Toner

Abstract

To provide a toner that is excellent in charge rising properties and low temperature fixability, exhibits stable electrification characteristics even after continuous printing, and has stable electrification characteristics even after long-term storage, thereby always providing stable images.SOLUTION: A toner has toner particles containing a binder resin and wax. The binder resin contains a polyester resin. The wax contains hydrocarbon wax and ester wax. The ester wax contains at least one compound selected from the group consisting of a monoester compound and a diester compound. The polyester resin contains a polyester resin A containing a monomer unit corresponding to an isophthalic acid and a monomer unit corresponding to a dodecenylsuccinic acid in a specific amount. The value of the ratio of the content W1 of the hydrocarbon wax to the content W2 of the ester wax (W1 / W2) is 0.15-0.80.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a toner for developing an electrostatic charge image used in an image forming apparatus such as electrophotography and electrostatic printing.

Background Art

[0002] Typical devices using toner in electrophotography include laser printers and copiers. In recent years, in particular, in addition to stable image quality of laser printers, high productivity is required. To improve productivity, by achieving both excellent charge rising property and low-temperature fixing property, the speed until the initial printout can be improved, and stable image quality can be provided by maintaining the raised charge.

[0003] As a method for improving low-temperature fixing property, the melting viscosity is reduced by designing the glass transition temperature (Tg) of the toner binder resin to be low, reducing the molecular weight of the toner binder resin, etc., and the plasticizing effect of a crystalline material compatible with the toner binder resin. However, these methods have a problem that the change in chargeability after long-term storage is large due to the relaxation phenomenon occurring in the toner binder resin itself or between the toner binder resin and the compatible material.

[0004] Patent Document 1 describes that by using isophthalic acid or dodecenyl succinic acid to improve the compatibility with a crystalline material, the low-temperature fixing property and the glossiness of the image are improved, and further, the heat-resistant storage property is improved by taking a core-shell structure. Also, in Patent Document 2, a hydrocarbon wax having a specific acid value and hydroxyl value is reacted in a polyester resin structure. Thereby, the dispersion state of the wax in the aggregated toner is controlled, and the compatibility and separability between the polyester resin and the wax at the time of fixing are improved, so that the low-temperature fixing property and the hot offset resistance are improved. Furthermore, Patent Document 3 describes that by using a polyester having a furan ring skeleton, the compatibility with an ester wax is improved, and the heat-resistant storage property and the low-temperature fixing property are improved.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, the above - mentioned documents have problems in order to achieve further high - speed operation and stable image quality. For example, in Patent Document 1, in order to enhance the shielding property by the core - shell structure, it is necessary to design a shell layer with a high solubility parameter (SP value). Therefore, the compatibility between the shell material and crystalline materials such as wax decreases. In order to cope with further high - speed operation, the low - temperature fixing property may not be sufficient. Furthermore, by arranging a polyester resin with a high solubility parameter (SP value) on the toner particle surface, image defects may occur due to the continuous increase in toner charge when continuous printing is carried out.

[0007] In Patent Document 2, it is possible to achieve both the improvement of the dispersion state of wax and the compatibility and separability of the added wax. However, due to the improvement of compatibility, there are many compatible components of wax that were not crystallized after toner production. Therefore, when the toner is stored for a long time, the compatible components of wax migrate to the toner surface, resulting in a significant decrease in chargeability.

[0008] In Patent Document 3, by changing the composition of the polyester, the heat-resistant storage property and the compatibility between the polyester resin and the wax have been improved. However, although the influence under a high-temperature environment could be reduced, as in Patent Document 2, when stored for a long period, the compatibility component of the wax migrates to the toner surface, resulting in a significant decrease in the chargeability.

[0009] The present disclosure relates to a toner having toner particles containing a binder resin and a wax, which is excellent in charge rising property and low-temperature fixing property, exhibits stable chargeability even during continuous printing, and further has stable chargeability even when stored for a long period, thereby always providing a stable image.

Means for Solving the Problems

[0010] The present disclosure is a toner having toner particles containing a binder resin and a wax, the binder resin contains a polyester resin, the wax contains a hydrocarbon wax and an ester wax, the ester wax contains at least one compound selected from the group consisting of a monoester compound and a diester compound, the polyester resin contains a polyester resin A having a monomer unit corresponding to isophthalic acid and a monomer unit corresponding to dodecenyl succinic acid, the content of the monomer unit corresponding to isophthalic acid in the polyester resin A is 15.0 to 30.0% by mass, the content of the monomer unit corresponding to dodecenyl succinic acid in the polyester resin A is 3.0 to 20.0% by mass, Regarding a toner, the value W1 / W2 of the ratio of the content W1 of the hydrocarbon wax to 100 parts by mass of the binder resin to the content W2 of the ester wax to 100 parts by mass of the binder resin is 0.15 to 0.80.

Advantages of the Invention

[0011] According to the present disclosure, there is provided a toner that has excellent charging rise property and low-temperature fixing property, exhibits stable charging property even during continuous printing, and has stable charging property even after long-term storage, thereby always providing stable image quality.

Brief Description of the Drawings

[0012]

Figure 1

Embodiments for Carrying Out the Invention

[0013] 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 limit and the upper limit which are the endpoints, unless otherwise specified. When numerical ranges are described stepwise, the upper limit and the lower limit of each numerical range can be arbitrarily combined. Also, in the present disclosure, a description such as "at least one selected from the group consisting of XX, YY, and ZZ" means any one of XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY, and ZZ.

[0014] The inventors of the present invention have intensively studied the compatibility of wax with polyester resin and the crystallization of wax in order to obtain a toner having excellent low-temperature fixing property and image stability. In particular, it has been found that by controlling the content of monomer units corresponding to specific acids used in the polyester resin and the content ratio of hydrocarbon wax and specific ester wax, the above-described problems of low-temperature fixing property and stable charging property can be solved.

[0015] That is, the present disclosure is a toner having toner particles containing a binder resin and wax, the binder resin contains a polyester resin, the wax contains a hydrocarbon wax and an ester wax, The ester wax contains at least one compound selected from the group consisting of a monoester compound and a diester compound. The polyester resin contains a polyester resin A having a monomer unit corresponding to isophthalic acid and a monomer unit corresponding to dodecenyl succinic acid. The content of the monomer unit corresponding to isophthalic acid in the polyester resin A is 15.0 to 30.0% by mass. The content of the monomer unit corresponding to dodecenyl succinic acid in the polyester resin A is 3.0 to 20.0% by mass. Regarding the toner, the value W1 / W2 of the ratio of the content W1 of the hydrocarbon wax to 100 parts by mass of the binder resin to the content W2 of the ester wax to 100 parts by mass of the binder resin is 0.15 to 0.80.

[0016] In the toner of the present disclosure, the binder resin includes a polyester resin A which is a polyester resin containing a monomer unit corresponding to isophthalic acid and a monomer unit corresponding to dodecenyl succinic acid. The polyester resin A improves the compatibility between the wax and the binder resin. The monomer unit corresponding to isophthalic acid contains an aromatic group and greatly contributes to maintaining the chargeability. A monomer unit corresponding to terephthalic acid having a similar structure can also obtain the effect of maintaining the chargeability.

[0017] However, due to the linear molecular structure of terephthalic acid, compared with a polyester resin having a monomer unit corresponding to isophthalic acid, it is considered that the molecular mobility is inferior and the compatibility with other molecules is poor. Therefore, the compatibility with an ester wax or the like is insufficient, and the low-temperature fixability may be insufficient. On the other hand, the monomer unit corresponding to dodecenyl succinic acid has a low polarity structurally due to being derived from an alkyl chain, and has an effect of enhancing the compatibility with a low-polarity material such as an ester wax. In particular, the alkyl chain of dodecenyl succinic acid can exhibit higher compatibility by existing as a side chain in the polyester resin.

[0018] For these reasons, the polyester resin A according to the present disclosure is a polyester resin that combines the chargeability resulting from excellent charge retention and high compatibility. However, the inventors recognized that it is difficult to obtain a toner having stable chargeability even after long-term storage with only the above-described design. Specifically, the state of existence of the wax may not be stable. Therefore, the inventors attempted to improve the charge stability after long-term storage by using, in combination with an ester wax having excellent compatibility with the polyester resin A, a hydrocarbon wax having excellent crystallinity.

[0019] As a result, the inventors, after controlling the content of the above monomer units, used, as the wax, a hydrocarbon wax and an ester wax selected from the group consisting of a monoester compound and a diester compound in combination, and by controlling the content ratio of these waxes, found that in addition to excellent low-temperature fixability, extremely stable charge characteristics can be obtained even during long-term storage.

[0020] The inventors presume that this effect is manifested by the following mechanism. A polyester resin having a monomer unit corresponding to isophthalic acid has excellent chargeability and also excellent molecular mobility. Therefore, when the polyester resin A and the wax are in a compatible state, wax molecules are likely to approach the polyester resin A and strong interactions are manifested.

[0021] On the other hand, the monomer unit corresponding to dodecenyl succinic acid has a long-chain alkyl group, so it is likely to interact with the hydrocarbon wax, and the formation of nuclei due to the crystallization of the hydrocarbon wax is likely to occur. Furthermore, the crystallization of the ester wax is promoted by the nuclei formed by the crystallization of the hydrocarbon wax, and the crystallization proceeds. From the above mechanism, it is presumed that the crystallization of the wax from a highly compatible state occurs rapidly, and immediately after toner production, there is little compatible component of the wax with the polyester resin A, and the state of existence of the wax is stable even after long-term storage, so that no change in chargeability occurs.

[0022] Therefore, the content of the monomer unit corresponding to isophthalic acid in the polyester resin A (hereinafter also referred to as the isophthalic acid unit) needs to be 15.0 to 30.0% by mass. When the content of the isophthalic acid unit is less than 15.0% by mass, the molecular mobility of the polyester resin A is insufficient, the interaction with the wax component is insufficient, and the crystallization rate is not sufficient, so the chargeability after long-term storage changes. On the other hand, when the content of the isophthalic acid unit exceeds 30.0% by mass, although it has excellent molecular mobility, the compatibility with the wax increases, so a component that cannot crystallize is formed in the ester wax, which will impair the chargeability after long-term storage.

[0023] Therefore, the content of the isophthalic acid unit in the polyester resin A needs to be 15.0 to 30.0% by mass, preferably 18.0 to 28.0% by mass, more preferably 20.0 to 25.0% by mass. If it is within the above range, it has excellent compatibility with the ester wax, excellent low-temperature fixing property, and furthermore, nuclei are easily generated by the crystallization of the hydrocarbon wax, so a toner with little charge change after long-term storage can be obtained. The content of the isophthalic acid unit in the polyester resin A can be controlled by the addition amount of isophthalic acid, which is a polyvalent carboxylic acid component used when obtaining the polyester resin.

[0024] In addition, the content of the monomer unit corresponding to dodecenyl succinic acid in the polyester resin A (hereinafter also referred to as the dodecenyl succinic acid unit) needs to be 3.0 to 20.0% by mass. When the content of the dodecenyl succinic acid unit is less than 3.0% by mass, the compatibility with the ester wax is insufficient, so sufficient low-temperature fixing property cannot be obtained. On the other hand, when the dodecenyl succinic acid unit is more than 20.0% by mass, it is considered that the compatibility between the polyester resin A and the wax is too high, and crystallization does not proceed, so the chargeability after long-term storage changes.

[0025] Therefore, the content of dodecenyl succinic acid units in the polyester resin A needs to be 3.0 to 20.0% by mass, preferably 5.0 to 18.0% by mass, and more preferably 7.0 to 15.0% by mass. The content of dodecenyl succinic acid units in the polyester resin A can be controlled by the addition amount of dodecenyl succinic acid, which is a polyvalent carboxylic acid component used when obtaining the polyester resin.

[0026] In addition, the monomer unit corresponding to isophthalic acid in the polyester resin A has a structure in which isophthalic acid forms an ester bond, and is represented by, for example, the following formula (I). The monomer unit corresponding to dodecenyl succinic acid in the polyester resin A has a structure in which dodecenyl succinic acid forms an ester bond, and is represented by, for example, the following formula (D).

Chemical formula

[0027] Furthermore, the value W1 / W2 of the content W1 of hydrocarbon wax with respect to 100 parts by mass of the binder resin to the content W2 of ester wax with respect to 100 parts by mass of the binder resin needs to be 0.15 to 0.80. When W1 / W2 is less than 0.15, there is little hydrocarbon wax that serves as the nucleus of wax crystals, so the crystallization of ester wax cannot be promoted, and the chargeability will still change significantly after long-term storage.

[0028] On the other hand, when W1 / W2 is too large (more than 0.80), the ratio of hydrocarbon wax is too high, so the crystallization of hydrocarbon wax alone is likely to occur, which inhibits the interaction of hydrocarbon wax with dodecenyl succinic acid units, and only ester wax interacts with dodecenyl succinic acid units. Therefore, the ester wax is likely to maintain a compatible state with the polyester resin A, and the crystallization of the ester wax is difficult to proceed, so the change in chargeability after long-term storage cannot be suppressed.

[0029] Therefore, the ratio value W1 / W2 needs to be 0.15 to 0.80, preferably 0.20 to 0.70, and more preferably 0.25 to 0.55.

[0030] Next, the molecular weight of the ester wax is preferably 500 to 1000, and more preferably 600 to 900. This is because waxes with a molecular weight in the above range are excellent in compatibility with the polyester resin A and the crystallization rate from the compatible state.

[0031] In the present disclosure, the molecular weight of the ester wax is a value calculated from the structure of the ester wax. Also, in the case of an ester wax derived from a natural product or a synthetic wax using a monomer derived from a natural product or a polymer in the monomer component, when having a molecular weight distribution, the peak molecular weight of the molecular weight distribution obtained by GPC analysis is defined as the molecular weight of the ester wax.

[0032] In addition, the content W1 of the hydrocarbon wax with respect to 100 parts by mass of the binder resin is, for example, 0.5 to 12.0 parts by mass, and preferably 0.5 to 7.0 parts by mass. If it is in the above range, the amount of nuclei formation of the hydrocarbon wax generated in the toner becomes more appropriate, and the crystallization of the ester wax can be further promoted. W1 is more preferably 1.0 to 5.0 parts by mass, and still more preferably 1.5 to 4.5 parts by mass.

[0033] Furthermore, the content W2 of the ester wax with respect to 100 parts by mass of the binder resin is, for example, 2.0 to 33.0 parts by mass, and preferably 3.0 to 20.0 parts by mass. If it is in the above range, it is excellent in compatibility with the polyester resin A and excellent in low-temperature fixability. In addition, if it is in the above range, the ester wax is likely to separate from the state of being compatible in the polyester resin A and the crystallization is further promoted. W2 is more preferably 5.0 to 17.5 parts by mass, and more preferably 7.5 to 15.0 parts by mass.

[0034] In addition, the binder resin may contain a resin other than the polyester resin A. In that case, based on the mass of the binder resin, the content ratio of the polyester resin A is preferably 50.0 to 100.0% by mass, more preferably 60.0 to 100.0% by mass, still more preferably 70.0 to 100.0% by mass, and even more preferably 85.0 to 100.0% by mass. Further, in addition to the polyester resin A, a polyester resin other than the polyester resin A may be used. The content ratio of the polyester resin A in the polyester resin is preferably 50.0 to 100.0% by mass, more preferably 75.0 to 100.0% by mass, still more preferably 80.0 to 100.0% by mass, and even more preferably 90.0 to 100.0% by mass. Within the above ranges, it is easier to obtain more excellent low-temperature fixability and chargeability.

[0035] In addition, the content ratio of the monomer unit corresponding to dodecenyl succinic acid based on the mass of the binder resin is, for example, 1.5 to 20.0% by mass, preferably 3.0 to 20.0% by mass, and more preferably 5.0 to 15.0% by mass. When within the above ranges, the chargeability after long-term storage is more stable. The content of the dodecenyl succinic acid unit can be controlled by adjusting the contents of the polyester resin A and other resins used in producing the toner particles.

[0036] The ester wax contains at least one compound selected from the group consisting of a monoester compound and a diester compound. The ester wax preferably contains a monoester compound, and the monoester compound includes a compound represented by the following formula (1). R 1 -COO-R 2 ···(1) (R 1 and R 2 each independently represents an alkyl group having 18 to 24 carbon atoms (preferably 18 to 22, more preferably 20 to 22).)

[0037] The ester wax having the structure of formula (1) is excellent in crystallization because of its sufficiently long alkyl chain length, and the proportion of ester groups is sufficient to be compatible with the polyester resin A. Further, due to the relatively small molecular weight of the ester wax structure, it also has excellent mobility in the binder resin, making it easy to interact with the crystal nucleus component derived from hydrocarbon wax.

[0038] In addition, the toner particles preferably contain a compound A which is at least one compound selected from the group consisting of the compound represented by the following formula (2) and the compound represented by formula (3). R 3 -O-(A 1 -O) n -X ···(2) (In formula (2), R 3 represents an alkyl group having 8 to 24 carbon atoms, A 1 represents an ethylene group (-CH2CH2-) or a propylene group (-CH(CH3)CH2-), n is an integer of 5 to 60, and X is H, CH2COOH, CH2SO3H, CH2COONa, or CH2SO3Na.) R 4 -Ph-O-(A 2 -O) m -X ···(3) (In formula (3), R 4 represents an alkyl group having 8 to 24 carbon atoms, Ph represents a phenylene group, A 2 represents an ethylene group or a propylene group, m is an integer of 5 to 60, and X is H, CH2COOH, CH2SO3H, CH2COONa, or CH2SO3Na .)

[0039] From the viewpoint of improving long-term storage stability, it is preferable to enhance the crystallinity of the hydrocarbon wax and the ester wax in the toner particles. When the crystallinity of the wax is enhanced, the charge amount is less likely to saturate when continuous printing is repeated, and the charge amount may change. Therefore, it is preferable that the toner particles contain the compound A. When the compound A is present, the charge stability when continuous printing is repeated is more excellent.

[0040] This is due to the improvement of the charge mobility within the toner particles, which is derived from the polyether structure of Compound A. If it has the structure of Formula (2) or (3), it has a high affinity with Polyester Resin A and preferably exhibits the interaction of the polyether moiety. Therefore, from the perspective of the affinity with Polyester Resin A, in Formula (2), R 3 is preferably an alkyl group having 8 to 24 carbon atoms, more preferably 10 to 18 carbon atoms. Further, in Formula (3), R 4 is preferably an alkyl group having 8 to 24 carbon atoms, more preferably 9 to 12 carbon atoms.

[0041] Furthermore, in order to obtain more excellent charge mobility within the toner particles, in Formula (2), n is preferably 5 to 60, more preferably 6 to 30, and even more preferably 8 to 20. Also, in Formula (3), m is preferably 5 to 60, more preferably 6 to 30, and even more preferably 8 to 20.

[0042] The extraction amount of Compound A extracted from the toner with ethanol, based on the mass of the toner, is, for example, 10 to 2000 ppm, preferably less than 10 to 1000 ppm. In the toner, charges are generated by triboelectrification on the surface of the toner particles. When the extraction amount of Compound A is within the above range, the generated charges become uniform on the surface of the toner particles, and excessive charges can be efficiently released. The above extraction amount is more preferably 30 to 500 ppm, and even more preferably 50 to 300 ppm.

[0043] The extraction amount of Compound A is adjusted according to the addition amount of Compound A added during the toner manufacturing process. The addition timing of Compound A may be during the toner particle manufacturing process or after the toner particle manufacturing. From the perspective of improving the interactivity with Polyester Resin A, it is preferably added during the toner particle manufacturing process, and from the perspective of uniformly existing on the surface of the toner particles, it is preferably added Compound A in an aqueous medium.

[0044] Furthermore, in the cross-sectional observation of toner using a transmission electron microscope, let As be the average ratio of the area occupied by the wax domain in the surface layer region from the surface of the toner particles to a depth of 200 nm. At this time, As is, for example, 0.0 to 5.0 area%, and preferably 0.0 to 1.0 area%. This indicates that when As is 0.0 to 1.0 area%, there is little wax near the surface of the toner particles.

[0045] In the present disclosure, by promoting the crystallization of the ester wax, the state of the wax after long-term storage is stabilized and the change in chargeability is suppressed, but it is difficult to completely crystallize the ester wax. In particular, since there may be a compatible component of the ester wax remaining around the wax domain, by setting As to 0.0 to 1.0 area%, the migration of the compatible component to the surface of the toner particles can be further suppressed. More preferably, As is 0.0 to 0.5 area%. As can be adjusted by controlling the amount of wax added and forming a core-shell structure on the toner particles and controlling the thickness of the shell layer.

[0046] The toner particles preferably contain boron atoms. When the content of boron atoms based on the mass of the toner particles is 1.0 to 100.0 mass ppm, the toner particles are more excellent in charge rising property and are more likely to obtain toner particles that are excellent in charge stability when stored for a long time. Since boron atoms have a large ionization potential and easily form covalent bonds, it is considered that they interact with a large number of ester groups of the polyester resin A. As a result, it is considered that boron atoms are likely to be dispersed in the polyester resin A containing boron atoms, and the charge retention of the toner is improved. Furthermore, it is considered that by forming a pseudo-crosslinked state through boron atoms due to the interaction between boron atoms and a large number of ester groups of the polyester resin A, the movement of the ester wax that could not be completely crystallized is suppressed, and toner with excellent long-term storage properties can be obtained.

[0047] The content of boron atoms based on the mass of toner particles is more preferably 1.0 to 30.0 ppm by mass, and even more preferably 3.0 to 15.0 ppm by mass. Boron atoms can be present in toner particles by adding a compound containing boron atoms during the toner particle manufacturing process, and the abundance can be adjusted by the addition amount of the compound containing boron atoms.

[0048] [Constituent components of toner] Each component constituting the toner and the manufacturing method of the toner will be described in more detail. [Binder resin] Toner particles contain a binder resin. The binder resin contains a polyester resin. The polyester resin contains a polyester resin A. The binder resin may contain resins other than the polyester resin as described above. The binder resin preferably contains 50% by mass or more of the polyester resin. The content ratio of the polyester resin in the binder resin is preferably 50.0 to 100.0% by mass, more preferably 70.0 to 100.0% by mass, even more preferably 80.0 to 100.0% by mass, and even more preferably 90.0 to 100.0% by mass. Within the above range, it is easier to obtain more excellent low-temperature fixability and chargeability. Examples of binder resins other than polyester resin A are as follows.

[0049] The binder resin is not particularly limited, and examples include styrene acrylic resin, polyester resin, epoxy resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, mixed resins and composite resins thereof. Styrene acrylic resin and polyester resin are preferred in terms of being inexpensive, easily available and having excellent low-temperature fixability.

[0050] Polyester resins such as polyester resin A are obtained by selecting suitable ones from polycarboxylic acids, polyols, hydroxycarboxylic acids, etc. and combining them, and synthesizing them using a conventionally known method such as the transesterification method or the polycondensation method.

[0051] A polyvalent carboxylic acid is a compound containing two or more carboxy groups in one molecule. Among these, a dicarboxylic acid is a compound containing two carboxy groups in one molecule and is preferably used.

[0052] Polyester resin A needs to contain 15.0 to 30.0% by mass of isophthalic acid units and 3.0 to 20.0% by mass of dodecenyl succinic acid units as polyvalent carboxylic acids. Further, as the content ratio of isophthalic acid units, it is preferably 40 mol% or more and 90 mol% or less, more preferably 50 mol% or more and 80 mol% or less in 100 mol% of the polyvalent carboxylic acid component of polyester resin A. Furthermore, as the content ratio of dodecenyl succinic acid units, it is preferably 5 mol% or more and 40 mol% or less, more preferably 10 mol% or more and 25 mol% or less in 100 mol% of the polyvalent carboxylic acid component of polyester resin A. Examples of polyvalent carboxylic acids other than the above-mentioned polyvalent carboxylic acids of polyester resin A are as follows.

[0053] Examples of dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, suberic acid, phthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, o-phenylenediacetic acid, diphenylacetic acid, diphenyl-p,p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracenedicarboxylic acid, cyclohexanedicarboxylic acid, and the like.

[0054] Examples of polycarboxylic acids other than dicarboxylic acids include trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, pyrenetetracarboxylic acid, itaconic acid, glutaconic acid, and the like. These may be used alone or in combination of two or more.

[0055] A polyol is a compound containing two or more hydroxyl groups in one molecule. Among these, a diol is a compound containing two hydroxyl groups in one molecule and is preferably used. Specifically, ethylene glycol, diethylene glycol, triethylene glycol, 1,2 - propylene glycol, 1,3 - propylene glycol, 1,4 - butanediol, 1,5 - pentanediol, 1,6 - hexanediol, 1,7 - heptanediol, 1,8 - octanediol, 1,9 - nonanediol, 1,10 - decanediol, 1,11 - undecanediol, 1,12 - dodecanediol, 1,13 - tridecanediol, 1,14 - tetradecanediol, 1,18 - octadecanediol, 1,14 - eicosanedecanediol, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, 1,4 - cyclohexanediol, 1,4 - cyclohexanedimethanol, 1,4 - butenediol, neopentyl glycol, 1,4 - cyclohexanediol, polytetramethylene glycol, hydrogenated bisphenol A, bisphenol A, bisphenol F, bisphenol S, alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols, and the like.

[0056] Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols. Particularly preferred are alkylene oxide adducts of bisphenols and the combination of these with alkylene glycols having 2 to 12 carbon atoms.

[0057] Examples of polyols having a valency of 3 or higher include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, hexamethylolmelamine, hexaethylolethyleneamine, tetramethylolbenzoguanamine, tetraethylolethyleneamine, sorbitol, trisphenol PA, phenol novolak, cresol novolak, and alkylene oxide adducts of the above polyhydric phenols. These may be used alone or in combination of two or more.

[0058] In addition to dodecenyl succinic acid and isophthalic acid, the polyvalent carboxylic acid may contain at least one selected from the group consisting of terephthalic acid, sebacic acid, and trimellitic acid, and preferably contains at least one selected from the group consisting of sebacic acid and trimellitic acid. The polyol preferably contains an alkylene oxide (ethylene oxide, propylene oxide) adduct of bisphenol A (for example, 1 to 10 mol, preferably 1 to 5 mol) and at least one selected from the group consisting of alkylene glycols having 2 to 6 carbon atoms. More preferably, it contains at least one selected from the group consisting of alkylene glycols having 2 to 6 carbon atoms.

[0059] The weight average molecular weight Mw of the polyester resin A is preferably 10,000 to 100,000, more preferably 20,000 to 50,000. The acid value of the polyester resin A is preferably 10.0 to 40.0 mgKOH / g, more preferably 15.0 to 25.0 mgKOH / g. The hydroxyl value of the polyester resin A is preferably 20.0 to 50.0 mgKOH / g, more preferably 25.0 to 35.0 mgKOH / g.

[0060] Examples of the styrene acrylic resin include a homopolymer composed of the following polymerizable monomers, a copolymer obtained by combining two or more of these, or a mixture thereof. Styrenic monomers such as styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene and p-phenylstyrene; (Meth)acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dimethyl phosphate ethyl (meth)acrylate, diethyl phosphate ethyl (meth)acrylate, dibutyl phosphate ethyl (meth)acrylate and 2-benzoyloxyethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid, maleic acid; Vinyl ether monomers such as vinyl methyl ether, vinyl isobutyl ether; Vinyl ketone monomers such as vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone; Polyolefins such as ethylene, propylene, butadiene.

[0061] Styrene acrylic resin can use a polyfunctional polymerizable monomer as needed. Examples of the polyfunctional polymerizable monomer include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2,2'-bis(4-((meth)acryloxydiethoxy)phenyl)propane, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

[0062] In addition, in order to control the degree of polymerization, it is also possible to further add a known chain transfer agent and polymerization inhibitor.

[0063] Examples of the polymerization initiator for obtaining styrene acrylic resin include organic peroxide initiators and azo polymerization initiators. Examples of the organic peroxide initiator include benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, bis(4-t-butylcyclohexyl) peroxydicarbonate, 1,1-bis(t-butylperoxy)cyclododecane, t-butyl peroxymaleic acid, bis(t-butylperoxy)isophthalate, methyl ethyl ketone peroxide, tert-butyl peroxy-2-ethylhexanoate, diisopropyl peroxydicarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and tert-butyl-peroxypivalate.

[0064] ​Examples of azo polymerization initiators include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobismethylbutyronitrile, 2,2'-azobis-(methyl isobutyrate), and the like.

[0065] In addition, as the polymerization initiator, a redox initiator obtained by combining an oxidizing substance and a reducing substance can also be used. Examples of the oxidizing substance include hydrogen peroxide, inorganic peroxides such as persulfates (sodium salt, potassium salt, and ammonium salt), and oxidizing metal salts of tetravalent cerium salts.

[0066] Examples of the reducing substance include reducing metal salts (divalent iron salts, monovalent copper salts, and trivalent chromium salts), ammonia, lower amines (amines having about 1 to 6 carbon atoms such as methylamine and ethylamine), amino compounds such as hydroxylamine, reducing sulfur compounds such as sodium thiosulfate, sodium hydrosulfite, sodium bisulfite, sodium sulfite, and sodium formaldehyde sulfoxylate, lower alcohols (having 1 to 6 carbon atoms), ascorbic acid or its salts, and lower aldehydes (having 1 to 6 carbon atoms).

[0067] The polymerization initiator is selected with reference to the 10-hour half-life temperature and is used alone or in combination. The addition amount of the polymerization initiator varies depending on the target degree of polymerization, but generally, 0.5 parts by mass or more and 20.0 parts by mass or less are added per 100.0 parts by mass of the polymerizable monomer.

[0068] <Hydrocarbon wax and ester wax> The toner particles contain wax. The wax contains hydrocarbon wax and ester wax. Known waxes can be used as the hydrocarbon wax and ester wax. Hydrocarbon waxes specifically include petroleum waxes typified by paraffin wax, microcrystalline wax, and petrolactam and their derivatives, hydrocarbon waxes obtained by the Fischer-Tropsch process and their derivatives, polyolefin waxes typified by polyethylene and their derivatives. Derivatives include oxides, block copolymers with vinyl monomers, and graft-modified products. Also included are alcohols such as higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid or their acid amides, esters, and ketones; hydrogenated castor oil and its derivatives, vegetable waxes, and animal waxes.

[0069] Among the hydrocarbon waxes, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, and polyolefin (e.g., polyethylene) are preferred, and Fischer-Tropsch wax is more preferred.

[0070] As ester waxes, esters of monohydric alcohols and aliphatic carboxylic acids such as behenyl behenate, stearyl stearate, and palmityl palmitate, or esters of dibasic carboxylic acids and aliphatic alcohols; esters of dihydric alcohols and aliphatic carboxylic acids such as ethylene glycol distearate, sebacic acid dibehenyl, and hexanediol dibehenate, or esters of dibasic carboxylic acids and aliphatic alcohols; natural ester waxes such as carnauba wax and rice wax. These can be used alone or in combination. Among these, from the viewpoints of crystallinity and compatibility, esters of monohydric alcohols and aliphatic carboxylic acids such as behenyl behenate, stearyl stearate, and palmityl palmitate are preferred.

[0071] The melting point of the ester wax is preferably 55 to 95°C, more preferably 65 to 85°C. The melting point of the hydrocarbon wax is preferably 55 to 95°C, more preferably 65 to 85°C.

[0072] ​Furthermore, as other ester waxes, within the range that does not impair the effects of the present disclosure, esters of trivalent alcohols such as glyceryl tribehenate and aliphatic carboxylic acids, or esters of trivalent carboxylic acids and aliphatic alcohols; esters of tetravalent alcohols such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate and aliphatic carboxylic acids, or esters of tetravalent carboxylic acids and aliphatic alcohols; esters of hexavalent alcohols such as dipentaerythritol hexastearate and dipentaerythritol hexapalmitate and aliphatic carboxylic acids, or esters of hexavalent carboxylic acids and aliphatic alcohols; esters of polyhydric alcohols such as polyglyceryl behenate and aliphatic carboxylic acids, or esters of polyvalent carboxylic acids and aliphatic alcohols; may be used in combination.

[0073] <Compound A> Also, the toner particles preferably contain Compound A, which is at least one compound selected from the group consisting of the compound represented by formula (2) and the compound represented by formula (3). R 3 -O-(A 1 -O) n -X ···(2) (In formula (2), R 3 represents an alkyl group having 8 to 24 carbon atoms, A 1 represents an ethylene group (-CH2CH2-) or a propylene group (-CH(CH3)CH2-), n is an integer of 5 to 60, and X is H, CH2COOH, CH2SO3H, CH2COONa, or CH2SO3Na.) R 4 -Ph-O-(A 2 -O) m -X ···(3) (In formula (3), R 4 represents an alkyl group having 8 to 24 carbon atoms, Ph represents a phenylene group, A 2 represents an ethylene group or a propylene group, m is an integer of 5 to 60, and X is H, CH2COOH, CH2SO3H, CH2COONa, or CH2SO3Na.)

[0074] The method for producing the above compound is not particularly limited, and any method can be used. For example, it can be obtained by adding a predetermined amount of ethylene oxide or propylene oxide to an aliphatic alcohol according to the purpose. A catalyst can be used for the addition reaction of propylene oxide. As the catalyst, alkali hydroxides such as NaOH and KOH, and those mainly composed of magnesium oxide described in JP-A-8-323200 can be used. The former can obtain a polyethylene glycol alkyl ether or polypropylene glycol alkyl ether with a relatively wide addition mole number distribution, and the latter can obtain a compound with a relatively narrow addition mole number distribution. Compound A may also be used as a surfactant exemplified in the method for producing a toner described below.

[0075] <Colorant> The toner particles may contain a colorant. Known pigments and dyes can be used as the colorant. From the viewpoint of excellent weather resistance, a pigment is preferable as the colorant.

[0076] Examples of cyan-based colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specifically, the following can be mentioned. C.I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66.

[0077] Examples of magenta-based colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, the following can be mentioned. C.I. Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254, and C.I. Pigment Violet 19.

[0078] Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following: C.I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185, 191, and 194.

[0079] Examples of black colorants include those obtained by toning to black using the above yellow colorants, magenta colorants, and cyan colorants, as well as carbon black.

[0080] These colorants can be used alone, as a mixture, or even in a solid solution state. It is preferable to use the colorant in an amount of 1.0 to 20.0 parts by mass based on 100.0 parts by mass of the binder resin.

[0081] <Charge control agent and charge control resin> The toner particles may contain a charge control agent or a charge control resin. As the charge control agent, known ones can be used, and in particular, a charge control agent with a fast triboelectrification speed and capable of stably maintaining a certain triboelectrification amount is preferable. Further, when the toner particles are produced by the suspension polymerization method, a charge control agent with low polymerization inhibitory properties and substantially no solubilized product in an aqueous medium is particularly preferable.

[0082] Examples of toners with controlled charging properties include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acid and dicarboxylic acid-based metal compounds, aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, phenolic derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthenic acid-based compounds, boron compounds, quaternary ammonium salts, calixarenes, and charge control resins.

[0083] Examples of charge control resins include polymers or copolymers having a sulfonic acid group, a sulfonate group, or a sulfonic acid ester group. As polymers having a sulfonic acid group, a sulfonate group, or a sulfonic acid ester group, polymers containing 2% by mass or more of a sulfonic acid group-containing acrylamide-based monomer or a sulfonic acid group-containing methacrylamide-based monomer in the copolymerization ratio are preferred, and polymers containing 5% by mass or more are more preferred.

[0084] The charge control resin preferably has a glass transition temperature (Tg) of 35°C or higher and 90°C or lower, a peak molecular weight (Mp) of 10,000 or higher and 30,000 or lower, and a weight average molecular weight (Mw) of 25,000 or higher and 50,000 or lower. When this is used, favorable triboelectric charging properties can be imparted without affecting the thermal properties required for toner particles. Furthermore, when the charge control resin contains a sulfonic acid group, for example, the dispersibility of the charge control resin itself and the dispersibility of colorants in the polymerizable monomer composition are improved, and the coloring power, transparency, and triboelectric charging properties can be further improved.

[0085] These charge control agents or charge control resins may be added alone or in combination of two or more. The addition amount of the charge control agent or charge control resin is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, more preferably 0.5 parts by mass or more and 10.0 parts by mass or less, based on 100.0 parts by mass of the binder resin.

[0086] [Method for manufacturing toner] The method for producing the toner 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. Here, the toner is preferably produced by an emulsion aggregation method.

[0087] The method for producing the toner includes the following steps (1) to (3) (1) A dispersion step of preparing a resin fine particle dispersion liquid containing a resin such as a binder resin, and a dispersion step of preparing a wax fine particle dispersion liquid containing wax (2) An aggregation step of aggregating the resin fine particles contained in the resin fine particle dispersion liquid and the wax fine particles containing wax to form aggregates, and (3) A fusion step of heating and fusing the aggregates in this order. It is preferable that the toner manufacturing method is such that a boron compound is added in at least one of the aggregation step and the fusion step.

[0088] Also, during or after the fusion step, the following steps (4) to (6) (4) A spheroidization step of further heating the aggregates while raising the temperature, (5) A cooling step of cooling the aggregates at a cooling rate of 0.1 °C / second or more, and (6) An annealing step of heating and holding the aggregates at a temperature equal to or higher than the crystallization temperature or the glass transition temperature of the resin are preferably included in this order.

[0089] When the toner is produced by the emulsion aggregation method, it is preferable because the toner shape can be controlled and boric acid is easily uniformly dispersed near the surface of the toner. The details of the emulsion aggregation method will be described below.

[0090] <Emulsion Aggregation Method> The emulsion aggregation method is a method in which, for a target particle size, an aqueous dispersion liquid of fine particles made of a constituent material of toner particles, which is sufficiently small, is prepared in advance, and the fine particles are aggregated in an aqueous medium until they reach the particle size of the toner particles, and the resin is fused by heating or the like to produce toner particles. That is, in the emulsion aggregation method, a dispersion step of preparing a fine particle dispersion liquid composed of the constituent materials of toner particles, an aggregation step of aggregating the fine particles composed of the constituent materials of toner particles and controlling the particle diameter until it becomes the particle diameter of toner particles, a fusion step of fusing the resin contained in the obtained aggregated particles, a spheroidization step of further melting by heating or the like to control the surface shape of the toner, a subsequent cooling step, filtering the obtained toner, removing excessive polyvalent metal ions in a metal removal step, a filtering / washing step of washing with ion-exchanged water or the like, and removing the moisture of the washed toner particles and drying The toner particles are manufactured through the steps.

[0091] (Step of preparing a resin fine particle dispersion liquid (dispersion step)) The resin fine particle dispersion liquid can be prepared by known methods, but is not limited to these methods. Examples of known methods include an emulsion polymerization method, a self-emulsification method, an inverse phase emulsification method in which a water-based medium is added to a resin solution dissolved in an organic solvent to emulsify the resin, or a forced emulsification method in which the resin is forcibly emulsified by high-temperature treatment in a water-based medium without using an organic solvent.

[0092] Specifically, the resin is dissolved in an organic solvent capable of dissolving these, and a surfactant or a basic compound is added. At this time, if the resin is a crystalline resin having a melting point, it may be heated to a temperature above the melting point and dissolved. Subsequently, while stirring with a homogenizer or the like, the water-based medium is slowly added to precipitate the resin fine particles. Then, the solvent is removed by heating or reducing the pressure to prepare an aqueous dispersion liquid of the resin fine particles. As the organic solvent used for dissolving the resin, any solvent capable of dissolving the resin can be used, but it is preferable to use an organic solvent that forms a homogeneous phase with water, such as toluene, from the viewpoint of suppressing the generation of coarse powder.

[0093] Although the surfactant used during the above emulsification is not particularly limited, examples include anionic surfactants such as sulfate ester salts, sulfonates, carboxylates, phosphate esters, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. The surfactant may be used alone or in combination of two or more.

[0094] Examples of the basic compound used during the dispersion step include inorganic bases such as sodium hydroxide and potassium hydroxide; and organic bases such as ammonia, triethylamine, trimethylamine, dimethylaminoethanol, and diethylaminoethanol. The basic compound may be used alone or in combination of two or more.

[0095] Also, the 50% particle size (D50) based on the volume distribution of the resin fine particles in the aqueous dispersion of the resin fine particles is preferably 0.05 μm to 1.0 μm, more preferably 0.05 μm to 0.4 μm. By adjusting the 50% particle size (D50) based on the volume distribution within the above range, it becomes easier to obtain toner particles having a volume average particle size of 3 μm to 10 μm, which is an appropriate volume average particle size as toner particles. For the measurement of the 50% particle size (D50) based on the volume distribution, a dynamic light scattering particle size distribution analyzer NanoTrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.) is used.

[0096] (Wax Fine Particle Dispersion) A wax fine particle dispersion containing a wax such as an ester wax or a hydrocarbon wax can be prepared by the known methods listed below, but is not limited to these techniques. The wax fine particle dispersion is prepared by adding wax to an aqueous medium containing a surfactant, heating it to a temperature equal to or higher than the melting point of the wax, and dispersing it into particles using a homogenizer having a strong shearing ability (for example, "ClearMix W Motion" manufactured by M Technique Co., Ltd.) or a pressure discharge type disperser (for example, "Gorin Homogenizer" manufactured by Gorin Co., Ltd.), and then cooling it to a temperature lower than the melting point of the wax.

[0097] The dispersed particle size of the wax fine particle dispersion in the aqueous dispersion preferably has a volume distribution-based 50% particle size (D50) of 0.03 μm to 1.0 μm, more preferably 0.1 μm to 0.5 μm. It is more preferable that there are no coarse particles of 1 μm or more. The dispersed particle size of the wax fine particle dispersion dispersed in the aqueous medium can be measured using a dynamic light scattering particle size distribution analyzer (NanoTrac UPA-EX150: manufactured by Nikkiso Co., Ltd.).

[0098] (Colorant fine particle dispersion) If necessary, a colorant fine particle dispersion may be used. The colorant fine particle dispersion can be prepared by known methods listed below, but is not limited to these methods. It can be prepared by mixing a colorant, an aqueous medium, and a dispersant using a mixer such as a known stirrer, emulsifier, and disperser. As the dispersant used here, known ones such as surfactants and polymer dispersants can be used. Both the surfactant and the polymer dispersant can be removed in the cleaning process described later, but from the viewpoint of cleaning efficiency, the surfactant is preferred.

[0099] Examples of surfactants include anionic surfactants such as sulfate salts, sulfonate salts, phosphate esters, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, nonionic surfactants or anionic surfactants are preferred. Also, a nonionic surfactant and an anionic surfactant may be used in combination. The surfactant may be used alone or in combination of two or more. The concentration of the surfactant in the aqueous medium is preferably 0.5% by mass to 5% by mass.

[0100] The content of the colorant fine particles in the colorant fine particle dispersion is not particularly limited, but is preferably 1% by mass to 30% by mass based on the total mass of the colorant fine particle dispersion. Also, from the viewpoint of the dispersibility of the colorant in the finally obtained toner, the dispersion particle diameter of the colorant fine particles in the aqueous dispersion of the colorant is preferably such that the 50% particle diameter (D50) based on the volume distribution is 0.5 μm or less. Also, for the same reason, the 90% particle diameter (D90) based on the volume distribution is preferably 2 μm or less. The dispersion particle diameter of the colorant fine particles dispersed in the aqueous medium is measured with a dynamic light scattering particle size distribution analyzer (NanoTrack UPA-EX150: manufactured by Nikkiso Co., Ltd.). Examples of the mixer such as a known stirrer, emulsifier, and disperser used when dispersing the colorant in the aqueous medium include an ultrasonic homogenizer, jet mill, pressure homogenizer, colloid mill, ball mill, sand mill, and paint shaker. These may be used alone or in combination.

[0101] (Mixing step) In the mixing step, a mixed liquid is prepared by mixing the resin fine particle dispersion, the wax fine particle dispersion, and, if necessary, the colorant fine particle dispersion. It can be carried out using a known mixing device such as a homogenizer and a mixer.

[0102] (Step of forming aggregate particles (aggregation step)) In the aggregation step, the fine particles contained in the mixed solution prepared in the mixing step are aggregated to form aggregates having a target particle size. At this time, a flocculant is added and mixed, and at least one of heating and mechanical power is appropriately applied as necessary to form aggregates in which resin fine particles, wax fine particles, and colorant fine particles are aggregated.

[0103] Examples of the flocculant include cationic surfactants of quaternary salts, organic flocculants such as polyethyleneimine; inorganic metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride, calcium nitrate; inorganic ammonium salts such as ammonium sulfate, ammonium chloride, ammonium nitrate; and inorganic flocculants such as divalent or higher metal complexes. Also, it is possible to add an acid to lower the pH and cause soft aggregation, and for example, sulfuric acid, nitric acid, etc. can be used. It is also possible to add an acid to lower the pH and cause soft aggregation, and for example, sulfuric acid or nitric acid can be used.

[0104] The flocculant may be added in either the form of a dry powder or an aqueous solution dissolved in an aqueous medium, but in order to cause uniform aggregation, it is preferably added in the form of an aqueous solution. Also, the addition and mixing of the flocculant are preferably carried out at a temperature equal to or lower than the glass transition temperature or melting point of the resin contained in the mixed solution. By performing the mixing under this temperature condition, aggregation proceeds relatively uniformly. The mixing of the flocculant into the mixed solution can be carried out using a known mixing device such as a homogenizer and a mixer. The aggregation step is a step of forming aggregates having a toner particle size in an aqueous medium. The volume average particle size of the aggregates produced in the aggregation step is preferably 3 μm to 10 μm. The volume average particle size can be measured with a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter) by the Coulter method.

[0105] (A shell forming step of further adding and aggregating resin fine particles containing a resin for the shell to the dispersion containing the aggregates to form aggregates having a shell) After forming aggregated particles (core particles) by an aggregation process, it is preferable to have a shell formation process in which resin fine particles containing a resin for the shell are further added and aggregated to form a shell. That is, the toner particles preferably have core particles containing a binder resin and a shell on the surface of the core particles. As the resin for the shell, the same resin as the binder resin may be used, or another resin may be used. The addition amount of the resin for the shell is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, and still more preferably 20 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the binder resin contained in the core particles.

[0106] The resin of the shell is not particularly limited, and the resins described above can be used as the binder resin. The resin of the shell preferably contains a polyester resin. As the resin of the shell, the polyester resin A having an isophthalic acid unit and a dodecenyl succinic acid unit described above may be used.

[0107] When forming the shell, it is preferable to make the toner particles contain Compound A by further adding Compound A to the dispersion containing aggregates together with the resin fine particles containing the resin for the shell. This is because by adding Compound A during shell formation, Compound A can be present in the binder resin and on the toner surface.

[0108] In addition, when forming the shell, in order to make it easier for the toner particles to contain boron, it is preferable to add a boron compound to the dispersion containing aggregates together with the resin fine particles containing the resin for the shell in the shell formation step. The boron compound may be boric acid or a compound that can be changed to boric acid by pH control or the like during toner production. For example, at least one selected from the group consisting of boric acid, borax, organic boric acid, borate, boric acid ester, etc. may be mentioned. For example, the boron compound may be added and controlled so that boric acid is contained in the aggregates. Preferably, the pH is controlled under acidic conditions in the aggregation step, and the shell formation step is carried out.

[0109] In the shell forming step, the presence of boric acid makes it easier for the resin for the shell to aggregate uniformly on the core particles, thereby reducing the area of the wax domain near the surface.

[0110] Boric acid may be present in the aggregate in an unsubstituted state. The boron compound is preferably at least one selected from the group consisting of boric acid and borax. When the toner is produced in an aqueous medium, from the viewpoints of reactivity and production stability, a borate is added as the boron compound. Specifically, the boron compound more preferably contains at least one selected from the group consisting of sodium tetraborate, borax, ammonium borate, etc., and is more preferably borax.

[0111] Borax is represented by the decahydrate of sodium tetraborate Na2B4O7 and changes to boric acid in an acidic aqueous solution. Therefore, when used in an acidic environment in an aqueous medium, borax is preferably used. As the addition method, it may be added in either the form of a dry powder or an aqueous solution dissolved in an aqueous medium. However, in order to cause uniform aggregation, it is preferably added in the form of an aqueous solution. The concentration of the aqueous solution may be appropriately changed according to the concentration to be contained in the toner, for example, it is 1 to 20% by mass. In order to change it to boric acid, it is preferable to adjust the pH to acidic conditions before, during or after the addition. For example, it may be controlled to 1.5 to 5.0, preferably 2.0 to 4.0.

[0112] (Step of obtaining a dispersion liquid containing toner particles (fusion step)) In the fusion step, in the dispersion liquid containing the aggregate obtained in the aggregation step, under the same stirring as in the aggregation step, first, the aggregation is stopped. The stop of aggregation is carried out by adding an aggregation inhibitor such as a base capable of adjusting pH, a chelating compound, or an inorganic salt compound such as sodium chloride. After the dispersion state of the aggregated particles in the dispersion becomes stable due to the action of the aggregation inhibitor, it is heated to a temperature equal to or higher than the glass transition temperature or melting point of a resin such as a binder resin to fuse the aggregated particles and adjust them to a desired particle size. Note that the volume-based 50% particle size (D50) of the toner particles is preferably 3 μm to 10 μm.

[0113] (Step of obtaining the desired surface shape of the toner (spheroidization step)) During or after the fusion step, it is preferable to go through a spheroidization step of further raising the temperature and holding it until the toner particles reach a desired roundness or surface shape. As the temperature of the specific spheroidization step, for example, it is 85°C or higher, preferably 90°C or higher, and preferably 95°C or lower. Examples of the heating time of the spheroidization step include a heating time of 1 hour or more, 2 hours or more, and 3 hours or more. The upper limit is, for example, 5 hours or less. By this step, hydrogen bonds derived from boric acid are likely to be formed in the toner particles.

[0114] (Cooling step) After the spheroidization step, it is preferable to go through a cooling step of controlling the cooling rate to cool the temperature of the dispersion liquid containing the obtained toner particles to a temperature lower than the crystallization temperature or glass transition temperature of the crystalline components of resins such as binder resins and waxes such as hydrocarbon waxes and ester waxes. By going through the cooling step, changes in the domain shape associated with the crystallization of the crystalline components of the wax can be suppressed. As a result, it becomes easier to control the ratio of the domain area of the crystalline components by the wax near the surface of the toner particles. Specific cooling rates are 0.1°C / second or more, preferably 0.5°C / second or more, more preferably 2°C / second or more, and even more preferably 4°C / second or more. The upper limit is, for example, 20°C / second or less, 15°C / second or less.

[0115] (Annealing step) After the cooling step, an annealing step of heating and holding at a temperature equal to or higher than the crystallization temperature or glass transition temperature of the resin and lower than the crystallization temperature of the wax may be performed. By going through the annealing step, the crystalline components that were compatible with the resin in the toner particles can be crystallized, and changes in the domain shape can be further suppressed.

[0116] (Post-treatment process) In the method for manufacturing toner, further, post-treatments such as a cleaning process, a solid-liquid separation process, and a drying process may be performed, and toner particles in a dried state can be obtained by performing the post-treatment process. The obtained toner particles may be used as toner as they are, but in the external addition process, an external additive such as silica fine particles may be externally added to the toner particles obtained in the drying process.

[0117] (External addition process) As the external addition conditions, the state of adhesion of the external additive and the state of coating of the toner particles with the external additive can be arbitrarily controlled by the rotational speed (rpm) of the stirring spring provided in the external addition machine and the external addition time. Furthermore, in order to adhere more firmly, it is effective to increase the rotational speed and lengthen the external addition time. In particular, by increasing the rotational speed, the adhesion strength can be further increased. Also, since the external additive particles with a small particle size form aggregates, the external additive is coated on the toner particles while performing a crushing treatment by controlling the external addition conditions. The crushability can be enhanced by increasing the rotational speed and lengthening the external addition time, but in order to further promote crushing while suppressing the adhesion strength, it is effective to decrease the rotational speed and lengthen the external addition time.

[0118] The weight average particle size (D4) of the toner is preferably 4.0 to 12.0 μm, more preferably 4.0 to 8.0 μm.

[0119] 〔Measurement methods for each physical property〕 Next, the measurement methods for each physical property according to the present disclosure will be described. <Measurement of the weight average particle size (D4) and number average particle size (D1) of toner or toner particles> The weight average particle size (D4) and number average particle size (D1) of the toner or toner particles are measured and calculated using a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube and the dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) attached for measurement condition setting and measurement data analysis at an effective measurement channel number of 25,000 channels. The electrolytic aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of about 1% by mass. For example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used.

[0120] Before measurement and analysis, the settings of the dedicated software are made as follows. On the "Change Screen of Standard Measurement Method (SOM)" of the dedicated software, set the total count number in the control mode to 50,000 particles, the number of measurements to 1 time, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter, Inc.). By pressing the measurement button for threshold / noise level, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the flash of the aperture tube after measurement. On the "Conversion Setting Screen from Pulse to Particle Size" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less.

[0121] The specific measurement method is as follows. (1) Pour about 200 ml of the electrolytic aqueous solution into a 250 ml round-bottom glass beaker dedicated to Multisizer 3, set it on the sample stand, and stir with a stirrer rod counterclockwise at 24 rotations per second. Then, remove the dirt and air bubbles in the aperture tube by using the "Flash of Aperture Tube" function of the dedicated software. (2) Put about 30 ml of the electrolytic aqueous solution into a 100 ml flat-bottomed beaker made of glass, and add about 0.3 ml of a dilution obtained by diluting "Contaminon N" (a 10% by mass aqueous solution of a neutral detergent for precision measuring instrument cleaning with pH 7 composed of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water by 3 times the mass as a dispersant. (3) Put a predetermined amount of ion-exchanged water into the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora150" (manufactured by Niseki Kikai Bios Co., Ltd.) with a built-in oscillator of 50 kHz and a phase shift of 180 degrees and an electrical output of 120 W, and add about 2 ml of the Contaminon N into this water tank. (4) Set the beaker in (2) above in the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height position of the beaker so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized. (5) While irradiating the electrolytic aqueous solution in the beaker in (4) above with ultrasonic waves, add about 10 mg of toner or toner particles little by little to the electrolytic aqueous solution and disperse them. Then, continue the ultrasonic dispersion treatment for another 60 seconds. In ultrasonic dispersion, adjust appropriately so that the water temperature in the water tank is between 10°C and 40°C. (6) Using a pipette, drop the electrolytic aqueous solution in (5) in which toner or toner particles are dispersed into the round-bottomed beaker in (1) installed in the sample stand, and adjust so that the measured concentration is about 5%. Then, perform the measurement until the number of measured particles reaches 50,000. (7) Analyze the measurement data with the dedicated software attached to the device to calculate the weight average particle size (D4). When set to graph / volume% in the dedicated software, the "average diameter" on the "analysis / volume statistical value (arithmetic mean)" screen is the weight average particle size (D4), and when set to graph / number% in the dedicated software, the "average diameter" on the "analysis / number statistical value (arithmetic mean)" screen is the number average particle size (D1).

[0122] <Measurement of acid value> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of the resin is measured in accordance with JIS K 0070-1992. Specifically, it is measured according to the following procedure. (1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 ml of ethyl alcohol (95 vol%), add ion-exchanged water to make 100 ml, and obtain a phenolphthalein solution. Dissolve 7 g of special grade potassium hydroxide in 5 ml of water, add ethyl alcohol (95 vol%) to make 1 L. Put it in an alkali-resistant container so as not to contact carbon dioxide gas, etc., leave it for 3 days, and then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution is obtained from the amount of the potassium hydroxide solution required for neutralization by taking 25 ml of 0.1 mol / l hydrochloric acid into an Erlenmeyer flask, adding several drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution. The 0.1 mol / l hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0123] (2) Procedure (A) This test Precisely weigh 2.0 g of the pulverized resin sample into a 200 ml Erlenmeyer flask, add 100 ml of a toluene / ethanol (2:1) mixed solution, and dissolve it over 5 hours. Then, add several drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds. (B) Blank test Perform the same titration as the above operation except that no sample is used (that is, only the toluene / ethanol (2:1) mixed solution is used).

[0124] (3) Substitute the obtained results into the following formula to calculate the acid value. A = [(C - B) × f × 5.61] / S Here, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (ml), C: addition amount of potassium hydroxide solution in this test (ml), f: factor of potassium hydroxide solution, S: mass of sample (g).

[0125] <Method for Measuring Hydroxyl Value> The hydroxyl value is the number of milligrams of potassium hydroxide required to neutralize acetic acid bound to hydroxyl groups when acetylating 1 g of the sample. The hydroxyl value of the binder resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure. (1) Preparation of Reagents Put 25 g of special grade acetic anhydride into a 100 ml volumetric flask, add pyridine to make the total volume 100 ml, and shake well to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas, etc. Dissolve 1.0 g of phenolphthalein in 90 ml of ethyl alcohol (95 vol%), add ion-exchanged water to make 100 ml, and obtain a phenolphthalein solution. Dissolve 35 g of special grade potassium hydroxide in 20 ml of water, add ethyl alcohol (95 vol%) to make 1 L. Put it in an alkali-resistant container and leave it for 3 days so as not to come into contact with carbon dioxide gas, etc., then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution is determined from the amount of the potassium hydroxide solution required for neutralization by taking 25 ml of 0.5 mol / l hydrochloric acid into an Erlenmeyer flask, adding several drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution. The 0.5 mol / l hydrochloric acid used is prepared according to JIS K 8001-1998.

[0126] (2) Procedure (A) This Test Precisely weigh 1.0 g of the sample into a 200 ml round-bottom flask, and accurately add 5.0 ml of the above-mentioned acetylating reagent to it using a whole pipette. At this time, when the sample is difficult to dissolve in the acetylating reagent, add a small amount of special grade toluene to dissolve it. Place a small funnel on the mouth of the flask and immerse about 1 cm of the bottom of the flask in a glycerin bath at about 97 °C for heating. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the root of the neck of the flask with thick paper with round holes. After 1 hour, take out the flask from the glycerin bath and allow it to cool. After cooling, add 1 ml of water from the funnel and shake to hydrolyze acetic anhydride. Further, in order to hydrolyze completely, heat the flask in the glycerin bath again for 10 minutes. After cooling, wash the funnel and the walls of the flask with 5 ml of ethyl alcohol. Add a few drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. Note that the end point of the titration is when the light red color of the indicator continues for about 30 seconds. (B) Blank test Perform titration in the same manner as the above operation except that no sample is used.

[0127] (3) Substitute the obtained results into the following formula to calculate the hydroxyl value. A = [{(B - C) × 28.05 × f} / S] + D Here, A: hydroxyl value (mgKOH / g), B: amount of potassium hydroxide solution added in the blank test (ml), C: amount of potassium hydroxide solution added in this test (ml), f: factor of potassium hydroxide solution, S: mass of sample (g), D: acid value of sample (mgKOH / g).

[0128] <Method for measuring the content of isophthalic acid units and dodecenyl succinic acid units in polyester resin A, toner or toner particles> The content of isophthalic acid units and dodecenyl succinic acid units contained in polyester resin A and toner is measured using pyrolysis gas chromatography-mass spectrometer (hereinafter, pyrolysis GC / MS) and NMR. Specifically, the following operations are performed. (1) Weigh 50 mg of polyester resin A, toner or toner particles accurately into an 8 mL glass sample bottle, add 1 mL of deuterated chloroform, then cover the bottle and disperse it by an ultrasonic disperser for 1 Dissolve it with time dispersion. Then, filter it through a 0.4 μm diameter membrane filter and collect the filtrate. At this time, the deuterated chloroform-insoluble matter remains on the membrane filter. (2) Regarding the filtrate, 1 perform 1H-NMR measurement and 13 13C-NMR measurement, assign the components contained in the toner from the spectrum, and calculate the contents of the isophthalic acid unit and dodecenyl succinic acid unit contained in the toner. (3) If the identification is insufficient, further analyze it by pyrolysis GC / MS, perform derivatization treatment such as methylation if necessary, and perform composition analysis. (4-1) The contents of the isophthalic acid unit and dodecenyl succinic acid unit in the polyester resin A are calculated in terms of mass from the results of the identified composition analysis. When separating the polyester resin from the toner, known means can be used. (4-2) The contents of the isophthalic acid unit and dodecenyl succinic acid unit based on the mass of the binder resin can be calculated by calculating the amount of the binder resin in the toner according to <Method for Measuring Content W1 of Hydrocarbon Wax and Content W2 of Ester Wax Contained in Toner> described later, and calculating the content ratio of the monomer unit corresponding to dodecenyl succinic acid based on the mass of the binder resin from these values.

[0129] (NMR measurement conditions) Bruker AVANCE 500 manufactured by Bruker BioSpin Corporation Measured nucleus: 1 1H, 13 13C Measurement frequency: 500.1 MHz Number of integrations: 16 times, 2048 times Measurement temperature: room temperature

[0130] (Pyrolysis GC / MS measurement conditions) Pyrolysis device: TPS-700 manufactured by JEOL Ltd. Pyrolysis temperature: appropriate value at 400 °C to 600 °C GC / MS instrument: ISQ manufactured by Thermo Fisher Scientific K.K. Column: "HP5-MS" (Agilent / 19091S-433), length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm GC / MS conditions Inlet conditions: InletTemp: 250 °C SplitFlow: 50 mL / min GC temperature rising conditions: 40 °C (5 min) → 10 °C / min (300 °C) → 300 °C (20 min)

[0131] <Measurement of molecular weight of polyester resin> The molecular weight (weight average molecular weight Mw) of the polyester resin is measured by gel permeation chromatography (GPC) as follows. First, dissolve the polyester resin 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 sample solution is adjusted so that the concentration of the components soluble in THF is 0.8 mass%. Using this sample solution, measurements are performed under the following conditions. · Instrument: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation) · Column: Shodex LF-404, two connected LF-404 (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, a 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) is used.

[0132] <Identification of the Molecular Structures of Hydrocarbon Wax and Ester Wax Contained in Toner> First, hydrocarbon wax and ester wax are isolated from toner by the following separation operations. The toner is dispersed in ethanol, which is a poor solvent for the toner, and the temperature is raised to a temperature exceeding the melting point of the wax. At this time, pressure may be applied as necessary. By this operation, the wax whose melting point has been exceeded is melted and extracted into ethanol. When heating and further applying pressure, the wax can be separated from the toner by solid-liquid separation while maintaining the pressure. Next, the wax is obtained by drying and solidifying the extract. By fractionating the obtained wax by molecular weight, it is possible to isolate hydrocarbon wax and ester wax. Next, the molecular structures of the isolated hydrocarbon wax and ester wax are identified. The identification of the molecular structure uses pyrolysis gas chromatography-mass spectrometer (hereinafter, pyrolysis GC / MS) and NMR.

[0133] Specifically, the following operations are performed. (1) 50 mg of toner is precisely weighed into an 8 mL glass sample bottle, 1 mL of deuterated chloroform is added, then the lid is put on, and it is dispersed and dissolved for 1 hour by an ultrasonic disperser. Next, filtration is performed using a 0.4 μm diameter membrane filter, and the filtrate is collected. At this time, the deuterated chloroform-insoluble matter remains on the membrane filter. (2) Regarding the filtrate, 1 1H-NMR measurement is performed, and the spectra are assigned to each monomer of hydrocarbon wax and ester wax. (3) Analysis is performed by pyrolysis GC / MS. If necessary, derivatization treatment such as methylation is performed to calculate the molecular weights of hydrocarbon wax and ester wax.

[0134] (NMR Measurement Conditions) Bruker AVANCE 500 manufactured by Bruker BioSpin Corporation Measurement Nucleus: 1 1H Measurement Frequency: 500.1 MHz Number of Integrations: 16 times Measured Temperature: Room Temperature

[0135] (Measurement Conditions for Pyrolysis GC / MS) Pyrolysis Device: TPS-700 manufactured by Nippon Analytical Industry Co., Ltd. Pyrolysis Temperature: Appropriate value at 400°C to 600°C GC / MS Device: ISQ manufactured by Thermo Fisher Scientific K.K. Column: "HP5-MS" (Agilent / 19091S-433), length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm GC / MS Conditions Inlet Conditions: InletTemp: 250°C SplitFlow: 50 mL / min GC Temperature Rising Conditions: 40°C (5 min) → 10°C / min (300°C) → 300°C (20 min)

[0136] <Content W1 of Hydrocarbon Wax and Content W2 of Ester Wax Contained in Toner Measurement Method> When taking 100 parts by mass of the binder resin in the toner, the content W1 of the hydrocarbon wax and the content W2 of the ester wax are calculated by the following procedure. First, determine the mass X1 of the tetrahydrofuran (THF) soluble component, the mass X2 of the insoluble component, and the incineration residue ash X3 of the insoluble component in the toner. Next, it can be calculated by determining the content ratio w1 of the hydrocarbon wax and the content w2 of the ester wax in the toner.

[0137] Specifically, 1.5 g of toner is precisely weighed and placed in a pre-weighed cylindrical filter paper (product name: No. 86R, size 28×100 mm, manufactured by Advantec Toyo Co., Ltd.), and then set in a Soxhlet extractor. Using 200 mL of tetrahydrofuran (THF) as the solvent, extraction is carried out for 20 hours, and during this time, extraction is performed at a reflux rate such that the extraction cycle of the solvent is once every 5 minutes. After the extraction is completed, the cylindrical filter paper is taken out, air-dried, and then vacuum-dried at 40 °C for 8 hours. The mass of the cylindrical filter paper containing the extraction residue is weighed, and by subtracting the mass of the cylindrical filter paper, the mass of the extraction residue is taken as the mass X2 (g) of the tetrahydrofuran (THF) insoluble matter in the toner. Also, the mass X1 (g) of the tetrahydrofuran (THF) soluble matter in the toner is determined from the following formula (A). X1 = 1.5 - X2 (A)

[0138] Next, the content X3 (g) of components other than the resin component is determined by the following procedure. 1.5 g of toner is precisely weighed into a pre-weighed 30 mL magnetic crucible. The magnetic crucible is placed in an electric furnace and heated at 900 °C for 3 hours, cooled in the electric furnace, further cooled in a desiccator at room temperature for 1 hour or more, and the mass of the crucible containing the incineration residual ash is weighed. By subtracting the mass of the crucible, the incineration residual ash X3 (g) is calculated.

[0139] Furthermore, the extract obtained by the above operation is filtered through a solvent-resistant membrane filter "Micron Disc" (manufactured by Tosoh Corporation) with a pore diameter of 0.2 μm to obtain a sample solution. Using this sample solution, measurements are carried out under the following conditions. Apparatus: HLC8320 GPC (Detector: RI) (manufactured by Tosoh Corporation) Column: Shodex LF-404, two connected LF-404 (manufactured by Showa Denko KK) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 ml / min Oven temperature: 40.0 °C Sample injection volume: 0.10 ml Measure the total area S of the molecular weight distribution of the tetrahydrofuran (THF)-soluble content in the obtained toner, the peak area P1 derived from the hydrocarbon wax having a molecular weight corresponding to the wax identified by the above-described method, and the area P2 derived from the ester wax. Then, from the following calculation formula (B), the amount w1 of the hydrocarbon wax in the toner can be obtained, and from the following calculation formula (C), the amount w2 of the ester wax in the toner can be obtained. w1=(X1×P1 / S) ={(1.5-X2)×P1 / S} ···(B) w2=(X1×P2 / S) ={(1.5-X2)×P2 / S} ···(C) Also, from the total area S of the molecular weight distribution of the tetrahydrofuran (THF)-soluble content in the toner and the area P W derived from all waxes by the above GPC, the amount R of the binder resin in the toner can be obtained from the following formula (R). R={X1+(X2-X3)}-(X1×P W / S) ···(R) From the obtained amount w1 of the hydrocarbon wax, the content w2 of the ester wax, and the amount R of the binder resin, the content W1 of the hydrocarbon wax and the content W2 of the ester wax with respect to 100 parts by mass of the binder resin can be obtained.

[0140] <Measurement of the extraction amount of compound A extracted with ethanol> The extraction amount of compound A extracted from the toner with ethanol is 1 determined as follows using 1H-NMR (nuclear magnetic resonance) measurement. First, 50 ml of ethanol and 5 g of toner are accurately weighed into a sample vial and mixed well, and then irradiated with ultrasonic waves for 30 minutes using a benchtop ultrasonic cleaner (trade name "B2510JMTH", manufactured by Branson) with an oscillation frequency of 42 kHz and an electrical output of 125 W. Then, filtration is performed using a solvent-resistant membrane filter "Maeshory Disk" (manufactured by Tosoh Corporation) with a pore diameter of 0.2 μm. After removing ethanol from the filtrate with an evaporator, it is dissolved in deuterated chloroform (1% TMS) containing 10 mg of trimethylsilane (TMS),1 Analyze by \(^1H\)-NMR to identify the structure of Compound A. Separately, perform \(^1H\)-NMR measurement on the identified Compound A, and calculate the extraction amount (ppm) of Compound A extracted from the toner using a calibration curve based on the TMS intensity standard. The calibration curve is created from the ratio of the TMS intensity to the peak intensity of the hydrogen of the ethylene oxide group in the vicinity of 3.0 - 5.0 ppm. The measuring apparatus and measuring conditions are as follows.

[0141] (Measurement conditions for NMR) Bruker AVANCE 500 manufactured by Bruker BioSpin Corporation Nucleus measured: 1 H Measuring frequency: 500.1 MHz Number of integrations: 1024 times Measuring temperature: room temperature

[0142] (Calculation of the average ratio \(A_s\) of the area occupied by the wax domains in the surface layer region from the surface of the toner particles to a depth of 200 nm) The distribution state of the crystallized wax in the toner is observed by a transmission electron microscope for the cross-section of the toner particles, and \(A_s\) is calculated from the cross-sectional area of the domains formed by the crystallized wax, and evaluated with the average value of 100 arbitrarily selected toner particles. Specifically, toner is embedded with a visible light curable embedding resin (D-800, manufactured by Nisshin EM Co., Ltd.), cut to a thickness of 60 nm using an ultrasonic ultramicrotome (EM5, manufactured by Leica), and Ru staining is performed using a vacuum staining apparatus (manufactured by Filgen). Thereafter, observation is carried out at an acceleration voltage of 120 kV using a transmission electron microscope (H7500, manufactured by Hitachi). For the toner cross-section to be observed, 100 particles within ±2.0 μm from the weight average particle diameter are selected and photographed. Using image processing software (Photoshop (registered trademark) 5.0, manufactured by Adobe) for the obtained images, the distinction between the domains of the crystallized wax component and the resin region is clarified. Specifically, the domains of the crystallized wax component can be distinguished as follows. Using the image processing software, the taken TEM image is binarized by setting the threshold of brightness (gray level 255) to 160. At this time, the crystallized wax component of the toner and the photocurable resin D800 become the bright part, and the part other than the crystalline resin component of the toner becomes the dark part. The contour of the toner can be distinguished by the brightness and darkness of the toner and the photocurable resin.

[0143] Masking is performed while leaving the surface layer region from the toner particle surface (cross-section contour) to a depth of 200 nm in the cross-section of the toner particle. Specifically, a line is drawn from the center of gravity of the toner particle cross-section to a point on the contour of the toner particle cross-section. On this line, the position 200 nm in the direction from the contour to the center of gravity is specified. Then, this operation is performed for one round with respect to the contour of the toner particle cross-section to clarify the surface layer region from the contour of the toner particle cross-section to 200 nm. The occupancy area percentage of the domain of the crystallized wax component in the area of the obtained surface layer region is calculated, and this is designated as As.

[0144] <Quantification method of boron atoms based on the mass of toner particles> The content of boron (B) atoms based on the mass of toner particles is quantified using an inductively coupled plasma mass spectrometer (ICP-MS). As a pretreatment, the toner particles are subjected to the following acid decomposition to obtain a measurement solution for ICP-MS, and then ICP-MS measurement is performed to quantify the content of boron atoms in the toner particles.

[0145] [Pretreatment] Apparatus: Microwave Pretreatment Apparatus (ETHOS SEL), manufactured by Milestone General Sample amount: 50 mg To 50 mg of toner particles, 5.00 mL of 68% nitric acid (manufactured by Kanto Chemical Co., Ltd., for atomic absorption analysis) was added, and acid digestion was performed using the said apparatus. The acid digestion was carried out in two steps to obtain a desired measurement solution for ICP-MS. The acid digestion conditions are as follows. First stage of acid digestion The heating temperature and holding time during acid digestion were carried out under the following settings. Room temperature, 60 °C (2 minutes), 40 °C (2 minutes), 160 °C (6 minutes), 220 °C (8 minutes), 180 °C (1 minute), 220 °C (4 minutes), 220 °C (held for 30 minutes), cooled to room temperature (25 °C). Second stage of acid digestion The heating temperature and holding time during acid digestion were carried out under the following settings. Add 3 mL of nitric acid, room temperature, 180 °C (5 minutes), 150 °C (1 minute), 220 °C (2 minutes), 220 °C (held for 27 minutes), cooled to room temperature (25 °C). The solution obtained above was made up to 50 mL with ultrapure water. It was further diluted 100-fold with ultrapure water to obtain a measurement solution for ICP-MS.

[0146] [Quantification of Boron Atoms in Toner Particles by Inductively Coupled Plasma Mass Spectrometer] The content of boron atoms in the measurement solution for ICP-MS obtained above was quantified using the following apparatus and conditions. Apparatus: Inductively Coupled Plasma Mass Spectrometer ICP-MS NexION 350D, manufactured by PerkinElmer Measurement mode: Standard mode, calibration curve method Element to be measured: Boron Mass number: 11.0093 Scan mode: Peak hopping Dwell time: 50 ms Detector: Dual Peristaltic pump speed: 20.0 rpm Thereby, the content of boron atoms based on the mass of the toner particles was quantified.

[0147] <Method for Obtaining Toner Particles by Removing Externally Added Agents from Toner> Dissolve 160 g of sucrose (manufactured by Kinoshita Chemical Co., Ltd.) in 100 mL of ion-exchanged water while heating with a hot plate to prepare a thick sucrose solution. Place 31 g of the above thick sucrose solution and 6 mL of Contaminon N (a 10% by mass aqueous solution of a neutral detergent for precision measuring instrument cleaning with a pH of 7, composed of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) in a centrifuge tube (capacity 50 ml). Add 1.0 g of toner thereto, and loosen the toner clumps with a spatula or the like. Shake the centrifuge tube in a shaker (sold by AS ONE Corporation) at 300 spm (strokes per min) for 20 minutes. After shaking, transfer the solution to a glass tube (50 mL) for a swinging rotor and separate it in a centrifuge (manufactured by Kokusan Co., Ltd., model H-9R) at 3500 rpm for 30 minutes.

[0148] By this operation, the toner particles and the externally added agents are separated. Visually confirm that the toner particles and the aqueous solution are sufficiently separated, and collect the separated toner particles in the uppermost layer with a spatula or the like. After filtering the collected toner particles with a pressure-reducing filter, dry them in a dryer for 1 hour or more to obtain a sample for measurement. Repeat this operation a plurality of times to ensure the required amount.

Example

[0149] Hereinafter, the present disclosure will be described in more detail using examples and comparative examples. The present disclosure is not limited in any way by the following examples as long as the gist thereof is not exceeded. In the description of the following examples, "parts" means parts by mass unless otherwise specified.

[0150] <Synthesis of Polyester Resin 1> · 500 parts by mass of bisphenol A-propylene oxide 2 mol adduct · 460 parts by mass of bisphenol A-ethylene oxide 2 mol adduct · 330 parts by mass of isophthalic acid · 160 parts by mass of dodecenyl succinic acid The above monomers were charged into a flask equipped with a stirring device, a nitrogen inlet tube, a temperature sensor, and a rectification column, and the temperature was raised to 195°C in 1 hour, and it was confirmed that the inside of the reaction system was stirred uniformly. 1.2 parts by mass of tin distearate was added to 100 parts of these monomers. Further, while distilling off the generated water, the temperature was raised from 195°C to 240°C over 5 hours, and a dehydration condensation reaction was carried out at 240°C for another 2 hours. Next, the temperature was lowered to 190°C, 40 parts by mass of trimellitic anhydride was gradually added, and the reaction was continued at 190°C for 1 hour. As a result, polyester resin 1 having an acid value of 21.8 mgKOH / g, a hydroxyl value of 28.7 mgKOH / g, and a weight average molecular weight of 32,000 was obtained. Polyester resin 1 is shown in Tables 1-1 and 1-2.

[0151] <Synthesis of Polyester Resins 2 to 18> In the synthesis example of polyester resin 1, except that the polyester raw materials used were changed as shown in Table 1, polyester resins 2 to 18 were obtained in the same manner as in the synthesis example of polyester resin 1. Polyester resins 2 to 18 are shown in Tables 1-1 and 1-2.

[0152]

Table 1-1

[0153]

Table 1-2

[0154] <Production Example of Ester Wax 1> 100 parts of behenyl alcohol as an alcohol monomer and 100 parts of behenic acid as a carboxylic acid monomer were added to a reaction vessel equipped with a thermometer, a nitrogen inlet tube, a stirrer, a Dean-Stark trap, and a Dimroth condenser tube, and an esterification reaction was carried out at 200°C for 15 hours. Twenty parts of toluene and twenty-five parts of isopropanol were added to the obtained ester compound, and 190 parts of a 10% aqueous potassium hydroxide solution corresponding to 1.5 times the acid value of the ester compound were added, followed by stirring at 70 °C for 4 hours. Thereafter, the aqueous layer was removed. Further, 20 parts of ion-exchanged water was added and the mixture was stirred at 70 °C for 1 hour, after which the aqueous layer was removed and washing was performed. The above washing step was repeated until the pH of the removed aqueous layer became neutral. Thereafter, under the conditions of 200 °C and 1 kPa, the pressure was reduced to remove the solvent, and behenyl behenate (ester compound 1), which is an ester compound of behenyl alcohol and behenic acid, the final target product, was obtained. The physical properties of the obtained ester wax 1 are shown in Table 2.

[0155] <Production Examples of Ester Waxes 2 and 3> Ester waxes 2 and 3 were obtained in the same manner as in the production example of ester wax 1, except that the monomers were changed so that the compounds in Table 2 were obtained. The physical properties of the obtained ester waxes 2 and 3 are shown in Table 2.

[0156] <Ester Wax 4> Ester wax 4 was prepared using Purified Carnauba Wax Special Grade 1 Powder manufactured by Nippon Wax Co., Ltd. As a result of measuring the molecular weight of the ester wax by GPC analysis, the molecular weight was distributed in the range of 650 to 1050, the peak molecular weight was 850, and the melting point was 83 °C.

[0157]

Table 2

[0158] <Synthesis of Compound A1> 280 parts by mass of 1-dodecanol and 15.5 parts by mass of potassium hydroxide were charged into a 2 L autoclave. After dehydration at 115°C and 10.5 kPa, 720 parts by mass of ethylene oxide was added at 150°C while being pressured in at 0.3 MPa for an addition reaction. After completion of the reaction, aging was carried out at the same reaction temperature for 6 hours and then cooled to 80°C. 250 parts by mass of a synthetic adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd., Kyoward 600S) was added to the obtained reaction composition, and after treatment at 4.0 kPa for 1 hour, the catalyst was removed by filtration to obtain Compound A1 shown in Table 3.

[0159] <Synthesis of Compounds A2 - A10> In the synthesis example of Compound A1, Compounds A2 - A10 were obtained in the same manner as in the synthesis example of Compound A1, except that the raw materials used were changed as shown in Table 3. For Compounds A2 - A10, see Table 3.

[0160] <Synthesis of Compound A11> Into a 1000 mL five-necked flask equipped with a reflux tube, a dissolved oxygen concentration meter, and a stirring blade, 100 parts by mass of Compound A1, 5 parts by mass of 5% Pt - 1% Bi / C (manufactured by Evonik, Lot. TP - 2 / 0230) as a catalyst, and 420 parts by mass of ion-exchanged water were charged. Then, while stirring under the condition of 400 rpm, the temperature was raised to 70°C under nitrogen flow, and nitrogen was continuously flowed for 15 minutes after reaching 70°C. Thereafter, it was switched to oxygen and flowed under the condition of 90 mL / min for 18 hours for reaction to obtain Compound A11. For Compound A11, see Table 3.

[0161]

Table 3

[0162] <Preparation of Resin Particle Dispersion of Polyester Resin 1> 50 parts by mass of the above-mentioned methyl ethyl ketone and 20 parts by mass of isopropyl alcohol were charged into a container. Then, 100 parts by mass of polyester resin 1 was gradually charged, stirred, and completely dissolved to obtain a polyester resin 1 solution. The container containing this polyester resin 1 solution was set at 65°C, and while stirring, a total of 5 parts of a 10% aqueous ammonia solution was gradually added dropwise. Further, 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min for phase inversion emulsification. Further, the solvent was removed under reduced pressure using an evaporator to obtain a resin particle dispersion of polyester resin 1. When the particle size of the resin particle dispersion of polyester resin 1 was measured using a particle size measuring device (LA-950, manufactured by Horiba, Ltd.), the volume average particle size of the resin particle dispersion of polyester resin 1 was 105 nm. Also, the solid content of the resin particle dispersion of polyester resin 1 was adjusted to 20% by mass with ion-exchanged water.

[0163] <Preparation of Resin Fine Particle Dispersions of Polyester Resins 2 to 18> In the preparation of the resin particle dispersion of polyester resin 1, resin fine particle dispersions of polyester resins 2 to 18 were prepared in the same manner as the preparation of the resin particle dispersion of polyester resin 1, except that polyester resin 1 was changed to polyester resins 1 to 18, respectively.

[0164] <Preparation of Colorant Particle Dispersion> · 45 parts of copper phthalocyanine (Pigment Blue 15:3) · 5 parts of an ionic surfactant Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) · 190 parts of ion-exchanged water The above components were mixed and dispersed for 1 hour using a high-pressure impact type disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) to prepare an aqueous dispersion (colorant fine particle dispersion) with a concentration of 20% by mass of colorant fine particles in which the colorant was dispersed.

[0165] <Preparation of Hydrocarbon Wax Particle Dispersion> · 45 parts of hydrocarbon wax (HNP-9, manufactured by Nippon Seiro Co., Ltd.) · 5 parts of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) · 190 parts of ion-exchanged water After the above was put into a mixing container equipped with a stirring device, it was heated to 90 °C and circulated through a Clear Mix W motion (manufactured by M Technique) for 60 minutes for dispersion treatment. The conditions for the dispersion treatment were as follows. · Rotor outer diameter: 3 cm · Clearance: 0.3 mm · Rotor rotation speed: 19,000 r / min · Screen rotation speed: 19,000 r / min After the dispersion treatment, it was cooled to 40 °C under the cooling treatment conditions of a rotor rotation speed of 1,000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10 °C / min to obtain a hydrocarbon wax dispersion with a volume average particle diameter of 160 nm and a solid content of 20 mass%.

[0166] <Preparation of Ester Wax Dispersion 1> · 45 parts of ester wax 1 · 5 parts of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) · 190 parts of ion-exchanged water After the above was put into a mixing container equipped with a stirring device, it was heated to 90 °C and circulated through a Clear Mix W motion (manufactured by M Technique) for 60 minutes for dispersion treatment. The conditions for the dispersion treatment were as follows. · Rotor outer diameter: 3 cm · Clearance: 0.3 mm · Rotor rotation speed: 19,000 r / min · Screen rotation speed: 19,000 r / min After the dispersion treatment, it was cooled to 40 °C under the cooling treatment conditions of a rotor rotation speed of 1,000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10 °C / min to obtain Ester Wax Dispersion 1 with a volume average particle diameter of 170 nm and a solid content of 20 mass%.

[0167] <Adjustment of Ester Wax Dispersions 2 to 4> In the preparation of the ester wax dispersion liquid 1, ester wax dispersions 2 to 4 were obtained in the same manner except that ester wax 1 was changed to ester waxes 2 to 4, respectively.

[0168] <Manufacture of Toner Particles 1> · 750 parts of the resin particle dispersion liquid of polyester resin 1 · 70 parts of the colorant particle dispersion liquid · 30 parts of the hydrocarbon wax dispersion liquid · 120 parts of the ester wax dispersion liquid 1 · 1000 parts of ion-exchanged water First, as the core formation step, each of the above materials was put into a round stainless steel flask and mixed. Subsequently, it was dispersed at 5000 r / min for 10 minutes using a homogenizer Ultraturrax T50 (manufactured by IKA). After adding a 1.0% nitric acid aqueous solution and adjusting the pH to 3.0, it was heated to 45 °C while appropriately adjusting the rotation speed so that the mixed liquid was stirred using a stirring blade in a water bath for heating.

[0169] The volume average particle diameter of the formed aggregated particles was appropriately confirmed using a Coulter Multisizer III. When aggregated particles (cores) with a volume average particle diameter of 5.0 μm were formed, as the shell formation step, the following materials were added and stirred for another 1 hour to form a shell. · 250 parts of the resin particle dispersion liquid of polyester resin 1 · 300 parts of ion-exchanged water · 100 parts of a 3.0 mass% aqueous solution of compound A1 · 50 parts of a 2.0 mass% aqueous borax solution (Borax; Sodium tetraborate decahydrate manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) Thereafter, as the spheroidization step, the pH was adjusted to 9.0 using a 5% sodium hydroxide aqueous solution, and it was heated to 90 °C while continuing stirring. Thereafter, the average circularity of the formed aggregated particles was appropriately measured using a flow-type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation). Heating was carried out until the average circularity of the aggregated particles reached 0.970 (the heating time was 3 hours). Then, as a cooling process, ice was quickly added so that the cooling rate was 10 °C / second or more, and it was cooled to 25 °C to obtain a dispersion of toner particles 1.

[0170] The dispersion of toner particles 1 was adjusted to pH = 5.0 - 7.0 by adding hydrochloric acid for neutralization treatment, and then solid-liquid separation was carried out at a pressure of 0.3 Mpa with a pressure filter to obtain a toner cake. This was reslurried with ion-exchanged water to form a dispersion again, and then solid-liquid separation was carried out at a pressure of 0.3 Mpa with the aforementioned filter to obtain a toner cake. Furthermore, 2000 parts by mass of ion-exchanged water was added to the toner cake, and washing was carried out while applying a pressure of 0.3 Mpa for dehydration treatment. Furthermore, after air drying was carried out while maintaining 0.2 Mpa, the toner cake was taken out and subjected to a disintegration treatment. The disintegrated toner cake was dried in a vacuum dryer at 40 °C for 12 hours, and then classified to obtain toner particles 1. The manufacturing conditions and analysis results for toner particles 1 are shown in Tables 4-1, 4-2, and 5.

[0171] <Manufacture of Toner Particles 2 - 57 and Comparative Toner Particles 1 - 8 (Toner Particles 58 - 65)> In the manufacture of toner particles 1, except for changing to the conditions shown in Table 4, the same procedure was carried out to obtain toner particles 2 - 14. The manufacturing conditions and analysis results for toner particles 2 - 56 and comparative toner particles 1 - 8 (toner particles 58 - 65) are shown in Tables 4-1, 4-2, and 5.

[0172]

Table 4-1

[0173]

Table 4-2

[0174]

Table 5

[0175] 〔Example 1〕 · Toner particles 1: 100.0 parts · RX10 (manufactured by Nippon Aerosil Co., Ltd.): 2.0 parts · RX200 (manufactured by Nippon Aerosil Co., Ltd.): 1.5 parts Using a Henschel mixer FM10C (manufactured by Nippon Coke Co., Ltd.), the above materials were mixed at 3000 rpm for 7.5 minutes to obtain Toner 1. Regarding the obtained Toner 1, evaluation was performed according to the following procedure.

[0176] <Reproduction of the long-term storage state of the toner> Originally, the long-term storage state is the state of being placed at room temperature for 2 to 3 years. However, in the present disclosure, in order to accelerate and reproduce the long-term storage state of the toner, storage was performed according to the following procedure. First, a toner for which the reproduction of the long-term storage state has not been performed is used as the initial toner. 200 g of the initial toner placed in a container was placed in a constant temperature bath at 40°C / 90 Rh% for 20 days. Further, the toner that had been aged at 23°C / 40 Rh% for 3 days was used as the long-term storage toner for toner evaluation.

[0177] <Measurement of the charge amount of the toner> First, the charge amount was measured as follows. Weigh 9.5 g of a charge measurement carrier (Japan Society for Imaging Science and Technology standard carrier: spherical carrier N-01 with a ferrite core surface-treated) into a 50 mL polyethylene container. Next, weigh 0.5 g of the toner to be measured into the polyethylene container containing the aforementioned carrier, and close the cap. Next, set the above container on a shaker (Model-YS-LD: manufactured by Yayoiken Co., Ltd.), and set the time to reach a predetermined number of times under the shaking condition of 100 times / minute and shake it. Within 1 minute thereafter, put 0.4 g of the shaken sample into a metal measurement container 2 shown in Fig. 1 with a 500-mesh screen 3 at the bottom, and cover it with a metal lid 4. Measure the total mass of the measurement container 2 at this time, and let the value be W1 (g). Next, set the potential of the potentiometer 9 at this time to 0 V (volt).

[0178] Next, in the suction machine 1 (the part in contact with the measurement container 2 is at least an insulator), suck from the suction port 7, adjust the air volume control valve 6, and make the pressure of the vacuum gauge 5 2.5 kPa (±0.1 kPa) within 10 seconds. Note that the time from measuring W1 to starting suction is within 30 seconds. Then suck for 3 minutes to remove the toner particles by suction. Let the potential of the potentiometer 9 at this time be V (volt). Here, 8 is a capacitor and its capacitance is C (μF). Next, weigh the total mass of the measurement container after suction, and let the value at this time be W2 (g). The toner charge amount (mC / kg) of this sample is calculated by the following formula. Charge amount (mC / kg) = C × V / (W1 - W2) The charge amount was measured under normal temperature and humidity environment (temperature 23°C, humidity 50%RH: NN environment).

[0179] <Evaluation of Toner Chargeability> The chargeability of the toner described above was evaluated from the following viewpoints. · Charge rising property of the initial toner The charge rising property of the initial toner was carried out by shaking so that the number of shaking times was 100 times and 300 times in the above-described toner charge amount measurement. Thereafter, based on the charge amount Q1 after 300 times, measure the charge amount Q2 after shaking 100 times, and evaluate it by the change ratio Q2 / Q1 × 100.

[0180] · Overcharge property of initial toner The overcharge property of the initial toner was measured by shaking the toner so that the number of shaking times was 300 times and 1200 times in the above-described toner charge measurement. Thereafter, based on the charge amount Q1 after 300 times of shaking, the charge amount Q3 after 1200 times of shaking was measured and evaluated by the change ratio Q3 / Q1×100.

[0181] · Charge retention property of long-term stored toner The charge retention property of the long-term stored toner was measured by measuring the charge amount Q1 of the initial toner with 300 times of shaking and the charge amount Q4 of the long-term stored toner with 300 times of shaking in the above-described toner charge measurement, and evaluated by the change ratio Q4 / Q1×100.

[0182] <Toner image confirmation> · Fixing property evaluation The process cartridge filled with toner was left at 25°C and 40%RH for 48 hours. Using the LBP-712Ci modified to operate even without the fixing unit, an unfixed image of an image pattern with 9-point evenly arranged 10mm×10mm square images was output over the entire transfer paper. The toner loading amount on the transfer paper was 0.80mg / cm 2 and the fixing lower limit temperature and the fixing upper limit temperature were evaluated while changing the temperature at 5°C intervals in the range of 100°C to 220°C. Note that A4 paper (「Prober Bond Paper」: 105g / m2, manufactured by Fox River Co., Ltd.) was used as the transfer paper. As the fixing unit, the fixing unit of the LBP-712Ci was removed externally, and an external fixing unit modified to operate outside the laser beam printer was used. Note that the external fixing unit increased the fixing temperature in 5°C increments from 120°C and performed fixing under the condition of a process speed of 360mm / sec. The fixed image was visually confirmed, and the lowest temperature at which no cold offset occurred was defined as the fixing lower limit temperature.

[0183] · Image stability evaluation To confirm the influence of charging stability on the image, image output was performed and evaluated for the initial toner and the toner after long-term storage. For the image output, a modified model of a commercially available Canon laser beam printer LBP7700C was used. The modification was made such that the rotation speed of the developing roller became 360 mm / sec by changing the evaluation machine body and software. 200 g of toner was loaded into the toner cartridge of the LBP7700C, and image output was performed in an environment of normal temperature and normal humidity NN (25°C / 50%RH) using this toner cartridge.

[0184] As a result of the evaluation, toners with excellent charging rise characteristics in the initial toner were excellent in density stability, and the image densities of the 1st, 5th, and 10th images were stable when continuously outputting 10 solid black images. Also, for toners with excellent overcharging characteristics in the initial toner, there was no change in the density of the solid black image immediately after outputting 200 solid white images continuously after outputting the 10th solid black image. Furthermore, for toners with excellent charge retention in the long-term storage toner, the image densities of the 1st, 5th, and 10th images were stable, and in addition, the same image densities as the test results obtained with the initial toner were obtained. Regarding the charging rise property Q2 / Q1×100, overcharging property Q3 / Q1×100, and charge retention property Q4 / Q1×100, results were good if they were between 70.0 and 130.0, and they appeared as image defects when they were less than 70.0 or greater than 130.0. The evaluation results of toner particle 1 are shown in Table 6.

[0185]

Table 6

[0186] 〔Examples 2 to 57, Comparative Examples 1 to 8〕 Using toner particles 2 to 57 and comparative toner particles 1 to 8 (toner particles 58 to 65), external addition treatment was performed in the same manner as for toner 1 to obtain toners 2 to 57 and comparative toners 1 to 8. Evaluation was performed in the same manner as for toner 1 using each of the obtained toners. The results are shown in Table 6.

[0187] The present disclosure relates to the following configuration. (Configuration 1) A toner having toner particles containing a binder resin and a wax, wherein the binder resin contains a polyester resin, the wax contains a hydrocarbon wax and an ester wax, the ester wax contains at least one compound selected from the group consisting of a monoester compound and a diester compound, the polyester resin contains a polyester resin A having a monomer unit corresponding to isophthalic acid and a monomer unit corresponding to dodecenyl succinic acid, the content of the monomer unit corresponding to isophthalic acid in the polyester resin A is 15.0 to 30.0% by mass, the content of the monomer unit corresponding to dodecenyl succinic acid in the polyester resin A is 3.0 to 20.0% by mass, the value W1 / W2 of the ratio of the content W1 of the hydrocarbon wax to 100 parts by mass of the binder resin to the content W2 of the ester wax to 100 parts by mass of the binder resin is 0.15 to 0.80, A toner characterized by the above. (Configuration 2) The toner according to Configuration 1, wherein the molecular weight of the ester wax is 500 to 1000. (Configuration 3) The toner according to Configuration 1 or 2, wherein the content W1 of the hydrocarbon wax with respect to 100 parts by mass of the binder resin is 0.5 to 7.0 parts by mass. (Configuration 4) The toner according to any one of Configurations 1 to 3, wherein the content W2 of the ester wax with respect to 100 parts by mass of the binder resin is 3.0 to 20.0 parts by mass. (Configuration 5) The toner according to any one of Configurations 1 to 4, wherein the content of the monomer unit corresponding to dodecenyl succinic acid based on the mass of the binder resin is 3.0 to 20.0% by mass. (Configuration 6) The content W1 of the hydrocarbon wax with respect to 100 parts by mass of the binder resin is 0.5 to 7.0 parts by mass, The content W2 of the ester wax with respect to 100 parts by mass of the binder resin is 3.0 to 20.0 parts by mass, The content of the monomer unit corresponding to dodecenyl succinic acid based on the mass of the binder resin is 3.0 to 20.0% by mass, The toner according to any one of Constitutions 1 to 5. (Constitution 7) The ester wax contains the monoester compound, The monoester compound includes a compound represented by the following formula (1), The toner according to any one of Constitutions 1 to 6. R 1 -COO-R 2 ···(1) (R 1 and R 2 each independently represents an alkyl group having 18 to 24 carbon atoms.) (Constitution 8) The toner according to any one of Constitutions 1 to 7, wherein the toner particles contain at least one compound A selected from the group consisting of a compound represented by the following formula (2) and a compound represented by the following formula (3). R 3 -O-(A 1 -O) n -X (2) (In formula (2), R 3 represents an alkyl group having 8 to 24 carbon atoms, A 1 represents an ethylene group or a propylene group, n is an integer of 5 to 60, and X is H, CH2COOH, CH2SO3H, CH2COONa, or CH2SO3Na.) R 4 -Ph-O-(A 2 -O) m -X (3) (In formula (3), R 4 represents an alkyl group having 8 to 24 carbon atoms, Ph represents a phenylene group, A 2represents an ethylene group or a propylene group, m is an integer from 5 to 60, and X is H, CH2COOH, CH2SO3H, CH2COONa, or CH2SO3Na.) (Configuration 9) The toner according to Configuration 8, wherein the extraction amount of the compound A extracted from the toner with ethanol is 10 to 2000 ppm. (Configuration 10) In the cross-sectional observation of the toner using a transmission electron microscope, when the average ratio of the area occupied by the domain of the wax in the surface layer region from the surface of the toner particles to a depth of 200 nm is As, The toner according to any one of Configurations 1 to 9, wherein As is 0.0 to 1.0 area%. (Configuration 11) The toner particles contain a boron atom, The toner according to any one of Configurations 1 to 10, wherein the content of the boron atom based on the mass of the toner particles is 1.0 to 100.0 mass ppm. (Configuration 12) The toner according to any one of Configurations 1 to 11, wherein the content ratio of the polyester resin A based on the mass of the binder resin is 50.0 to 100.0 mass%.

Explanation of symbols

[0188] 1 ······ Suction machine 2 ······ Measuring container 3 ······ 500-mesh screen 4 ······ Metal lid 5 ······ Vacuum gauge 6 ······ Air volume adjustment valve 7 ······ Suction port 8 ······ Capacitor 9 ······ Potentiometer

Claims

1. A toner having toner particles containing a binder resin and a wax, wherein the binder resin contains a polyester resin, the wax contains a hydrocarbon wax and an ester wax, the ester wax contains at least one compound selected from the group consisting of a monoester compound and a diester compound, the polyester resin contains a polyester resin A having a monomer unit corresponding to isophthalic acid and a monomer unit corresponding to dodecenyl succinic acid, the content of the monomer unit corresponding to isophthalic acid in the polyester resin A is 15.0 to 30.0% by mass, the content of the monomer unit corresponding to dodecenyl succinic acid in the polyester resin A is 3.0 to 20.0% by mass, the value W1 / W2 of the ratio of the content W1 of the hydrocarbon wax to 100 parts by mass of the binder resin to the content W2 of the ester wax to 100 parts by mass of the binder resin is 0.15 to 0.80, a toner characterized by the above.

2. The toner according to claim 1, wherein the molecular weight of the ester wax is 500 to 1000.

3. The toner according to claim 1 or 2, wherein the content W1 of the hydrocarbon wax with respect to 100 parts by mass of the binder resin is 0.5 to 7.0 parts by mass.

4. The toner according to claim 1 or 2, wherein the content W2 of the ester wax with respect to 100 parts by mass of the binder resin is 3.0 to 20.0 parts by mass.

5. The toner according to claim 1 or 2, wherein the content of the monomer unit corresponding to dodecenyl succinic acid based on the mass of the binder resin is 3.0 to 20.0% by mass.

6. The content W1 of the hydrocarbon wax with respect to 100 parts by mass of the binder resin is 0.5 to 7.0 parts by mass, the content W2 of the ester wax with respect to 100 parts by mass of the binder resin is 3.0 to 20.0 parts by mass, the content of the monomer unit corresponding to dodecenyl succinic acid based on the mass of the binder resin is 3.0 to 20.0% by mass, the toner according to claim 1 or 2.

7. The ester wax contains the monoester compound, the monoester compound includes a compound represented by the following formula (1), the toner according to claim 1 or 2. R １ -COO-R ２ ...(1) (R １ and R ２ each independently represents an alkyl group having 18 to 24 carbon atoms.)

8. The toner according to claim 1 or 2, wherein the toner particles contain a compound A which is at least one compound selected from the group consisting of a compound represented by the following formula (2) and a compound represented by formula (3). R ３ -O-(A １ -O) ｎ -X (2) (In formula (2), R ３ represents an alkyl group having 8 to 24 carbon atoms, A １ represents an ethylene group or a propylene group, n is an integer of 5 to 60, and X is H, CH ２ COOH, CH ２ S O ３ H, CH ２ COONa, or CH ２ SO ３ Na. ) R ４ -Ph-O-(A ２ -O) ｍ -X (3) (In formula (3), R ４ represents an alkyl group having 8 to 24 carbon atoms, Ph represents a phenylene group, A ２ represents an ethylene group or a propylene group, m is an integer of 5 to 60, and X is H, CH ２ COOH, CH ２ SO ３ H, CH ２ COONa, or CH ２ SO ３ Na.)

9. The toner according to claim 8, wherein the extraction amount of the compound A extracted from the toner with ethanol is 10 to 2000 ppm.

10. In the cross-sectional observation of the toner using a transmission electron microscope, when the average ratio of the area occupied by the domain of the wax in the surface layer region from the surface of the toner particles to a depth of 200 nm is As, The toner according to claim 1 or 2, wherein As is 0.0 to 1.0 area%.

11. The toner particles contain a boron atom, The toner according to claim 1 or 2, wherein the content of the boron atom based on the mass of the toner particles is 1.0 to 100.0 mass ppm.

12. The toner according to claim 1 or 2, wherein the content ratio of the polyester resin A based on the mass of the binder resin is 50.0 to 100.0 mass%.

Images