Toner and toner manufacturing method

Abstract

To provide a toner that can have excellent low temperature fixability and high temperature offset resistance, and has excellent developability in a low temperature and low humidity environment.SOLUTION: A toner has a toner particle that contains a resin component having a crystalline resin and an amorphous resin. The resin component contains a THF insoluble. In the resin component, the content ratio of the THF insoluble is 5.0-80.0% by mass. When the maximum endothermic peak temperature in DSC measurement of the THF insoluble is Tm, and the endothermic quantity of the maximum endothermic peak is H(I), the formula (1) and the formula (2) are satisfied. When cross-section observation is performed for 100 toner particles, in every cross-section observation, a domain-matrix structure is observed which is composed of a matrix containing the crystalline resin and domains containing the amorphous resin. Of the 100 toner particles for which the cross-section observation is performed, the number of toner particles in which all the observed domains have a major axis of 1.0 μm or less is 20 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a toner used in an electrophotographic image forming apparatus. [Background technology]

[0002] In recent years, there has been an increasing demand for energy-saving measures in electrophotographic image forming apparatuses. As a countermeasure for energy saving, toner with excellent low-temperature fixability is required in order to reduce the amount of heat used for fixing the toner.

[0003] The use of crystalline resins in toners has been investigated as a way to improve the low-temperature fixability of toners. Amorphous resins, which are commonly used as binder resins in toners, do not exhibit clear endothermic peaks in differential scanning calorimetry (DSC) measurements. On the other hand, crystalline resins exhibit endothermic peaks in DSC measurements. Crystalline resins have the property that they hardly soften up to their melting point due to the regular arrangement of long-chain alkyl groups between or within molecules. Due to this property, crystalline resins undergo a rapid melting of the crystals at the melting point, i.e., sharp melting, which is accompanied by a rapid drop in viscosity.

[0004] For this reason, crystalline resins have attracted attention as materials that have excellent sharp melting properties and improve the low-temperature fixability of toner. Crystalline vinyl resins are known as one type of crystalline resin. Crystalline vinyl resins are vinyl polymers containing monomer units with long-chain alkyl groups. That is, crystalline vinyl resins have a main chain skeleton and long-chain alkyl groups as side chains. The long-chain alkyl groups in the side chains are regularly arranged and crystallized, resulting in the resin exhibiting crystallinity.

[0005] Furthermore, toners containing a large proportion of crystalline resin have poor elasticity at high temperatures and are prone to high-temperature offset. Therefore, a known method is to ensure elasticity at high temperatures by incorporating not only a crystalline resin but also an amorphous resin into the toner.

[0006] Patent Document 1 proposes a toner containing a crosslinked polyester and a crystalline vinyl resin for the purpose of improving low-temperature fixability and high-temperature offset resistance. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] WO2019 / 073731 Summary of the Invention [Problem to be solved by the invention]

[0008] However, as a result of the inventors' investigation of Patent Document 1, it was found that the developability is likely to decrease when outputting an image in a low-temperature, low-humidity environment. Specifically, it was found that the non-image area of ​​the fixed image is likely to be contaminated.

[0009] The present invention provides a toner that can have excellent low-temperature fixability and high-temperature offset resistance, and also has excellent developability in a low-temperature, low-humidity environment. [Means for solving the problem]

[0010] The present invention provides a toner having toner particles containing a resin component having a crystalline resin and an amorphous resin, The resin component contains a tetrahydrofuran-insoluble component, the content of the tetrahydrofuran insoluble matter in the resin component is 5.0% by mass to 80.0% by mass, When the maximum endothermic peak temperature in the differential scanning calorimeter (DSC) measurement of the tetrahydrofuran insoluble matter is defined as Tm [°C] and the endothermic amount of the maximum endothermic peak is defined as H(I) [J / g], The Tm [°C] satisfies the following formula (1), 55.0≦Tm≦80.0 (1) The H(I) [J / g] satisfies the following formula (2), 10.0≦H(I)≦80.0 (2) When the cross sections of 100 toner particles were observed, In each cross-sectional observation, a domain matrix structure composed of a matrix containing the crystalline resin and a domain containing the amorphous resin was observed, Among 100 toner particles whose cross sections have been observed, the number of toner particles in which all of the observed domains have a major axis of 1.0 μm or less is 20 or more. The toner is characterized by the above. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a toner that has excellent low-temperature fixability and high-temperature offset resistance, as well as excellent developability in a low-temperature, low-humidity environment. [Brief explanation of the drawings]

[0012]

Figure 1

[0013] The expressions "xx or more and xx or less" or "xx to xx" that represent a numerical range mean a numerical range that includes the endpoints, that is, the lower limit and the upper limit, unless otherwise specified.

[0014] (Meth)acrylate means acrylate and / or methacrylate, and (meth)acrylic acid means acrylic acid and / or methacrylic acid.

[0015] When numerical ranges are stated in stages, the upper and lower limits of each numerical range can be combined in any way.

[0016] A monomer unit is a unit that constitutes a polymer, and refers to the reacted form of a monomer (polymerizable monomer). For example, one section of carbon-carbon bond in the main chain of a polymer formed by polymerizing a vinyl monomer is considered to be one monomer unit. A vinyl monomer can be represented by the following formula (Z), and a vinyl monomer unit is a structural unit of a polymer, and is the reacted form of a monomer represented by the following formula (Z). A polymer obtained by the polymerization reaction of a vinyl monomer is a vinyl polymer. A monomer unit may also be simply referred to as a "unit."

[0017] [ka]

[0018] [In formula (Z), R Z1 represents a hydrogen atom or an alkyl group, and R Z2 represents an optional substituent.] The crystalline resin refers to a resin that shows a clear endothermic peak in a differential scanning calorimeter (DSC) measurement using the resin, toner particles, or toner as a measurement sample.

[0019] THF refers to tetrahydrofuran.

[0020] In cross-sectional observation of toner particles, a portion containing a crystalline resin refers to a portion having a value of 127 or less when the change in brightness from black to white is expressed as a range of 0 to 255 in image analysis of a cross-sectional image of a toner particle stained with ruthenium, as described below. Similarly, a portion containing an amorphous resin refers to a value of 128 or more. In other words, when a binarization process is performed in which portions having a value of 127 or less are expressed as black and portions having a value of 128 or more are expressed as white, portions whose main component is a crystalline resin are portions shown in black, and portions whose main component is an amorphous resin are portions shown in white.

[0021] As a result of intensive studies by the present inventors, it has been found that a toner having the above-described constituent requirements can have excellent low-temperature fixing properties and excellent developability. The mechanisms that are speculated and each of the constituent requirements will be described in detail below.

[0022] <Mechanism by which the effects of the present invention are exhibited> Regarding the mechanism by which the effects of the present invention are exhibited, the present inventors speculate as follows.

[0023] A toner having excellent high-temperature offset resistance can be obtained because the resin component has a tetrahydrofuran (hereinafter also referred to as THF) insoluble content. This is because a resin insoluble in THF generally has excellent high-temperature elasticity.

[0024] By satisfying the above formulas (1) and (2) for the THF insoluble content, while having excellent high-temperature offset resistance, the resin component contained in the toner can be easily plasticized at low temperatures, and compatibility with excellent low-temperature fixing properties can be achieved.

[0025] In addition, in the cross-sectional observation of toner particles, the fact that a matrix containing a crystalline resin is observed means that the physical properties of the toner are likely to depend on the crystalline resin, and a toner having excellent low-temperature fixing properties can be obtained. Also, the fact that a domain containing an amorphous resin is observed means that the excellent high-temperature elasticity exhibited by the amorphous resin is achieved without impairing the low-temperature fixing properties exhibited by the crystalline resin, and compatibility between the low-temperature fixing properties and the high-temperature offset resistance can be achieved.

[0026] Furthermore, among 100 toner particles subjected to cross-sectional observation, in a toner in which the number of toner particles in which all the observed domains have a major axis of 1.0 μm or less is 20 or more, toner particles having no coarsened domains are likely to be obtained. As a result, the charge distribution of the entire toner is unlikely to become broad, and a toner having excellent developability can be obtained.

[0027] <THF insoluble content> When the maximum endothermic peak temperature in a differential scanning calorimeter (DSC) measurement of the tetrahydrofuran-insoluble portion of the toner of the present invention is Tm [°C] and the endothermic amount of the maximum endothermic peak is H(I) [J / g], Tm [°C] satisfies the above formula (1), and H(I) [J / g] satisfies the above formula (2).

[0028] The THF-insoluble component in the resin component generally has better high-temperature elasticity than THF-soluble resins, and therefore improves the high-temperature offset resistance of the toner. The THF-insoluble component in the resin component is a resin with a crosslinked structure.

[0029] The fact that the THF-insoluble portion in the resin component satisfies the above formulas (1) and (2) means that the resin has excellent high-temperature elasticity and crystallinity. When the THF-insoluble portion satisfies the above formula (1), the THF-insoluble portion melts near Tm, which facilitates plasticization of the resin contained in the toner, making it easier to obtain a toner with excellent low-temperature fixing properties and high-temperature offset resistance.

[0030] When Tm is 55.0°C or higher, the melting initiation temperature of the THF-insoluble matter does not become too low, and the fixing temperature of the toner is easily maintained at an appropriate level. It is more preferably 58.0°C or higher, and even more preferably 60.0°C or higher. Furthermore, when Tm is 80.0°C or lower, the melting initiation temperature of the THF-insoluble matter does not become too high, and the resin contained in the toner is easily plasticized at low temperatures, making it easy to obtain a toner with excellent low-temperature fixing properties. It is more preferably 77.0°C or lower, and even more preferably 67.0°C or lower. Tm can be controlled by the composition of the THF-insoluble matter and the amount of crystalline components in the THF-insoluble matter.

[0031] Furthermore, the above H(I) of 10.0 J / g or more means that the crystalline portion of the THF-insoluble matter absorbs heat, which in turn facilitates plasticization of the resin components contained in the toner. It is preferably 11.5 J / g or more, more preferably 13.0 J / g or more, and even more preferably 16.5 J / g or more. Furthermore, if H(I) is 80.0 J / g or less, the amount of heat absorption is not excessive, so the crystalline portion of the THF-insoluble matter is not overly plasticized, and the resin components contained in the toner are also not overly plasticized. As a result, the toner's elasticity is easily maintained during fixing, making it easier to obtain a toner with excellent high-temperature offset resistance. It is preferably 65.0 J / g or less, more preferably 50.0 J / g or less, and even more preferably 40.0 J / g or less.

[0032] The THF-insoluble matter satisfying the above formulas (1) and (2) can be introduced into the toner by producing a resin component by mixing the THF-insoluble matter, or by producing a resin component by mixing a crystalline resin and an amorphous resin together using a radical initiator to cause a crosslinking reaction between the resins.

[0033] When the endothermic amount of the maximum endothermic peak in a differential scanning calorimeter (DSC) measurement of the toner is defined as H(T) [J / g], it is preferable that the toner satisfy the following formula (3): H(I) [J / g] and H(T) [J / g].

[0034] 3.0%≦H(I) / H(T)≦20.0% (3) H(T) refers to the endothermic amount of the endothermic peak that contributes most to toner melting. When the endothermic amount of the THF-insoluble matter is within the above range relative to the endothermic amount that contributes most to toner melting, it is believed that the melting of the THF-insoluble matter contributes to toner melting at an appropriate ratio, making it easier to obtain a toner with excellent high-temperature offset resistance. This is because THF-insoluble resins generally maintain a certain degree of elasticity even at temperatures above Tm, making it easier for the toner's elasticity to be properly maintained during fixing. Therefore, it is preferably 3.0% or more, more preferably 4.0% or more. It is also preferably 20.0% or less, more preferably 15.0% or less, and even more preferably 12.0% or less.

[0035] H(I) and H(I) / H(T) can be controlled by adjusting the content of the crystalline resin used in producing the resin component, the degree of crosslinking between the crystalline resin and the amorphous resin, etc. The degree of crosslinking can be controlled by the amount of polymerization initiator added in producing the resin component (binder resin), the content of carbon-carbon double bonds in the amorphous resin in producing the resin component, etc.

[0036] The content of the THF-insoluble matter in the resin component that satisfies the formulas (1) and (2) is 5.0% by mass or more and 80.0% by mass or less. When it is 5.0% by mass or more, a toner having excellent low-temperature fixability and high-temperature offset resistance is easily obtained. It is preferably 20.0% by mass or more, and more preferably 30.0% by mass or more. That is, a preferred content is 30.0% by mass to 80.0% by mass. Furthermore, when the content of the THF-insoluble matter in the resin component is 80.0% by mass or less, the elasticity of the toner is not too high and is easily maintained appropriately. It is preferably 70.0% by mass or less, and more preferably 67.0% by mass or less.

[0037] The content of the THF-insoluble matter in the resin component can be controlled by the degree of crosslinking between the crystalline resin and the amorphous resin, the composition and molecular weight of the resin before crosslinking, etc. The degree of crosslinking can be controlled by the amount of polymerization initiator added when producing the resin component, the content of carbon-carbon double bonds contained in the amorphous resin when producing the resin component, etc., as will be described later.

[0038] <Domain matrix structure> When 100 toner particles are subjected to cross-sectional observation, a domain matrix structure composed of a matrix containing a crystalline resin and domains containing an amorphous resin is observed in each cross-sectional observation. Preferably, a domain matrix structure composed of a matrix composed of a crystalline resin and domains composed of an amorphous resin is observed. In addition, to obtain toner particles having the above-described domain matrix structure, it is preferable to produce a resin component by mixing a crystalline resin and an amorphous resin.

[0039] The domain matrix structure can be obtained by controlling the mass ratio and viscosity ratio of the crystalline resin and amorphous resin used in producing toner particles. It is believed that the domain matrix structure is easily formed when a crystalline resin and an amorphous resin that is difficult to mix with the crystalline resin are used in the resin mixing process. Examples of amorphous resins that are difficult to mix with crystalline resins include crosslinked amorphous resins.

[0040] Furthermore, among 100 toner particles whose cross sections are observed, the number of toner particles in which all of the observed domains have a major axis of 1.0 μm or less is 20 or more, preferably 40 or more, more preferably 60 or more, and even more preferably 80 or more. There is no particular upper limit, but it is 100 or less.

[0041] The present inventors have found that a toner controlled as described above is less likely to have coarse domains in the toner particles and can have excellent developability. The present inventors speculate that the reason for this is as follows.

[0042] It is believed that toner particles that do not have coarse domains within the toner particle tend to have a uniform charge amount within the toner particle. The more toner particles with a uniform charge amount within the toner particle, the more likely it is that the charge distribution of the entire toner becomes sharp, and it is less likely that a toner having a charge amount outside the range of charge amounts suitable for development will be produced. As a result, the present inventors speculate that such a toner is less likely to adhere to non-image areas in a fixed image, which in turn makes it easier for the toner to be developed only in image areas, making it easier to obtain a toner with excellent developability.

[0043] Furthermore, it is considered that the filler effect is enhanced, so that the high-temperature elasticity of the toner is easily exhibited sufficiently, and the toner is likely to have excellent high-temperature elasticity.

[0044] As an example of a means for achieving the number of toner particles in which all observed domains have a major axis of 1.0 μm or less within the above range, in the present invention, a crosslinked resin obtained by crosslinking a highly polar portion of a crystalline resin with an amorphous resin is contained. The present inventors' speculation about this mechanism will be explained using Figure 1.

[0045] The crosslinked resin 4 is a crosslinked resin formed by crosslinking a high-polarity portion of a crystalline resin with an amorphous resin, and therefore contains an amorphous portion 5 derived from the amorphous resin and a crystalline portion 6, which is a low-polarity portion of the crystalline resin. Therefore, in the toner particle 1, the amorphous portion 5 in the crosslinked resin 4 is thought to approach the domain 3, while the crystalline portion 6 tends to face the direction of the matrix 2. As a result, it is speculated that the domain 3 tends to be surrounded by the crystalline portion 6. The present inventors speculate that the presence of the low-polarity crystalline portion 6 on the surface of such domain 3 tends to generate repulsion with other domains, preventing aggregation between the domains. Furthermore, since the crosslinked resin 4 contains the crystalline portion 6, it is thought that it easily plasticizes the surrounding resins. Furthermore, since it is a crosslinked resin, it has high elasticity at high temperatures, and therefore it is thought that a toner with excellent low-temperature fixability and high-temperature offset resistance can be easily obtained.

[0046] The present inventors believe that the incorporation of the above-mentioned crosslinked resin is possible by adjusting the compositions of the crystalline resin and amorphous resin used during production to satisfy the formulas (5), (6), and (7) described below.

[0047] Furthermore, among 100 toner particles whose cross sections have been observed, it is preferable that the number of toner particles having a domain with a major axis of 5.0 μm or more is 0. In other words, it is preferable that no domain with a major axis of 5.0 μm or more is observed.

[0048] <Resin component> The resin component contains a crystalline resin and an amorphous resin. When the resin component contains a crystalline resin, a toner having excellent low-temperature fixing properties is easily obtained. When the resin component contains an amorphous resin, a toner having excellent high-temperature offset resistance is easily obtained.

[0049] The resin component of the present invention is preferably a binder resin. That is, the present invention provides a toner having toner particles containing a binder resin having a crystalline resin and an amorphous resin, the binder resin contains a tetrahydrofuran-insoluble component, The binder resin preferably contains the tetrahydrofuran-insoluble matter in an amount of 5.0% by mass to 80.0% by mass.

[0050] <Vinyl Polymer A and Monomer Unit A1> The crystalline resin is preferably a vinyl polymer A having a monomer unit A1 represented by the following formula (A). When the toner contains the vinyl polymer A, it is easy to obtain a toner having excellent low-temperature fixing properties. This is because R 2 This is thought to be because the long-chain alkyl groups represented by the following formula (I) are easily aggregated, making it easy to obtain a resin component with excellent crystallinity. In addition, the vinyl polymer A is preferably a resin that is soluble in THF.

[0051] [ka]

[0052] (In formula (A), R 1 represents H or CH3, and R 2 represents an alkyl group having 18 to 36 carbon atoms. The vinyl polymer A having the monomer unit A1 can be incorporated as a monomer unit of the vinyl polymer A by vinyl polymerization of a (meth)acrylic acid ester having an alkyl group having 18 to 36 carbon atoms as a polymerizable monomer (hereinafter also referred to as a first polymerizable monomer).

[0053] The first polymerizable monomer is a (meth)acrylate having a chain hydrocarbon group having 18 to 36 carbon atoms.

[0054] Examples of the chain hydrocarbon group having 18 to 36 carbon atoms include a chain unsaturated hydrocarbon group having 18 to 36 carbon atoms and a chain saturated hydrocarbon group having 18 to 36 carbon atoms (hereinafter, the chain saturated hydrocarbon group will also be referred to as an alkyl group). Of the (meth)acrylates having a chain hydrocarbon group having 18 to 36 carbon atoms, preferred are (meth)acrylates having an alkyl group having 18 to 36 carbon atoms.

[0055] Examples of (meth)acrylates having an alkyl group having 18 to 36 carbon atoms include (meth)acrylates having a linear alkyl group having 18 to 36 carbon atoms [octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, montanyl (meth)acrylate, myricyl (meth)acrylate, and dodoriacontyl (meth)acrylate, etc.] and (meth)acrylates having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth)acrylate, etc.].

[0056] Among these, from the viewpoint of low-temperature fixability and high-temperature offset resistance of the toner, (meth)acrylates having a linear alkyl group with 18 to 36 carbon atoms are preferred. More preferred are (meth)acrylates having a linear alkyl group with 18 to 34 carbon atoms, and even more preferred are (meth)acrylates having a linear alkyl group with 18 to 30 carbon atoms. Even more preferred is at least one selected from the group consisting of stearyl (meth)acrylate and behenyl (meth)acrylate.

[0057] In the above formula (A), R 2 is an alkyl group having 18 to 36 carbon atoms, preferably an alkyl group having 18 to 34 carbon atoms, more preferably an alkyl group having 18 to 30 carbon atoms, and even more preferably an alkyl group having 18 or 22 carbon atoms. 2 is preferably a linear alkyl group. 1 is preferably hydrogen.

[0058] The first polymerizable monomer and the monomer unit A1 may be used alone or in combination of two or more kinds.

[0059] Furthermore, from the viewpoint of the low-temperature fixability and developability of the toner, the content of the monomer unit A1 in the vinyl polymer A is preferably 30.0% by mass or more and 99.9% by mass or less. If the content of the monomer unit A1 in the vinyl polymer A is 30.0% by mass or more, crystalline sites are easily obtained by aggregation (blocking) of the monomer units A1, and the crystallinity of the vinyl polymer A is easily increased. Furthermore, the presence of the vinyl polymer A in the toner tends to increase the crystallinity of the matrix, and as a result, low-polarity crystalline portions tend to gather on the surface of the domains, which tends to prevent aggregation of the domains and make it easy to obtain a toner with excellent developability. Therefore, the content is preferably 30.0% by mass or more, more preferably 40.0% by mass or more, and even more preferably 45.0% by mass or more. Furthermore, if the content of the monomer unit A1 in the vinyl polymer A is 99.9% by mass or less, the polarity of the vinyl polymer A is not excessively low, and therefore the SP for improving dispersibility described below can be easily obtained.A Therefore, the content is more preferably 99.9% by mass or less, more preferably 85.0% by mass or less, and even more preferably 75.0% by mass or less.

[0060] When the vinyl polymer A has two or more types of monomer units A1, the content of the monomer units A1 in the vinyl polymer A is the sum of the respective contents.

[0061] Furthermore, the amount of vinyl polymer A used when producing a resin component by mixing resins is preferably 40.0 parts by mass or more per 100.0 parts by mass of the total amount of the resins to be mixed.

[0062] <Monomer unit A2> The vinyl polymer A further has a monomer unit A2, and the SP value of the monomer unit A1 is A1 (J / cm 3 ) 0.5 , the SP value of the monomer unit A2 is SP A2 (J / cm 3 ) 0.5 Then, SP A1 and SP A2 It is preferable that satisfies the following formula (4).

[0063] 3.0≦SP A2 -SP A1 ≦25.0 (4) Here, the SP value is an abbreviation for soluble parameter, and is a numerical value that serves as an index of solubility. The calculation method will be described later.

[0064] The unit of the SP value in the present invention is (J / cm 3 ) 0.5 However, 1 (cal / cm 3 ) 0.5 =2.045×10 3 (J / m 3 ) 0.5 by (cal / cm 3 ) 0.5 can be converted into units of

[0065] By satisfying the above formula (4), the monomer unit A2 has a sufficiently high polarity compared to the low-polarity monomer unit A1, and each monomer unit is easily aggregated. As a result, crystalline portions are easily formed by aggregation (blocking) of the monomer units A1, which is preferable because it is easy to obtain a toner with excellent low-temperature fixability.

[0066] The above effect is more pronounced, so the above SP A2 -SP A1 is preferably 4.0 or more, and more preferably 5.0 or more. A2 -SP A1 If the α-to-β ratio is 25.0 or less, the compatibility between the crystalline resin and the amorphous resin is facilitated during fixing, making it possible to obtain a toner with sufficient low-temperature fixability even in a faster fixing process, which is preferable. Furthermore, this is preferable because it is less likely to produce a vinyl polymer A with a variable structure, such as a vinyl polymer A having a particularly large amount of monomer unit A1 or monomer unit A2, and the toner properties tend to be more uniform. Therefore, the α-to-β ratio is preferably 25.0 or less, more preferably 20.0 or less, and even more preferably 15.0 or less.

[0067] The monomer unit A2 can be incorporated as a monomer unit of the vinyl polymer A by vinyl polymerization of a corresponding vinyl monomer as a polymerizable monomer (hereinafter also referred to as a second polymerizable monomer; details will be described later).

[0068] The monomer unit A2 corresponds to a vinyl-based monomer unit satisfying the above formula (4). The monomer unit A2 and the second polymerizable monomer may be used alone or in combination of two or more.

[0069] The SP value of vinyl polymer A is SP A (J / cm 3 ) 0.5 The SP value of the amorphous resin used in the production of the resin component is SP P (J / cm 3 )0.5 When the formula (5) is satisfied, it is preferable that the following formulae (5) and (6) are satisfied. (Hereinafter, the amorphous resin used in producing the resin component will also be referred to as amorphous resin P.) 0<|SP P -SP A |≦10.0 (5) |SP P -SP A |>|SP P -SP A2 |···(6) 6.0≦|SP P -SP A |≦10.0 (7) By satisfying the above formula (5), the difference in polarity between the vinyl polymer A and the amorphous resin P is not too large, and the affinity between the vinyl polymer A and the amorphous resin P is easily maintained. As a result, the crosslinking reaction between the vinyl polymer A and the amorphous resin is easily carried out, and as described above, the presence of the crosslinked resin makes it difficult for the domains to aggregate, making it difficult for the domains to become coarse and easy to obtain a toner with excellent developability. Furthermore, because the affinity is properly maintained, it is difficult to obtain a toner containing a particularly large amount of the vinyl polymer A, and the content ratio of each resin between toner particles is less likely to vary, and the properties of the obtained toner are also less likely to vary. For the above reasons, it is preferable to satisfy the above formula (5), and it is more preferable to satisfy the above formula (7).

[0070] Furthermore, by satisfying the above formula (6), the domains containing the amorphous resin are less likely to become coarse, which makes it easier to obtain a toner with excellent developability. The present inventors speculate that the mechanism by which this effect is obtained is as follows.

[0071] By satisfying the above formula (6), it is believed that the amorphous resin P is more likely to have a greater affinity with the monomer unit A2, which has a high SP value, than with a monomer unit A1, which has a low SP value. This is thought to facilitate the crosslinking reaction between the vinyl polymer A and the amorphous resin P, thereby producing a crosslinked resin in the vicinity of the monomer unit A2. As a result, as shown in Figure 1, the amorphous portions of the crosslinked resin derived from the amorphous resin P are more likely to approach the domains, and the crystalline portions of the vinyl polymer A, which are composed of the monomer units with a low SP value, are more likely to face the matrix. It is believed that the repulsive force acting between the crystalline portions of this crosslinked resin and other domains prevents the aggregation of domains. This is thought to reduce the likelihood of the formation of coarse domains resulting from the aggregation of domains.

[0072] The content of the monomer unit A2 in the vinyl polymer A is preferably 1.0% by mass or more and 70.0% by mass or less. A is likely to be appropriately controlled, and the above formulas (5), (6), and (7) are likely to be satisfied.

[0073] Furthermore, if the content of the monomer unit A2 in the vinyl polymer A is 1.0% by mass or more, the elasticity of the vinyl polymer A is less likely to decrease, and the high-temperature offset resistance of the toner is less likely to decrease. Furthermore, crystalline moieties are more likely to be formed by the aggregation (blocking) of the monomer units A1, and a toner with excellent low-temperature fixability is more likely to be obtained. Therefore, the content is preferably 1.0% by mass or more, more preferably 10.0% by mass or more, and even more preferably 20.0% by mass. Furthermore, if the content of the monomer unit A2 in the vinyl polymer A is 70.0% by mass or less, the crystallinity of the vinyl polymer A is less likely to decrease, and a toner with excellent low-temperature fixability is more likely to be obtained. Therefore, the content is preferably 70.0% by mass or less, more preferably 60.0% by mass or less, more preferably 50.0% by mass or less, and even more preferably 40.0% by mass or less.

[0074] When the vinyl polymer A has two or more types of monomer units A2, the content of the monomer units A2 in the vinyl polymer A is the sum of the respective contents. The monomer unit A2 and the second polymerizable monomer may be used alone or in combination of two or more types.

[0075] Examples of the second polymerizable monomer include the polymerizable monomers listed below. Monomers containing a cyano group: for example, acrylonitrile, methacrylonitrile, etc. Monomers having a hydroxy group: for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. Monomers having an amide bond: for example, acrylamide, monomers obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 3 to 30 carbon atoms and an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid), etc. Monomers having a urea bond: for example, monomers obtained by reacting an amine having 3 to 22 carbon atoms [primary amines (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines (diethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, cyclohexylamine, etc.] with an isocyanate having 3 to 30 carbon atoms and an ethylenically unsaturated bond. Monomers having a carboxy group: for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate, etc.

[0076] Among these, it is preferable to use a monomer having a cyano group, a hydroxy group, an amide bond, or a urea bond, and more preferably, the second polymerizable monomer is a monomer having an ethylenically unsaturated bond and at least one functional group selected from the group consisting of a cyano group, a hydroxy group, an amide bond, and a urea bond.

[0077] Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, and vinyl octylate are also preferably used as the second polymerizable monomer. Vinyl esters are non-conjugated monomers, and tend to maintain a moderate level of reactivity with the first polymerizable monomer. This is thought to facilitate aggregation of monomer units A1 in the vinyl polymer A. In other words, crystalline sites are easily formed by aggregation (blocking) of monomer units A1, making it easier to obtain a toner with excellent low-temperature fixability.

[0078] Furthermore, the monomer unit A2 is preferably at least one monomer unit selected from the group consisting of a monomer unit represented by the following formula (A21) and a monomer unit represented by the following formula (A22).

[0079] [ka]

[0080] [ka]

[0081] (In formulas (A21) and (A22), X represents a single bond or an alkylene group having 1 to 6 carbon atoms; R 4 is a cyano group (-C≡N), -C(=O)NHR 7 (R 7 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, -COOR 8 (R 8 represents an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) or a hydroxyalkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms), -NHCOOR 9 (R 9 is an alkyl group having 1 to 4 carbon atoms), -NH-C(=O)-NH(R 10 )2(R10 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms), -COO(CH2)2NHCOOR 11 (R 11 is an alkyl group having 1 to 4 carbon atoms), or -COO(CH2)2-NH-C(=O)-NH(R 12 )2(R 12 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms), and R 6 represents an alkyl group having 1 to 4 carbon atoms, and R 3 and R 5 each independently represents a hydrogen atom or CH3. <Monomer unit A3> The vinyl polymer A may contain a monomer unit A3 which does not correspond to either the monomer unit A1 or the monomer unit A2, as long as the content ratio of the monomer unit A1 and the monomer unit A2 described above is not impaired.

[0082] Monomer unit A3 can be incorporated as a monomer unit of a polymer by vinyl polymerization of a monomer corresponding to monomer unit A3 (hereinafter referred to as a third polymerizable monomer; specific examples will be described later) as a polymerizable monomer.

[0083] As the third polymerizable monomer, among the polymerizable monomers listed in the section on the second polymerizable monomer, a polymerizable monomer that does not satisfy the above formula (4) can be used.

[0084] In addition, the following polymerizable monomers which do not have the above-mentioned cyano group, amide bond, urethane bond, hydroxy group, urea bond, or carboxy group can also be used.

[0085] For example, styrene and derivatives thereof such as styrene and o-methylstyrene, (meth)acrylic acid esters such as n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, and the like.

[0086] When these satisfy the above formula (4), they can be used as the second polymerizable monomer.

[0087] Among these, the monomer unit A3 is preferably at least one monomer unit selected from the group consisting of a monomer unit represented by the following formula (A31) and a monomer unit represented by the following formula (A32): These monomer units can be introduced by adding the corresponding monomer during the copolymerization reaction for producing the vinyl polymer A. Among these, from the viewpoints of low-temperature fixability, high-temperature offset resistance, and pulverizability of the resin component, the monomer unit A3 is more preferably a monomer unit represented by the following formula (A31):

[0088] [ka]

[0089] [ka]

[0090] (In formula (A32), R 13 indicates H or CH3.) The content of the monomer unit A3 in the vinyl polymer A is preferably 1.0% by mass or more and 60.0% by mass or less.

[0091] If the content of the monomer unit A3 in the vinyl polymer A is 1.0% by mass or more, the elasticity of the toner is easily improved, and a toner with excellent high-temperature offset resistance and durability is easily obtained. Therefore, the content is preferably 1.0% by mass or more, and more preferably 5.0% by mass or more. Furthermore, if the content of the monomer unit A3 in the vinyl polymer A is 60.0% by mass or less, the crystallinity of the vinyl polymer A is less likely to decrease. Therefore, the content is preferably 60.0% by mass or less, more preferably 40.0% by mass or less, and even more preferably 30.0% by mass or less.

[0092] The monomer unit A3 and the third polymerizable monomer may be used alone or in combination of two or more thereof. The vinyl polymer A may have a monomer unit other than the monomer units A1, A2, and A3.

[0093] <Other aspects of vinyl polymer A> The content of the THF-soluble vinyl polymer A in the resin component is preferably 20.0% by mass or more and 95.0% by mass or less. A content of 20.0% by mass or more means that a sufficient amount of the THF-soluble vinyl polymer A is contained in the resin component, which makes it easier to maintain the elasticity of the toner appropriately and to obtain a toner with excellent low-temperature fixability. Therefore, the content is preferably 20.0% by mass or more, more preferably 30.0% by mass or more, and even more preferably 40.0% by mass or more. Furthermore, if the content is 95.0% by mass or less, the elasticity of the toner is less likely to be too low. Therefore, the content is preferably 95.0% by mass or less, more preferably 80.0% by mass or less, more preferably 70.0% by mass or less, and even more preferably 60.0% by mass or less.

[0094] The weight average molecular weight (Mw) of the vinyl polymer A is preferably from 10,000 to 200,000, more preferably from 20,000 to 100,000, and even more preferably from 40,000 to 80,000.

[0095] The vinyl polymer A may be used alone or in combination of two or more kinds.

[0096] <Amorphous resin P> The amorphous resin (amorphous resin P) used in producing the resin component preferably has a carbon-carbon double bond, from the viewpoint of facilitating the crosslinking reaction with the vinyl polymer A. The amorphous resin P may also be contained in the toner.

[0097] The weight average molecular weight (Mw) of the amorphous resin P is preferably 2,000 to 40,000, more preferably 10,000 to 35,000, and even more preferably 15,000 to 30,000.

[0098] The amorphous resin P may be used alone or in combination of two or more kinds.

[0099] <Amorphous polyester P> The amorphous resin P is preferably an amorphous polyester (hereinafter, the amorphous polyester according to the present invention will also be referred to as amorphous polyester P.) The polyester is a condensation polymer of an alcohol component and a carboxylic acid component.

[0100] There are no particular limitations on the method for producing the amorphous polyester P, and it is possible to produce the amorphous polyester P, which is a condensation polymer of the corresponding alcohol component and carboxylic acid component, by carrying out a condensation polymerization reaction of the alcohol component and the carboxylic acid component. The alcohol component and the carboxylic acid component may be used alone or in combination of two or more.

[0101] The amorphous polyester P is preferably a polyester having at least one of an unsaturated carboxylic acid component and an unsaturated alcohol component as a constituent component.

[0102] The amorphous polyester P preferably has a structure formed by condensation polymerization of a saturated alcohol component and / or a saturated carboxylic acid component in addition to an unsaturated carboxylic acid component or an unsaturated alcohol component. These saturated alcohol components and / or saturated carboxylic acid components may be used alone or in combination of two or more.

[0103] The nonlinear amorphous polyester P can be produced, for example, by condensation polymerization of an unsaturated carboxylic acid component and / or an unsaturated alcohol component, as well as a saturated alcohol component, a trivalent or higher polyol component.Similarly, it can also be produced by condensation polymerization of a saturated carboxylic acid component, as well as a trivalent or higher carboxylic acid component.

[0104] In the step of carrying out the polycondensation reaction of the alcohol component and the carboxylic acid component, the reaction is preferably carried out in an inert gas (nitrogen gas, etc.) atmosphere at a temperature of 150 to 280°C. It is more preferably 160 to 250°C, and even more preferably 170 to 235°C. Carrying out the polycondensation reaction at a reaction temperature within the above range allows the constituent components to react sufficiently. From the viewpoint of ensuring the polycondensation reaction, the reaction time is preferably 30 minutes to 40 hours, more preferably 2 to 40 hours.

[0105] An esterification catalyst can be used during the production of the amorphous polyester P (during the condensation polymerization reaction).

[0106] Examples of the esterification catalyst include tin-containing catalysts (e.g., dibutyltin oxide), antimony dioxide, titanium-containing catalysts (e.g., titanium alkoxides, potassium oxalate titanate, titanium terephthalate, titanium terephthalate alkoxide, titanium dihydroxybis(triethanolaminate), titanium monohydroxytris(triethanolaminate), titanyl bis(triethanolaminate) and intramolecular condensation polymers thereof, titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, and titanium diisopropoxyditerephthalate), zirconium-containing catalysts (e.g., zirconyl acetate), and zinc acetate.

[0107] Among these, titanium-containing catalysts are preferred. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.

[0108] A stabilizer may be added to achieve polymerization stability, such as hydroquinone, methylhydroquinone, and hindered phenol compounds.

[0109] The alcohol component of the amorphous polyester P includes unsaturated alcohol components and saturated alcohol components. Among them, alcohols having 1 to 30 carbon atoms are preferred. Furthermore, the alcohol component of the amorphous polyester P is preferably an aliphatic alcohol component having 1 to 6 carbon atoms.

[0110] Among the aliphatic alcohol components having 1 to 6 carbon atoms, polyhydric alcohols having 2 to 6 carbon atoms are preferred from the viewpoints of low-temperature fixability, high-temperature offset resistance, and developability. Alkylene glycols having 2 to 6 carbon atoms are more preferred, and ethylene glycol is even more preferred. That is, the amorphous polyester P preferably has a structure formed by condensation polymerization of polyhydric alcohols having 2 to 6 carbon atoms, more preferably a structure formed by condensation polymerization of alkylene glycols having 2 to 6 carbon atoms, and even more preferably a structure formed by condensation polymerization of ethylene glycol. Examples of polyhydric alcohols having 2 to 6 carbon atoms include ethylene glycol, propylene glycol, pentaerythritol, and neopentyl glycol. By having these structures, the above SP P is appropriately controlled, the above formulas (5), (6), and (7) are easily satisfied, and a toner having excellent developability is easily obtained.

[0111] In the amorphous polyester P, the content of the structure obtained by condensation polymerization of an aliphatic alcohol component having 1 to 6 carbon atoms is more preferably 10.0% by mass or more. P is appropriately controlled, making it easier to satisfy the above formulas (5), (6), and (7). Therefore, the content is preferably 10.0 mass % or more, more preferably 20.0 mass % or more, and even more preferably 30.0 mass % or more.

[0112] Furthermore, based on the total mass of structures present in the amorphous polyester P that are formed by condensation polymerization of alcohol components, the content of structures formed by condensation polymerization of aliphatic alcohol components having 1 to 6 carbon atoms is preferably 15.0 mass% or more, more preferably 25.0 mass% or more, and even more preferably 40.0 mass% or more.

[0113] Examples of the aliphatic alcohol component having 1 to 6 carbon atoms include unsaturated aliphatic alcohols such as unsaturated monools having 3 to 6 carbon atoms (e.g., 2-propen-1-ol) and unsaturated diols having 4 to 6 carbon atoms. Examples of the saturated aliphatic alcohols include alkanols having 1 to 6 carbon atoms (e.g., methanol, ethanol, isopropanol), alkylene glycols having 2 to 6 carbon atoms (e.g., ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol), and polyols having 3 to 8 or more valences.

[0114] Examples of the carboxylic acid component of the amorphous polyester P include the following unsaturated carboxylic acids and saturated carboxylic acids. Examples of the unsaturated carboxylic acids include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated polycarboxylic acids, and anhydrides and lower alkyl esters of these acids.

[0115] The unsaturated monocarboxylic acid includes unsaturated monocarboxylic acids having 3 to 80 carbon atoms, and specific examples thereof include acrylic acid, methacrylic acid, propiolic acid, 2-butenoic acid, crotonic acid, isocrotonic acid, 3-butenoic acid, anglicanic acid, tiglic acid, 4-pentenoic acid, 2-ethyl-2-butenoic acid, 10-undecenoic acid, 2,4-hexadienoic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, and nervonic acid.

[0116] The unsaturated dicarboxylic acid includes unsaturated dicarboxylic acids having 4 to 50 carbon atoms, and specific examples thereof include alkenylsuccinic acids such as dodecenylsuccinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and glutaconic acid.

[0117] The unsaturated polycarboxylic acid may be a vinyl polymer of an unsaturated carboxylic acid (having a number average molecular weight (Mn) of 450 to 10,000 as determined by gel permeation chromatography (GPC)).

[0118] Among the above unsaturated carboxylic acids, from the viewpoint of achieving both low-temperature fixability and high-temperature offset resistance, acrylic acid, methacrylic acid, alkenylsuccinic acid such as dodecenylsuccinic acid, maleic acid, fumaric acid, and combinations thereof are preferred. Acrylic acid, methacrylic acid, maleic acid, fumaric acid, and combinations thereof are more preferred. Furthermore, the unsaturated carboxylic acid may be an anhydride or lower alkyl ester of these acids.

[0119] Examples of the saturated carboxylic acid include aliphatic monocarboxylic acids having 2 to 50 carbon atoms (such as stearic acid and behenic acid), aromatic monocarboxylic acids having 7 to 37 carbon atoms (such as benzoic acid), aliphatic dicarboxylic acids having 2 to 50 carbon atoms (such as oxalic acid, malonic acid, succinic acid, adipic acid, benzoic acid, and sebacic acid), aromatic dicarboxylic acids having 8 to 86 carbon atoms (such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid), aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and aliphatic tricarboxylic acids having 6 to 36 carbon atoms (such as hexanetricarboxylic acid).

[0120] The saturated carboxylic acids may also be anhydrides or lower alkyl (having 1 to 4 carbon atoms) esters (methyl ester, ethyl ester, isopropyl ester, etc.) of these carboxylic acids.

[0121] Among the saturated carboxylic acids, aromatic carboxylic acids having 7 to 87 carbon atoms, alkanedicarboxylic acids having 2 to 50 carbon atoms, aromatic dicarboxylic acids having 8 to 20 carbon atoms, and aromatic polycarboxylic acids having 9 to 20 carbon atoms are preferred. By using the saturated carboxylic acids, toners having excellent low-temperature fixability and high-temperature offset resistance are easily obtained. Furthermore, from the viewpoints of low-temperature fixability, high-temperature offset resistance, and chargeability, benzoic acid, adipic acid, alkylsuccinic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, and combinations thereof are more preferred. Even more preferred are adipic acid, terephthalic acid, trimellitic acid, and combinations thereof. Furthermore, anhydrides or lower alkyl esters of these acids may also be used.

[0122] <Carbon-carbon double bond content> The content of carbon-carbon double bonds (double bond equivalent) in the amorphous resin P is preferably 0.02 mmol / g to 0.80 mmol / g, and more preferably 0.20 mmol / g to 0.70 mmol / g.

[0123] Within the above range, the crosslinking reaction between the crystalline resin and the amorphous resin is likely to proceed favorably, and the toner is likely to preferably contain a THF-insoluble component that satisfies the above formulas (1) and (2). Furthermore, since a resin in which the crystalline resin and the amorphous resin are crosslinked is likely to be contained, aggregation between domains is likely to be prevented, and a toner with excellent developability is likely to be obtained.

[0124] <Weight average molecular weight (Mw) of amorphous polyester P> The weight-average molecular weight (Mw) of the amorphous polyester P is preferably 2000 to 40000, more preferably 10000 to 35000, and even more preferably 15000 to 30000. When the weight-average molecular weight (Mw) of the amorphous polyester P is within the above range, it is thought that the domain size in the domain matrix structure does not become too large, and coarse domains are less likely to be included.

[0125] The amorphous polyester P may be used alone or in combination of two or more.

[0126] <Crosslinking reaction between crystalline resin A and amorphous resin P> The THF-insoluble component preferably contains a resin obtained by a crosslinking reaction between crystalline resin A and amorphous resin P. That is, the THF-insoluble component preferably contains a resin in which a crystalline resin and an amorphous resin are bonded together, and the THF-insoluble component preferably has a structure in which at least a portion of the crystalline resin and the amorphous resin are bonded together. (Hereinafter, a resin in which crystalline resin A and amorphous resin P are bonded together will be referred to as crosslinked resin L.)

[0127] Methods for bonding crystalline resin A and amorphous resin P include a method of using a radical initiator on a mixture in which crystalline resin A and amorphous resin P are dissolved or melted, and a method of using a crosslinking agent having functional groups that react with both crystalline resin A and amorphous resin P.

[0128] The radical initiator used in the method of crosslinking using a radical initiator is not particularly limited, and examples thereof include inorganic peroxides, organic peroxides, azo compounds, etc. These radical reaction initiators may also be used in combination.

[0129] When both crystalline resin A and amorphous resin P have carbon-carbon double bonds, it is believed that the carbon-carbon double bonds are cleaved by the radical initiator, causing crosslinking between crystalline resin A and amorphous resin P.

[0130] The crosslinking agent having a functional group reactive with both the crystalline resin A and the amorphous resin P is not particularly limited. Examples include a crosslinking agent having an epoxy group, a crosslinking agent having an isocyanate group, a crosslinking agent having an oxazoline group, a crosslinking agent having a carbodiimide group, a crosslinking agent having a hydrazide group, and a crosslinking agent having an aziridine group. In a method of crosslinking using a crosslinking agent having a functional group reactive with both the crystalline resin A and the amorphous resin P, both the crystalline resin A and the amorphous resin P must have a functional group reactive with the crosslinking agent.

[0131] A resin in which at least a portion of the crystalline resin A crosslinked by the above method and the amorphous resin P are bonded together (i.e., a crosslinked resin L in which the crystalline resin A and the amorphous resin P are crosslinked) can be used in the production of toner. Furthermore, when producing toner by the melt-kneading method, toner particles containing a resin in which the crystalline resin A and the amorphous resin P are bonded together can also be produced by melt-kneading a raw material mixture containing the crystalline resin A and the amorphous resin P in the presence of the above-mentioned radical initiator or crosslinking agent.

[0132] The content of crosslinked resin L can be controlled by the composition and molecular weight of crystalline resin A and amorphous resin P during production of the resin component, and the degree of bonding between crystalline resin A and amorphous resin P. The degree of bonding can be controlled by the type and amount of the radical reaction initiator described above, the content of carbon-carbon double bonds in amorphous resin P during production of the resin component, etc.

[0133] For example, the crosslinked resin L is preferably a resin obtained by melt-kneading an amorphous polyester resin having a carbon-carbon double bond as the amorphous resin P and a vinyl polymer A as the crystalline resin A, while adding a radical reaction initiator to the mixture to carry out a crosslinking reaction.

[0134] By producing the crosslinked resin L using the crystalline resin A and the amorphous resin P, at least a portion of the crystalline resin A and the amorphous resin P are bonded to form the crosslinked resin L.

[0135] The radical reaction initiator used for the crosslinking reaction is not particularly limited, and examples thereof include inorganic peroxides, organic peroxides, azo compounds, etc. These radical reaction initiators may also be used in combination.

[0136] The inorganic peroxide is not particularly limited, but examples thereof include hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate.

[0137] The organic peroxide is not particularly limited, and examples thereof include benzoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α-bis(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexanoate, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, and lauroyl peroxide. Examples of peroxyalkylene compounds include methyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butylperoxyisopropyl monocarbonate, and t-butyl peroxyacetate.

[0138] The azo compound or diazo compound is not particularly limited, but examples thereof include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobisisobutyronitrile.

[0139] Among these, organic peroxides are preferred because they have high initiator efficiency and do not produce toxic by-products such as cyanide compounds. Furthermore, initiators with high hydrogen abstraction ability are even more preferred because the crosslinking reaction proceeds efficiently and only a small amount is required. Examples of such initiators include radical initiators such as t-butylperoxyisopropyl monocarbonate, benzoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α-bis(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, and di-t-hexyl peroxide.

[0140] When mixing vinyl polymer A and amorphous polyester P, the mixing ratio (mass of polymer A used during mixing / mass of amorphous polyester used during mixing) is preferably (40 / 60) to (95 / 5), more preferably (50 / 50) to (80 / 20). Within this range, the crosslinking reaction between vinyl polymer A and amorphous polyester P proceeds smoothly, making it easier to obtain a toner with excellent low-temperature fixability, high-temperature offset resistance, and developability. When the mixing ratio is outside the range of (50 / 50) to (80 / 20), it is preferable to add 2.0 parts by mass or more of radical initiator per 100.0 parts by mass of the total mass of vinyl polymer A and amorphous polyester P used during mixing. If the ratio is less than 2.0 parts by mass, the crosslinking reaction between vinyl polymer A and amorphous polyester P may not proceed sufficiently, failing to satisfy the above formulas (1) and (2).

[0141] <Two-component developer> The toner can be used as a one-component developer, but may also be used as a two-component developer containing the toner of the present invention and a magnetic carrier.

[0142] Examples of magnetic carriers include surface-oxidized iron powder, unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, oxide particles, magnetic materials such as ferrite, and magnetic material-dispersed resin carriers (so-called resin carriers) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state.

[0143] When the toner is mixed with a magnetic carrier to be used as a two-component developer, the carrier mixing ratio is preferably 2% by mass or more and 15% by mass or less, based on the total mass of the two-component developer. More preferably, it is 4% by mass or more and 13% by mass or less. Good results are usually obtained within this range.

[0144] <Various additives> In addition to the resin component (binder resin), the toner may contain, if necessary, one or more additives selected from a colorant, a release agent, a charge control agent, a fluidizing agent, etc. Materials other than the resin component used in the toner are described below.

[0145] <Release agent> To impart releasability during fixing, the toner may contain a release agent, such as a polyolefin copolymer, a polyolefin wax, a microcrystalline wax, a paraffin wax, an aliphatic hydrocarbon wax such as Fischer-Tropsch wax, or an ester wax.

[0146] The molecular weight of the release agent is preferably 1,000 or more. It is believed that a molecular weight of 1,000 or more makes the release agent less compatible with the crystalline portion of the vinyl polymer A. This makes it easier for the release agent to seep out onto the surface of the toner particles during fixing, which tends to improve the release properties. Furthermore, since the crystalline portion and the release agent are less compatible with each other, the crystallinity of the crystalline portion is less likely to be impaired.

[0147] Here, the molecular weight of the release agent refers to the peak top molecular weight (Mp) measured by gel permeation chromatography (GPC). The measurement method will be described later.

[0148] The molecular weight of the release agent is preferably at least 1500. There is no particular upper limit, but from the viewpoint of ensuring releasability, it is preferably at most 10000, more preferably at most 5000.

[0149] The release agent is not particularly limited as long as it has a molecular weight of 1000 or more, and examples thereof include the following.

[0150] Aliphatic hydrocarbon waxes: low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, Fischer-Tropsch wax, or waxes obtained by oxidizing or adding an acid to these.

[0151] Ester waxes containing fatty acid esters as the main component can also be used. From the viewpoint of molecular weight, the ester wax is preferably a trifunctional or higher functional ester wax, more preferably a tetrafunctional or higher functional ester wax.

[0152] Tri- or higher functional ester waxes can be obtained, for example, by condensing a tri- or higher functional acid with a long-chain linear saturated alcohol, or by condensing a tri- or higher functional alcohol with a long-chain linear saturated fatty acid.

[0153] Examples of tri- or higher functional alcohols that can be used in ester wax include, but are not limited to, the following. A mixture of multiple ester waxes can also be used.

[0154] Glycerin, trimethylolpropane, erythritol, pentaerythritol, sorbitol, and condensates thereof include so-called polyglycerins such as diglycerin, triglycerin, tetraglycerin, hexaglycerin, and decaglycerin, which are condensed with glycerin, ditrimethylolpropane, which is condensed with trimethylolpropane, and dipentaerythritol and trispentaerythritol, which are condensed with tristrimethylolpropane and pentaerythritol.

[0155] Among these, a structure having a branched structure is preferred, pentaerythritol or dipentaerythritol is more preferred, and dipentaerythritol is particularly preferred.

[0156] Long-chain saturated fatty acids have the general formula C n H 2n+1 Those represented by COOH, in which n is 5 or more and 28 or less, are preferred.

[0157] Examples of long-chain, straight-chain saturated fatty acids include, but are not limited to, the following. Mixtures of these acids may also be used. Examples include caproic acid, caprylic acid, octylic acid, nonylic acid, decanoic acid, dodecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Myristic acid, palmitic acid, stearic acid, and behenic acid are preferred in terms of the melting point of the wax.

[0158] Examples of tri- or higher functional acids include, but are not limited to, the following. Mixtures of these acids may also be used. Examples include trimellitic acid and butanetetracarboxylic acid.

[0159] Long-chain saturated alcohols are C n H 2n+1 Those represented by OH, in which n is 5 or more and 28 or less, are preferably used.

[0160] Examples of long-chain linear saturated alcohols include, but are not limited to, the following. Mixtures of these alcohols are also possible. Examples include capryl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and behenyl alcohol. Myristyl alcohol, palmityl alcohol, stearyl alcohol, and behenyl alcohol are preferred in terms of the melting point of the wax.

[0161] The release agent preferably has a softening point of 50°C to 170°C as measured by a flow tester, and examples thereof include polyolefin wax, natural wax, aliphatic alcohols having 30 to 50 carbon atoms, fatty acids having 30 to 50 carbon atoms, and mixtures thereof.

[0162] Examples of polyolefin waxes include (co)polymers of olefins (such as ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof) [including those obtained by (co)polymerization and thermally degradable polyolefins], oxides of olefin (co)polymers with oxygen and / or ozone, maleic acid modified olefin (co)polymers [for example, modified products of maleic acid and its derivatives (maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate, etc.)], copolymers of olefins and unsaturated carboxylic acids [(meth)acrylic acid, itaconic acid, maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [(meth)acrylic acid alkyl (C1 to C18) esters and alkyl maleates (C1 to C18) esters, etc.], and Sasol wax.

[0163] Examples of natural waxes include carnauba wax, montan wax, paraffin wax, and rice wax. Examples of fatty alcohols having 30 to 50 carbon atoms include triacontanol. Examples of fatty acids having 30 to 50 carbon atoms include triacontanol.

[0164] The release agent preferably contains an aliphatic hydrocarbon wax, and more preferably is an aliphatic hydrocarbon wax. Aliphatic hydrocarbon waxes have low polarity and therefore tend to exude from the polymer A during fixing.

[0165] The content of the release agent in the toner is preferably 1.0% by mass or more and 30.0% by mass or less. A content of 1.0% by mass or more is preferable because it improves the release properties of the toner. Therefore, a content of 1.0% by mass or more is preferable, and 2.0% by mass or more is more preferable. Furthermore, if the content is 30.0% by mass or less, the release agent is less likely to be exposed on the toner particle surface. Therefore, a content of 30.0% by mass or less is preferable, and 25.0% by mass or less is more preferable.

[0166] The melting point of the release agent is preferably 80°C or higher and 120°C or lower. If the melting point is 80°C or higher, the release agent is less likely to be exposed on the surface of the toner particles. Therefore, the melting point is preferably 80°C or higher, and more preferably 85°C or higher. Furthermore, if the melting point is 120°C or lower, the release agent melts appropriately during fixing, making it easier to obtain a toner with excellent low-temperature fixing properties and high-temperature offset resistance. Therefore, the melting point is preferably 120°C or lower, and more preferably 110°C or lower.

[0167] The release agents may be used alone or in combination of two or more.

[0168] <Magnetic material> Examples of magnetic materials include the following:

[0169] Iron oxides such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel, and alloys and mixtures thereof of the above metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, bismuth, calcium, manganese, titanium, tungsten, and vanadium.

[0170] <Coloring agent> Examples of colorants include the following:

[0171] Examples of black colorants include carbon black, and those toned to black using a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, a pigment may be used alone, or a dye and a pigment may be used in combination. From the viewpoint of the image quality of full-color images, it is preferable to use a dye and a pigment in combination.

[0172] Examples of pigments for magenta toner include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0173] Dyes for magenta toner include solvent dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, and 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, and 27; and CI Disperse Violet 1; and basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0174] Examples of pigments for cyan toner include CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, and 17; CI Vat Blue 6; and CI Acid Blue 45, and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.

[0175] An example of a dye for cyan toner is CI Solvent Blue 70.

[0176] Yellow toner pigments include the following: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Vat Yellow 1, 3, 20.

[0177] An example of a dye for yellow toner is CI Solvent Yellow 162.

[0178] These colorants can be used alone or in combination, or in the form of a solid solution.

[0179] <Charge control agent> A charge control agent may be contained to stabilize the chargeability of the toner. The charge control agent is preferably an organic metal complex or a chelate compound. Examples of the charge control agent include a monoazo metal complex, an acetylacetone metal complex, a metal complex of an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid, and metal salts thereof. The charge control agent may be added internally or externally to the toner.

[0180] <Inorganic fine particles> The toner may contain inorganic fine particles as needed. The inorganic fine particles may be added internally to the toner particles or may be mixed with the toner as an external additive. Examples of inorganic fine particles include silica fine particles, titanium oxide fine particles, alumina fine particles, and fine particles of their double oxides. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferred for improving flowability and uniform charging.

[0181] The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0182] The content of the external additive is preferably 0.1 to 10.0 parts by mass with respect to 100 parts by mass of toner particles. The toner particles and the external additive can be mixed using a known mixer such as a Henschel mixer.

[0183] <Superplasticizer> A fluidizing agent may be added to adjust the fluidity of the toner, and examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder.

[0184] <Toner manufacturing method> The method for producing the toner of the present invention is not particularly limited, and can be, for example, a pulverization method, a suspension polymerization method, a solution suspension method, an emulsion aggregation method, a dispersion polymerization method, etc., but from the viewpoint of developability and high-temperature offset resistance, a pulverization method is preferred, which can further improve dispersibility. That is, the method for producing the toner of the present invention is preferably a toner production method including a step of melt-kneading a mixture containing a crystalline resin, an amorphous resin, and a radical initiator to obtain a kneaded product, and a step of pulverizing the kneaded product to obtain a pulverized product.

[0185] Furthermore, as described above, from the viewpoint of developability, high-temperature offset resistance, and low-temperature fixability, the method for producing the toner of the present invention is as follows: A step of melt-kneading a mixture containing a crystalline vinyl polymer A, an amorphous resin P having a carbon-carbon double bond, and a radical initiator to obtain a kneaded product; and A step of pulverizing the kneaded product to obtain a pulverized product, the vinyl polymer A has a monomer unit A1 represented by the above formula (A), the vinyl polymer A further has a monomer unit A2, The SP value of the vinyl polymer A is A (J / cm 3 ) 0.5 year, The SP value of the amorphous resin P is P (J / cm 3 ) 0.5 year, The SP value of the monomer unit A1 is SPA1 (J / cm 3 ) 0.5 year, The SP value of the monomer unit A2 is SP A2 (J / cm 3 ) 0.5 When The SP A1 and the SP A2 satisfies the above formula (4), The SP A and the SP P satisfies the above formula (5), The SP A2 , the SP A and the SP P It is preferable that the toner manufacturing method satisfies the above formula (6).

[0186] To produce toner using the pulverization method, (i) The resin components constituting the toner, and optionally colorants, magnetic materials, waxes, and other additives, are thoroughly mixed using a mixer such as a Henschel mixer or a ball mill. (ii) melt-kneading the resulting mixture using a thermal kneader such as a twin-screw kneading extruder, a heating roll, a kneader, or an extruder to make the resins compatible with each other; (iii) After cooling and solidifying, the mixture is pulverized and classified to obtain toner particles.

[0187] In order to control the shape and surface properties of the toner particles, it is preferable to have a surface treatment step in which the toner particles are passed through a surface treatment device that continuously applies mechanical impact force after pulverization or classification. By controlling the treatment time of this surface treatment step, it is possible to control the surface shape of the toner particles and the adhesive force of the toner particles.

[0188] Furthermore, if necessary, desired external additives may be thoroughly mixed in a mixer such as a Henschel mixer to obtain a toner.

[0189] Examples of mixers include the following: Henschel mixer (manufactured by Nippon Coke and Engineering Co., Ltd.); Super mixer (manufactured by Kawata Corporation); Ribocone (manufactured by Okawara Manufacturing Co., Ltd.); Nauta mixer, Turbulizer, Cyclomix (manufactured by Hosokawa Micron Corporation); Spiral pin mixer (manufactured by Pacific Machinery Works Co., Ltd.); and Lödige mixer (manufactured by Matsubo Corporation).

[0190] Examples of kneaders include the following: KRC kneader (manufactured by Kurimoto Iron Works); Buss-Co kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by The Japan Steel Works); PCM kneader (manufactured by Ikegai Iron Works); three-roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); Kneadex (manufactured by Mitsui Mining Co., Ltd.); MS-type pressure kneader, kneader-ruder (manufactured by Nippon Spindle Co., Ltd.); and Banbury mixer (manufactured by Kobe Steel, Ltd.).

[0191] Examples of pulverizers include the following: Counter Jet Mill, Micron Jet, Innomizer (manufactured by Hosokawa Micron Corporation); IDS-type mill, PJM jet pulverizer (manufactured by Nippon Pneumatic Mfg. Co., Ltd.); Cross Jet Mill (manufactured by Kurimoto Iron Works Co., Ltd.); Urmax (manufactured by Nisso Engineering Co., Ltd.); SK Jet-O-Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); Turbo Mill (manufactured by Turbo Industrial Co., Ltd.); and Super Rotor (manufactured by Nisshin Engineering Co., Ltd.).

[0192] Examples of classifiers include the following: Cruseal, Micron Classifier, and Spedic Classifier (manufactured by Seishin Enterprise Co., Ltd.); Turbo Classifier (manufactured by Nisshin Engineering Co., Ltd.); Micron Separator, Turboplex (ATP), and TSP Separator (manufactured by Hosokawa Micron Corporation); Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), and Dispersion Separator (manufactured by Nippon Pneumatic Industry Co., Ltd.); and YM Microcut (manufactured by Yaskawa Corporation).

[0193] Examples of surface treatment devices include Faculty (manufactured by Hosokawa Micron Corporation), Mechanofusion (manufactured by Hosokawa Micron Corporation), Nobilta (manufactured by Hosokawa Micron Corporation), Hybridizer (manufactured by Nara Kikai Co., Ltd.), Innomizer (manufactured by Hosokawa Micron Corporation), Theta Composer (manufactured by Tokuju Kogyosho Co., Ltd.), and Mechanomill (manufactured by Okada Seiko Co., Ltd.).

[0194] Examples of sieving devices used to sift out coarse particles include Ultrasonic (manufactured by Koei Sangyo Co., Ltd.), Resonaseave, Gyrosifter (manufactured by Tokuju Kogyosho Co., Ltd.), Vibrasonic System (manufactured by Dalton Co., Ltd.), Soniclean (manufactured by Shinto Kogyo Co., Ltd.), Turbo Screener (manufactured by Turbo Industry Co., Ltd.), Microsifter (manufactured by Makino Sangyo Co., Ltd.), and circular vibrating sieves.

[0195] <Various measurement methods, etc.> Various measurement methods will be described below.

[0196] <Method for observing the cross section of a toner particle using a transmission electron microscope (TEM) and measuring the major axis and number of domains> The domain matrix structure is observed after the cross section of the toner particle is stained with ruthenium.

[0197] First, a single layer of toner was sprayed onto a cover glass (Matsunami Glass Co., Ltd., square cover glass No. 1). Then, using an osmium plasma coater (Filgen, OPC80T), a protective layer of Os (5 nm) and naphthalene (20 nm) was applied to the toner. Next, a PTFE tube (Φ1.5 mm x Φ3 mm x 3 mm) was filled with photocurable resin D800 (JEOL Ltd.), and the cover glass was gently placed on top of the tube, with the toner in contact with the photocurable resin D800. After irradiating the resin with light, the cover glass and tube were removed to form a cylindrical resin with toner particles embedded in its outermost surface. An ultrasonic ultramicrotome (Leica, UC7) was used to cut the outermost surface of the cylindrical resin at a cutting speed of 0.6 mm / s, along the radius of the toner particles (4.0 μm for a weight average particle diameter (D4) of 8.0 μm) to expose the cross-section of the toner particles. Next, the toner particle was cut to a thickness of 250 nm to prepare a thin section sample of the toner particle cross section. By cutting in this manner, the cross section of the central part of the toner particle can be obtained.

[0198] The obtained thin section sample was stained for 15 minutes in a 500 Pa atmosphere of RuO4 gas using a vacuum electron staining device (Filgen, VSC4R1H), and then subjected to STEM observation using a TEM (JEOL, JEM2800).

[0199] The probe size in STEM observation was 1 nm, and the image size was 1024 × 1024 pixels.

[0200] The obtained bright-field images were binarized using image processing software "Image-Pro Plus (Media Cybernetics)." In this binarization, when the change in brightness from black to white is expressed as a gradation from 0 to 255, areas below 127 gradations are expressed as black, and areas above 128 gradations are expressed as white.

[0201] In observing the cross section of a toner particle, the parts containing crystalline resin are the parts that appear black when the above-mentioned binarization process is performed, and the parts containing amorphous resin are the parts that appear white when the above-mentioned binarization process is performed.

[0202] From the images obtained by STEM observation after binarization, it was determined whether a domain-matrix structure was observed in the cross section of the toner particle, and whether the domain and matrix contained a crystalline resin or an amorphous resin, respectively.

[0203] Next, toner particles to be observed for measuring the major axis of the domains are selected as follows: First, the cross-sectional area of ​​the toner particle is determined from the cross-sectional image of the toner particle, and the diameter of a circle having an area equal to that cross-sectional area (equivalent circle diameter) is determined. Toner particles for which the absolute value of the difference between this equivalent circle diameter and the weight-average particle diameter (D4) of the toner particles is 1.0 μm or less are selected as the observation target. Then, cross-sectional observation of the toner particles is continued until the number of toner particles for which the absolute value of the difference between the diameter of a circle having an area equal to the cross-sectional area of ​​the toner particle and the weight-average particle diameter (D4) of the toner particles is 1.0 μm or less is reached to 100.

[0204] Next, the major axes of all domains (white areas if the domains are made of an amorphous resin) observed in the cross section of the toner particle selected for observation are measured. Among these, the domain with the largest major axis is selected, and this major axis is taken as the domain's longest diameter. This measurement is performed on 100 selected toner particles, and the number of toner particles with a domain's longest diameter of 1.0 μm or less is counted.

[0205] <Principle of ruthenium dyeing> When the cross section of a toner particle is stained with ruthenium, the crystalline resin component is stained more with ruthenium than the amorphous resin component, resulting in clearer contrast and making it easier to observe the cross section of the toner particle. This is because RuO4 has a strong oxidizing power and oxidizes the long-chain alkyl and alkylene groups that increase crystallinity, and as a result, the crystalline resin component is stained more strongly than the amorphous resin component.

[0206] Furthermore, the higher the crystallinity of the resin component, the greater the amount of ruthenium atoms present, and the more ruthenium atoms present, the less electron beams are transmitted through the resin component. Therefore, a resin component with higher crystallinity is observed to be more strongly stained in an electron microscope image. Conversely, an amorphous resin component is observed to be weakly stained or not stained at all. From this, it can be determined that the strongly stained portion is a portion containing a crystalline resin, and the weakly stained portion or non-stained portion is a portion containing an amorphous resin.

[0207] <Method for analyzing the matrix and domain in cross-sectional observation of toner particles> First, a thin section is prepared as a reference sample for the abundance.

[0208] Crystalline resin A was thoroughly dispersed in a visible light-curable resin (Aronix LCR Series D800) and then cured by irradiating it with short-wavelength light. The resulting cured product was cut using an ultramicrotome equipped with a diamond knife to prepare 250 nm thin flake samples. Thin flake samples of amorphous resin P were also prepared in the same manner.

[0209] Crystalline resin A and amorphous resin P were also mixed at ratios of 0 / 100, 30 / 70, 70 / 30, and 100 / 0 by mass, and melt-kneaded to prepare kneaded products. These were also similarly dispersed in visible light-curable resin, cured, and then cut out to prepare thin flake samples.

[0210] Next, the cross sections of the cut samples were observed using a transmission electron microscope (JEOL JEM-2800) (TEM-EDX), and elemental mapping was performed using EDX. The elements to be mapped were carbon, oxygen, and nitrogen.

[0211] The mapping conditions are as follows:

[0212] Accelerating voltage: 200 kV Electron beam irradiation size: 1.5 nm Live time limit: 600 seconds Dead time: 20~30 Mapping resolution: 256 x 256 Based on the spectral intensity of each element (average over a 10 nm square area), calculate (oxygen element intensity / carbon element intensity) and (nitrogen element intensity / carbon element intensity), and create a calibration curve for the mass ratio of crystalline resin A to amorphous resin P. If the monomer unit of crystalline resin A contains nitrogen atoms, use the calibration curve of (nitrogen element intensity / carbon element intensity) for future quantification.

[0213] The toner particle sample is then analyzed.

[0214] Toner particles are thoroughly dispersed in a visible light curable resin (Aronix LCR Series D800) and then cured by irradiating it with short wavelength light. The resulting cured product is cut using an ultramicrotome equipped with a diamond knife to prepare 250 nm thin samples. The cut samples are then observed using a transmission electron microscope (JEOL JEM-2800 electron microscope) (TEM-EDX). Cross-sectional images of the toner particles are obtained, and elemental mapping is performed using EDX. The elements to be mapped are carbon, oxygen, and nitrogen.

[0215] The toner particle cross-section to be observed is selected as follows: First, the cross-sectional area of ​​the toner particle is calculated from the toner particle cross-sectional image, and then the diameter of a circle having an area equal to that cross-sectional area (equivalent circle diameter) is calculated. Only toner particle cross-sectional images where the absolute value of the difference between this equivalent circle diameter and the weight-average particle diameter (D4) of the toner particle is within 1.0 μm are observed.

[0216] For the domains and matrix confirmed in the observed image, the (oxygen element intensity / carbon element intensity) and / or (nitrogen element intensity / carbon element intensity) ratio is calculated based on the spectral intensity of each element (average of 10 nm square).The ratio of crystalline resin A to amorphous resin P can be calculated by comparing the calculation results with the above-mentioned calibration curve.

[0217] <Method for measuring the content of various monomer units in a resin> The content ratio of each monomer unit in the resin is measured by 1H-NMR under the following conditions.

[0218] Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Accumulation count: 64 times Measurement temperature: 30℃ Sample: 50 mg of the measurement sample is placed in a sample tube with an inner diameter of 5 mm, deuterated chloroform (CDCl3) is added as a solvent, and the mixture is dissolved in a thermostatic bath at 40° C. As an example of measurement, the content ratio of each monomer unit in vinyl polymer A is calculated as follows.

[0219] obtained 1 From the H-NMR chart, a peak that is independent of the peaks attributable to the constituent elements of the monomer unit A1 is selected from the peaks attributable to the constituent elements of the other monomer units, and the integral value S1 of this peak is calculated. Similarly, a peak that is independent of the peaks attributable to the constituent elements of the monomer unit A2 is selected from the peaks attributable to the constituent elements of the other monomer units, and the integral value S2 of this peak is calculated.

[0220] Furthermore, when the monomer unit A3 is incorporated, a peak that is independent of the peaks attributable to the constituent elements of the monomer unit A3 is selected from the peaks attributable to the constituent elements of the other monomer units, and the integral value S3 of this peak is calculated.

[0221] The content of the monomer unit A1 is determined using the above integral values ​​S1, S2, and S3 as follows: where n1, n2, and n3 are the numbers of hydrogen atoms in the constituent elements to which the peak of interest for each site belongs.

[0222] Content of Monomer Unit A1 (mol%)= {(S1 / n1) / ((S1 / n1)+(S2 / n2)+(S3 / n3))}×100 Similarly, the content ratios of the monomer unit A2 and the monomer unit A3 are determined as follows.

[0223] Content of Monomer Unit A2 (mol%)= {(S2 / n2) / ((S1 / n1)+(S2 / n2)+(S3 / n3))}×100 Content of Monomer Unit A3 (mol%)= {(S3 / n3) / ((S1 / n1)+(S2 / n2)+(S3 / n3))}×100 In addition, when a polymerizable monomer that does not contain a hydrogen atom in the constituent elements other than the vinyl group is used in the vinyl polymer A, 13 Measured nuclei using C-NMR 13 C, and measurements were taken in single pulse mode. 1 Calculate in the same manner by H-NMR.

[0224] Furthermore, when a toner or toner particles is used as a measurement sample, the peaks of the release agent and other resins may overlap, making it impossible to observe the independent peaks of the various monomer units in the vinyl polymer A. This may make it impossible to calculate the content ratio of the various monomer units in the vinyl polymer A. In such cases, a vinyl polymer A' can be produced by performing a similar suspension polymerization without using a release agent or other resin, and the vinyl polymer A' can be considered as the vinyl polymer A and analyzed.

[0225] When measuring resins such as amorphous polyester P, the content ratios of various monomer units are calculated using the above-mentioned measuring device and conditions.

[0226] <Method for measuring the content of THF insoluble matter in resin components> 1.5 g of the toner sample (0.7 g if the sample contains only resin components) is precisely weighed (W1 [g]), placed in a pre-weighed cylindrical filter paper (product name: No. 86R, size 28 × 100 mm, manufactured by Advantec Toyo Co., Ltd.), and set in a Soxhlet extractor.

[0227] Extraction was performed for 18 hours using 200 mL of THF as the solvent, with the reflux rate set so that the solvent extraction cycle occurred approximately once every 5 minutes. To extract the THF-insoluble matter, the thimble was first removed after the extraction was complete, air-dried, and then vacuum-dried at 40°C for 8 hours. The mass of the thimble containing the extraction residue was then weighed, and the mass of the extraction residue (W2 [g]) was calculated by subtracting the mass of the thimble.

[0228] Furthermore, when recovering the THF-soluble matter, it is possible to recover it by thoroughly distilling off the THF from the soluble matter in the THF using an evaporator.

[0229] Next, the mass (W3 [g]) of the components other than the resin component is determined by the following procedure (in the above procedure, if the measurement sample contains only the resin component, W3 is set to 0 g).

[0230] Approximately 2 g of toner was precisely weighed (W) into a pre-weighed 30 mL magnetic crucible. a [g]).

[0231] The magnetic crucible was placed in an electric furnace and heated to approximately 900°C for approximately 3 hours, then allowed to cool in the electric furnace, and then allowed to cool in a desiccator at room temperature for at least 1 hour. The mass of the crucible containing the incineration ash was weighed, and the mass of the crucible was subtracted to determine the incineration ash content (W b Calculate [g].

[0232] Then, the mass (W3 [g]) of the incineration ash content in the sample W1 [g] is calculated using the following formula (8).

[0233] W3 = W1 × (W b / W a )···(8) In this case, the content of the THF-insoluble matter in the resin component of the toner can be calculated by the following formula (9).

[0234] Content of THF-insoluble matter in resin components (mass%) = {(W2 - W3) / (W1 - W3)} × 100 (9) <Quantitative method for carbon-carbon double bond content> The carbon-carbon double bond content (double bond equivalent) in a polyester having a carbon-carbon double bond can be determined by measuring the protons or carbons of the carbon-carbon double bond using a nuclear magnetic resonance (NMR) spectrometer.

[0235] (Sample preparation) In an NMR sample tube, weigh 100 mg of sample, 10 mg of sodium trimethylsilylpropanesulfonate as an internal standard, and 10 mg of Cr(AcAc)3 as a relaxation reagent. Then, add 0.45 mL of a deuterated solvent (e.g., deuterated pyridine) to dissolve the sample thoroughly.

[0236] (Measurement conditions) Equipment: Bruker BioSpin "AVANCE III HD400" Measurement nuclei: 13 C Measurement frequency: 125.77MHz Sample rotation speed: 6kHz Accumulation count: 24,000 times Measurement temperature: room temperature (Analysis and Calculation) The double bond content (mmol / g) is calculated from the area ratio of the peaks of the double bond carbons derived from the unsaturated carboxylic acid component and the unsaturated alcohol component to the peak of the carbon derived from the methyl group of the internal standard substance.

[0237] For example, for unsaturated carboxylic acid components such as maleic acid and fumaric acid, the double bond content (mmol / g) is calculated from the area ratio of the double bond carbon peak (164.6 ppm) to the area ratio of the carbon peak of the methyl group portion of the internal standard substance (0 ppm).

[0238] <Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn) of resin> The molecular weight distribution (weight average molecular weight (Mw) and number average molecular weight (Mn)) of the resin is measured by gel permeation chromatography (GPC) as follows.

[0239] First, the sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in THF is 0.8 mass%. This sample solution is used for measurements under the following conditions.

[0240] Apparatus: HLC8120 GPC (detector: RI) (Tosoh Corporation) Column: Shodex KF-801, 802, 803, 804, 805, 806, 807 (7 columns, manufactured by Showa Denko Co., Ltd.) Eluent: tetrahydrofuran (THF) Flow rate: 1.0mL / min Oven temperature: 40.0℃ Sample injection volume: 0.10 mL To calculate the molecular weight of a sample, a molecular weight calibration curve prepared using standard polystyrene resins (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0241] <Measurement of maximum endothermic peak temperature (Tm, melting point) and endothermic amount> The endothermic heat of the sample is measured using a DSC Q1000 (manufactured by TA Instruments) under the following conditions.

[0242] Heating rate: 10°C / min Measurement start temperature: 20℃ Measurement end temperature: 200℃ The melting points of indium and zinc are used to correct the temperature of the detector, and the heat of fusion of indium is used to correct the amount of heat.

[0243] Specifically, approximately 5 mg of sample is weighed out and placed in an aluminum pan for differential scanning calorimetry, with an empty silver pan used as a reference.

[0244] In the measurement, the temperature is raised to 200°C once (first heating process), then lowered to 20°C, and then heated again (second heating process). In the DSC curve obtained in this second heating process, the peak-top temperature (Tm, melting point) of the maximum endothermic peak in the temperature range of 20 to 200°C is determined. The maximum endothermic peak is the peak having the maximum value of the amount of heat absorbed per unit temperature in the range of 20 to 200°C. The amount of heat absorbed at the maximum endothermic peak refers to the integrated value of the maximum endothermic peak.

[0245] The reason why the above measurement is not performed during the first temperature rise is that resins and the like manufactured through a manufacturing process that includes a heat treatment may exhibit behavior due to the heat treatment (such as an endothermic peak due to relaxation of the resin) during the first temperature rise of the DSC measurement. If this behavior overlaps with the original behavior of the sample, accurate measurement may become difficult.

[0246] However, it is known that the behavior of these components is uniformed by the first heating process, and the behavior resulting from the heat treatment disappears or becomes small during the second heating process after the sample is cooled. Therefore, in the present invention, the above measurement is performed during the second heating process in order to measure the original behavior of the sample.

[0247] H(I) (J / g) and H(T) (J / g) in the present invention can be calculated by the following formulas (11) and (12).

[0248] H(I)(J / g) = {(integral value of the endothermic peak when the THF-insoluble fraction is used as a sample) × W2 / (W2-W3)} × 100 (11) H(T) (J / g) = (Integrated value of the maximum endothermic peak when the toner is used as the sample) × W1 / (W1 - W3)} × 100 ··· (12) When using the THF-insoluble content as the sample, after separating inorganic fine particles and magnetic substances from the toner particles by the method for separating inorganic fine particles described later, performing the Soxhlet extraction described above on the toner particles enables recovery of the THF-insoluble content serving as the sample from the toner particles.

[0249] <Calculation method of SP value> The SP value of the polymerizable monomer, the SP value of the monomer unit, and the SP value of the resin are determined as follows according to the calculation method proposed by Fedors.

[0250] Regarding the object of calculation, for the atoms or atomic groups (monomer units) of the molecular structure, the evaporation energy (Δei) (cal / mol) and the molar volume (Δvi) (cm 3 / mol) are obtained from the table described in "polym. Eng. Sci., 14(2), 147 - 154(1974)", and (4.184 × ΣΔei / ΣΔvi) 0.5 is taken as the SP value (J / cm 3 ) 0.5 and used as such.

[0251] Note that SP A1 and SP A2 are calculated by the same calculation method as above for the atoms or atomic groups of the molecular structure in the state where the double bond of the polymerizable monomer has been cleaved by polymerization.

[0252] SP A1 and SP A2 are obtained by dividing the evaporation energy of the monomer unit by the molar volume.

[0253] SP AFirst, the evaporation energy (Δei) and molar volume (Δvi) of the monomer unit derived from the constituting polymerizable monomer are determined for each monomer unit, and the product of each monomer unit and the molar ratio (j) of each monomer unit in the vinyl polymer A is calculated. Then, the sum of the evaporation energies of each monomer unit is divided by the sum of the molar volumes to determine SP. A is calculated using the following formula:

[0254] SP A ={4.184×(Σj×ΣΔei) / (Σj×ΣΔvi)} 0.5 SP P About SP A The calculation is performed in the same manner as above, except that the unsaturated components added during the polymerization reaction in the production of the amorphous polyester are excluded from the calculation. [Example]

[0255] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the scope of the present invention. In the following formulations, parts are by weight unless otherwise specified.

[0256] <Production Example of Polymer A-1> The following materials were placed in a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere.

[0257] Toluene: 100.0 parts Behenyl acrylate (first polymerizable monomer): 67.0 parts (25.3 mol%) Acrylonitrile (second polymerizable monomer): 22.0 parts (59.5 mol%) Styrene (third polymerizable monomer): 11.0 parts (15.2 mol%) t-Butyl peroxypivalate (NOF Corporation: Perbutyl PV): 0.5 parts The reactor was heated to 70°C while stirring at 200 rpm, and a polymerization reaction was carried out for 12 hours, obtaining a solution in which the polymer of the polymerizable monomer composition was dissolved in toluene. Subsequently, the solution was cooled to 25°C, and then the solution was poured into 1000.0 parts of methanol while stirring, to precipitate the methanol-insoluble matter. The obtained methanol-insoluble matter was filtered, washed with methanol, and then vacuum-dried at 40°C for 24 hours to obtain polymer A-1. The weight-average molecular weight (Mw) of polymer A-1 was 30,000, and the SP calculated by the above-mentioned method was 1000. A The DSC measurement of Polymer A-1 showed a clear endothermic peak, indicating that the polymer was a crystalline resin. The physical properties of Polymer A-1 are shown in Table 1.

[0258] <Polymer A-2 to A- 5 Manufacturing example> Polymers A-2 to A-3 were prepared in the same manner as for Polymer A-1, except that the amount of each polymerizable monomer added was changed as shown in Table 1. 5 Polymers A-2 to A- 5 The polymers A-2 to A-3 were crystalline resins that showed clear endothermic peaks in DSC measurements. 5 The physical properties are shown in Table 1.

[0259] [Table 1]

[0260] The abbreviations in Table 1 are as follows: BEA: Behenyl acrylate AN: Acrylonitrile MA: methacrylic acid St: styrene SP in Table 1 A1 , SP A2 , SP A The unit is (J / cm 3 ) 0.5 and was calculated by the above calculation method. Furthermore, Mw in Table 1 was measured by the above measurement method.

[0261] <Production example of amorphous resin P-1> The following materials were placed in a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere.

[0262] Ethylene glycol: 50.0 parts Terephthalic acid: 50.0 parts Titanium diisopropoxybistriethanolamine: 2.5 parts The above materials were reacted for 2 hours under a nitrogen stream at 230°C while distilling off the water produced. The mixture was then reacted for 5 hours under a reduced pressure of 2.5 kPa, and then cooled to 180°C. One part of tert-butylcatechol was added as a polymerization inhibitor, followed by 10.0 parts of fumaric acid. The mixture was reacted for 8 hours under a reduced pressure of 0.5 to 2.5 kPa, and then removed to obtain amorphous resin P-1. The physical properties of amorphous resin P-1 are shown in Table 2.

[0263] <Production Examples of Amorphous Resins P-2 to P-9> Amorphous resins P-2 to P-9 were obtained in the same manner as for amorphous resin P-1, except that the amount of each polymerizable monomer added was changed as shown in Table 2. The physical properties of amorphous resins P-2 to P-9 are shown in Table 2.

[0264] [Table 2]

[0265] The abbreviations in Table 2 are as follows: EG: Ethylene glycol PeE: Pentaerythritol NPG: Neopentyl glycol BPA·EO: Bisphenol A·ethylene oxide adduct (average number of moles: 2.0) BPA·PO: Bisphenol A·propylene oxide adduct (average number of moles: 2.0) TPA: Terephthalic acid ADA: Adipic acid FuA: Fumaric acid The Mw and double bond equivalent in Table 2 were measured by the above-mentioned method, and SP P was calculated using the above calculation method.

[0266] <Production example of binder resin C-1> 60 parts of polymer A-1 and 40 parts of amorphous resin P-1 were mixed and fed into a twin-screw kneader (Kurimoto Iron Works, S5KRC kneader) at 40 kg / h. At the same time, 3.0 parts of t-butylperoxyisopropyl monocarbonate as a radical reaction initiator was fed at 0.4 kg / h, and the mixture was kneaded and extruded at 100 rpm for 5 minutes at 160°C to carry out the reaction. Nitrogen was then flowed through the vent to remove the organic solvent while mixing. The mixture obtained by mixing was cooled to obtain binder resin C-1.

[0267] <Binder resin C-2~ C-11, C-14, C-16, C-17, C-19~ C-21 manufacturing example> Binder resins C-2 to C-3 were prepared in the same manner as binder resin C-1, except that the polymer A and amorphous resin P used were changed as shown in Table 3. C-11, C-14, C-16, C-17, C-19~ We got C-21.

[0268] [Table 3]

[0269] SP in Table 3 P and SP A was calculated using the above calculation method.

[0270] <Toner 1 manufacturing example> Binder resin C-1: 100 parts by weight Carbon black (Nipex 35, manufactured by Orion Engineered Carbons): 5.0 parts by mass Release agent (Excelex 15341PA, manufactured by Mitsui Chemicals): 5.0 parts by mass The above materials were premixed in a Henschel mixer, and then melt-kneaded using a twin-screw extruder (product name: PCM-30, manufactured by Ikegai Iron Works) with the temperature set so that the melt temperature at the discharge port was 150°C. The resulting kneaded material was cooled, coarsely pulverized using a hammer mill, and then finely pulverized using a pulverizer (product name: Turbo Mill T250, manufactured by Turbo Kogyo Co., Ltd.). The resulting finely pulverized powder was classified using a multi-division classifier utilizing the Coanda effect to obtain toner particles 1 having a weight average particle size (D4) of 7.2 μm.

[0271] To 100.0 parts by mass of toner particles 1, 1.0 part by mass of hydrophobic silica fine powder (number average particle diameter of primary particles: 10 nm) that had been surface-treated with hexamethyldisilazane was added, and the mixture was mixed using a Henschel mixer at 3200 rpm for 2 minutes to obtain toner 1. The physical properties of toner 1 are shown in Table 4.

[0272] <Toner 2~ 11、14、16、17、19~ 21 Manufacturing Examples> Toners 2 to 3 were prepared in the same manner as Toner 1, except that the type of binder resin C-1 used was changed as shown in Table 4. 11、14、16、17、19~ Toner 21 was obtained. 11、14、16、17、19~ The physical properties of 21 are shown in Table 4.

[0273] Toner 1~ 11、14、16、17、19~ Among the toner particles 21, only in toner 20, toner particles having domains with a major axis of 5.0 μm or more were observed in cross-section observation of the toner particles, but not in the other toners.

[0274] [Table 4]

[0275] The physical properties of the toner in Table 4 were measured by the above-mentioned measurement methods. The content of polymer A in the resin component is a calculated value of the ratio of the mass of polymer A soluble in THF to the mass of the resin component.

[0276] Example 1 Toner 1 was evaluated as follows, and the evaluation results are shown in Table 5.

[0277] <Evaluation of low-temperature fixability of toner> For the evaluation of low-temperature fixability, a modified color laser printer (product name: HP Color LaserJet 3525dn, manufactured by HP) was used as the image forming apparatus, and white paper (Canon Office Planner: 64 g / m 2 The image forming apparatus was modified to allow the fixing temperature and process speed to be changed, and to allow the fixing unit to be removed.

[0278] First, the fixing unit was removed from the image forming apparatus, and then the toner was removed from the black cartridge, and 100 g of Toner 1 was filled into the cartridge.

[0279] Next, an unfixed toner image (toner amount: 0.9 mg / cm) measuring 2.0 cm in length and 15.0 cm in width was printed on the evaluation paper using an image forming apparatus. 2 ) was formed at a position 1.0 cm from the top end in the paper feed direction.

[0280] Hereinafter, an external fixing device capable of operating outside the laser beam printer was used to fix the unfixed images. In a room temperature and humidity environment (23°C, 60% RH), the process speed of the external fixing device was set to 410 mm / s, and the temperature was increased in 5°C increments starting from an initial temperature of 100°C, at which point the unfixed images were fixed at each temperature. The minimum fixing temperature at which low-temperature offset did not occur was determined for each of the fixed images obtained, and this minimum fixing temperature value was used to evaluate the low-temperature fixability of the toner. A minimum fixing temperature of less than 135°C was deemed to be indicative of the effects of the present invention. The evaluation results are shown in Table 5.

[0281] The low-temperature offset is a visible image defect that occurs when the fixing temperature is not high enough to melt the toner.

[0282] <Evaluation of Toner High-Temperature Offset Resistance> Using the image forming apparatus and evaluation paper used in the evaluation of the low-temperature fixability of the toner described above, the high-temperature offset resistance of Toner 1 was evaluated as follows: The evaluation method involved fixing the toner at a temperature that would likely cause high-temperature offset, and measuring the difference in reflection density between the position where high-temperature offset occurred and the white area where no toner was present.

[0283] Using the image forming apparatus, an unfixed image (toner amount: 0.3 mg / cm) was printed on evaluation paper using the filled toner 1, with a leading edge margin of 5 mm, a width of 100 mm, and a length of 100 mm. 2 ) was created.

[0284] In this evaluation, an external fixing device capable of operating outside the laser beam printer was used to fix the unfixed image. Fixation was performed in a normal temperature and humidity environment (temperature 23°C / relative humidity 50%) at a process speed of 410 mm / s and a fixing temperature of 200°C, yielding a fixed image. The reflection density of the resulting fixed image was measured at the position where toner offset occurred. The reflection density was measured using a Macbeth densitometer (manufactured by Macbeth) with an SPI filter. The absolute value of the difference between the reflection density of the white area where no toner was present and the reflection density of the position where offset occurred was defined as the offset density, and this value was used to evaluate the high-temperature offset resistance of the toner. A toner with an offset density of less than 0.15 was deemed to have achieved the effects of the present invention. The evaluation results are shown in Table 5.

[0285] <Evaluation of Toner Developability> Using the image forming apparatus and evaluation paper used in the evaluation of the low-temperature fixability of the toner described above, a horizontal line pattern with a print rate of 1% was printed on two sheets per job, and the machine was set to stop between jobs before the next job began. A total of 20,000 sheets were output using this setting, and then one white image evaluation sheet with a print rate of 0% was output. The white image evaluation sheet was evaluated according to the following criteria to evaluate the developability of Toner 1. The evaluation was performed in a low-temperature, low-humidity environment (temperature 15°C, humidity 10% RH), where the toner is prone to overcharging and non-image areas are prone to contamination.

[0286] The measurements on the white image evaluation paper were performed using a reflectometer (Reflectometer Model TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.) capable of measuring reflection density. The minimum reflection density of the entire white image evaluation paper after output was defined as Ds, and the average reflection density of the white image evaluation paper before output was defined as Dr. The developability was evaluated using (Dr - Ds) as an index. Dr is the average reflection density measured at five points, the four corners and the center of the evaluation paper.

[0287] Therefore, the smaller the (Dr-Ds) value, the better the toner's developability. A (Dr-Ds) value of less than 2.5 was determined to be one in which the effects of the present invention were achieved. The evaluation results are shown in Table 5.

[0288] <Example 2~ 11、14、16、 17> Toner 2~ 11、14、16、 17 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 5.

[0289] <Comparative example 2 ~4> Toner 1 9 1 to 21 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 5.

[0290] [Table 5] [Explanation of symbols]

[0291] 1 Toner particles 2. Matrix in toner particles 3 Domains in toner particles 4. Crosslinked resins made by crosslinking the highly polar parts of crystalline resins with amorphous resins 5. Amorphous portion in crosslinked resin 6 Crystalline portion in crosslinked resin

Claims

1. A toner having toner particles containing a resin component having a crystalline resin and an amorphous resin, The resin component contains a tetrahydrofuran-insoluble component, The content of the tetrahydrofuran-insoluble matter in the resin component is 5.0% by mass to 80.0% by mass, the amorphous resin is an amorphous polyester resin, the amorphous polyester resin has a structure obtained by condensation polymerization of ethylene glycol and a carboxylic acid component, When the maximum endothermic peak temperature in the differential scanning calorimetry (DSC) measurement of the tetrahydrofuran-insoluble fraction is defined as Tm [°C] and the endothermic heat of the maximum endothermic peak is defined as H(I) [J / g], The Tm [°C] satisfies the following formula (1), 55.0≦Tm≦80.0 (1) The H(I) [J / g] satisfies the following formula (2), 10.0≦H(I)≦80.0...(2) When the cross sections of 100 toner particles were observed, In each cross-sectional observation, a domain matrix structure composed of a matrix containing the crystalline resin and a domain containing the amorphous resin was observed, Among 100 toner particles whose cross sections have been observed, the number of toner particles in which all of the observed domains have a major axis of 1.0 μm or less is 20 or more. A toner characterized by:

2. When the endothermic amount of the maximum endothermic peak in the differential scanning calorimeter (DSC) measurement of the toner is H(T) [J / g], the H(I) [J / g] and the H(T) [J / g] satisfy the following formula (3): 3.0%≦H(I) / H(T)≦20.0%...(3) The toner according to claim 1 .

3. 3. The toner according to claim 1, wherein the crystalline resin is a vinyl polymer A having a monomer unit A1 represented by the following formula (A): 【Chemical 1】 (In formula (A), R １ is H or CH ３ indicates R ２ represents an alkyl group having 18 to 36 carbon atoms.)

4. 4. The toner according to claim 3, wherein the content of the monomer unit A1 in the vinyl polymer A is 30.0% by mass or more and 99.9% by mass or less.

5. the vinyl polymer A further has a monomer unit A2, The SP value of the monomer unit A1 is Ａ１ (J / cm ３ ) ０．５ , The SP value of the monomer unit A2 is SP Ａ２ (J / cm ３ ) ０．５ When The SP Ａ１ and the SP Ａ２ satisfies the following formula (4): 3.0≦SP Ａ２ -SP Ａ１ ≦25.0・・・(4) The toner according to claim 3 or 4.

6. the vinyl polymer A further has a monomer unit A2, The monomer unit A2 is at least one monomer unit selected from the group consisting of a monomer unit represented by the following formula (A21) and a monomer unit represented by the following formula (A22): The toner according to any one of claims 3 to 5. 【Chemistry 2】 【Chemistry 3】 (In formulas (A21) and (A22), X represents a single bond or an alkylene group having 1 to 6 carbon atoms; R ４ represents a cyano group (—C≡N), —C(═O)NHR ７ (R ７ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), a hydroxy group, —COOR ８ (R ８ represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms), —NHCOOR ９ (R ９ is an alkyl group having 1 to 4 carbon atoms), —NH—C(═O)—NH(R １０ ) ２ (R １０ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —COO(CH ２ ) ２ NHCOOR １１ (R １１ is an alkyl group having 1 to 4 carbon atoms), or —COO(CH ２ ) ２ -NH-C(=O)-NH(R １２ ) ２ (R １２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ６ represents an alkyl group having 1 to 4 carbon atoms, and R ３ and R ５ are each independently a hydrogen atom or CH ３ Indicates.)

7. 7. The toner according to claim 5, wherein the content of the monomer unit A2 in the vinyl polymer A is 1.0% by mass or more and 70.0% by mass or less.

8. the vinyl polymer A further has a monomer unit A3, The monomer unit A3 is at least one monomer unit selected from the group consisting of a monomer unit represented by the following formula (A31) and a monomer unit represented by the following formula (A32): The toner according to any one of claims 3 to 7. 【Chemistry 4】 【Chemistry 5】 (In formula (A32), R １３ is H or CH ３ Indicates.)

9. 9. The toner according to claim 1, wherein the content of the tetrahydrofuran insoluble matter in the resin component is 30.0% by mass to 80.0% by mass.

10. A method for producing the toner according to any one of claims 1 to 9, comprising: The manufacturing method comprises: a step of melt-kneading a mixture containing a crystalline vinyl polymer A, an amorphous resin P having a carbon-carbon double bond, and a radical initiator to obtain a kneaded product; and a step of pulverizing the kneaded product to obtain a pulverized product; Including, The vinyl polymer A has a monomer unit A1 represented by the following formula (A): the vinyl polymer A further has a monomer unit A2, the amorphous resin P is an amorphous polyester P, The amorphous polyester P has a structure obtained by condensation polymerization of an alcohol component and a carboxylic acid component, The alcohol component contains ethylene glycol, The SP value of the vinyl polymer A is Ａ (J / cm ３ ) ０．５ year, The SP value of the amorphous resin P is Ｐ (J / cm ３ ) ０．５ year, The SP value of the monomer unit A1 is Ａ１ (J / cm ３ ) ０．５ year, The SP value of the monomer unit A2 is SP Ａ２ (J / cm ３ ) ０．５ When The SP Ａ１ and the SP Ａ２ satisfies the following formula (4), 3.0≦SP Ａ２ -SP Ａ１ ≦25.0・・・(4) The SP Ａ and the SP Ｐ satisfies the following formula (5), 5000 Ｐ 2000 Ａ |≦10.0・・・(5) The SP Ａ２ , the SP Ａ and the SP Ｐ satisfies the following formula (6): 100 Ｐ 2000 Ａ 2000 Ｐ 2000 Ａ２ |・・・(6) A method for producing a toner comprising the steps of: 【Chemistry 6】 (In formula (A), R １ is H or CH ３ indicates R ２ represents an alkyl group having 18 to 36 carbon atoms.)

11. The SP Ａ and the SP Ｐ satisfies the following formula (7): 6.0≦|SP Ｐ 2000 Ａ |≦10.0・・・(7) The method for producing the toner according to claim 10.

12. 12. The method for producing a toner according to claim 10, wherein the amorphous polyester P contains the structure formed by condensation polymerization of the polyhydric alcohol having 2 to 6 carbon atoms in an amount of 10.0% by mass or more.

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