Toner and two-component developer

Abstract

To provide a toner exhibiting excellent low temperature fixability and scratch resistance.SOLUTION: A toner has a toner particle containing a binder resin containing an amorphous resin A and a crystalline polyester C. The amorphous resin A and the crystalline polyester C have a structure of specific chain aliphatic polyhydric alcohol. The amorphous resin A has a structure in which polyester is cross-linked by a vinyl polymer. The melting point of the crystalline polyester C and the weight average molecular weight of the amorphous resin A are within specific ranges.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a toner used in electrophotography, electrostatic recording, electrostatic printing, and the like, and a two-component developer using the toner. [Background technology]

[0002] In recent years, as full-color electrophotographic copying machines have come into widespread use, there has been a demand for additional performance improvements, such as increased speed and higher image quality, energy saving performance, and compatibility with a wide variety of media.

[0003] Specifically, toners that can be fixed at lower temperatures and have excellent low-temperature fixing properties are required to reduce power consumption in the fixing process as toners that can save energy. Furthermore, thick coated paper, which is one of the various media, contains a large amount of inorganic fine particles such as calcium carbonate to increase whiteness, which increases the friction force between the paper and the image, making the toner in the fixed image more likely to peel off from the paper. Therefore, toners with excellent abrasion resistance are required to suppress toner peeling due to friction between papers. Therefore, Patent Document 1 proposes a toner using a crystalline polyvinyl resin as a toner having excellent low-temperature fixing properties, and Patent Document 2 proposes a toner having alkenyl succinic acid as a carboxylic acid component of polyester as a toner having excellent abrasion resistance. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2018-156074 A [Patent Document 2] JP 2016-197207 A Summary of the Invention [Problem to be solved by the invention]

[0005] The toner described in Patent Document 1 has excellent low-temperature fixing properties because it uses a crystalline polyvinyl resin that has sharp melting properties and high hydrophobicity. On the other hand, it has been found that the crystalline polyvinyl resin has high affinity with wax, which inhibits the wax from bleeding out and makes it difficult to form a wax layer on the surface of the fixed image, which may result in poor abrasion resistance.

[0006] In addition, in the toner described in Patent Document 2, since the alkenyl succinic acid has a high affinity with the wax, the wax is more likely to be retained in the fixed image during fixing rather than being transferred to the fixing roller. Therefore, a certain degree of abrasion resistance can be obtained on paper types such as thin paper. On the other hand, the toner described in Patent Document 2 does not contain a plasticizer such as a crystalline polyester, and even if it does contain one, the presence of the alkenyl succinic acid promotes crystallization, and the expected plasticizing effect cannot be obtained, so that low-temperature fixing property may be poor.

[0007] For the above reasons, there are problems in satisfying low-temperature fixing property and abrasion resistance. Therefore, there is an urgent need to develop a toner that exhibits excellent low-temperature fixing property and abrasion resistance. The present disclosure provides a toner that exhibits excellent low-temperature fixing property and abrasion resistance and a two-component developer having the toner. [Means for solving the problem]

[0008] The present disclosure relates to a toner having toner particles containing a binder resin, The binder resin contains an amorphous resin A and a crystalline polyester C, The crystalline polyester C has a structure forming a polyester, which structure is a linear aliphatic polyalkoxy group. having a structure corresponding to that of (c), When the number of carbon atoms of the linear aliphatic polyhydric alcohol (c) is Cc, Cc satisfies the following formula (1): 2≦Cc≦6 (1) The amorphous resin A has a structure corresponding to the linear aliphatic polyhydric alcohol (a) as a structure forming a polyester, When the number of carbon atoms of the linear aliphatic polyhydric alcohol (a) is Ca, the Ca satisfies the following formula (2): 2≦Ca≦10 (2) The Ca and the Cc satisfy the following formula (3), 0≦│Ca-Cc│≦4 (3) The amorphous resin A has a structure in which a polyester is crosslinked with a vinyl polymer, When the weight average molecular weight measured from the tetrahydrofuran soluble portion of the amorphous resin A is defined as MwA, the MwA satisfies the following formula (4), 10000≦MwA≦100000 (4) The toner relates to a toner in which, when the melting point of the crystalline polyester C is Tc, the Tc satisfies the following formula (5). 90℃≦Tc≦100℃ (5) Effect of the Invention

[0009] According to the present disclosure, it is possible to provide a toner that exhibits excellent low-temperature fixing property and abrasion resistance, and a two-component developer that includes the toner. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] In the present disclosure, the description of "XX or more and YY or less" or "XX to YY" representing a numerical range means a numerical range including the lower and upper limits which are the endpoints, unless otherwise specified. When a numerical range is described in stages, the upper and lower limits of each numerical range can be arbitrarily combined. Furthermore, a monomer unit refers to the reacted form of a monomer substance in a polymer. Furthermore, a crystalline polyester is a resin that shows a clear endothermic peak in differential scanning calorimetry (DSC).

[0011] The present inventors have conducted research into toners that are excellent in low-temperature fixing property and abrasion resistance. The present inventors first investigated ways to improve resistance to abrasion by increasing the mechanical strength of the toner. They found that a certain level of molecular weight is required to achieve the effect of abrasion resistance, and as a result, the glass transition temperature and softening point of the toner increase, impairing low-temperature fixability.

[0012] Next, among the materials constituting the toner, the wax, which is a material with low surface energy, was examined to remain on the surface of the fixed image. Specifically, lowering the melting point of the wax can promote the wax seeping out onto the surface of the fixed image even in a situation where the toner is not easily heated, such as on thick paper, and a certain degree of effect was obtained on the abrasion resistance. However, in a situation where the toner is easily heated, such as on thin paper, the wax seeps out too much onto the surface of the fixed image. As a result, in a halftone image, which is a dot image with few adjacent toners, the wax becomes liquid when melted and flows down onto the paper surface, so that the wax cannot be supported on the toner, and the abrasion resistance is impaired.

[0013] On the other hand, when the melting point of the wax is increased, even in a situation where the toner is easily heated, such as on thin paper, the wax that has become liquid quickly solidifies and does not flow down to the paper surface, so the wax can be supported on the fixed image, and a certain degree of effect on abrasion resistance is obtained. However, when the melting point of the wax is increased, in a situation where the toner is not easily heated, such as on thick paper, the fixed image The wax is prevented from seeping out from the surface, making it difficult to form a wax layer on the surface of the fixed image, resulting in a loss of abrasion resistance. In other words, it became clear that it is difficult to achieve excellent abrasion resistance for various fixed images and paper types simply by controlling the exudation through the melting point of the wax.

[0014] Therefore, the present inventors further investigated the mechanism of the abrasion phenomenon and verified how a wax with low surface energy contributes to improving abrasion resistance. Specifically, in a fixed image with excellent abrasion resistance, not only the abraded fixed image but also the abraded paper side was analyzed. As a result, it was found that the paper on which the fixed image was rubbed did not contain toner components, but did contain wax components. In other words, the presence of wax with low surface energy in a fixed image with excellent rub resistance does not mean that the fixed image is not rubbed at all. Although the fixed image is rubbed, the presence of a wax layer that is easily scraped off means that the rub phenomenon is limited to the outermost layer of the image and does not extend to the toner layer, which is why it has excellent rub resistance.

[0015] The inventors further investigated the material to determine which physical property of wax is responsible for its function of being easily scraped and limiting the abrasion phenomenon to the outermost layer. As a result, it was revealed that the wax's function is not due to its composition having low surface energy, but due to its material structure, which is crystalline or amorphous. Specifically, it was found that a similar function can be expressed even in crystalline polyesters that have ester groups and do not have low surface energy. In other words, it was revealed that in order to express a similar function, it is necessary for the material to be crystalline. The reason for this is that, like crystalline materials, the molecules are folded in an orderly manner, so that they are easily scraped in an orderly manner when rubbed, and the rub phenomenon can be limited to the outermost layer. Furthermore, it was found that this function can be expressed in physical properties as a friction coefficient, and it was revealed that wax and crystalline polyesters have a sufficiently low friction coefficient compared to amorphous polyesters, etc.

[0016] For the above reasons, the present inventors departed from the study of increasing the mechanical strength of the toner and the study of supporting a wax with low surface energy on the surface of the fixed image, and instead conducted detailed study of supporting a crystalline polyester having crystallinity on the surface of the fixed image. This is because, compared to wax, crystalline polyester has a wider range of material options, and its melting point and polarity can be easily changed, and therefore, it was thought that it would be possible to achieve an effect of abrasion resistance that could not be achieved by controlling the exudation by the melting point of the wax.

[0017] However, when crystalline polyester is made compatible with amorphous resin, it acts as a plasticizer for the amorphous resin, so excellent low-temperature fixability is obtained, but since the crystalline polyester is difficult to crystallize, the effect of low friction coefficient is not obtained, and the abrasion resistance is also poor. On the other hand, when crystalline polyester is phase-separated from the amorphous resin, it does not act as a plasticizer for the amorphous resin, so low-temperature fixability is poor. Furthermore, since the crystalline polyester has low affinity for the amorphous resin, the crystalline polyester behaves like wax, and the crystalline polyester cannot be supported on the dots, and flows down to the paper surface. Therefore, it has been revealed that a layer of crystalline polyester cannot be formed on the surface of the fixed image, and the abrasion resistance is impaired.

[0018] That is, the present inventors recognized that, although the crystalline polyester and the amorphous resin are compatible with each other when melted, the crystalline polyester needs to be easily crystallized when cooled, and needs to be quickly solidified and not flow down to the paper surface, so that the crystalline polyester can be supported on the fixed image. An amorphous resin and a crystalline polyester that can satisfy such a relationship are essential.

[0019] The present inventors have further investigated and organized the phase changes of crystalline polyester in a time series. Specifically, the crystalline polyester must be compatible for low-temperature fixing, and the crystalline polyester must be phase-separated and crystallized for abrasion resistance. The phase change of compatibility and phase separation must occur in a short time from when the paper passes through the fixing nip until it is loaded onto the paper output tray.

[0020] The inventors of the present invention have conducted a more in-depth study because polarity adjustment of amorphous resins and crystalline polyesters only moves along the line of this trade-off between compatibility and phase separation, and it is not possible to achieve both low-temperature fixability and abrasion resistance. As a result, they have found that a specific amorphous resin and a specific crystalline polyester can achieve both low-temperature fixability and abrasion resistance. Specifically, by giving the crystalline polyester a specific structure (described later) and controlling the melting point, the intermolecular cohesive force is increased, promoting the folding of the molecules, and a crystalline polyester is developed that crystallizes in the short time between passing through the fixing nip and being loaded onto the output tray.

[0021] Furthermore, even if a crystalline polyester that crystallizes quickly as described above is used, by giving the amorphous resin a specific structure described later, an amorphous resin has been developed in which the crystalline polyester can be compatible with the amorphous resin when entering the fixing nip. Furthermore, the amorphous resin is configured such that the polyester is crosslinked with a vinyl polymer. As a result, the vinyl polymer, which is the crosslinked portion, is not compatible with the crystalline polyester. Therefore, the molecular mobility of the crosslinking points of the amorphous resin is not increased, and the crystalline polyester that phase-separates from the amorphous resin and crystallizes when the toner is loaded on the paper output tray after passing through the fixing nip can be prevented from seeping out of the toner.

[0022] That is, the toner of the present disclosure has toner particles containing a binder resin, and the binder resin contains an amorphous resin A and a crystalline polyester C. The crystalline polyester C has a structure that corresponds to the linear aliphatic polyhydric alcohol (c) as a structure that forms a polyester, and when the number of carbon atoms of the linear aliphatic polyhydric alcohol (c) is Cc, Cc satisfies the following formula (1). 2≦Cc≦6 (1) In addition, when the melting point of the crystalline polyester C is Tc, Tc satisfies the following formula (5). 90℃≦Tc≦100℃ (5)

[0023] When the number of carbon atoms of the linear aliphatic polyhydric alcohol (c) is in the above range, the intermolecular cohesive force of the crystalline polyester is increased, the folding of the molecules is promoted, and the crystallization occurs in a short time from passing through the fixing nip to being loaded on the paper discharge tray. As a result, the effect of a low friction coefficient is obtained, and excellent abrasion resistance is obtained. Cc is preferably 2 to 4, more preferably 2 to 3, and even more preferably 2.

[0024] The structure forming the polyester is a structure forming an ester bond. The structure corresponding to the linear aliphatic polyhydric alcohol (c) is a structure in which the linear aliphatic polyhydric alcohol (c) is condensed in the polyester. The structure corresponding to the linear aliphatic polyhydric alcohol (c) is represented, for example, by the following formula (I). It can also be said that the polyester has a monomer unit corresponding to the linear aliphatic polyhydric alcohol (c). The linear aliphatic polyhydric alcohol (c) is preferably a linear aliphatic diol having a carbon number Cc. [ka] In formula (I), R 1 is a straight-chain hydrocarbon group having carbon number Cc.

[0025] In addition, when the Tc of the crystalline polyester C is 90°C or more, the intermolecular cohesive force of the crystalline polyester C is increased, the folding of the molecules is promoted, and the crystallization occurs in a short time from passing through the fixing nip to being loaded onto the paper discharge tray. As a result, the friction coefficient is reduced, and excellent abrasion resistance is obtained. In addition, when the Tc is 100°C or less, a large amount of heat is not required for the crystalline polyester C to melt and the polyester of the amorphous resin A to plasticize, and therefore excellent low-temperature fixability is obtained. Tc is preferably 90 to 96°C, and more preferably 91 to 94°C.

[0026] The amorphous resin A has a structure corresponding to the linear aliphatic polyhydric alcohol (a) as a structure forming a polyester, When the number of carbon atoms of the linear aliphatic polyhydric alcohol (a) is Ca, Ca satisfies the following formula (2). 2≦Ca≦10 (2) Moreover, Ca and Cc satisfy the following formula (3). 0≦│Ca-Cc│≦4 (3)

[0027] When the carbon number Ca of the linear aliphatic polyhydric alcohol (a) is within the above range and |Ca-Cc| is within the above range, it indicates that the amorphous resin A has a structure with high affinity with the crystalline polyester C. Therefore, the crystalline polyester C with high crystallinity described above can penetrate into the molecular chain of the amorphous resin A through the locally existing structure with high affinity and become compatible, thereby exhibiting a plasticizing effect, and thus excellent low-temperature fixability can be obtained. Ca is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2. |Ca-Cc| is preferably 0 to 2, and more preferably 0. The linear aliphatic polyhydric alcohol (a) is preferably a linear aliphatic diol with a carbon number Ca.

[0028] The amorphous resin A has a structure in which a polyester is crosslinked with a vinyl polymer. When the amorphous resin A has the above-mentioned structure, the crystalline polyester C is compatible with the polyester contained in the amorphous resin A, whereas the vinyl polymer, which is the crosslinked portion contained in the amorphous resin A, is not compatible with the crystalline polyester C. Therefore, the molecular mobility of the crosslinked points of the amorphous resin A is not increased, and the crystalline polyester C, which phase-separates from the amorphous resin A and crystallizes when the toner is loaded on the paper output tray after passing through the fixing nip, is less likely to seep out of the toner. Therefore, the crystalline polyester C does not flow down onto the paper surface, and the crystalline polyester C can be supported on the fixed image, resulting in excellent abrasion resistance.

[0029] When the weight average molecular weight measured from the tetrahydrofuran soluble portion (THF soluble portion) of the amorphous resin A is defined as MwA, MwA satisfies the following formula (4). 10000≦MwA≦100000 (4) When the MwA of the amorphous resin A is 10,000 or more, the molecular mobility of the crosslinked amorphous resin A can be suppressed. Therefore, when the paper is stacked on the discharge tray after passing through the fixing nip, the crystalline polyester C, which is phase-separated from the amorphous resin and crystallized, can be prevented from seeping out of the toner. Therefore, the crystalline polyester C does not flow down to the paper surface, and the crystalline polyester C can be supported on the toner, so that excellent abrasion resistance can be obtained. In addition, when the MwA is 100,000 or less, the molecular weight is not too large while suppressing the molecular mobility of the amorphous resin, so that excellent low-temperature fixability can be obtained. The MwA is preferably 12,000 to 50,000, and more preferably 15,000 to 25,000.

[0030] The crystalline polyester C preferably satisfies one or both of the following (A) and (B). (A) Crystalline polyester C is a modified crystalline polyester having a structure in which a hydroxy group at the end of the main chain is condensed (terminally modified) with an aliphatic monocarboxylic acid having 15 to 31 carbon atoms (more preferably 18 to 26, and even more preferably 20 to 24). (B) Crystalline polyester C is a modified crystalline polyester having a structure in which a carboxy group at the end of the main chain is condensed (terminally modified) with an aliphatic monoalcohol having 15 to 30 carbon atoms (more preferably 18 to 26, and even more preferably 20 to 24 carbon atoms).

[0031] When the crystalline polyester C is the modified crystalline polyester, the main chain end acts as a crystal nucleating agent, promoting folding of the main chain. As a result, the crystallization rate of the crystalline polyester C is increased, so that crystallization is more likely to occur in a short time from passing through the fixing nip to being loaded on the discharge tray. As a result, the effect of reducing the friction coefficient is more obtained, and better abrasion resistance is obtained. In addition, since the polarity difference can be guaranteed with respect to the amorphous resin A, it is easy to function as a crystal nucleating agent, and the amount of the crystal nucleating agent at the main chain end can be appropriately controlled. Therefore, the crystallization rate of the crystalline polyester C can be increased, and crystallization occurs in a shorter time. As a result, the effect of reducing the friction coefficient is more obtained, and better abrasion resistance is obtained.

[0032] In the amorphous resin A, the vinyl polymer forming the crosslinked structure preferably has a structure corresponding to (meth)acrylic acid as a structure forming a vinyl polymer. The structure forming a vinyl polymer is a structure obtained by addition polymerization of a monomer. The structure corresponding to (meth)acrylic acid is a structure obtained by addition polymerization of (meth)acrylic acid in a vinyl polymer. That is, it is preferable that the vinyl polymer has a monomer unit of (meth)acrylic acid. For example, the vinyl polymer may contain poly(meth)acrylic acid.

[0033] When the crosslinked structure of the amorphous resin A has the above structure, the crosslinked points can form strong covalent bonds. Therefore, the molecular mobility of the crosslinked points of the amorphous resin A is not increased, and the crystalline polyester C that phase-separates from the amorphous resin A and crystallizes when the paper is stacked on the discharge tray after passing through the fixing nip can be prevented from seeping out of the toner. Therefore, the crystalline polyester is supported on the fixed image, and a crystalline polyester layer can be formed without flowing down to the paper surface, resulting in better abrasion resistance.

[0034] When the weight average molecular weight measured from the THF-soluble portion of the polyester in the amorphous resin A is defined as MwAP, it is preferable that MwAP satisfies the following formula (6). 3000≦MwAP≦8000 (6) When MwAP is within the above range, it indicates that the polyester is crosslinked in view of the weight average molecular weight of the amorphous resin A described above. Therefore, the molecular mobility of the crosslinked points of the amorphous resin A is not increased, and the crystalline polyester C that phase-separates from the amorphous resin A and crystallizes when the toner is loaded on the paper output tray after passing through the fixing nip can be prevented from seeping out of the toner. Therefore, the crystalline polyester C is supported on the dots and does not flow down onto the paper surface, forming a crystalline polyester layer, thereby obtaining better abrasion resistance. Moreover, the MwAP being in the above range indicates that the molecular weight of the polyester is not too large, and therefore, better low-temperature fixability can be obtained. The MwAP is more preferably 4,000 to 7,500, and further preferably 5,000 to 7,000.

[0035] From the viewpoint of abrasion resistance, it is more preferable that the relationship between MwAP and MwA satisfies the following formula (8): MwA / MwAP is further preferably from 2.7 to 4.0. 2.5≦MwA / MwAP≦6.0 (8)

[0036] It is preferable that the polyester in the amorphous resin A is a block copolymer having an amorphous polyester segment A1 and an amorphous polyester segment A2. And, only the amorphous polyester segment A1 corresponds to the linear aliphatic polyhydric alcohol (a). The structure corresponding to the linear aliphatic polyhydric alcohol (a) is a structure in which the linear aliphatic polyhydric alcohol (a) is condensed in the polyester, similar to the linear aliphatic polyhydric alcohol (c) described above.

[0037] When the amorphous resin A is the block copolymer, the linear aliphatic polyhydric alcohol (a) is densely present, and therefore the crystalline polyester C having a high degree of crystallinity described above penetrates into the molecular chain of the amorphous resin A through a structure corresponding to the linear aliphatic polyhydric alcohol (a) having a high affinity present locally, and is easily compatible with the linear aliphatic polyhydric alcohol (a), and can exert a plasticizing effect, resulting in better low-temperature fixability.

[0038] On the other hand, the vinyl polymer, which is the crosslinked portion, becomes less compatible with the crystalline polyester C. As a result, the molecular mobility of the crosslinked points of the amorphous resin A does not increase, and the crystalline polyester C, which phase-separates from the amorphous resin A and crystallizes when the toner is loaded onto the paper output tray after passing through the fixing nip, does not seep out of the toner. As a result, the crystalline polyester C does not flow down onto the paper surface, and can be supported on the fixed image, resulting in better abrasion resistance.

[0039] SP value of amorphous polyester segment A1 (J / cm 3 ) 0.5 is taken as SPA1, and the SP value (J / cm) of the amorphous polyester segment A2 is taken as 3 ) 0.5 is defined as SPA2. The SP value (J / cm 3 ) 0.5 In this case, it is preferable that SPA1 and SPA2 satisfy the following formula (7), and SPA and SPC satisfy the following formula (9). 0.8≦SPA1―SPA2≦2.5 (7) 0.7≦SPA―SPC≦2.0 (9)

[0040] When SPA1-SPA2 is within the above range, the block nature of the amorphous resin A becomes clear, and the structure corresponding to the linear aliphatic polyhydric alcohol (a) is more densely present. Therefore, the crystalline polyester C with high crystallinity described above can easily penetrate into the molecular chain of the amorphous resin A via the structure corresponding to the linear aliphatic polyhydric alcohol (a) and become compatible, and can exert a better plasticizing effect, resulting in better low-temperature fixability.

[0041] On the other hand, the vinyl polymer, which is the crosslinked portion, becomes less compatible with the crystalline polyester C. As a result, the molecular mobility of the crosslinked points of the amorphous resin A does not increase, and the crystalline polyester C, which phase-separates from the amorphous resin A and crystallizes when the toner is loaded onto the paper output tray after passing through the fixing nip, does not seep out of the toner. As a result, the crystalline polyester C does not flow down onto the paper surface, and can be supported on the fixed image, resulting in better abrasion resistance.

[0042] The ratio SPA1-SPA2 is more preferably 0.9 to 2.0. Moreover, from the viewpoint of abrasion resistance, it is more preferable that SPA and SPC satisfy the following formula (10). 0.8≦SPA―SPC≦1.0 (10)

[0043] The amorphous resin A is preferably the main component of the binder resin. The term "main component" means that the content is 50% by mass or more. The content of the amorphous resin A in the binder resin is preferably 80.0% by mass or more and 97.0% by mass or less, more preferably 85.0% by mass or more and 95.0% by mass or less, and even more preferably 86.0% by mass or more and 90.0% by mass or less.

[0044] The ratio of the tetrahydrofuran soluble content of amorphous resin A based on the mass of amorphous resin A is W When Ws is s (mass %), it is preferable that Ws satisfies the following formula (8). 90.0≦Ws≦100.0 (8) When Ws is within the above range, it is considered that the main component amorphous resin A is crosslinked locally, and the weight average molecular weight is not increased, but is crosslinked uniformly. Therefore, the molecular mobility of the crosslinked points of the amorphous resin A is not increased, and when the toner is loaded on the paper output tray after passing through the fixing nip, the crystalline polyester C that phase-separates from the amorphous resin A and crystallizes does not seep out from the toner. Therefore, the crystalline polyester C is supported on the fixed image, and the crystalline polyester C does not flow down to the paper surface, and a crystalline polyester layer can be formed, so that better abrasion resistance can be obtained. Ws is more preferably 95.0 to 100.0% by mass, and even more preferably 98.0 to 100.0% by mass.

[0045] <Amorphous resin A> The amorphous resin A has a structure in which a polyester is crosslinked with a vinyl polymer. The polyester is preferably a condensation polymer of a polyhydric alcohol (dihydric or trihydric or higher alcohol) and a polyvalent carboxylic acid (dihydric or trihydric or higher carboxylic acid), its acid anhydride, or its lower alkyl ester. Among them, the polyester is more preferably a condensation polymer of a dihydric alcohol and a divalent carboxylic acid, since the crosslinked structure is formed by the vinyl polymer unit.

[0046] As the polyhydric alcohol monomer of the polyester, the following polyhydric alcohol monomers can be used: Dihydric alcohol components include, for example, 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 bisphenol represented by formula (A) and its derivatives; [ka]

[0047] (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 of the diols include those represented by the formula (B). [ka]

[0048] Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, Examples of the alcohol include 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 preferably used. These dihydric alcohols and trihydric or higher alcohols can be used alone or in combination.

[0049] As the polybasic carboxylic acid monomer for the polyester, the following polybasic carboxylic acid monomers can be used. Examples of divalent carboxylic 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, isooctylsuccinic 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.

[0050] 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 divalent carboxylic acids and trivalent or higher carboxylic acids can be used alone or in combination.

[0051] Among them, as described above, the alcohol component preferably contains a linear aliphatic polyhydric alcohol (a) having Ca of 2 to 10, and more preferably contains ethylene glycol from the viewpoint of affinity with the linear aliphatic polyhydric alcohol (c). When the linear aliphatic polyhydric alcohol (a) is ethylene glycol, the amorphous resin A has a monomer unit having high affinity with the crystalline polyester C. Therefore, the crystalline polyester C having a high crystallization rate is compatible with the amorphous resin A at the time of the fixing nip, and thus a better low-temperature fixing property can be obtained.

[0052] The amorphous polyester segment A1 preferably contains 10 to 35 mass %, and more preferably 15 to 25 mass %, of a structure corresponding to the linear aliphatic polyhydric alcohol (a) having Ca of 2 to 10. The polyester in the amorphous resin A preferably contains 1 to 10 mass %, and more preferably 1 to 5 mass %, of a structure corresponding to the linear aliphatic polyhydric alcohol (a) having Ca of 2 to 10. When the amount of the structure corresponding to the linear aliphatic polyhydric alcohol (a) is within the above range, the amorphous resin A has a monomer unit that has high affinity with the crystalline polyester C. Therefore, the crystalline polyester C, which has a high crystallization rate, is compatible with the amorphous resin A at the fixing nip, and thus better low-temperature fixing property is obtained.

[0053] The method for producing the polyester is not particularly limited, and a known method can be used. For example, the above-mentioned alcohol monomer and carboxylic acid monomer are simultaneously charged, and polymerized through an esterification reaction or an ester exchange reaction and a condensation reaction to produce a polyester. The polymerization temperature is not particularly limited, but is preferably in the range of 180° C. to 290° C. In polymerizing the polyester, for example, a polymerization catalyst such as a titanium-based catalyst, a tin-based catalyst, zinc acetate, antimony trioxide, or germanium dioxide can be used. In particular, it is more preferable that the polyester of the amorphous resin A is a polyester polymerized using a tin-based catalyst.

[0054] The softening point TA of the amorphous resin A1 is preferably from 100.0 to 120.0°C, and more preferably from 104.0 to 110.0°C. As described above, the polyester of the amorphous resin A is preferably a block copolymer having an amorphous polyester segment A1 and an amorphous polyester segment A2.

[0055] The monomers used for the amorphous polyester segment A1 and the amorphous polyester segment A2 include the above-described polyhydric alcohols (dihydric or trihydric or higher alcohols) and polyvalent carboxylic acids (dihydric or trihydric or higher carboxylic acids), their acid anhydrides, or their lower alkyl esters. Among them, as described above, it is preferable that only the amorphous polyester segment A1 has a structure corresponding to the linear aliphatic polyhydric alcohol (a) having Ca of 2 to 10, and it is more preferable that the amorphous polyester segment A1 contains a structure corresponding to ethylene glycol from the viewpoint of affinity with the linear aliphatic polyhydric alcohol (c).

[0056] The amorphous polyester segment A1 is preferably a condensation polymer of a linear aliphatic polyhydric alcohol (a) having Ca in the above range and terephthalic acid. The amorphous polyester segment A2 is preferably a condensation polymer of a monomer mixture containing bisphenol represented by formula (A) and terephthalic acid. The content of the amorphous polyester segment A1 in the amorphous resin A is preferably 1 to 20 mass %, more preferably 5 to 12 mass %. The content of the amorphous polyester segment A2 in the amorphous resin A is preferably 80 to 98 mass %, more preferably 85 to 95 mass %.

[0057] The method for block copolymerization of the amorphous polyester segment A1 and the amorphous polyester segment A2 is not particularly limited and may be appropriately selected depending on the purpose. Examples of the method include the methods described in (1) to (3) below. From the viewpoint of the freedom of molecular design, the methods (1) and (3) are preferred, and the method (1) is more preferred.

[0058] (1) A method of dissolving or dispersing an amorphous polyester A1 previously prepared by polymerization reaction and an amorphous polyester A2 previously prepared by polymerization reaction in a suitable solvent, and copolymerizing them. If necessary, an extender having two or more functional groups that react with the hydroxyl group at the polymer chain end, such as a carboxy group, an isocyanate group, an epoxy group, or a carbodiimide group, may be used.

[0059] (2) A method in which an amorphous polyester A1 previously prepared by a polymerization reaction and an amorphous polyester A2 previously prepared by a polymerization reaction are fed into a twin-screw extruder together with an ester exchange catalyst, etc., and prepared by a reactive extrusion method using a twin-screw extruder, etc.

[0060] (3) A method in which a hydroxyl group of an amorphous polyester A1 previously prepared by a polymerization reaction is used as a polymerization initiation component, and an amorphous polyester A2 is copolymerized by ring-opening polymerization from the polymer chain end of the amorphous polyester A1.

[0061] The content of the structure crosslinked with a vinyl polymer in the amorphous resin A is preferably 0.1 to 6.0% by mass, and more preferably 1.5 to 3.0% by mass. The method for producing the amorphous resin A having a structure in which a polyester is crosslinked with a vinyl polymer is not particularly limited, but examples thereof include the following.

[0062] (i) A production method by carrying out an ester exchange reaction between a polymer containing a monomer component having an ester group such as an acrylic acid ester or a methacrylic acid ester and a polyester component. (ii) A production method in which an esterification reaction is carried out between a polymer containing a monomer component having a carboxylic acid group, such as acrylic acid or methacrylic acid, and a polyester component. (iii) A method of producing the polyester by polymerizing a monomer component constituting a styrene-acrylic copolymer portion in the presence of a polyester portion containing a monomer component having an unsaturated bond such as fumaric acid.

[0063] Among these, the manufacturing methods (i) and (ii) can crosslink the ends of the polyester units to form a network structure, thereby increasing the mobility of the polyester units in the plasticized main chain, and thus achieving excellent low-temperature fixability.

[0064] Examples of monomers used in the vinyl polymer as crosslinking sites include the following. Examples of the styrene derivatives include o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-phenylstyrene; α-methylene aliphatic monocarboxylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate; and unsaturated carboxylic acids such as acrylic acid and methacrylic acid.

[0065] In addition, various resin compounds known as binder resins can be used in combination with the crystalline polyester C and the amorphous resin A to the extent that the above effects are not impaired. Examples of such resin compounds include phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic resins, acrylic resins, methacrylic resins, polyvinyl acetate resins, silicone resins, polyester resins, polyurethanes, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumaroindene resins, and petroleum-based resins.

[0066] <Crystalline polyester C> A polyhydric alcohol (dihydric or trihydric or higher alcohol), a polyvalent carboxylic acid (dihydric or trihydric or higher carboxylic acid), an acid anhydride thereof, or a lower alkyl ester thereof are used as monomers for the crystalline polyester C. The crystalline polyester C is preferably a condensation polymer of an aliphatic dicarboxylic acid and an aliphatic diol.

[0067] The polyhydric alcohol monomer used in the crystalline polyester C may be any of the following polyhydric alcohol monomers. 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 Examples of the diol include α,ω-diol, 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, preferred examples include linear aliphatic and α,ω-diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0068] Polyhydric alcohol monomers other than the above polyhydric alcohols can also be used. Among the polyhydric alcohol monomers, examples of dihydric alcohol monomers include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol, etc. Among the polyhydric alcohol monomers, examples of 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.

[0069] The polycarboxylic acid monomer used in the crystalline polyester C may be any of the following polycarboxylic acid monomers. The polycarboxylic acid monomer is not particularly limited, but is preferably a chain-like (more preferably 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, and also includes those obtained by hydrolyzing the acid anhydrides or lower alkyl esters of these acids.

[0070] 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, and also include their acid anhydrides and lower alkyl esters.

[0071] Furthermore, among the other carboxylic acid monomers, examples of polyvalent carboxylic acids having a valence of three or more 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 their acid anhydrides and lower alkyl esters.

[0072] Among them, as described above, the alcohol component preferably has a linear aliphatic polyhydric alcohol (c) having a Cc of 2 to 6, and more preferably contains ethylene glycol from the viewpoint of affinity with the linear aliphatic polyhydric alcohol (a) and intermolecular cohesive force. When the linear aliphatic polyhydric alcohol (c) is ethylene glycol, the intermolecular cohesive force of the crystalline polyester C is increased, molecular folding is promoted, and crystallization occurs in a short time from passing through the fixing nip to being loaded on the paper discharge tray. As a result, the effect of reducing the friction coefficient is more easily obtained, and better abrasion resistance is obtained.

[0073] The crystalline polyester C is preferably a condensation polymer of a monomer mixture containing a linear aliphatic polyhydric alcohol (c) having Cc in the above range and a linear aliphatic diol having 6 to 22 carbon atoms (preferably 8 to 18 carbon atoms). The total content of the terminal aliphatic monocarboxylic acid condensation structure and the terminal aliphatic monoalcohol condensation structure in the crystalline polyester C is preferably 3 to 22 mass %, more preferably 5 to 15 mass %.

[0074] The weight average molecular weight Mwc of the crystalline polyester C is preferably 15000 to 80000, more preferably 15000 to 50000, and even more preferably 15000 to 25000. When the weight average molecular weight of the crystalline polyester C is within the above range, the relationship between the molecular mobility of the amorphous resin A and the viscosity of the crystalline polyester C when melted is more appropriately controlled. Therefore, the crystalline polyester C is easily supported on the fixed image, and the crystalline polyester C does not flow down to the paper surface, and a crystalline polyester layer can be formed, so that better abrasion resistance can be obtained.

[0075] The total of the acid value and hydroxyl value of the crystalline polyester C is preferably 0.1 mgKOH / g to 5.0 mgKOH / g. When the total of the acid value and hydroxyl value of the crystalline polyester C is within the above range, as described above, the crystalline polyester C is a modified crystalline polyester, and the main chain end acts as a crystal nucleating agent, promoting folding of the main chain. As a result, the crystallization rate of the crystalline polyester C is increased, and the effect of reducing the friction coefficient is further obtained, resulting in better abrasion resistance.

[0076] The crystalline polyester C can be produced according to a conventional polyester synthesis method. For example, the carboxylic acid monomer and the alcohol monomer are subjected to an esterification reaction or an ester exchange reaction, and then the crystalline polyester C can be obtained by carrying out a polycondensation reaction according to a conventional method under reduced pressure or by introducing nitrogen gas. Then, the desired crystalline polyester C can be obtained by further adding the above-mentioned aliphatic compound and carrying out an esterification reaction.

[0077] The above esterification or transesterification reaction can be carried out, if necessary, using a conventional esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, magnesium acetate, etc.

[0078] 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 appropriately determined.

[0079] In the esterification or transesterification reaction or polycondensation reaction, in order to increase the strength of the resulting crystalline polyester C, it is 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 first reacted, and then a trivalent or higher monomer is added and reacted.

[0080] <Wax> The toner particles may contain a wax. Examples of the wax include the following: 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 their block copolymers; waxes mainly composed of fatty acid esters such as carnauba wax; partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax; saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; brassidic acid unsaturated fatty acids such as oleostearic acid, valinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid and alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; saturated fats such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide acid bisamides; unsaturated fatty acid amides such as ethylene bisoleamide, hexamethylene bisoleamide, N,N' dioleyl adipamide, and N,N' dioleyl sebacamide; aromatic bisamides such as m-xylene bisstearamide and N,N' distearyl isophthalamide; fatty acid metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats.

[0081] Among these waxes, a hydrocarbon wax such as paraffin wax or Fischer-Tropsch wax is preferred from the viewpoint of suppressing blooming. That is, the wax preferably contains a hydrocarbon wax. More preferably, the wax is Fischer-Tropsch wax.

[0082] From the viewpoint of suppressing blooming, the content of the wax is preferably 2 parts by mass to 10 parts by mass, and more preferably 3 parts by mass to 8 parts by mass, relative to 100 parts by mass of the binder resin. The melting point of the wax is preferably 60°C or higher and 120°C or lower, and more preferably 90°C or higher and 110°C or lower.

[0083] <Coloring agent> The toner particles may contain a colorant as necessary. Examples of the colorant include the following. Examples of the black colorant include carbon black; and a colorant 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 a full-color image, it is preferable to use a dye and a pigment in combination.

[0084] Magenta toner pigments include the following: 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.

[0085] 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, 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, 27; CI Disperse Violet 1; CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; basic dyes such as CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

[0086] Examples of pigments for cyan toners include: CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; CI Vat Blue 6; CI Acid Blue 45, copper phthalocyanine pigments with 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton. Examples of dyes for cyan toners include CI Solvent Blue 70.

[0087] 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.

[0088] These colorants can 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, light resistance, OHP transparency, and dispersibility in toner particles. The content of the colorant is preferably 0.1 to 30.0 parts by mass with respect to 100 parts by mass of the binder resin.

[0089] <Charge control agent> The toner particles may contain a charge control agent as necessary. By blending a charge control agent, the charge characteristics can be stabilized, and the amount of triboelectric charge can be optimally controlled according to the development system. As the charge control agent, a known one can be used, but in particular, a metal compound of an aromatic carboxylic acid is preferred, which is colorless, has a high charging speed of the toner, and can stably maintain a constant amount of charge.

[0090] 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 or sulfonate ester on the side chain, polymeric compounds having carboxylate or carboxylate ester on the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0091] 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 parts by mass to 10.0 parts by mass, and more preferably 0.5 parts by mass to 10.0 parts by mass, based on 100 parts by mass of the binder resin.

[0092] <Inorganic fine particles> The toner may contain inorganic fine particles as necessary in addition to the above-mentioned silica fine particles. The inorganic fine particles may be added internally to the toner particles, or may be mixed with the toner as an external additive. Examples of inorganic fine particles include fine particles such as silica fine particles, titanium oxide fine particles, alumina fine particles, or composite oxide fine particles thereof. 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.

[0093] From the viewpoint of improving fluidity, inorganic fine particles as external additives should have a specific surface area of ​​50 m 2 / g~400m 2 From the viewpoint of improving durability and stability, it is preferable that the inorganic fine particles as the external additive 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.

[0094] The content of the external additive is preferably 0.1 parts by mass to 10.0 parts by mass with respect to 100 parts by mass of the toner particles. The toner particles and the external additive can be mixed using a known mixer such as a Henschel mixer.

[0095] <Developer> The toner can be used as a one-component developer, but in order to further improve dot reproducibility and provide stable images over a long period of time, it is preferable to use the toner as a two-component developer by mixing it with a magnetic carrier.

[0096] The toner is preferably a toner for use in a two-component developer. The two-component developer contains a toner and a magnetic carrier, and the toner is preferably the toner described above.

[0097] Examples of magnetic carriers that can be used include commonly known magnetic carriers 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) that contain a magnetic material and a binder resin that holds the magnetic material in a dispersed state.

[0098] 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.

[0099] <Method of manufacturing toner particles> The method for producing the toner particles is not particularly limited, and known methods such as a pulverization method, a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, and a dispersion polymerization method can be used. Among them, the pulverization method is preferred from the viewpoint of controlling the wax on the toner surface. In other words, the toner particles are preferably pulverized toner particles. The procedure for producing the toner using the pulverization method will be described below. The pulverization method includes, for example, a raw material mixing step of mixing a crystalline polyester C and an amorphous resin A as a binder resin, and, if necessary, other components such as a wax, a colorant, a charge control agent, etc., 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.

[0100] In the raw material mixing process, materials constituting the toner particles, such as binder resin, wax, and other components such as colorants and charge control agents as necessary, 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.).

[0101] Next, the mixed materials are melt-kneaded to disperse the materials in the binder resin. In the melt-kneading process, a batch-type kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used, and single-screw or twin-screw extruders are mainstream due to their advantage of allowing continuous production. Examples include a KTK type twin-screw extruder (manufactured by Kobe Steel, Ltd.), a TEM type twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikegai Iron Works Co., Ltd.), a twin-screw extruder (manufactured by KCK Corporation), a Co-kneader (manufactured by Buss Co., Ltd.), and Kneadex (manufactured by Nippon Coke and Engineering Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading is rolled with two rolls or the like and passed through a cooling process. The mixture may be cooled with water or the like at this stage.

[0102] The cooled resin composition is then pulverized to a desired particle size in a pulverization process. In the pulverization process, the resin composition is coarsely pulverized using a pulverizer such as a crusher, a hammer mill, or a feather mill. The resin composition is then finely pulverized using a pulverizer such as a Cryptron System (Kawasaki Heavy Industries), a Super Rotor (Nisshin Engineering), a Turbo Mill (Turbo Kogyo), or an air jet type pulverizer.

[0103] 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).

[0104] Thereafter, an external additive such as silica fine particles is added to the surface of the toner particles as necessary to obtain a toner. Methods for adding external additives include blending the classified toner with a predetermined amount of various known external additives, and stirring and mixing the blend using a mixer 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 & Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation) as an external additive machine.

[0105] The methods for measuring various physical properties are described below. (Method of separating each material from toner) By utilizing the difference in solubility of each material contained in the toner in a solvent, each material can be separated from the toner. The following various physical properties can be measured using each separated material. First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23°C, and the soluble matter (amorphous resin A, crystalline polyester C) is separated from the insoluble matter (wax, colorant, inorganic fine particles, etc.). Second separation: The soluble fraction (amorphous resin A, crystalline polyester C) obtained in the first separation is dissolved in tetrahydrofuran (THF) at 23°C, and the soluble fraction (amorphous resin A) and the insoluble fraction (crystalline polyester C) are separated. Third separation: The insoluble matter (wax, colorant, inorganic fine particles, etc.) obtained in the first separation is dissolved in MEK at 100°C, and the soluble matter (wax) is separated from the insoluble matter (colorant, inorganic fine particles, etc.).

[0106] <Method of determining the identity and content of monomer units of various polymerizable monomers in amorphous resin A and crystalline polyester C> The assignment and content ratio of monomer units of various polymerizable monomers in amorphous resin A and crystalline polyester C were measured. 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: 5.0μs Frequency range: 10500Hz Number of times: 64 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 this is dissolved in a constant temperature bath at 40°C to prepare the sample.

[0107] Obtained 1 The integral value S of the peaks attributable to the components of the monomer units of various polymerizable monomers in the H-NMR chart 1、 S 2、 S3, S n Calculate. The content ratio of the monomer units of various polymerizable monomers is the above integral values ​​S1, S2, S3 and S n Using the above, it is calculated as follows. Note that n1, n 2、 n3···n n is the number of hydrogens in the component to which the peak of interest for each site is assigned. Content ratio of monomer units of various polymerizable monomers (mol%)= {(S n / n n ) / ((S1 / n1)+(S2 / n2)+(S3 / n3)...+(S n / n n ))}×100

[0108] The amount of the monomer unit of each polymerizable monomer is calculated by changing the molecular term of 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 Measure nuclei using C-NMR 13Let it be C, and measurement is carried out in single - pulse mode, 1 It is calculated in the same way by

[0109] <SPA value, SPA1 value, SPA2 value of amorphous resin A, amorphous polyester segment A1, amorphous polyester segment A2, SP value of monomer unit by each polymerizable monomer of amorphous resin A, SPC value of crystalline polyester C, method for calculating SP value of monomer unit by each polymerizable monomer of crystalline polyester C> The SP value is obtained as follows according to the calculation method proposed by Fedors.

[0110] For the monomer unit by each polymerizable monomer, for the atoms or atomic groups in the molecular structure, the evaporation energy (Δei) (cal / mol) and molar volume (Δvi) (cm 3 / mol) are obtained from the table described in "Polym.Eng.Sci., 14(2), 147 - 154(1974)", and (ΣΔei / ΣΔvi) 0.5 is taken as the SP value (cal / cm 3 ) 0.5 Let it be. The unit of the SP value is 1 (cal / cm 3 ) 0.5 = 2.045 (J / cm 3 ) 0.5 and can be converted by this.

[0111] SPA, SPA1, SPA2, and SPC are calculated as follows. First, the evaporation energy (Δei) and molar volume (Δvi) of the monomer unit by the constituent polymerizable monomers are obtained for each monomer unit, and the product with the molar ratio (j) of each monomer unit in each resin is calculated respectively. Then, by substituting the sum of the evaporation energies and the sum of the molar volumes of each monomer unit into the following formula, the respective SP values are calculated. SP value = {(Σj×ΣΔei) / (Σj×ΣΔvi)} 0.5

[0112] <Measurement of weight - average molecular weight MwC of crystalline polyester C by GPC> The weight average molecular weight (Mw) of the toluene-soluble portion at 100° C. of the crystalline polyester C is measured by gel permeation chromatography (GPC) as follows. First, crystalline polyester C is dissolved in toluene at 100°C for 1 hour. The resulting solution is then filtered through a solvent-resistant membrane filter "Maeshori Disc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in toluene is about 0.1% by mass. This sample solution is used to perform measurements under the following conditions. Equipment: HLC-8121GPC / HT (Tosoh Corporation) Column: TSKgel GMHHR-H HT (7.8 cm ID x 30 cm) 2-unit (Tosoh Corporation) Detector: High temperature RI Temperature: 135℃ Solvent: Toluene Flow rate: 1.0mL / min Sample: 0.4mL of 0.1% sample injected The molecular weight of the sample was calculated using a molecular weight calibration method prepared using a monodisperse polystyrene standard sample. The viscosity is calculated by converting the viscosity to polyethylene using a conversion formula derived from the Mark-Houwink viscosity formula.

[0113] <Measurement of melting peak temperature (melting point) Tc (℃) of crystalline polyester C, etc.> The melting point (Tc) of crystalline polyester C was measured using a differential scanning calorimeter "Q2000" (TA The measurement is performed using a JIS K 12210 Instruments in accordance with ASTM D3418-82. The melting points of indium and zinc are used for temperature correction of the device detection unit, and the heat of fusion of indium is used for heat correction. Specifically, 3 mg of sample is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the measurement is performed under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 30℃ End of measurement temperature: 180℃ Measure from a measurement range of 30 to 180 °C at a heating rate of 10 °C / min. First, heat up to 180 °C and hold for 10 minutes, then cool down to 30 °C, and then heat up again. In this second heating process, the temperature at the maximum endothermic peak of the temperature-endothermic quantity curve in the range of 30 to 100 °C is defined as the melting point.

[0114] <Measurement of the weight-average molecular weights MwA, MwA1, MwA2, and MwAP of amorphous resin A, amorphous polyester segment A1, amorphous polyester segment A2, and polyester unit by GPC> The weight-average molecular weight (Mw) of the THF-soluble component is measured by gel permeation chromatography (GPC) as follows. First, dissolve the toner in tetrahydrofuran (THF) over 24 hours at room temperature. Then, filter the resulting solution through a solvent-resistant membrane filter "Micron Disc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. Note that the concentration of the components soluble in THF in the sample solution is adjusted to 0.8 mass%. Measure under the following conditions using this sample solution.

[0115] Apparatus: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation) Column: Seven columns of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko K.K.) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 ml / min Oven temperature: 40.0 °C Sample injection volume: 0.10 mL When calculating the molecular weight of the sample, use the molecular weight calibration curve prepared using a standard polystyrene resin (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation).

[0116] <Measurement of the softening point TA of amorphous resin A> The softening point is measured using a constant load extrusion type capillary rheometer "Flow property evaluation device Flow Tester CFT-500D" (Shimadzu Corporation) according to the manual that comes with the device. With this device, a constant load is applied from above the measurement sample by a piston while the measurement sample filled in a cylinder is heated and melted, and the molten measurement sample is extruded from a die at the bottom of the cylinder, and a flow curve showing the relationship between the piston descent amount and temperature can be obtained. As stated in the manual that comes with the "Flow characteristic evaluation device Flow Tester CFT-500D" The "melting temperature in the 1 / 2 method" is defined as the softening point. The melting temperature in the 1 / 2 method is calculated as follows. First, half the difference between the amount of piston descent (Smax) at the time when the outflow ends and the amount of piston descent (Smin) at the time when the outflow starts is calculated (this is called X; X=(Smax-Smin) / 2). Then, 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.

[0117] The measurement sample is prepared by compressing 1.0 g of resin at 10 MPa for 60 seconds using a tablet molding machine (e.g., NT-100H, manufactured by NPA Systems) in an environment of 25°C to form a cylindrical shape with a diameter of 8 mm. The specific operations for the measurement are performed according to the manual that comes with the device. The measurement conditions for the CFT-500D are as follows. Test mode: Temperature rise method Starting temperature: 50℃ Achieved temperature: 200℃ Measurement interval: 1.0℃ Heating rate: 4.0℃ / min Piston cross-sectional area: 1.000cm 2 Test load (piston load): 10.0kgf / cm 2 (0.9807MPa) Preheat time: 300 seconds Die hole diameter: 1.0mm Die length: 1.0mm

[0118] <Method for measuring the proportion Ws of THF-soluble content in amorphous resin A> The THF soluble fraction Ws is measured using a Soxhlet analyzer. A sample of 1 g of amorphous resin A is precisely weighed and placed in a cylindrical filter paper, and subjected to Soxhlet extraction with 200 ml of tetrahydrofuran (THF) for 20 hours. The cylindrical filter paper is then removed and vacuum dried at 40°C for 20 hours, and the mass of the residue is measured. The mass of the sample initially placed is W1 g, and the mass of the components in the extraction residue is W2 g. The proportion of THF soluble content of amorphous resin A, Ws, is calculated using the following formula. Ws (mass%)=(W1-W2) / W1×100 When the amorphous resin A is separated from the toner and measured, the MEK insoluble matter is added to W1 to obtain the value. EXAMPLES

[0119] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. In the following formulations, the parts are by weight unless otherwise specified.

[0120] <Production Example of Crystalline Polyester C1> Ethylene glycol: 9.0 parts (49.2 mol%) Tetradecanedioic acid: 81.0 parts (48.5 mol%) Behenic acid: 10.0 parts (2.3 mol%) Titanium tetrabutoxide (esterification catalyst): 0.5 parts The above materials were weighed and placed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet tube, and a thermocouple. Next, the atmosphere in the flask was replaced with nitrogen gas, and the temperature was gradually raised with stirring, and the reaction was carried out for 2 hours at a temperature of 200°C with stirring. The pressure in the reaction vessel was then lowered to 8.3 kPa, and the reaction was continued for 5 hours while maintaining the temperature at 200° C. The temperature was then lowered to stop the reaction, yielding crystalline polyester C1, which had a weight average molecular weight Mw of 18,000 and a melting point Tc of 92° C.

[0121] Crystalline polyester C1 was analyzed by NMR and found to contain 49.2 mol% of monomer units from ethylene glycol, 48.5 mol% of monomer units from tetradecanedioic acid, and 2.3 mol% of monomer units from behenic acid. The SP value (SPC) of crystalline polyester C1 was 20.0 (J / cm 3 ) 0.5 It was.

[0122] <Production Examples of Crystalline Polyester C2 to Crystalline Polyester C11> Crystalline polyesters C2 to C11 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 linear aliphatic polyhydric alcohol (c), polymerizable monomer, aliphatic monocarboxylic acid or aliphatic monoalcohol were changed as shown in Table 1. The physical properties of crystalline polyesters C2 to C11 are shown in Table 2. [Table 1] The abbreviations in Table 1 are as follows: ED: Ethylene glycol (carbon number 2) HD: Hexanediol (carbon number 6) OD: Octanediol (carbon number 8) TDA: tetradecanedioic acid BEA: Behenic acid (carbon number 22) PAA: Palmitic acid (carbon number 16) PEA: Pentanoic acid (carbon number 15) MOA: Montanic acid (carbon number 28) LAA: Russell acid (carbon number 32)

[0123] [Table 2] In the table, the unit of SP value such as SPC is (J / cm 3 ) 0.5 Mwc is the weight average molecular weight of crystalline polyester C. Tc is in °C.

[0124] <Production Example of Amorphous Polyester Segment A1-1> Ethylene glycol: 19.0 parts (50.1 mol%) Terephthalic acid: 81.0 parts (49.9 mol%) Titanium tetrabutoxide (esterification catalyst): 0.5 parts The above materials were weighed and placed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet tube, and a thermocouple. Next, the atmosphere in the flask was replaced with nitrogen gas, and the temperature was gradually raised with stirring, and the reaction was carried out for 2 hours at a temperature of 200°C with stirring. Furthermore, the pressure in the reaction tank was reduced to 8.3 kPa, and the reaction was carried out for 5 hours while maintaining the temperature at 200° C. After confirming that the weight average molecular weight reached 800, the temperature was reduced to stop the reaction, thereby obtaining amorphous polyester segment A1-1.

[0125] The amorphous polyester segment A1-1 was analyzed by NMR and found to contain 50.1 mol % of monomer units derived from ethylene glycol and 49.9 mol % of monomer units derived from terephthalic acid. The SP value of the amorphous polyester segment A1-1 was calculated by the above method, and the SP A1 is 22.6(J / cm 3 ) 0.5 It was.

[0126] <Production Examples of Amorphous Polyester Segment A1-2 to Amorphous Polyester Segment A1-5> Amorphous polyester segment A1-2 to amorphous polyester segment A1-5 were obtained by carrying out the reaction in the same manner as in the production example of amorphous polyester segment A1-1, except that the type and the number of parts of the linear aliphatic polyhydric alcohol polymerizable monomer were changed as shown in Table 3. The physical properties are shown in Table 3. [Table 3] The abbreviations in Table 3 are as follows: ED: Ethylene glycol (carbon number 2) HD: Hexanediol (carbon number 6) DD: Decanediol (carbon number 10) OD: Octanediol (carbon number 8) DDD: Dodecanediol (carbon number 12) TPA: Terephthalic acid SPA1-1 and SPA1-2 are the SP values ​​of the monomer units of each polymerizable monomer. MwA1 is the weight average molecular weight of the amorphous polyester segment A1.

[0127] <Production Example of Amorphous Polyester Segment A2-1> Propylene oxide adduct of bisphenol A (average number of moles added: 2.0 mol): 72.0 parts (49.9mol%) Terephthalic acid: 28.0 parts (50.1 mol%) Titanium tetrabutoxide (esterification catalyst): 0.5 parts The above materials were weighed and placed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet tube, and a thermocouple. Next, the atmosphere in the flask was replaced with nitrogen gas, and the temperature was gradually raised with stirring, and the reaction was carried out for 2 hours at a temperature of 200°C with stirring. Furthermore, the pressure in the reaction tank was reduced to 8.3 kPa, and the reaction was carried out for 5 hours while maintaining the temperature at 200° C. After confirming that the weight average molecular weight had reached 1,000, the temperature was reduced to stop the reaction, thereby obtaining amorphous polyester segment A2-1.

[0128] When the amorphous polyester segment A2-1 was analyzed by NMR, it was found to contain 49.9 mol % of monomer units due to a propylene oxide adduct of bisphenol A (average number of moles added: 2.0 mol) and 50.1 mol % of monomer units due to terephthalic acid. The SP value of the amorphous polyester segment A2-1 was calculated by the above method, and the SP A2 is 20.7(J / cm 3 ) 0.5 It was.

[0129] <Production Examples of Amorphous Polyester Segment A2-2 to Amorphous Polyester Segment A2-6> In the production example of the amorphous polyester segment A2-1, the reaction was carried out in the same manner as in the production example, except that the type and the number of parts of the linear aliphatic polyhydric alcohol polymerizable monomer were changed as shown in Table 4, to obtain the amorphous polyester segment A2-2 to the amorphous polyester segment A2-6. The physical properties are shown in Table 4. [Table 4] The abbreviations in Table 4 are as follows: PO2: Propylene oxide adduct of bisphenol A (average number of moles added: 2.0 mol) EO2: Ethylene oxide adduct of bisphenol A (average number of moles added: 2.0 mol) TPA: Terephthalic acid FA: Fumaric acid SA: Sebacic acid SPA2-1, SPA2-2, and SPA2-3 are the SP values ​​of the monomer units of each polymerizable monomer. MwA2 is the weight average molecular weight of the amorphous polyester segment A2.

[0130] <Production Example of Amorphous Resin A-1> Amorphous polyester segment A1-1: 8.0 parts (8.1 mol%) Amorphous polyester segment A2-1: 90.0 parts (73.0 mol%) Titanium tetrabutoxide (esterification catalyst): 0.5 parts The above materials were weighed and placed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet tube, and a thermocouple. Next, the atmosphere in the flask was replaced with nitrogen gas, and the temperature was gradually raised with stirring, and the reaction was carried out for 2 hours at a temperature of 200°C with stirring. The pressure in the reaction tank was then lowered to 8.3 kPa, and the reaction was continued for 5 hours while maintaining the temperature at 200° C. After confirming that the weight average molecular weight had reached 6000, the following materials were added. The reaction was continued for 2 hours, and after confirming that the softening point measured according to ASTM D36-86 had reached 106° C., the temperature was lowered to stop the reaction, and amorphous resin A1 was obtained. Methacrylic acid: 2.0 parts (18.9 mol%) t-Butyl peroxypivalate (NOF Corp.: Perbutyl PV): 0.5 parts The softening point TA of the obtained amorphous resin A1 was 106° C., the weight average molecular weight MwA of the amorphous resin A1 was 18,000, the weight average molecular weight MwAP of the polyester unit was 6,000, the proportion Ws of the THF soluble matter was 100.0 mass %, and SPA1-SPA2 was 1.9.

[0131] When the amorphous resin A1 was analyzed by NMR, it was found to contain 8.1 mol% of the amorphous polyester segment a1-1, 73.0 mol% of the amorphous polyester segment a2-1, and 18.9 mol% of the monomer unit of methacrylic acid. The SP value of the amorphous resin A-1 was calculated by the above method, and the SPA was 20.8 (J / cm 3 ) 0.5 It was.

[0132] <Production Examples of Amorphous Resin A-2 to Amorphous Resin A-7, Amorphous Resin A-9 to Amorphous Resin A-17, and Amorphous Resin A-27 to Amorphous Resin A-31> In the production example of amorphous resin A-1, the reaction was carried out in the same manner except that the types and parts of the amorphous polyester segment A1, the amorphous polyester segment A2, and the polymerizable monomer were changed as shown in Table 5, and amorphous resins A-2 to A-7, and amorphous resins A-9 to A-10 were obtained. Crystalline resin A-17, amorphous resin A-27 to amorphous resin A-31 were obtained. Their physical properties are shown in Table 6. Note that amorphous resin A29 using trimellitic acid is a resin that does not have a structure in which polyester is crosslinked with a vinyl polymer. [Table 5] The abbreviations in Table 5 are as follows: MA: methacrylic acid HA: Hexenoic acid OA: Octenoic acid ST: styrene TA: Trimellitic acid

[0133] [Table 6]

[0134] <Production Example of Amorphous Resin A-8> When the above amorphous resin A-1 was analyzed by NMR, it was found to contain 9.9 mol% of monomer units based on ethanediol, 46.1 mol% of monomer units based on a propylene oxide adduct of bisphenol A (average number of moles added: 2.0 mol), 39.4 mol% of monomer units based on terephthalic acid, and 4.6 mol% of monomer units based on methacrylic acid. Therefore, the aim of the amorphous resin A-8 is to create a random copolymer of amorphous resin A-1. Ethylene glycol: 1.4 parts (9.9 mol%) Propylene oxide adduct of bisphenol A (average number of moles added: 2.0 mol): 72.6 parts (46.1 mol%) Terephthalic acid: 24.0 parts (39.4 mol%) Titanium tetrabutoxide (esterification catalyst): 0.5 parts The above materials were weighed and placed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet tube, and a thermocouple. Next, the atmosphere in the flask was replaced with nitrogen gas, and the temperature was gradually raised with stirring, and the reaction was carried out for 2 hours at a temperature of 200°C with stirring.

[0135] Furthermore, the pressure in the reaction tank was reduced to 8.3 kPa, and the reaction was continued for 5 hours while maintaining the temperature at 200°C. After confirming that the weight average molecular weight reached 6000, the following materials were added and the reaction was continued for 2 hours. After confirming that the softening point, measured according to ASTM D36-86, reached 106°C, the temperature was reduced to stop the reaction, and amorphous resin A-8 was obtained. Methacrylic acid: 2.0 parts (4.6 mol%) t-Butyl peroxypivalate (NOF Corp.: Perbutyl PV): 0.5 parts The softening point TA of the obtained amorphous resin A8 was 106° C., the weight average molecular weight MwA of the amorphous resin A-8 was 18,000, the weight average molecular weight MwAP of the polyester unit was 6,000, and the proportion Ws of the THF soluble matter was 100.0 mass %.

[0136] When the amorphous resin A-8 was analyzed by NMR, it was found to contain 9.9 mol% of monomer units from ethylene glycol, 46.1 mol% of monomer units from a propylene oxide adduct of bisphenol A (average number of moles added: 2.0 mol), 39.4 mol% of monomer units from terephthalic acid, and 4.6 mol% of monomer units from methacrylic acid. The SP value of the amorphous resin A-8 was calculated by the above method, and the SP A is 20.8(J / cm 3 ) 0.5 It was.

[0137] <Production Examples of Amorphous Resin A-18 to Amorphous Resin A-26> In the production example of amorphous resin A-8, the reaction was carried out in the same manner as above except that the linear aliphatic polyhydric alcohol Ca and the type and number of polymerizable monomers were changed as shown in Table 7, to obtain amorphous resins A-18 to A-26. The physical properties are shown in Table 6. [Table 7] The abbreviations in Table 7 are as follows: ED: Ethylene glycol (carbon number 2) HD: Hexanediol (carbon number 6) DD: Decanediol (carbon number 10) PO2: Propylene oxide adduct of bisphenol A (average number of moles added: 2.0 mol) TPA: Terephthalic acid FA: Fumaric acid MA: methacrylic acid ST: styrene

[0138] <Toner 1 Manufacturing Example> Amorphous resin A-1: ​​75 parts Crystalline polyester C1: 10 parts Fischer-Tropsch wax (maximum endothermic peak temperature 100℃): 5 parts Carbon black: 5 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 a rotation time of 5 minutes, and then kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Co., Ltd.) set at a temperature of 130°C. The kneaded product obtained was cooled and coarsely crushed to 1 mm or less using a hammer mill to obtain a coarsely crushed product. The obtained coarsely crushed product was then transferred to a mechanical crusher (T-2 The mixture was finely pulverized using a Turbo Kogyo Co., Ltd. (F-50). Classification was then carried out using a Faculty (F-300, Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions were a classifying rotor rotation speed of 11,000 rpm and a dispersing rotor rotation speed of 7,200 rpm.

[0139] Toner particles 1:95 parts Large-diameter inorganic particles: 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, 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.

[0140] <Production Examples of Toner 2 to Toner 48> Toners 2 to 48 were obtained in the same manner as in Production Example of Toner 1, except that the types of amorphous resin A and crystalline polyester C in Production Example of Toner 1 were changed as shown in Table 8. The obtained physical properties are shown in Table 8. The amorphous resin A and the crystalline polyester C were separated from each of the obtained toners by the above-mentioned procedure, and MwA, Tc, and Ws were measured. The same results as those in Tables 2 and 6 were obtained. [Table 8]

[0141] <Magnetic Carrier 1 Manufacturing Example> Number average particle size: 0.30μm, magnetization strength under a magnetic field of (1000 / 4π(kA / m): 65Am 2 / kg) of magnetite 1 Number average particle size: 0.50μm, magnetization strength under a magnetic field of (1000 / 4π(kA / m): 65Am 2 / kg) of magnetite 2 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.

[0142] Phenol: 10% by weight Formaldehyde solution: 6% by weight (Formaldehyde 40% by mass, methanol 10% by mass, water 50% by mass) Magnetite treated with the above silane compound 1: 58% by mass Magnetite 2 treated with the above silane compound: 26% by mass 100 parts of the above material, 5 parts of 28% by mass ammonia aqueous solution, and 20 parts of water were placed in a flask, and the temperature was raised to 85°C in 30 minutes while stirring and mixing, and the mixture was held for 3 hours to polymerize and harden the resulting phenolic resin. The hardened phenolic resin was then cooled to 30°C, and water was added, after which the supernatant liquid was removed, and the precipitate was washed with water and then air-dried. This was then dried at a temperature of 60°C under reduced pressure (5 mmHg or less) to obtain a spherical magnetic carrier 1 with magnetic material dispersion. The 50% particle size (D50) based on volume was 34.21 μm.

[0143] <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 Enterprise Co., Ltd.) to obtain two-component developer 1.

[0144] <Production Examples of Two-Component Developer 2 to Two-Component Developer 48> In the production example of two-component developer 1, the same operation was carried out except for the changes shown in Table 8, to obtain two-component developer 2 to two-component developer 48.

[0145] <Example 1> The above two-component developer 1 was used for evaluation. The image forming apparatus used was a modified Canon imageRUNNER ADVANCE C5560 digital commercial printer, and two-component developer 1 was placed in the cyan developer. The modifications to the apparatus included the fixing temperature, process speed, and DC voltage V of the developer carrier. DC , the charging voltage of the electrostatic latent image carrier V D The laser power and the laser power can be freely set. The image output evaluation is performed by outputting a FFh image (solid image) with the desired image ratio, and adjusting the V so that the amount of toner on the FFh image on the paper is as desired. DC , V D The evaluation described below was performed by adjusting the laser power and the color level. FFh is a value obtained by expressing 256 gradations in hexadecimal, with 00h being the first gradation (white background) of the 256 gradations and FFh being the 256th gradation (solid background) of the 256 gradations. Evaluation was performed based on the following evaluation method, and the results are shown in Table 9.

[0146] [Abrasion resistance] Paper: OK Topcoat Matte N (128.0 g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner load on paper: 0.05mg / cm 2 (2Fh image) (The DC voltage of the developer carrier V DC , the charging voltage of the electrostatic latent image carrier V D , and adjusted by laser power) Evaluation image: 3m x 15cm image placed in the center of the A4 paper. Fixing test environment: Normal temperature and humidity environment (temperature 23°C / humidity 50% RH (hereinafter N / N)) Fixing temperature: 180℃ Process speed: 377mm / sec The above evaluation image was printed out and the abrasion resistance was evaluated. The difference in reflectance was used as the evaluation index for the abrasion resistance. First, the image portion of the evaluation image was rubbed (10 times back and forth) with a new evaluation paper under a load of 0.5 kgf using a Gakushin type abrasion fastness tester (AB-301: manufactured by Tester Sangyo Co., Ltd.). Then, the image portion was rubbed (10 times back and forth) with a new evaluation paper using a reflectometer (REFLECTOMETER MODEL Using a test strip (TC-6DS: manufactured by Tokyo Denshoku Co., Ltd.), the reflectance of the part that has been rubbed with a new evaluation paper and the reflectance of the part that has not been rubbed are measured. The difference in reflectance before and after rubbing was calculated using the following formula. The resulting difference in reflectance was evaluated according to the following evaluation criteria. If the evaluation was A to C, it was determined to be good. Reflectance difference = reflectance before friction - reflectance after friction (Evaluation Criteria) A: Less than 1.0% B: 1.0% or more and less than 2.0% C: 2.0% or more and less than 4.0% D: 4.0% or more

[0147] [Low temperature fixability] Paper: GFC-081 (81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner load on paper: 0.50mg / cm 2 (The DC voltage of the developer carrier V DC , the charging voltage of the electrostatic latent image carrier V 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 low humidity environment: Temperature 15℃ / Humidity 10%RH (hereinafter referred to as "L / L") Fixing temperature: 150℃ Process speed: 377mm / sec The above evaluation image was output, and the low-temperature fixing property was evaluated. The value of the decrease rate of image density was used as an evaluation index for the low-temperature fixing property. First, the image density at the center was measured using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). Next, the area where the image density was measured was subjected to a pressure of 4.9 kPa (50 g / cm 2 The fixed image was rubbed (five times back and forth) with Silbon paper under a load of 1000 g / m2, and the image density was measured again. The rate of decrease in image density before and after rubbing was calculated using the following formula. The rate of decrease in image density obtained was evaluated according to the following evaluation criteria. If the evaluation was A to C, it was judged to be good. Image density reduction rate (%) = (Image density before rubbing - Image density after rubbing) / Image density before rubbing x 100 (Evaluation Criteria) A: Image density reduction rate is 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 of 8% or more

[0148] <Examples 2 to 40 and Comparative Examples 1 to 8> The evaluation was carried out in the same manner as in Example 1, except that two-component developer 2 to two-component developer 48 were used. The evaluation results are shown in Table 9.

[0149] [Table 9]

[0150] The present disclosure relates to the following configurations. (Configuration 1) A toner having toner particles containing a binder resin, The binder resin contains an amorphous resin A and a crystalline polyester C, The crystalline polyester C has a structure corresponding to the linear aliphatic polyhydric alcohol (c) as a structure forming a polyester, When the number of carbon atoms of the linear aliphatic polyhydric alcohol (c) is Cc, Cc satisfies the following formula (1): 2≦Cc≦6 (1) The amorphous resin A has a structure corresponding to the linear aliphatic polyhydric alcohol (a) as a structure forming a polyester, When the number of carbon atoms of the linear aliphatic polyhydric alcohol (a) is Ca, the Ca satisfies the following formula (2): 2≦Ca≦10 (2) The Ca and the Cc satisfy the following formula (3), 0≦│Ca-Cc│≦4 (3) The amorphous resin A has a structure in which a polyester is crosslinked with a vinyl polymer, When the weight average molecular weight measured from the tetrahydrofuran soluble portion of the amorphous resin A is defined as MwA, the MwA satisfies the following formula (4), 10000≦MwA≦100000 (4) The toner is characterized in that, when the melting point of the crystalline polyester C is Tc, the Tc satisfies the following formula (5): 90℃≦Tc≦100℃ (5) (Configuration 2) The toner according to Configuration 1, wherein the crystalline polyester C satisfies one or both of the following (A) and (B): (A) The crystalline polyester C has a structure in which an aliphatic monocarboxylic acid having 15 to 31 carbon atoms is condensed with a hydroxy group at the end of the main chain. (B) The crystalline polyester C has a structure in which an aliphatic monoalcohol having 15 to 30 carbon atoms is condensed with a carboxy group at the end of the main chain. (Configuration 3) The toner according to configuration 1 or 2, wherein the vinyl polymer has a structure corresponding to (meth)acrylic acid as a structure forming the vinyl polymer. (Configuration 4) When the weight average molecular weight measured from the tetrahydrofuran soluble portion of the polyester in the amorphous resin A is defined as MwAP, The toner according to any one of configurations 1 to 3, wherein the MwAP satisfies the following formula (6): 3000≦MwAP≦8000 (6) (Configuration 5) the polyester in the amorphous resin A is a block copolymer having an amorphous polyester segment A1 and an amorphous polyester segment A2, 5. The toner according to any one of Configurations 1 to 4, wherein only the amorphous polyester segment A1 has a structure corresponding to the linear aliphatic polyhydric alcohol (a). (Configuration 6) The SP value (J / cm 3 ) 0.5 is taken as SPA1, and the SP value (J / cm) of the amorphous polyester segment A2 is taken as 3 ) 0.5 When SPA2 is used, The toner according to configuration 5, wherein the SPA1 and the SPA2 satisfy the following formula (7): 0.8≦SPA1―SPA2≦2.5 (7) (Configuration 7) The amorphous resin A is a main component of the binder resin, The toner according to any one of configurations 1 to 6, wherein when a ratio of a tetrahydrofuran soluble portion of the amorphous resin A based on the mass of the amorphous resin A is defined as Ws (mass %), the Ws satisfies the following formula (8): 90.0≦Ws≦100.0 (8) (Configuration 8) The toner according to any one of configurations 1 to 7, wherein the vinyl polymer contains poly(meth)acrylic acid. (Configuration 9) The Ca is 2, The toner according to any one of configurations 1 to 8, wherein Cc is 2. (Configuration 10) A two-component developer, The two-component developer contains a toner and a magnetic carrier, A two-component developer, wherein the toner is the toner according to any one of configurations 1 to 9.

Claims

1. A toner having toner particles containing a binder resin, The binder resin contains amorphous resin A and crystalline polyester C, The crystalline polyester C has a structure corresponding to a linear aliphatic polyhydric alcohol (c) as the structure that forms the polyester, When the number of carbon atoms in the linear aliphatic polyhydric alcohol (c) is denoted as Cc, Cc satisfies the following formula (1), 2 ≤ Cc ≤ 6 ... (1) The amorphous resin A has a structure corresponding to a linear aliphatic polyhydric alcohol (a) as the structure that forms the polyester, When the number of carbon atoms in the linear aliphatic polyhydric alcohol (a) is Ca, Ca satisfies the following formula (2), 2 ≤ Ca ≤ 10 ... (2) Ca and Cc satisfy the following formula (3), 0 ≤ |Ca - Cc| ≤ 4 ... (3) The amorphous resin A has a structure in which polyester is crosslinked with a vinyl polymer. When the weight-average molecular weight measured from the tetrahydrofuran-soluble components of the amorphous resin A is denoted as MwA, if MwA satisfies the following formula (4), 10000 ≤ MwA ≤ 100000 ... (4) A toner characterized in that, when the melting point of the crystalline polyester C is denoted as Tc, Tc satisfies the following formula (5). 90°C ≤ Tc ≤ 100°C ... (5)

2. The toner according to claim 1, wherein the crystalline polyester C satisfies one or both of the following conditions (A) and (B). (A) The crystalline polyester C has a structure in which an aliphatic monocarboxylic acid having 15 to 31 carbon atoms is condensed to the hydroxyl group at the end of the main chain. (B) The crystalline polyester C has a structure in which an aliphatic monoalcohol having 15 to 30 carbon atoms is condensed to the carboxyl group at the end of the main chain.

3. The toner according to claim 1 or 2, wherein the vinyl polymer has a structure corresponding to (meth)acrylic acid as the structure that forms the vinyl polymer.

4. When the weight-average molecular weight measured from the tetrahydrofuran-soluble portion of the polyester in the amorphous resin A is denoted as MwAP, The toner according to claim 1 or 2, wherein the MwAP satisfies the following formula (6). 3000 ≤ MwAP ≤ 8000 ... (6)

5. The polyester in the amorphous resin A is a block copolymer having amorphous polyester segment A1 and amorphous polyester segment A2. The toner according to claim 1 or 2, wherein only the amorphous polyester segment A1 has a structure corresponding to the linear aliphatic polyhydric alcohol (a).

6. The SP value (J / cm²) of the amorphous polyester segment A1 ３ ) ０．５ Let SPA1 be the SP value (J / cm²) of the amorphous polyester segment A2. ３ ) ０．５ When we call this SPA2, The toner according to claim 5, wherein the SPA1 and SPA2 satisfy the following formula (7). 0.8 ≤ SPA1 - SPA2 ≤ 2.5 ... (7)

7. The amorphous resin A is the main component of the binder resin, The toner according to claim 1 or 2, wherein when Ws (mass%) is the proportion of tetrahydrofuran-soluble content in the amorphous resin A based on the mass of the amorphous resin A, Ws satisfies the following formula (8). 90.0 ≤ Ws ≤ 100.0 ... (8)

8. The toner according to claim 1 or 2, wherein the vinyl polymer comprises poly(meth)acrylic acid.

9. The aforementioned Ca is 2, The toner according to claim 1 or 2, wherein the Cc is 2.

10. A two-component developer, The two-component developer contains toner and a magnetic carrier, A two-component developer wherein the toner is the toner described in claim 1 or 2.

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