toner

Abstract

To provide a toner excellent in image heat resistance, blooming resistance, and low-temperature fixability.SOLUTION: A toner has a toner particle containing a binder resin, the binder resin contains an amorphous polyester A and a crystalline polyester C, the amorphous polyester A has amorphous polyester segments a1 and a2, the amorphous polyester segment a2 has a monomer unit of a specific alcohol a, the crystalline polyester C is a polymer having a crystalline polyester segment c2 and a crystalline segment c1 bonded to the end of the crystalline polyester segment c2, the crystalline polyester segment c2 has a monomer unit of a specific alcohol b, an absolute difference between carbon numbers of the alcohol a and b is 4 or less, SP values of the amorphous polyester segments a1 and a2, and the crystalline segment c1 and the crystalline polyester segment c2 satisfy specific relationships.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to toners used in electrophotography, electrostatic recording, electrostatic printing, and the like. [Background technology]

[0002] In recent years, as electrophotographic full-color copying machines have become more widespread, there has been a demand for additional performance improvements, such as not only higher speed and higher image quality, but also energy saving and compatibility with a wide variety of media.

[0003] Specifically, as a toner that can meet energy conservation needs, a toner that can be fixed at a lower temperature and has excellent low-temperature fixability is required in order to reduce power consumption in the fixing process. Accordingly, Patent Document 1 proposes a toner that uses a crystalline polyester as the binder resin of the toner as a toner with excellent low-temperature fixability (Patent Document 1). Furthermore, demand for print-on-demand (POD) printing is also increasing, and there is a need for support for a wide variety of media, including not only plain paper but also cardboard and coated paper. Furthermore, there is a growing demand for robust image strength, such as heat resistance, for images printed on these media, regardless of the environment in which the printed matter is used or stored. Patent Document 2 discloses a toner that uses a nucleating agent and has excellent image heat resistance. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-046095 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-142632 Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, depending on the storage conditions, blooming may occur over time, in which crystalline materials such as wax and crystalline polyester are exposed on the toner surface. When blooming occurs, components such as a developer carrier are contaminated by the exposed wax, and therefore toners with excellent blooming resistance are desired.

[0006] The toner described in Patent Document 1 uses a crystalline polyester. Crystalline polyester has sharper melting properties than amorphous polyester and also acts as a plasticizer for amorphous polyester, making it an effective material for low-temperature fixation of toner. However, if the crystalline polyester is too compatible with the binder resin, heat resistance decreases. For example, when images are stored under high temperature and high humidity, problems such as images sticking together may occur, resulting in poor image heat resistance.

[0007] On the other hand, the toner described in Patent Document 2 uses a binder resin containing a crystalline resin, and further uses a nucleating agent, which makes it possible to improve the heat resistance of images. However, if the crystallization rate is insufficient, the crystalline polyester in the toner may bloom (bleed out of the crystalline polyester) over time depending on storage conditions. The bloomed crystalline polyester becomes thin flakes on the toner surface and, in some cases, falls off from the toner, reducing the storage stability and charging properties of the toner. Furthermore, the plasticization of the amorphous polyester becomes insufficient, resulting in reduced low-temperature fixability.

[0008] From the above, it is possible to obtain a toner that satisfies all of the low-temperature fixing property, image heat resistance, and blooming resistance. Therefore, there is an urgent need to develop a toner that not only exhibits excellent image heat resistance and blooming resistance, but also exhibits low-temperature fixability, ie, that can be fixed at a lower temperature. The present disclosure provides a toner that exhibits excellent image heat resistance and blooming resistance, and also exhibits low-temperature fixability that allows fixing at lower temperatures. [Means for solving the problem]

[0009] The present disclosure provides a toner having toner particles containing a binder resin, the binder resin contains an amorphous polyester A and a crystalline polyester C, the amorphous polyester A has an amorphous polyester segment a1 and an amorphous polyester segment a2, the amorphous polyester segment a2 has a monomer unit derived from a linear aliphatic polyhydric alcohol a having 2 to 10 carbon atoms as a monomer unit forming a polyester skeleton, The difference between the SP value of the amorphous polyester segment a2 and the SP value of the amorphous polyester segment a1 (the SP value of a2 - the SP value of a1) is 0.80 (cal / cm 3 ) 0.5 That's all, the crystalline polyester C is a polymer having a crystalline polyester segment c2 and a crystalline portion c1 bonded to an end of the crystalline polyester segment c2; the crystalline polyester segment c2 has a monomer unit derived from a linear aliphatic polyhydric alcohol b having 2 to 10 carbon atoms as a monomer unit forming a polyester skeleton, the absolute difference between the number of carbon atoms of the linear aliphatic polyhydric alcohol a and the number of carbon atoms of the linear aliphatic polyhydric alcohol b is 4 or less; The difference between the SP value of the crystalline polyester segment c2 and the SP value of the crystalline portion c1 (SP value of c2 - SP value of c1) is 0.75 (cal / cm 3 ) 0.5 That's all, The difference between the SP value of the amorphous polyester segment a1 and the SP value of the crystalline polyester segment c2 (the SP value of a1 - the SP value of c2) is 0.80 (cal / cm 3 ) 0.5 is as follows: The difference between the SP value of the amorphous polyester segment a2 and the SP value of the crystalline portion c1 (the SP value of a2 - the SP value of c1) is 2.00 (cal / cm 3 ) 0.5 The toner is as described above. [Effects of the Invention]

[0010] The present disclosure can provide a toner that exhibits excellent image heat resistance and blooming resistance, and also exhibits low-temperature fixability that allows fixing at a lower temperature. DETAILED DESCRIPTION OF THE INVENTION

[0011] In this disclosure, unless otherwise specified, the expressions "XX or more and YY or less" and "XX to YY" representing a numerical range refer to a numerical range including the lower and upper limits, which are the endpoints. Furthermore, a "monomer unit" refers to the reacted form of a monomer substance in a polymer. Furthermore, a "crystalline resin" refers to a resin in which an endothermic peak is observed in differential scanning calorimetry (DSC).

[0012] The present disclosure provides a toner having toner particles containing a binder resin, the binder resin contains an amorphous polyester A and a crystalline polyester C, the amorphous polyester A has an amorphous polyester segment a1 and an amorphous polyester segment a2, the amorphous polyester segment a2 has a monomer unit derived from a linear aliphatic polyhydric alcohol a having 2 to 10 carbon atoms as a monomer unit forming a polyester skeleton, The SP value of the amorphous polyester segment a2 and the SP value of the amorphous polyester segment a1 The difference between the SP value of a2 and the SP value of a1 is 0.80 (cal / cm 3 ) 0.5 That's all, the crystalline polyester C is a polymer having a crystalline polyester segment c2 and a crystalline portion c1 bonded to an end of the crystalline polyester segment c2; the crystalline polyester segment c2 has a monomer unit derived from a linear aliphatic polyhydric alcohol b having 2 to 10 carbon atoms as a monomer unit forming a polyester skeleton, the absolute difference between the number of carbon atoms of the linear aliphatic polyhydric alcohol a and the number of carbon atoms of the linear aliphatic polyhydric alcohol b is 4 or less; The difference between the SP value of the crystalline polyester segment c2 and the SP value of the crystalline portion c1 (SP value of c2 - SP value of c1) is 0.75 (cal / cm 3 ) 0.5 That's all, The difference between the SP value of the amorphous polyester segment a1 and the SP value of the crystalline polyester segment c2 (the SP value of a1 - the SP value of c2) is 0.80 (cal / cm 3 ) 0.5 is as follows: The difference between the SP value of the amorphous polyester segment a2 and the SP value of the crystalline portion c1 (the SP value of a2 - the SP value of c1) is 2.00 (cal / cm 3 ) 0.5 The toner is as described above.

[0013] The present inventors have been studying toners that exhibit excellent image heat resistance and blooming resistance, and also exhibit low-temperature fixability that allows fixing at lower temperatures. In order to improve low-temperature fixability, as shown in Patent Document 1, when crystalline polyester is made compatible with amorphous polyester, the crystalline polyester The polyester acts as a plasticizer for the amorphous polyester, but on the other hand, the heat resistance of the image is poor, and it is not possible to achieve both low-temperature fixability and heat resistance of the image.

[0014] Therefore, the present inventors considered that it is important to achieve a certain degree of phase separation between the amorphous polyester and the crystalline polyester without inhibiting fixation, and considered increasing the diffusion coefficient of the material to facilitate the formation of a folded structure as a means for increasing the crystallinity of the crystalline polyester in order to achieve phase separation between the amorphous polyester and the crystalline polyester. Specifically, one example is a method for instantly crystallizing the crystalline polyester after the fixing step by reducing the polarity of the crystalline polyester by capping the terminal hydroxyl and carboxyl groups to the utmost while reducing the molecular weight of the crystalline polyester. However, if the above-mentioned crystalline polyester is simply used, the crystalline polyester may bloom over time, causing flakes to form on the toner surface.

[0015] The mechanism behind blooming is unclear, but we believe that the crystalline polyester inside the toner consists of randomly oriented microcrystals that gather in a mosaic pattern to form a single domain, and that this crystalline polyester domain is dispersed in the binder resin. When stored for long periods under high temperature and humidity, even at temperatures below the melting point of the crystalline polyester, the microcrystals in the crystalline polyester domains are thought to migrate over a long period of time within the binder resin. It is believed that a force acts to align the orientation of the microcrystals and form large crystals (crystallization) that then stabilize. We speculate that this movement of the crystalline polyester sometimes causes the growth of giant crystals several micrometers long outward from the toner (blooming).

[0016] Therefore, the present inventors considered it important to suppress the movement of crystalline polyester in the toner, which tends to align the crystal orientation and grow, and focused on the structural relationship between crystalline polyester and amorphous polyester. As a result, the present inventors found that by providing crystalline polyester and amorphous polyester with portions having high and low affinity to each other, it is possible to control the relationship between miscibility and phase separation between crystalline polyester and amorphous polyester, and obtain a desired toner.

[0017] Specifically, the amorphous polyester and the crystalline polyester each have a portion made of a monomer with a similar structure. The amorphous polyester and the crystalline polyester also have portions with low affinity to each other and SP values ​​that are far apart, and portions with high affinity to each other and SP values ​​that are close. Because the amorphous polyester and the crystalline polyester have portions with high affinity to each other and SP values ​​that are close, the amorphous polyester and the crystalline polyester are compatible to a certain extent, allowing the crystalline polyester to function as a plasticizer and improving low-temperature fixability. Furthermore, by providing the amorphous polyester and the crystalline polyester with portions with low affinity to each other and SP values ​​that are far apart, the crystallinity of the crystalline polyester can be increased, improving image heat resistance.

[0018] Furthermore, since the amorphous polyester and the crystalline polyester have a monomer moiety with a similar structure, it is possible to suppress the tendency of the crystals to grow in a uniform orientation, thereby improving the blooming resistance. Therefore, it was found that the toner exhibits excellent image heat resistance and blooming resistance, as well as low-temperature fixability.

[0019] The toner has toner particles containing a binder resin. The binder resin contains an amorphous polyester A and a crystalline polyester C. Amorphous polyester A has an amorphous polyester segment a1 and an amorphous polyester segment a2. For example, amorphous polyester A is a block copolymer having an amorphous polyester segment a1 and an amorphous polyester segment a2. The term "block copolymer" used here refers to a copolymer in which two types of polyesters are bonded together. The amorphous polyester segment a2 has a monomer unit of a linear aliphatic polyhydric alcohol a having 2 to 10 carbon atoms as a monomer unit forming a polyester skeleton. The difference between the SP value of the amorphous polyester segment a2 and the SP value of the amorphous polyester segment a1 (the SP value of a2 - the SP value of a1) is 0.80 (cal / cm 3 ) 0.5 That's all.

[0020] When the amorphous polyester A has an amorphous polyester segment a1 and an amorphous polyester segment a2, it is possible to provide a polarity difference within the molecule, and it is possible to achieve both a site with high affinity and a site with low affinity to the crystalline polyester C. As a result, the binder resin becomes more easily plasticized, and excellent low-temperature fixability is obtained, while the crystallization rate of the crystalline polyester C increases, allowing efficient crystallization in the toner fixing process, and excellent heat and pressure resistance are obtained.

[0021] When the amorphous polyester segment a2 of the amorphous polyester A has a monomer unit with the above carbon number, and the crystalline polyester C has a monomer unit with the same carbon number, the amorphous polyester A and the crystalline polyester C have a certain affinity. As a result, the crystalline polyester C is supported on the amorphous polyester A, and excellent anti-blooming properties are obtained.

[0022] The number of carbon atoms in the linear aliphatic polyhydric alcohol a contained in the amorphous polyester segment a2 is preferably 2 to 8, more preferably 2 to 6, even more preferably 2 to 4, and still more preferably 2. The number of carbon atoms in the linear aliphatic polyhydric alcohol a contained in the amorphous polyester segment a2 can be controlled by the type of monomer. In the present disclosure, when the monomer unit for which the carbon number is to be calculated includes a plurality of monomer units, the carbon number is the average value based on the molar fraction of each monomer unit.

[0023] In addition, the SP value of the amorphous polyester segment a2 and the SP value of the amorphous polyester segment a When the difference from the SP value of 1 is within the above range, a polarity difference can be imparted within the molecule of amorphous polyester A, making it possible to achieve both a site with high affinity and a site with low affinity to crystalline polyester C. As a result, the binder resin becomes more easily plasticized, resulting in excellent low-temperature fixability, while the crystallization rate of crystalline polyester C increases, allowing efficient crystallization in the toner fixing process, resulting in excellent heat and pressure resistance.

[0024] The difference between the SP value of the amorphous polyester segment a2 and the SP value of the amorphous polyester segment a1 (the SP value of a2 - the SP value of a1) is preferably 1.00 (cal / cm 3 ) 0.5 More preferably, it is 1.20 (cal / cm 3 ) 0.5 The upper limit is not particularly limited, but is preferably 1.80 (cal / cm 3 ) 0.5More preferably, it is 1.60 (cal / cm 3 ) 0.5 The difference in SP value between the amorphous polyester segment a1 and the amorphous polyester segment a2 can be controlled by the type of monomer.

[0025] SP value of amorphous polyester segment a1 (cal / cm 3 ) 0.5 is preferably 10.00 to 11.00, more preferably 10.20 to 10.40. SP value of amorphous polyester segment a2 (cal / cm 3 ) 0.5 is preferably 11.00 to 12.00, more preferably 11.50 to 11.80.

[0026] The crystalline polyester C is a polymer having a crystalline polyester segment c2 and a crystalline portion c1 bonded to the end of the crystalline polyester segment c2. The crystalline polyester segment c2 has a monomer unit of a linear aliphatic polyhydric alcohol b having 2 to 10 carbon atoms as a monomer unit forming a polyester skeleton. The difference between the SP value of the crystalline polyester segment c2 and the SP value of the crystalline portion c1 (SP value of c2 - SP value of c1) is 0.75 (cal / cm 3 ) 0.5 That's all.

[0027] When the crystalline polyester C has a crystalline polyester segment c2 and a crystalline portion c1 at its end, a polarity difference can be created within the molecule, and it is possible to achieve both a portion with high affinity and a portion with low affinity to the amorphous polyester A. As a result, the binder resin becomes more easily plasticized, resulting in excellent low-temperature fixability, while the crystallization rate of the crystalline polyester increases, allowing efficient crystallization in the toner fixing process and providing excellent heat and pressure resistance.

[0028] When the crystalline polyester segment c2 of the crystalline polyester C has a monomer unit with the above carbon number, it is easy to form a folded structure, allowing the crystalline polyester C to crystallize instantly after the fixing step, thereby achieving the effect of excellent heat and pressure resistance. The number of carbon atoms in the linear aliphatic polyhydric alcohol a in the crystalline polyester segment a2 is preferably 2 to 8, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2. The number of carbon atoms in the linear aliphatic polyhydric alcohol a in the crystalline polyester segment a2 can be controlled by the type of monomer.

[0029] Furthermore, when the difference between the SP value of the crystalline polyester segment c2 and the SP value of the crystalline portion c1 (the SP value of c2 - the SP value of c1) is within the above range, the compatibility of the crystalline polyester C with the amorphous polyester A can be suppressed, thereby increasing the crystallinity of the crystalline polyester C and achieving the effect of excellent heat and pressure resistance. The difference between the SP value of the crystalline polyester segment c2 and the SP value of the crystalline portion c1 (SP value of c2 - SP value of c1) is preferably 0.80 (cal / cm 3 ) 0.5 More preferably, it is 1.00 (cal / cm 3 ) 0.5 More preferably, it is 1.20 (cal / cm 3 ) 0.5 The upper limit is not particularly limited, but is preferably 1.50 (cal / cm 3 ) 0.5 More preferably, it is 1.30 (cal / cm 3 ) 0.5 The difference in SP value between the crystalline portion c1 and the crystalline polyester segment c2 is as follows: , can be controlled by the type of monomer.

[0030] SP value of crystalline part c1 (cal / cm 3 ) 0.5 is preferably 8.50 to 9.20, more preferably 8.60 to 9.00. SP value of crystalline polyester segment c2 (cal / cm 3 ) 0.5 is preferably 9.50 to 10.50, more preferably 9.80 to 10.20.

[0031] The absolute difference between the number of carbon atoms of the linear aliphatic polyhydric alcohol a and the number of carbon atoms of the linear aliphatic polyhydric alcohol b is 4 or less. When the difference in the number of carbon atoms between the linear aliphatic polyalcohol a and the linear aliphatic polyalcohol b is within the above range, this indicates that structurally similar monomer units are contained in the amorphous polyester A and the crystalline polyester C. As a result, the amorphous polyester A and the crystalline polyester C have a certain degree of affinity, which can suppress the tendency for the crystals to grow in a uniform orientation, thereby achieving excellent anti-blooming properties. The difference in the number of carbon atoms between the linear aliphatic polyhydric alcohol a and the linear aliphatic polyhydric alcohol b is preferably 2 or less, and more preferably 0. The difference in the number of carbon atoms between the linear aliphatic polyhydric alcohol a and the linear aliphatic polyhydric alcohol b can be controlled by the type of monomer.

[0032] The difference between the SP value of the amorphous polyester segment a1 and the SP value of the crystalline polyester segment c2 (SP value of a1 - SP value of c2) is 0.80 (cal / cm 3 ) 0.5 The following is the result. When the difference in SP value between the amorphous polyester segment a1 and the crystalline polyester segment c2 is within the above range, it indicates that the amorphous polyester A and the crystalline polyester C each have a segment with high affinity. Therefore, the compatibility of the crystalline polyester C with the amorphous polyester A can be improved. Therefore, excellent low-temperature fixability can be obtained.

[0033] The difference between the SP value of the amorphous polyester segment a1 and the SP value of the crystalline polyester segment c2 (the SP value of a1 - the SP value of c2) is preferably 0.70 (cal / cm 3 ) 0.5 Less than or equal to 0.60 (cal / cm 3) 0.5 It is preferably 0.40 (cal / cm 3 ) 0.5 The lower limit is not particularly limited, but is 0.10 (cal / cm 3 ) 0.5 The difference in SP value between the amorphous polyester segment a1 and the crystalline polyester segment c2 can be controlled by the type of monomer.

[0034] The difference between the SP value of the amorphous polyester segment a2 and the SP value of the crystalline portion c1 (SP value of a2 - SP value of c1) is 2.00 (cal / cm 3 ) 0.5 That's all. When the difference in SP value between the amorphous polyester segment a2 and the crystalline portion c1 is within the above range, the compatibility of the crystalline polyester C with the amorphous polyester A can be suppressed, thereby increasing the degree of crystallinity and achieving the effect of excellent heat and pressure resistance.

[0035] The difference in SP value between the amorphous polyester segment a2 and the crystalline portion c1 (the SP value of a2 - the SP value of c1) is preferably 2.20 (cal / cm 3 ) 0.5 More preferably, it is 2.40 (cal / cm 3 ) 0.5 The upper limit is not particularly limited, but is preferably 3.50 (cal / cm 3 ) 0.5 It is preferably 3.00 (cal / cm 3 ) 0.5 The difference in SP value between the amorphous polyester segment a2 and the crystalline portion c1 can be controlled by the type of monomer.

[0036] The crystalline polyester segment c2 is preferably a condensation polymer of a linear aliphatic polyhydric alcohol b and an aliphatic dicarboxylic acid. That is, the crystalline polyester segment c2 is preferably a condensation polymer of a monomer unit of a linear aliphatic polyhydric alcohol b and an aliphatic dicarboxylic acid. It is preferable that the straight-chain aliphatic polyhydric alcohol b has a carbon number N1 and the aliphatic dicarboxylic acid has a carbon number N2, and it is preferable that N1 and N2 satisfy the following formula (1) from the viewpoint of image heat resistance. N2 / N1≧2.0 (1)

[0037] When the difference in the number of carbon atoms between the monomers in the crystalline polyester segment c2 is within the above range, the intermolecular interaction can be enhanced, thereby increasing the crystallinity. Therefore, better image heat resistance can be obtained. The N2 / N1 relationship can be controlled by the type of monomer. N2 / N1 is more preferably 3.0 or more, even more preferably 4.0 or more, and even more preferably 5.0 or more. There is no particular upper limit, but it is preferably 9.0 or less.

[0038] The crystalline moiety c1 is, for example, a crystallizable moiety that can act as a crystal nucleating agent, and is preferably a monomer unit condensed at the end of the crystalline polyester C. The crystalline portion c1 is preferably at least one of a monomer unit of an aliphatic monocarboxylic acid and a monomer unit of an aliphatic monoalcohol, and more preferably a monomer unit of an aliphatic monocarboxylic acid. The crystalline portion c1 has a hydrocarbon group having 9 to 30 carbon atoms (preferably 15 to 25, more preferably 19 to 23) bonded to the end of the crystalline polyester segment c2 via an ester bond. This further improves the heat resistance of the image.

[0039] When the crystalline moiety c1 has the above carbon number and terminally modifies the crystalline polyester segment c2, it tends to act as a starting point for the folding structure of the main chain of the crystalline polyester C, like a crystal nucleating agent. Furthermore, the polarity of the crystalline polyester C itself can be reduced, and the compatibility of the crystalline polyester C with the amorphous polyester A can be suppressed, thereby increasing the degree of crystallinity and achieving better heat resistance of the image.

[0040] In terms of image heat resistance, the content of the structure (terminally modified structure) in which the crystalline moiety c1 is bonded to the main chain terminal of the crystalline polyester segment c2 in the crystalline polyester C is preferably 60.0 mol% or more. It is more preferably 80.0 mol% or more, even more preferably 90.0 mol% or more, and even more preferably 95.0 mol% or more. There is no particular upper limit, but it is preferably 100.0 mol% or less, 99.9 mol% or less, or 99.0 mol% or less. The content of the terminal-modified structure can be controlled by the amount of the terminal-modifying aliphatic monocarboxylic acid or aliphatic monoalcohol added.

[0041] In the crystalline polyester C, when the hydroxyl group and / or carboxyl group at the main chain terminal is modified in the above ratio, it indicates that a highly polar functional group has been modified. As a result, the compatibility of the crystalline polyester C with the amorphous polyester A, which is the main binder, can be suppressed, thereby increasing the crystallinity and achieving better image heat resistance.

[0042] From the viewpoint of anti-blooming properties, it is preferable that the absolute difference between the number of carbon atoms in the linear aliphatic polyhydric alcohol a and the number of carbon atoms in the linear aliphatic polyhydric alcohol b is 0. When amorphous polyester A and crystalline polyester C contain monomer units based on linear aliphatic polyhydric alcohols with the same number of carbon atoms, the affinity between them is high. As a result, amorphous polyester A and crystalline polyester C have a certain degree of affinity, which can suppress the tendency for the crystals to grow in a uniform orientation, resulting in better blooming resistance.

[0043] The amorphous polyester segment a1 preferably has a monomer unit based on a polyhydric aromatic phenol from the viewpoint of low-temperature fixability. When the amorphous segment a1 has a monomer unit based on a polyhydric aromatic phenol, it is possible to further increase the affinity between the amorphous polyester A and the crystalline polyester C. Therefore, during fixing, the molten crystalline polyester C becomes compatible with the amorphous polyester A, and the effect of better low-temperature fixing property is obtained.

[0044] The toner is made by measuring the softening point of amorphous polyester A by a flow tester. A The softening point of the molten mixture of amorphous polyester A and crystalline polyester C in the toner at the mass ratio of amorphous polyester A to crystalline polyester C is defined as T M (℃). T A and T M The difference between (T A -T M ) is preferably 7 to 20°C from the viewpoint of low-temperature fixability. T A and T M When the difference is within the above range, the molten crystalline polyester C is compatible with the amorphous polyester A during fixing, and therefore, a superior low-temperature fixability effect can be obtained.

[0045] T A and T M The difference between T and T is preferably 8 to 20°C, more preferably 10 to 20°C. A and T M The difference can be controlled by the amount of crystalline polyester added and the SP value.

[0046] In measuring the storage modulus G' of a toner, when the storage modulus at 60°C during heating is defined as G' during heating, and the storage modulus at 60°C during cooling is defined as G' during cooling, it is preferable that G' during heating / G' during cooling is 3.0 or more from the viewpoint of heat resistance and pressure resistance. When the G' during heating / G' during cooling is within the above range, the amorphous polyester A and the crystalline polyester C have a certain affinity, resulting in a high degree of crystallinity, while the molten crystalline polyester C is compatible with the amorphous polyester A during fixing. Therefore, superior heat and pressure resistance can be achieved. The G' during heating / G' during cooling is preferably 5.0 or more, more preferably 7.0 or more. There is no particular upper limit, but it is preferably 15.0 or less, more preferably 13.0 or less, and even more preferably 11.0 or less. The storage modulus G' can be controlled by the amount of crystalline polyester added and the SP value. A preferred toner composition is described in detail below.

[0047] [Amorphous polyester A] Monomers used for the amorphous polyester segment a1 and the amorphous polyester segment a2 of the amorphous polyester A include the following in addition to the linear aliphatic polyhydric alcohol a having 2 to 10 carbon atoms. Polyhydric alcohols (dihydric, trihydric or higher alcohols), polycarboxylic acids (dihydric, trihydric or higher carboxylic acids), acid anhydrides thereof or lower alkyl esters thereof are used.

[0048] As the polyhydric alcohol monomer, the following polyhydric alcohol monomers can be used. Examples of dihydric alcohol components include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenols represented by formula (A) and derivatives thereof; TIFF0007799527000001.tif22170

[0049] (In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x+y is 0 or more and 10 or less.) Examples include diols represented by formula (B). TIFF0007799527000002.tif52170

[0050] Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene. Among these, glycerol, trimethylolpropane, and pentaerythritol are preferred. These dihydric and trihydric or higher alcohols can be used alone or in combination.

[0051] As the polycarboxylic acid monomer for the polyester resin, the following polycarboxylic acid monomers can be used. Examples of dicarboxylic acid components include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, anhydrides of these acids, and lower alkyl esters thereof. Of these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenylsuccinic acid are preferably used.

[0052] Examples of trivalent or higher carboxylic acids, their acid anhydrides, and their lower alkyl esters include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empol trimer acid, their acid anhydrides, and their lower alkyl esters. Among these, 1,2,4-benzenetricarboxylic acid, i.e., trimellitic acid or its derivatives, is particularly preferred because it is inexpensive and the reaction can be easily controlled. These dicarboxylic acids and tricarboxylic or higher carboxylic acids can be used alone or in combination.

[0053] The amorphous polyester A has an amorphous polyester segment a1 and an amorphous polyester segment a2. The amorphous polyester segment a2 has a monomer unit of a linear aliphatic polyhydric alcohol a having 2 to 10 carbon atoms as a unit forming a polyester skeleton. Examples of the linear aliphatic polyhydric alcohol a having 2 to 10 carbon atoms include ethylenediol. , propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol.

[0054] The amorphous polyester segment a2 is preferably a condensation polymer of a linear aliphatic polyhydric alcohol a and a dicarboxylic acid component. The content of the monomer unit of the linear aliphatic polyhydric alcohol a in the amorphous polyester segment a2 is preferably 20 to 50 mass%, more preferably 25 to 40 mass%. The content of the monomer unit of the dicarboxylic acid component in the amorphous polyester segment a2 is preferably 50.0 to 80.0 mass%, more preferably 60.0 to 75.0 mass%.

[0055] The amorphous polyester segment a1 preferably has a monomer unit based on a polyhydric aromatic phenol. The polyhydric aromatic phenol is preferably at least one selected from the group consisting of hydrogenated bisphenol A, bisphenol represented by the above formula (A), and derivatives thereof. More preferably, it is at least one selected from the group consisting of alkylene (ethylene or propylene) oxide adducts of bisphenol A represented by formula (A). The amorphous polyester segment a1 preferably contains 50.0 to 70.0 mass %, more preferably 60.0 to 70.0 mass %, of the monomer unit based on a polyhydric aromatic phenol.

[0056] The amorphous polyester segment a1 is preferably a condensation polymer of a dicarboxylic acid component containing a linear aliphatic polyhydric alcohol having 6 to 14 carbon atoms (preferably 8 to 12 carbon atoms) and a polyhydric aromatic phenol. The content of the monomer unit of the dicarboxylic acid component containing a linear aliphatic polyhydric alcohol having 6 to 14 carbon atoms in the amorphous polyester segment a1 is preferably 30.0 to 50.0 mass%, more preferably 30.0 to 40.0 mass%. The content of the amorphous polyester segment a1 in the amorphous polyester A is preferably 70.0 to 95.0 mass%, more preferably 75.0 to 85.0 mass%, and the content of the amorphous polyester segment a2 in the amorphous polyester A is preferably 5.0 to 30.0 mass%, more preferably 15.0 to 25.0 mass%.

[0057] The method for producing the polyester is not particularly limited, and known methods can be used. For example, the aforementioned alcohol monomer and carboxylic acid monomer are simultaneously charged and polymerized via an esterification reaction or transesterification reaction and a condensation reaction to produce a polyester resin. The polymerization temperature is not particularly limited, but is preferably in the range of 180°C to 290°C. Polymerization of the polyester can use polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, and germanium dioxide. In particular, it is more preferable that the amorphous polyester A is a polyester resin polymerized using a tin-based catalyst.

[0058] [Crystalline Polyester C] The crystalline polyester C is a polymer having a crystalline polyester segment c2 and a crystalline portion c1 bonded to the end of the crystalline polyester segment c2. Monomers used for the crystalline polyester segment c2 include polyhydric alcohols (dihydric, trihydric or higher alcohols), polycarboxylic acids (dihydric, trihydric or higher carboxylic acids), their acid anhydrides or their lower alkyl esters. The crystalline polyester segment c2 is preferably a condensation polymer of a linear aliphatic polyhydric alcohol b having 2 to 10 carbon atoms (preferably 2 to 6, more preferably 2 to 4, and even more preferably 2) and an aliphatic dicarboxylic acid.

[0059] The polyhydric alcohol monomers used in crystalline polyester C include the following polyhydric alcohols: A choline monomer can be used. The polyhydric alcohol monomer is not particularly limited, but is preferably a chain (more preferably a straight-chain) aliphatic diol, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, and neopentyl glycol. Among these, particularly preferred are straight-chain aliphatic α,ω-diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0060] Polyhydric alcohol monomers other than the above polyhydric alcohols can also be used. Among the polyhydric alcohol monomers, dihydric alcohol monomers include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol; and the like. Furthermore, among the polyhydric alcohol monomers, trihydric or higher polyhydric alcohol monomers include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; and aliphatic alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.

[0061] The polycarboxylic acid monomer used in the crystalline polyester C may be any of the following polycarboxylic acid monomers. While the polycarboxylic acid monomer is not particularly limited, it is preferably a chain (more preferably a linear) aliphatic dicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, as well as hydrolyzed versions of these acid anhydrides or lower alkyl esters.

[0062] Polycarboxylic acids other than the above polycarboxylic acid monomers can also be used. Among the other polycarboxylic acid monomers, examples of dicarboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid, aliphatic carboxylic acids such as n-dodecylsuccinic acid and n-dodecenylsuccinic acid, and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, as well as acid anhydrides or lower alkyl esters thereof.

[0063] Furthermore, among the other carboxylic acid monomers, examples of trivalent or higher polyvalent carboxylic acids include aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and pyromellitic acid, and aliphatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, and 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, as well as derivatives such as acid anhydrides and lower alkyl esters of these.

[0064] The crystalline polyester C is a polymer having a crystalline polyester segment c2 and a crystalline portion c1 bonded to the end of the crystalline polyester segment c2. The crystalline polyester segment c2 has a monomer unit of a linear aliphatic polyhydric alcohol b having 2 to 10 carbon atoms as a unit forming a polyester skeleton. Examples of the linear aliphatic polyhydric alcohol b having 2 to 10 carbon atoms include ethylenediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol.

[0065] The content of monomer units derived from linear aliphatic polyhydric alcohol b having 2 to 10 carbon atoms (preferably 2 to 6, more preferably 2 to 4, and even more preferably 2) in the crystalline polyester segment c2 is preferably 15.0 to 40.0 mass%, more preferably 17.0 to 35.0 mass%. The content of monomer units derived from aliphatic dicarboxylic acids in the crystalline polyester segment c2 is preferably 60.0 to 85.0 mass%, more preferably 65.0 to 83.0 mass%. The content of the crystalline polyester segment c2 in the crystalline polyester C is preferably 80.0 to 99.0 mass %, more preferably 90.0 to 98.0 mass %, and even more preferably 94.0 to 97.0 mass %. The content of the monomer unit constituting the crystalline portion c1 in the crystalline polyester C is preferably 1.0 to 20.0% by mass, and more preferably 2.0 to 10.0% by mass.

[0066] The content of the crystalline polyester C in the binder resin is preferably 3 to 20% by mass, more preferably 8 to 15% by mass. Within this range, the low-temperature fixability, heat and pressure resistance, and blooming resistance become better. The content of the amorphous polyester A in the binder resin is preferably from 80 to 97% by mass, more preferably from 85 to 92% by mass.

[0067] The crystalline polyester C can be produced by a conventional polyester synthesis method. For example, the carboxylic acid monomer and the alcohol monomer are subjected to an esterification reaction or a transesterification reaction, followed by a conventional polycondensation reaction under reduced pressure or by introducing nitrogen gas to obtain the crystalline polyester segment c2. Thereafter, at least one selected from the group consisting of aliphatic monocarboxylic acids and aliphatic monoalcohols (preferably aliphatic monocarboxylic acids) having 10 to 30 carbon atoms (preferably 15 to 25, more preferably 19 to 23) is added and an esterification reaction is carried out to form a crystalline portion c1 at the end of the crystalline polyester segment c2, thereby obtaining crystalline polyester C.

[0068] The above esterification or transesterification reaction can be carried out, if necessary, using a conventional esterification or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, or magnesium acetate.

[0069] The polycondensation reaction can be carried out using a conventional polymerization catalyst, such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide, etc. The polymerization temperature and the amount of catalyst are not particularly limited and may be determined appropriately.

[0070] In the esterification or transesterification reaction or polycondensation reaction, in order to increase the strength of the resulting crystalline polyester C, it is also possible to use a method in which all of the monomers are charged at once, or in order to reduce the amount of low-molecular-weight components, a divalent monomer is reacted first, and then a trivalent or higher valent monomer is added and reacted.

[0071] [wax] The toner particles may contain wax. The wax is not particularly limited, and known waxes may be used. For example, the following waxes may be used. Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; Oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; Waxes whose main component is fatty acid esters, such as carnauba wax; Partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.

[0072] Among these, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, and fatty acid ester waxes such as carnauba wax are preferred from the viewpoint of low-temperature fixability and hot offset resistance of the toner. From the viewpoint of toner fixing and separation properties, hydrocarbon waxes are more preferred.

[0073] The wax content in the toner particles is preferably 1.0 part by mass or more and 20.0 parts by mass or less relative to 100 parts by mass of the binder resin. When the wax content is in this range, hot offset resistance at high temperatures is further improved.

[0074] Furthermore, from the viewpoint of achieving both the storage stability and hot offset resistance of the toner, it is preferable that the peak temperature of the maximum endothermic peak of the toner satisfies the following conditions. That is, in the endothermic curve during temperature rise measured by a differential scanning calorimeter (DSC), the peak temperature of the maximum endothermic peak present in the temperature range of 30°C or higher and 200°C or lower is preferably 50°C or higher and 110°C or lower.

[0075] [Coloring agent] The toner particles may contain a colorant as needed. Examples of colorants include the following: 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.

[0076] 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.

[0077] 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.

[0078] Examples of pigments for cyan toners include CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, and 17; CI Vat Blue 6; CI Acid Blue 45; and copper phthalocyanine pigments in which one to five phthalimidomethyl groups are substituted on the phthalocyanine skeleton. Examples of dyes for cyan toners include CI Solvent Blue 70.

[0079] Yellow toner pigments include 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. Yellow toner dyes include CI Solvent Yellow 162.

[0080] These colorants may be used alone or in combination, or in the form of a solid solution. The colorant is selected in consideration of hue angle, chroma, brightness, lightfastness, transparency on overhead projectors (OHPs), and dispersibility in toner particles. The content of the colorant is preferably 0.1 to 30.0 parts by mass relative to the total amount of the resin components.

[0081] [Charge control agent] The toner particles may contain a charge control agent as needed. By incorporating a charge control agent, the charging characteristics can be stabilized and the amount of triboelectric charge can be optimally controlled according to the development system. As the charge control agent, known agents can be used, but particularly, metal compounds of aromatic carboxylic acids are preferred because they are colorless, have a high charging speed of the toner, and can stably maintain a constant amount of charge.

[0082] Examples of negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds having sulfonic acid or carboxylic acid on the side chain, polymeric compounds having sulfonate salts or sulfonate esters on the side chain, polymeric compounds having carboxylate salts or carboxylate esters on the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0083] The charge control agent may be added internally or externally to the toner particles. The content of the charge control agent is preferably 0.2 to 10.0 parts by mass, more preferably 0.5 to 10.0 parts by mass, per 100 parts by mass of the binder resin.

[0084] [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 the 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. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0085] From the viewpoint of improving fluidity, inorganic particles as external additives should have a specific surface area of ​​50m 2 / g~400m 2 From the viewpoint of improving durability and stability, the inorganic fine particles as the external additive preferably have a specific surface area of ​​10 m 2 / g~50m 2 In order to achieve both improved fluidity and durability and stability, inorganic fine particles having a specific surface area within the above range may be used in combination.

[0086] 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.

[0087] [Developer] The toner can be used as a one-component developer, but in order to further improve dot reproducibility and to provide stable images over a long period of time, it is preferable to mix the toner with a magnetic carrier and use it as a two-component developer.

[0088] Examples of magnetic carriers that can be used include generally known ones such as iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, and oxide particles thereof; magnetic materials such as ferrite; and magnetic material-dispersed resin carriers (so-called resin carriers) containing magnetic materials and a binder resin that holds the magnetic materials in a dispersed state.

[0089] When the toner is mixed with a magnetic carrier to be used as a two-component developer, the mixing ratio of the magnetic carrier is preferably 2% by mass to 15% by mass, and more preferably 4% by mass to 13% by mass, in terms of the toner concentration in the two-component developer.

[0090] [Method of manufacturing toner particles] The method for producing the toner particles is not particularly limited, and known methods such as a pulverization method (melt-kneading method), an emulsion aggregation method, and a dissolution suspension method can be used. The procedure for producing toner by the pulverization method is described below. The pulverization method includes, for example, a raw material mixing step of mixing crystalline polyester C and amorphous polyester A as binder resins, and other components such as wax, colorant, and charge control agent as needed, a step of melting and kneading the mixed raw materials to obtain a resin composition, and a step of pulverizing the obtained resin composition to obtain toner particles.

[0091] In the raw material mixing process, materials constituting the toner particles, such as binder resin, and optionally other components such as wax, colorant, and charge control agent, are weighed out in predetermined amounts, blended, and mixed. Examples of mixing devices include a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.).

[0092] Next, the mixed materials are melt-kneaded to disperse the materials in the binder resin. In this melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. Single- or twin-screw extruders are the mainstream due to their advantage of continuous production. Examples include a KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), a TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikegai Iron Works), a twin-screw extruder (manufactured by KCK Corporation), a Ko-Kneader (manufactured by Buss Co., Ltd.), and a Kneadex (manufactured by Nippon Coke and Engineering Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading may be rolled using a twin roll or the like and cooled with water or the like in a cooling process.

[0093] The cooled resin composition is then crushed to the desired particle size in a crushing process. In the crushing process, the resin composition is coarsely crushed using a crusher such as a crusher, hammer mill, or feather mill. The resin composition is then finely crushed using a crusher such as a Kryptron System (Kawasaki Heavy Industries), a Super Rotor (Nisshin Engineering), a Turbo Mill (Turbo Kogyo), or an air jet type fine crusher.

[0094] Thereafter, as necessary, the mixture is classified using a classifier or sieve such as an inertial classification type Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal classification type Turboplex (manufactured by Hosokawa Micron Corporation), a TSP Separator (manufactured by Hosokawa Micron Corporation), or a Faculty (manufactured by Hosokawa Micron Corporation).

[0095] The obtained toner particles may be used as they are as a toner. Alternatively, the toner may be obtained by treating the surface of the toner with an external additive. Examples of methods for externally adding external additives include a method in which classified toner and various known external additives are mixed in predetermined amounts, and stirred and mixed using a mixing device such as a double con mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation) as an external additive machine.

[0096] The methods for measuring various physical properties are explained below. (Method of separating each material from toner) The materials contained in the toner can be separated from the toner by utilizing the difference in solubility in the solvent of each material. First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23°C, and the soluble matter (amorphous polyester A) is separated from the insoluble matter (crystalline polyester C, wax, colorant, inorganic fine particles, etc.). Second separation: The insoluble matter obtained in the first separation (crystalline polyester C, wax, colorant, inorganic fine particles, etc.) is dissolved in MEK at 100°C, and the soluble matter (crystalline polyester C, wax) is separated from the insoluble matter (colorant, inorganic fine particles, etc.). Third separation: The soluble matter (crystalline polyester C, wax) obtained in the second separation is dissolved in chloroform at 23°C, and the soluble matter (crystalline polyester C) is separated from the insoluble matter (wax).

[0097] [Method for measuring the content of monomer units of various polymerizable monomers in amorphous polyester A and crystalline polyester C] The content ratio of the monomer units of various polymerizable monomers in amorphous polyester A and crystalline polyester C was measured as follows: 1 H-NMR was performed under the following conditions. 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 sample is dissolved in a thermostatic bath at 40°C.

[0098] obtained 1 From the H-NMR chart, the integral value S of the peaks assigned to the constituent elements of the monomer units of various polymerizable monomers 1、 S 2、S3, S n Calculate. The content ratio of the monomer units of various polymerizable monomers is determined by the above integral values ​​S1, S2, S3 and S n It is calculated as follows using the following: 2、 n3···n n is the number of hydrogen atoms in the constituent element to which the peak of interest for each site is assigned. Content ratio (mol%) of monomer units of various polymerizable monomers = {(S n / n n ) / ((S1 / n1)+(S2 / n2)+(S3 / n3)...+(S n / n n ))}×100

[0099] The amount of the monomer unit of each polymerizable monomer is calculated by changing the molecular term in the same operation. Note that, when a polymerizable monomer that does not contain a hydrogen atom is used in the monomer unit of each polymerizable monomer, 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.

[0100] [SP value calculation method] The SP values ​​of the amorphous polyester segment a1, the amorphous polyester segment a2, the crystalline portion c1, and the crystalline polyester segment c2 are determined as follows according to the calculation method proposed by Fedors. For each monomer unit of polymerizable monomer, the evaporation energy (Δei) (cal / mol) and molar volume (Δvi) (cm) for the atom or atomic group in the molecular structure are calculated from the table in "Polym. Eng. Sci., 14(2), 147-154 (1974)". 3 / mol), and calculate (ΣΔei / ΣΔvi) 0.5 SP value (cal / cm 3 ) 0.5 Let's say.

[0101] <Measurement of the Weight-Average Molecular Weight of Crystalline Polyester C by GPC> The weight-average molecular weight (Mw) of the o-dichlorobenzene-soluble fraction of crystalline polyester C at 100 °C is measured by gel permeation chromatography (GPC) as follows. First, crystalline polyester C is dissolved in o-dichlorobenzene at 100 °C over 1 hour. Then, the resulting solution is filtered through a solvent-resistant membrane filter "MAESORI DISK" (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 the components soluble in o-dichlorobenzene is about 0.1 mass%. Using this sample solution, measurements are carried out under the following conditions. Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation) Column: TSKgel GMHHR-H HT (7.8 cm I.D × 30 cm) in series (manufactured by Tosoh Corporation) Detector: RI for high temperature Temperature: 135 °C Solvent: o-dichlorobenzene Flow rate: 1.0 mL / min Sample: Inject 0.4 mL of a 0.1% sample

[0102] For calculating the molecular weight of the sample, a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample is used. Further, it is calculated by performing polyethylene conversion using a conversion formula derived from the Mark-Houwink viscosity equation.

[0103] <Method for Measuring the Acid Value of Crystalline Polyester C> The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of crystalline polyester C is measured in accordance with JIS K 0070-1992, and specifically, it is measured according to the following procedure.

[0104] (1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume) and add ion-exchanged water to make 100 mL to obtain a phenolphthalein solution. Dissolve 7 g of special-grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Place the solution in an alkali-resistant container to avoid contact with carbon dioxide, allow to stand for 3 days, then filter to obtain a potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container. The potassium hydroxide solution factor is determined by placing 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of phenolphthalein solution, and titrating with potassium hydroxide solution to determine the amount of potassium hydroxide solution required for neutralization. The 0.1 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0105] (2) Operation (A) Main test 2.0 g of the ground crystalline polyester C sample is accurately weighed into a 200 mL Erlenmeyer flask, and 100 mL of a mixed solution of toluene / ethanol (2:1) is added and dissolved over 5 hours. Next, add a few drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for 30 seconds. (B) Blank Test The titration is carried out in the same manner as above, except that no sample is used (i.e., only the toluene / ethanol (2:1) mixed solution is used).

[0106] (3) The obtained results are substituted into the following formula to calculate the acid value. A=[(CB)×f×5.61] / S where A is the acid value (mgKOH / g), B is the amount of potassium hydroxide solution added for the blank test (mL), C is the amount of potassium hydroxide solution added for the main test (mL), f is the factor of the potassium hydroxide solution, and S is the mass of the sample (g).

[0107] <Method for measuring the hydroxyl value of crystalline polyester C> The hydroxyl value is the number of milligrams of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when acetylating 1 g of a sample. The hydroxyl value of crystalline polyesters is measured in accordance with JIS K 0070-1992, and specifically, it is measured according to the following procedure. (1) Preparation of reagents Place 25 g of special-grade acetic anhydride in a 100 mL volumetric flask, add pyridine to make the total volume 100 mL, and shake thoroughly to obtain the acetylation reagent. Store the obtained acetylation reagent in an amber bottle to avoid contact with moisture, carbon dioxide, etc. Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), and add ion-exchanged water to make 100 mL to obtain a phenolphthalein solution. Dissolve 35 g of special-grade potassium hydroxide in 20 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Place in an alkali-resistant container to avoid contact with carbon dioxide and leave for 3 days, then filter to obtain potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by placing 25 mL of 0.5 mol / L hydrochloric acid in an Erlenmeyer flask, adding several drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution, and then determining the amount of potassium hydroxide solution required for neutralization. The 0.5 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0108] (2) Operation (A) Main test Accurately weigh 1.0 g of the ground crystalline polyester C sample into a 200 ml round-bottom flask, and accurately add 5.0 ml of the acetylation reagent using a volumetric pipette. If the sample is difficult to dissolve in the acetylation reagent, add a small amount of special-grade toluene to dissolve it. Place a small funnel on the neck of the flask and immerse about 1 cm of the bottom of the flask in a glycerin bath at about 97°C. To prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is recommended to cover the base of the neck of the flask with a piece of cardboard with a round hole. After 1 hour, remove the flask from the glycerin bath and allow it to cool. After allowing it to cool, add 1 ml of water through the funnel and shake to hydrolyze the acetic anhydride. To further complete the hydrolysis, heat the flask again in the glycerin bath for 10 minutes. After allowing it to cool, wash the funnel and the walls of the flask with 5 ml of ethyl alcohol. Add a few drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The endpoint of the titration is when the light red color of the indicator lasts for about 30 seconds. (B) Blank test The titration is carried out in the same manner as above, except that no crystalline polyester sample is used. (3) The obtained results are substituted into the following formula to calculate the hydroxyl value. A = [{(BC) × 28.05 × f} / S] + D where A: hydroxyl value (mgKOH / g), B: amount of potassium hydroxide solution added in the blank test (ml), C: amount of potassium hydroxide solution added in the main test (ml), f: potassium hydroxide solution factor, S: sample (g), D: acid value of crystalline polyester (mgKOH / g).

[0109] [Method for calculating the content of the structure in which the crystalline portion c1 is bonded to the main chain terminal of the crystalline polyester segment c2 in the crystalline polyester C (content of the terminal-modified structure)] The proportion of terminally modified structures in crystalline polyester C is calculated using the acid value, hydroxyl value, and molecular weight determined above. Specifically, the number of moles of terminal functional groups per gram of crystalline polyester C is calculated using the following formula: Number of moles of terminal functional groups = (acid value + hydroxyl value) / (1000 x 56.105) Next, the number of moles per 1 g of crystalline polyester C is calculated from the molecular weight of crystalline polyester C. Number of moles per 1g of crystalline polyester C = 1 / Mw The amount of terminal functional groups is calculated from the ratio of each monomer unit of the crystalline polyester C calculated by the above NMR. Specifically, in the case of an ester product of a dicarboxylic acid and a dialcohol, the amount of functional groups is set to 2. When a trivalent or higher monomer is used, the amount of terminal functional groups can be calculated from its molar ratio. Percentage of terminally modified structures in crystalline polyester C (mol%) = [1 - number of moles of terminal functional groups / (number of moles per 1 g of crystalline polyester × amount of functional groups)] × 100

[0110] [Softening point T A and T M Measurement of Softening point T A and T M Measurements are performed using a constant-load extrusion capillary rheometer, the "Flow Tester CFT-500D Flow Property Evaluation Device" (Shimadzu Corporation), according to the manual that comes with the device. With this device, a constant load is applied from above the sample by a piston, while the sample filled in the cylinder is heated and melted, and the molten sample is extruded from the die at the bottom of the cylinder, allowing a flow curve to be obtained that shows the relationship between the piston depression (mm) and temperature (°C). The "melting temperature in the 1 / 2 method" described in the manual attached to the "Flow Tester CFT-500D, a flow property evaluation device" is used as the softening point. The melting temperature in the 1 / 2 method is calculated as follows: First, half of the difference between the amount of piston descent at the end of outflow (Smax) and the amount of piston descent at the start of outflow (Smin) is calculated (this is called X; X = (Smax - Smin) / 2). The temperature at which the amount of piston descent on the flow curve is the sum of X and Smin is the melting temperature in the 1 / 2 method.

[0111] The sample used is a 1.2 g sample compressed at 25°C for 60 seconds using a tablet press (e.g., a standard manual Newton press NT-100H, manufactured by NPA Systems Co., Ltd.) at 10 MPa to form a cylindrical sample with a diameter of 8 mm. The specific procedures for measurement are carried out according to the manual that comes with the device. The measurement conditions for the CFT-500D are as follows: Test mode: Temperature rising method Starting temperature: 60℃ Achieved temperature: 200℃ Measurement interval: 1.0℃ Heating rate: 4.0℃ / min Piston cross-sectional area: 1.000cm 2 Test load (piston load): 5.0 kgf Preheat time: 300 seconds Die hole diameter: 1.0mm Die length: 1.0mm

[0112] (T M (measurement of The mass ratio of the amorphous polyester A and the crystalline polyester C in the toner is calculated from the mass of each material obtained by the separation of each material described above. The amorphous polyester A and the crystalline polyester C separated from the toner by the procedure described above are mixed in the calculated mass ratio and used as a sample. The softening point T M get.

[0113] [Method for measuring storage modulus (G' during heating and G' during cooling)] The measurement device used is a rotating plate rheometer "ARES" (manufactured by TA INSTRUMENTS). The measurement sample is prepared by compressing 0.2 g of toner into a disk shape with a diameter of 8 mm and a thickness of 2.0±0.3 mm at 10 MPa for 60 seconds using a tablet compression machine in an environment of 25°C. The molded sample is mounted on a parallel plate and heated from room temperature (25°C) to 110°C over 15 minutes to shape the sample. After that, it is cooled to the measurement start temperature and measurement begins. At this time, it is important to set the sample so that the initial normal force is 0. In addition, as described below, the influence of the normal force can be canceled out in subsequent measurements by turning on the auto tension adjustment. Measurements were performed under the following conditions, with the storage modulus at 60°C during the temperature rise process being defined as G' during temperature rise, and the storage modulus at 60°C during the temperature fall process being defined as G' during temperature fall.

[0114] The measurement is carried out under the following conditions: (1) Use parallel plates with a diameter of 8 mm. (2) The frequency is set to 6.28 rad / sec (1.0 Hz). (3) The initial applied strain is set to 0.01%. (4) Measurement is performed at a temperature ramp rate of 2.0°C / min between 30 and 150°C. The measurement is performed under the following automatic adjustment mode settings. Measurement is performed in automatic strain adjustment mode (Auto Strain). (5) Set the maximum applied strain to 40.0%. (6) Set the maximum torque (Max Allowed Torque) to 150.0 g·cm and the minimum torque (Min Allowed Torque) to 0.2 g·cm. (7) Set the strain adjustment to 1.0% of the current strain. During the measurement, the automatic tension adjustment mode is used. Tension) is adopted. (8) Set Auto Tension Direction to Compression. (9) Set the initial static force to 10.0 g and the auto tension sensitivity to 40.0 g. (10) The operating condition of the auto tension is a sample modulus of 1.0 × 10 3 Pa or more. [Example]

[0115] 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.

[0116] [Example 1] <Production of amorphous polyester segment a1-1> Polyhydric alcohol; Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane 65 parts Polycarboxylic acid; tetradodecanedioic acid 35 parts The above monomer components were placed in a reaction vessel equipped with a stirrer that had been thoroughly heated and dried, and 0.05 parts of titanium tetrabutoxide was added per 100 parts of the above mixture. Nitrogen gas was introduced into the vessel to maintain an inert atmosphere, and the temperature was raised to 260°C to polymerize the amorphous polyester segment a1-1.

[0117] <Production of amorphous polyester segments a1-2 to a1-4> Amorphous polyester segments a1-2 to a1-4 were obtained in the same manner as in the production example of amorphous polyester segment a1-1, except that the types and amounts of the polycarboxylic acid monomer and polyhydric alcohol monomer were changed to those shown in Table 1.

[0118] [Table 1] The abbreviations in Table 1 are as follows: BPA-PO: Bisphenol A propylene oxide adduct BPA-EO: Bisphenol A ethylene oxide adduct TDA: tetradecanedioic acid DDA: Dodecanedioic acid SA: Suberic acid TPA: Terephthalic acid

[0119] <Production of amorphous polyester segment a2-1> Polycarboxylic acid; terephthalic acid 73 parts Linear aliphatic polyhydric alcohol a; ethylenediol 27 parts The above monomer components were placed in a reaction vessel equipped with a stirrer that had been thoroughly heated and dried, and 0.05 parts of titanium tetrabutoxide was added per 100 parts of the above mixture. Nitrogen gas was introduced into the vessel to maintain an inert atmosphere, and the temperature was raised to 260°C to polymerize the amorphous polyester segment a2-1.

[0120] <Production of amorphous polyester segments a2-2 to a2-4> Amorphous polyester segments a2-2 to a2-4 were obtained in the same manner as in the production example of amorphous polyester segment a2-1, except that the types and amounts of the polycarboxylic acid monomer and polyhydric alcohol monomer were changed to those shown in Table 2.

[0121] [Table 2] The abbreviations in Table 2 are as follows: TPA: Terephthalic acid ED: Ethylenediol (ethylene glycol) BD: butanediol HD: hexanediol DD: Dodecanediol

[0122] <Production example of amorphous polyester A1> Amorphous polyester segment a1-1: 80 parts Amorphous polyester segment a2-1: 20 parts The above materials were placed in a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. Then, 1.0 part of tin 2-ethylhexanoate (esterification catalyst) was added as a catalyst for 100 parts of the total amount of segments. The atmosphere in the flask was then purged with nitrogen gas, and the temperature was gradually raised with stirring. The reaction was allowed to proceed for 2.5 hours while stirring at 200°C. The pressure in the reaction vessel was then reduced to 8.3 kPa and maintained at this temperature for 1 hour. The reaction was then cooled to 180°C and returned to atmospheric pressure (first reaction step).

[0123] Trimellitic anhydride: 0.04 parts tert-Butylcatechol (polymerization inhibitor): 0.1 parts The above materials were then added, the pressure in the reactor was reduced to 8.3 kPa, and the reaction was continued for 15 hours while maintaining the temperature at 160°C. After confirming that the softening point of the reaction product measured according to ASTM D36-86 reached 140°C, the temperature was reduced to stop the reaction (second reaction step). In this way, amorphous polyester A1 was obtained.

[0124] <Production of amorphous polyesters A2 to A7> Amorphous polyesters A2 to A7 were obtained in the same manner as in the production example of amorphous polyester A1, except that the types and amounts of amorphous polyester segments a1 and a2 were changed to those shown in Table 3. Table 4 shows the physical properties of amorphous polyesters A2 to A7.

[0125] [Table 3] [Table 4] In Table 4, the SP value difference is the difference (a2-a1) between the SP value of the amorphous polyester segment a2 and the SP value of the amorphous polyester segment a1. The unit of the SP value is (cal / cm 3 ) 0.5 is.

[0126] <Production of crystalline polyester segment c2-1> Linear aliphatic polyhydric alcohol b; ethylenediol 20 parts Aliphatic dicarboxylic acid; dodecanedioic acid 80 parts The above monomer components were placed in a reaction vessel equipped with a stirrer that had been thoroughly heated and dried, and 0.05 parts of titanium tetrabutoxide was added to 100 parts of the above mixture. Nitrogen gas was introduced into the vessel to maintain an inert atmosphere, and the temperature was raised to 260°C to polymerize the crystalline polyester segment c2-1.

[0127] <Production of Crystalline Polyester Segments c2-2 to c2-5> Crystalline polyester segments c2-2 to c2-5 were obtained in the same manner as in the production example of crystalline polyester segment c2-1, except that the types and amounts of linear aliphatic polyhydric alcohol b and aliphatic dicarboxylic acid were changed to those shown in Table 5.

[0128] [Table 5] The abbreviations in Table 5 are as follows: ED: Ethylenediol HD: hexanediol OD: Octanediol BD: butanediol DD: Dodecanediol DDA: Dodecanedioic acid

[0129] <Production example of crystalline polyester C1> Crystalline part c1; Behenic acid: 4 parts Crystalline polyester segment c2-1: 96 parts Esterification catalyst: titanium tetrabutoxide: 0.5 parts The above materials were weighed and placed in a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. After the atmosphere in the flask was replaced with nitrogen gas, the temperature was gradually raised with stirring, and the mixture was allowed to react at 200°C for 2 hours with stirring. The pressure inside the reaction vessel was then reduced to 8.3 kPa, and the reaction was carried out for 5 hours while maintaining the temperature at 200° C. After that, the temperature was lowered to stop the reaction, and a crystalline polyester C1 was obtained.

[0130] <Production Examples of Crystalline Polyesters C2 to C14> Crystalline polyesters C2 to C14 were obtained by carrying out the reaction in the same manner as in the production example of crystalline polyester C1, except that the types and parts of the crystalline moieties c1 and crystalline polyester segments c2 were changed as shown in Table 6. The physical properties of crystalline polyesters C2 to C14 are shown in Table 7.

[0131] [Table 6] The abbreviations in Table 6 are as follows: BA: Behenic acid DA: Decanoic acid NA: Nonanoic acid MA: melissic acid DKA: Dotriacontanoic acid HA: hexanoic acid

[0132] [Table 7] In Table 7, the SP value difference indicates the difference (c2-c1) between the SP value of the crystalline polyester segment c2 and the SP value of the crystalline portion c1. The unit of the SP value is (cal / cm 3 ) 0.5 The terminal modification ratio is the content (mol %) of the structure in which the crystalline portion c1 is bonded to the main chain terminal of the crystalline polyester segment c2 in the crystalline polyester C.

[0133] <Toner 1 manufacturing example> Amorphous polyester A1: 90 parts Crystalline polyester C1: 10 parts Fischer-Tropsch wax (maximum endothermic peak temperature 76°C): 5 parts Carbon black: 10 parts The above materials were mixed using a Henschel mixer (FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 1500 rpm for 5 minutes, and then kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at a temperature of 130°C. The resulting kneaded mixture was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized product. The coarsely pulverized product was then finely pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification was performed using a Faculty (F-300, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions were a classifying rotor rotation speed of 11000 rpm and a dispersing rotor rotation speed of 7200 rpm.

[0134] Toner particles 1:100 parts Silica particle A: Fumed silica surface-treated with hexamethyldisilazane (Median diameter (D50) based on number is 120 nm) 4 parts Small inorganic particles: Titanium oxide particles surface-treated with isobutyltrimethoxysilane (Median diameter (D50) based on number is 10 nm) 1 part The above materials were mixed in a Henschel mixer (FM-75 model, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 1900 rpm for a rotation time of 10 minutes to obtain Toner 1 exhibiting negative charging properties.

[0135] <Production Examples of Toner 2 to Toner 20> The same procedure as in the production example of Toner 1 was carried out except that the type of amorphous polyester A and the type of crystalline polyester C were changed as shown in Table 8. Toner 20 was obtained. The physical properties of the obtained toner are shown in Table 8. [Table 8] In the table, the difference in carbon number between a and b indicates the absolute difference between the carbon number of the linear aliphatic polyhydric alcohol a and the carbon number of the linear aliphatic polyhydric alcohol b. A and T M The SP value difference between a1 and c2 indicates the difference (a1-c2) between the SP value of the amorphous polyester segment a1 and the SP value of the crystalline polyester segment c2. The SP value difference between a2 and c1 indicates the difference (a2-c1) between the SP value of the amorphous polyester segment a2 and the SP value of the crystalline portion c1. The unit of the SP value is (cal / cm 3 ) 0.5 is.

[0136] <Magnetic Carrier 1 Manufacturing Example> Number average particle size: 0.30 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) of magnetite 1 Number average particle size: 0.50 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) magnetite2 To 100 parts of each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and the mixture was mixed and stirred at high speed in a container at 100° C. or higher to treat each of the fine particles. Phenol: 10% by weight Formaldehyde solution: 6% by mass (Formaldehyde 40% by mass, methanol 10% by mass, water 50% by mass) Magnetite treated with the above silane compound 1: 58 mass% Magnetite 2 treated with the above silane compound: 26% by mass 100 parts of the above material, 5 parts of a 28% by mass aqueous ammonia solution, and 20 parts of water were placed in a flask, and the mixture was heated to 85°C over 30 minutes while stirring and mixing, and then held for 3 hours to cause a polymerization reaction, and the resulting phenolic resin was cured.

[0137] The cured phenolic resin was then cooled to 30°C, and water was added. The supernatant was removed, and the precipitate was washed with water and air-dried. This was then dried under reduced pressure (5 mmHg or less) at 60°C to obtain spherical magnetic carrier 1 with dispersed magnetic material. The volume-based 50% particle size (D50) was 34.21 μm.

[0138] <Production example of two-component developer 1> 92.0 parts of magnetic carrier 1 and 8.0 parts of toner 1 were mixed in a V-type mixer (V-20, manufactured by Seishin Enterprises) to obtain two-component developer 1.

[0139] <Production Examples of Two-Component Developers 2 to 20> In the production example of two-component developer 1, the same procedure was carried out except for the changes shown in Table 9, to obtain two-component developer 2 to two-component developer 20. [Table 9]

[0140] [evaluation] The above two-component developer 1 was used for evaluation. The image forming apparatus used was a modified Canon imageRUNNER ADVANCE C5560 digital commercial printing printer, and two-component developer 1 was placed in the black developing unit. The modifications to the apparatus included the fixing temperature, process speed, and DC voltage V of the developer carrier. DC , the charging voltage V of the electrostatic latent image carrier D The image output evaluation was carried out by outputting a FFh image (solid image) with the desired image ratio, and adjusting V so that the amount of toner on the FFh image on the paper was the desired amount. DC , V D The temperature and laser power were adjusted and the evaluation described below was carried out. FFh is a value that represents 256 gradations in hexadecimal, with 00h being the first gradation of the 256 gradations (white background) and FFh being the 256th gradation of the 256 gradations (solid area). The evaluation was carried out based on the following evaluation methods, and the results are shown in Table 10.

[0141] [Low temperature fixability] Paper: GFC-081 (81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner amount on paper: 0.50 mg / cm 2 (The DC voltage of the developer carrier V DC , the charging voltage V of the electrostatic latent image carrier D , and adjusted by laser power) Evaluation image: A 2cm x 5cm image placed in the center of the A4 paper. Test environment: Low temperature and humidity environment: Temperature 15°C / Humidity 10% RH (hereinafter referred to as "L / L") Fixing temperature: 150℃ Process speed: 377 mm / sec The above evaluation image was output, and the low-temperature fixability was evaluated. The value of the image density reduction rate was used as an evaluation index for low-temperature fixability. The image density reduction rate was measured using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite Corporation) by first measuring the image density at the center. Next, the part where the image density was measured was subjected to pressure of 4.9 kPa (50 g / cm 2The fixed image is rubbed (five times back and forth) with Silbon paper under a load of 1000 kJ / cm2, and the image density is measured again. The rate of decrease in image density before and after rubbing was calculated using the following formula. The resulting rate of decrease in image density was evaluated according to the following evaluation criteria. A rating of A to C was considered to be good. Image density reduction rate = (image density before friction - image density after friction) / image density before friction x 100 (Evaluation criteria) A: Image density reduction rate less than 3% B: Image density reduction rate: 3% to less than 5% C: Image density reduction rate: 5% to less than 8% D: Image density reduction rate 8% or more

[0142] [Image heat resistance (heat and pressure resistance)] Paper:CS-680(68.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner loading: 1.20mg / cm 2 Evaluation image: 100cm in the center of the above A4 paper 2 Place an image (10cm x 10cm) Fixing test environment: Low temperature and low humidity environment, 15°C / 10%RH (hereinafter referred to as "L / L") Process speed: 450 mm / sec Fixing temperature: Low temperature fixability evaluation temperature + 10°C Using the image forming apparatus, one fixed image was output under the above conditions, and a stack of paper (CS-680 500 sheets) was placed on top of it. The output and the stack of paper were then placed in a thermostatic chamber set at 65°C and 40% RH. and left it for 10 hours. Next, the printed matter and the sheet of paper on it were removed from the thermostatic chamber and left to cool for one hour. The sheets were peeled off. The density of the image adhered to the paper was evaluated using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). A rating of A to C was considered to be good. (Evaluation criteria: Image density adhered to paper) A: Less than 0.10 B: 0.10 or more and less than 0.30 C: 0.30 or more and less than 0.50 D: 0.50 or more

[0143] [Blooming resistance] Instead of observing actual changes over time in an expected environment over a period of 2 to 3 years, blooming resistance was evaluated by conducting a heat cycle test in which the toner was exposed to temperatures and humidity higher than expected and then returned to room temperature repeatedly, and the toner was left in the harsh environment and then image formation was performed, and the image density was measured. The better the blooming resistance of the toner, the more inhibited the leaching of crystalline polyester C to the toner surface is, even after being left in a harsh environment, and the leached crystalline polyester C does not contaminate the developer carrier, causing a decrease in image density. A Canon imagePress C800 full-color copier was used as the image forming apparatus, and the two-component developer to be evaluated was placed in a black developer container of the image forming apparatus, and the toner to be evaluated was placed in a black toner container, and the evaluation described below was performed.

[0144] The modification was to remove the mechanism that discharges excess magnetic carrier from the developing unit. The evaluation paper was plain paper GF-C081 (A4, basis weight 81.4 g / m 2 (sold by Canon Marketing Japan Inc.) was used. The amount of toner on the paper in a FFh image (solid image) is 0.45 mg / cm 2 FFh is the 256 gradations expressed in hexadecimal, with 00h being the first gradation of the 256 gradations (white background) and FF being the 256th gradation of the 256 gradations (solid area). Using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite), 50,000 FFh images measuring 5 cm x 5 cm were printed, and the image density of the first and 50,000th sheets was measured. The amount of change in image density between the toner before and after being left under the harsh storage conditions described below was evaluated according to the following criteria. (Evaluation criteria: change in image density) A: Less than 0.05 B: 0.05 or more and less than 0.10 C: 0.10 or more and less than 0.20 D:0.20 or more

[0145] - Harsh storage conditions The toner to be evaluated was placed in a constant temperature and humidity chamber set at 25°C / 60%RH. The atmosphere inside the chamber was then linearly changed to 50°C / 90%RH over 12 hours. The temperature was then lowered to 25°C / 90%RH over 12 hours, and then raised to 50°C / 90%RH over another 12 hours. This cycle of lowering and raising was repeated 20 times. After the 20th temperature increase cycle was completed, the atmosphere inside the chamber was lowered to 40°C / 90% RH over 6 hours, and then left at 40°C / 90% RH for 10 days. Finally, the atmosphere was lowered to 25°C / 60% RH over 6 hours, and the toner was then removed from the constant temperature and humidity chamber.

[0146] <Examples 2 to 11 and Comparative Examples 1 to 9> The evaluation was carried out in the same manner as in Example 1, except that two-component developers 2 to 20 were used. Table 10 shows the evaluation results.

[0147] [Table 10]

Claims

1. A toner having toner particles containing a binder resin, the binder resin contains an amorphous polyester A and a crystalline polyester C, the amorphous polyester A has an amorphous polyester segment a1 and an amorphous polyester segment a2, the amorphous polyester segment a2 has a monomer unit derived from a linear aliphatic polyhydric alcohol a having 2 to 10 carbon atoms as a monomer unit forming a polyester skeleton, The difference between the SP value of the amorphous polyester segment a2 and the SP value of the amorphous polyester segment a1 (the SP value of a2 - the SP value of a1) is 0.80 (cal / cm ３ ) ０．５ That's all, the crystalline polyester C is a polymer having a crystalline polyester segment c2 and a crystalline portion c1 bonded to an end of the crystalline polyester segment c2, the crystalline polyester segment c2 has a monomer unit derived from a linear aliphatic polyhydric alcohol b having 2 to 10 carbon atoms as a monomer unit forming a polyester skeleton, the absolute difference between the number of carbon atoms of the linear aliphatic polyhydric alcohol a and the number of carbon atoms of the linear aliphatic polyhydric alcohol b is 4 or less; The difference between the SP value of the crystalline polyester segment c2 and the SP value of the crystalline portion c1 (SP value of c2 - SP value of c1) is 0.75 (cal / cm ３ ) ０．５ That's all, The difference between the SP value of the amorphous polyester segment a1 and the SP value of the crystalline polyester segment c2 (the SP value of a1 - the SP value of c2) is 0.80 (cal / cm ３ ) ０．５ is as follows: The difference between the SP value of the amorphous polyester segment a2 and the SP value of the crystalline portion c1 (the SP value of a2 - the SP value of c1) is 2.00 (cal / cm ３ ) ０．５ A toner characterized by the above.

2. the crystalline polyester segment c2 has a monomer unit derived from the linear aliphatic polyhydric alcohol b and a monomer unit derived from an aliphatic dicarboxylic acid, 2. The toner according to claim 1, wherein N1 represents the number of carbon atoms in the linear aliphatic polyhydric alcohol b and N2 represents the number of carbon atoms in the aliphatic dicarboxylic acid, and N1 and N2 satisfy the following formula (1): N2 / N1≧2.0...(1)

3. the crystalline portion c1 is at least one of a monomer unit derived from an aliphatic monocarboxylic acid and a monomer unit derived from an aliphatic monoalcohol, 3. The toner according to claim 1, wherein the crystalline portion c1 has a hydrocarbon group having 9 to 30 carbon atoms bonded to an end of the crystalline polyester segment c2 via an ester bond.

4. The toner according to any one of claims 1 to 3, wherein the crystalline polyester C has a structure in which the crystalline portion c1 is bonded to the main chain terminal of the crystalline polyester segment c2 at a content ratio of 60.0 mol % or more.

5. 5. The toner according to claim 1, wherein an absolute difference between the number of carbon atoms of the linear aliphatic polyhydric alcohol a and the number of carbon atoms of the linear aliphatic polyhydric alcohol b is 0.

6. 6. The toner according to claim 1, wherein the amorphous polyester segment a1 has a monomer unit derived from a polyhydric aromatic phenol.

7. The softening point of the amorphous polyester A measured by a flow tester is T Ａ (°C), The softening point of the molten mixture obtained by mixing the amorphous polyester A and the crystalline polyester C at the mass ratio of the amorphous polyester A and the crystalline polyester C in the toner is T Ｍ (°C), the T Ａ and the T Ｍ The difference between (T Ａ -T Ｍ 7. The toner according to claim 1, wherein the temperature of the toner is 7 to 20°C.

8. In measuring the storage modulus G' of the toner, when the storage modulus at 60°C during heating is defined as G' during heating, and the storage modulus at 60°C during cooling is defined as G' during cooling, 8. The toner according to claim 1, wherein G' during temperature rise / G' during temperature fall is 3.0 or more.

9. 9. The toner according to claim 1, wherein the content of the crystalline polyester C in the binder resin is 3 to 20% by mass.

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