toner

Abstract

The present invention provides a toner having excellent low-temperature fixing properties and storage stability. The toner of the present invention is characterized by containing colored resin particles and external additives, the colored resin particles contain a binding resin, a colorant, a softening agent, and a charge control agent, the colorant is a yellow colorant composed of a yellow pigment that does not contain a chlorine atom, the glass transition temperature (Tg) of the toner satisfies 45°C < Tg (°C) < 100°C, the glass transition temperature is determined from a temperature dependence curve of the loss tangent (tan δ) of the toner obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz, the loss tangent (tan δ) of the toner at the glass transition temperature (Tg) is less than 1.870, and the toner satisfies specific formula (I-1) and formula (II-2).

Description

[0001] This application is a divisional application of the invention patent application with application number 202180010533.6, the original application being filed on January 29, 2021, and the invention being entitled "Toner". Technical Field

[0002] This invention relates to a toner for developing electrostatic latent images in electrophotography, electrostatic recording, and electrostatic printing. Background Technology

[0003] In image forming apparatuses such as electrophotographic devices, electrostatic recording devices, and electrostatic printing devices, a fixed image is formed by developing an electrostatic latent image formed on a photoreceptor with a toner, transferring the toner image onto a transfer material such as paper, and then fixing it by heating or other means.

[0004] In such image forming apparatuses, the goal is to achieve high image quality and high-speed printing, requiring toners capable of producing high-quality images. In recent years, efforts have been made to develop toners that utilize the viscoelasticity of binding resins or toners.

[0005] For example, Patent Document 1 discloses a polyester resin used as a binder resin in a colorant, wherein the loss modulus (G”) is G” = 1 × 10⁻⁶ from the glass transition temperature (Tg) to the loss modulus (G”). 4 There exists a minimum value of tanδ for the bonding resin at a temperature of Pa, which is less than 1.2. The storage modulus (G') at the temperature corresponding to this minimum value of tanδ is G' = 5 × 10⁻⁶. 5 Pa or above, and in G”=1×10 4 The value of tanδ at a temperature of Pa is greater than 3.0.

[0006] Patent Document 2 discloses an image forming method that combines a fixing member and a toner. The fixing member has a surface layer in which a wear-resistant additive with a volume average particle size of 1 μm or less is dispersed. The toner, when measured in a dynamic viscoelastic temperature dependence test, exhibits a tanδ peak in the range of 40°C to 70°C, and this peak value is less than 2.0. Patent Document 2 also discloses a method for controlling this peak value to be less than 2.0, which involves using an amorphous polyester resin as a binder resin for the toner and dispersing particles with a particle size of 0.1 μm or less in the toner; and a method for using a combination of crystalline and amorphous polyester resins as a binder resin for the toner.

[0007] Patent Document 3 discloses a toner for electrostatic image development, which contains a binder resin, a colorant, a release agent, and a charge control agent. The release agent contains a wax with polar groups, and its tanδ value, measured using a viscoelasticity measuring device at 10 kHz frequency and 500 Pa at temperatures between 80 and 145°C, is 1 to 2. A fracture point can be observed below 180°C in the temperature-tanδ curve. Patent Document 3 states that polyester resin is preferably used as the binder resin.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 11-194542;

[0011] Patent Document 2: Japanese Patent Application Publication No. 2009-151005;

[0012] Patent document 3: Japanese Patent Application Publication No. 2013-88503. Summary of the Invention

[0013] The problem the invention aims to solve

[0014] However, in toners that can produce high-quality images, although a good balance between low-temperature fixing and preservation is required, it is difficult to improve both the low-temperature fixing and preservation properties of toners in a balanced way using existing methods of adjusting the viscoelasticity of the binder resin or toner.

[0015] The purpose of this invention is to provide a toner with excellent low-temperature fixing and preservation properties.

[0016] Solution for solving the problem

[0017] In order to achieve the above objectives, the inventors conducted in-depth research and discovered the viscoelastic properties of the toner, which led to the completion of this invention. This toner can effectively improve the low-temperature fixing properties of the toner and inhibit adhesion during storage.

[0018] That is, the first colorant of the present invention is characterized in that it contains coloring resin particles and external additives, wherein the coloring resin particles include a binding resin, a colorant, a softener, and a charge control agent.

[0019] The glass transition temperature (Tg) of the above-mentioned toner satisfies 45℃ < Tg (℃) < 100℃. The glass transition temperature is determined based on the temperature dependence curve of the loss tangent (tanδ) of the toner obtained by dynamic viscoelasticity measurement at a measurement frequency of 24Hz.

[0020] In the temperature dependence curve of the loss tangent (tanδ) mentioned above, when the loss tangent (tanδ) at 45℃ is denoted as tanδ(45℃), the loss tangent (tanδ) at the glass transition temperature (Tg) is denoted as tanδ(Tg), the loss tangent (tanδ) at 100℃ is denoted as tanδ(100℃), and the loss tangent (tanδ) at 130℃ is denoted as tanδ(130℃), the following conditions are met:

[0021] and

[0022] .

[0023] In the first colorant of the present invention described above, a flow tester was used at a pressure of 10.0 kgf / cm². 2 The softening temperature (T) in the 1 / 2 method determined under the conditions of [condition] 1 / 2 It can be greater than 154℃ and less than 220℃.

[0024] In the first toner of the present invention described above, the loss tangent (tanδ) at the glass transition temperature (Tg) can be less than 1.870°.

[0025] In the first toner of the present invention described above, in the temperature dependence curve of the loss tangent (tanδ), the loss tangent (tanδ) at 100°C can be 0.800 or more and 1.100 or less, and the loss tangent (tanδ) at 130°C can be 0.800 or more and 1.280 or less.

[0026] In the first colorant of the present invention, the adhesive resin may contain a polymer of one or more polymeric monomers, wherein the polymeric monomers include at least one monovinyl monomer selected from styrene, acrylate and methacrylate.

[0027] In the first colorant of the present invention, the weight-average molecular weight of the polymer contained in the binder resin may be 3.00 × 10⁻⁶. 5 Above and 7.00×10 5 the following.

[0028] Furthermore, the second colorant of the present invention is characterized in that it contains coloring resin particles and external additives, wherein the coloring resin particles comprise a binding resin, a colorant, a softener, and a charge control agent.

[0029] The glass transition temperature (Tg) of the above-mentioned toner satisfies 45℃ < Tg (℃) < 100℃. The glass transition temperature is determined based on the temperature dependence curve of the loss tangent (tanδ) of the toner obtained by dynamic viscoelasticity measurement at a measurement frequency of 24Hz.

[0030] In the temperature dependence curve of the loss tangent (tanδ) mentioned above, when the loss tangent (tanδ) at 45℃ is denoted as tanδ(45℃), the loss tangent (tanδ) at the glass transition temperature (Tg) is denoted as tanδ(Tg), the loss tangent (tanδ) at 100℃ is denoted as tanδ(100℃), and the loss tangent (tanδ) at 130℃ is denoted as tanδ(130℃), the following conditions are met:

[0031] and .

[0032] In the second toner of the present invention described above, the apparent glass transition temperature (Tg2) of the toner when heated at a heating rate of 1000 K / s, as determined by differential scanning calorimetry using a high-speed differential scanning calorimeter, can be 68°C to 74°C, and the exothermic onset temperature of the toner when cooled at a cooling rate of 1000 K / s can be 50°C to 62°C.

[0033] In the second colorant of the present invention described above, a flow tester was used at a pressure of 5.0 kgf / cm². 2 The softening temperature (T) in the 1 / 2 method determined under the conditions of [condition] 1 / 2 It can be greater than 124℃ and less than 159℃.

[0034] In the second toner of the present invention described above, the loss tangent (tanδ) at the glass transition temperature (Tg) can be less than 2.410.

[0035] In the second toner of the present invention described above, in the temperature dependence curve of the loss tangent (tanδ), the loss tangent (tanδ) at 100°C can be 0.900 or more and 1.400 or less, and the loss tangent (tanδ) at 130°C can be 1.000 or more and 2.500 or less.

[0036] In the second colorant of the present invention, the adhesive resin may contain a polymer of one or more polymeric monomers, wherein the polymeric monomers include at least one monovinyl monomer selected from styrene, acrylate and methacrylate.

[0037] In the second colorant of the present invention, the weight-average molecular weight of the polymer contained in the binder resin can be 2.00 × 10⁻⁶.4 Above and 1.00×10 5 the following.

[0038] Invention Effects

[0039] According to the present invention, a toner with excellent low-temperature fixing properties and preservation properties is available. Attached Figure Description

[0040] Figure 1 A graph showing the temperature dependence of the loss tangent (tanδ) of the toner of Example I-1.

[0041] Figure 2 A graph showing the temperature dependence of the loss tangent (tanδ) of the toner of Example II-1.

[0042] Figure 3 A graph illustrating the method for calculating the apparent glass transition temperature (Tg2) of a toner during heating and the exothermic onset temperature of the toner during cooling in high-speed differential scanning calorimetry. Detailed Implementation

[0043] I. The first toner of the present invention

[0044] The first colorant of the present invention is characterized in that it contains coloring resin particles and external additives, wherein the coloring resin particles comprise a binding resin, a colorant, a softener, and a charge control agent.

[0045] The glass transition temperature (Tg) of the above-mentioned toner satisfies 45℃ < Tg (℃) < 100℃. The glass transition temperature is determined based on the temperature dependence curve of the loss tangent (tanδ) of the toner obtained by dynamic viscoelasticity measurement at a measurement frequency of 24Hz.

[0046] In the temperature dependence curve of the loss tangent (tanδ) mentioned above, when the loss tangent (tanδ) at 45℃ is denoted as tanδ(45℃), the loss tangent (tanδ) at the glass transition temperature (Tg) is denoted as tanδ(Tg), the loss tangent (tanδ) at 100℃ is denoted as tanδ(100℃), and the loss tangent (tanδ) at 130℃ is denoted as tanδ(130℃), the following conditions are met:

[0047] and

[0048] .

[0049] The viscoelastic properties of the first colorant of the present invention, the manufacturing method of the coloring resin particles used in the first colorant of the present invention and the coloring resin particles, the external additives used in the first colorant of the present invention, and the performance of the first colorant of the present invention will be described in sequence below.

[0050] Furthermore, in this invention, the "~" in the numerical range refers to the values ​​recorded before and after it as the lower limit and upper limit.

[0051] I-1. Viscoelastic properties of the first toner of the present invention

[0052] The first toner of the present invention exhibits the following characteristics in the temperature dependence curve of the loss tangent (tanδ) obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz: The curve is within the range of 45°C to 145°C. Specifically, when there is at least one peak in the range of greater than 45°C and less than 100°C, and the temperature above which tanδ reaches its maximum value, tanδ decreases with increasing temperature. Then, tanδ decreases intermittently or continuously, reaches a minimum value, becomes a fixed value at a certain temperature, or continues to decrease. In the case where tanδ reaches a minimum value, as the temperature increases further from the temperature at which the minimum value is reached, tanδ increases slowly, then continues to increase or becomes a substantially fixed value above a certain temperature.

[0053] Furthermore, the first toner of the present invention satisfies the following conditions when the glass transition temperature (Tg) determined from the temperature dependence curve of the loss tangent (tanδ) is greater than 45°C and less than 100°C, and the loss tangent (tanδ) at 45°C is denoted as tanδ(45°C), the loss tangent (tanδ) at the glass transition temperature (Tg) is denoted as tanδ(Tg), the loss tangent (tanδ) at 100°C is denoted as tanδ(100°C), and the loss tangent (tanδ) at 130°C is denoted as tanδ(130°C):

[0054] and

[0055] .

[0056] In this invention, the loss tangent (tanδ) is defined as the ratio (G'' / G') of the loss modulus (G'') to the storage modulus (G') as determined by dynamic viscoelasticity measurement.

[0057] Furthermore, in this invention, according to Rule B of JIS Z 8401:1999, the value of tanδ is accurate to three decimal places. In the above formulas (I-1) and (I-2), each tanδ value accurate to three decimal places is used. Moreover, each value is accurate such that the significant figures of (tanδ(Tg)-tanδ(45℃)) / (Tg-45) shown in formula (I-1) are three, and the significant figures of (tanδ(130℃)-tanδ(100℃)) / 30 shown in formula (I-2) are two.

[0058] In this invention, the glass transition temperature (Tg) of the toner is determined as follows: in the temperature dependence curve of the loss tangent (tanδ) of the toner obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz, among the more than one peak in the temperature region greater than 45°C and less than 100°C, the lowest temperature at which tanδ reaches its maximum value is the peak on the lowest temperature side. Minor fluctuations caused by the measurement, such as noise, are not interpreted as the aforementioned peak. Furthermore, in this invention, the temperature dependence curve of the loss tangent (tanδ) obtained by dynamic viscoelasticity measurement is sometimes referred to as a temperature-tanδ curve.

[0059] In the first toner of the present invention, the above-mentioned dynamic viscoelasticity was measured using a rotating flat plate rheometer (TA Instruments, ARES-G2), with parallel plates or cross plates under the following conditions.

[0060] Frequency: 24Hz

[0061] Sample set: The test piece (8mm in diameter and 2-4mm in thickness) is clamped with an 8mm φ plate under a 20g load. The temperature is raised to 80℃ to fuse the test piece to the clamp. Then the temperature is restored to 45℃ and the heating is started.

[0062] Heating rate: 5℃ / minute

[0063] Temperature range: 45℃~150℃

[0064] The test piece can be made, for example, by injecting 0.2g of the first colorant of the present invention into a cylindrical mold with an 8mmφ diameter and applying pressure of 1.0MPa for 30 seconds to form an 8mmΦ cylindrical molded body with a thickness of 2-4mm.

[0065] The first toner of this invention exhibits specific viscoelasticity in the temperature-tanδ curve, satisfying equations (I-1) and (I-2) above. This results in a toner that achieves a balanced improvement in both low-temperature fixing and storage properties, making it a toner with superior performance that was previously difficult to achieve. Equation (I-1) represents the range of slopes of the straight lines passing through tanδ (45°C) and tanδ (Tg) in the temperature-tanδ curve, and equation (I-2) represents the range of slopes of the straight lines passing through tanδ (100°C) and tanδ (130°C). During fixing and storage, the toner does not deform drastically upon reaching a certain temperature, but rather deforms slowly over time as the temperature increases or is maintained at a certain temperature. Based on this property of toners, the inventors discovered that the characteristics of a toner that achieves a good balance between low-temperature fixing and preservation are reflected in the slopes of the lines passing through tanδ (45℃) and tanδ (Tg), and the slopes of the lines passing through tanδ (100℃) and tanδ (130℃). The inventors further conducted in-depth research and found that by adjusting the slopes of the lines passing through tanδ (45℃) and tanδ (Tg), the adhesion characteristics of the toner during long-term preservation can be easily controlled; and by adjusting the slopes of the lines passing through tanδ (100℃) and tanδ (130℃), the fixing properties of the toner can be easily controlled.

[0066] The smaller the value of (tanδ(Tg)-tanδ(45℃)) / (Tg-45) shown in the above formula (I-1) is within the above-mentioned numerical range, the easier it is to suppress the adhesion of the toner during storage, thus improving its shelf life. The smaller the difference between tanδ(Tg) and tanδ(45℃), or the higher Tg is, the smaller the value of (tanδ(Tg)-tanδ(45℃)) / (Tg-45) will be. By keeping the difference between tanδ(Tg) and tanδ(45℃) not too large, the viscosity of the toner will not be too high, that is, the back-and-forth movement of polymer chains between toner particles can be suppressed, thus presumably suppressing adhesion. In addition, by keeping Tg not too low, the decrease in elasticity at low temperatures can be suppressed, thus presumably suppressing adhesion. Furthermore, by keeping the value in the above formula (I-1) below the above-mentioned upper limit, the deterioration of the shelf life of the toner can be suppressed. By setting the value in equation (I-1) above the lower limit, the increase in fixing temperature can be easily suppressed, thus suppressing the deterioration of low-temperature fixing performance.

[0067] On the other hand, the larger the value of (tanδ(130℃)-tanδ(100℃)) / 30 shown in the above formula (I-2) is within the above numerical range, the more likely the fixing temperature will decrease, and the lower the fixing performance will be. During fixing, the toner slowly deforms as the temperature rises. In actual fixing, from the time the paper with transferred toner enters the roller until it exits, there is at least a temperature gradient from 100°C to 130°C. The larger the value of (tanδ(130℃)-tanδ(100℃)) / 30 shown in the above formula (I-2), the faster the tanδ of the toner increases after heating, that is, the faster the viscosity of the toner increases, which suggests that fixing at a lower temperature can be achieved. Furthermore, by exceeding the lower limit value in the above formula (I-2), the gloss of the formed image becomes better. On the other hand, by using a value less than the upper limit in the above formula (I-2), the adhesion of the toner during storage can be suppressed, thus inhibiting the deterioration of its shelf life.

[0068] Furthermore, the inventors have discovered that toners exhibiting viscoelasticity satisfying equations (I-1) and (I-2) above in the temperature-tanδ curve, especially when used in a flow tester at a pressure of 10.0 kgf / cm², are particularly effective. 2 The softening temperature (T) of the toner in the 1 / 2 method was determined under the following conditions. 1 / 2 The above-mentioned effects will be achieved when the temperature is greater than 154℃ and less than 220℃.

[0069] To obtain a toner that exhibits viscoelasticity satisfying equations (I-1) and (I-2) above in the temperature-tanδ curve, the viscoelasticity of the toner can be controlled by, for example, appropriately changing the composition, molecular weight, and content of the binder resin, the type and content of the colorant, the viscosity of the colorant raw material, the glass transition temperature (Tg) and content of the charge control agent, the type and molecular weight of the softener, and the type and content of external additives. Among these, adjusting the molecular weight and composition of the binder resin, the type and content of the colorant, and the viscosity of the colorant raw material is effective. The molecular weight and composition of the binder resin in the toner have a significant impact on the viscoelasticity of the toner in the low-temperature region below the glass transition temperature. Therefore, adjusting the molecular weight and composition of the binder resin in the toner is effective in order to satisfy equation (I-1) above. On the other hand, the type and content of the colorant in the toner, and the viscosity of the colorant raw material have a significant impact on the viscoelasticity of the toner in the temperature range of 100°C to 130°C. Therefore, in order to make the viscoelasticity satisfy the above equation (I-2), it is effective to adjust the type and content of the colorant contained in the toner, as well as the viscosity of the colorant raw material. More specifically, by adopting the preferred method of each component described later, the temperature-tanδ curve of the toner can satisfy the above equations (I-1) and (I-2).

[0070] The temperature-tanδ curve of the first toner of the present invention obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz satisfies the following equation (I-1).

[0071]

[0072] From the perspective of easily suppressing the adhesion of toners during storage and improving shelf life, the upper limit in the above formula (I-1) is preferably less than 7.40 × 10⁻⁶. -2 More preferably less than 7.20×10 -2 On the other hand, from the perspective of easily suppressing the rise in fixing temperature, the lower limit in the above formula (I-1) is preferably 5.60 × 10⁻⁶. -2 The above is preferred, with 6.00×10 being more ideal. -2 above.

[0073] The temperature-tanδ curve of the first toner of the present invention obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz satisfies the following equation (I-2).

[0074]

[0075] In terms of improving the low-temperature fixing properties of the toner and making the resulting image glossier, the lower limit in the above formula (I-2) is preferably greater than -1.5 × 10⁻⁶. -3 More preferably greater than 0.1×10 -3 On the other hand, from the perspective of easily suppressing preservation deterioration, the upper limit in the above formula (I-2) is preferably less than 5.0 × 10. -2 More preferably less than 4.0 × 10 -2 Further preferred is less than 2.0×10 -2 .

[0076] The glass transition temperature (Tg) of the first toner of the present invention satisfies 45°C < Tg (°C) < 100°C. This glass transition temperature is determined based on the temperature dependence curve of the loss tangent (tanδ) of the toner obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz. From the perspective of suppressing a sharp decrease in elasticity at low temperatures and suppressing adhesion, the aforementioned glass transition temperature (Tg) is preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 65°C or higher. On the other hand, from the perspective of preventing the softening start temperature of the toner from becoming too high, thereby improving low-temperature fixing performance, the aforementioned glass transition temperature (Tg) is preferably 90°C or lower, more preferably 80°C or lower, and even more preferably 75°C or lower.

[0077] Furthermore, the first toner of the present invention preferably has a loss tangent (tanδ) of less than 1.900, more preferably less than 1.870, and even more preferably less than 1.860. By keeping the tanδ (Tg) below the aforementioned upper limit, it is easy to suppress the adhesion of the toner during storage and to improve its shelf life.

[0078] The lower limit of the above-mentioned tanδ(Tg) is not particularly limited, but from the perspective of making the fixing performance good, it is preferably 1.000 or more, and more preferably 1.100 or more.

[0079] The first toner of the present invention preferably has a loss tangent (tanδ) of tanδ (45°C) of 0.300 or less, more preferably 0.200 or less, and even more preferably 0.150 or less. By keeping the above-mentioned tanδ (45°C) below the above-mentioned upper limit value, it is easy to suppress the adhesion of the toner during storage and to improve its shelf life.

[0080] The lower limit of tanδ (45°C) is not particularly limited, but from the perspective of making the fixing properties good, it is preferable to be greater than 0.000, and more preferably 0.050 or more.

[0081] Furthermore, from the viewpoint of easily improving the low-temperature fixing properties of the toner, the tanδ (100°C) of the loss tangent (tanδ) of the first toner of the present invention is preferably 0.600 or more, more preferably 0.700 or more, and even more preferably 0.800 or more. On the other hand, from the viewpoint of easily suppressing the deterioration of the toner's shelf life, it is preferably 1.200 or less, more preferably 1.100 or less, and even more preferably 1.050 or less.

[0082] Furthermore, from the viewpoint of easily improving the low-temperature fixing properties of the toner, the tanδ (130°C) of the loss tangent (tanδ) of the first toner of the present invention is preferably 0.800 or more, more preferably 0.900 or more, and even more preferably 0.950 or more. On the other hand, from the viewpoint of easily suppressing the deterioration of the toner's shelf life, it is preferably 2.000 or less, more preferably 1.500 or less, and even more preferably 1.280 or less.

[0083] Furthermore, the first colorant of the present invention is preferably tested using a flow tester at a pressure of 10.0 kgf / cm². 2 The softening temperature (T) in the 1 / 2 method determined under the conditions of [condition] 1 / 2 The softening temperature is greater than 154℃ and less than 220℃. 1 / 2Toners within the above range exhibit viscoelasticity that satisfies equations (I-1) and (I-2) in the temperature-tanδ curve, thereby particularly improving low-temperature fixing and preservation properties in a balanced manner.

[0084] From the perspective of improving preservation, the aforementioned softening temperature (T) 1 / 2 The preferred temperature is 158°C or higher, more preferably 160°C or higher. On the other hand, from the perspective of improving low-temperature fixing performance, the aforementioned softening temperature (T...) 1 / 2 Preferably, the temperature is below 210°C, and more preferably below 200°C.

[0085] The softening temperature (T) of the first toner of the present invention 1 / 2 The softening temperature (T0) can be adjusted by factors such as the composition and molecular weight of the binder resin, and the type and content of the colorant. The more cross-linking polymeric monomers used in the binder resin are added, the higher the softening temperature (T0). 1 / 2 The softening temperature (T) tends to increase as the weight-average molecular weight of the polymer in the binding resin increases. 1 / 2 The tendency for the softening temperature (T) to increase is further observed. Furthermore, by using a colorant that easily increases the viscosity of the colorant, as described later, the aforementioned softening temperature (T) of the first colorant of the present invention is [not specified]. 1 / 2 It is easy to fall within the above range.

[0086] The flow testing apparatus described above was used at a pressure of 10.0 kgf / cm². 2 The softening temperature (T) in the 1 / 2 method determined under the conditions of [condition] 1 / 2 The softening temperature (T0) can be determined by measuring the flow curve (piston stroke - temperature) under the following conditions using a flow testing apparatus (trade name CFT-500C) manufactured by Shimadzu Corporation. Specifically, in the flow curve, half the difference between the piston stroke at the end of the flow and the minimum value of the piston stroke can be calculated, and the softening temperature (T0) can be obtained by combining the obtained value with the temperature at the location of the sum of the minimum value and the obtained value. 1 / 2 ).

[0087] (Measurement conditions)

[0088] Starting temperature: 35℃

[0089] Heating rate: 3℃ / minute

[0090] Preheating time: 5 minutes

[0091] Cylinder pressure: 10.0 kgf / cm 2 (10kg method)

[0092] Die head bore diameter: 0.5mm

[0093] Die head length: 1.0mm

[0094] Sample dosage: 1.0–1.3 g

[0095] I-2. Method for manufacturing colored resin particles

[0096] Generally, the manufacturing methods for coloring resin particles are broadly classified into: dry methods such as pulverization; and wet methods such as emulsion polymerization, suspension polymerization, and dissolution suspension polymerization. Wet methods are preferred because they readily yield toners with excellent printing properties, such as image reproducibility. Among wet methods, polymerization methods such as emulsion polymerization and suspension polymerization are preferred because they readily produce toners with micron-sized particles and small particle size distributions. Among polymerization methods, suspension polymerization is more preferred.

[0097] In the emulsion polymerization coagulation method described above, emulsified polymerizable monomers are polymerized to obtain a resin microparticle emulsion, which is then coagulated with a colorant dispersion to produce colored resin particles. Alternatively, the dissolution-suspension method described above can also involve dissolving or dispersing a solution of binder resin, colorant, or other toning agents in an organic solvent in an aqueous medium to form droplets, and then removing the organic solvent to produce colored resin particles. Both methods can utilize known techniques.

[0098] The coloring resin particles used in the first colorant of the present invention can be manufactured by a wet process or a dry process, preferably by a wet process, and can be manufactured by a suspension polymerization process, which is particularly preferred in the wet process, through the following process.

[0099] (A) Suspension polymerization method

[0100] (A-1) Preparation process of polymeric monomer composition

[0101] First, a polymerizable monomer composition is prepared by mixing polymerizable monomers, colorants, softeners, charge control agents, and other additives such as molecular weight regulators as needed. The mixing during the preparation of the polymerizable monomer composition is performed using, for example, a media disperser.

[0102] In this invention, a polymerizable monomer refers to a monomer having polymerizable functional groups, which polymerize to form an adhesive resin. Monovinyl monomers are preferably used as the main component of the polymerizable monomer. Examples of monovinyl monomers include: styrene; styrene derivatives such as vinyltoluene and α-methylstyrene; acrylic acid and methacrylic acid; acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and dimethylaminoethyl acrylate; methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and dimethylaminoethyl methacrylate; nitrile compounds such as acrylonitrile and methacrylonitrile; amide compounds such as acrylamide and methacrylamide; and olefins such as ethylene, propylene, and butene.

[0103] These monovinyl monomers can be used alone or in combination of two or more.

[0104] Among these, the aspects that easily satisfy the above equations (I-1) and (I-2) from the temperature-tanδ curve of the toner, and the above softening temperature (T) 1 / 2 Based on the preferred aspects described above, the polymerizable monomer preferably comprises at least one monovinyl monomer selected from styrene, styrene derivatives, acrylates and methacrylates, more preferably at least one monovinyl monomer selected from styrene, acrylates and methacrylates, and even more preferably styrene and at least one monomer selected from acrylates and methacrylates.

[0105] Furthermore, the temperature-tanδ curve of the toner easily satisfies the above equations (I-1) and (I-2), as well as the above softening temperature (T). 1 / 2 From the perspective of the above-mentioned preferred range, as an acrylate, it is preferably selected from at least one of n-butyl acrylate, propyl acrylate and 2-ethylhexyl acrylate, and as a methacrylate, it is preferably selected from at least one of n-butyl methacrylate, propyl methacrylate and 2-ethylhexyl methacrylate.

[0106] Furthermore, the styrene content in 100 parts by mass of the monovinyl monomer is preferably 60 parts by mass or more and 90 parts by mass or less, more preferably 65 parts by mass or more and 85 parts by mass or less, and even more preferably 70 parts by mass or more and 80 parts by mass or less. The higher the styrene content, the higher the softening temperature (T0). 1 / 2 The higher the α value, the higher the glass transition temperature (Tg) of the toner tends to be.

[0107] Furthermore, the temperature-tanδ curve of the toner easily satisfies the above equations (I-1) and (I-2), as well as the above softening temperature (T).1 / 2 Based on the preferred range described above, the monovinyl monomer preferably contains styrene and at least one selected from acrylates and methacrylates, and the mass ratio of styrene to the total mass of acrylates and methacrylates (styrene:(meth)acrylate) is preferably in the range of 50:50 to 90:10, more preferably in the range of 60:40 to 80:20, and particularly preferably in the range of 70:30 to 75:25.

[0108] When the aforementioned polymerizable monomer contains polymerizable monomers other than the aforementioned monovinyl monomer, the content of the aforementioned monovinyl monomer can be appropriately adjusted such that the temperature-tanδ curve of the colorant satisfies the aforementioned formulas (I-1) and (I-2). The total amount of the aforementioned monovinyl monomer is not particularly limited relative to 100 parts by mass of the aforementioned polymerizable monomer, but is preferably 90 parts by mass or more, more preferably 95 parts by mass or more.

[0109] From the aspects that the temperature-tanδ curve easily satisfies the above equations (I-1) and (I-2), and the above softening temperature (T) 1 / 2 From the perspective of the above-mentioned preferred scope, the first colorant of the present invention preferably uses any crosslinkable polymerizable monomer together with a monovinyl monomer. A crosslinkable polymerizable monomer refers to a monomer having two or more polymerizable functional groups. Examples of crosslinkable polymerizable monomers include, for example: aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and their derivatives; ester compounds such as ethylene glycol dimethacrylate and diethylene glycol dimethacrylate, which are formed by esterification of two or more carboxylic acids with alcohols having two or more hydroxyl groups; other divinyl compounds such as N,N-divinylaniline and divinyl ether; and compounds having three or more vinyl groups, wherein at least one is preferably selected from divinylbenzene, divinylnaphthalene, and their derivatives. These crosslinkable polymerizable monomers can be used individually or in combination of two or more.

[0110] In this invention, the crosslinkable polymeric monomer is typically used in a proportion of 0.10 to 2.00 parts by weight, preferably 0.50 to 1.50 parts by weight, more preferably 0.65 to 1.00 parts by weight, and particularly preferably 0.70 to 0.90 parts by weight, relative to 100 parts by weight of the monovinyl monomer. The higher the content of the crosslinkable polymeric monomer, the greater the tendency for the polymer of the polymeric monomer to have a higher weight-average molecular weight, and the aforementioned softening temperature (T0). 1 / 2The higher the content of cross-linking polymeric monomers, the smaller the tanδ at 100℃ and 130℃ in the temperature-tanδ curve of the toner, and the smaller the value of (tanδ(130℃)-tanδ(100℃)) / 30 shown in the above formula (I-2).

[0111] The aforementioned polymerizable monomers may contain both monovinyl monomers and macromonomers. By including macromonomers in the aforementioned polymerizable monomers, the balance between toner shelf life and low-temperature fixing properties can be improved.

[0112] Examples of macromonomers include reactive oligomers and polymers with polymerizable carbon-carbon unsaturated double bonds at the ends of their molecular chains and a number-average molecular weight typically between 1,000 and 30,000. Examples of such macromonomers include styrene macromonomers, styrene-acrylonitrile macromonomers, polyacrylate macromonomers, and polymethacrylate macromonomers. From the perspective of easily controlling the glass transition temperature (Tg) of the toner, at least one selected from polyacrylate macromonomers and polymethacrylate macromonomers is preferred. Examples of acrylates that can be used as polyacrylate macromonomers include, for example, acrylates similar to those that can be used as the aforementioned monovinyl monomers; examples of methacrylates that can be used as polymethacrylate macromonomers include, for example, methacrylates similar to those that can be used as the aforementioned monovinyl monomers. Among them, from the perspective that the glass transition temperature (Tg) of the toner is easily within the above-mentioned preferred range, it is preferable to use the macromonomer described below: by including the macromonomer in the above-mentioned polymerizable monomer, the glass transition temperature (Tg) of the resulting adhesive resin is higher than that of the case where it is not included.

[0113] Commercially available products can be used as the aforementioned macromonomers. Examples of commercially available macromonomers include the AA-6, AS-6, AN-6S, AB-6, and AW-6S series of macromonomers manufactured by Toa Synthetic Co., Ltd.

[0114] The aforementioned macromolecular monomers can be used alone or in combination of two or more.

[0115] When the polymerizable monomer contains the macromonomer, the content of the macromonomer can be appropriately adjusted in such a way that the temperature-tanδ curve of the toner satisfies the above formula (I-1) and above formula (I-2), without particular limitation. It is preferred to use 0.03 to 5 parts by mass, more preferably 0.05 to 1 part by mass, relative to 100 parts by mass of the above monovinyl monomer.

[0116] The content of the polymerizable monomer can be appropriately adjusted in such a way that the temperature-tanδ curve of the colorant satisfies the above formula (I-1) and above formula (I-2), without particular limitation. The total content of the polymerizable monomer is preferably 60 to 95 parts by mass relative to 100 parts by mass of all solid components contained in the above polymerizable monomer composition, more preferably 65 to 90 parts by mass, and even more preferably 70 to 90 parts by mass.

[0117] Furthermore, in this invention, solid components refer to all components other than solvents, including liquid monomers.

[0118] The colorant contained in the first colorant of the present invention can be appropriately selected from colorants used in conventional colorants, without particular limitation, but it is preferable to use a colorant that easily increases the viscosity of the colorant. Here, a colorant that easily increases the viscosity of the colorant refers to a colorant with relatively high intermolecular forces between itself and the binder resin contained in the colorant, and relatively high intermolecular forces between the colorants themselves. Typically, a colorant that easily increases the viscosity of the colorant is a colorant that can form hydrogen bonds with the binder resin. For example, when the colorant contains a polymeric monomer comprising styrene and at least one monovinyl monomer selected from acrylates and methacrylates as the binder resin, and the colorant is a colorant having at least one functional group selected from hydroxyl, aldehyde, carbonyl, carboxyl, ester, ether, amino, amide, and cyano groups, the colorant easily forms hydrogen bonds with the monomer units of the acrylate or methacrylate from the polymer contained as the binder resin. Furthermore, the more of the aforementioned functional groups a colorant contains in one molecule, the easier it is to increase the viscosity of the colorant.

[0119] Furthermore, the smaller the particle size of the colorant contained in the toner, the higher the intermolecular forces generated between the binding resins and between the colorants, thus the viscosity of the toner is more likely to increase.

[0120] By using a colorant that easily increases the viscosity of the toner, the aforementioned softening temperature (T) of the toner is easily lowered. 1 / 2 The above-mentioned preferred range is defined as follows. Furthermore, since using a colorant that easily increases the viscosity of the toner results in a higher reaction rate of the polymerizable monomers in the subsequent polymerization process, the weight-average molecular weight of the polymer of the polymerizable monomers increases. Therefore, it is also easier to lower the aforementioned softening temperature (T0) of the toner. 1 / 2 The above-mentioned preferred range is defined as follows.

[0121] Furthermore, when using a colorant that easily increases the viscosity of the toner, there is a tendency for the value of (tanδ(130℃)-tanδ(100℃)) / 30, as shown in the temperature-tanδ curve of the toner, to decrease.

[0122] As a colorant that easily increases the viscosity of the toner as described above, a preferred colorant is, for example, a mixture of a colorant, a polymeric monomer, and a molecular weight regulator of the same type and content ratio as the polymeric monomer composition that can be used to manufacture the toner, with a viscosity preferably of 200 to 1500 mPa·s, more preferably 240 to 1000 mPa·s.

[0123] In the first colorant of the present invention, it is preferable to select the type and content of the colorant, as well as the type and content of the polymerizable monomer, such that the viscosity of the mixture is within the aforementioned range. By ensuring that the viscosity of the mixture is within the aforementioned range, the temperature-tanδ curve of the colorant readily satisfies the aforementioned formulas (I-1) and (I-2), and the aforementioned softening temperature (T). 1 / 2 It is easy to achieve a good balance between low-temperature fixing and preservation within the above-mentioned preferred range.

[0124] Furthermore, for example, the viscosity of the mixture can be kept within the aforementioned range by combining the colorant, which tends to increase the viscosity of the toner, with a polymerizable monomer comprising styrene and at least one monovinyl monomer selected from acrylates and methacrylates. Additionally, there is a tendency that the smaller the particle size of the colorant, the higher the viscosity of the mixture.

[0125] The colorant contained in the first colorant of this invention can be any colorant that can be used in existing colorants, and there is no particular limitation. When making a colored colorant, black, cyan, yellow, and magenta colorants can be used.

[0126] As a black colorant, it is possible to use materials such as carbon black, titanium black, and magnetic powders such as zinc oxide and nickel oxide.

[0127] As cyan colorants, cyan pigments such as copper phthalocyanine pigments and their derivatives, anthraquinone pigments, and cyan dyes can be used. Specifically, examples include: CI Pigment Blue 2, 3, 6, 15, 15:1, 15:2, 15:3, 15:4, 16, 17:1, 60; CI Solvent Blue 70, etc.

[0128] As a yellow colorant, azo pigments such as monoazo and diazo pigments, fused polycyclic pigments, and yellow dyes can be used. Specifically, examples include: CI Pigment Yellow 3, 12, 13, 14, 15, 17, 62, 65, 73, 74, 83, 93, 97, 120, 138, 155, 180, 181, 185, 186, 213, 214; CI Solvent Yellow 98, 162, etc.

[0129] As a coloring agent for magenta, various types of magenta pigments can be used, such as azo pigments (monoazo and diazo pigments), fused polycyclic pigments (quinacridone pigments), and magenta dyes. Specifically, examples include: CI Pigment Red 31, 48, 57:1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 149, 150, 163, 170, 184, 185, 187, 202, 206, 207, 209, 237, 238, 251, 254, 255, 269; CI Pigment Violet 19; CI Solvent Red 1, 3, 8, 23, 2... 4, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, 27; CI Disperse Violet 1; CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28, etc.

[0130] The above-mentioned colorants can be used alone or in combination of two or more.

[0131] The colorant contained in the first colorant of the present invention readily satisfies the above-mentioned formulas (I-1) and (I-2) from the temperature-tanδ curve of the colorant, and readily reaches the above-mentioned softening temperature (T). 1 / 2 From the perspective of the aforementioned preferred range, it is preferable to use a yellow colorant composed of yellow pigments. From the viewpoint of making it easier to increase the viscosity of the colorant as described above, it is more preferable to use a yellow colorant composed of yellow pigments that do not contain chlorine atoms. It is even more preferable to use a yellow colorant composed of azo-based yellow pigments that do not contain chlorine atoms. It is even more preferable to use a yellow colorant composed of diazo-based yellow pigments that do not contain chlorine atoms. Specifically, for example, at least one selected from CI Pigment Yellow 155 and CI Pigment Yellow 93 is preferred, and CI Pigment Yellow 155 is more preferred.

[0132] The colorant content is typically 1 to 20 parts by mass relative to 100 parts by mass of the polymerizable monomer, preferably 5 to 15 parts by mass, and more preferably 7 to 13 parts by mass. By keeping the colorant content within the above range, the temperature-tanδ curve of the toner easily satisfies the above formulas (I-1) and (I-2). Furthermore, the softening temperature (T) of the toner... 1 / 2 It is easy to fall within the above preferred range.

[0133] The polymerizable monomer composition contains a softener. By containing a softener, the release property of the toner from the fixing roller during fixing can be improved. As a softener, any softener that can generally be used as a toner softener or a release agent can be used without particular restriction. Examples include low molecular weight polyolefin waxes and their modified waxes; petroleum waxes such as paraffin wax; mineral waxes such as ceresin wax; synthetic waxes such as Fischer-Tropsch wax; and ester waxes such as dipentaerythritol ester and carnauba wax. Among these, ester waxes are preferred from the perspective of adjusting the viscoelasticity of the toner and improving the balance between toner retention and low-temperature fixing properties; synthetic ester waxes obtained by esterification of alcohols and carboxylic acids are more preferred; and polyfunctional ester waxes obtained by esterification of polyols and monocarboxylic acids are even more preferred.

[0134] As a polyfunctional ester wax, at least one selected from pentaerythritol ester compounds, glycerol ester compounds, and dipentaerythritol ester compounds is preferred. Examples of such preferred polyfunctional ester waxes include: pentaerythritol tetrapalmitate, pentaerythritol tetrabenzyl ester, pentaerythritol tetrastearate, etc.; glycerol ester compounds such as hexaglycerol tetrabenzyl ester tetrapalmitate, hexaglycerol octabenzyl ester, hexaglycerol pentabenzyl ester, hexaglycerol tetrabenzyl ester, hexaglycerol hexabenzyl ester, triglycerol pentabenzyl ester, diglycerol tetrabenzyl ester, triglycerol tribenzyl ester; and dipentaerythritol hexamyristate, dipentaerythritol hexapalmitate, etc.

[0135] The weight-average molecular weight (Mw) of the aforementioned softening agent is not particularly limited, but is preferably in the range of 400 to 3500, more preferably in the range of 500 to 3000. The higher the weight-average molecular weight (Mw) of the aforementioned softening agent, the higher the softening temperature (T) of the toner. 1 / 2 The higher the tendency.

[0136] The weight-average molecular weight (Mw) of the aforementioned softener can be determined using the same method as that used for the weight-average molecular weight (Mw) of the polymers described later. Furthermore, in the case of ester waxes, after solvent extraction, they are hydrolyzed into alcohols and carboxylic acids for compositional analysis, thereby allowing the molecular weight to be calculated from the structural formula. The weight-average molecular weight (Mw) result for ester waxes is the same as the result of the molecular weight calculated from the structural formula.

[0137] Furthermore, from the perspective of adjusting the viscoelasticity of the toner, improving the balance between the toner's shelf life and low-temperature fixing properties, the melting point of the aforementioned softener is preferably in the range of 50 to 90°C, more preferably in the range of 60 to 85°C, and even more preferably in the range of 70 to 80°C.

[0138] The content of the aforementioned softener is not particularly limited. From the perspective of adjusting the viscoelasticity of the toner, improving the balance between the toner's preservation and low-temperature fixing properties, it is preferable to use it at a ratio of 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, relative to 100 parts by weight of the aforementioned monovinyl monomer.

[0139] In addition, the above-mentioned softeners can be used alone or in combination of two or more.

[0140] The polymerizable monomer composition contains a charge control agent that is positively or negatively charged. This can improve the charge of the toner.

[0141] As a charge control agent, there is no particular limitation as long as it is a charge control agent commonly used as a charge control agent for toners. Among charge control agents, positively charged or negatively charged control resins are preferred from the perspective of high compatibility with polymerizable monomers and the ability to impart stable charge (charge stability) to toner particles. Furthermore, from the viewpoint of obtaining a positively charged toner, positively charged charge control resins are more preferred.

[0142] As a charge-controlling resin with positive or negative charge, a functional group copolymer can be used. As a positively charged charge-controlling resin, a functional group copolymer can be used, for example, that contains structural units with functional groups such as amino, quaternary ammonium, or quaternary ammonium salt groups; examples include polyamine resins, quaternary ammonium copolymers, and quaternary ammonium salt copolymers. As a negatively charged charge-controlling resin, a functional group copolymer can be used, for example, that contains structural units with functional groups such as sulfonic acid groups, sulfonate groups, carboxylic acid groups, or carboxylate groups; examples include sulfonic acid copolymers, sulfonate copolymers, carboxylic acid copolymers, and carboxylate copolymers.

[0143] From the perspective of easily satisfying the above formulas (I-1) and (I-2) in the temperature-tanδ curve of the toner, the functional group-containing copolymer that can be used as a positively or negatively charged control resin preferably has a proportion of functional group-containing structural units of 10% by mass or less, more preferably 9% by mass or less. On the other hand, from the perspective of improving the charged stability and shelf life of the toner, the proportion of functional group-containing structural units of the functional group-containing copolymer is preferably 0.5% by mass or more. By making the charged control resin sufficiently contain functional groups, the charged control resin is easily present locally near the surface of the colored resin particles, and the charged control resin functions like a shell of the colored resin particles, thereby presumably improving the shelf life of the toner.

[0144] Among them, the functional group copolymers that can be used as positively or negatively charged control resins are preferably styrene-acrylic resins, based on the aspects of high compatibility with the above-mentioned polymerizable monomers and easy satisfaction of the above-mentioned formulas (I-1) and (I-2) in the temperature-tanδ curve of the toner.

[0145] Furthermore, the glass transition temperature (Tg) of the aforementioned functional group-containing copolymers, which can be used as positively or negatively charged control resins, is preferably 50–110°C, more preferably 60–100°C. When the glass transition temperature (Tg) of the aforementioned functional group-containing copolymers is within the aforementioned range, the above formulas (I-1) and (I-2) are easily satisfied in the temperature-tanδ curve of the toner, and the toner's shelf life can be improved. The aforementioned functional group-containing copolymers tend to exist locally near the surface of the coloring resin particles and can function like a shell. Therefore, when the Tg of the aforementioned functional group-containing copolymers is within the aforementioned range, by making the Tg sufficiently high, the shelf life of the toner can be presumed to be improved.

[0146] In addition, the glass transition temperature (Tg) of the above-mentioned functional group copolymer can be determined using the same method as that for the glass transition temperature (Tg) of the above-mentioned toner.

[0147] Furthermore, the weight-average molecular weight Mw of the above-mentioned functional group-containing copolymers that can be used as positively or negatively charged control resins is preferably 5,000 to 30,000, more preferably 10,000 to 25,000.

[0148] Examples of charge control agents other than positively charged charge control resins include aniline black dyes, quaternary ammonium salts, triaminotriphenylmethane compounds, and imidazole compounds.

[0149] Examples of charge control agents other than negatively charged charge control resins include azo dyes containing metals such as Cr, Co, Al, and Fe, metal salicylate compounds, and alkyl metal salicylate compounds.

[0150] The above-mentioned charge control agents can be used alone or in combination of two or more.

[0151] In this invention, the charge control agent is typically used at a ratio of 0.01 to 10 parts by weight, preferably 0.03 to 8 parts by weight, relative to 100 parts by weight of the monovinyl monomer. When the content of the charge control agent is 0.01 parts by weight or more, the generation of fog can be suppressed; on the other hand, when the amount of charge control agent added is 10 parts by weight or less, printing contamination can be suppressed.

[0152] Furthermore, the polymerizable monomer composition preferably contains a molecular weight regulator.

[0153] As a molecular weight regulator, there are no particular limitations as long as it is a molecular weight regulator commonly used as a colorant. Examples include thiols such as tert-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, and 2,2,4,6,6-pentamethylheptane-4-thiol; and dithiuram disulfides such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, N,N'-dimethyl-N,N'-diphenylthiuram disulfide, and N,N'-di(octadecyl)-N,N'-diisopropylthiuram disulfide. These molecular weight regulators can be used alone or in combination of two or more.

[0154] From the aspects that the temperature-tanδ curve of the toner easily satisfies the above equations (I-1) and (I-2), and the above softening temperature (T) 1 / 2 Based on the aforementioned preferred range, the first colorant of the present invention preferably adjusts the content of the molecular weight regulator so that the weight-average molecular weight Mw of the polymer contained in the binder resin is within the preferred range described later. The molecular weight regulator is preferably used in a ratio of 1.0 to 3.0 parts by weight, more preferably 1.1 to 2.0 parts by weight, relative to 100 parts by weight of the monovinyl monomer. Furthermore, there is a tendency that the higher the content of the molecular weight regulator, the lower the weight-average molecular weight of the polymer contained in the binder resin, and the aforementioned softening temperature (T) of the colorant... 1 / 2The higher the content of the molecular weight regulator, the greater the value of (tanδ(Tg)-tanδ(45℃)) / (Tg-45) shown in Equation (I-1) and the greater the value of (tanδ(130℃)-tanδ(100℃)) / 30 shown in Equation (I-2) in the temperature-tanδ curve of the toner. Furthermore, the higher the content of the molecular weight regulator, the lower the glass transition temperature (Tg) of the toner, and the greater the tanδ in Tg, the tanδ at 100℃, and the tanδ at 130℃.

[0155] (A-2) The suspension process (droplet formation process) to obtain the suspension.

[0156] Next, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer, and a polymerization initiator is added to form droplets of the polymerizable monomer composition. The polymerization initiator can be added after the polymerizable monomer composition is dispersed in the aqueous medium and before droplet formation, as described above, or it can be added to the polymerizable monomer composition before it is dispersed in the aqueous medium.

[0157] There are no particular limitations on the method of droplet formation. Devices capable of strong stirring, such as (inline type) emulsifiers (manufactured by Taihei Kiko Co., Ltd., trade name: Milder) and high-speed emulsifiers (manufactured by Pleximix Co., Ltd., trade name: TKHomo MixerMARKII type), can be used.

[0158] Examples of polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate; azo compounds such as 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(2-methyl-N-(2-hydroxyethyl)propionamide), 2,2'-azobis(2-amidinylpropane)dichloride, 2,2'-azobis(2,4-dimethylpentanonitrile), and 2,2'-azobisisobutyronitrile; and organic peroxides such as di-tert-butyl peroxide, benzoyl peroxide, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide-2-ethylbutyrate, tert-hexyl peroxide-2-ethylbutyrate, diisopropyl peroxide dicarbonate, di-tert-butyl peroxide-isophthalate, and tert-butyl peroxide-isobutyrate.

[0159] Among these, organic peroxides are preferred because they can reduce residual polymerizable monomers and have excellent printing durability. Among organic peroxides, peroxide esters are preferred because they have good initiator efficiency and can also reduce residual polymerizable monomers, and non-aromatic peroxide esters, i.e., peroxide esters without aromatic rings, are more preferred.

[0160] These polymerization initiators can be used individually or in combination of two or more.

[0161] The amount of polymerization initiator added for the polymerization reaction of the polymerizable monomer composition is preferably 0.1 to 20 parts by weight relative to 100 parts by weight of the monovinyl monomer, more preferably 0.3 to 15 parts by weight, and particularly preferably 1 to 10 parts by weight.

[0162] In this invention, aqueous medium refers to a medium in which water is the main component.

[0163] In this invention, the aqueous medium preferably contains a dispersing stabilizer. Examples of dispersing stabilizers include sulfates such as barium sulfate and calcium sulfate; carbonates such as barium carbonate, calcium carbonate, and magnesium carbonate; phosphates such as calcium phosphate; metal oxides such as alumina and titanium oxide; inorganic compounds such as metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and iron hydroxide; water-soluble polymers such as polyvinyl alcohol, methylcellulose, and gelatin; anionic surfactants; nonionic surfactants; and amphoteric surfactants. One or more of these dispersing stabilizers can be used.

[0164] Among the aforementioned dispersion stabilizers, inorganic compounds are preferred as the aqueous medium containing the dispersion stabilizer, and colloids of water-insoluble metal hydroxides are particularly preferred. By using inorganic compounds, especially colloids of water-insoluble metal hydroxides, the particle size distribution of the coloring resin particles can be narrowed. Furthermore, the amount of dispersion stabilizer residue after washing can be reduced. Therefore, the resulting polymeric toner can vividly reproduce images without deteriorating its environmental stability.

[0165] (A-3) Polymerization process

[0166] As described in (A-2) above, after droplet formation of the polymerizable monomer composition, the polymerizable monomer composition is supplied to the polymerization reaction in the presence of a polymerization initiator, thereby forming colored resin particles. That is, the aqueous dispersion medium in which the droplets of the polymerizable monomer composition are dispersed is heated to initiate polymerization and form an aqueous dispersion of colored resin particles.

[0167] The heating conditions described above are preferably adjusted in such a way that the weight-average molecular weight (Mw) of the polymer of the polymeric monomers falls within the preferred range described later. There are no particular limitations on these conditions. The heating temperature is preferably 50°C or higher, more preferably 60–95°C. Furthermore, the heating time is preferably 1 to 20 hours, more preferably 2 to 15 hours.

[0168] Coloring resin particles can be used directly as a toner or added as an external additive. Preferably, these coloring resin particles are used as the core layer of so-called core-shell (or "capsule-type") coloring resin particles. Core-shell type coloring resin particles have a structure where a shell layer formed from a different material than the core layer covers the outer side of the core layer. By coating the core layer, formed from a material with a low softening point, with a material having a higher softening point, the above equations (I-1) and (I-2) can be easily satisfied in the temperature-tanδ curve, thus uniformly improving the low-temperature fixing and preservation properties of the toner.

[0169] The method for manufacturing core-shell colored resin particles using the aforementioned colored resin particles is not particularly limited and can be manufactured using existing known methods. From the perspective of manufacturing efficiency, in-situ polymerization and phase separation methods are preferred.

[0170] The following describes the manufacturing method of core-shell colored resin particles using in-situ polymerization.

[0171] By adding a polymerizable monomer (shell polymerizable monomer) and a polymerization initiator to an aqueous medium in which colored resin particles are dispersed, polymerization can be carried out to obtain core-shell type colored resin particles.

[0172] As the shell polymerizable monomer, the same monomers as those described above can be used. Among them, monomers that yield polymers with a Tg exceeding 80°C are preferred, either alone or in combination, such as styrene, acrylonitrile, and methyl methacrylate.

[0173] Examples of polymerization initiators for the polymerization of shell-forming polymerizable monomers include persulfate metal salts such as potassium persulfate and ammonium persulfate; and water-soluble polymerization initiators such as azo initiators like 2,2'-azobis(2-methyl-N-(2-hydroxyethyl)propionamide) and 2,2'-azobis(2-methyl-N-(1,1-bis(hydroxymethyl)-2-hydroxyethyl)propionamide). These can be used individually or in combination of two or more. The amount of polymerization initiator is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, relative to 100 parts by weight of the shell-forming polymerizable monomer.

[0174] The polymerization temperature of the shell is preferably 50°C or higher, more preferably 60–95°C. Furthermore, the polymerization reaction time is preferably 1 hour to 20 hours, more preferably 2 hours to 15 hours.

[0175] (A-4) Washing, filtering, dehydration and drying processes

[0176] The aqueous dispersion of the colored resin particles obtained by polymerization is preferably subjected to repeated filtration, washing to remove the dispersant stabilizer, dehydration and drying operations as needed, following conventional methods after polymerization termination.

[0177] As a cleaning method as described above, when using an inorganic compound as a dispersion stabilizer, it is preferable to remove the dispersion stabilizer by adding an acid or alkali to the aqueous dispersion of the coloring resin particles to dissolve the stabilizer in water. When using a colloid of a water-insoluble inorganic hydroxide as a dispersion stabilizer, it is preferable to add an acid to adjust the pH of the aqueous dispersion of the coloring resin particles to below 6.5. As the added acid, inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid can be used; as well as organic acids such as formic acid and acetic acid. Sulfuric acid is particularly preferred because it has high removal efficiency and low burden on manufacturing equipment.

[0178] The methods for dehydration and filtration can be various well-known methods, without particular limitations. Examples include centrifugal filtration, vacuum filtration, and pressure filtration. Furthermore, the methods for drying are also not particularly limited, and various methods can be used.

[0179] (B) Crushing method

[0180] When manufacturing colored resin particles using a pulverizing method, the process is carried out through, for example, the following steps.

[0181] First, the binder resin, colorant, softener, charge control agent, and other additives as needed are mixed using a mixer such as a ball mill, V-type mixer, FM Mixer (trade name), high-speed dissolver, internal mixer, or Forberg mixer. Next, the mixture obtained above is heated and kneaded using a pressure kneader, twin-screw extruder, or roller mill. The resulting mixture is then coarsely pulverized using a hammer mill, milling mill, or roller mill. Finally, after fine pulverization using a jet mill or high-speed rotary mill, it is classified into the desired particle size using a classifier such as an air classifier or classifier to obtain colored resin particles produced by the pulverization method.

[0182] Furthermore, the binding resin, colorant, softener, and charge control agent used in the pulverization method can be those listed in the suspension polymerization method described in (A) above. Moreover, the colored resin particles obtained by the pulverization method can be used to manufacture core-shell type colored resin particles by methods such as in-situ polymerization, just as the colored resin particles obtained by the suspension polymerization method described in (A) above.

[0183] In addition to the above, resins that have been widely used in toners can also be used as adhesive resins. Specifically, examples of adhesive resins that can be used in the pulverization method include polystyrene, styrene-butyl acrylate copolymers, polyester resins, and epoxy resins.

[0184] I-3. Colored resin particles

[0185] Colored resin particles can be obtained by manufacturing methods such as (A) suspension polymerization or (B) pulverization.

[0186] The coloring resin particles contained in the first colorant of the present invention will be described below. Furthermore, the coloring resin particles described below include both core-shell type and non-core-shell type coloring resin particles.

[0187] The coloring resin particles used in the first colorant of the present invention comprise a binding resin, a colorant, a softener, and a charge control agent, and may further contain other additives as needed.

[0188] As the binding resin contained in the aforementioned coloring resin particles, examples include polymers obtained by polymerizing the polymerizable monomers described in the suspension polymerization method (A) above. Furthermore, in this invention, the polymer can be either a homopolymer or a copolymer. The preferred polymerizable monomers derived from each structural unit of the aforementioned polymer are the same as the preferred polymerizable monomers described in the suspension polymerization method (A) above. The colorant readily satisfies the above formulas (I-1) and (I-2) and the above softening temperature (T) from the temperature-tanδ curve. 1 / 2 From the perspective of easily improving the low-temperature fixing and preservation properties of the toner within the aforementioned preferred range and in a balanced manner, the binder resin contained in the aforementioned coloring resin particles preferably contains a polymer comprising one or more polymeric monomers selected from at least one monovinyl monomer chosen from styrene, acrylates and methacrylates, more preferably a polymer comprising styrene and one or more polymeric monomers selected from at least one acrylate and methacrylates, and even more preferably a polymer comprising a polymeric monomer comprising styrene, at least one polymeric monomer selected from acrylates and methacrylates, and at least one polymeric monomer selected from divinylbenzene, divinylnaphthalene and their derivatives.

[0189] Furthermore, the structure and proportion of each structural unit in all the structural units of the aforementioned polymer can be determined by the amount of feed used in the synthesis of the polymer. Additionally, it can be determined by... 1 The integral value from the H-NMR measurement is calculated.

[0190] The toner readily satisfies equations (I-1) and (I-2) above, and the softening temperature (T) above, as shown in the temperature-tanδ curve. 1 / 2 From the perspective of easily improving the low-temperature fixing and preservation properties of the toner within the above-mentioned preferred range, the weight-average molecular weight (Mw) of the polymer contained in the binder resin is preferably 1.00 × 10⁻⁶. 5 Above and 1.00×106 The following applies. From the perspective of improving the preservation of the toner, the lower limit of the aforementioned weight-average molecular weight Mw is more preferably 2.00 × 10⁻⁶. 5 The above is further preferred to be 3.00×10 5 The above is further preferred to be 3.1×10 5 Furthermore, from the perspective of improving the low-temperature fixing properties of the toner, the upper limit of the aforementioned weight-average molecular weight Mw is more preferably 7.00 × 10⁻⁶. 5 The following is a further preferred value: 5.50 × 10 5 The following is a further preferred value: 5.00 × 10 5 The following. Additionally, the polymer contained in the bonding resin typically refers to a polymer of the aforementioned polymerizable monomers.

[0191] There is a tendency that the smaller the weight-average molecular weight (Mw) of the polymer, the lower the Tg of the toner and the larger the tanδ(Tg). Therefore, there is a tendency for the value of (tanδ(Tg)-tanδ(45℃)) / (Tg-45) shown in formula (I-1) to be larger. Furthermore, there is a tendency that the smaller the weight-average molecular weight (Mw) of the polymer, the larger both tanδ(100℃) and tanδ(130℃) of the toner. However, since the increase in tanδ(130℃) is more likely to be greater, there is a tendency for the value of (tanδ(130℃)-tanδ(100℃)) / 30 shown in formula (I-2) to be larger. In addition, there is a tendency that the larger the weight-average molecular weight (Mw) of the polymer, the higher the softening temperature (Tg) of the toner. 1 / 2 The higher the weight-average molecular weight (Mw) of the polymer, the easier it is to suppress deterioration in shelf life.

[0192] Furthermore, in this invention, the weight-average molecular weight (Mw) of the polymer can be calculated using the polystyrene conversion in GPC. As a sample for GPC testing, the polymer to be tested is typically dissolved in tetrahydrofuran (THF). When measuring the weight-average molecular weight (Mw) of the polymer contained in the binder resin, a colorant is dissolved in tetrahydrofuran (THF) as a sample for GPC testing. The weight-average molecular weight (Mw) of the polymer contained in the binder resin can be calculated by subtracting the peaks obtained from the measurement results after pre-measuring polymers other than the polymer contained in the binder resin, i.e., charge control resins and softeners.

[0193] The binder resin contained in the aforementioned coloring resin particles is typically a polymer of the aforementioned polymeric monomers. When the toner satisfies the ranges of formulas (I-1) and (I-2) in the temperature-tanδ curve, it may contain small amounts of polyester resins, epoxy resins, etc., which are commonly used as binders in the past, as well as unreacted polymeric monomers. Preferably, the content of polyester resin in 100 parts by mass of the aforementioned binder resin is 5 parts by mass or less, more preferably 1 part by mass or less, even more preferably 0.1 parts by mass or less, and particularly preferably no polyester resin. By keeping the content of polyester resin below the aforementioned upper limit, the environmental stability of the toner can be improved, and in particular, changes in the charge of the toner due to humidity variations can be suppressed.

[0194] Furthermore, when the adhesive resin contains a resin other than the polymer of the polymeric monomer, from the perspective that the toner easily satisfies the above formulas (I-1) and (I-2) in the temperature-tanδ curve, the content of the polymer of the polymeric monomer in 100 parts by mass of the adhesive resin is preferably 95 parts by mass or more, more preferably 97 parts by mass or more, and even more preferably 99 parts by mass or more.

[0195] Furthermore, in this invention, the molecular weight regulator used during the polymerization reaction is considered to be included in the binder resin.

[0196] From the perspective that the toner readily satisfies the above formulas (I-1) and (I-2) in the temperature-tanδ curve, the total content of the above-mentioned adhesive resin is preferably 60 to 95 parts by mass, more preferably 65 to 90 parts by mass, and even more preferably 70 to 85 parts by mass, relative to 100 parts by mass of all solid components contained in the above-mentioned coloring resin particles.

[0197] Furthermore, in the above-mentioned adhesive resin, which comprises 100% by mass, the proportion of structural units derived from styrene is preferably 60 to 90% by mass, more preferably 65 to 85% by mass, and even more preferably 70 to 80% by mass.

[0198] Furthermore, in the above-mentioned adhesive resin, which comprises 100% by mass, the proportion of structural units derived from crosslinking polymeric monomers is preferably 0.10 to 2.00% by mass, more preferably 0.50 to 1.50% by mass, and even more preferably 0.65 to 1.00% by mass.

[0199] The colorants, softeners, and charge control agents contained in the above-mentioned colored resin particles are the same as those listed in the suspension polymerization method (A) above.

[0200] The content of the colorant contained in the above-mentioned colored resin particles is appropriately adjusted according to the type of colorant in order to obtain the desired coloring and to make the colorant satisfy the above formula (I-1) and above formula (I-2) in the temperature-tanδ curve. There is no particular limitation. Relative to 100 parts by mass of the above-mentioned adhesive resin, the content of the colorant contained in the above-mentioned colored resin particles is preferably 1 to 20 parts by mass, more preferably 5 to 15 parts by mass, and even more preferably 7 to 13 parts by mass.

[0201] From the perspective of improving the balance between the toner's preservation and low-temperature fixing properties, the content of the softener contained in the coloring resin particles is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, relative to 100 parts by weight of the above-mentioned binder resin.

[0202] Relative to 100 parts by weight of the aforementioned adhesive resin, the content of the charge control agent contained in the aforementioned coloring resin particles is preferably 0.01 to 15 parts by weight, more preferably 0.03 to 8 parts by weight. By setting the content of the charge control agent to the aforementioned lower limit or above, the generation of fog can be suppressed; on the other hand, by setting the content of the charge control agent to the aforementioned upper limit or below, printing contamination can be suppressed.

[0203] The volume average particle size (Dv) of the coloring resin particles is preferably 3 to 15 μm, more preferably 4 to 12 μm. By setting the Dv to 3 μm or more, the flowability of the toner can be improved, and the deterioration of transfer properties and reduction in image density can be suppressed. By setting the Dv to 15 μm or less, the reduction in image resolution can be suppressed.

[0204] Furthermore, the ratio of the volume average particle size (Dv) to the number average particle size (Dn) of the colored resin particles (Dv / Dn) is preferably 1.0 to 1.3, more preferably 1.0 to 1.2. By making Dv / Dn 1.3 or less, the reduction in transferability, image density, and resolution can be suppressed. In addition, the volume average particle size and number average particle size of the colored resin particles can be measured using, for example, a particle size analyzer (Beckman Coulter, trade name: Multisizer).

[0205] From the viewpoint of image reproducibility, the average roundness of the colored resin particles is preferably 0.96 to 1.00, more preferably 0.97 to 1.00, and even more preferably 0.98 to 1.00.

[0206] By ensuring that the average roundness of the aforementioned colored resin particles is 0.96 or higher, the reproducibility of printed fine lines can be improved. The average roundness of the colored resin particles of the present invention is 1 or less, specifically 1 when the test sample is a perfectly spherical shape.

[0207] In this invention, roundness refers to the value of the circumference of a circle having the same projected area as the particle image divided by the circumference of the particle's projected image. Average roundness is an indicator of the unevenness of the sample surface and can be used as a simple method to quantitatively represent the shape of particles. The more complex the surface shape of the sample, the smaller the average roundness value.

[0208] The roundness of the colored resin particles can be determined, for example, as follows: Using an aqueous solution containing the colored resin particles as the sample solution, a flow cytometry particle imaging analyzer (e.g., Sysmex Corporation, trade name: FPIA-2100, etc.) is used to capture a projected image of the colored resin particles in the sample solution. Based on this projected image, the circumference of the circle with the same projected area as the particle and the circumference of the particle's projected image are measured. The roundness is then calculated using formula 1: (Roundness) = (Circumference of the circle with the same projected area as the particle) / (Circumference of the particle's projected image). The average roundness is the average of the roundness of all the colored resin particles contained in the sample solution.

[0209] I-4. The first toner of the present invention

[0210] The first colorant of the present invention can also use coloring resin particles directly as colorant. However, from the viewpoint of adjusting the charge, flowability and storage properties of the colorant, the above-mentioned coloring resin particles can also be mixed and stirred together with external additives to perform external additive treatment, thereby causing the external additives to adhere to the surface of the coloring resin particles and making a single-component colorant.

[0211] In addition, single-component toners can be mixed and stirred with mixed carrier particles to form two-component developers.

[0212] There are no particular limitations on the type of mixer used for external additive processing, as long as it is a mixing device that can cause the external additive to adhere to the surface of the coloring resin particles. Mixers capable of mixing and stirring, such as FM Mixer (trade name, manufactured by Nippon Kogyo Kogyo Co., Ltd.), Super Mixer (trade name, manufactured by Kawada Seisakusho Co., Ltd.), Q Mixer (trade name, manufactured by Nippon Kogyo Kogyo Co., Ltd.), Mechanofusion System (trade name, manufactured by Hosokawa Micron Group Co., Ltd.), and Mechano Mill (trade name, manufactured by Okada Seiko Co., Ltd.), can be used for external additive processing.

[0213] Examples of external additives include: inorganic microparticles such as silica, titanium dioxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, calcium phosphate, and cerium oxide; and organic microparticles such as polymethyl methacrylate resin, silicone resin, and melamine resin. Among these, inorganic microparticles are preferred, and among inorganic microparticles, at least one type selected from silica and titanium dioxide is preferred, with microparticles composed of silica being particularly preferred.

[0214] In addition, these external additives can be used individually, or preferably in combination of two or more.

[0215] In the first colorant of the present invention, the external additive is typically used at a ratio of 0.05 to 6 parts by weight, preferably 0.2 to 5 parts by weight, relative to 100 parts by weight of coloring resin particles. By making the content of the external additive 0.05 parts by weight or more, the generation of transfer residue can be suppressed, and by making the content of the external additive 6 parts by weight or less, the generation of haze can be suppressed.

[0216] The temperature-tanδ curve of the first toner of the present invention satisfies the above-described formulas (I-1) and (I-2), thereby ensuring good shelf life of the first toner and suppressing the decrease in the adhesion-causing temperature (heat resistance temperature). The adhesion-causing temperature (heat resistance temperature) of the first toner of the present invention is preferably 53°C or higher, more preferably 54°C or higher, and even more preferably 55°C or higher. Furthermore, in the present invention, the adhesion-causing temperature of the toner refers to the highest temperature at which, when the toner is stored at a certain temperature for 8 hours, the mass of the agglomerated toner is less than 5% by mass of the total toner. The adhesion-causing temperature of the toner can be measured using the same method as the method used to determine the heat resistance temperature of the toner in the embodiments described later.

[0217] The first toner of the present invention, by satisfying the above formulas (I-1) and (I-2) in the temperature-tanδ curve, exhibits good low-temperature fixing properties and can suppress the rise of the fixing temperature. The fixing temperature of the first toner of the present invention is preferably below 180°C, more preferably below 170°C, and even more preferably below 160°C. Furthermore, in the present invention, the fixing temperature of the toner refers to the lowest temperature at which a fixing rate of 80% or more can be obtained when printing a completely black image on paper using a printer and performing a scratch test on a completely black area, calculated according to the following formula, is the ratio of the image density (ID(after)) after the scratch test to the image density (ID(before)) before the scratch test.

[0218] Fixing rate (%) = [ID(after) / ID(before)] × 100

[0219] The above scratch test was conducted as follows: the test part was attached to the firmness tester with tape, a load of 500g was applied, and the scratching terminal wrapped with cotton cloth was used to scratch back and forth 5 times.

[0220] Furthermore, in this invention, a completely black area refers to an area where all points (imaginary points controlling the printer control unit) within that area are covered with developer.

[0221] II. The second colorant of the present invention

[0222] The second colorant of the present invention is characterized in that it contains coloring resin particles and external additives, wherein the coloring resin particles comprise a binding resin, a colorant, a softener, and a charge control agent.

[0223] The glass transition temperature (Tg) of the above-mentioned toner satisfies 45℃ < Tg (℃) < 100℃. The glass transition temperature is determined based on the temperature dependence curve of the loss tangent (tanδ) of the toner obtained by dynamic viscoelasticity measurement at a measurement frequency of 24Hz.

[0224] In the above temperature dependence curve of loss tangent (tanδ), when the loss tangent (tanδ) at 45℃ is denoted as tanδ(45℃), the loss tangent (tanδ) at the glass transition temperature (Tg) is denoted as tanδ(Tg), the loss tangent (tanδ) at 100℃ is denoted as tanδ(100℃), and the loss tangent (tanδ) at 130℃ is denoted as tanδ(130℃), the following conditions are met:

[0225] and

[0226] .

[0227] The viscoelastic properties of the second colorant of the present invention, the manufacturing method of the coloring resin particles used in the second colorant of the present invention and the coloring resin particles, the external additives used in the second colorant of the present invention, and the performance of the second colorant of the present invention will be described in sequence below.

[0228] II-1. Viscoelastic properties of the second toner of the present invention

[0229] The second toner of the present invention exhibits the following characteristics in the temperature dependence curve of the loss tangent (tanδ) obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz, within the range of 45°C to 145°C: Specifically, it has at least one peak in the range of greater than 45°C and less than 100°C. When the temperature is greater than the temperature at which tanδ reaches its maximum, tanδ decreases with increasing temperature, then decreases incrementally or continuously, and after reaching its minimum, tanδ slowly increases with further increasing temperature.

[0230] Furthermore, the second toner of the present invention satisfies the following conditions when the glass transition temperature (Tg) determined from the temperature dependence curve of the loss tangent (tanδ) is greater than 45°C and less than 100°C, and the loss tangent (tanδ) at 45°C is denoted as tanδ(45°C), the loss tangent (tanδ) at the glass transition temperature (Tg) is denoted as tanδ(Tg), the loss tangent (tanδ) at 100°C is denoted as tanδ(100°C), and the loss tangent (tanδ) at 130°C is denoted as tanδ(130°C):

[0231] and

[0232] .

[0233] In equations (II-1) and (II-2) above, the values ​​of tanδ are used with a precision of three decimal places. Furthermore, the value of (tanδ(Tg)-tanδ(45℃)) / (Tg-45) shown in equation (II-1) is a value with a precision of three significant figures, and the value of (tanδ(130℃)-tanδ(100℃)) / 30 shown in equation (II-2) is a value with a precision of two significant figures.

[0234] In the second toner of the present invention, the above-mentioned dynamic viscoelasticity measurement is performed under the same apparatus and conditions as the first toner of the present invention.

[0235] The second toner of the present invention has specific viscoelasticity in the temperature-tanδ curve that satisfies the above formulas (II-1) and (II-2), and is a toner that improves both low-temperature fixing and preservation properties in a balanced way. It is a toner with excellent performance that was previously difficult to achieve.

[0236] The smaller the value of (tanδ(Tg)-tanδ(45℃)) / (Tg-45) shown in the above formula (II-1) is within the above-mentioned numerical range, the easier it is to suppress the adhesion of the toner during storage and improve its shelf life. The smaller the difference between tanδ(Tg) and tanδ(45℃), or the higher Tg is, the smaller the value of (tanδ(Tg)-tanδ(45℃)) / (Tg-45) is. By keeping the difference between tanδ(Tg) and tanδ(45℃) not too large, the viscosity of the toner will not be too high, that is, the back-and-forth movement of polymer chains between toner particles can be suppressed, so adhesion is presumably suppressed. In addition, by keeping Tg not too low, the decrease in elasticity at low temperatures can be suppressed, so adhesion is presumably suppressed. Furthermore, by keeping Tg less than the above-mentioned upper limit value in the above formula (II-1), the deterioration of the shelf life of the toner can be suppressed, and the ejection of the toner after being placed at high temperatures can be easily suppressed. By setting the value in equation (II-1) above to a value greater than the lower limit, it is easy to suppress the increase in fixing temperature, thus suppressing the deterioration of low-temperature fixing performance.

[0237] On the other hand, the larger the value of (tanδ(130℃)-tanδ(100℃)) / 30 shown in the above formula (II-2) is within the above numerical range, the more likely the fixing temperature will decrease, and the lower the fixing performance will be. During fixing, the toner slowly deforms as the temperature rises. In actual fixing, from the time the paper with transferred toner enters the roller until it exits, there is at least a temperature gradient from 100°C to 130°C. The larger the value of (tanδ(130℃)-tanδ(100℃)) / 30 shown in the above formula (II-2), the faster the tanδ of the toner increases after heating, that is, the faster the viscosity of the toner increases. From this, it can be inferred that fixing at a lower temperature can be achieved. Furthermore, by exceeding the lower limit value in the above formula (II-2), the gloss of the formed image becomes better. On the other hand, by using a value less than the upper limit in the above formula (II-2), the adhesion of the toner during storage can be suppressed, thus inhibiting the deterioration of its shelf life. Furthermore, by using a value less than the upper limit in the above formula (II-2), it is easy to suppress the spraying that occurs after being placed at high temperatures.

[0238] Furthermore, the inventors have discovered that toners exhibiting viscoelasticity satisfying equations (II-1) and (II-2) above in the temperature-tanδ curve, especially when used in a flow tester at a pressure of 5.0 kgf / cm², are particularly effective. 2 The softening temperature (T) of the toner in the 1 / 2 method was determined under the following conditions. 1 / 2 The above-mentioned effects will be achieved when the temperature is greater than 124℃ and less than 159℃.

[0239] To obtain a toner that exhibits viscoelasticity satisfying equations (II-1) and (II-2) above in the temperature-tanδ curve, the viscoelasticity of the toner can be controlled by, for example, appropriately changing the composition, molecular weight, and content of the binder resin, the type and content of the colorant, the glass transition temperature (Tg) and content of the charge control agent, the type and molecular weight of the softener, and the type and content of external additives. Adjusting the molecular weight and composition of the binder resin, and the type and content of the colorant, is particularly effective. The molecular weight and composition of the binder resin in the toner have a significant impact on the viscoelasticity of the toner in the low-temperature region below the glass transition temperature. Therefore, adjusting the molecular weight and composition of the binder resin in the toner is effective in ensuring that the viscoelasticity satisfies equation (II-1) above. On the other hand, the type and content of the colorant in the toner have a significant impact on the viscoelasticity of the toner in the temperature range of 100°C to 130°C. Therefore, adjusting the type and content of colorants in the toner is effective in order to make the viscoelasticity satisfy the above formula (II-2). More specifically, by adopting the preferred method of each component described later, the temperature-tanδ curve of the toner can satisfy the above formulas (II-1) and (II-2).

[0240] The temperature-tanδ curve of the second toner of the present invention obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz satisfies the following equation (II-1).

[0241]

[0242] In particular, considering the ease of suppressing the adhesion of the toner during storage, improving its shelf life, and suppressing spraying after high-temperature storage, the upper limit in the above formula (II-1) is preferably less than 7.40 × 10⁻⁶. -2 On the other hand, from the perspective of easily suppressing the rise in fixing temperature, the lower limit in the above formula (II-1) is preferably 5.50 × 10⁻⁶. -2 The above is preferred, with 5.60×10 being more desirable. -2 The above is further preferred to be 5.90×10 -2 The above is further preferred to be 6.50×10 -2 above.

[0243] The temperature-tanδ curve of the second toner of the present invention obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz satisfies the following equation (II-2).

[0244]

[0245] In terms of improving the low-temperature fixing properties of the toner and making the resulting image glossier, the lower limit in formula (II-2) is preferably greater than 3.0 × 10⁻⁶. -3 More preferably greater than 3.5×10 -3 A further preferred value is 1.20 × 10⁻⁶. -2 That's all. On the other hand, from the perspective of easily suppressing preservation deterioration and easily suppressing ejection after high-temperature storage, the upper limit in the above formula (II-2) is preferably less than 4.1 × 10. -2 More preferably less than 3.8×10 -2 More preferably 3.2×10 -2 the following.

[0246] The glass transition temperature (Tg) of the second toner of the present invention satisfies 45°C < Tg (°C) < 100°C. This glass transition temperature is determined based on the temperature dependence curve of the loss tangent (tanδ) of the toner obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz. From the perspective of suppressing a sharp decrease in elasticity at low temperatures and suppressing adhesion, the glass transition temperature (Tg) is preferably greater than 70°C, more preferably greater than 73°C. On the other hand, from the perspective of preventing the softening start temperature of the toner from becoming too high, thereby improving low-temperature fixing performance, the glass transition temperature (Tg) is preferably 90°C or less, more preferably 85°C or less.

[0247] Furthermore, the second toner of the present invention preferably has a loss tangent (tanδ) of less than 2.410, more preferably less than 2.320, and even more preferably less than 2.300. By keeping the tanδ (Tg) below the aforementioned upper limit, it is easy to suppress adhesion of the toner during storage, to improve its shelf life, and to suppress ejection after being placed at high temperatures.

[0248] The lower limit of the above-mentioned tanδ(Tg) is not particularly limited, but from the perspective of making the fixing performance good, it is preferably 1.000 or more, and more preferably 1.100 or more.

[0249] The second toner of the present invention preferably has a loss tangent (tanδ) of tanδ (45°C) of 0.200 or less, more preferably 0.100 or less, and even more preferably 0.050 or less. By keeping the above-mentioned tanδ (45°C) below the above-mentioned upper limit value, it is easy to suppress the adhesion of the toner during storage, easy to improve its shelf life, and easy to suppress spraying after being placed at high temperature.

[0250] There is no specific limitation on the lower limit of tanδ (45℃) mentioned above, as long as it is above 0.000.

[0251] Furthermore, from the viewpoint of easily improving the low-temperature fixing properties of the toner, the tanδ (100°C) of the loss tangent (tanδ) of the second toner of the present invention is preferably 0.800 or more, more preferably 0.900 or more, and even more preferably 0.950 or more. On the other hand, from the viewpoint of easily suppressing the deterioration of the toner's shelf life and easily suppressing the occurrence of spraying after being placed at high temperature, it is preferably 1.500 or less, and more preferably 1.400 or less.

[0252] Furthermore, from the viewpoint of easily improving the low-temperature fixing properties of the toner, the second toner of the present invention preferably has a loss tangent (tanδ) of tanδ (130°C) of 1.000 or more. On the other hand, from the viewpoint of easily suppressing the deterioration of the toner's shelf life and easily suppressing the occurrence of spraying after being placed at high temperature, it is preferably 3.000 or less, more preferably 2.500 or less, and even more preferably 2.300 or less.

[0253] Furthermore, the second colorant of the present invention is preferably tested using a flow tester at a pressure of 5.0 kgf / cm. 2 The softening temperature (T) in the 1 / 2 method determined under the conditions of [condition] 1 / 2 The softening temperature is greater than 124℃ and less than 159℃. 1 / 2 Toners within the aforementioned range exhibit viscoelasticity satisfying equations (II-1) and (II-2) in their temperature-tanδ curves, thereby particularly improving low-temperature fixing and storage properties in a balanced manner, and easily suppressing ejection after high-temperature storage. Furthermore, by setting the toner to the aforementioned softening temperature (T... 1 / 2 Within the above range, the fixing temperature of the toner is reduced, thus the toner has good operability and can easily suppress the generation of volatile organic compounds (VOCs) and nanoparticles (UFPs) such as styrene and siloxanes caused by heating during toner fixing.

[0254] From the perspective of improving preservation, the aforementioned softening temperature (T) 1 / 2 The softening temperature (T) is preferably 126°C or higher, more preferably 130°C or higher, and even more preferably 140°C or higher. On the other hand, from the perspective of improving low-temperature fixing performance, the aforementioned softening temperature (T) 1 / 2 Preferably, the temperature is below 165°C, more preferably below 163°C, and even more preferably below 159°C.

[0255] The softening temperature (T) of the second colorant of the present invention 1 / 2The softening temperature (T0) can be adjusted by factors such as the composition and molecular weight of the bonding resin, the type and content of the colorant, and the content of the styrene-based thermoplastic elastomer. The lower the amount of crosslinking polymerizable monomer added to the bonding resin, the lower the aforementioned softening temperature (T0). 1 / 2 The lower the content of styrene-based thermoplastic elastomers, the lower the softening temperature (T). 1 / 2 The softening temperature (T) tends to decrease as the polymer content of the bonding resin increases. Furthermore, the higher the weight-average molecular weight of the polymer contained in the bonding resin, the higher the aforementioned softening temperature (T). 1 / 2 The tendency to increase is increasing.

[0256] The flow testing apparatus described above was used at a pressure of 5.0 kgf / cm². 2 The softening temperature (T) in the 1 / 2 method determined under the conditions of [condition] 1 / 2 The softening temperature (T0) can be determined by measuring the flow curve (piston stroke - temperature) under the following conditions using a flow testing apparatus (trade name CFT-500C) manufactured by Shimadzu Corporation. Specifically, in the flow curve, half the difference between the piston stroke at the end of the flow and the minimum value of the piston stroke can be calculated, and the softening temperature (T0) can be obtained by combining the obtained value with the temperature at the location of the sum of the minimum value and the obtained value. 1 / 2 ).

[0257] (Measurement conditions)

[0258] Starting temperature: 35℃

[0259] Heating rate: 3℃ / minute

[0260] Preheating time: 5 minutes

[0261] Cylinder pressure: 5.0 kgf / cm 2 (5kg method)

[0262] Die head bore diameter: 0.5mm

[0263] Die head length: 1.0mm

[0264] Sample dosage: 1.0–1.3 g

[0265] II-2. Thermal properties of toners

[0266] In addition, toners with improved low-temperature fixing properties tend to spray out of the developing roller after being placed at high temperatures. Therefore, a toner with excellent low-temperature fixing properties, good storage properties, and the ability to suppress spraying after being placed at high temperatures is needed.

[0267] The second toner of the present invention can easily suppress ejection after being placed at high temperatures. In particular, when the apparent glass transition temperature (Tg2) of the second toner of the present invention is 68°C to 74°C when heated at a heating rate of 1000 K / s and the exothermic onset temperature of the toner is 50°C to 62°C when cooled at a cooling rate of 1000 K / s, as determined by differential scanning calorimetry using a high-speed differential scanning calorimeter, it can evenly improve both low-temperature fixing and preservation properties and suppress ejection after being placed at high temperatures.

[0268] The second toner of the present invention preferably has an apparent glass transition temperature (Tg2) of 68°C to 74°C when heated at a heating rate of 1000 K / s, and an exothermic onset temperature of 50°C to 62°C when cooled at a cooling rate of 1000 K / s, as determined by differential scanning calorimetry using a high-speed differential scanning calorimeter.

[0269] In this invention, differential scanning calorimetry (DSC) using the above-mentioned high-speed differential scanning calorimeter can be performed using an ultra-high-speed DSC device (Mettler-Toledo, Flash DSC) under the temperature conditions described in (1) to (5) below.

[0270] (1) Hold at 0℃ for 0.1 seconds.

[0271] (2) Increase the temperature from 0℃ to 150℃ at a rate of 1000K / second.

[0272] (3) Keep at 150℃ for 60 seconds.

[0273] (4) Cool from 150℃ to 0℃ at -1000K / second.

[0274] (5) Hold at 0℃ for 1 second.

[0275] Figure 3 This paper shows the method for calculating the apparent glass transition temperature (Tg2) of a toner when heated at a rate of 1000 K / s and the exothermic onset temperature of the toner when cooled at a rate of 1000 K / s in high-speed differential scanning calorimetry.

[0276] The following temperature is taken as the apparent glass transition temperature (Tg2): the temperature at which the tangent line drawn from the line extending the baseline of the low temperature side to the high temperature side in the DSC curve during heating intersects the point where the gradient is greatest in the stepwise change part of the glass transition or in the curve of the endothermic peak caused by enthalpy relaxation.

[0277] In addition, the following temperature is used as the exothermic start temperature: the temperature at which the exothermic peak begins to appear when the curve deviates from the previous baseline in the DSC curve during cooling.

[0278] The inventors have discovered that when the apparent glass transition temperature and exothermic onset temperature are measured at a high heating and cooling rate of 1000 K / s, the same as during fixing, the behavior of the components in the toner composition in a state of coexistence and interaction can be indirectly evaluated in response to phenomena such as rapid heating and cooling, thereby enabling control of the low-temperature fixing properties of the toner.

[0279] When heating at a low rate of 10 K / s, as in typical DSC measurements, semi-crystalline samples containing amorphous components may undergo structural reorganization and recrystallization during the heating process, manifesting as peaks. When these peaks overlap at the glass transition temperature, it becomes difficult to identify the correct temperature. In contrast, heating at a high rate of 1000 K / s does not allow sufficient time for recrystallization, thus allowing for a more accurate reproduction of the heating behavior during fixing. Since heating at 1000 K / s is purely endothermic, multiple peaks may merge into one, simplifying the apparent phase transition during fixing.

[0280] Furthermore, when cooling at a low rate of 10 K / s, as in typical DSC measurements, amorphous components like resins and crystalline components like softeners slowly separate from their miscible state. Therefore, the crystallization initiation temperature of the crystalline components can be considered less affected by the amorphous components. In contrast, when cooling at a high rate of 1000 K / s, amorphous components like resins and crystalline components like softeners cool rapidly from their miscible state, so phase separation is not possible; that is, crystallization of the crystalline components occurs while they interfere with each other. It is evident that the order of the exothermic initiation temperatures between toners measured at the same high cooling rate of 1000 K / s as during fixing sometimes differs from the order of the exothermic initiation temperatures between toners measured at a low cooling rate of 10 K / s. The exothermic onset temperature, measured at a high cooling rate of 1000 K / s, the same as that during fixing, can be considered as the temperature at which the crystalline components in the toner begin to crystallize under the influence of the surrounding amorphous components during fixing.

[0281] The second toner of the present invention has excellent low-temperature fixing properties and good storage properties, and can suppress ejection after being placed at high temperatures. It has an apparent glass transition temperature (Tg2) of 68°C to 74°C when heated at a heating rate of 1000 K / s and an exothermic onset temperature of 50°C to 62°C when cooled at a cooling rate of 1000 K / s.

[0282] When the exothermic start temperature is low within the specific range mentioned above, it means that during the fixing process, when the toner is heated to melt and then rapidly cooled, the fluidity of the molten binder resin is maintained, and the crystallization of the softener is slow. It can be assumed that the toner diffuses on the paper surface, which makes it easier to achieve good fixing properties.

[0283] By setting the apparent glass transition temperature (Tg2) and the exothermic onset temperature below the aforementioned upper limits, low-temperature fixing performance becomes good. Furthermore, by setting the apparent glass transition temperature (Tg2) and the exothermic onset temperature above the aforementioned lower limits, storage deterioration can be suppressed, and ejection after high-temperature storage can be prevented.

[0284] To obtain a toner with thermal properties that satisfy the aforementioned specific range of apparent glass transition temperature (Tg2) and exothermic onset temperature, the thermal properties of the toner can be controlled, for example, by appropriately changing the composition, molecular weight and content of the binder resin, the type and content of the colorant, the glass transition temperature (Tg) and content of the charge control agent, the type and molecular weight of the softener, and the type and content of external additives. Adjusting the molecular weight and composition of the binder resin, and the type and content of the colorant, is particularly effective. More specifically, by employing the preferred configurations of the components described later, the aforementioned specific range of apparent glass transition temperature (Tg2) and exothermic onset temperature can be satisfied.

[0285] From the perspective of easily suppressing the rise in fixing temperature, the upper limit of the above-mentioned apparent glass transition temperature (Tg2) is preferably 73°C or less, and more preferably 72°C or less.

[0286] Furthermore, from the perspective of easily suppressing the adhesion of toner during storage, easily improving shelf life, and easily suppressing spraying after being placed at high temperatures, the lower limit of the above-mentioned exothermic start temperature is preferably 52°C or higher, more preferably 54°C or higher. On the other hand, from the perspective of easily suppressing the increase of fixing temperature, the upper limit of the above-mentioned exothermic start temperature is preferably 60°C or lower, more preferably 58°C or lower.

[0287] II-3. Method for manufacturing colored resin particles

[0288] The coloring resin particles used in the second colorant of the present invention can be manufactured by the same wet or dry method as the coloring resin particles used in the first colorant of the present invention, preferably by the wet method, and can be manufactured by the suspension polymerization method, which is particularly preferred in the wet method, through the following process.

[0289] (A) Suspension polymerization method

[0290] (A-1) Preparation process of polymeric monomer composition

[0291] First, a polymerizable monomer composition is prepared by mixing polymerizable monomers, colorants, softeners, charge control agents, and other additives such as molecular weight regulators and styrene-based thermoplastic elastomers, as needed. The mixing during the preparation of the polymerizable monomer composition is performed using, for example, a media disperser. Furthermore, in the following description, the coloring resin particles used in the first colorant of the present invention are sometimes referred to as the first coloring resin particles of the present invention, and the coloring resin particles used in the second colorant of the present invention are sometimes referred to as the second coloring resin particles of the present invention.

[0292] As the polymerizable monomer used in the manufacture of the second colored resin particles of the present invention, examples can be the same polymerizable monomer used in the manufacture of the first colored resin particles of the present invention. The polymerizable monomer used in the manufacture of the second colored resin particles of the present invention preferably contains a monovinyl monomer as the main component, and may also contain macromolecular monomers or crosslinking polymerizable monomers.

[0293] The temperature-tanδ curve of the toner easily satisfies the above equations (II-1) and (II-2), and the above softening temperature (T). 1 / 2 Based on the above-mentioned preferred range and the fact that the above-mentioned apparent glass transition temperature (Tg2) and the above-mentioned exothermic onset temperature of the toner are easily within the above-mentioned specific range, the above-mentioned polymerizable monomer preferably contains at least one monovinyl monomer selected from styrene, styrene derivatives, acrylates and methacrylates, more preferably contains at least one monovinyl monomer selected from styrene, acrylates and methacrylates, and even more preferably contains styrene and at least one selected from acrylates and methacrylates.

[0294] Furthermore, the temperature-tanδ curve of the toner easily satisfies the above equations (II-1) and (II-2), and the softening temperature (T) is also relevant. 1 / 2 The colorant is preferably selected from the above-mentioned preferred range, and the apparent glass transition temperature (Tg2) and exothermic onset temperature of the colorant are preferably selected from the above-mentioned specific range. As an acrylate, it is preferably selected from at least one of n-butyl acrylate, propyl acrylate and 2-ethylhexyl acrylate. As a methacrylate, it is preferably selected from at least one of n-butyl methacrylate, propyl methacrylate and 2-ethylhexyl methacrylate.

[0295] Furthermore, in a total of 100 parts by mass of the monovinyl monomer, the styrene content is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, further preferably 80 parts by mass or more, and even more preferably 90 parts by mass or more. The higher the styrene content, the higher the apparent glass transition temperature (Tg2) and softening temperature (Tg2) of the colorant.1 / 2 The higher the α value, the higher the glass transition temperature (Tg) of the toner tends to be.

[0296] Furthermore, the temperature-tanδ curve of the toner easily satisfies the above equations (II-1) and (II-2), and the softening temperature (T) is also relevant. 1 / 2 Based on the aspects of the preferred range described above, and the apparent glass transition temperature (Tg2) and exothermic onset temperature of the toner being within the specific range described above, the monovinyl monomer preferably contains styrene and at least one selected from acrylates and methacrylates, and the mass ratio of styrene to the total mass of acrylates and methacrylates (styrene:(meth)acrylate) is preferably in the range of 50:50 to 90:10, more preferably in the range of 60:40 to 80:20, and particularly preferably in the range of 70:30 to 80:20.

[0297] When the aforementioned polymerizable monomer contains polymerizable monomers other than the aforementioned monovinyl monomer, the content of the aforementioned monovinyl monomer can be appropriately adjusted so that the temperature-tanδ curve of the toner satisfies the aforementioned formulas (II-1) and (II-2), and preferably further adjusted so that the aforementioned apparent glass transition temperature (Tg2) and the aforementioned exothermic onset temperature of the toner are within the aforementioned specific ranges. The total amount of the aforementioned monovinyl monomer is not particularly limited relative to 100 parts by mass of the aforementioned polymerizable monomer, but is preferably 90 parts by mass or more, more preferably 95 parts by mass or more. Furthermore, one type of monovinyl monomer can be used alone or in combination of two or more types.

[0298] As a macromonomer, from the perspective of easily controlling the apparent glass transition temperature (Tg2) and the glass transition temperature (Tg) in the temperature-tanδ curve of the toner, at least one macromonomer selected from polyacrylate macromonomers and polymethacrylate macromonomers can preferably be used. Examples of acrylates that can be used as polyacrylate macromonomers include, for example, acrylates that can be used as the aforementioned monovinyl monomers; examples of methacrylates that can be used as polymethacrylate macromonomers include, for example, methacrylates that can be used as the aforementioned monovinyl monomers. As a macromonomer, from the perspective of easily keeping the apparent glass transition temperature (Tg2) and the glass transition temperature (Tg) in the temperature-tanδ curve of the toner within the aforementioned preferred range, it is preferable to appropriately select a macromonomer that, by including the macromonomer in the polymerizable monomer, results in a higher glass transition temperature (Tg) of the resulting adhesive resin compared to the case where it is not included.

[0299] When the aforementioned polymerizable monomer contains the aforementioned macromonomer, the content of the macromonomer can be appropriately adjusted so that the temperature-tanδ curve of the toner satisfies the aforementioned formulas (II-1) and (II-2), without particular limitation. It is preferable to use 0.03 to 5 parts by mass, more preferably 0.05 to 1 part by mass, relative to 100 parts by mass of the aforementioned monovinyl monomer. Furthermore, one type of macromonomer can be used alone, or two or more types can be used in combination.

[0300] When the aforementioned polymerizable monomer contains the aforementioned crosslinking polymerizable monomer, from the aforementioned softening temperature (T) 1 / 2 From the perspectives of easily achieving the above-mentioned preferred range, easily achieving the above-mentioned apparent glass transition temperature (Tg2) and exothermic onset temperature within the above-mentioned specific range, and easily improving gloss, the content of crosslinkable polymeric monomer relative to 100 parts by weight of the monovinyl monomer is preferably 0.5 parts by weight or less, more preferably 0.1 parts by weight or less, even more preferably 0.05 parts by weight or less, and most preferably does not contain crosslinkable polymeric monomer. Furthermore, one type of crosslinkable polymeric monomer can be used alone or two or more types can be used in combination.

[0301] The content of the polymerizable monomers can be appropriately adjusted so that the temperature-tanδ curve of the toner satisfies the above formulas (II-1) and (II-2). It is preferable to further adjust the content so that the above-mentioned apparent glass transition temperature (Tg2) and the above-mentioned exothermic onset temperature of the toner are within the above-mentioned specific ranges. There is no particular limitation. The total content of the polymerizable monomers is preferably 60 to 95 parts by mass, more preferably 65 to 90 parts by mass, and even more preferably 70 to 85 parts by mass, relative to 100 parts by mass of all solid components contained in the above-mentioned polymerizable monomer composition.

[0302] The colorant contained in the second colorant of the present invention can be any colorant that has been used in colorants in the past, and there is no particular limitation. When making a colored colorant, black, cyan, yellow, and magenta colorants can be used. As black, cyan, yellow, and magenta colorants, examples of colorants that are the same as those that can be used in the first colorant of the present invention can be cited.

[0303] The colorant contained in the second colorant of the present invention readily satisfies the above-mentioned formulas (II-1) and (II-2) and the above-mentioned softening temperature (T) by adjusting the temperature-tanδ curve of the colorant. 1 / 2Based on the advantages of easily achieving the above-mentioned preferred range, thereby easily improving the low-temperature fixing and preservation properties of the toner, and easily maintaining the apparent glass transition temperature (Tg2) and exothermic onset temperature of the toner within the above-mentioned specific range, it is preferable to use a cyan colorant containing a cyan pigment, a yellow colorant containing a combination of a yellow dye and a yellow pigment, or a magenta colorant containing a magenta pigment. More preferably, a cyan colorant containing a phthalocyanine-based cyan pigment, a yellow colorant containing a combination of a yellow dye and a chlorine-containing yellow pigment, or a magenta colorant containing a quinacridone-based magenta pigment is used. Even more preferably, a cyan colorant containing at least one of CI Pigment Blue 15:3 and CI Pigment Blue 15:4, a yellow colorant containing a combination of CI Solvent Yellow 98 and CI Pigment Yellow 214, or a magenta colorant containing at least one of CI Pigment Red 122 and CI Pigment Violet 19 is used.

[0304] Furthermore, considering excellent weather resistance and image density, quinacridone-based fuchsin pigments, as preferred fuchsin colorants, can preferably be a mixture of CI Pigment Violet 19 and CI Pigment Red 122. The mixture of CI Pigment Violet 19 and CI Pigment Red 122 can be manufactured using methods such as those described in U.S. Patent No. 3,160,510, which involves simultaneously recrystallizing the mixture in sulfuric acid or other suitable solvents, followed by salt milling as needed and solvent treatment; or the method described in German Patent Application Publication No. 1217,333, which involves cyclizing a mixture of substituted diaminoterephthalic acids and then solvent treatment.

[0305] Furthermore, in the mixed crystals of CI pigment violet 19 and CI pigment red 122, the ratio of CI pigment violet 19 to CI pigment red 122 used by mass is typically 80:20 to 20:80, preferably 70:30 to 30:70, and more preferably 60:40 to 40:60.

[0306] The colorant content is typically 1 to 20 parts by mass relative to 100 parts by mass of the polymerizable monomer, preferably 5 to 15 parts by mass, and more preferably 7 to 13 parts by mass. By keeping the colorant content within the above range, the temperature-tanδ curve of the toner easily satisfies the above formulas (II-1) and (II-2). Furthermore, the softening temperature (T) of the toner is... 1 / 2 The colorant is readily within the aforementioned preferred range, and consequently, the apparent glass transition temperature (Tg2) and exothermic onset temperature of the colorant are readily within the aforementioned specific range. Furthermore, one colorant can be used alone or in combination of two or more.

[0307] The polymerizable monomer composition contains a softener. By containing a softener, the release property of the toner from the fixing roller during fixing can be improved. As a softener, any softener or release agent that can be used as a toner under normal circumstances can be used without particular limitation, and examples include softeners similar to those used in the first coloring resin particles of the present invention.

[0308] The weight-average molecular weight (Mw) of the aforementioned softening agent is not particularly limited, but is preferably in the range of 400 to 3500, more preferably in the range of 500 to 3000. The higher the weight-average molecular weight (Mw) of the aforementioned softening agent, the higher the softening temperature (T) of the toner. 1 / 2 The higher the tendency, the higher the apparent glass transition temperature (Tg2) and the higher the exothermic onset temperature of the toner.

[0309] Furthermore, from the perspective of adjusting the viscoelasticity of the toner and adjusting the apparent glass transition temperature (Tg2) and the exothermic onset temperature to improve the balance between the toner's preservation and low-temperature fixing properties, the melting point of the softener is preferably in the range of 50 to 90°C, more preferably in the range of 60 to 85°C, and even more preferably in the range of 70 to 80°C.

[0310] The content of the softener is not particularly limited. From the perspective of adjusting the viscoelasticity of the toner and adjusting the apparent glass transition temperature (Tg2) and the exothermic onset temperature to improve the balance between the toner's preservation and low-temperature fixing properties, it is preferable to use 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the above-mentioned monovinyl monomer.

[0311] In addition, the above-mentioned softeners can be used alone or in combination of two or more.

[0312] The polymerizable monomer composition contains a charge control agent that is positively or negatively charged. This enhances the charge of the toner.

[0313] As a charge control agent, there is no particular limitation as long as it is a charge control agent commonly used as a charge control agent for toners. Among charge control agents, positively charged or negatively charged control resins are preferred from the perspective of high compatibility with polymerizable monomers and the ability to impart stable charge (charge stability) to toner particles. Furthermore, from the viewpoint of obtaining a positively charged toner, positively charged charge control resins are more preferred.

[0314] Examples of charge-controlled resins, such as the functional group copolymers that can be used for the first colored resin particles of the present invention, are examples of charge-controlled resins that are positively or negatively charged.

[0315] From the perspective that the toner's temperature-tanδ curve easily satisfies the above-mentioned formulas (II-1) and (II-2), and that the toner's apparent glass transition temperature (Tg2) and exothermic onset temperature are easily within the aforementioned specific ranges, the functional group-containing copolymer that can be used as a positively or negatively charged control resin preferably has a proportion of functional group-containing structural units of 3% by mass or less, more preferably 2.5% by mass or less. On the other hand, from the perspective of improving the toner's charge stability and shelf life, and easily suppressing ejection after high-temperature storage, the proportion of functional group-containing structural units in the functional group-containing copolymer is preferably 0.5% by mass or more. Since the charged control resin sufficiently contains functional groups, it is easy for the charged control resin to exist locally near the surface of the colored resin particles, and the charged control resin functions like a shell for the colored resin particles, thereby presumably improving the toner's shelf life and suppressing ejection after high-temperature storage.

[0316] Among these, the functional group-containing copolymers that can be used as positively or negatively charged control resins are preferably styrene-acrylic resins, based on the aspects of high compatibility with the aforementioned polymerizable monomers, easy satisfaction of the aforementioned formulas (II-1) and (II-2) in the temperature-tanδ curve of the toner, and easy for the aforementioned apparent glass transition temperature (Tg2) and the aforementioned exothermic onset temperature of the toner to be within the aforementioned specific ranges.

[0317] Furthermore, the glass transition temperature (Tg) of the aforementioned functional group-containing copolymers, which can be used as positively or negatively charged control resins, is preferably 50–110°C, more preferably 60–100°C. When the glass transition temperature (Tg) of the aforementioned functional group-containing copolymers is within the aforementioned range, the temperature-tanδ curve of the toner easily satisfies the aforementioned formulas (II-1) and (II-2), and the aforementioned apparent glass transition temperature (Tg2) and the aforementioned exothermic onset temperature of the toner are easily within the aforementioned specific ranges. In addition, the shelf life of the toner can be improved. The aforementioned functional group-containing copolymers tend to exist locally near the surface of the colored resin particles and can function like a shell. Therefore, when the Tg of the aforementioned functional group-containing copolymers is within the aforementioned range, since the Tg is sufficiently high, it can be assumed that the shelf life of the toner is improved.

[0318] Furthermore, the weight-average molecular weight Mw of the above-mentioned functional group-containing copolymers that can be used as positively or negatively charged control resins is preferably 5,000 to 30,000, more preferably 10,000 to 25,000.

[0319] As a positively or negatively charged charge control agent other than the charge control resin, examples of charge control agents are the same as those used in the first colored resin particles of the present invention.

[0320] In this invention, the charge control agent is typically used at a ratio of 0.01 to 10 parts by weight, preferably 0.03 to 8 parts by weight, relative to 100 parts by weight of the monovinyl monomer. When the content of the charge control agent is 0.01 parts by weight or more, the generation of fogging can be suppressed; on the other hand, when the amount of the charge control agent added is 10 parts by weight or less, printing contamination can be suppressed. Furthermore, one type of charge control agent can be used alone, or two or more types can be used in combination.

[0321] Furthermore, the polymerizable monomer composition preferably contains a molecular weight regulator. There are no particular limitations on the molecular weight regulator, as long as it is a molecular weight regulator commonly used as a colorant; examples include, for instance, the same molecular weight regulators that can be used in the manufacture of the first colored resin particles of the present invention.

[0322] In the second toner of the present invention, the toner's temperature-tanδ curve readily satisfies the above-mentioned formulas (II-1) and (II-2), and the softening temperature (T) is... 1 / 2 The content of the molecular weight regulator is preferably adjusted so that the weight-average molecular weight (Mw) of the polymer contained in the binder resin is within the preferred range described above, taking into account aspects that are easily within the preferred range, and the apparent glass transition temperature (Tg2) and exothermic onset temperature of the toner are easily within the specific range described above. The molecular weight regulator is preferably used in a ratio of 1.0 to 3.0 parts by mass, more preferably 1.1 to 2.0 parts by mass, relative to 100 parts by mass of the monovinyl monomer. Furthermore, two or more molecular weight regulators can be used alone or in combination. There is a tendency that the higher the content of the molecular weight regulator, the lower the weight-average molecular weight of the polymer contained in the binder resin, and the lower the softening temperature (Tg2) of the toner. 1 / 2 The more molecular weight regulator is present, the lower the apparent glass transition temperature (Tg2) and exothermic onset temperature of the toner tend to be. Furthermore, the higher the content of the molecular weight regulator, the larger the values ​​of (tanδ(Tg)-tanδ(45℃)) / (Tg-45) shown in Equation (II-1) and (tanδ(130℃)-tanδ(100℃)) / 30 shown in Equation (II-2) in the toner's temperature-tanδ curve tend to be. Additionally, the higher the content of the molecular weight regulator, the lower the glass transition temperature (Tg) of the toner tends to be, and the higher the tanδ in Tg, the tanδ at 100℃, and the tanδ at 130℃ tend to be.

[0323] The polymerizable monomer composition may further contain a styrene-based thermoplastic elastomer. By containing the styrene-based thermoplastic elastomer, the aforementioned softening temperature (T0) of the colorant is reduced.1 / 2 The above-mentioned preferred range is easily found. Here, styrene-based thermoplastic elastomers refer to random, block, graft, or other copolymers of styrene monomers and at least one other monomer selected from monoolefins and dienes that can copolymerize with styrene monomers, as well as hydrogenated products of these copolymers.

[0324] Furthermore, by including styrene-based thermoplastic elastomers in the toner, the heat resistance temperature of the toner can be maintained, and the fixing properties of the toner can be improved.

[0325] Representative examples of styrene-based thermoplastic elastomers include, for instance, styrene-butadiene-styrene block copolymers, styrene-butadiene block copolymers, styrene-isoprene-styrene block copolymers, styrene-isoprene block copolymers, styrene-butadiene-isoprene-styrene block copolymers, and hydrogenated versions of these; styrene-ethylene-butene-styrene block copolymers, styrene-ethylene-propylene-styrene block copolymers, and styrene-ethylene-ethylene-propylene-styrene block copolymers.

[0326] Among these styrene-based thermoplastic elastomers, from the viewpoint of optimizing the balance between toner preservation and low-temperature fixing properties, styrene-isoprene-styrene block copolymers can be preferred.

[0327] The styrene content in the aforementioned styrene-based thermoplastic elastomer is preferably 15-70% by mass, more preferably 15-60% by mass, and even more preferably 20-40% by mass. By ensuring the styrene content is above the lower limit, the proportion of hydrocarbon units will not be too high, and the toner after fixing will not easily peel off from the fixing surface, thus suppressing the decrease in fixing performance. On the other hand, by ensuring the styrene content is below the upper limit, the compatibility with the binder resin will not become too high, thus suppressing the decrease in the toner's shelf life.

[0328] The weight-average molecular weight (Mw) of the above-mentioned styrene-based thermoplastic elastomer is not particularly limited, but from the perspective of maintaining the heat resistance temperature of the toner and improving the fixing properties of the toner, it is preferably 50,000 to 350,000, and more preferably 80,000 to 250,000.

[0329] The content of the above-mentioned styrene-based thermoplastic elastomer is preferably such that the above-mentioned softening temperature (T) of the colorant is reached. 1 / 2 The toner is adjusted in such a way that the above-mentioned preferred range is reached, and the above-mentioned apparent glass transition temperature (Tg2) and the above-mentioned exothermic onset temperature are within the above-mentioned preferred range. There is no particular limitation. It is preferred to use 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 2 to 6 parts by mass relative to 100 parts by mass of the above-mentioned monovinyl monomer.

[0330] In addition, the above-mentioned styrene-based thermoplastic elastomers can be used alone or in combination of two or more.

[0331] (A-2) The suspension process (droplet formation process) to obtain the suspension.

[0332] The droplet formation process performed in the manufacture of the second colored resin particles of the present invention can be the same as the droplet formation process performed in the manufacture of the first colored resin particles of the present invention.

[0333] (A-3) Polymerization process

[0334] The polymerization process performed in the manufacture of the second coloring resin particles of the present invention can be the same as the polymerization process performed in the manufacture of the first coloring resin particles of the present invention, and preferably, the core-shell type coloring resin particles are produced in the same manner as the first coloring resin particles of the present invention. By coating the core layer formed of a material having a low softening point with a material having a higher softening point, the above formulas (II-1) and (II-2) can be easily satisfied in the temperature-tanδ curve, and the low-temperature fixing and preservation properties of the toner can be improved in a balanced manner.

[0335] (A-4) Washing, filtering, dehydration and drying processes

[0336] The cleaning, filtering, dehydration, and drying processes performed in the manufacture of the second colored resin particles of the present invention can be the same as the cleaning, filtering, dehydration, and drying processes performed in the manufacture of the first colored resin particles of the present invention.

[0337] (B) Crushing method

[0338] When manufacturing colored resin particles using a pulverizing method, a pulverizing method, for example, that can be used in the manufacture of the first colored resin particles of the present invention, can be employed.

[0339] II-4. Colored Resin Particles

[0340] Colored resin particles can be obtained by manufacturing methods such as (A) suspension polymerization or (B) pulverization.

[0341] The coloring resin particles contained in the second colorant of the present invention will be described below. Furthermore, the coloring resin particles described below include both core-shell type and non-core-shell type coloring resin particles.

[0342] The coloring resin particles used in the second colorant of the present invention comprise a binding resin, a colorant, a softener, and a charge control agent, and may further contain other additives such as styrene-based thermoplastic elastomers as needed.

[0343] As a binder resin containing the aforementioned colored resin particles, examples include polymers obtained by polymerizing the polymeric monomers described in the suspension polymerization method (A) above. Furthermore, the polymer containing the aforementioned polymeric monomers as a binder resin can form a cross-linked bond with a styrene-based thermoplastic elastomer within the colored resin particles. The preferred polymeric monomers for each structural unit of the aforementioned polymer are the same as those described in the suspension polymerization method (A) above. The colorant readily satisfies the above formulas (II-1) and (II-2) and the softening temperature (T) from the temperature-tanδ curve. 1 / 2 Based on the consideration that the above-mentioned preferred range, the above-mentioned apparent glass transition temperature (Tg2) and the above-mentioned exothermic onset temperature of the toner are easily within the above-mentioned specific range, and the low-temperature fixing and storage properties of the toner are easily and evenly improved, the binder resin contained in the above-mentioned coloring resin particles preferably contains a polymer containing one or more polymeric monomers selected from at least one monovinyl monomer selected from styrene, acrylate and methacrylate, and more preferably contains a polymer containing styrene and one or more polymeric monomers selected from at least one acrylate and methacrylate.

[0344] The toner readily satisfies equations (II-1) and (II-2) above, and the softening temperature (T) above, as shown in the temperature-tanδ curve. 1 / 2 From the perspective of easily achieving the above-mentioned preferred range, easily achieving the above-mentioned apparent glass transition temperature (Tg2) and the above-mentioned exothermic onset temperature within the above-mentioned specific range, and easily and evenly improving the low-temperature fixing and storage properties of the toner, the weight-average molecular weight Mw of the polymer contained in the binder resin is preferably 1.00 × 10⁻⁶. 4 Above and 2.00×10 5 The following applies. From the perspective of improving the preservation of the toner, the lower limit of the aforementioned weight-average molecular weight Mw is more preferably 2.00 × 10⁻⁶. 4 The above is further preferred to be 3.00×10 4 Furthermore, from the perspective of improving the low-temperature fixing properties of the toner, the upper limit of the aforementioned weight-average molecular weight Mw is more preferably 1.50 × 10⁻⁶. 5 Hereinafter, 1.00 × 10 is further preferred. 5 The following. Additionally, the polymer contained in the bonding resin typically refers to a polymer of the aforementioned polymerizable monomers.

[0345] There is a tendency that the smaller the weight-average molecular weight (Mw) of the polymer, the lower the Tg of the toner and the larger the tanδ(Tg). Therefore, there is a tendency for the value of (tanδ(Tg)-tanδ(45℃)) / (Tg-45) shown in formula (II-1) to be larger. Furthermore, there is a tendency that the smaller the weight-average molecular weight (Mw) of the polymer, the larger both tanδ(100℃) and tanδ(130℃) of the toner. However, since the increase in tanδ(130℃) is more likely to be greater, there is a tendency for the value of (tanδ(130℃)-tanδ(100℃)) / 30 shown in formula (II-2) to be larger. In addition, there is a tendency that the larger the weight-average molecular weight (Mw) of the polymer, the higher the softening temperature (Tg) of the toner. 1 / 2 The tendency for the apparent glass transition temperature (Tg2) and exothermic onset temperature of the toner to be higher is also observed. Furthermore, by keeping the weight-average molecular weight Mw of the polymer below the aforementioned upper limit, it is easier to suppress the deterioration of shelf life.

[0346] Furthermore, the weight-average molecular weight Mw of the polymer contained in the binder resin can be determined using the same method as described in the first colored resin particles of the present invention. In the second colored resin particles of the present invention, examples of polymers other than the polymer contained in the binder resin include charge control resins, plasticizers, and styrene-based thermoplastic elastomers.

[0347] The binder resin contained in the aforementioned coloring resin particles is typically a polymer of the aforementioned polymeric monomers. In the temperature-tanδ curve, by ensuring the toner satisfies the ranges of formulas (II-1) and (II-2) above, it can contain small amounts of polyester resins, epoxy resins, and unreacted polymeric monomers, which are commonly used as binders in the past. Preferably, the content of polyester resin in 100 parts by mass of the aforementioned binder resin is 5 parts by mass or less, more preferably 1 part by mass or less, even more preferably 0.1 parts by mass or less, and particularly preferably no polyester resin. By keeping the content of polyester resin below the aforementioned upper limit, the environmental stability of the toner can be improved, and in particular, changes in the charge of the toner due to humidity variations can be suppressed.

[0348] Furthermore, when the adhesive resin contains a resin other than the polymer of the polymeric monomer, from the perspective that the toner easily satisfies the above formulas (II-1) and (II-2) in the temperature-tanδ curve, and that the above apparent glass transition temperature (Tg2) and the above exothermic onset temperature of the toner are easily within the above specific ranges, the content of the polymer of the polymeric monomer in 100 parts by mass of the adhesive resin is preferably 95 parts by mass or more, more preferably 97 parts by mass or more, and even more preferably 99 parts by mass or more.

[0349] From the perspective that the toner readily satisfies the above formulas (II-1) and (II-2) in the temperature-tanδ curve, and that the above-mentioned apparent glass transition temperature (Tg2) and the above-mentioned exothermic onset temperature of the toner are readily within the above-mentioned specific ranges, the total content of the above-mentioned binder resin is preferably 60 to 95 parts by mass, more preferably 65 to 90 parts by mass, and even more preferably 70 to 85 parts by mass, relative to 100 parts by mass of all solid components contained in the above-mentioned coloring resin particles.

[0350] The colorants, softeners, charge control agents, and styrene-based thermoplastic elastomers contained in the above-mentioned colored resin particles are the same as those listed in (A) suspension polymerization method.

[0351] The content of the colorant contained in the above-mentioned colored resin particles is appropriately adjusted according to the type of colorant in order to obtain the desired coloring and to make the colorant satisfy the above-mentioned formulas (II-1) and (II-2) in the temperature-tanδ curve. Preferably, it is appropriately adjusted according to the type of colorant in order to make the above-mentioned apparent glass transition temperature (Tg2) and the above-mentioned exothermic onset temperature of the colorant within the above-mentioned specific range. There is no particular limitation. Relative to 100 parts by mass of the above-mentioned binder resin, the content of the colorant contained in the above-mentioned colored resin particles is preferably 1 to 20 parts by mass, more preferably 5 to 15 parts by mass, and even more preferably 7 to 13 parts by mass.

[0352] From the perspective of improving the balance between the toner's preservation and low-temperature fixing properties, the content of the softener contained in the coloring resin particles is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, relative to 100 parts by weight of the above-mentioned binder resin.

[0353] Relative to 100 parts by weight of the aforementioned adhesive resin, the content of the charge control agent contained in the aforementioned coloring resin particles is preferably 0.01 to 15 parts by weight, more preferably 0.03 to 8 parts by weight. By setting the content of the charge control agent to the aforementioned lower limit or above, the generation of fog can be suppressed; on the other hand, by setting the content of the charge control agent to the aforementioned upper limit or below, printing contamination can be suppressed.

[0354] The content of the styrene-based thermoplastic elastomer contained in the above-mentioned colored resin particles is appropriately adjusted so that the toner satisfies the above-mentioned formulas (II-1) and (II-2) in the temperature-tanδ curve. It is preferable to adjust it appropriately so that the above-mentioned apparent glass transition temperature (Tg2) and the above-mentioned exothermic onset temperature of the toner are within the above-mentioned specific range. There is no particular limitation. Relative to 100 parts by mass of the above-mentioned adhesive resin, the content of the above-mentioned styrene-based thermoplastic elastomer contained in the above-mentioned colored resin particles is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 2 to 6 parts by mass.

[0355] The volume average particle size (Dv) of the coloring resin particles is preferably 3 to 15 μm, more preferably 4 to 12 μm. By setting the Dv to 3 μm or more, the flowability of the toner can be improved, and the deterioration of transfer properties and reduction in image density can be suppressed. By setting the Dv to 15 μm or less, the reduction in image resolution can be suppressed.

[0356] Furthermore, the ratio of the volume average particle size (Dv) to the number average particle size (Dn) of the colored resin particles (Dv / Dn) is preferably 1.0 to 1.3, more preferably 1.0 to 1.2. By making Dv / Dn 1.3 or less, it is possible to suppress the reduction in transferability, image density, and resolution.

[0357] From the viewpoint of image reproducibility, the average roundness of the colored resin particles is preferably 0.96 to 1.00, more preferably 0.97 to 1.00, and even more preferably 0.98 to 1.00.

[0358] By making the average roundness of the above-mentioned colored resin particles 0.96 or higher, the reproducibility of printed fine lines can be improved.

[0359] II-5. The second toner of the present invention

[0360] The second colorant of the present invention can also be made directly from coloring resin particles. However, from the viewpoint of adjusting the charge, flowability and storage properties of the colorant, the above-mentioned coloring resin particles can also be mixed and stirred together with external additives to perform external additive treatment, so that the external additives adhere to the surface of the coloring resin particles to make a single-component colorant.

[0361] In addition, single-component toners can be mixed and stirred with mixed carrier particles to form two-component developers.

[0362] The mixer used for external additive processing is not particularly limited as long as it is a stirring device that can cause the external additive to adhere to the surface of the coloring resin particles. Examples of such stirring devices include those that are the same as those used in the manufacture of the first colorant of the present invention.

[0363] As an external additive, examples of external additives that are the same as those that can be used in the first colorant of the present invention can be cited, and external additives preferred in the first colorant of the present invention can be used in the same way.

[0364] In the second colorant of the present invention, the external additive is typically used at a ratio of 0.05 to 6 parts by weight, preferably 0.2 to 5 parts by weight, relative to 100 parts by weight of coloring resin particles. By making the content of the external additive 0.05 parts by weight or more, the generation of transfer residue can be suppressed; by making the content of the external additive 6 parts by weight or less, the generation of haze can be suppressed. In addition, one type of external additive can be used alone or two or more types can be used in combination.

[0365] The temperature-tanδ curve of the second toner of the present invention satisfies the above-described formulas (II-1) and (II-2), thereby ensuring good shelf life and suppressing the decrease in adhesion-causing temperature (heat resistance temperature). The adhesion-causing temperature (heat resistance temperature) of the second toner of the present invention is preferably 53°C or higher, more preferably 54°C or higher, and even more preferably 55°C or higher.

[0366] The temperature-tanδ curve of the second toner of the present invention satisfies the above-described formulas (II-1) and (II-2), thereby providing good low-temperature fixing properties and suppressing the rise in fixing temperature. The fixing temperature of the second toner of the present invention is preferably below 170°C, more preferably below 160°C, and even more preferably below 150°C.

[0367] Furthermore, the apparent glass transition temperature (Tg2) and exothermic onset temperature of the second toner of the present invention are within the aforementioned specific ranges, and the temperature-tanδ curve of the toner satisfies the aforementioned formula (II-1), thereby exhibiting good preservation properties and easily suppressing ejection after high-temperature storage. In the ejection test of the second toner of the present invention after high-temperature storage, the stopping time (ejection time (seconds)) of the phenomenon of toner overflowing (ejection) from the developing roller of the ink cartridge is preferably 0 seconds to 15 seconds, more preferably a short ejection time, and even more preferably no ejection. In addition, in the present invention, the ejection test of the toner after high-temperature storage is conducted under the following conditions: the toner cartridge of the developing device of a commercially available non-magnetic single-component developing printer is filled with toner, the ink cartridge filled with toner is sealed to prevent it from being affected by humidity, and then placed in a high-temperature environment (temperature: 45°C) for 5 days, followed by a test at 23°C and 50% RH. The spray test of the toner can be determined by the same test as the spray test of the toner after high-temperature storage in the examples described later.

[0368] Example

[0369] The present invention will be further described below with examples and comparative examples, but the present invention is not limited to these examples. Furthermore, unless otherwise specified, parts and percentages are based on mass.

[0370] Furthermore, the weight-average molecular weight (Mw) of the polymer was calculated using GPC's polystyrene conversion. The sample for analysis was prepared by dissolving the polymer in tetrahydrofuran (THF) to a concentration of 2 mg / mL, sonicating for 10 minutes, and then filtering through a 0.45 μm membrane filter. The analytical conditions were: temperature: 40°C; solvent: tetrahydrofuran; flow rate: 1.0 mL / min; concentration: 0.2 wt%; sample injection volume: 100 μL; column: GPC TSKgel Multipore HXL-M (30 cm × 2 columns) manufactured by Tosoh Corporation. The determination was performed with a linear correlation coefficient of Log(Mw) - elution time of ≥0.98 for weight-average molecular weight (Mw) between 1000 and 300000. In addition, for the weight-average molecular weight Mw of the polymer contained in the binder resin in the colorant, the colorant is dissolved in THF to prepare a sample. The weight-average molecular weight Mw is calculated by subtracting the pre-determined peaks of the charge control resin, softener and styrene-based thermoplastic elastomer from the GPC results obtained by the above determination method.

[0371] <Example I Series: The First Toner of the Invention>

[0372] [Example I-1]

[0373] 1. Manufacturing of colored resin particles

[0374] (1) Preparation of nuclear polymeric monomer compositions:

[0375] Wet milling was performed using a media disperser (Asada Iron Works Co., Ltd., trade name: PICO MILL) on 70 parts of styrene as a polymerizable monomer, 30 parts of n-butyl acrylate, 0.1 parts of polymethyl methacrylate macromonomer (Toa Synthetic Chemical Industry Co., Ltd., trade name: AA6, Tg=94℃), 0.72 parts of divinylbenzene, 1.25 parts of tetraethylthiuram disulfide as a molecular weight regulator, and 8 parts of CI Pigment Yellow 155 (product name: TonerYellow3GP CT, Clariant) as a colorant. The viscosity of the mixture obtained by wet milling was measured using the following method, and the result was 974 mPa·s.

[0376] (Methods for measuring viscosity)

[0377] Viscosity was measured using a Type B viscometer (Brookfield Instruments, instrument name "Digital Rheometer DV-I+"). The mixture obtained through the above wet grinding was brought to 25°C using a constant temperature water bath. The spindle was then rotated at 60 rpm for one minute, and the viscosity was measured. The following spindle was selected based on the viscosity range being measured.

[0378] Less than 100 mPa·s: Spindle No. 1

[0379] 100 mPa·s or higher but less than 200 mPa·s: Spindle No. 2

[0380] 200 mPa·s or higher but less than 1500 mPa·s: Spindle No. 3

[0381] Add 0.5 parts of charged control resin (styrene-acrylic resin containing quaternary ammonium salt, functional group amount 8 by mass) and 6.0 parts of synthetic ester wax (pentaerythritol tetrabenzyl ester, melting point 76°C) to the mixture obtained by the above wet pulverization, mix and dissolve to prepare a polymerizable monomer composition for core.

[0382] (2) Preparation of aqueous dispersion media:

[0383] On the other hand, a magnesium hydroxide colloidal dispersion was prepared by slowly adding an aqueous solution of sodium hydroxide dissolved in 50 parts of ion-exchanged water to an aqueous solution of magnesium chloride dissolved in 280 parts of ion-exchanged water while stirring.

[0384] (3) Preparation of shell polymerizable monomers:

[0385] On the other hand, an aqueous dispersion of shell polymerizable monomers was prepared by micro-dispersing 2 parts of methyl methacrylate and 130 parts of water using an ultrasonic emulsifier.

[0386] (4) Granulation process:

[0387] The above-mentioned core polymerizable monomer composition was added to the above-mentioned magnesium hydroxide colloidal dispersion (5.3 parts magnesium hydroxide), and the mixture was stirred further. Then, 6 parts of tert-butyl peroxide-2-ethylbutyrate were added as a polymerization initiator. The dispersion containing the polymerization initiator was dispersed at 15,000 rpm using an inline emulsifying disperser (manufactured by Taihei Kiko Co., Ltd., trade name: Milder) to form droplets of the core polymerizable monomer composition.

[0388] (5) Suspension polymerization process:

[0389] A dispersion containing droplets of the core-shell polymerizable monomer composition was added to a reactor, and the temperature was raised to 90°C to carry out a polymerization reaction. After the polymerization conversion rate reached approximately 100%, a solution containing 0.1 parts of 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide] (manufactured by Wako Pure Chemical Industries, Ltd., trade name: VA-086, water-soluble initiator) as a shell polymerization initiator was added to the reactor. The polymerization was then continued at 95°C for 4 hours, and the reaction was terminated by cooling with water to obtain an aqueous dispersion of core-shell colored resin particles.

[0390] (6) Post-processing steps:

[0391] While stirring the aqueous dispersion of the coloring resin particles, sulfuric acid was added until the pH reached below 4.5 for acid washing (25°C, 10 minutes). The filtered coloring resin particles were then washed with water, and the washing water was filtered off. The conductivity of the filtrate at this point was 20 μS / cm. The coloring resin particles after washing and filtration were further dehydrated and dried to obtain dried coloring resin particles.

[0392] (7) Volume average particle size (Dv), number average particle size (Dn), and particle size distribution (Dv / Dn)

[0393] Weigh approximately 0.1 g of the above-mentioned colored resin particles into a beaker, and add 0.1 mL of an aqueous solution of surfactant (manufactured by Fujifilm Corporation, trade name: DRIWEL) as a dispersant. Further add 10–30 mL of Isoton II to the beaker, and disperse the particles using a 20 W ultrasonic disperser for 3 minutes. Then, using a particle size analyzer (manufactured by Beckman Coulter, trade name: Multisizer), under the conditions of pore size 100 μm, medium, Isoton II, and 100,000 particles, measure the volume average particle size (Dv) and number average particle size (Dn) of the colored resin particles, and calculate the particle size distribution (Dv / Dn).

[0394] 2. Manufacturing of toners

[0395] The colorant of Example I-1 was prepared by adding 0.2 parts of hydrophobically treated silica microparticles with an average particle size of 7 nm, 0.76 parts of hydrophobically treated silica microparticles with an average particle size of 20 nm, and 1.91 parts of hydrophobically treated silica microparticles with an average particle size of 50 nm to 100 parts of coloring resin particles and mixing them using a high-speed mixer (manufactured by Nippon Kogyo Co., Ltd., trade name: FM mixer).

[0396] [Examples I-2 to I-11, Comparative Examples I-1 to I-2]

[0397] In Example I-1, in the above "(1) Preparation of the polymeric monomer composition for the core" in "1. Manufacturing of colored resin particles", each material was added according to Table 1 below. Otherwise, the same procedure as in Example I-1 was followed to obtain the toners of Examples I-2 to I-11 and Comparative Examples I-1 to I-2.

[0398] [Table 1]

[0399]

[0400] In addition, the abbreviations in Table 1 are shown below.

[0401] ST: Styrene

[0402] BA: n-Butyl acrylate

[0403] DVB: Divinylbenzene

[0404] AA6: Polymethacrylate macromonomer (manufactured by Dong-A Synthetic Chemical Industry Co., Ltd., trade name: AA6, Tg=94℃)

[0405] TET: Tetraethylthiuram disulfide

[0406] PY155: CI Pigment Yellow 155

[0407] PY93: CI Pigment Yellow 93

[0408] In addition, the detailed names of each product name of the colorant in Table 1 are shown below.

[0409] TY3GP-CT: Product name Toner Yellow 3GP CT, manufactured by Clariant.

[0410] VY5GD: Product name VERSAL YELLOW 5GD, manufactured in Sydney.

[0411] CY3G: Product name Cromophytal Yellow D 1040, manufactured by BASF.

[0412] Furthermore, the mass % in ST and DVB in Table 1 refers to the proportion of structural units from ST and the proportion of structural units from DVB in a total of 100% mass of adhesive resin, calculated as the proportion (mass %) of ST or DVB relative to a total of 100% mass of polymerizable monomers and molecular weight regulators used to synthesize adhesive resin.

[0413] In addition, the weight-average molecular weight (Mw) of the polymer contained in the bonding resin is the value shown in Table 1 multiplied by 10. 5 The value after that.

[0414] [Determination of viscoelasticity]

[0415] Dynamic viscoelasticity was measured for the toners obtained in each embodiment and comparative example to obtain temperature dependence curves of the loss tangent (tanδ). The dynamic viscoelasticity was measured using a rotating flat-plate rheometer (TA Instruments, ARES-G2) with a cross-grid under the following conditions. The test pieces were prepared by injecting 0.2 g of toner into an 8 mm Φ cylindrical mold and applying pressure of 1.0 MPa for 30 seconds to form an 8 mm Φ cylindrical mold with a thickness of 3 mm.

[0416] (Conditions for dynamic viscoelasticity determination)

[0417] Frequency: 24Hz

[0418] Sample set: The test piece (3mm thick) is clamped with an 8mm Φ plate under a 20g load. The temperature is raised to 80℃ to fuse the test piece to the clamp. Then the temperature is restored to 45℃ and the heating is started.

[0419] Heating rate: 5℃ / minute

[0420] Temperature range: 45℃~150℃

[0421] The temperature dependence curves of the loss tangent (tanδ) of the toners obtained in each embodiment exhibit the following linear shapes: From 45°C to the glass transition temperature (Tg) shown in Table 2, tanδ increases sharply from near 0 to near 1.6 with increasing temperature, reaching a maximum at Tg. From Tg to near 100°C, tanδ decreases to near 0.8–0.9 with increasing temperature, reaching a minimum. From this minimum temperature to 150°C, tanδ increases slowly with increasing temperature and then becomes a essentially fixed value. As an example, in… Figure 1 The temperature dependence curve of the loss tangent (tanδ) of the toner obtained in Example I-1 is shown. Furthermore, the dynamic viscoelasticity measurements were performed in the range from 45°C to 150°C. Figure 1 The results shown are from 45°C to 145°C.

[0422] Furthermore, from the obtained temperature-tanδ curves, the loss tangent tanδ(45℃), glass transition temperature (Tg), loss tangent tanδ(Tg) at glass transition temperature (Tg), loss tangent tanδ(100℃) at 100℃, and loss tangent tanδ(130℃) at 130℃ for each toner are obtained. The values ​​of (tanδ(Tg)-tanδ(45℃)) / (Tg-45) shown in the above formula (I-1) and (tanδ(130℃)-tanδ(100℃)) / 30 shown in the above formula (I-2) are calculated.

[0423] Softening temperature (T) 1 / 2 [Determination of]

[0424] Determine the pressure at 10.0 kgf / cm² using a Shimadzu CFT-500C flow testing apparatus under the following test conditions. 2 The softening temperature (T) in the 1 / 2 method was used to determine the toners obtained in each embodiment and each comparative example. 1 / 2 ).

[0425] (Measurement conditions)

[0426] Starting temperature: 35℃

[0427] Heating rate: 3℃ / minute

[0428] Preheating time: 5 minutes

[0429] Cylinder pressure: 10.0 kgf / cm 2

[0430] Die head bore diameter: 0.5mm

[0431] Die head length: 1.0mm

[0432] Sample dosage: 1.0–1.3 g

[0433] [evaluate]

[0434] (1) Heat resistance temperature of toner

[0435] Add 10g of toner to a 100mL polyethylene container, seal it, and immerse the container in a constant-temperature water bath set to the specified temperature. After 8 hours, remove the container. Transfer the toner from the container to a 42-mesh sieve with minimal vibration and place it on a powder tester (manufactured by Hosokawa Micron Group Co., Ltd., trade name: Powder Tester (registered trademark) PT-R). Set the sieve amplitude to 1.0mm and vibrate for 30 seconds. Measure the mass of the toner remaining on the sieve and use this as the mass of the agglomerated toner.

[0436] The highest temperature at which the mass of the condensed toner reaches 0.5g or less is recorded as the toner's heat resistance temperature. The higher the heat resistance temperature, the less likely the toner is to clump together during storage, resulting in better preservation.

[0437] (2) Fixing temperature of toner

[0438] A commercially available non-magnetic single-component developing printer was modified to allow for adjustable fuser roller temperature. Starting at 120°C, the fuser roller temperature was increased by 5°C increments, and the toner's fixing rate was measured at each temperature. The temperature-fixing rate relationship was determined, and the lowest temperature at which a fixing rate of 80% or higher was recorded as the toner's fixing temperature. A lower fixing temperature indicates better low-temperature fixing properties of the toner.

[0439] Additionally, the fixation rate is calculated by the image density ratio of the completely black area on the test paper before and after the scratch test. When the image density before the scratch test is recorded as ID(before) and the image density after the scratch test is recorded as ID(after), the fixation rate (%) = [ID(after) / ID(before)] × 100. The scratch test is performed as follows: the test portion of the test paper is attached to the durability tester with tape, a load of 500g is applied, and the paper is scratched back and forth 5 times with a scratching terminal wrapped with cotton cloth.

[0440] (3) Gloss (gloss level)

[0441] A commercially available non-magnetic single-component developing printer (24-sheet printer; printing speed = 24 sheets / minute) was modified to allow for temperature adjustment of the fuser roller. After filling the toner cartridge in the developing unit of the printer with 100g of toner, printing paper was placed in the printer.

[0442] Adjust the printer so that the toner dosage on the completely black area of ​​the paper is 0.35 mg / cm². 2 Next, the temperature of the fixing roller (fixing temperature) was set to 170°C, and a 5cm square all-black image was printed on paper (manufactured by Cowans Group, trade name: initiative multipurpose paper). The gloss value of the 5cm square all-black area was measured using a gloss meter (manufactured by Nippon Denko Co., Ltd., trade name: VGS-SENSOR) at an incident angle of 60°. A higher gloss value indicates a more glossy image.

[0443] [Table 2]

[0444]

[0445] [Inspection]

[0446] The toner of Comparative Example I-1 has a value of -3.0 × 10⁻³ for (tanδ(130℃) - tanδ(100℃)) / 30 as shown in the temperature-tanδ curve above (I-2). -3 The viscoelasticity is as follows, resulting in a high fixing temperature and poor fixing performance at low temperatures. Furthermore, the toner in Comparative Example I-1 was not sufficiently dissolved in THF, therefore the weight-average molecular weight (Mw) of the polymer contained in the binder resin could not be determined.

[0447] The toner of Comparative Example I-2 has a value of 7.60 × 10⁻⁶ in the temperature-tanδ curve, as shown in Equation (I-1) above: (tanδ(Tg) - tanδ(45℃)) / Tg - 45. -2 The above-mentioned viscoelasticity results in a low heat resistance temperature, meaning that the toner is prone to sticking together during storage, thus exhibiting poor shelf life.

[0448] On the other hand, the toners in Examples I-1 to I-11 are toners that have viscoelasticity that satisfies the above formulas (I-1) and (I-2) in the temperature-tanδ curve. Therefore, they have high heat resistance temperature, meaning that the toners are not prone to sticking during storage, resulting in excellent storage performance. They also have low fixing temperature, excellent low-temperature fixing performance, and consequently, excellent gloss.

[0449] <Example II Series: The Second Toner of the Invention>

[0450] [Manufacturing Example II-1: Manufacturing of Magenta Pigment A]

[0451] 2,5-Di(4-methylphenylamino)terephthalic acid was cyclized in phosphoric acid to synthesize 2,9-dimethylquinacridone (CI Pigment Red 122). Water was added to the resulting phosphoric acid dispersion of 2,9-dimethylquinacridone, and the mixture was filtered and separated, then further washed with water. Water was added again to the washed 2,9-dimethylquinacridone to prepare an aqueous dispersion with a solid content of 20%.

[0452] Similarly, an aqueous dispersion of quinacridone (CI Pigment Violet 19) with a solid content of 20% was prepared using 2,5-diphenylaminoterephthalic acid.

[0453] A pigment mixture was prepared by adding 250 parts of ethanol to 250 parts of an aqueous dispersion of 20% dimethyl quinacridone (CI Pigment Red 122) and 250 parts of an aqueous dispersion of 20% quinacridone (CI Pigment Violet 19) to the above-mentioned solid components. This mixture was transferred to a container equipped with a condenser, and the pigments were ground while reacting under reflux for 5 hours. After the reaction was completed, the pigments were separated from the reaction solution by filtration, washed, dried, and pulverized to obtain magenta pigment A, a mixed crystal of magenta pigment (i.e., a mixed crystal of CI Pigment Red 122 and CI Pigment Violet 19). The mass ratio of each pigment in this mixed crystal was CI Pigment Red 122 : CI Pigment Violet 19 = 1 : 1.

[0454] [Manufacturing Example II-2: Manufacturing of Elastomer a]

[0455] 23.2 kg of cyclohexane, 1.5 mmol of N,N,N',N'-tetramethylethylenediamine (TMEDA), and 1.70 kg of styrene were added to a pressure reactor. While stirring at 40 °C, 99.1 mmol of n-butyllithium was added, and polymerization continued for 1 hour while the temperature was increased to 50 °C. The polymerization conversion rate of styrene was 100% by mass. Next, while maintaining the temperature at 50–60 °C, 6.03 kg of isoprene was continuously added to the reactor over 1 hour. After the isoprene addition was complete, polymerization continued for another 1 hour to form a styrene-isoprene diblock copolymer. The polymerization conversion rate of isoprene was 100% by mass. Then, 15.0 mmol of dimethyldichlorosilane was added as a coupling agent, and a coupling reaction was carried out for 2 hours to form a styrene-isoprene-styrene triblock copolymer. Finally, 198 mmol of methanol was added as a polymerization terminator, and the mixture was thoroughly mixed to terminate the reaction, thus obtaining a reaction solution containing a block copolymer composition. Then, 0.3 parts of 2,6-di-tert-butyl-p-cresol as an antioxidant were added to 100 parts of the thus obtained reaction solution (containing 30 parts of polymer components), and the mixture was stirred. The mixed solution was then added dropwise in small amounts to hot water heated to 85-95°C to evaporate the solvent and obtain a precipitate. The precipitate was pulverized and dried with hot air at 85°C, thereby recovering the block copolymer composition. The obtained block copolymer composition (elastomer a) contained 24% by mass of styrene monomer units and had a weight-average molecular weight (Mw) of 106,000.

[0456] [Example II-1]

[0457] 1. Manufacturing of colored resin particles

[0458] (1) Preparation of nuclear polymeric monomer compositions:

[0459] The following were wet-milled using a media disperser (manufactured by Asada Iron Works Co., Ltd., trade name: PICO MILL): 74 parts of styrene as a polymerizable monomer, 26 parts of n-butyl acrylate, 0.1 parts of polymethyl methacrylate macromonomer (manufactured by Toa Synthetic Chemical Industry Co., Ltd., trade name: AA6, Tg=94℃), 0.50 parts of tetraethyl thiuram disulfide as a molecular weight regulator, and 8.0 parts of magenta pigment A (a mixture of CI pigment red 122 and CI pigment violet 19) obtained in the above-mentioned manufacturing example 1 as a colorant.

[0460] Add 10.0 parts of charged control resin (CCR1: styrene-acrylic resin containing quaternary ammonium salt, functional group amount 1 by mass) and 12.0 parts of synthetic ester wax 1 (hexaglycerol octabenzene ester, melting point 70°C) and 2.0 parts of elastomer a obtained in the above manufacturing example II-2 as a styrene-based thermoplastic elastomer to the mixture obtained by the above wet pulverization, mix and dissolve to prepare a core polymerizable monomer composition.

[0461] (2) Preparation of aqueous dispersion media:

[0462] On the other hand, a magnesium hydroxide colloidal dispersion was prepared by slowly adding an aqueous solution of sodium hydroxide dissolved in 50 parts of ion-exchanged water to an aqueous solution of magnesium chloride dissolved in 280 parts of ion-exchanged water while stirring.

[0463] (3) Preparation of shell polymerizable monomers:

[0464] On the other hand, an aqueous dispersion of shell polymerizable monomers was prepared by micro-dispersing 2 parts of methyl methacrylate and 130 parts of water using an ultrasonic emulsifier.

[0465] (4) Granulation process:

[0466] The above-mentioned core polymerizable monomer composition was added to the above-mentioned magnesium hydroxide colloidal dispersion (5.3 parts magnesium hydroxide), and the mixture was stirred further. Then, 6 parts of tert-butyl peroxide-2-ethylbutyrate were added as a polymerization initiator. The dispersion containing the polymerization initiator was dispersed at 15,000 rpm using an inline emulsifying disperser (manufactured by Taihei Kiko Co., Ltd., trade name: Milder) to form droplets of the core polymerizable monomer composition.

[0467] (5) Suspension polymerization process:

[0468] A dispersion containing droplets of the core-shell polymerizable monomer composition was added to a reactor, and the temperature was raised to 90°C to carry out a polymerization reaction. After the polymerization conversion rate reached approximately 100%, a solution containing 0.1 parts of 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide] (manufactured by Wako Pure Chemical Industries, Ltd., trade name: VA-086, water-soluble initiator) as a shell polymerization initiator was added to the reactor. The polymerization was then continued at 95°C for 4 hours, and the reaction was terminated by cooling with water to obtain an aqueous dispersion of core-shell colored resin particles.

[0469] (6) Post-processing steps:

[0470] While stirring the aqueous dispersion of the coloring resin particles, sulfuric acid was added until the pH reached below 4.5 for acid washing (25°C, 10 minutes). The filtered coloring resin particles were then washed with water, and the washing water was filtered off. The conductivity of the filtrate at this point was 20 μS / cm. The coloring resin particles after washing and filtration were further dehydrated and dried to obtain dried coloring resin particles.

[0471] The volume average particle size (Dv), number average particle size (Dn), and particle size distribution (Dv / Dn) of the obtained colored resin particles were measured in the same manner as in Example I series.

[0472] 2. Manufacturing of toners

[0473] The colorant of Example II-1 was prepared by adding 0.2 parts of hydrophobically treated silica microparticles with an average particle size of 7 nm, 0.76 parts of hydrophobically treated silica microparticles with an average particle size of 20 nm, and 1.91 parts of hydrophobically treated silica microparticles with an average particle size of 50 nm to 100 parts of coloring resin particles and mixing them using a high-speed mixer (manufactured by Nippon Kogyo Co., Ltd., trade name: FM mixer).

[0474] [Examples II-2 to II-17, Comparative Examples II-1 to II-7]

[0475] In Example II-1, when performing the above-mentioned "(1) Preparation of the polymeric monomer composition for the core" in "1. Manufacturing of colored resin particles", each material was added according to Table 3 below. Otherwise, the process was carried out in the same way as in Example II-1, and the colorants of Examples II-2 to II-17 and Comparative Examples II-1 to II-7 were obtained.

[0476] [Table 3]

[0477]

[0478] Additionally, the abbreviations in Table 3 are shown below. Furthermore, some of the abbreviations in Table 3 are also listed in Table 1, as described above.

[0479] PB15∶3:CI Pigment Blue 15∶3

[0480] PY214: CI Pigment Yellow 214

[0481] SY98: CI Solvent Yellow 98

[0482] CCR1: A styrene-acrylic resin containing quaternary ammonium salts, with functional groups accounting for 1% by mass.

[0483] CCR2: A styrene-acrylic resin containing quaternary ammonium salts, with functional groups accounting for 0.5% by mass.

[0484] Ester wax 1: Hexaglycerol octaheterocyanate (melting point 70℃)

[0485] Ester wax 2: Pentaerythritol tetrabenzyl ester (melting point 76℃)

[0486] Ester Wax 3: Pentaerythritol Tetrastearate (Melting point 76℃)

[0487] Furthermore, in Table 3, the type of colorant "PY214 / SY98" and the part quantity "6.4 / 1.28" for Examples II-16 to II-17 and Comparative Examples II-5 to II-6 refer to the use of 6.4 parts of CI Pigment Yellow 214 and 1.28 parts of CI Solvent Yellow 98 as colorants. The type of colorant "PY214 / SY98" and the part quantity "8.0 / 1.6" for Comparative Example II-7 refer to the use of 8.0 parts of CI Pigment Yellow 214 and 1.6 parts of CI Solvent Yellow 98 as colorants.

[0488] In addition, the weight-average molecular weight (Mw) of the polymer contained in the bonding resin is the value shown in Table 3 multiplied by 10. 4 The value after that.

[0489] [Determination of viscoelasticity]

[0490] The toners obtained in each embodiment and each comparative example were subjected to the same dynamic viscoelasticity determination as in the series of Examples I, and the temperature dependence curves of the loss tangent (tanδ) were obtained.

[0491] The temperature dependence curves of the loss tangent (tanδ) of the toners obtained in each embodiment are as follows: From 45°C to the glass transition temperature (Tg) shown in Table 4, tanδ increases sharply from near 0 to near 2.0 with increasing temperature, reaching a maximum at Tg. From Tg to near 100°C, tanδ decreases to near 1.0–1.2 with increasing temperature, reaching a minimum. From the temperature of this minimum to 150°C, tanδ increases slowly with increasing temperature. As an example, in… Figure 2 The temperature dependence curve of the loss tangent (tanδ) of the toner obtained in Example II-1 is shown. Furthermore, the dynamic viscoelasticity measurements were performed in the range from 45°C to 150°C. Figure 2 The results shown are from 45°C to 145°C.

[0492] Furthermore, from the obtained temperature-tanδ curves, the loss tangent tanδ(45℃), glass transition temperature (Tg), loss tangent tanδ(Tg) at glass transition temperature (Tg), loss tangent tanδ(100℃) at 100℃, and loss tangent tanδ(130℃) at 130℃ of each toner are obtained. The values ​​of (tanδ(Tg)-tanδ(45℃)) / (Tg-45) shown in the above formula (II-1) and (tanδ(130℃)-tanδ(100℃)) / 30 shown in the above formula (II-2) are calculated.

[0493] Softening temperature (T) 1 / 2 [Determination of]

[0494] Determine the pressure of a flow testing apparatus (trade name CFT-500C) manufactured by Shimadzu Corporation under the following test conditions: 5.0 kgf / cm². 2 The softening temperature (T) in the 1 / 2 method was used to determine the toners obtained in each embodiment and each comparative example. 1 / 2 ).

[0495] (Measurement conditions)

[0496] Starting temperature: 35℃

[0497] Heating rate: 3℃ / minute

[0498] Preheating time: 5 minutes

[0499] Cylinder pressure: 5.0 kgf / cm 2

[0500] Die head bore diameter: 0.5mm

[0501] Die head length: 1.0mm

[0502] Sample dosage: 1.0–1.3 g

[0503] [High-speed DSC measurement]

[0504] High-speed differential scanning calorimetry (DSC) was performed on the toners obtained in each embodiment and each comparative example to obtain DSC curves during heating and cooling. In the differential scanning calorimetry (DSC) using the high-speed differential scanning calorimeter described above, as a sample pretreatment, silicone oil was applied to the chip sensor using the tip of a brush to spread it out. By applying silicone oil to the chip sensor, the measured toner will not fuse to the chip sensor, thereby removing the measured toner and enabling the reuse of the same chip sensor. As a result, the baseline between samples is stable, and data with good reproducibility can be obtained. About 10 toner particles were placed on the chip sensor coated with silicone oil, and the toner was measured using an ultra-high-speed DSC device (Mettler-Toledo, Flash DSC) under a nitrogen flow under the temperature conditions described below (1) to (5).

[0505] (1) Hold at 0℃ for 0.1 seconds.

[0506] (2) Heat from 0℃ to 150℃ at a rate of 1000K / second.

[0507] (3) Keep at 150℃ for 60 seconds.

[0508] (4) Cool from 150℃ to 0℃ at -1000K / second.

[0509] (5) Hold at 0℃ for 1 second.

[0510] Figure 3 This paper shows the method for calculating the apparent glass transition temperature (Tg2) of a toner when heated at a rate of 1000 K / s and the exothermic onset temperature of the toner when cooled at a rate of 1000 K / s in high-speed differential scanning calorimetry.

[0511] The following temperature is taken as the apparent glass transition temperature (Tg2): the temperature at which the tangent line drawn from the line extending the baseline of the low temperature side to the high temperature side in the DSC curve during heating intersects the point where the gradient is greatest in the part of the glass transition that is stepwise or in the curve of the endothermic peak caused by enthalpy relaxation.

[0512] In addition, the following temperature is used as the exothermic start temperature: the temperature at which the exothermic peak begins to appear when the curve deviates from the previous baseline in the DSC curve during cooling.

[0513] [evaluate]

[0514] The heat resistance temperature of the toner, the fixing temperature of the toner, and the gloss of the image were determined using the same methods as in Example I series.

[0515] In addition, the heat resistance temperature and fixing temperature of the toners in each embodiment and each comparative example were evaluated according to the following evaluation criteria.

[0516] (Evaluation criteria for heat resistance temperature)

[0517] ◎:Above 58℃

[0518] ○: Temperatures above 53℃ and below 57℃

[0519] ×: Below 52℃

[0520] (Evaluation criteria for fixing temperature)

[0521] ○: Less than 180℃

[0522] ×: Above 180℃

[0523] (3) Spray test of the toner after high temperature storage

[0524] For commercially available printers using a non-magnetic, single-component developing method, toner is filled into the toner cartridge of the developing unit.

[0525] Seal the ink cartridge filled with toner to protect it from humidity. Place it in this state at a high temperature (45°C) for 5 days. Then, at 23°C and 50% RH, use an electric screwdriver (Panasonic EZ6220) to rotate the developing roller mounted on the cartridge at 400 revolutions per minute (equivalent to a printing speed of 40 ppm). This will check whether toner overflows (ejects) from the developing roller of the cartridge. If ejection occurs, record the time it takes for the toner to stop overflowing (ejecting) as the ejection time (in seconds). If no ejection occurs, record the ejection time as 0 seconds.

[0526] [Table 4]

[0527]

[0528] [Inspection]

[0529] The toners of Comparative Examples II-1, II-2, and II-7 exhibit a value of 2.1 × 10⁻¹⁰ (tanδ(130℃) - tanδ(100℃)) / 30 as shown in Equation (II-2) above in the temperature-tanδ curve. -3 The following viscoelasticity results in high fixing temperature and poor fixing performance at low temperatures.

[0530] The toners of Comparative Examples II-3 and II-5 have a value of 7.60 × 10⁻⁶ in the temperature-tanδ curve, as shown in Equation (II-1) above (tanδ(Tg)-tanδ(45℃)) / (Tg-45). -2 The above-mentioned viscoelasticity results in a low heat resistance temperature, meaning that the toner is prone to sticking during storage, thus exhibiting poor shelf life and poor spraying characteristics after being placed at high temperatures.

[0531] The toner of Comparative Example II-4 has a value of 5.00 × 10⁻⁶ (tanδ(Tg) - tanδ(45℃)) / (Tg - 45℃) as shown in the temperature-tanδ curve above (II-1). -2 The following viscoelasticity results in high fixing temperature and poor fixing performance at low temperatures.

[0532] The toner of Comparative Example II-6 has a value of 7.60 × 10⁻⁶ (tanδ(Tg) - tanδ(45℃)) / (Tg - 45) as shown in the temperature-tanδ curve above (II-1). -2 The value of (tanδ(130℃)-tanδ(100℃)) / 30 shown in the above formula (II-2) is 4.4×10. -2 The above-mentioned viscoelasticity results in a lower heat resistance temperature and poorer storage properties compared to Comparative Example II-5.

[0533] On the other hand, the toners of Examples II-1 to II-17 exhibit viscoelasticity that satisfies formulas (II-1) and (II-2) above in the temperature-tanδ curve, thus exhibiting high heat resistance. This means the toners are less prone to sticking during storage, resulting in excellent shelf life. Furthermore, they have low fixing temperatures, excellent low-temperature fixing properties, and consequently, excellent gloss. In addition, the toners of Examples II-1 to II-17 also exhibit excellent ejection characteristics after high-temperature storage.

Claims

1. A toner, characterized in that, It contains colored resin particles and external additives. The colored resin particles comprise a binding resin, a colorant, a softener, and a charge control agent. The colorant is a yellow colorant composed of a yellow pigment that does not contain chlorine atoms. The glass transition temperature (Tg) of the toner satisfies 45℃ < Tg (℃) < 100℃. The glass transition temperature was determined based on the temperature dependence curve of the loss tangent (tanδ) of the toner obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz. The loss tangent (tanδ) of the toner at the glass transition temperature (Tg) is less than 1.870°. In the temperature dependence curve of the loss tangent (tanδ), when the loss tangent (tanδ) at 45℃ is denoted as tanδ(45℃), the loss tangent (tanδ) at the glass transition temperature (Tg) is denoted as tanδ(Tg), the loss tangent (tanδ) at 100℃ is denoted as tanδ(100℃), and the loss tangent (tanδ) at 130℃ is denoted as tanδ(130℃), the following conditions are met: and 。 2. The toner according to claim 1, wherein, The toner was tested using a flow tester at a pressure of 10.0 kgf / cm². 2 The softening temperature (T) in the 1 / 2 method determined under the conditions of [condition] 1 / 2 (Above 154℃ and below 220℃) 3. The toner according to claim 1 or 2, wherein, The toner has a loss tangent (tanδ) of ≥0.800 and ≤1.100 at 100°C and a loss tangent (tanδ) of ≥0.800 and ≤1.280 at 130°C, as shown in the temperature dependence curve of the loss tangent (tanδ).

4. The toner according to claim 1 or 2, wherein, The adhesive resin is a polymer containing one or more polymerizable monomers, wherein the polymerizable monomers include at least one monovinyl monomer selected from styrene, acrylates and methacrylates.

5. The toner according to claim 1 or 2, wherein, The adhesive resin contains polymers with a weight-average molecular weight of 3.00 × 10⁻⁶. 5 Above and 7.00×10 5 the following.

6. A toner, characterized in that, It contains colored resin particles and external additives, wherein the colored resin particles include a binder resin, a colorant, a softener, a charge control agent, and a styrene-based thermoplastic elastomer. The glass transition temperature (Tg) of the toner satisfies 45℃ < Tg (℃) < 100℃. The glass transition temperature was determined based on the temperature dependence curve of the loss tangent (tanδ) of the toner obtained by dynamic viscoelasticity measurement at a measurement frequency of 24 Hz. The loss tangent (tanδ) of the toner at the glass transition temperature (Tg) is less than 2.

410. In the temperature dependence curve of the loss tangent (tanδ), when the loss tangent (tanδ) at 45℃ is denoted as tanδ(45℃), the loss tangent (tanδ) at the glass transition temperature (Tg) is denoted as tanδ(Tg), the loss tangent (tanδ) at 100℃ is denoted as tanδ(100℃), and the loss tangent (tanδ) at 130℃ is denoted as tanδ(130℃), the following conditions are met: and .

7. The toner according to claim 6, wherein, The apparent glass transition temperature (Tg2) of the toner when heated at a rate of 1000 K / s was 68℃~74℃, and the exothermic onset temperature of the toner when cooled at a rate of 1000 K / s was 50℃~62℃, as determined by differential scanning calorimetry using a high-speed differential scanning calorimeter.

8. The toner according to claim 6 or 7, wherein, The toner was tested using a flow tester at a pressure of 5.0 kgf / cm². 2 The softening temperature (T) in the 1 / 2 method determined under the conditions of [condition] 1 / 2 (Above 124℃ and below 159℃) 9. The toner according to claim 6 or 7, wherein, In the temperature dependence curve of the loss tangent (tanδ), the loss tangent (tanδ) at 100°C is 0.900 or more and 1.400 or less, and the loss tangent (tanδ) at 130°C is 1.000 or more and 2.500 or less.

10. The toner according to claim 6 or 7, wherein, The adhesive resin is a polymer containing one or more polymerizable monomers, wherein the polymerizable monomers include at least one monovinyl monomer selected from styrene, acrylates and methacrylates.

11. The toner according to claim 6 or 7, wherein, The adhesive resin contains polymers with a weight-average molecular weight of 2.00 × 10⁻⁶. 4 Above and 1.00×10 5 the following.

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