. Item 17. The toner according to any one of Items 1 to 16.   The toner according to claim 1, wherein the toner has a weight average molecular weight of 15,000 to 80,000.   In the molecular weight distribution chart measured by gel permeation chromatography (GPC) of tetrahydrofuran (THF) soluble matter of the toner, the molecular weight height when the molecular weight of the main peak is M1 is H (M1), When the molecular weight height of a molecular weight of 4,000 is H (4,000), H (4,000) and H (M1) are H (4,000): H (M1) = (0.100 to 0 .950): 1.00 is satisfied, The toner according to any one of claims 1 to 18, wherein:   In the chart of molecular weight distribution measured by GPC of tetrahydrofuran (THF) soluble matter in the toner, the integrated value (S1) in the region where the molecular weight is 300 to 2,000 and the region where the molecular weight is 2,000 to 15,000. The ratio of the integral value (S2) and the integral value (S3) in the region having a molecular weight of 15,000 to 1,000,000 is S1: S2: S3 = (0.01 to 0.95): 1.00 The toner according to claim 1, wherein the toner is (1.00 to 8.00).   21. The toner according to claim 1, wherein the toner contains 0.01 to 15.00 parts by mass of a sulfur element-containing polymer per 100 parts by mass of the binder resin.

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