toner

Abstract

To provide a toner that is excellent in low temperature fixability, and excellent in electrification characteristics including image stability and image density uniformity after continuous printing.SOLUTION: A toner has toner particles containing a binder resin. The toner particle contains a compound A having a specific polyether structure and ester wax. The binder resin contains a polyester resin. The polyester resin has a monomer unit corresponding to a dodecenylsuccinic acid. The SP value of the ester wax (cal / cm3)0.5 is 8.70-9.00.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 the electrophotographic method include laser printers and copiers. In recent years, in particular, in addition to stable image quality of laser printers, high productivity is required. In order 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, or the plasticizing effect of a crystalline material compatible with the toner binder resin. However, these methods have a problem that the image quality changes greatly due to relaxation phenomena occurring in the toner binder resin itself or in materials compatible with the toner binder resin.

[0004] In Patent Document 1, the acid value / hydroxyl value of an ester composition is adjusted to enhance the affinity with the toner binder resin, thereby improving low-temperature fixing property, hot offset resistance, and durability. Furthermore, a method for improving the storage stability by crystallizing the ester composition at room temperature has been proposed. In Patent Document 2, the SP value of an organosilicon polymer, the domain diameter and SP value of an ester wax, and the SP value of a binder resin are controlled to enhance their compatibility, thereby improving low-temperature fixing property. Furthermore, the crosslink density of the organosilicon polymer is controlled to improve durability.

[0005] In Patent Document 3, the low-temperature fixability is enhanced by controlling the melting point of the crystalline polyester resin according to the resin composition, and the meltability of the toner is controllable by controlling the content of the block polymer, the resin composition, and the molecular weight. As a result, density unevenness and gloss unevenness of the image are reduced and the image quality is improved. In addition, in Patent Document 4, the dispersibility of each material constituting the toner is enhanced by the toner mother particles containing a nonionic surfactant, and the chargeability is controlled by the toner containing tin oxide particles as an external additive. As a result, even when continuous printing is performed after leaving in a high-temperature and high-humidity environment, excellent color streaking suppression property is achieved.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, the above-described documents had problems in order to achieve further high speed and stable image quality. In Patent Document 1, in order to improve the low-temperature fixability, hot offset resistance, and durability, it is necessary to adjust the acid value / hydroxyl value of the ester wax and enhance the affinity with the toner binder resin. However, when the affinity between the ester wax and the toner binder resin is enhanced, the chargeability at startup decreases, and there arises a problem that image quality variations occur between the initial image and the image after continuous printing.

[0008] In Patent Document 2, in order to improve the low-temperature fixability, it is necessary to control the resin composition of the binder resin and enhance the affinity between the toner binder resin and the ester wax. However, when the affinity between the toner binder resin and the ester wax is enhanced, as in Patent Document 1, the chargeability at the start-up decreases, and there arises a problem that the image quality varies between the initial image and the image after continuous printing.

[0009] When attempting to improve the low-temperature fixability with respect to Patent Document 3, increasing the amount of wax added can be cited as a means. However, although the low-temperature fixability is improved when the amount of wax added is increased, the compatibility with the toner binder resin increases, and as in Patent Documents 1 and 2, the chargeability significantly decreases, and the image stability and image density uniformity deteriorate.

[0010] Also, in Patent Document 4, a nonionic surfactant is contained in the toner, and the chargeability is controlled by externally adding tin oxide particles, providing excellent color streaking suppression even when left in a high-temperature and high-humidity environment and then continuous printing is performed. However, in the case of the toner configuration described in Patent Document 4, the compatibility between the wax and the binder resin is low, and the low-temperature fixability may not be sufficient. That is, the present disclosure provides a toner having excellent low-temperature fixability and further excellent charging characteristics such as image stability and image density uniformity during continuous printing.

Means for Solving the Problems

[0011] The present disclosure is a toner having toner particles containing a binder resin, wherein the toner particles contain at least one compound A selected from the group consisting of a compound represented by the following formula (1) and a compound represented by (2), and an ester wax, the binder resin contains a polyester resin, the polyester resin has a monomer unit corresponding to dodecenyl succinic acid, the SP value (cal / cm 3 ) 0.5 is 8.70 to 9.00, relates to a toner. R 1 -O-(A 1 -O) n -X ···(1) (In formula (1), R 1 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 2 -Ph-O-(A 2 -O) m -X ···(2) (In formula (2), R 2 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.)

Advantages of the Invention

[0012] According to the present disclosure, it is possible to provide a toner having excellent low-temperature fixability and excellent charging characteristics such as image stability and image density uniformity during continuous printing.

Modes 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 the 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, for example, the 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] In order to obtain a toner excellent in low-temperature fixability and charging properties, and further excellent in image stability and image density uniformity during continuous printing, the inventors have intensively studied the compatibility and chargeability of wax with polyester resin. And the inventors have found that the above-described problems can be solved by including a monomer unit corresponding to a specific acid in the polyester resin in the toner, controlling the SP value of the ester wax, and further including a compound having a polyether structure.

[0015] That is, the present disclosure is a toner having toner particles containing a binder resin, The toner particles contain at least one compound A selected from the group consisting of a compound represented by the following formula (1) and a compound represented by (2), and an ester wax, The binder resin contains a polyester resin, The polyester resin has a monomer unit corresponding to dodecenyl succinic acid, The SP value (cal / cm 3 ) 0.5 of the ester wax is 8.70 to 9.00, relates to a toner. R 1 -O-(A 1 -O) n -X ···(1) (In formula (1), R 1 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 2 -Ph-O-(A 2 -O) m -X ···(2) (In formula (2), R 2 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.

[0016] The toner of the present disclosure contains, as a binder resin, a polyester resin containing monomer units corresponding to dodecenyl succinic acid. By this polyester resin, the compatibility with wax is improved. The monomer units corresponding to dodecenyl succinic acid are structurally low-polar due to the alkyl chain, and thus have the effect of enhancing the compatibility with low-polar materials such as ester wax. In particular, the alkyl chain of dodecenyl succinic acid exists as a side chain with respect to the polyester molecule, so that higher compatibility can be exhibited. Also, by controlling the SP value (cal / cm 3 ) 0.5 of the ester wax to 8.70 to 9.00, the chargeability is improved.

[0017] The monomer units corresponding to dodecenyl succinic acid in the polyester resin have a structure in which dodecenyl succinic acid forms an ester bond, and are represented by, for example, the following formula (D). [Chemical formula]

[0018] However, with only the above-described design, overcharging occurs during continuous printing, resulting in a decrease in the leading-edge density and a deterioration in the image density uniformity. Therefore, an attempt was made to improve the charge stability by incorporating a compound having a polyether structure into the toner particles. As a result, it was found that by containing the toner particles with Compound A which is at least one compound selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2), excellent low-temperature fixability can be obtained, and stable chargeability can also be obtained even when continuous printing is repeated.

[0019] The inventors presume that this effect is manifested by the following mechanism. The monomer unit corresponding to dodecenyl succinic acid has a highly polar succinic acid moiety and a low-polarity long-chain alkyl moiety. Therefore, it becomes easier for the ester wax, which is a low-polarity material, to approach the monomer unit corresponding to dodecenyl succinic acid, and the interaction between the highly polar portion of the dodecenyl succinic acid and the ester group portion of the ester wax is strongly manifested. Due to this interaction, a more polar portion is generated. This highly polar portion is likely to accumulate charges and contribute to charge retention. In addition, the polyether structure of Compound A has a function of improving the mobility of charges within the toner particles. Furthermore, since the structure of Compound A has a high affinity with the polyester resin, the interaction of the polyether moiety is preferably manifested. Based on the above mechanism, it is presumed that the charging property at the start and the charging stability when continuous printing is repeated are excellent.

[0020] Therefore, the SP value (cal / cm 3 ) 0.5 of the ester wax needs to be 8.70 to 9.00. When the SP value of the ester wax is less than 8.70, the interaction with the polyester resin becomes weak, and the charging property after continuous printing is impaired. On the other hand, when the SP value of the ester wax is higher than 9.00, the compatibility with the polyester resin becomes low, and the fixing property deteriorates. Therefore, the SP value of the ester wax needs to be 8.70 to 9.00, preferably 8.80 to 8.90.

[0021] Also, when the toner particles contain Compound A, which is at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2), the charging stability during continuous printing is excellent. This is due to the improvement in the mobility of charges within the toner particles, which is derived from the polyether structure of Compound A. With the structures of formula (1) and formula (2), the affinity with the polyester resin is high, and the interaction of the polyether moiety is preferably manifested.

[0022] R 1-O-(A 1 -O) n -X ···(1) R 2 -Ph-O-(A 2 -O) m -X ···(2) From the perspective of affinity with the polyester resin, in formula (1), R 1 is preferably an alkyl group having 8 to 24 carbon atoms, more preferably an alkyl group having 10 to 18 carbon atoms. Also, in formula (2), R 2 is preferably an alkyl group having 8 to 24 carbon atoms, more preferably an alkyl group having 9 to 12 carbon atoms. Further, in order to obtain excellent charge mobility within the toner particles, in formula (1), n is preferably 5 to 60, more preferably 6 to 30, and even more preferably 8 to 20. In order to obtain excellent charge mobility, in formula (2), m is preferably 5 to 60, more preferably 6 to 30, and even more preferably 8 to 20.

[0023] R 1 、R 2 If the number of carbon atoms of R 1 、R 2 is less than the above lower limit, the intermolecular interaction between alkyl groups decreases, and it becomes difficult for compound A to approach dodecenyl succinic acid or ester wax, making it difficult to hold charges inside the toner, and the charging stability on the toner surface decreases. Therefore, it is considered that the density uniformity after continuous printing decreases. Also, if the number of carbon atoms of R

[0024] exceeds the above upper limit, the molecular weight of compound A becomes too large and it becomes difficult to move inside the toner, resulting in a decrease in charge transportability inside the toner and a low charging rise property, so it is considered that the density stability after continuous printing decreases.If n and m are less than the above lower limit, the affinity between Compound A and the polyester resin decreases, making it difficult to retain charges inside the toner, resulting in a decrease in the charge stability on the toner surface. Therefore, it is considered that the density uniformity after continuous printing decreases. On the other hand, if n and m exceed the above upper limit, the molecular weight of Compound A becomes too large, making it difficult to move inside the toner, resulting in a decrease in the charge transportability inside the toner and a low charge rising property, so it is considered that the density stability after continuous printing decreases.

[0025] In Formula (1) or Formula (2), A 1 or A 2 represents an ethylene group (-CH2CH2-) or a propylene group (-CH(CH3)CH2-), preferably an ethylene group. In Formula (1) or Formula (2), X is H, CH2COOH, CH2SO3H, CH2COONa, or CH2SO3Na, preferably H, but may also be CH2COOH or CH2SO3H.

[0026] Next, the SP value (cal / cm 3 ) 0.5 of the ester wax is 8.70 to 9.00. The molecular weight of the ester wax is, for example, 500 to 2000, preferably 500 to 1000, and more preferably 500 to 800. This is because the ester wax that satisfies the above conditions is excellent in compatibility with the polyester resin and the crystallization rate from the compatible state. As the ester wax that satisfies the above conditions, it is preferable to use an ester wax (diester wax) having two or more (bifunctional) ester structures in the molecule.

[0027] In the present disclosure, the molecular weight of the ester wax is a value calculated from the structure of the ester wax. In the case of a wax having a molecular weight distribution, such as a natural product-derived ester wax or a synthetic wax using a natural product or a monomer component derived from a polymer as a monomer component, the peak molecular weight of the molecular weight distribution obtained by GPC analysis is taken as the molecular weight of the ester wax.

[0028] Examples of ester waxes include ethylene glycol distearate, ethylene glycol dibehenate, ethylene glycol dipalmitate, 1,4-butanediol distearate, 1,4-butanediol dibehenate, 1,4-butanediol dipalmitate, 1,6-hexanediol distearate, 1,6-hexanediol dibehenate, 1,6-hexanediol dipalmitate, 1,8-octanediol distearate, 1,8-octanediol dibehenate, 1,8-octanediol dipalmitate, 1,10-decanediol distearate, 1,10-decanediol dibehenate, 1,10-decanediol dipalmitate, distearyl succinate, dipalmityl succinate, dibehenyl succinate, distearyl adipate, dipalmityl adipate, dibehenyl adipate, distearyl suberate, dipalmityl suberate, dibehenyl suberate, distearyl dodecanoate, dipalmityl dodecanoate, dibehenyl dodecanoate, and the like.

[0029] Among them, the ester wax preferably contains a diester wax which is a compound represented by the following formula (3). R 3 -COO-R 5 -OCO-R 4 ···(3) (R 3 and R 4 each independently represents an alkyl group having 17 to 22 carbon atoms, and R 5 represents an alkylene group having 2 to 6 carbon atoms.)

[0030] The ester wax having the structure of formula (3) is excellent in crystallization because the alkyl chain lengths represented by R 3 and R 4 are sufficiently long, and the proportion of the ester group is sufficiently contained to be compatible with the polyester resin. Further, since the alkylene chain length represented by R 5 is short, the interaction between the high-polarity group portion of the monomer unit corresponding to dodecenyl succinic acid and the ester group portion of the wax is more strongly expressed. In formula (3), R 3 and R 4Each is independently preferably an alkyl group having 17 to 22 carbon atoms, more preferably 17 to 19 carbon atoms, and R 5 is an alkylene group having 2 to 6 carbon atoms is preferably an alkylene group having 2 to 4 carbon atoms. The melting point of the ester wax is preferably 60 to 90 °C.

[0031] Furthermore, the content of the ester wax in the toner particles is, for example, 2.5 to 25.0 parts by mass, preferably 3.0 to 20.0 parts by mass, and more preferably 10.0 to 15.0 parts by mass with respect to 100 parts by mass of the binder resin. If it is within the above range, the compatibility with the polyester resin is excellent, and the low-temperature fixability is excellent. In addition, if it is within the above range, it is easy to separate from the state of being compatible in the polyester resin and crystallization is promoted.

[0032] In addition, the binder resin may contain a resin other than the polyester resin. In that case, based on the mass of the binder resin, the content ratio of the polyester resin 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. If it is within the above range, it is easy to obtain more excellent low-temperature fixability and chargeability.

[0033] 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, 2.5 to 22.0% by mass, preferably 3.0 to 20.0% by mass, and more preferably 5.0 to 14.0% by mass. When it is within the above range, the chargeability is more likely to be stable. The content ratio of the monomer unit corresponding to dodecenyl succinic acid in the binder resin can be controlled by adjusting the amount of dodecenyl succinic acid when producing the binder resin.

[0034] The extraction amount of Compound A extracted from toner with ethanol, based on the mass of the toner, is, for example, 10 to 1200 ppm, preferably 10 to 1000 ppm. In the toner, charges are generated due to 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 excess charges can be efficiently released. The above extraction amount is more preferably 30 to 500 ppm, and even more preferably 50 to 300 ppm.

[0035] The extraction amount of Compound A is adjusted according to the addition amount of Compound A added during the toner manufacturing process. The timing of adding Compound A may be during the toner particle manufacturing process or after the toner particle manufacturing. From the viewpoint of improving the interactivity with the polyester resin, it is preferable to add it during the toner particle manufacturing process, and from the viewpoint of uniformly existing on the surface of the toner particles, it is preferable to add Compound A in an aqueous medium.

[0036] Furthermore, in the cross-sectional observation of the toner using a transmission electron microscope, let the average ratio of the area occupied by the domain of wax including ester wax in the surface layer region from the surface of the toner particles to a depth of 200 nm be As. At this time, As is, for example, 0.0 to 2.0 area%, preferably 0.0 to 1.0 area%. This indicates that when As is within the above range, there is less wax near the surface of the toner particles.

[0037] In the present disclosure, by promoting the crystallization of the ester wax, the state of the wax after continuous printing is stabilized to suppress changes in the chargeability, but it is difficult to completely crystallize the ester wax. Especially when there are remaining compatible components of the ester wax around the wax domain, by setting As as above, the migration of the compatible components to the surface of the toner particles can be further suppressed. As is more preferably 0.0 to 0.5 area%. As can be adjusted by the addition amount of the wax and by forming a core-shell structure on the toner particles and controlling the thickness of the shell layer.

[0038] The toner particles preferably contain boron atoms. When the content of boron atoms based on the mass of the toner particles is, for example, 1.0 to 55.0 ppm, preferably 1.0 to 50.0 ppm, it is easy to obtain toner particles with excellent charge rising property and further excellent charge stability. 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 possessed by the polyester resin. As a result, it is considered that boron atoms are easily dispersed in the polyester resin containing boron atoms, and the charge retention of the toner is improved. Furthermore, it is considered that by forming a pseudo-crosslinked state via boron atoms due to the interaction between boron atoms and a large number of ester groups possessed by the polyester resin, the movement of ester wax that could not be completely crystallized is suppressed, and a toner with more excellent charge stability can be obtained.

[0039] The content of boron atoms is more preferably 3.0 to 30.0 ppm, and even more preferably 3.0 to 15.0 ppm. Boron atoms can be present in the toner particles by adding a compound containing boron atoms during the toner particle manufacturing process, and the content can be adjusted by the addition amount of the compound containing boron atoms.

[0040] [Constituent components of toner] Each component constituting the toner and the manufacturing method of the toner will be described in more detail. <Binder resin> The toner particles contain a binder resin. The binder resin contains a polyester resin. 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. Examples of binder resins other than the polyester resin are as follows.

[0041] The binding resin is not particularly limited, and examples thereof include styrene acrylic 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 fixing properties.

[0042] The polyester resin is obtained by selecting and combining suitable ones from polyvalent carboxylic acids, polyols, hydroxycarboxylic acids, etc., and synthesizing them using conventionally known methods such as the transesterification method or the polycondensation method.

[0043] The polyvalent carboxylic acid is a compound containing two or more carboxy groups in one molecule. Among these, dicarboxylic acid is a compound containing two carboxy groups in one molecule and is preferably used.

[0044] The polyester resin preferably contains 3.0 to 20.0% by mass of the monomer unit corresponding to dodecenyl succinic acid as the polyvalent carboxylic acid. Also, the content ratio of the monomer unit corresponding to dodecenyl succinic acid is preferably 5 to 40 mol%, more preferably 10 to 25 mol% in 100 mol% of the polyvalent carboxylic acid component of the polyester resin. The polyvalent carboxylic acids other than dodecenyl succinic acid in the polyester resin are as follows.

[0045] Examples of the dicarboxylic acid 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, isophthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, o-phenylenediacetic acid, Examples of dicarboxylic acids include diphenylacetic acid, diphenyl-p,p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, cyclohexane dicarboxylic acid, and the like.

[0046] Examples of polycarboxylic acids other than dicarboxylic acids include trimellitic acid, trimesic acid, pyromellitic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, pyrene tricarboxylic acid, pyrene tetracarboxylic acid, itaconic acid, glutaconic acid, and the like. These may be used alone or in combination of two or more.

[0047] A polyol is a compound containing two or more hydroxyl groups in one molecule. Among them, 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.

[0048] Among these, preferred ones are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols. Particularly preferred ones are alkylene oxide adducts of bisphenols and a combination thereof with alkylene glycols having 2 to 12 carbon atoms.

[0049] Examples of the polyol having a trivalent or higher valency include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, hexamethylolmelamine, hexaethylolemelamine, tetramethylolbenzoguanamine, tetraethylolebenzoguanamine, sorbitol, trisphenol PA, phenol novolak, cresol novolak, and alkylene oxide adducts of the above polyvalent phenols. These may be used alone or in combination of two or more.

[0050] More preferably, the polyvalent carboxylic acid contains at least one selected from the group consisting of terephthalic acid, isophthalic acid, sebacic acid, and trimellitic acid in addition to dodecenyl succinic acid. More preferably, the polyol contains at least one selected from the group consisting of alkylene oxide (ethylene oxide, propylene oxide) adducts of bisphenol A (for example, 1 to 10 moles, preferably 1 to 5 moles) and alkylene glycols having 2 to 6 carbon atoms.

[0051] The weight average molecular weight Mw of the polyester resin is preferably 10,000 to 100,000, and more preferably 20,000 to 50,000. The acid value of the polyester resin is preferably 10.0 to 40.0 mgKOH / g, and more preferably 15.0 to 25.0 mgKOH / g. Also, the hydroxyl value of the polyester resin is preferably 20 .0 to 50.0 mgKOH / g, and more preferably 25.0 to 35.0 mgKOH / g.

[0052] 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. Styrene-based 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-based 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, and maleic acid; Vinyl ether-based monomers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl ketone-based monomers such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl isopropenyl ketone; Polyolefins such as ethylene, propylene, and butadiene.

[0053] 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, pentaerythritol tetra(meth)acrylate, divinylbenzene, divinylnaphthalene, divinyl ether, and the like.

[0054] In addition, in order to control the degree of polymerization, it is also possible to further add known chain transfer agents and polymerization inhibitors.

[0055] 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.

[0056] 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.

[0057] In addition, a redox initiator obtained by combining an oxidizing substance and a reducing substance can also be used as the polymerization initiator. Examples of oxidizing substances include hydrogen peroxide, inorganic peroxides such as persulfates (sodium salts, potassium salts, and ammonium salts), and oxidizing metal salts of tetravalent cerium salts.

[0058] Examples of reducing substances 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).

[0059] 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.

[0060] <Wax> The toner particles contain wax, and the wax contains ester wax. The toner particles may contain known waxes to such an extent that the effects of the present disclosure are not impaired, in addition to the ester wax. Specific examples of waxes other than ester wax include hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin (e.g., polyethylene), petroleum waxes represented by petrolatum and their derivatives, montan wax and its derivatives, and the like. It is preferable that waxes other than ester wax contain hydrocarbon waxes. The content of other waxes is preferably 1.0 to 5.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

[0061] <Compound A> Compound A is at least one compound selected from the group consisting of the compound represented by the following formula (1) and the compound represented by (2). R 1 -O-(A 1 -O) n -X ···(1) (In formula (1), R 1 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 2 -Ph-O-(A 2 -O) m -X ···(2) (In formula (2), R 2 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.)

[0062] The method for producing the above compound is not particularly limited, and any method can be used. For example, ethylene oxide or propylene oxide can be added to an aliphatic alcohol in a predetermined amount according to the purpose. It can be obtained by quantitative addition. 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 alkyl ether or polypropylene alkyl ether having a relatively wide addition mole number distribution, and the latter can obtain a compound having 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.

[0063] <Colorant> The toner particles may contain a colorant. As the colorant, known pigments and dyes can be used. From the viewpoint of excellent weather resistance, a pigment is preferable as the colorant.

[0064] Examples of cyan 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.

[0065] Examples of magenta 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.

[0066] 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.

[0067] Examples of black colorants include those toned to black using the above yellow colorants, magenta colorants, and cyan colorants, as well as carbon black.

[0068] 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.

[0069] <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 the ability to stably maintain 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 the aqueous medium is particularly preferable.

[0070] Examples of those for controlling the toner to be negatively charged include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicar Examples include boronic acid-based metal compounds, aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, phenol 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.

[0071] Examples of the charge control resin include polymers or copolymers having a sulfonic acid group, a sulfonate group, or a sulfonic acid ester group. As the polymer having a sulfonic acid group, a sulfonate group, or a sulfonic acid ester group, a polymer containing a sulfonic acid group-containing acrylamide-based monomer or a sulfonic acid group-containing methacrylamide-based monomer in a copolymerization ratio of 2% by mass or more is particularly preferable, and a polymer containing 5% by mass or more is more preferable.

[0072] 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, preferable triboelectric charging characteristics can be imparted without affecting the thermal characteristics required for toner particles. Further, when the charge control resin contains a sulfonic acid group, for example, the dispersibility of the charge control resin itself and the dispersibility of a colorant in a polymerizable monomer composition are improved, and the coloring power, transparency, and triboelectric charging characteristics can be further improved.

[0073] 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 part by mass or more and 20.0 parts by mass or less, more preferably 0.5 part by mass or more and 10.0 parts by mass or less, based on 100.0 parts by mass of the binder resin.

[0074] [Method for producing toner] The method for manufacturing 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 manufactured by the emulsion aggregation method.

[0075] The method for manufacturing 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 an ester 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 an ester wax to form aggregates, and (3) A fusion step of heating and fusing the aggregates in this order. It is preferable that the method for manufacturing the toner is such that a boron compound is added in at least one of the aggregation step and the fusion step.

[0076] Also, during or after the fusion step, the following steps (4) to (6) (4) A spheroidization step of further heating the aggregates while increasing 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.

[0077] When the toner is manufactured 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.

[0078] <Emulsion Aggregation Method> The emulsion aggregation method is a method of preparing in advance an aqueous dispersion liquid of fine particles made of a constituent material of toner particles that is sufficiently small for a target particle diameter, aggregating the fine particles in an aqueous medium until they reach the particle diameter of the toner particles, and fusing the resin by heating or the like to manufacture 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 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 melting by heating or the like to control the surface shape of the toner, a subsequent cooling step, filtering the obtained toner, a metal removal step of removing excessive polyvalent metal ions, a filtration / washing step of washing with ion-exchanged water or the like, and a step of removing the moisture of the washed toner particles and drying them, through which the toner particles are manufactured.

[0079] (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 inversion emulsification method in which an aqueous 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 heat treatment in an aqueous medium without using an organic solvent.

[0080] 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, an aqueous medium is slowly added to precipitate resin fine particles. Then, the solvent is removed by heating or reducing the pressure to prepare an aqueous dispersion liquid of resin fine particles. As the organic solvent used for dissolving the resin, any organic 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.

[0081] The surfactant used during the emulsification is not particularly limited. For example, anionic surfactants such as sulfate ester salts, sulfonates, carboxylates, phosphate esters, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols can be mentioned. The surfactant may be used alone or in combination of two or more kinds.

[0082] 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 kinds.

[0083] 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, and 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 easy to obtain toner particles having a volume average particle size of 3 μm to 10 μm, which is appropriate 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.

[0084] (Wax fine particle dispersion liquid) The wax fine particle dispersion liquid containing ester wax can be prepared by the known methods listed below, but is not limited to these methods. 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, dispersing it into particles using a homogenizer having a strong shearing ability (for example, "Clear Mix 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.

[0085] 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. Further, it is 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 (Nano Track UPA - EX150: manufactured by Nikkiso Co., Ltd.).

[0086] (Coloring agent fine particle dispersion) If necessary, a coloring agent fine particle dispersion may be used. The coloring agent 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 coloring agent, 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 washing process described later, but from the viewpoint of washing efficiency, the surfactant is preferred.

[0087] 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.

[0088] 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. Further, from the viewpoint of the dispersibility of the colorant in the finally obtained toner, the dispersed 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 dispersed 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, a jet mill, a pressure homogenizer, a colloid mill, a ball mill, a sand mill, and a paint shaker. These may be used alone or in combination.

[0089] (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.

[0090] (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, so as to form aggregates in which resin fine particles, wax fine particles, and colorant fine particles are aggregated.

[0091] 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. It is also possible to add an acid to lower the pH and cause soft aggregation, for example, sulfuric acid or nitric acid can be used.

[0092] The flocculant 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. Further, 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 carrying out the mixing under this temperature condition, the 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 by a particle size distribution analyzer using the Coulter method (Coulter Multisizer III: manufactured by Coulter).

[0093] (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 forming 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 40 parts by mass or less, more preferably 10 parts by mass or more and 35 parts by mass or less, based on 100 parts by mass of the binder resin contained in the core particles. 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, a polyester resin having a monomer unit corresponding to dodecenyl succinic acid described above may be used.

[0094] 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.

[0095] In addition, when forming the shell, in order to make it easier for the toner particles to contain boron, in the shell forming process, 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. 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 process, and the shell forming process is carried out.

[0096] In the shell formation step, the presence of boric acid makes it easier for the shell resin to aggregate uniformly on the core particles, thereby reducing the area of the wax domain near the surface.

[0097] Boric acid only needs to 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, it is preferable to add a borate as the boron compound. Specifically, the boron compound more preferably contains at least one selected from the group consisting of sodium tetraborate, borax, and ammonium borate, and even more preferably is borax.

[0098] 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 preferable to add it 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.

[0099] (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 aggregation is stopped by adding an aggregation inhibitor such as a base capable of adjusting the 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.

[0100] (Step of obtaining the desired surface shape of the toner (spheroidization step)) During or after the fusion step, it is preferable to further raise the temperature and pass through a spheroidization step in which the toner particles are held until they have 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 longer, 2 hours or longer, and 3 hours or longer. The upper limit is, for example, 5 hours or shorter. By this step, hydrogen bonds derived from boric acid are likely to be formed in the toner particles.

[0101] (Cooling step) After the spheroidization step, it is preferable to pass through a cooling step in which the temperature of the dispersion liquid containing the obtained toner particles is cooled while controlling the cooling rate 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 passing 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 ester wax near the surface of the toner particles. Specific cooling rates are 0.1°C / second or higher, preferably 0.5°C / second or higher, more preferably 2°C / second or higher, and even more preferably 4°C / second or higher. The upper limit is, for example, 20°C / second or lower, 15°C / second or lower

[0102] (Annealing step) After the cooling step, an annealing step may be performed in which the temperature is heated and held 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. By passing 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.

[0103] (Post-treatment process) In the method for manufacturing toner, further, post-treatment processes 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.

[0104] (External addition 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. As 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.

[0105] Furthermore, in order to adhere more firmly, it is effective to increase the rotational speed and lengthen the external addition time. In particular, the adhesion strength can be further increased by increasing the rotational speed. In addition, 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 advance the crushing while suppressing the adhesion strength, it is effective to lower the rotational speed and lengthen the external addition time. 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.

[0106] [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 by 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 dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data, with an effective number of measurement channels of 25,000 channels. The electrolytic aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water so that the concentration is about 1% by mass. For example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used.

[0107] Before performing 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 set 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.

[0108] 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 revolutions per second. Then, use the "Flash of Aperture Tube" function of the dedicated software to remove dirt and bubbles in the aperture tube. (2) Place approximately 30 ml of the electrolytic aqueous solution into a 100 ml glass flat-bottom beaker, and add approximately 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.) three times by mass with ion-exchanged water as a dispersant. (3) Place a predetermined amount of ion-exchanged water into the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora150" (manufactured by Nikka Kikai Bios Co., Ltd.) with an electrical output of 120 W, which incorporates two oscillators with an oscillation frequency of 50 kHz and a 180-degree phase shift, and add approximately 2 ml of the Contaminon N into this water tank. (4) Set the beaker in (2) above into 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) with ultrasonic waves, add and disperse approximately 10 mg of toner or toner particles little by little into the electrolytic aqueous solution. Then, continue the ultrasonic dispersion treatment for another 60 seconds. In ultrasonic dispersion, appropriately adjust the water temperature in the water tank to be 10°C or higher and 40°C or lower. (6) Using a pipette, drop the electrolytic aqueous solution in (5) in which toner or toner particles are dispersed into the round-bottom beaker in (1) placed in the sample stand, and adjust so that the measured concentration becomes approximately 5%. Then, perform the measurement until the number of measured particles reaches 50,000. (7) Analyze the measurement data using 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).

[0109] <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 in 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.

[0110] (2) Operation (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 faint 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).

[0111] (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).

[0112] <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 so as not to come into contact with carbon dioxide gas, etc., leave it standing 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 0.5 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.

[0113] (2) Operation (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 punched in it. 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, shake it, and hydrolyze the acetic anhydride. Further, in order to completely hydrolyze, 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 several 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 persists for about 30 seconds. (B) Blank test Conduct a titration in the same manner as the above operation except that no sample is used.

[0114] (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 the potassium hydroxide solution, S: mass of the sample (g), D: acid value of the sample (mgKOH / g).

[0115] <Method for measuring the content ratio of monomer units corresponding to dodecenyl succinic acid based on the mass of the binder resin> The content ratio of monomer units corresponding to dodecenyl succinic acid based on the mass of the binder resin is measured using a pyrolysis gas chromatography mass spectrometer (hereinafter, pyrolysis GC / MS) and NMR. Specifically, the following operations are performed. (1) Weigh 50 mg of toner precisely into an 8 mL glass sample bottle, add 1 mL of deuterated chloroform, then cover it and disperse and dissolve it with an ultrasonic disperser for 1 hour. Next, filter it through a membrane filter with a diameter of 0.4 μm 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 content ratio of the monomer unit corresponding to dodecenyl succinic acid 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 conduct composition analysis. (4) Calculate the amount of binder resin in the toner according to the <Method for Measuring the Content of Ester Wax in Toner> described later, and from these values, the content ratio of the monomer unit corresponding to dodecenyl succinic acid based on the mass of the binder resin can be calculated.

[0116] (Measurement conditions for NMR) Bruker AVANCE 500 manufactured by Bruker BioSpin Corporation Nuclei for measurement: 1 1H, 13 13C Measurement frequency: 500.1 MHz Number of accumulations: 16 times, 2048 times Measurement temperature: room temperature

[0117] (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: Inlet Temp: 250 °C Split Flow: 50 mL / min GC Temperature Rising Conditions: 40 °C (5 min) → 10 °C / min (300 °C) → 300 °C (20 min)

[0118] <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, perform the measurement under the following conditions. · Apparatus: HLC8120 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 When calculating the molecular weight of the sample, use the molecular weight calibration curve prepared using a standard polystyrene resin (for example, product 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).

[0119] <Identification of Molecular Structure of Ester Wax Contained in Toner> First, wax contained in toner is isolated from the toner by the following separation operation. 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 the ester wax. Even when waxes other than the ester wax are mixed, they can be isolated by this separation operation. Next, the molecular structure of the isolated ester wax is identified. The molecular structure is identified using pyrolysis gas chromatography-mass spectrometer (hereinafter referred to as pyrolysis GC / MS) and NMR.

[0120] 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 using 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 spectrum is assigned to the ester wax. (3) Analysis is performed by pyrolysis GC / MS. If necessary, derivatization treatment such as methylation is performed to calculate the molecular weight of the ester wax.

[0121] (Measurement conditions for NMR) Bruker AVANCE 500 manufactured by Bruker BioSpin Corporation Nucleus measured: 1 1H Measurement frequency: 500.1 MHz Number of integrations: 16 times Measurement temperature: room temperature

[0122] (Measurement Conditions for Pyrolysis GC / MS) Pyrolyzer: TPS-700 manufactured by Nippon Analytical Industry Co., 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 Program: 40 °C (5 min) → 10 °C / min (300 °C) → 300 °C (20 min)

[0123] <Method for Measuring Ester Wax Content in Toner>[[]] The content W of ester wax with respect to 100 parts by mass of the binder resin in the toner is 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 mass X3 of the incineration residue of the insoluble component in the toner. Next, it can be calculated by determining the content w of ester wax in the toner. Specifically, accurately weigh 1.5 g of toner, place it in a pre-weighed cylindrical filter paper (product name: No. 86R, size 28 × 100 mm, manufactured by Advantec Toyo Co., Ltd.), and set it in a Soxhlet extractor. Use 200 mL of tetrahydrofuran (THF) as the solvent and extract for 20 hours, and perform the extraction at a reflux rate such that the extraction cycle of the solvent is once every 5 minutes. After removing the cylindrical filter paper after the extraction and air-drying it, vacuum-dry it at 40 °C for 8 hours, weigh the mass of the cylindrical filter paper containing the extraction residue, and subtract the mass of the cylindrical filter paper to obtain the mass of the extraction residue as the mass X2 (g) of the tetrahydrofuran (THF) insoluble component in the toner. Also, the mass X1 (g) of the tetrahydrofuran (THF) soluble component in the toner is determined from the following formula (A). X1 = 1.5 - X2 (A) Next, the content X3 (g) of components other than the resin component is determined by the following procedure. Weigh precisely 1.5 g of toner into a 30 mL magnetic crucible that has been pre-weighed. Place the magnetic crucible in an electric furnace and heat it at 900 °C for 3 hours. Let it cool in the electric furnace, then cool it in a desiccator at room temperature for 1 hour or more. Weigh the mass of the crucible containing the incinerated residual ash, and subtract the mass of the crucible to calculate the incinerated residual ash X3 (g).

[0124] Furthermore, filter the extract obtained by the above operation through a solvent-resistant membrane filter “Micros Disc” with a pore size of 0.2 μm (manufactured by Tosoh Corporation) to obtain a sample solution. Using this sample solution, measurements are performed 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 components in the obtained toner, and the area P derived from the ester wax having a molecular weight corresponding to the wax identified by the above-described method. From the following calculation formula (B), the amount w of ester wax in the toner can be determined. w = (X1 × P / S) = {(1.5 - X2) × P / S} ··· (B) Also, from the total area S of the molecular weight distribution of the tetrahydrofuran (THF)-soluble components in the toner and the area P derived from all waxes by the above GPC W the amount R of the binder resin in the toner can be determined from the following formula (R). R = {X1 + (X2 - X3)} - (X1 × P W / S) ··· (R) From the obtained content w of the ester wax and the amount R of the binder resin, the content of the ester wax with respect to 100 parts by mass of the binder resin can be determined.

[0125] <Calculation Method for SP Value of Ester Wax> The SP value of the ester wax was determined as follows according to the calculation method proposed by Fedors. When calculating the SP value (cal / cm 3 ) 0.5 of the ester wax, for the atoms or atomic groups in the molecular structure of the identified ester wax, the evaporation energy (Δei) (cal / mol) and molar volume (Δvi) (cm 3 / mol) were obtained from the table described in "Polym. Eng. Sci., 14(2), 147 - 154(1974)", and calculated by the following formula (4) . Formula (4): SP value of ester wax = (ΣΔei / ΣΔvi) 0.5

[0126] <Measurement of Extraction Amount of Compound A Extracted by Ethanol> The extraction amount of compound A extracted from the toner by ethanol is 1 determined as follows using H-NMR (nuclear magnetic resonance) measurement. First, 50 ml of ethanol and 5 g of toner were precisely weighed and well mixed in a sample bottle, and then ultrasonic waves were irradiated for 30 minutes using a tabletop ultrasonic cleaner (trade name "B2510JMTH", manufactured by Branson) with an oscillation frequency of 42 kHz and an electrical output of 125 W. Then, filtration was performed using a solvent-resistant membrane filter "Maeshori Disk" (manufactured by Tosoh Corporation) with a pore diameter of 0.2 μm. After removing ethanol from the filtrate using an evaporator, it was dissolved in deuterated chloroform (1% TMS) containing 10 mg of trimethylsilane (TMS), 1 analyzed by H-NMR, and the structure of compound A was identified. Separately, 1 H-NMR measurement of the identified compound A was performed, and the extraction amount (ppm) of compound A extracted from the toner was calculated using a calibration curve based on the TMS intensity standard. The calibration curve was created from the ratio of the TMS intensity to the peak intensity of hydrogen from the ethylene oxide group in the vicinity of 3.0 - 5.0 ppm. The measuring device and measurement conditions are as follows.

[0127] (NMR measurement conditions) Bruker AVANCE 500 manufactured by Bruker BioSpin Corporation Nucleus measured: 1 H Measurement frequency: 500.1 MHz Number of integrations: 1024 times Measurement temperature: room temperature

[0128] <Calculation of the average ratio As 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 As 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, the toner is embedded in a visible light-curable embedding resin (D-800, manufactured by Nisshin EM Co., Ltd.), cut to a thickness of 60 nm with an ultrasonic ultramicrotome (EM5, manufactured by Leica), and Ru staining is performed with a vacuum staining apparatus (manufactured by Filgen). Then, observation is carried out at an acceleration voltage of 120 kV with a transmission electron microscope (H7500, manufactured by Hitachi). For the toner cross-section to be observed, 100 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. With 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 parts, and the parts other than the crystalline resin component of the toner become the dark parts. The contour of the toner can be distinguished by the brightness and darkness of the toner and the photocurable resin.

[0129] Masking is performed while leaving the surface layer region from the toner particle surface (cross-sectional contour) to a depth of 200 nm in the cross-section of the toner particles. 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, a position 200 nm in the direction from the contour to the center of gravity is specified. Then, this operation is performed for one full circumference with respect to the contour of the toner particle cross-section to identify 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.

[0130] <Method for Quantifying Boron Atoms Based on the Mass of Toner Particles> The content of boron (B) atoms based on the mass of the toner particles is quantified by 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 the ICP-MS measurement is carried out to quantify the content of boron atoms in the toner particles.

[0131] [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 decomposition was carried out using the above apparatus. The acid decomposition was performed in two steps to obtain the desired measurement solution for ICP-MS. The acid decomposition conditions are as follows. First stage of acid decomposition The heating temperature and holding time during acid decomposition were carried out according to 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 decomposition The heating temperature and holding time during acid decomposition were carried out according to 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.

[0132] [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.

[0133] [Method for Obtaining Toner Particles by Removing Externally Added Agents from Toner] Add 160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) to 100 mL of ion-exchanged water and dissolve it while stirring in hot water to prepare a thick sucrose solution. Put 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 instruments with a pH of 7 composed of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) into a centrifuge tube (capacity 50 ml). Add 1.0 g of toner here and loosen the toner clumps with a spatula or the like. Shake the centrifuge tube with 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 with a centrifuge (manufactured by Kokusan Co., Ltd., model H-9R) at 3500 rpm for 30 minutes.

[0134] By this operation, the toner particles and the externally added agents are separated. The toner particles and the aqueous solution are sufficiently separated. Visually confirm that it is separated, and collect the toner particles separated on the top layer with a spatula or the like. After filtering the collected toner particles with a vacuum filter, dry them with a dryer for 1 hour or more to obtain a sample for measurement. Repeat this operation multiple times to ensure the required amount.

Example

[0135] 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 based on mass unless otherwise specified.

[0136] <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 terephthalic acid · 160 parts by mass of dodecenyl succinic anhydride The above monomers were charged into a flask equipped with a stirring device, a nitrogen inlet tube, a temperature sensor, and a rectification column, heated to 195°C in 1 hour, and it was confirmed that the reaction system was uniformly stirred. 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. Then, the temperature was lowered to 190°C, and 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 with an acid value of 19.9 mgKOH / g, a hydroxyl value of 31.7 mgKOH / g, and a weight average molecular weight of 32,000 was obtained. Regarding polyester resin 1, the synthesis conditions and analysis results are shown in Tables 1 and 2.

[0137] <Synthesis of Polyester Resins 2 to 9> In the synthesis example of polyester resin 1, polyester resins 2 to 9 were obtained in the same manner as in the synthesis example of polyester resin 1, except that the raw materials used were changed as shown in Table 1. For polyester resins 2 to 9, the synthesis conditions and analysis results are shown in Tables 1 and 2.

[0138]

Table 1

[0139]

Table 2

[0140] <Synthesis example of ester wax 1> Into a reaction vessel equipped with a thermometer, a nitrogen inlet tube, a stirrer, a Dean-Stark trap, and a Dimroth condenser, 10 parts of ethylene glycol as an alcohol monomer and 100 parts of stearic acid as a carboxylic acid monomer were added, and an esterification reaction was carried out at 200 °C for 15 hours. 20 parts of toluene and 25 parts of isopropanol were added to the obtained ester compound, and 190 parts of a 10% potassium hydroxide aqueous solution corresponding to 1.5 times the acid value of the ester compound were added, and the mixture was stirred at 70 °C for 4 hours. Then, the water tank part was removed. Further, 20 parts of ion-exchanged water was added and the mixture was stirred at 70 °C for 1 hour, and then the water tank part was removed and washing was carried out. The above washing step was repeated until the pH of the removed water tank became neutral. Thereafter, the pressure was reduced under the conditions of 200 °C and 1 kPa to remove the solvent, and ethylene glycol distearate (ester wax 1), which is an ester compound of ethylene glycol and stearic acid, the final target product, was obtained. For the obtained ester wax 1, the synthesis conditions and analysis results are shown in Tables 3 and 4.

[0141] <Production examples of ester waxes 2 to 10> In the synthesis example of ester wax 1, except for changing the raw materials used as shown in Table 3, ester waxes 2 to 10 were obtained in the same manner as in the synthesis example of ester wax 1. Regarding the obtained ester waxes 2 to 10, the synthesis conditions and analysis results are shown in Tables 3 and 4.

[0142]

Table 3

[0143]

Table 4

[0144] <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, an addition reaction was carried out while injecting 720 parts by mass of ethylene oxide at 150°C under 0.3 MPa. After the reaction was completed, aging was carried out at the same reaction temperature for 6 hours, and then it was 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 5. After aging at the same reaction temperature for 6 hours, it was 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 5.

[0145] <Synthesis of Compounds A2 to A9, A11, A13 to A16> In the synthesis example of Compound A1, except for changing the raw materials used as shown in Table 3, Compounds A2 to A9, A11, A13 to A16 were obtained in the same manner as in the synthesis example of Compound A1. Regarding Compounds A2 to A9, A11, A13 to A16, they are shown in Table 5.

[0146] <Synthesis of Compound A10> 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 added. 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, the gas was switched to oxygen and flowed for 18 hours under the condition of 90 mL / min to cause a reaction, and Compound A10 was obtained. Compound A10 is shown in Table 5.

[0147] <Synthesis of Compound A12> 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 A11, 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 added. 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, the gas was switched to oxygen and flowed for 18 hours under the condition of 90 mL / min to cause a reaction, and Compound A12 was obtained. Compound A12 is shown in Table 5.

[0148]

Table 5

[0149] <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 put into a container. Then, 100 parts by mass of polyester resin 1 was gradually added, and stirring was carried out to completely dissolve it 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 10% aqueous ammonia solution was gradually added dropwise, and further 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min to carry out 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 this 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.

[0150] <Preparation of Resin Particle Dispersions of Polyester Resins 2 to 9> In the preparation of the resin particle dispersion of polyester resin 1, resin fine particle dispersions of polyester resins 2 to 9 were prepared in the same manner except that polyester resin 1 was changed to polyester resins 2 to 9.

[0151] <Preparation of Coloring Agent 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 (coloring agent fine particle dispersion) with a concentration of 20% by mass of coloring agent fine particles in which the coloring agent was dispersed.

[0152] <Preparation of Hydrocarbon Wax Particle Dispersion> · 45 parts of hydrocarbon wax (HNP-9, manufactured by Nippon Seiro Co., Ltd.) · 5 parts of an ionic surfactant Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) · 190 parts of ion-exchanged water After charging the above into a mixing container equipped with a stirrer, 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 liquid with a volume average particle diameter of 160 nm and a solid content of 20 mass%.

[0153] <Preparation of Ester Wax Dispersion Liquid 1> · 45 parts of ester wax 1 · 5 parts of anionic surfactant Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) · 190 parts of ion-exchanged water After charging the above into a mixing container equipped with a stirrer, 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 Liquid 1 with a volume average particle diameter of 170 nm and a solid content of 20 mass%.

[0154] <Adjustment of Ester Wax Dispersion Liquids 2 to 10> Ester Wax Dispersion Liquids 2 to 10 were obtained in the same manner as in the preparation of Ester Wax Dispersion Liquid 1, except that ester wax 1 was changed to ester waxes 2 to 10.

[0155] <Manufacture of Toner Particles 1> · 750 parts of resin particle dispersion of polyester resin 1 · 70 parts of colorant particle dispersion · 30 parts of hydrocarbon wax dispersion 1 · 130 parts of ester wax dispersion 1 · 1000 parts of ion-exchanged water First, as a 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 Ultra Turrax T50 (manufactured by IKA). 1.0% nitric acid aqueous solution was added and the pH was adjusted to 3.0 After that, in a water bath for heating, while appropriately adjusting the rotation speed such that the mixed solution was stirred using a stirring blade, it was heated to 45 °C

[0156] The volume average particle diameter of the formed aggregated particles was appropriately confirmed using a Coulter Multisizer III. When aggregated particles (cores) with a particle diameter of 5.0 μm were formed, as a shell formation step, each of the following materials was added and stirred for an additional 1 hour to form a shell · 250 parts of resin particle dispersion of polyester resin 1 · 300 parts of ion-exchanged water · 100 parts of 3.0 mass% aqueous solution of compound A1 · 50 parts of 2.0 mass% borax aqueous solution (Borax; Sodium tetraborate decahydrate manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) Thereafter, as a spheroidization step, the pH was adjusted to 9.0 using a 5% sodium hydroxide aqueous solution, and while continuing stirring, it was heated to 90 °C 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 (heating time was 3 hours). Thereafter, as a cooling step, ice was quickly added so that the cooling rate was 10 °C / second or more and cooled to 25 °C to obtain a dispersion of toner particles 1

[0157] 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 using 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 using the aforementioned filter to obtain a toner cake. Further, 2000 parts by mass of ion-exchanged water was added to the toner cake, and while maintaining a pressure of 0.3 MPa for dehydration treatment, washing was carried out. Further, after air drying was carried out while maintaining 0.2 Mpa, the toner cake was taken out and subjected to disintegration treatment. The disintegrated toner cake was dried in a vacuum dryer at 40 °C for 12 hours, and then subjected to classification treatment to obtain toner particles 1. Regarding toner particles 1, the manufacturing conditions and analysis results are shown in Tables 6 and 7.

[0158] <Manufacture of Toner Particles 2 - 45 and Comparative Toner Particles 1 - 11> 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 - 45 and comparative toner particles 1 - 11. Regarding toner particles 2 - 45 and comparative toner particles 1 - 11, the manufacturing conditions and analysis results are shown in Tables 6 and 7.

[0159]

Table 6

[0160]

Table 7

[0161] [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 carried out according to the following procedure.

[0162] [Evaluation method] [Evaluation of low-temperature fixing property] A process cartridge filled with Toner 1 was left standing at 25°C and a humidity of 40% RH for 48 hours. Using an LBP-712Ci modified to operate even without the fixing unit, an unfixed image of an image pattern with 9-point evenly arranged 10 mm × 10 mm square images across the entire transfer paper was output. The toner loading on the transfer paper was 0.80 mg / 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. The transfer paper used was A4 paper ("Prober Bond Paper": 105 g / m 2 , manufactured by Fox River). For 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. The external fixing unit was heated in increments of 5°C from 120°C, and fixing was performed under the condition of a process speed of 360 mm / sec. The fixed image was visually confirmed, and the lowest temperature at which cold offset did not occur was taken as the fixing lower limit temperature.

[0163] [Evaluation of Concentration Stability and Concentration Uniformity] As an evaluation device, a Color Laser Jet Enterprise 6701dn manufactured by HP was prepared and modified so that the printing speed could be changed. Using the process cartridge filled with the above toner 1, in an environment of normal temperature and humidity NN (25°C / 50% RH), at a printing speed of 75 sheets per minute, a horizontal line with an image ratio of 1% was continuously printed on 15,000 sheets of paper (printing) for a durability test, and then the concentration stability and concentration uniformity were evaluated. For the evaluation of concentration stability and concentration uniformity, after the above durability test, a solid black image was output on the first sheet, a horizontal line image was output from the second sheet to the 99th sheet, and a solid black image was output again on the 100th sheet. Regarding the solid black images on the first and 100th sheets, the image densities at six points, namely the left, center, and right parts on the lines 10 cm and 20 cm from the upper end of the transfer material, were measured, and the average value was calculated. The concentration stability was evaluated from the difference between the average concentration value of the first sheet and the average concentration value of the 100th sheet. Also, for the solid black image on the 100th sheet, the image density uniformity was evaluated from the difference between the average values of the image densities at 1 cm and 10 cm from the upper end of the transfer material. The transfer material used was GF-C081 of A4 size (manufactured by Canon, 81.4 g / m 2 ), and for the density measurement, X-rite ex act advance (manufactured by X-rite) was used.

[0164] The evaluation criteria are as follows. · Judgment criteria for concentration stability evaluation (Evaluation criteria) A: The difference between the average concentration values of the first and 100th sheets is less than 0.04 B: The difference between the average concentration values of the first and 100th sheets is 0.04 or more and less than 0.07 C: The difference between the average concentration values of the first and 100th sheets is 0.07 or more and less than 0.10 D: The difference between the average concentration values of the first and 100th sheets is 0.10 or more

[0165] · Judgment criteria for concentration uniformity evaluation (Evaluation criteria) A: The difference in the average values of the image densities at 1 cm and 10 cm from the upper end of the transfer material is less than 0.04 B: The difference in the average values of the image densities at 1 cm and 10 cm from the upper end of the transfer material is 0.04 or more and less than 0.07 C: The difference in the average values of the image densities at 1 cm and 10 cm from the upper end of the transfer material is 0.07 or more and less than 0.10 D: The difference in the average values of the image densities at 1 cm and 10 cm from the upper end of the transfer material is 0.10 or more

[0166] As a result of evaluating Toner 1, the densities of the first and 100th solid black images were both 1.40 or more, and furthermore, the difference in the average values of those densities was less than 0.04, indicating stability. Also, regarding the 100th solid black image, the difference in the average values of the image densities at 1 cm and 10 cm from the upper end of the transfer material was less than 0.04, and it was also excellent in terms of density uniformity. The evaluation results of Toner 1 are shown in Table 8.

[0167]

Table 8

[0168] 〔Examples 2 to 45 and Comparative Examples 1 to 11〕 Table 8 shows the evaluation results obtained in the same manner as in Example 1 for Examples 2 to 45 and Comparative Examples 1 to 11.

[0169] This disclosure relates to the following configuration. (Configuration 1) A toner having toner particles containing a binder resin, wherein the toner particles contain at least one compound A selected from the group consisting of a compound represented by the following formula (1) and a compound represented by (2), and an ester wax, the binder resin contains a polyester resin, the polyester resin has a monomer unit corresponding to dodecenyl succinic acid, the SP value (cal / cm 3 ) 0.5 of the ester wax is 8.70 to 9.00, characterized in that it is a toner. R 1 -O-(A 1 -O) n -X ···(1) (In formula (1), R 1 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 2 -Ph-O-(A 2 -O) m -X ···(2) (In formula (2), R 2 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.) (Constitution 2) The toner according to Constitution 1, wherein the molecular weight of the ester wax is 500 to 1000. (Constitution 3) The toner according to Constitution 1 or 2, wherein the content of the ester wax in the toner is 3.0 to 20.0 parts by mass with respect to 100 parts by mass of the binder resin. (Constitution 4) The toner according to any one of Constitutions 1 to 3, wherein the content ratio 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. (Constitution 5) The toner according to any one of Constitutions 1 to 4, wherein the extraction amount of the compound A extracted from the toner with ethanol is 10 to 1000 ppm based on the mass of the toner. (Constitution 6) The content of the ester wax in the toner is 3.0 to 20.0 parts by mass with respect to 100 parts by mass of the binder resin, the content ratio 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 extraction amount of the compound A extracted from the toner with ethanol is 10 to 1000 ppm based on the mass of the toner. The toner according to any one of Configurations 1 to 5. (Configuration 7) The toner according to any one of Configurations 1 to 6, wherein the ester wax contains a compound represented by the following formula (3). R 3 -COO-R 5 -OCO-R 4 ···(3) (R 3 and R 4 each independently represents an alkyl group having 17 to 22 carbon atoms, and R 5 represents an alkylene group having 2 to 6 carbon atoms.) (Configuration 8) 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 including the ester 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 7, wherein As is 0.0 to 1.0 area%. (Configuration 9) The toner particles contain a boron atom, and the content of the boron atom based on the mass of the toner particles is 1.0 to 50.0 ppm. The toner according to any one of Configurations 1 to 8. (Configuration 10) The toner according to any one of Configurations 1 to 9, wherein the content ratio of the polyester resin based on the mass of the binder resin is 50.0 to 100.0 mass%.

Claims

1. A toner having toner particles containing a binder resin, wherein the toner particles contain at least one compound A selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), and an ester wax, the binder resin contains a polyester resin, the polyester resin has a monomer unit corresponding to dodecenyl succinic acid, The SP value (cal / cm ３ ) ０．５ of the ester wax is 8.70 to 9.00, and the toner is characterized by this. R １ -O-(A １ -O) ｎ -X...(1) (In formula (1), R １ 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 SO ３ H, CH ２ COONa, or CH ２ SO ３ Na.) R ２ -Ph-O-(A ２ -O) ｍ -X...(2) (In formula (2), R ２ 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.)

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 of the ester wax in the toner is 3.0 to 20.0 parts by mass with respect to 100 parts by mass of the binder resin.

4. The toner according to claim 1 or 2, wherein the content ratio 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.

5. The toner according to claim 1 or 2, wherein the extraction amount of the compound A extracted from the toner with ethanol is 10 to 1000 ppm based on the mass of the toner.

6. The content of the ester wax in the toner is 3.0 to 20.0 parts by mass with respect to 100 parts by mass of the binder resin, the content ratio 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, and the extraction amount of the compound A extracted from the toner with ethanol is 10 to 1000 ppm based on the mass of the toner, and the toner is the toner according to claim 1 or 2.

7. The toner according to claim 1 or 2, wherein the ester wax contains a compound represented by the following formula (3). R ３ -COO-R ５ -OCO-R ４ ... (3) (R ３ and R ４ each independently represents an alkyl group having 17 to 22 carbon atoms, and R ５ represents an alkylene group having 2 to 6 carbon atoms.)

8. 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 including the ester 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%.

9. The toner particles contain a boron atom, and the content of the boron atom based on the mass of the toner particles is 1.0 to 50.0 ppm, and the toner according to claim 1 or 2.

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

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