JP4290050B2 - Yellow toner and image forming method - Google Patents

Description

  The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, a magnetic recording method, a toner jet method, and the like, and an image forming method. More specifically, the present invention relates to a yellow toner used in an image recording apparatus that can be used in a copying machine, a printer, a facsimile, a plotter, and the like, and an image forming method.

  In recent years, color images have been widely used and demands for higher image quality have been increasing. In digital full-color copiers and printers, a color image original is color-separated with B (blue), G (green), and R (red) color filters, and then a latent image having a dot diameter of 20 μm to 70 μm corresponding to the original image. The image is developed using Y (yellow), M (magenta), C (cyan), and Bk (black) developers. Therefore, the colorant in each color developer greatly affects the image quality.

  In the paint field, yellow colorants are required to have high hiding power and high coloring power in order to give an impression equivalent to other colors to human sensitivity, and colorants having a large primary particle diameter have been used in many cases. . On the other hand, in the toner field, as an important element of the colorant added to the toner, not only the coloring power but also the transparency is good.

  There are various factors that deteriorate the transparency, but various proposals have been made to improve the transparency by reducing the dispersed particle diameter of the colorant in the toner. Pigment-based colorants have a limit in reducing the dispersed particle size in the toner, whereas dye-based colorants have excellent dispersibility, and it is known that good transparency can be obtained. (For example, see Patent Documents 1 and 2).

  However, when a dye is used, the dye adheres to the fixing member at the time of heat fixing, and image smearing occurs due to contamination at the fixing portion.

  For this reason, for example, a method has been proposed in which oil is applied to a fixing member such as a fixing roller or a sheet to suppress image smearing due to contamination of the fixing portion (for example, see Patent Document 3). On the other hand, depending on the dye used, there is a problem that the dye has a high affinity for the fixing oil, so that there is a problem that dyeing to a fixing roller or the like is likely to occur. There has been proposed a toner manufacturing method that does not require fixing oil, such as attaching and obtaining toner (see, for example, Patent Document 4).

  By the way, conventionally, as a method of developing an electrostatic image with toner in order to form a full-color image, a two-component development method using a mixture of toner and carrier has been common.

  However, in recent years, non-magnetic one-component development in which toner is charged using a toner application blade or a toner supply roller in contact with a toner carrier as a development method due to demands for reduction in size, weight, and cost of the apparatus. A method has been proposed and implemented. In such a non-magnetic one-component developing method, a large mechanical stress (friction, impact, etc.) is applied to the toner, so that the toner is liable to be deteriorated, and when a dye is used, member contamination occurs. On the other hand, it has been proposed that the contamination of the member with the dye can be suppressed by controlling the type and amount of the wax component contained (see, for example, Patent Document 5).

JP 61-112160 A Japanese Patent Laid-Open No. 7-20651 JP-A-8-234612 JP 7-56390 A Japanese Unexamined Patent Publication No. 2000-105485

  In recent years, digital full-color copiers and printers are often used in the output of text documents in the office, and there is a demand for images with reduced gloss that can be obtained by oilless fixing. It is often used, and an appropriate gloss level is required to obtain a beautiful image close to a photograph. For this reason, the toner is required to have an appropriate softness that gives an appropriate gloss to the fixed image.

  However, in the prior art, when a dye is used as a colorant for the toner, a toner having an appropriate hardness is used to suppress contamination of the member. I can't get it.

  As described above, a yellow toner that is excellent in transparency and coloring power, and that can achieve both suppression of member contamination and image glossiness has not been obtained.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a toner that solves the above-mentioned problems of the prior art.

  That is, an object of the present invention is to provide a yellow toner excellent in transparency and coloring power, and an image forming method.

  Furthermore, an object of the present invention is to provide a yellow toner exhibiting excellent durability free from member contamination, and an image forming method.

  Furthermore, an object of the present invention is to provide a yellow toner and an image forming method capable of obtaining a beautiful fixed image close to a photograph having an appropriate glossiness.

In order to achieve the above object, the present invention provides a yellow toner containing at least a binder resin, a colorant, and a wax component,
As the colorant, C.I. I. Solvent Yellow 162, C.I. I. Solvent Yellow 163, C.I. I. Disperse Yellow 54, and C.I. I. Containing any dye selected from the group consisting of Disperse Yellow 64;
When the mass of the colorant extracted from 0.1 g / liter of a sodium hydroxide aqueous solution from 1 g of the toner is A (mg),
0.2 ≦ A ≦ 4.0
Satisfied,
The toner has a storage elastic modulus G ′ (140 ° C.) at 140 ° C. of 2.0 × 10 ³ dN / m ² or more and less than 2.0 × 10 ⁴ dN / m ² .
The present invention relates to a yellow toner characterized in that the temperature when the viscosity of the toner by a flow tester temperature rising method is 1.0 × 10 ³ Pa · s is 115 ° C. or more and less than 130 ° C.

  In addition, the present invention uses a one-component developing device including a toner application blade and a toner supply roller that are in contact with a toner carrier, and uses a static image formed on a latent image carrier having a charging member that contacts the surface. The present invention relates to an image forming method for developing a charge image with toner, wherein the toner is used with the yellow toner.

  According to the present invention, C.I. I. In yellow toners using dyes such as Solvent Yellow 162, the transparency and coloring power peculiar to dyes are maintained by defining the amount of colorant extracted with an aqueous sodium hydroxide solution and the range of thermal properties of the toner. At the same time, it is possible to provide a yellow toner and an image forming method capable of producing a fixed image having excellent durability with no member contamination and having an appropriate glossiness.

  Hereinafter, the present invention will be described in detail.

As a result of intensive studies, the present inventors have at least a yellow toner containing a binder resin, a colorant, and a wax component,
As the colorant, C.I. I. Solvent Yellow 162, C.I. I. Solvent Yellow 163, C.I. I. Disperse Yellow 54, and C.I. I. Containing any dye selected from the group consisting of Disperse Yellow 64;
When the mass of the colorant extracted from 0.1 g / liter of a sodium hydroxide aqueous solution from 1 g of the toner is A (mg),
0.2 ≦ A ≦ 4.0
Satisfied,
The toner has a storage elastic modulus G ′ (140 ° C.) at 140 ° C. of 2.0 × 10 ³ dN / m ² or more and less than 2.0 × 10 ⁴ dN / m ² .
Transparency peculiar to a dye by using a yellow toner characterized in that the temperature when the viscosity of the toner by a flow tester temperature rising method is 1.0 × 10 ³ Pa · s is 115 ° C. or more and less than 130 ° C. In addition, the present inventors have found that a fixed image having an appropriate glossiness can be obtained while maintaining the coloring power and exhibiting excellent durability without contamination of the members.

  When a dye is used as a colorant, particularly in a non-magnetic one-component development method in which the toner is charged using a toner coating blade or a toner supply roller in contact with the toner carrier, a large mechanical stress (friction) is applied to the toner. , Impact, etc.), toner deterioration is likely to occur, and member contamination is likely to occur. In particular, a toner having thermal characteristics for obtaining a fixed image having an appropriate glossiness as in the present invention is likely to adhere to various members, particularly a charging member and a photosensitive drum, so that the contamination of the member is deteriorated. However, it has been found that the contamination of the components can be effectively suppressed by regulating the amount of dye extracted by the aqueous sodium hydroxide solution. The reason is not clear, but it is presumed that the above problem could be alleviated because the free dye presumed to be the cause of the component contamination and the toner free matter dyed with the dye could be reduced.

  The yellow toner of the present invention contains C.I. I. Solvent Yellow 162, C.I. I. Solvent Yellow 163, C.I. I. Disperse Yellow 54, C.I. I. Contains any dye selected from Disperse Yellow 64. The dye is excellent in coloring power, transparency, and color, and has high affinity with the wax component. Therefore, depending on the production conditions of the toner, it can be easily included in the toner. Used as a colorant for the yellow toner of the invention.

  Among the above dyes, C.I. I. Solvent Yellow 162 is excellent in compatibility with a binder resin, a wax component, and the like, and is most preferably used in terms of coloring power, transparency, and color.

The yellow toner of the present invention has a storage elastic modulus G ′ (140 ° C.) at 140 ° C. of 2.0 × 10 ³ dN / m ² or more and less than 2.0 × 10 ⁴ dN / m ^2. The temperature at which the toner viscosity becomes 1.0 × 10 ³ Pa · s is 115 ° C. or more and less than 130 ° C.

By setting G ′ (140 ° C.) to 2.0 × 10 ³ dN / m ² or more and less than 2.0 × 10 ⁴ dN / m ² , the thermal characteristics in the binder part of the toner are preferable. I can do it. Specifically, it is possible to obtain a toner having excellent toner offset resistance in addition to image glossiness. When G ′ (140 ° C.) is less than 2.0 × 10 ³ dN / m ² , the offset resistance is poor. On the other hand, when G ′ (140 ° C.) exceeds 2.0 × 10 ⁴ dN / m ² , an image having low image gloss and unevenness is obtained.

  In the present invention, G ′ (140 ° C.) is determined by the following method.

ARES (Rheometric Scientific F.E. Co., Ltd.) was used as a measuring device. Under the following conditions, the storage elastic modulus G ′ in the temperature range of 60 to 200 ° C. was measured.
Measurement jig: Use a circular parallel plate with a diameter of 8 mm. A shallow cup corresponding to the circular parallel plate is used on the actuator side. The gap between the bottom of the shallow cup and the circular plate is about 2 mm.
・ Measurement sample: Toner is used after being pressure-molded to form a disk-shaped sample having a diameter of about 8 mm and a height of about 2 mm.
-Measurement frequency: 6.28 radians / second-Measurement distortion setting: After setting the initial value to 0.1%, measurement is performed in automatic measurement mode.
-Sample extension correction: Adjust in automatic measurement mode.
Measurement temperature: The temperature is raised from 60 to 200 ° C. at a rate of 2 ° C. per minute.

  The storage elastic modulus G ′ at 140 ° C. when the storage elastic modulus G ′ was measured in the temperature range of 60 to 200 ° C. by the above method was defined as G ′ (140 ° C.).

On the other hand, by adjusting the measurement temperature when the viscosity of the toner by the flow tester temperature rising method is 1.0 × 10 ³ Pa · s to 115 ° C. or more and less than 130 ° C., the toner taking into account the influence of the wax component and the colorant The overall thermal characteristics can be made favorable. More specifically, it is possible to obtain a toner having excellent storage stability, durability stability, and resistance to peeling of a fixed image.

If the temperature at which the toner viscosity is 1.0 × 10 ³ Pa · s by the flow tester heating method is less than 115 ° C., a preferable image excellent in image glossiness can be obtained in the initial image, but storage is possible. The toner is inferior in durability and durability. On the other hand, when the temperature exceeds 130 ° C., the toner particles cannot be sufficiently deformed during the fixing process in high-speed printing, and an image having an inferior anchor effect on the recording material is obtained.

  In addition, the numerical value in this invention is calculated | required with the following method.

As an apparatus, a flow tester CFT-500D (manufactured by Shimadzu Corporation) was used, and measurement was performed under the following conditions.
Sample: About 1.1 g of toner was weighed and molded with a pressure molding machine to prepare a sample.
-Die hole diameter: 0.5mm
-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 of the toner at 50 to 200 ° C. was measured, and the measurement temperature when the viscosity was 1.0 × 10 ³ Pa · s was determined.

In the yellow toner of the present invention, when the mass of the colorant extracted from 0.1 g / liter of a sodium hydroxide aqueous solution from 1 g of the toner is A (mg),
0.2 ≦ A ≦ 4.0
Satisfied.

  A is the mass of the colorant present on the toner surface per gram of toner. By satisfying 0.2 ≦ A ≦ 4.0 in the binder properties of the toner of the present invention, it becomes possible to achieve both contamination of the member and long-term durability and high fixability with long-term durability. If A is less than 0.2, sufficient coloring power cannot be obtained, resulting in a poor image. On the other hand, when A exceeds 4.0, contamination of the charging member and the photosensitive drum is remarkably deteriorated and durability is lowered.

  The yellow toner of the present invention contains an oxycarboxylic acid represented by the following formula [1] and a polar resin having a sulfur atom, which leads to good dispersibility and charging characteristics of the colorant, Since transparency and coloring power are improved with good balance, it is preferable.

〔上記式［１］中、（Ａｒ）は下記の群より選ばれ、Ｘ₁は、水素原子、ナトリウム原子、カリウム原子、アンモニウム又は脂肪族アンモニウムを示す。〕

[In the above formula [1], (Ar) is selected from the following group, and X ₁ represents a hydrogen atom, a sodium atom, a potassium atom, ammonium or aliphatic ammonium. ]

  Examples of the resin having a sulfur atom used in the present invention include a polymer having a sulfonic acid group, and in particular, a sulfonic acid group-containing (meth) acrylamide monomer is 2% by mass or more, preferably 5% by mass. And / or styrene and / or styrene having a glass transition temperature (Tg) of 40 to 90 ° C. and a peak molecular weight of 10,000 to 30,000, preferably a weight average molecular weight of 25,000 to 40,000. Examples thereof include a polymer compound composed of a (meth) acrylic acid copolymer. When this is used, preferred charging characteristics can be enjoyed without affecting the thermal characteristics required of the toner particles. Further, since the charge control agent contains a sulfonic acid group, the dispersibility of the charge control agent itself in the binder resin and the dispersibility of the colorant are improved, and coloring power, transparency, and charging characteristics are improved. Significantly improved.

  As said sulfonic acid group containing (meth) acrylamide type monomer, what is represented by following General formula [2] is preferable, and 2-acrylamide-2-methylpropanoic acid and 2-methacrylamide-2 are specifically mentioned. -Methyl propanoic acid etc. are mentioned.

〔上記一般式［２］中、Ｒ₄は水素原子、又はメチル基を示し、Ｒ₅とＲ₆は、それぞれ水素原子、Ｃ₁〜Ｃ₁₀のアルキル基、アルケニル基、アリール基、又はアルコキシ基を示し、ｎは１〜１０の整数を示す。〕

[In the general formula [2], R ₄ represents a hydrogen atom or a methyl group, and R ₅ and R ₆ represent a hydrogen atom, a C _{1 to} C ₁₀ alkyl group, an alkenyl group, an aryl group, or an alkoxy group, respectively. N represents an integer of 1-10. ]

In the yellow toner of the present invention, when the mass of oxycarboxylic acid extracted from 0.1 g / liter of a sodium hydroxide aqueous solution in 1 g of toner is B (mg), the colorant mass A (mg) In relation
0.10 ≦ A / B ≦ 8.0
Is preferably satisfied. When A / B is less than 0.10, the environmental charging characteristics become unstable, and the contamination of the charging member and the photosensitive drum worsens, which is not preferable. When A / B exceeds 8.0, sufficient toner charging characteristics cannot be obtained, which is not preferable.

  In the yellow toner of the present invention, the colorant is preferably 1.0 to 6.5 parts by mass per 100 parts by mass of the binder resin. If it is less than 1.0 part by mass, sufficient coloring power cannot be obtained, which is not preferable. On the other hand, if it exceeds 6.5 parts by mass, the charging member and the photosensitive drum are contaminated and the charging characteristics are deteriorated, which is not preferable.

  The yellow toner of the present invention includes the dye used in the present invention and C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 155, C.I. I. Any pigment selected from Pigment Yellow 74 may be used in combination. I. It is preferable to use together Pigment Yellow 93. Use of the pigment in combination is preferable from the viewpoint of improving light resistance and stabilizing the charging of the toner.

  In the yellow toner of the present invention, the mass ratio of the content of the dye and pigment used as the colorant is preferably 20:80 to 80:20. By the above ratio, the dispersibility of the pigment can be further enhanced by the excellent compatibility effect of the dye used in the present invention to the binder resin, and more stable charging characteristics and good transparency can be obtained. Obtainable. In addition, the high dispersibility in the binder resin produced by the combined use of the colorant makes it possible to effectively exude the wax component at the time of image fixing. A fixed image having a degree can be obtained.

  When the ratio of the dye is less than 20, sufficient coloring power cannot be obtained, and satisfactory saturation cannot be obtained. On the other hand, if the ratio of the dye exceeds 80, it tends to cause harmful effects such as a decrease in light resistance and charging stability and contamination of members.

  The yellow toner of the present invention preferably has an average circularity of 0.950 to 0.995 from the viewpoint of excellent transferability.

  The average circularity in the present invention is used as a simple method for quantitatively expressing the shape of the particles. In the present invention, the average circularity is measured using a flow type particle image analyzer “FPIA-1000” manufactured by Toa Medical Electronics. The circularity (ai) of each particle measured for a particle group having a circle-equivalent diameter of 3 μm or more was determined by the following equation (1), and the circularity of all particles measured as shown by the following equation (2): The value obtained by dividing the sum of degrees by the total number of particles (m) is defined as the average circularity (a).

  Further, the mode circularity means that the circularity is divided into 61 parts every 0.01 from 0.40 to 1.00, and the measured circularity of each particle is assigned to each divided range, and the frequency value in the circularity frequency distribution. Is the maximum circularity of the peak.

  In addition, “FPIA-1000”, which is a measuring apparatus used in the present invention, calculates the circularity of each particle, and then calculates the average circularity and the mode circularity. A calculation method is used in which 0.40 to 1.00 is divided into 61 classes, and the average circularity and mode circularity are calculated using the center value and frequency of the dividing points. However, the errors with the average circularity and mode circularity values calculated by this calculation formula are very small and can be substantially ignored.In the present invention, the calculation time can be shortened and For reasons of handling data such as simplification of the calculation formula, such a calculation formula partially modified by using the concept of the calculation formula that directly uses the circularity of each particle described above may be used.

  Measuring means are as follows. A dispersion is prepared by dispersing 5 mg of the developer in 10 ml of water in which about 0.1 mg of the surfactant is dissolved, and the dispersion is irradiated with ultrasonic waves (20 KHz, 50 W) for 5 minutes. Measurement is performed with the above apparatus at 20,000 particles / μl, and average circularity and mode circularity of a particle group having a circle-equivalent diameter of 3 μm or more are obtained.

  The average circularity in the present invention is an index of the degree of unevenness of the developer, and is 1.000 when the developer is a perfect sphere, and the circularity becomes smaller as the surface shape becomes more complicated.

  In this measurement, the reason why the circularity is measured only for the particle group having an equivalent circle diameter of 3 μm or more is that the particle group of the external additive existing independently of the toner particles in the particle group having an equivalent circle diameter of less than 3 μm. This is because the circularity of the toner particle group cannot be accurately estimated due to the influence of such a large amount.

  The yellow toner of the present invention preferably has a weight average particle diameter D4 of 3 to 10 μm. In a toner having a weight average particle size of less than 3 μm, the transfer residual toner on the photoconductor increases due to a decrease in transfer efficiency. Furthermore, in addition to an increase in the entire surface area of the toner, the fluidity and agitation as a powder decrease, and it becomes difficult to uniformly charge individual toner particles, so fog and transferability tend to deteriorate, This is not preferable because it tends to cause uneven image unevenness. When the weight average particle diameter of the toner exceeds 10 μm, the characters and line images are likely to be scattered and high resolution is difficult to obtain. Furthermore, as the device becomes higher in resolution, the reproduction of one dot tends to deteriorate.

  The weight average particle diameter and number average particle diameter of the toner of the present invention can be measured by various methods such as Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Inc.). Specifically, it can be measured as follows. Using Coulter Multisizer (manufactured by Coulter), an interface (manufactured by Nikka) and PC9801 personal computer (manufactured by NEC) for outputting number distribution and volume distribution were connected, and the electrolyte was 1% NaCl using first grade sodium chloride. Adjust the aqueous solution. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. The measurement procedure is as follows. 100 to 150 ml of the electrolytic aqueous solution is added, and 2 to 20 mg of a measurement sample is further added. The electrolyte in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number distribution of toner particles of 2 μm or more are measured by using the aperture with the Coulter Multisizer. And calculate. Then, the volume-based weight average particle diameter (D4) obtained from the volume distribution according to the present invention and the number-based average particle diameter obtained from the number distribution, that is, the number average particle diameter (D1) are obtained.

  The yellow toner of the present invention contains a binder resin as an essential component. Examples of the binder resin for the toner used in the present invention include commonly used styrene- (meth) acrylic copolymers, polyester resins, epoxy resins, and styrene-butadiene copolymers. In a method for directly obtaining toner particles by a polymerization method, a monomer for forming them is used. Specifically, styrene; styrene monomers such as o- (m-, p-) methylstyrene, m- (p-) ethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, acrylic acid Propyl, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acryl (Meth) acrylic acid ester monomers such as dimethylaminoethyl acrylate and diethylaminoethyl (meth) acrylate; ene monomers such as butadiene, isoprene, cyclohexene, (meth) acrylonitrile and acrylamide are preferably used. . These may be used alone or in general so that the theoretical glass transition temperature (Tg) described in the publication Polymer Handbook 2nd edition III-p139-192 (John Wiley & Sons) is 40-75 ° C. It is used by appropriately mixing the monomer. When the theoretical glass transition temperature is less than 40 ° C., problems are likely to occur from the viewpoint of storage stability and durability stability of the toner, whereas when it exceeds 75 ° C., the transparency of the OHP image is lowered.

  The yellow toner of the present invention has a wax component as an essential component. Specific examples of the wax component used in the present invention include paraffin wax, microcrystalline wax, petroleum wax such as petrolactam and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof according to the Fischer-Tropsch method, Polyolefin waxes typified by polyethylene and derivatives thereof, natural waxes such as carnauba wax and candelilla wax, and derivatives thereof include oxides, block copolymers with vinyl monomers, and graft modified products. included. Examples thereof include alcohols such as higher aliphatic alcohols; aliphatics such as stearic acid and palmitic acid or compounds thereof; acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, and animal waxes. These can be used alone or in combination. The release agent used in the present invention has a main endothermic peak temperature (melting point) in a DSC curve measured according to “ASTM D3418-82” in the range of 30 to 120 ° C., more preferably in the range of 40 to 90 ° C. A compound is preferable because it can improve the fixing property and further the transparency.

  As a method for producing the toner according to the present invention, a resin containing a binder resin, a colorant, a wax component or the like is melt-kneaded with a pressure kneader or the like, and the cooled kneaded product is finely adjusted to a desired toner particle size. A pulverization method in which a finely pulverized product is further classified to adjust the particle size distribution to obtain a toner; described in JP-B-36-10231, JP-A-59-53856, and JP-A-59-61842 A direct toner production method using a suspension polymerization method; a spherical toner is produced by atomizing a melt-kneaded product in air using a disk or a multi-fluid nozzle described in JP-B-56-13945 A known method such as an emulsion polymerization method represented by a soap-free polymerization method can be used, but in order to precisely control the particle shape of the toner satisfying the above conditions, a suspension is used. Polymerization method Ri are desirably prepared in water.

  Control of the amount of colorant and oxycarboxylic acid extracted with a 0.1 mol / liter sodium hydroxide aqueous solution of the yellow toner of the present invention, the weight average particle diameter of the toner and the average circularity of the toner is controlled by a suspension polymerization method. In the toner production method according to the method, it is possible to adjust the pH of the aqueous dispersion medium during the polymerization reaction from the granulation step to the polymerization step.

  The amount of the colorant and the amount of oxycarboxylic acid extracted by the 0.1 mol / liter sodium hydroxide aqueous solution of the yellow toner of the present invention can also be controlled by adjusting the temperature and time of the drying process.

  The toner produced by the suspension polymerization method is prepared by mixing a binder resin, a colorant, a wax component, a polymerization initiator and the like to prepare a polymerizable monomer composition. It is produced by dispersing in a medium to produce particles of a polymerizable monomer composition, and polymerizing styrene monomer in the particles of the polymerizable monomer composition in an aqueous medium.

  In the present invention, a polar resin such as a polyester resin or a polycarbonate resin can be used in combination with the above-described binder resin.

  For example, when a toner is directly produced by suspension polymerization or the like, when a polar resin is added during the polymerization reaction from the dispersion step to the polymerization step, a polymerizable monomer composition that becomes toner particles and an aqueous dispersion medium are exhibited. Depending on the balance of polarity, the added polar resin can be controlled to form a thin layer on the surface of the toner particles or to have a gradient from the toner particle surface toward the center. At this time, by using a polar resin having an interaction with the colorant, it is possible to make the presence state of the colorant in the toner a desirable form.

  The addition amount of the polar resin is preferably 1 to 25 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the binder resin. If the amount is less than 1 part by mass, the presence state of the polar resin in the toner particles becomes non-uniform. Conversely, if the amount exceeds 25 parts by mass, the thin layer of the polar resin formed on the surface of the toner particles becomes thick.

  Specific examples of the polar resin used in the present invention include polyester resins, epoxy resins, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and styrene-maleic acid copolymers. In particular, a polyester resin having a peak molecular weight of 3,000 to 10,000 is preferable because it can improve the fluidity, negative triboelectric charging characteristics, and transparency of toner particles.

  Furthermore, in the present invention, it is preferable to use a crosslinking agent during the synthesis of the binder resin in order to increase the mechanical strength of the toner particles and control the molecular weight of the toner molecules.

  As the crosslinking agent used in the present invention, difunctional linking agents such as 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 Japan Drugs), and include those instead dimethacrylate above diacrylate.

  Polyfunctional crosslinkers include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy, polyethoxy Phenyl) propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and triallyl trimellitate. These crosslinking agents are preferably used in an amount of 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the monomer.

  The toner of the present invention may contain a charge control agent in order to stabilize the charge characteristics. As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable. Further, when the toner is produced using a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable. However, it is not essential to add a charge control agent to the toner of the present invention, and the toner does not necessarily contain a charge control agent by actively utilizing frictional charging with the toner layer thickness regulating member or the toner carrier. There is no need to let it.

  When the toner of the present invention is produced by suspension polymerization, specific examples of the polymerization initiator include 2,2′-azobis- (2,4-dimethylvaleronitrile) and 2,2′-azobisiso. Azo or diazo such as butyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile Polymerization initiators; peroxide polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, tert-butyl-peroxypivalate are used . Although the usage-amount of these polymerization initiators changes with the target degree of polymerization, generally 3-20 mass parts is used with respect to 100 mass parts of polymerizable vinylic monomers. The kind of the polymerization initiator varies slightly depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

  When the toner of the present invention is produced by the suspension polymerization method, known inorganic and organic dispersants can be used as the dispersant used when preparing the aqueous dispersion medium. Specifically, as the inorganic dispersant, for example, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, Examples include calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. Examples of organic dispersants that can be used include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, carboxymethylcellulose sodium salt, and starch.

  Commercially available nonionic, anionic and cationic surfactants can also be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate can be used.

  When the toner of the present invention is produced by the suspension polymerization method, the inorganic dispersant is preferably a water-insoluble dispersant as the dispersant used in preparing the aqueous dispersion medium, and the acid-soluble inorganic water-soluble inorganic dispersant. Should be used. Moreover, in this invention, when preparing a water-based dispersion medium using a slightly water-soluble inorganic dispersing agent, these dispersing agents are 0.2-2. It is preferable to use it in such a ratio that it becomes 0 parts by mass. Moreover, in this invention, it is preferable to prepare an aqueous dispersion medium using 300-3,000 mass parts water with respect to 100 mass parts of polymerizable monomer compositions.

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

  In the toner of the present invention, a charge control agent can be mixed with toner particles and used as necessary. This technique also makes it possible to control the optimum triboelectric charge amount according to the development system.

  In the toner of the present invention, it is also a very preferable usage form that an inorganic fine powder having an average primary particle diameter of 4 to 80 nm is added as a fluidizing agent in an amount of 0.1 to 4% by mass relative to the whole toner. Inorganic fine powder is added to improve the fluidity of the toner and to make the toner base particles evenly charged. However, the inorganic chargeable powder is treated to make it hydrophobic and adjust the toner charge amount and improve the environmental stability. It is also preferable to provide such functions.

  When the average primary particle size of the inorganic fine powder is larger than 80 nm, good toner fluidity cannot be obtained, and the toner particles are likely to be non-uniformly charged, and the triboelectric chargeability under low humidity is not uniform. Therefore, problems such as an increase in fog, a decrease in image density, and a decrease in durability cannot be avoided. When the average primary particle size of the inorganic fine powder is smaller than 4 nm, the cohesiveness between the inorganic fine particles is increased, and the aggregate is not a primary particle but an aggregate having a wide particle size distribution having a strong cohesive property that is difficult to break even by crushing treatment. It is easy to behave, and image defects due to development of the aggregate, damage to the image carrier or toner carrier, and the like are likely to occur. In order to make the charge distribution of the toner particles more uniform, the average primary particle size of the inorganic fine powder is preferably 6 to 35 nm.

  The average primary particle diameter of the inorganic fine powder is a photograph of the toner magnified by a scanning electron microscope, and is further mapped with the elements contained in the inorganic fine powder by an elemental analysis means such as XMA attached to the scanning electron microscope. It can be measured by measuring 100 or more primary particles of inorganic fine powder that are attached to or detached from the toner surface and obtaining the number average diameter while contrasting the photograph of the toner.

  The content of the inorganic fine powder can be quantified using a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

  As the inorganic fine powder to be added to the toner of the present invention, fine powder such as silica, titanium oxide, alumina or their double oxides can be used. Of the titanium oxides, titania is particularly preferable.

For example, as the silica, both a so-called dry method produced by vapor phase oxidation of silicon halide or a dry silica called fumed silica, and a so-called wet silica produced from water glass or the like can be used. Dry silica is preferred because it has less silanol groups on the surface and in the silica fine powder and less production residue such as Na ₂ O, SO ₃ ^2- . In dry silica, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. Is also included.

  The addition amount of such inorganic fine powder having an average primary particle size of 4 to 80 nm is preferably 0.1 to 4.0 parts by mass with respect to 100 parts by mass of the toner base particles, and the addition amount is 0.1. If the amount is less than part by mass, the effect is not sufficient.

  The inorganic fine powder is preferably hydrophobized from the viewpoint of improving characteristics in a high humidity environment. When the inorganic fine powder added to the toner absorbs moisture, the charge amount as the toner is remarkably lowered, and the developability and transferability are easily lowered.

  As treatment agents for hydrophobic treatment, treatment agents such as silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds, and organic titanium compounds may be used alone or in combination. And may be processed.

  Among them, inorganic fine powder treated with silicone oil is preferable, and more preferably, the inorganic fine powder treated with silicone oil at the same time or after hydrophobizing treatment can increase the charge amount of toner particles even in a high humidity environment. It is good for maintaining high and reducing selective developability.

  The processing conditions for the inorganic fine powder include, for example, a silylation reaction as the first stage reaction to eliminate active hydrogen groups on the surface by chemical bonding, and then a hydrophobic thin film is formed on the surface with silicone oil as the second stage reaction. can do. As a usage-amount of a silylating agent, 5-50 mass parts is preferable with respect to 100 mass parts of inorganic fine powder. If it is less than 5 parts by mass, it is not sufficient to eliminate the active hydrogen groups on the surface of the inorganic fine particles, and if it exceeds 50 parts by mass, the siloxane compound produced by the reaction of the excess silylating agent serves as a paste to serve as the inorganic fine particles. Aggregation occurs and image defects are likely to occur.

The silicone oil preferably has a viscosity at 25 ° C. of 10 to 200,000 mm ² / s, and more preferably 3,000 to 80,000 mm ² / s. If it is less than 10 mm ² / s, the inorganic fine powder is not stable, and the image quality tends to deteriorate due to heat and mechanical stress. If it exceeds 200,000 mm ² / s, uniform processing tends to be difficult.

  As a treatment method using silicone oil, for example, inorganic fine powder treated with a silane compound and silicone oil may be directly mixed using a mixer such as a Henschel mixer, or a method of spraying silicone oil onto the inorganic fine powder. May be used. Alternatively, after dissolving or dispersing silicone oil in an appropriate solvent, inorganic fine powder may be added and mixed to remove the solvent. A method using a sprayer is more preferable in that the formation of aggregates of inorganic fine powder is relatively small.

  The treatment amount of silicone oil is 1 to 23 parts by mass, preferably 5 to 20 parts by mass with respect to 100 parts by mass of the inorganic fine powder. If the amount of the silicone oil is too small, good hydrophobicity cannot be obtained, and if it is too large, aggregation of inorganic fine particles tends to occur.

The toner of the present invention has a primary particle size of more than 30 nm (preferably a specific surface area of less than 50 m ² / g), more preferably a primary particle size of 50 nm or more (preferably a specific surface area of 30 m ² ) for the purpose of improving cleaning properties. It is also one of preferable modes to add inorganic or organic fine particles close to spherical shape (less than / g). For example, spherical silica particles, spherical polymethylsilsesquioxane particles, spherical resin particles and the like are preferably used.

  The developer used in the present invention may further contain other additives, for example, a lubricant powder such as a polyethylene fluoride powder, a zinc stearate powder, a polyvinylidene fluoride powder, or a cerium oxide powder within a range that does not substantially adversely affect the developer. Abrasives such as silicon carbide powder and strontium titanate powder; or fluidity-imparting agents such as titanium oxide powder and aluminum oxide powder; anti-caking agents; and organic fine particles and inorganic fine particles of opposite polarity as developability improvers A small amount can also be used. These additives can also be used after hydrophobizing the surface.

  Hereinafter, the present invention will be specifically described with reference to production examples and examples, but this does not limit the present invention in any way.

(Production example of polar polymer)
A polar polymer which is a resin having a sulfur atom used in the present invention was produced by the following procedure.

  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, 250 parts by mass of methanol as a solvent, 150 parts by mass of 2-butanone and 100 parts by mass of 2-propanol, As a monomer, 82 parts by mass of styrene, 10 parts by mass of 2-ethylhexyl acrylate, and 8 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added and heated to reflux temperature while stirring. A solution obtained by diluting 1 part by mass of t-butylperoxy-2-ethylhexanoate 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, t-butylperoxy was further added. A solution prepared by diluting 1 part by mass of 2-ethylhexanoate 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. Furthermore, 500 parts by mass of deionized water was added while maintaining the temperature, and the mixture was stirred for 2 hours at 80 to 100 revolutions per minute so as not to disturb the interface between the organic layer and the aqueous layer, and then allowed to stand for 30 minutes for separation. Later, the aqueous layer was discarded, and anhydrous sodium sulfate was added to the organic layer for dehydration.

  Next, the polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less using a cutter mill equipped with a 150 mesh screen. The obtained polar polymer had a Tg of about 75 ° C.

<Example 1>
After adding 450 parts by mass of 0.1M Na ₃ PO ₄ aqueous solution to 400 parts by mass of ion-exchanged water and heating to 60 ° C., using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), 10,000 rpm Was stirred at. To this, 68 parts by mass of 1.0 M CaCl ₂ aqueous solution was added to obtain an aqueous medium containing calcium phosphate.

on the other hand,
Styrene 83 parts by mass n-butyl acrylate 17 parts by mass C.I. I. Solvent Yellow 162 2.5 parts by mass C.I. I. Pigment Yellow 93 2.5 parts by mass The above polar polymer 0.3 parts by mass Aluminum compound of dialkyl salicylic acid 0.5 parts by mass Saturated polyester 5 parts by mass (acid value 10 mgKOH / g, peak molecular weight 11,000)
Ester wax (endothermic peak = 66 ° C.) 12 parts by mass divinylbenzene 0.05 part by mass The above formulation is heated to 60 ° C. and uniform at 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). Dissolved and dispersed in In this, 3.5 mass parts of polymerization initiators 2,2′-azobis (2,4-dimethylvaleronitrile) were dissolved to prepare a polymerizable monomer composition. The polymerizable monomer composition is charged into the aqueous medium, and the polymerizable monomer composition is granulated by stirring at 10,000 rpm with a TK homomixer at 70 ° C. in an N ₂ atmosphere. Then, while stirring with a paddle stirring blade, when the polymerization conversion rate of the polymerizable vinyl monomer reached 90%, a 0.1 mol / liter sodium hydroxide aqueous solution was added to adjust the pH of the aqueous dispersion medium to 8%. I made it. Furthermore, it heated up at 80 degreeC with the temperature increase rate of 40 degreeC / Hr, and was made to react for 4 hours. After completion of the polymerization reaction, the pressure was reduced. The residual monomer was distilled off, and after cooling, hydrochloric acid was added to adjust the pH to 1.4, and the mixture was stirred for 6 hours to dissolve the calcium phosphate salt. After filtering and washing with water, it was dried at 40 ° C. for 12 hours to obtain toner particles (1).

  With respect to 100 parts by mass of the toner particles, 1.0 part by mass of hydrophobic silica fine powder (average primary particle size 7 nm) surface-treated with hexamethylene disilazane, 0.15 part by mass of rutile titanium oxide fine powder (average primary) The toner (1) of the present invention was obtained by dry-mixing 0.5 parts by mass of a particle size of 45 nm) and 0.5 parts by mass of rutile-type titanium oxide fine powder (average primary particle size of 200 nm) with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) for 5 minutes.

  When the weight average particle diameter and average circularity of toner (1) were calculated using a flow type particle image measuring apparatus manufactured by Toa Medical Electronics Co., Ltd., they were 6.8 μm and 0.984, respectively.

  Table 1 shows the physical property values of the toner.

  The toner (1) is a non-magnetic one-component developer (1), and LBP-2510 (manufactured by Canon Inc.) is used as an evaluation machine. 80% RH) and low temperature and low humidity conditions (temperature 15 ° C., humidity 10% RH). The evaluation was performed by filling the cyan cartridge with 190 g of toner (1) and mounting it in the cyan station, and mounting the dummy cartridges in the other stations, and performing a single color evaluation.

(1) Coloring power In the range of 0.1 mg / cm ² to 1.0 mg / cm ² , several types of solid images with different toner amounts were prepared using plain paper for copying machines (75 g / m ² ) as a transfer material. The image density was measured using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.), and the relationship between the toner amount on the transfer paper and the image density was determined. In particular, the toner amount on the transfer paper was 0.5 mg / cm. ^The coloring power was evaluated relatively with the image density corresponding to the case of ² .
A: Toner amount on transfer paper is 0.5 mg / cm ² and image density is 1.4 or more B: Toner amount on transfer paper is 0.5 mg / cm ² , image density is 1.35 or more, 1.40 Less than C: Toner amount on transfer paper is 0.5 mg / cm ² , image density is 1.20 or more, less than 1.35 D: Toner amount on transfer paper is 0.5 mg / cm ² and image density is Less than 1.20

(2) OHP transparency The image on the OHP sheet “CG3700” (manufactured by 3M) was converted into a transmission image by OHP “9550” (manufactured by 3M), and the image projected on the white wall surface was the spectral radiance meter “PR650” L ^* a ^* b ^* c ^* standardized by the International Commission on Illumination (manufactured by Photo Research) was measured, and lightness (L ^* ) and saturation (c ^* ) were evaluated.
A: L ^* value is 85 or more and c ^* value is 70 or more B: L ^* value is 85 or more and c ^* value is 60 or more and less than 70 C: L ^* value is 80 or more and less than 85 and c ^* Value is less than 70 D: L ^* Value is less than 80 and c ^* value is less than 70

(3) Image Glossiness A solid image with a toner amount of 0.5 mg / cm ² was created using plain paper for copying machines (75 g / m ² ) as a transfer material, and “PG-3D” (Nippon Denshoku Industries Co., Ltd.) Was used to measure the image glossiness at a measurement optical part angle of 75 °.
A: 25 or more B: 20 or more, less than 25 C: 15 or more, less than 20 D: less than 15

(4) Contamination 3,000 images with a printing ratio of 2% using ordinary copying machine plain paper (75 g / m ² ) transfer material in a high-temperature, high-humidity environment (30 ° C, 80% RH) After printing out, the charging member and the photosensitive drum were observed.
A: Very good B: Good C: No problem in practical use D: Somewhat difficult

(5) Image density Transfer of ordinary copying machine plain paper (75 g / m ² ) under high temperature and high humidity (30 ° C, 80% RH) and low temperature and low humidity (15 ° C, 10% RH). In an image forming test in which up to 5,000 images with a printing ratio of 2% were printed out using a material, a solid image was output at the initial stage and at the end of durability evaluation, and the density was measured for evaluation. The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to an image of a white background portion having a document density of 0.00.
A: Very good 1.40 or more B: Good 1.35 or more, less than 1.40 C: No problem in practical use 1.00 or more, less than 1.35 D: Somewhat difficult Less than 1.00

(6) Image fog Transfer of ordinary plain paper for copying machines (75 g / m ² ) in a high temperature and high humidity environment (30 ° C., 80% RH) and a low temperature and low humidity environment (15 ° C., 10% RH). In the image output test that prints up to 10,000 images with a printing ratio of 2% using the material, the white background portion of the printout image measured by “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku) The fog density (%) was calculated from the difference between the whiteness and the whiteness of the transfer paper, and the image fog at the end of the durability evaluation was evaluated. The filter used was amber light for cyan, blue for yellow, and green for magenta and black.
A: Very good Less than 0.5% B: Good 0.5% or more to less than 1.0% C: No problem in practical use 1.0% or more to less than 1.5% D: Somewhat difficult 1.5% more than

  In the present invention, the C rank or higher is within the allowable range.

<Example 2>
C. I. The addition amount of Solvent Yellow 162 is 0.5 parts by mass. I. The same procedure as in Example 1 was performed except that the number of added parts of Pigment Yellow 93 was changed to 4.5 parts by mass.

<Example 3>
C. I. Solvent Yellow 162 was added to 4.25 parts by mass, C.I. I. The same procedure as in Example 1 was performed except that the number of added parts of Pigment Yellow 93 was changed to 0.75 parts by mass.

<Example 4>
C. I. The addition amount of Solvent Yellow 162 was changed to 2.4 parts by mass, and C.I. I. Pigment Yellow 93 is C.I. I. The same procedure as in Example 1 was performed except that Pigment Yellow 155 (3.6 parts by mass) was used.

<Example 5 >
C. I. The addition amount of Solvent Yellow 162 was changed to 2.4 parts by mass, and C.I. I. Pigment Yellow 93 is C.I. I. It replaced with Pigment Yellow 95 (1.6 mass parts), and was carried out similarly to Example 1 except not adding a polar polymer.

<Example 6 >
C. I. The addition part of Solvent Yellow 162 was changed to 4 parts by mass, and C.I. I. The same procedure as in Example 1 was conducted except that Pigment Yellow 93 was not added.

<Example 7 >
C. I. Solvent Yellow 162 to C.I. I. Instead of Disperse Yellow 54 (4.8 parts by mass), C.I. I. Pigment Yellow 93 is C.I. I. It replaced with Pigment Yellow 155 (1.2 mass parts), and was carried out similarly to Example 1 except not adding a polar polymer.

<Example 8 >
The following materials are mixed in advance, melt-kneaded with a twin screw extruder, the cooled kneaded product is coarsely pulverized with a hammer mill, the coarsely pulverized product is finely pulverized with a jet mill, and the resulting finely pulverized product is classified and classified. It was set as the powder (d).
・ Polyester resin 100 parts by mass [bisphenol A propylene oxide adduct / bisphenol A ethylene oxide adduct / terephthalic acid derivative]
・ C. I. Disperse Yellow 64 3 parts by mass C.I. I. Pigment Yellow 185 2 parts by mass Charge control agent (aluminum compound of dialkylsalicylic acid) 3 parts by mass Paraffin wax (melting point = 65 ° C) 10 parts by mass

A toner ( 8 ) was prepared using the classified powder (d), and the same procedure as in Example 1 was performed.

<Example 9 >
The colorant to be added is C.I. I. Example 8 was repeated except that only Solvent Yellow 163 (8 parts by mass) was used.

<Comparative Example 1>
C. I. Solvent Yellow 162 to C.I. I. Instead of Solvent Yellow 163 (3 parts by mass), C.I. I. Pigment Yellow 93 is C.I. I. Pigment Yellow 95 (3 parts by mass) was changed, the addition part of divinylbenzene was changed to 0.5 part by mass, and the addition part of the polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was changed to 3.0. The procedure was the same as in Example 1 except that the polymerization temperature was changed to 60 parts by mass from the start of polymerization.

<Comparative example 2>
C. I. Solvent Yellow 162 to C.I. I. Instead of Disperse Yellow 54 (4.8 parts by mass), C.I. I. Pigment Yellow 93 is C.I. I. The same procedure as in Example 1 was followed except that Pigment Yellow 74 (3.2 parts by mass) was used.

<Comparative Example 3>
C. I. Solvent Yellow 162 to C.I. I. Instead of Disperse Yellow 64 (4.8 parts by mass), C.I. I. Pigment Yellow 93 was changed to 1.2 parts by mass, divinylbenzene was not added, and the temperature of the drying step for obtaining toner particles was changed to 60 ° C.

<Comparative example 4>
The polyester resin was changed to 83 parts by mass of styrene / 17 parts by mass of n-butyl acrylate. I. Disperse Yellow 64 is C.I. I. Instead of Solvent Yellow 162 (5.4 parts by mass), C.I. I. The same procedure as in Example 8 was conducted except that the number of added parts of Pigment Yellow 185 was changed to 0.6 parts by mass.

  The physical properties of the produced toner are shown in Table 1, and the evaluation results are shown in Table 2.

Claims (12)

A yellow toner containing at least a binder resin, a colorant, and a wax component,
As the colorant, C.I. I. Solvent Yellow 162, C.I. I. Solvent Yellow 163, C.I. I. Disperse Yellow 54, and C.I. I. Containing any dye selected from the group consisting of Disperse Yellow 64;
When the mass of the colorant extracted from 0.1 g / liter of a sodium hydroxide aqueous solution from 1 g of the toner is A (mg),
0.2 ≦ A ≦ 4.0
Satisfied,
The toner has a storage elastic modulus G ′ (140 ° C.) at 140 ° C. of 2.0 × 10 ³ dN / m ² or more and less than 2.0 × 10 ⁴ dN / m ² .
A yellow toner having a temperature of 115 ° C. or more and less than 130 ° C. when the viscosity of the toner by a flow tester heating method is 1.0 × 10 ³ Pa · s.   As a coloring agent, C.I. I. The yellow toner according to claim 1, further comprising Solvent Yellow 162. Colorant, yellow toner according to claim 1 or 2, characterized in that a 1.0 to 6.5 parts by weight per 100 parts by weight of the binder resin. C. I. Pigment Yellow 93, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 155, C.I. I. The yellow toner according to any one of claims 1 to 3, characterized by containing one of the pigment selected from Pigment Yellow 74. C. I. The yellow toner according to any one of claims 1 to 3, characterized in that it contains Pigment Yellow 93. The yellow toner according to claim 4 or 5 , wherein a mass ratio of the content of the dye and the pigment used as the colorant is 20:80 to 80:20. The yellow toner according to any one of claims 1 to 6, wherein an average circularity of from 0.950 to 0.995. The yellow toner according to any one of claims 1 to 7 weight-average particle diameter D4 is characterized in that it is a 3 to 10 [mu] m. The yellow toner according to any one of claims 1 to 8, characterized in that it is manufactured in water. The yellow toner according to any one of claims 1 to 9, characterized in that it is produced by suspension polymerization. An electrostatic charge image formed on a latent image holding member having a charging member in contact with the surface using a one-component developing device having a toner application blade in contact with the toner carrier and a toner supply roller is made of toner. In the image forming method to be developed,
The toner is a yellow toner containing at least a binder resin, a colorant, and a wax component,
As the colorant, C.I. I. Solvent Yellow 162, C.I. I. Solvent Yellow 163, C.I. I. Disperse Yellow 54, and C.I. I. Containing any dye selected from the group consisting of Disperse Yellow 64;
When the mass of the colorant extracted from 0.1 g / liter of a sodium hydroxide aqueous solution from 1 g of the toner is A (mg),
0.2 ≦ A ≦ 4.0
Satisfied,
The toner has a storage elastic modulus G ′ (140 ° C.) at 140 ° C. of 2.0 × 10 ³ dN / m ² or more and less than 2.0 × 10 ⁴ dN / m ² .
An image forming method, wherein the temperature when the viscosity of the toner is 1.0 × 10 ³ Pa · s by a flow tester heating method is 115 ° C. or more and less than 130 ° C. The toner, image forming method according to claim 11 which is a toner according to any one of claims 2 to 10.