TONER

Abstract

A toner comprising a toner particle containing an amorphous polyester resin and a crystalline polyester resin is provided, wherein the amorphous polyester resin comprises a modified amorphous polyester resin having a linear alkyl compound condensed at one end, and the crystalline polyester resin comprises a modified crystalline polyester resin having a linear alkyl compound condensed at one end, wherein the number mean D A (nm) of the longitudinal axis lengths of the crystals of the crystalline polyester resin considered on the cross-section of a sample A obtained by melting the toner at 150 °C and then cooling the toner to 25 °C, and the number mean D B(nm) of the longitudinal axis lengths of the crystals of the crystalline polyester resin, which are viewed on the cross-section of a sample B obtained by leaving sample A at 50 °C for 72 hours, satisfy specific relationships.

Description

BACKGROUND Technical Area

[0001] The present disclosure relates to a toner used in electrophotographic systems, electrostatic recording systems and electrostatic printing systems. Description of the related prior art

[0002] In recent years, there has been a growing demand for electrophotographic devices, such as full-color printers and copiers, to offer added value, including high productivity, high image quality, and high stability. To achieve high productivity, it is essential to melt the toner more quickly during the fusing step. Specifically, a toner is needed that can be fixed at a lower temperature and exhibits excellent low-temperature fusing properties.

[0003] The published Japanese patent application No. 2004-046095 discloses a toner with excellent low-temperature fixability, a toner containing a crystalline polyester as a binder resin. The crystalline polyester has a higher melting point than an amorphous polyester and acts as a plasticizer for the amorphous polyester. Therefore, the crystalline polyester is a material that is effective for fixing the toner at low temperatures.

[0004] However, if the compatibility between the crystalline polyester and the amorphous polyester is increased to improve low-temperature fixability, a case may arise where the crystalline polyester does not crystallize in a toner, and the charge conservation property is impaired. Therefore, published Japanese patent application No. 2016-110150 discloses a manufacturing process for the accelerated crystallization of a crystalline polyester by annealing a toner to achieve both low-temperature fixability and charge conservation properties.

[0005] In a toner containing a crystalline resin with low-temperature fixability, the binder resin and plasticizer in the toner melt, which forms a fixed image, often remain compatible. As a result, the toner's heat resistance decreases, and the toner melt tends to adhere to the back of the paper, which may have an output image or another fixed image on it, potentially causing an image defect. One such defect is sheet adhesion.

[0006] Particularly in the case of double-sided printing, fixed image elements are inevitably placed in contact with each other, which can lead to image defects more readily than in single-sided printing. Therefore, a toner capable of achieving both low-temperature fixation and resistance to paper adhesion was required.

[0007] Meanwhile, if a fixed image printed using a toner containing a crystalline resin is stored for a long period, the crystalline resin can gradually anneal, crystallization can progress, and a needle-like crystal domain with a large aspect ratio can form in the fixed image. Once crystallized, the resin becomes brittle, and if the fixed image is bent, cracks can easily appear, potentially leading to image defects.

[0008] According to investigations by the present inventors, the toner of the disclosed Japanese patent application No. 2016-110150 fulfills both the low-temperature fixability and charge retention properties by annealing in the toner state; however, crystallization is delayed after fixing. As a result, the resistance to sheet adhesion decreases, and crystallization progresses during long-term storage, resulting in a decrease in resistance to wrinkling. SUMMARY

[0009] The present disclosure provides a toner that exhibits excellent low-temperature fixability and charge retention properties, suppresses sheet adhesion immediately after fixing, and does not easily lose its resistance to wrinkling, even during long-term storage.

[0010] The present disclosure relates to a toner comprising a toner particle comprising an amorphous polyester resin and a crystalline polyester resin, wherein the amorphous polyester resin comprises a modified amorphous polyester resin having at least one linear alkyl compound condensed at one end, selected from the group consisting of linear C16-24 aliphatic monocarboxylic acids and linear C16-24 aliphatic monoalcohols; the crystalline polyester resin comprises a modified crystalline polyester resin having at least one linear alkyl compound condensed at one end, selected from the group consisting of linear C16-24 aliphatic monocarboxylic acids and linear C16-24 aliphatic monoalcohols; and when a cross-section of a sample A, obtained by melting the toner at 150 °C and subsequently cooling the toner to 25 °C at a rate of 100 °C / min, is viewed using a transmission electron microscope, and a number mean of the longitudinal axis lengths of the crystals of the crystalline polyester resin viewed on the cross-section is defined as D A (nm) is taken, and when a cross-section of a sample B, obtained by leaving sample A at 50 °C for 72 hours, is viewed using a transmission electron microscope, and a number mean of the longitudinal axis lengths of the crystals of the crystalline polyester resin viewed in the cross-section is defined as D B (nm) is taken the D A and the D B the following expressions (1) and (2) satisfy: 10 nm≤DA≤100 nm 1 nm ≤ DB − DA ≤ 20 nm

[0011] The present disclosure provides a toner that exhibits excellent low-temperature fixability and charge retention properties, suppresses sheet adhesion immediately after fixing, and does not readily lose its resistance to wrinkling, even during long-term storage. Features of the present disclosure will become apparent from the following description of embodiments. The following description of embodiments is illustrated by examples. DESCRIPTION OF THE EXECUTION FORMS

[0012] In the present disclosure, “from XX to YY” or “XX to YY” indicates a numerical range that includes a lower bound and an upper bound, which are endpoints unless otherwise specified. Where numerical ranges are described in steps, an upper bound and a lower bound of each numerical range may be combined as desired. Furthermore, in the present disclosure, for example, a description such as “at least one selected from the group consisting of XX, YY, and ZZ” means 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. If XX is a group, multiple XX may be selected from the group, and the same applies to YY and ZZ.

[0013] The term "monomer unit" refers to a reacted form of a monomer substance in a polymer.

[0014] A crystalline polyester resin refers to a resin that has a main framework exhibiting crystallinity and an endothermic peak, which is observed during differential scanning calorimetry (DSC) measurement.

[0015] The present disclosure relates to a toner comprising a toner particle comprising an amorphous polyester resin and a crystalline polyester resin, wherein the amorphous polyester resin comprises a modified amorphous polyester resin having at least one linear alkyl compound condensed at one end, selected from the group consisting of linear C16-24 aliphatic monocarboxylic acids and linear C16-24 aliphatic monoalcohols; the crystalline polyester resin comprises a modified crystalline polyester resin having at least one linear alkyl compound condensed at one end, selected from the group consisting of linear C16-24 aliphatic monocarboxylic acids and linear C16-24 aliphatic monoalcohols; and when a cross-section of a sample A, obtained by melting the toner at 150 °C and subsequently cooling the toner to 25 °C at a rate of 100 °C / min, is viewed using a transmission electron microscope, and a number mean of the longitudinal axis lengths of the crystals of the crystalline polyester resin viewed on the cross-section is defined as D A (nm) is taken, and when a cross-section of a sample B, obtained by leaving sample A at 50 °C for 72 hours, is viewed using a transmission electron microscope, and a number mean of the longitudinal axis lengths of the crystals of the crystalline polyester resin viewed in the cross-section is defined as D B (nm) is taken the D A and the D B the following expressions (1) and (2) satisfy: 10 nm≤DA≤100 nm 1 nm ≤ DB − DA ≤ 20 nm

[0016] The present inventors have intensively investigated a toner that exhibits excellent low-temperature fixability and charge conservation properties, suppresses sheet adhesion immediately after fixing, and does not readily lose its resistance to wrinkling, even during long-term storage. As a result, the present inventors have found that the toner described above can solve the problem. First, it is important to maintain a microcrystalline state in which the crystal domains remain virtually unchanged when the toner is melted and then rapidly cooled, and after annealing. It is also important that both the amorphous polyester resin and the crystalline polyester resin contained in the toner are terminally modified by a linear long-chain alkyl group having a specific chain length.

[0017] The inventors believe that the mechanism by which the effects of the present revelation are shown is as follows.

[0018] The step of melting the toner at 150 °C and then rapidly cooling it to 25 °C at a rate of 100 °C / min to obtain sample A simulates the cooling rate of the toner after melting during fixing, and the state of the fixed substance immediately after fixing can be considered by loading a similar change onto the toner. Therefore, it is assumed that the toner in which the crystalline polyester resin crystallizes, thereby fulfilling condition (1), hardens even immediately after fixing, and sheet adhesion resistance becomes advantageous.

[0019] The step of allowing sample A to stand at 50 °C for 72 h to obtain sample B is a test to accelerate the state where the fixed substance, after standing for a long time, is in a sufficiently advanced transition state for evaluation. Therefore, the satisfaction of expression (2) means that the change in the size of the crystal domains after standing for 72 hours at 50 °C is very small; that is, the change in the size of the crystal domains in the fixed substance, after standing for a long time, is very small.

[0020] Therefore, the fulfillment of expressions (1) and (2) means that the crystal domains hardly change, even after a long period of time, and remain in a microcrystalline state. It is assumed that if the fixed substance is folded immediately after fixation and after a long period of time, the crystal domain is small and the starting point for crack formation is unlikely to occur. Therefore, it is possible to improve the resistance to folding.

[0021] Therefore, it is assumed that after rapid cooling, the crystalline polyester resin crystallizes immediately and forms microcrystals with small crystal domains, and the crystal domains hardly increase in size after a long period of time, thereby achieving both resistance to sheet adhesion and resistance to wrinkling.

[0022] Furthermore, the amorphous polyester resin and the crystalline polyester resin in the toner each contain a modified amorphous polyester resin and a modified crystalline polyester resin, respectively, in which a linear aliphatic monocarboxylic acid or a linear aliphatic monoalcohol, having a specific chain length, is condensed at the ends. That is, the ends of the amorphous polyester resin and the crystalline polyester resin are modified by a linear alkyl compound of a specific length. It is assumed that the terminal alkyl chain of the modified amorphous polyester resin and the terminal alkyl chain of the modified crystalline polyester resin interact with each other to reduce the size of the crystal domains.Therefore, it is assumed that the crystalline polyester resin crystallizes in the microcrystalline state in a range that satisfies expression (2) when the crystalline polyester resin is in a sufficient transition state, and the resistance to sheet adhesion and the resistance to wrinkling have been further improved.

[0023] It is assumed that if the carbon number of the terminal alkyl chain of the modified amorphous polyester resin and that of the terminal alkyl chain of the modified crystalline polyester resin are within the above-mentioned range, the carbon numbers are close to each other, and therefore the interaction is enhanced and an effect similar to that of a eutectic is shown.

[0024] The following describes a preferred toner constitution.

[0025] A toner particle contains an amorphous polyester resin and a crystalline polyester resin. The toner particle contains an amorphous polyester resin and a crystalline polyester resin, for example, as the binder resin. The binder resin preferably contains a polyester resin as a major component with regard to low-temperature fixability. The term "major component" means that its content is 50 wt% or more. The content ratio of the polyester resin in binder resins containing an amorphous polyester resin and a crystalline polyester is, for example, 50 to 100 wt%, preferably 80 to 100 wt%, and more preferably 90 to 100 wt%. Furthermore, the toner particle can contain a resin other than the amorphous polyester resin and the crystalline polyester resin in such an extent that the effects of the present disclosure are not impaired. Amorphous polyester resin

[0026] The amorphous polyester resin comprises a modified amorphous polyester resin with at least one linear alkyl compound condensed to one end, selected from the group consisting of linear C16-24 aliphatic monocarboxylic acids and linear C16-24 aliphatic monoalcohols. That is, the modified amorphous polyester resin includes a polyester chain with a monomer unit corresponding to a linear alkyl compound at its end. The modified amorphous polyester preferably comprises a condensation polymer of a carboxylic acid and an alcohol, with an aromatic diol as the main component.

[0027] An alcohol with an aromatic diol as the main component means that the aromatic diol content is 50% by mass or more in all alcohols that constitute the modified amorphous polyester resin, except for the monoalcohol, which is condensed to form a molecular chain that will be described later.

[0028] The aromatic diol used in the modified amorphous polyester resin is not particularly limited, but examples may include bisphenol derivatives represented by formula (A) below and diols represented by formula (B) below. The aromatic diol is preferably a bisphenol derivative represented by formula (A).

[0029] In the formula, R represents an ethylene group or a propylene group, x and y are each an integer of 1 or greater, and the average value of x + y is 2 to 7.

[0030] In the formula, R' or represents, and x' and y' are each an integer of 0 or greater, and the average of x' + y' is 0 to 10.

[0031] Examples of bisphenol derivatives represented by formula (A) may include the following.

[0032] Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (3.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene (2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (2.0)-polyoxyethylene (2,0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (6)-2,2-bis(4-hydroxyphenyl)propane and the like.

[0033] Examples of alcohols, other than the bisphenol derivatives represented by formula (A) or the diols represented by formula (B), may include the following.

[0034] Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, Polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetriol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like.

[0035] These alcohols can be used alone, or two or more of them can be used in combination.

[0036] As mentioned above, the main component of the alcohol is preferably an aromatic diol. In the alcohol, the content of the aromatic diol in all alcohols constituting the modified amorphous polyester resin, except for the monoalcohol which is condensed to the end of the modified amorphous polyester resin to form a linear alkyl chain, is preferably 80 to 100 wt% and more preferably 90 to 100 wt%.

[0037] Examples of carboxylic acids used in the modified amorphous polyester resin may include the following polyvalent carboxylic acids. Examples of dicarboxylic acids may include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, and the like. Among these, at least one dicarboxylic acid is preferably selected from the group consisting of maleic acid, fumaric acid, and terephthalic acid.

[0038] Examples of tricarboxylic acids or other polycarboxylic acids may include the following: 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxy)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empoltrimeric acid, anhydrides thereof and lower alkyl esters thereof, and the like.

[0039] Among these, 1,2,4-benzenetricarboxylic acid (that is, trimellitic acid) or a derivative thereof is preferred because it is not expensive and the reaction can be easily controlled.

[0040] These dicarboxylic acids, tricarboxylic acids and other polycarboxylic acids can be used alone, or two or more of them can be used in combination.

[0041] The main component of the carboxylic acids constituting the modified amorphous polyester resin is preferably a dicarboxylic acid. The term "main component" as used here refers to the case where the dicarboxylic acid content in all the carboxylic acids constituting the modified amorphous polyester resin is 50 wt% or more. In the carboxylic acids, the dicarboxylic acid content in all carboxylic acids constituting the modified amorphous polyester resin, except for the monocarboxylic acid that is condensed to the end of the modified amorphous polyester resin to form a linear alkyl group at the end of the molecular chain, is preferably 80 to 100 wt% and more preferably 90 to 100 wt%.

[0042] The amorphous polyester resin preferably contains a modified amorphous polyester resin with at least one linear alkyl compound condensed at one end, selected from the group consisting of a linear C16-24 alkyl monocarboxylic acid and a linear C16-24 alkyl monoalcohol condensed at one end.

[0043] The modified amorphous polyester resin can have a molecular chain end to which linear alkyl compounds having a variety of chain lengths are fused, and can also have a molecular chain end to which a linear alkyl compound having a chain length other than the range above is fused, provided that the effects of the present disclosure are not impaired. It is preferred that 90 wt% or more of the terminally modified linear alkyl compound has carbon atoms within the range of 16 to 24, and it is more preferred that 100 wt% of it has carbon atoms within the range of 16 to 24.

[0044] If a carboxyl group is present at a molecular chain end of the amorphous polyester resin prior to the condensation of the linear alkyl compound, a condensation reaction with a linear aliphatic monoalcohol occurs.

[0045] Meanwhile, if a hydroxy group is present at a molecular chain end of the amorphous polyester resin prior to the condensation of the linear alkyl compound, a condensation reaction with a linear aliphatic monocarboxylic acid occurs.

[0046] Accordingly, when the linear alkyl group is condensed to the end of the molecular chain, it becomes a group formed by the elimination of a hydrogen atom in the hydroxyl group of the linear aliphatic monoalcohol, or a group formed by the elimination of -OH in the carboxyl group of the linear aliphatic monocarboxylic acid. In this case, a linear chain alkyl group means an alkyl group contained within a group formed by the elimination of a hydrogen atom in a hydroxyl group of a linear aliphatic monoalcohol, or a group formed by the elimination of -OH in a hydroxyl group of the linear aliphatic monocarboxylic acid.

[0047] If the modified amorphous polyester resin has a branched chain, the molecular chain ends include the end of the branched chain.

[0048] Examples of linear C16 to C24 aliphatic monocarboxylic acids may include the following: palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), nonadecylic acid, arachidic acid (icosanoic acid), heneicosylic acid, behenic acid (docosanoic acid), tricosanoic acid and tetracosanoic acid.

[0049] Meanwhile, examples of linear C16 to C24 aliphatic monoalcohols may include the following: Palmityl alcohol (hexadecanol), Heptadecanol, Stearyl alcohol (octadecanol), Nonadecanol, Arachidyl alcohol (icosanol), Heneicosanol, Behenyl alcohol, Lignoseryl alcohol, Tricosanol and Tetracosanol.

[0050] If the number of carbon atoms is less than 16, the interaction between the linear chain alkyls would be insufficient, the modified crystalline polyester resin cannot be restricted by the modified amorphous polyester resin, and the crystal domain of the crystalline polyester resin becomes large, thus reducing its low-temperature fixability as a toner and decreasing its resistance to wrinkling of a fixed substance after long-term storage. If the number of carbon atoms is too low, crystallization is difficult, and the core structure cannot be maintained, thus delaying crystallization and reducing the charge conservation properties of the toner and the resistance to sheet adhesion of the fixed substance.

[0051] However, if the number of carbon atoms is greater than 24, the mobility of the linear chain alkyl segment becomes too high, so that the modified amorphous polyester resin cannot retain the linear chain alkyl segment of the modified crystalline polyester resin, and the crystal domain becomes large. As a result, the low-temperature fixability decreases, and the resistance to wrinkling of the fixed substance after long-term storage is reduced. The number of carbon atoms of the linear alkyl compound condensed to one end of the modified amorphous polyester resin is preferably 18 to 22 and more preferably 18 to 20.

[0052] The terminally modified amorphous polyester resin may exhibit crystallinity derived from the terminal linear alkyl chain. A modified amorphous polyester resin alone that exhibits a degree of crystallinity of 10% or less when left to stand at 30 °C and 80% RH for 1 week is considered an amorphous polyester resin.

[0053] The degree of crystallinity was measured using a MiniFlex 600 X-ray diffractometer (manufactured by Rigaku Corp.). A powdered sample was placed on a non-reflective sample plate and measured under the following conditions. X-ray source: CuKα radiation Power: 40 kV, 15 mA Gap system: DS = 0.625°, SS = 8 mm, RS = 13 mm Detector: D / teX Ultra Scanning method: 2θ / θ continuous scan Measuring range (2θ): 5° to 60° Step size (2θ) 0.02°

[0054] The degree of crystallinity was defined as the percentage obtained when the sum of the integrated intensities derived from the crystals is divided by the sum of the integrated intensities of all peaks after subtracting the background from the measurement results and performing peak separation.

[0055] The modified amorphous polyester resin can be produced using a conventional polyester synthesis method. For example, the carboxylic acid monomer and alcohol monomer mentioned above are esterified or transesterified. A condensation polymerization reaction is then carried out under reduced pressure or by introducing nitrogen gas, following a standard procedure, to obtain the desired polyester resin.

[0056] However, if the linear aliphatic monocarboxylic acid or the linear aliphatic monoalcohol, which forms the ends of the molecular chain, are present simultaneously, the linear alkyl compound forms the ends of the molecular chain during the reaction between the carboxylic acid monomer and the alcohol monomer. Therefore, the ends act as end caps, and there is a possibility that the molecular chain will be extremely shortened. Thus, the linear alkyl compound can be added to the reaction system after the reaction between the carboxylic acid monomer and the alcohol monomer has progressed.

[0057] The esterification or transesterification reaction can optionally be carried out using conventional esterification or transesterification catalysts, such as sulfuric acid, titanium butoxide, dibutyltin oxide, tin 2-ethylhexanoate, manganese acetate and magnesium acetate.

[0058] The condensation polymerization reaction can be carried out using a common polymerization catalyst, such as titanium butoxide, dibutyltin oxide, tin 2-ethylhexanoate, tin acetate, zinc acetate, zinc disulfide, antimony trioxide, and germanium dioxide. The polymerization temperature and the amount of catalyst are not particularly limited and can be suitably determined.

[0059] The proportion (modification rate) of the ends to which a linear alkyl compound is condensed among the molecular chain ends of the modified amorphous polyester resin is, for example, 0.5 mol% or more and less than 25 mol%, preferably 1 mol% or more and less than 25 mol%, more preferably 2 to 15 mol%, and even more preferably 2 to 10 mol%. If the modification rate of the molecular chain ends of the modified amorphous polyester resin is 1 mol% or more, the modified amorphous polyester resin can interact better with the terminal alkyls of the modified crystalline polyester resin. Conversely, if the modification rate of the molecular chain ends of the modified amorphous polyester resin is less than 25 mol%, the distance between the modified crystalline polyesters that have interacted with the modified amorphous polyester is suitably maintained, and the crystal domain is slightly reduced.

[0060] The modification rate refers to the proportion of ends at which a linear alkyl compound is condensed (carboxy and hydroxyl groups) of a polyester resin. Exhibiting the modification rate described above means that the polyester molecular chain contained in the modified amorphous polyester resin includes a polyester molecular chain in which a linear alkyl compound is condensed at a chain end with the modification rate described above. That is, the modified amorphous polyester resin can be a mixture of a polyester molecular chain in which a linear alkyl compound has been condensed at a chain end and a polyester molecular chain in which a linear alkyl compound has not been condensed at a chain end.

[0061] The glass transition temperature (Tg) of the modified amorphous polyester resin, measured using differential scanning calorimetry (DSC), is preferably from 40.0 °C to 60.0 °C and more preferably from 45.0 °C to 52.0 °C. When the Tg is within the above range, both low-temperature fixability and blocking resistance are readily achieved.

[0062] The number-averaged molecular weight Mn of the modified amorphous polyester resin is preferably 1500 to 10000, or 2000 to 4000. The weight-averaged molecular weight Mw of the modified amorphous polyester resin is preferably 2000 to 20000, 3000 to 10000, or 3000 to 8000.

[0063] The amorphous polyester resin may further contain an amorphous polyester resin B, which differs from the modified amorphous polyester resin. The amorphous polyester resin B may be a condensation polymer of an alcohol and a carboxylic acid, except for a monoalcohol and a monocarboxylic acid in the modified amorphous polyester resin described above.

[0064] The alcohol preferably contains an aromatic diol. The aromatic diol content in all alcohols constituting the amorphous polyester resin B is preferably 80 to 100 wt% and more preferably 90 to 100 wt%.

[0065] The carboxylic acid is preferably at least one selected from the group consisting of maleic acid, fumaric acid, and terephthalic acid. The amorphous polyester resin B is preferably crosslinked with a trivalent carboxylic acid, such as trimellitic acid or trimellitic anhydride.

[0066] The glass transition temperature (Tg) of the amorphous polyester resin B, measured using a differential scanning calorimeter (DSC), is preferably from 50.0 °C to 70.0 °C and more preferably from 50.0 °C to 65.0 °C.

[0067] The number-averaged molecular weight Mn of the amorphous polyester resin B can preferably be 2000 to 10000, or 2500 to 6000. The weight-averaged molecular weight Mw of the amorphous polyester resin B can preferably be 2000 to 20000, or 5000 to 15000.

[0068] The proportion of modified amorphous polyester resin in the amorphous polyester resin can be, for example, 50 to 95 wt%, or 60 to 80 wt%.

[0069] The content ratio of amorphous polyester resin B in the amorphous polyester resins can be, for example, 5 to 50 wt%, or 20 to 40 wt%.

[0070] The content ratio of the modified amorphous polyester resin, based on the mass of the toner particles, can be, for example, 20.0 to 80.0 wt%, or 40.0 to 60.0 wt%.

[0071] The content ratio of the amorphous polyester resin B, based on the mass of the toner particle, can be, for example, 5.0 to 40.0 wt%, 10.0 to 30.0 wt%, or 15.0 to 25.0 wt%. Crystalline polyester

[0072] The toner particles contain a crystalline polyester resin. This crystalline polyester resin is a modified crystalline polyester resin with at least one linear alkyl compound fused to one end, selected from the group consisting of linear C16-24 aliphatic monocarboxylic acids and linear C16-24 aliphatic monoalcohols. That is, the modified crystalline polyester resin contains a polyester chain with a monomer unit corresponding to the linear alkyl compound at its end. The crystalline polyester resin has, for example, a main framework with crystallinity and preferably a weight-averaged molecular weight of 5000 or more.

[0073] Examples of monomers used in the modified crystalline polyester resin can include polyhydric alcohols (di-, tri-, or other polyhydric alcohols), polycarboxylic acids (di-, tri-, or other polycarboxylic acids), anhydrides thereof, and lower alkyl esters thereof. The structure, except for the end to which the linear alkyl compound is condensed in the modified crystalline polyester resin, is preferably a condensation polymer of an aliphatic dicarboxylic acid and an aliphatic diol.

[0074] The following polyhydric alcohol monomers can be used as polyhydric alcohol monomers in the modified crystalline polyester resin. The polyhydric alcohol monomer is not particularly limited, but is preferably a chain-like (more preferably linear) aliphatic diol. Examples of polyhydric alcohol monomers include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, and neopentyl glycol.

[0075] Among these, linear aliphatic α,ω-diols, such as ethylene glycol, diethylene glycol, 1,4-butanediol and 1,6-hexanediol, are particularly preferred.

[0076] Polyhydric alcohol monomers, in addition to the polyhydric alcohols listed above, may also be used. Examples of dihydric alcohol monomers among the above include aromatic alcohols such as polyoxyethylene-bisphenol A or polyoxypropylene-bisphenol A; 1,4-cyclohexanedimethanol; and the like. Examples of trihydric or further polyhydric alcohol monomers include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; and aliphatic alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.

[0077] The following polycarboxylic acid monomers can be used as polycarboxylic acid monomers in the modified crystalline polyester resin. The polyvalent carboxylic acid monomer is not particularly limited, but is preferably a chain-like (more preferably linear) aliphatic dicarboxylic acid.

[0078] Specific examples of these may include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutamic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid and itaconic acid, and also anhydrides or lower alkyl esters of these polycarboxylic acids.

[0079] It is also possible to use polycarboxylic acids other than the polycarboxylic acid monomers mentioned above. Examples of other polycarboxylic acid monomers include aromatic carboxylic acids, such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids, such as n-dodecyl succinic acid and n-dodecenyl succinic acid; alicyclic carboxylic acids, such as cyclohexanedicarboxylic acid; and also anhydrides or lower alkyl esters of these acids.

[0080] Examples of tricarboxylic acids or other polycarboxylic acids, including other carboxylic acid monomers, may include aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and pyromellitic acid; and aliphatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, and 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, as well as anhydrides or lower alkyl esters of these polycarboxylic acids.

[0081] The aliphatic dicarboxylic acid is preferably a linear C2-16 (preferably C8-14) aliphatic dicarboxylic acid. The aliphatic diol is preferably a linear C2-16 (preferably C2-6) aliphatic diol. The content of the monomer units formed by polymerization of a linear aliphatic C2-16 (preferably C8-14) dicarboxylic acid in the modified crystalline polyester resin is preferably 8 to 45 wt% and more preferably 20 to 35 wt%. The content of the monomer units formed by polymerization of a linear C2-16 (preferably C2-6) aliphatic diol in the modified crystalline polyester resin is preferably 15 to 50 wt% and more preferably 25 to 45 wt%.

[0082] The crystalline polyester resin comprises a modified crystalline polyester resin with at least one linear alkyl compound fused to one end, selected from the group consisting of linear C16-24 aliphatic monocarboxylic acids and linear C16-24 aliphatic monoalcohols. The crystalline polyester resin preferably comprises a modified crystalline polyester resin having a molecular chain end to which at least one linear alkyl compound selected from the group consisting of a linear C16 to C24 alkyl monocarboxylic acid and a linear C16 to C24 alkyl monoalcohol is fused.

[0083] The modified crystalline polyester resin can have molecular chain ends to which linear alkyl compounds having a variety of chain lengths are fused, and can also have a molecular chain end to which a linear alkyl compound having a chain length outside the range above is fused, provided that the effects of the present disclosure are not impaired. It is preferred that 90 wt% or more of the terminally modified linear alkyl compound has carbon atoms within the range of 16 to 24, and it is more preferred that 100 wt% of it has carbon atoms within the range of 16 to 24.

[0084] Examples of linear C16 to C24 aliphatic monocarboxylic acids may include the following: palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), nonadecylic acid, arachidic acid (icosanoic acid), heneicosylic acid, behenic acid (docosanoic acid), tricosanoic acid and tetracosanoic acid.

[0085] Meanwhile, examples of linear C16 to C24 aliphatic monoalcohols may include the following: Palmityl alcohol (hexadecanol), Heptadecanol, Stearyl alcohol (octadecanol), Nonadecanol, Arachidyl alcohol (icosanol), Heneicosanol, Behenyl alcohol, Lignoseryl alcohol, Tricosanol and Tetracosanol.

[0086] If the number of carbon atoms is less than 16, the interaction between linear alkyl groups is insufficient, so the modified crystalline polyester resin is not restricted by the terminal alkyl of the modified amorphous polyester resin, and the crystal domain of the crystalline polyester resin becomes large. As a result, the low-temperature fixability of the toner decreases, and the resistance to wrinkling of the fixed substance after long-term storage is reduced. If the number of carbon atoms is too low, crystallization is difficult, and the core structure cannot be maintained, thus delaying crystallization and reducing the charge conservation properties of the toner and the resistance to sheet adhesion of the fixed substance.

[0087] Meanwhile, if the number of carbon atoms exceeds 24, the mobility of the linear chain alkyl segment becomes too high, so that the linear chain alkyl segment of the modified amorphous polyester resin cannot restrict the modified crystalline polyester resin, and the crystal domain becomes large. As a result, the low-temperature fixability of the toner decreases, and the resistance of the fixed substance to wrinkling after long-term storage is reduced.

[0088] The modified crystalline polyester resin can be produced using a conventional polyester synthesis method. For example, a crystalline polyester resin can be obtained by subjecting the aforementioned dicarboxylic acid and diol to an esterification or transesterification reaction, followed by a polycondensation reaction under reduced pressure or by introducing nitrogen gas using a conventional procedure. Subsequently, the aforementioned linear alkyl compound is added, and an esterification reaction is carried out to obtain the desired modified crystalline polyester resin.

[0089] The esterification or transesterification reaction can optionally be carried out using common esterification or transesterification catalysts, such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate and magnesium acetate.

[0090] The polycondensation reaction can be carried out using a common polymerization catalyst, such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, sulfide, antimony trioxide, and germanium dioxide. The polymerization temperature and the amount of catalyst are not particularly limited and can be suitably determined.

[0091] In an esterification or transesterification reaction, or a polycondensation reaction, all monomers can be added in batches to increase the strength of the resulting modified crystalline polyester resin, or a divalent monomer can be reacted first to reduce the low molecular weight components, and then a trivalent or higher valent monomer can be added, followed by the reaction.

[0092] In the synthesis of the crystalline polyester resin containing a modified crystalline polyester resin, it is preferred to polycondense at least one (preferably the above-mentioned linear aliphatic monocarboxylic acid) selected from the group consisting of the above-mentioned linear aliphatic monocarboxylic acids and linear aliphatic monoalcohols, as well as an aliphatic diol and an aliphatic dicarboxylic acid.

[0093] In the modified crystalline polyester resin, the proportion of monomer units formed by the polymerization of aliphatic diols is preferably 30 to 50 mol%, and more preferably 35 to 45 mol%. In the modified crystalline polyester resin, the proportion of monomer units formed by the polymerization of aliphatic dicarboxylic acids is preferably 5 to 45 mol%, and more preferably 10 to 35 mol%. The proportion of the at least one (preferably one of the aforementioned linear aliphatic monocarboxylic acids) selected from the group consisting of the aforementioned linear aliphatic monocarboxylic acids and linear aliphatic monoalcohols is preferably 15 to 60 mol%, and more preferably 20 to 30 mol%.

[0094] The content ratio of the monomer unit from a linear alkyl compound at the molecular chain end of the modified crystalline polyester resin is preferably 1.0 to 30.0 wt%, more preferably 2.0 to 25.0 wt% and even more preferably 4.0 to 12.0 wt%.

[0095] In the modified crystalline polyester resin, the proportion of monomer units formed by the polymerization of aliphatic diols is preferably 10 to 40 wt% and more preferably 15 to 25 wt%. In the modified crystalline polyester resin, the proportion of monomer units formed by the polymerization of aliphatic dicarboxylic acids is preferably 40 to 85 wt%, more preferably 60 to 80 wt%.

[0096] The proportion of modified crystalline polyester resin in the crystalline polyester resin can be, for example, 50 to 100 wt%, 80 to 100 wt%, or 90 to 100 wt%. The crystalline polyester resin can be a modified crystalline polyester resin.

[0097] The salary ratio W C The proportion of crystalline polyester resin (for example, modified crystalline polyester resin), based on the mass of the toner particles, is preferably 3.0 to 25.0 wt%, more preferably 5.0 to 20.0 wt%, and even more preferably 5.0 to 18.0 wt%. It is preferred from the perspective of achieving a high degree of all properties, including low-temperature fixability, charge retention, resistance to sheet adhesion, and resistance to wrinkling. The melting point of the modified crystalline polyester is preferably 60 °C to 105 °C, more preferably 65 °C to 100 °C, and even more preferably 70 °C to 95 °C.

[0098] The weight-average molecular weight (Mw) of the modified crystalline polyester resin is preferably 10,000 to 30,000 and more preferably 15,000 to 25,000. When the Mw is 10,000 or higher, compatibility with the modified amorphous polyester resin decreases, and crystallization is accelerated, thus facilitating improvements in charge conservation properties and sheet adhesion resistance. When the Mw is 30,000 or lower, the terminal alkyl group of the modified amorphous polyester resin slightly restricts the modified crystalline polyester resin, resulting in a smaller crystal domain and slightly improving low-temperature fixability and wrinkling resistance.

[0099] The number-averaged molecular weight of the modified crystalline polyester resin can preferably be 1000 to 10000, or 2000 to 7000.

[0100] The proportion (modification rate) of the ends to which a linear alkyl compound is fused among the molecular chain ends of the modified crystalline polyester resin is, for example, 15 to 75 mol%, preferably 20 to 70 mol%, more preferably 35 to 65 mol%, and even more preferably 45 to 60 mol%. When the proportion is within the above range, the interaction between the terminal alkyl of the modified crystalline polyester resin and the modified amorphous polyester resin is enhanced, the modified crystalline polyester resin is easier to confine, the crystal domain is smaller, and the low-temperature fixability and resistance to wrinkling are easier to improve.

[0101] The modification rate refers to the proportion of the ends where a linear alkyl compound is fused to the ends (carboxy and hydroxyl groups) of a polyester resin. Exhibiting the modification rate described above means that the polyester molecular chain contained in the modified crystalline polyester resin includes a polyester molecular chain in which a linear alkyl compound is fused to a molecular chain end at the modification rate described above. This means that the modified crystalline polyester resin can be a mixture of a polyester molecular chain in which a linear alkyl compound has been fused to a molecular chain end and a polyester molecular chain in which no linear alkyl compound has been fused to a molecular chain end.

[0102] The toner is melted at 150 °C and then cooled to 25 °C at a rate of 100 °C / min to obtain sample A. A cross-section of sample A is examined using a transmission electron microscope (TEM), and the number-mean of the longitudinal axis lengths of the crystalline polyester resin crystals viewed on the cross-section is determined as D. A (nm) defined.

[0103] Sample A is then left to stand at 50°C for 72 hours to obtain sample B. A cross-section of sample B is examined using a transmission electron microscope (TEM), and the number-mean of the longitudinal axis lengths of the crystalline polyester resin crystals viewed in the cross-section is determined as D. B (nm) defined.

[0104] In this case, it is necessary that D A and D B The following expressions (1) and (2) satisfy. 10 nm≤DA≤100 nm 1 nm ≤ DB − DA ≤ 20 nm

[0105] As described above, the step of melting the toner and then cooling it to 25 °C at a rate of 100 °C / min to obtain sample A simulates the temperature change of the fixed substance during fixation. At this stage, sheet adhesion resistance is improved if the crystalline polyester resin crystallizes to satisfy expression (1). Additionally, it is necessary to satisfy expression (2) after subsequent exposure to 50 °C for 72 hours. Fulfillment of expression (2) means that crystal growth from 1 to 20 nm can be suppressed, and wrinkling resistance is improved.

[0106] It is preferred that D A from 10 nm to 50 nm. It is preferred that D B Expression (2) is satisfied and is, for example, from 15 nm to 100 nm and from 20 nm to 70 nm. That is, it is preferred that D A and DB satisfy the following expressions (3) and (4): 10 nm≤DA≤50 nm 20 nm ≤ DB ≤ 70 nm

[0107] For example, (D B - D A ) 1 nm to 12 nm, or 3 nm to 12 nm.

[0108] As a means of adjusting D A Within the aforementioned area, a method for using a modified crystalline polyester resin and a modified amorphous polyester resin, in which a linear alkyl compound has been condensed to one end, can be described. To D A To reduce this, either one or both of the modification rates of the modified crystalline polyester resin and the modified amorphous polyester resin should be increased. To reduce D A To increase the performance, one or both of the modification rates of the modified crystalline polyester resin and the modified amorphous polyester resin should be reduced.

[0109] As a means of adjusting (D B - D A Within the aforementioned range, a process for using a modified crystalline polyester resin and a modified amorphous polyester resin in which a linear alkyl compound has been condensed at one end, and a process for producing a small weight-averaged molecular weight Mw of the modified amorphous polyester resin (for example, less than 10,000) can be mentioned. To (D B - D A To reduce (D B - D A To increase the alkyl chains, it is assumed that the difference between their lengths needs to be made greater.

[0110] To reduce the DB (density), the modification rate of the modified amorphous polyester resin should be increased. To increase the DB, the modification rate of the modified amorphous polyester resin should be reduced.

[0111] From the point of view of low-temperature fixability, the average aspect ratio of crystals of the crystalline polyester resin, when considering the cross-section of sample B, is, for example, 2.0 to 8.0, and preferably 2.5 to 5.0.

[0112] To reduce the average aspect ratio, the modification rate of the modified amorphous polyester resin should be increased. To increase the average aspect ratio, the modification rate of the modified amorphous polyester resin should be decreased.

[0113] Additionally, the SP value of the modified amorphous polyester resin is given as SP A (cal / cm 3 ) 0,5and the SP value of the modified crystalline polyester resin as SP C (cal / cm 3 ) 0,5 taken. In this case, (SP A - SP C ) for example, 0.7 to 1.3. It is preferred that SP A and SP C The following expression (5) regarding compatibility and ease of crystallization must be met. SP A - SP C is more strongly preferred between 0.9 and 1.1. 0.8≤SPA−SPC≤1.2

[0114] The ratio of crystalline polyester resin content, based on the mass of the toner particle, is called W. C (mass %). When examining a cross-section of sample A through a transmission electron microscope (TEM), an average area ratio of the crystals of the crystalline polyester resin in the area of ​​an observation region is given as S. A (Area % taken). At this point, S A / W Cfor example, 0.05 to 0.5. It is preferred that W C and S A satisfy the following expression (6). 0.1≤SA / WC≤0.4

[0115] The ratio of crystalline polyester resin content, based on the mass of the toner particle, is called W. C (mass %). When examining a cross-section of sample B through a transmission electron microscope (TEM), an average area ratio of the crystals of the crystalline polyester resin in the area of ​​an observation region is given as S. B (Area % taken). At this point, S B / W C for example, 0.2 to 1.0. It is preferred that W C and S B satisfy the following expression (7). 0.3≤SB / WC≤0.8

[0116] If the value of S A / W CIf the value of S is 0.1 or higher, resistance to leaf adhesion is further improved. Furthermore, if the value of S B / W C If the value is 0.8 or less, the resistance to wrinkles is further improved.

[0117] To S A To reduce this, the modification rate of the modified crystalline polyester resin should be reduced. To S A To increase the modification rate, the modification rate of the modified crystalline polyester resin should be increased.

[0118] To S B To reduce the modification rate, the modification rate of the modified amorphous polyester resin should be increased, or the modification rate of the modified crystalline polyester resin should be reduced. To reduce the modification rate, the modification rate of the modified amorphous polyester resin should be increased, or the modification rate of the modified crystalline polyester resin should be reduced. B To increase the modification rate, the modification rate of the modified amorphous polyester resin should be reduced, or the modification rate of the modified crystalline polyester resin should be increased.

[0119] It is preferred that the number of carbon atoms in the linear alkyl compound condensed to one end of the modified crystalline polyester resin is greater than that of the linear alkyl compound condensed to one end of the modified amorphous polyester resin. If the number of carbon atoms in the linear alkyl compound modifying the end of the amorphous polyester is small, the amorphous polyester resin can interact rapidly with the crystalline polyester resin, provided the two resins are compatible. As a result, crystallization is further accelerated, and both charge conservation and sheet adhesion resistance are further improved.

[0120] The difference between the number of carbon atoms in the linear alkyl compound condensed onto one end of the modified amorphous polyester resin and the number of carbon atoms in the linear alkyl compound condensed onto one end of the modified crystalline polyester resin is preferably 1 to 6, or 2 to 4.

[0121] Examples of preferred combinations of the modified amorphous polyester resin and the modified crystalline polyester resin may include the following. It is particularly preferred that the linear alkyl compound condensed to one end of the modified amorphous polyester resin is stearic acid, and the linear alkyl compound condensed to one end of the modified crystalline polyester resin is behenic acid. This combination enables higher-order interactions between the crystalline polyester resin and the amorphous polyester resin, resulting in the rapid crystallization of the crystalline polyester resin into a more finely dispersed state.

[0122] Additionally, it is preferred that the modified crystalline polyester resins have a monomer unit corresponding to ethylene glycol and a monomer unit corresponding to dodecanedioic acid. It is more preferred that the structure, except for the end of the modified crystalline polyester resin, is a condensation polymer of ethylene glycol and dodecanedioic acid.

[0123] If the modified crystalline polyester resin contains a monomer unit corresponding to ethylene glycol, the linear alkyl group is modified at the end of the portion exhibiting a high ester group concentration. When the ester group concentration is high, the crystalline polyester resin more readily approximates the structure of the amorphous polyester resin. Therefore, the interaction between the terminal alkyl groups of the modified crystalline polyester resin and the modified amorphous polyester resin is further enhanced.

[0124] If the modified crystalline polyester resin has a monomer unit corresponding to dodecanedioic acid, faster crystallization and a suitable melting point can be achieved. Release agent

[0125] The toner particles may contain a release agent. Examples of release agents include the following: Hydrocarbon waxes, such as low molecular weight polyethylene, low molecular weight polypropylene, an alkylene copolymer, microcrystalline wax, paraffin wax and Fischer-Tropsch wax; oxides of hydrocarbon waxes, such as an oxidized polyethylene wax, or block copolymers thereof; waxes containing a fatty acid ester, such as carnauba wax, as the main component; and partially or completely deoxidized fatty acid esters, such as deoxidized carnauba wax.

[0126] Additionally, examples of these may include the following: saturated linear fatty acids, such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids, such as brassidic acid, eleostearic acid, and parinaric acid; saturated alcohols, such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols, such as sorbitol; esters of fatty acids, such as palmitic acid, stearic acid, behenic acid, and montanic acid, and alcohols, such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides, such as linoleic acid amide, oleic acid amide, and lauric acid amide; saturated fatty acid bisamides, such as methylenebisstearic acid amide, ethylenebiscaprylic acid amide, ethylenebislauric acid amide, and hexamethylenebisstearic acid amide;Unsaturated fatty acid amides, such as ethylene bisoleic amide, hexamethylene bisoleic amide, N,N'-dioleyladipamide, and N,N'-dioleylsebacamide; aromatic bisamides, such as m-xylenebisstearamide and N,N'-distearylisophthalamide; aliphatic metal salts, such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate (commonly known as metal soap); waxes in which vinyl monomers, such as styrene and acrylic acid, are grafted onto aliphatic hydrocarbon waxes; partially esterified products of fatty acids and polyhydric alcohols, such as behenic monoglyceride; and methyl ester compounds containing a hydroxyl group, obtained by hydrogenation of vegetable oils and fats.

[0127] Among these release agents, hydrocarbon waxes, such as paraffin wax and Fischer-Tropsch wax, are preferred from the point of view of low-temperature fixability.

[0128] The release agent content is preferably 1 to 10 parts by mass relative to 100 parts by mass of the binder resin. Here, the binder resin refers, for example, to the sum of the aforementioned crystalline polyester resin and the aforementioned amorphous polyester resin. Dispersing agent

[0129] If the toner particle contains a release agent, it preferably contains a dispersant to disperse the wax in the resin. A known dispersant can be used, but if the wax is a hydrocarbon wax, it is preferred to contain a polymer with a structure formed by a reaction between a vinyl resin component and a hydrocarbon compound to disperse the wax in the resin. Among these, a graft polymer obtained by grafting a vinyl monomer onto a polyolefin is preferred.

[0130] The inclusion of the polymer increases the compatibility between the wax and the resin, and defects such as loading errors and elemental contamination due to faulty wax dispersion are less likely to occur. Additionally, the dispersion agent content is preferably between 1.0 and 15 parts by mass of the binder resin. Within this range, the dispersion of the wax in the amorphous resin is likely to be uniform.

[0131] The polyolefin is not particularly limited, as long as it is a polymer or copolymer of unsaturated hydrocarbons, and various polyolefins can be used. Polyethylene or polypropylene are particularly preferred. A wide variety of these can be used.

[0132] Examples of monomers that contain a vinyl group may include the following.

[0133] Styrene-based units, including styrene and derivatives thereof, such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene and pn-dodecylstyrene; Amino group-containing α-methylene-aliphatic monocarboxylic acid esters, such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; nitrogen-atom-containing vinyl-based units, including acrylic acid or methacrylic acid derivatives, such as acrylonitrile, methacrylonitrile and acrylamide; unsaturated dibasic acids, such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, and mesaconic acid; unsaturated dibasic acid anhydrides, such as maleic anhydride, citraconic anhydride, itaconic anhydride, and alkenyl succinic anhydride; half-esters of unsaturated dibasic acids, such as methyl maleate half-esters, ethyl maleate half-esters, butyl maleate half-esters, methyl citraconic acid half-esters, ethyl citraconic acid half-esters, butyl citraconic acid half-esters, methyl itaconic acid half-esters, methyl alkenyl succinic acid half-esters, methyl fumaric acid half-esters, and methyl mesaconic acid half-esters; unsaturated dibasic acid esters, such as dimethyl maleic acid and dimethyl fumaric acid; α,β-unsaturated acids, such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid; α,β-unsaturated anhydrides, such as croton anhydride and cehin anhydride, anhydrides of the above-mentioned α,β-unsaturated acid anhydrides with a lower fatty acid;Carboxy group-containing vinyl-based units, such as alkenylmalonic acid, alkenylglutaric acid and alkenyladipic acid, anhydrides thereof, and monoesters thereof; Hydroxy group-containing vinyl-based units, such as acrylic acid or methacrylic acid esters, for example 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, 4-(1-hydroxy-1-methylbutyl)styrene and 4-(1-hydroxy-1-methylhexyl)styrene; Ester units composed of acrylic acid esters, including acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; Ester units composed of methacrylic acid esters containing α-methylenealiphatic monocarboxylic acids, such as cyclohexyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate. A variety of these can be used.

[0134] The dispersing agent can be obtained by known methods, such as the reaction between these polymers or the reaction between a monomer of one polymer and the other polymer. colorant

[0135] The toner particle may contain a colorant. Examples of colorants include the following.

[0136] Examples of black colorants include carbon black; and those tuned to black using yellow, magenta, and cyan colorants. Although the colorant may contain a pigment alone, for the sake of image quality in full-color images, it is preferable to use a dye and a pigment in combination to enhance color definition.

[0137] Examples of magenta toner pigments may include the following pigments. CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269 and 282; CI Pigment Violet 19; CI Pigment Red 1, 2, 10, 13, 15, 23, 29 and 35.

[0138] Examples of magenta toner dyes may include the following: CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, and 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, and 27; oil-soluble dyes, such as CI Disperse Violet 1, CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40; and basic dyes, e.g. BCI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27 and 28.

[0139] Examples of cyan toner pigments may include the following pigments: CI Pigment Blue 2, 3, 15; 2, 15: 3, 15: 4, 16 and 17; CI Vat Blue 6; CI Acid Blue 45; and copper phthalocyanine pigments in which 1 to 5 phthalimide methyl groups are substituted on the phthalocyanine backbone.

[0140] Examples of cyan toner dyes include CI Solvent Blue 70.

[0141] Examples of yellow toner pigments may include the following pigments: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, and 185; and CI Vat Yellow 1, 3, and 20.

[0142] Examples of yellow toner dyes may include CI Solvent Yellow 162.

[0143] The colorant content is preferably 0.1 to 30 parts by mass, relative to 100 parts by mass of the binder resin. Load control device

[0144] The toner particles can optionally contain a charge-controlling agent. Known agents can be used as charge-controlling agents in the toner. In particular, metal compounds of aromatic carboxylic acids, which are colorless, can charge the toner at high speed, and can stably maintain a specific charge level, are preferred.

[0145] Examples of negative charge-controlling agents include metal salicylate compounds, metal naphthoate compounds, dicarboxylic acid metal compounds, polymer-like compounds containing sulfonic acid or carboxylic acid in the side chain, polymer-like compounds containing sulfonate or sulfonic acid esters in the side chain, polymer-like compounds containing carboxylate or carboxylic acid esterified sections in the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes. Examples of positive charge-controlling agents include quaternary ammonium salts, high-molecular-weight compounds containing quaternary ammonium salts in the side chain, guanidine compounds, and imidazole compounds. The charge-controlling agent can be added internally or externally to the toner particle. The amount of charge-controlling agent added is preferably 0.05 to 10 parts by mass relative to 100 parts by mass of the binder resin. Inorganic fine particles

[0146] The toner may optionally contain an inorganic particle. This inorganic particle can be added internally to the toner particle or mixed with it as an external additive. An inorganic fine powder, such as silica, titanium dioxide, or aluminum oxide, is preferred as an external additive. The inorganic fine powder is preferably made hydrophobic with a hydrophobic agent, such as a silane compound, a silicone oil, or a mixture thereof.

[0147] The external additive for improving flowability is preferably an inorganic fine powder with a specific surface area of ​​50 m². 2 / g up to 400 m 2 / g. To stabilize shelf life, an inorganic fine powder with a specific surface area of ​​10 m² is used. 2 / g up to 50 m 2 / g preferred. To achieve both improved flowability and stable shelf life, inorganic fine powder with a specific surface area in the above-mentioned range can be used in combination.

[0148] The external additive is preferably used in an amount of 0.1 to 10.0 parts by mass, relative to 100 parts by mass of a toner particle. The toner particle and the external additive can be mixed using a known mixer, such as a Henschel mixer. developer

[0149] The toner can also be used as a single-component developer, but it is preferred to mix the toner with a magnetic carrier and use the resulting mixture as a two-component developer to further improve dot repeatability and to deliver stable images over a long period of time.

[0150] When the toner is mixed with a magnetic carrier and the resulting mixture is used as a two-component developer, the mixing ratio of the magnetic carrier at that time is preferably 2 wt% to 15 wt%, and more preferably 4 wt% to 13 wt% or less, than the toner concentration in the two-component developer. Magnetic carrier

[0151] Commonly known materials can be used as the magnetic support, for example iron oxide; metal particles of iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, strontium, or a rare earth component, and an alloy particle thereof or an oxide particle thereof; magnetic bodies, such as ferrite or magnetite; and a magnetic body-dispersed resin support (so-called resin support) containing the magnetic body and a binder resin that keeps the magnetic body in a dispersed state; magnetic supports in the form of ferrite or magnetite particles with pores filled with a resin.

[0152] The magnetic substrate can be the aforementioned magnetic body directly, or a magnetic body in which the surface of the aforementioned magnetic body is coated with a resin core can be used. From the perspective of improving the toner's loading performance, it is preferable to use a magnetic body in which the surface of the aforementioned magnetic body is coated with a resin core as the magnetic substrate.

[0153] The resin used to coat the core is not particularly limited, and known resins can be selected and used as long as the toner properties are not impaired. For example, resins such as a (meth)acrylic resin, a silicone resin, a urethane resin, polyethylene, polyethylene terephthalate, polystyrene, and a phenolic resin, or a copolymerized polymer and a polymer mixture containing these resins, can be used. In particular, from the perspective of loading properties and the prevention of foreign material adhesion to the carrier particle surfaces, it is preferable to use a (meth)acrylic resin or a silicone resin.In particular, a (meth)acrylic resin comprising alicyclic hydrocarbon groups, such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclopentyl group, a cyclobutyl group or a cyclopropyl group, is particularly preferred because the surface (coating film surface) of the resin coating layer covering the surface of the magnetic body becomes smooth, and the adhesion of toner-derived components, such as a binder resin, a release agent and an external additive, can be suppressed. Manufacturing process

[0154] A method for producing a toner particle is not particularly limited, and a known method, such as a pulverization process, a suspension polymerization process, a solution-suspension process, an emulsion aggregation process, or a dispersion polymerization process, can be used.

[0155] The following describes a toner manufacturing procedure using the pulverization method.

[0156] In the raw material mixing step, materials constituting the toner particle, such as a crystalline polyester resin, an amorphous polyester resin, and optionally other components including a release agent, a colorant, and a charge control agent, are weighed out in specific quantities, then blended and mixed. Examples of mixing devices include a double-cone mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a Mechano hybrid (manufactured by Nippon Coke & Engineering Co., Ltd.).

[0157] The mixed material is then melted and kneaded to disperse wax or similar substances in a binder resin. The kneading outlet temperature can be adjusted depending on the binder resin and colorant used, but is generally preferred to be between 100 °C and 180 °C. A batch kneader, such as a pressure kneader, or a Banbury mixer and a continuous kneader can be used in the melt-kneading step, and single-screw or twin-screw extruders have become the standard due to the superiority of continuous production.

[0158] Examples include a KTK-type twin-screw extruder (manufactured by Kobe Steel, Ltd.), a TEM-type twin-screw extruder (manufactured by Toshiba Machinery Corp.), a PCM kneader (manufactured by Ikegai Corp.), a twin-screw extruder (manufactured by KCK Engineering KK), a co-kneader (manufactured by BUSS), and a Niedex (manufactured by Nihon Coke & Engineering Co., Ltd.). Additionally, the resin composition obtained by melt kneading can be rolled with two rollers and cooled with water in a cooling step.

[0159] Next, the cooled resin composition is pulverized to a desired particle diameter in the pulverization step. In this step, for example, after coarse pulverization of the cooled resin composition in a pulverizer such as a crusher, hammer mill, or spring mill, further fine pulverization is carried out, for example, in the Krypton system (manufactured by Kawasaki Heavy Industries, Ltd.), Super Rotor (manufactured by Nisshin Engineering Inc.), Turbo Mill (manufactured by Freund-Turbo Corp.), or an air jet-type fine pulverizer.

[0160] If necessary, classification can then be carried out using a classifier such as an inertial classification system Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal classification system Turboplex (manufactured by Hosokawa Micron Corp.), TSP separator (manufactured by Hosokawa Micron Corp.) or Faculty (manufactured by Hosokawa Micron Corp.), or a sieving machine to obtain a classified product (toner particles).

[0161] The toner particle can be used as is. A toner can be obtained by applying an external additive to the surface of the toner particle, if necessary. Examples of methods for applying an external additive according to an external additive treatment may include a process in which a toner particle and various known external additives are mixed in specific quantities and stirred using a mixing device such as a double-cone mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano hybrid (manufactured by Nippon Coke & Engineering Co., Ltd.), or a Nobilta mixer as an external addition machine.

[0162] Next, a method for measuring each physical property will be described.

[0163] Measurement of the average area ratio, the number mean of the longitudinal axis lengths, and the average aspect ratio of crystals of crystalline polyester resin Evaluation of the dispersion state of crystals of the crystalline polyester resin in samples A and B by TEM

[0164] The examination of cross-sections of samples A and B by transmission electron microscopy (TEM) and evaluation of the crystals of the crystalline polyester resin can be carried out as follows. The preparation procedures for sample A and sample B were as follows.

[0165] Sample A is prepared using the following procedure. An osmium film (5 nm) and a naphthalene film (20 nm) are formed on a toner as protective films using an osmium plasma coater (OPC 80T, Filgen, Inc.), and the toner is embedded in a light-curing resin D800 (JEOL Ltd.). Sample A is then prepared using a differential calorimeter “DSC 7020” (manufactured by Hitachi High-Tech Corp.). The sample, placed in an aluminum crucible, is introduced into the instrument, which is set to 25 °C, and the temperature is then increased to 150 °C at a ramp rate of 10 °C / min. After the sample is held for 5 minutes to melt the toner, the toner is cooled to 25 °C at a rate of 100 °C / min to obtain Sample A.

[0166] A sample A is collected, taken from an aluminum crucible, a cross-section is examined using the procedure described later, and a number mean D is determined.A the longitudinal axis lengths of the crystals of the crystalline polyester resin, and an average area ratio S A are measured.

[0167] Sample B is prepared from sample A, which was prepared using the procedure described above with a blower constant temperature controller "DFN600" (manufactured by Yamato Scientific Co., Ltd.). Sample A is placed in a device set to 50 °C and left to stand for 72 hours, and then collected to obtain sample B. The cross-section of the resulting sample B is examined using the procedure described later, and a number mean D is determined. B the longitudinal axis lengths, an average aspect ratio, and an average area ratio S B measured the crystalline polyester resin crystals.

[0168] The crystalline polyester resin can be clearly distinguished by staining the cross-section of either sample A or sample B with ruthenium. The crystalline polyester resin stains less intensely than the organic components that make up the interior of the toner. It is assumed that the staining material penetrates the crystalline polyester resin less readily than the organic component in the toner due to the difference in density.

[0169] Because the number of ruthenium atoms varies depending on the intensity of the staining, a strongly stained area will show many of the atoms as black in the viewed image, without transmission for electron beams, while a weakly stained area is likely to transmit electron beams and therefore appears as white in the viewed image.

[0170] Sample A or sample B is cut to expose the sample cross-section with a thickness of 60 nm (or 70 nm) at a cutting speed of 1 mm / s using an ultrasonic ultramicrotome (UC7, Leica).

[0171] The resulting cross-section was stained for 15 minutes in a 500 Pa RuO4 gas atmosphere using a vacuum electron staining instrument (VSC 4R 1H, manufactured by Filgen, Inc.), and STEM analysis was performed using a TEM (JEM 2800, JEOL Ltd.) in STEM mode. The STEM sample size was 1 nm, and an image was acquired at a resolution of 1024 × 1024 pixels.

[0172] The resulting image is binarized using image processing software "Image-Pro Plus (Media Cybernetics)" (threshold 120 / 255 steps). Since binarization allows for the extraction of a crystal domain, the size of the crystal domain is measured. In cross-sectional analysis of 20 randomly selected samples, all measurable long-axis and short-axis lengths of the crystal domain of the crystalline polyester resin are measured.

[0173] The mean value D is calculated from the measured lengths. A , the numerical mean D B , and the average aspect ratio is calculated.

[0174] Furthermore, the average area proportions (S A , S BThe area fraction of the crystalline polyester resin crystals on the cross-sections of sample A and sample B is calculated. The area fraction is calculated from 20 sample cross-sections with longitudinal diameters of 3.0 µm or greater, taken from randomly selected sample cross-sections. For a given measurement area, a region is selected that does not extend to the embedding resin within the cross-section (100 nm within the interface with the embedding resin). The total area ratio of the crystalline polyester resin domains within the selected region is calculated, and the arithmetic mean of 20 cross-sections is used. Separation of each material from the toner

[0175] The separation of the materials from the toner can be achieved by exploiting differences in solubility in a solvent. An example of this is shown below.

[0176] First separation: A toner is dissolved in methyl ethyl ketone (MEK) at 23 °C to separate soluble substances (the amorphous polyester resin) and insoluble components (the crystalline polyester resin, wax, wax dispersion agent, dye, inorganic fine particles and the like).

[0177] Second separation: The insoluble substances (the crystalline polyester resin, wax, wax dispersion agent, dye, inorganic fine particles and the like) obtained in the first separation are dissolved in MEK at 100 °C to separate soluble substances (the crystalline polyester resin, wax and wax dispersion agent) and insoluble substances (dye and inorganic fine particles).

[0178] Third separation: The soluble substances (the crystalline polyester resin, wax and wax dispersion) obtained in the second separation are dissolved in chloroform at 23 °C to separate soluble substances (the crystalline polyester resin) and insoluble substances (wax and wax dispersion).

[0179] Based on the mass of each material, such as the crystalline polyester resin separated by the above separation process, the content of each material can be calculated.

[0180] Additionally, the amorphous polyester resin can be separated into the modified amorphous polyester resin and the amorphous polyester resin B, for example according to molecular weights, by a known agent such as GPC.

[0181] Calculation of the content ratio of the monomer units of modified amorphous polyester resin and modified crystalline polyester resin

[0182] The concentrations of the constituent monomers in the modified amorphous polyester resin and the modified crystalline polyester resin are calculated using NMR according to the following procedure.

[0183] First, 5 mg of a resin to be measured are weighed, dissolved in THF-d or chloroform-d, and a 1 The samples were subjected to ¹H NMR measurement, and the composition ratio was calculated from the integral values ​​of the respective peaks. The detailed apparatus conditions are as follows. Measurement conditions Measuring device: JNM-ECA 400FT-NMR (JEOL) Measured core: 1 H Solvent: THF-d or Chloroform-d Measurement frequency: 400 MHz Pulse width: 5.0 µs Frequency range: 10500 Hz Accumulation count: 64 times Measurement temperature: Room temperature Measurement of the glass transition temperature (Tg) of resin

[0184] The glass transition temperature (Tg) is measured according to ASTM D 3418-82 using a Q2000 differential calorimeter (manufactured by TA Instruments). The melting points of indium and zinc are used to correct the temperature of an instrument's detection unit, and the heat of fusion of indium is used to correct the heat quantity.

[0185] Specifically, 3 mg of a resin or toner are weighed precisely and placed in an aluminum crucible. An empty aluminum crucible serves as a reference. The measurement is then performed within the measurement temperature range of 30 °C to 200 °C at a rate of 10 °C / min. During the measurement, the temperature is raised to 200 °C, then lowered to 30 °C, and finally raised again. The specific heat change is obtained during this second temperature increase process, within the temperature range of 40 °C to 100 °C. The intersection point of the midpoints of the baselines before and after the specific heat change and the differential heat curve is defined as the glass transition temperature of the resin.

[0186] Measurement of the melting point of modified crystalline polyester resin

[0187] The melting point of a modified crystalline polyester resin is measured according to ASTM D 3418-82 using a differential calorimeter “Q2000” (manufactured by TA Instruments).

[0188] The melting points of indium and zinc are used to correct the temperature of an instrument's detection unit, and the heat of fusion of indium is used to correct the amount of heat. Specifically, 3 mg of a sample are accurately weighed and placed in an aluminum crucible, and the measurement is performed under the following conditions using an empty aluminum crucible as a reference. Rate of increase: 10 °C / min Measurement start temperature: 30 °C Measuring temperature: 180 °C

[0189] The measurements are performed within the measuring range of 30 °C to 180 °C at a rate of 10 °C / min. The temperature is raised once to 180 °C and held at that temperature for 10 minutes, then lowered to 30 °C, and subsequently raised again. The temperature at which the endothermic quantity curve reaches its maximum endothermic peak in the range of 30 °C to 100 °C during this second temperature increase is defined as the melting point. Procedure for calculating the SP value

[0190] The SP values ​​of the modified amorphous polyester resin and the modified crystalline polyester resin are calculated using a method proposed by Fedors. For an atom or group of atoms in the molecular structure, the vaporization energy (Δei) (cal / mol) and the molar volume (Δvi) (cm³) are determined. 3 / mol) from the table in “Polym. Eng. Sci., 14(2), 147-154 (1974)” and (ΣΔei / ΣΔvi) 0,5 is referred to as the SP value (cal / cm²). 3 ) 0,5 defined.

[0191] Measurement of the molecular weight of amorphous polyester resin, such as weight-averaged molecular weight of modified amorphous polyester resin by GPC

[0192] The molecular weight distribution of THF-soluble components in an amorphous polyester resin is measured using gel permeation chromatography (GPC) as follows.

[0193] First, a resin is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is then filtered through a solvent-resistant Myshori Disk membrane filter (manufactured by Tosoh Corp.) with a pore size of 0.2 µm, yielding a sample solution. It is important to note that the sample solution is adjusted so that the concentration of the component soluble in THF is 0.8 wt%. The sample solution is then used to perform the measurement under the following conditions. Device: HLC 8120GPC (Detector: RI) (manufactured by Tosoh Corp.) Column: Seven connected Shodex KF-801, 802, 803, 804, 805, 806 and 807 columns (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

[0194] A molecular weight calibration curve was used to calculate the molecular weight of the sample, which was prepared using a standard polystyrene resin (for example, trade name “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 and A-500” manufactured by Tosoh Corp.).

[0195] Molecular weight measurement, such as weight-averaged molecular weight Mw of modified crystalline polyester resin by GPC

[0196] First, a modified crystalline polyester resin is dissolved in o-dichlorobenzene at room temperature for 24 hours. The resulting solution is then filtered through a solvent-resistant Myshori Disk membrane filter (manufactured by Tosoh Corp.) with a pore diameter of 0.2 µm to obtain a sample solution. It is important to note that the sample solution is adjusted so that the concentration of the component soluble in THF is 0.8 wt%. The sample solution is then used to perform the measurement under the following conditions. Device: HLC-8121GPC / HT (manufactured by Tosoh Corp.) Column: 2 series of TSKgel GMHHR-HHT 7.8 cm inner diameter × 30 cm (manufactured by Tosoh Corp.) Detector: RI for high temperatures Temperature: 135 °C Solvent: o-Dichlorobenzene (with 0.05% ionol addition) Flow rate: 1.0 mL / min. Sample: Inject 0.4 mL of the 0.1% sample.

[0197] A measurement is performed under the conditions described above, and the molecular weight calibration curve, prepared using a monodisperse polystyrene standard sample, is used to calculate the molecular weight of a sample. Subsequently, the molecular weights are calculated using a polyethylene conversion formula derived from the Mark-Houwink viscosity formula. Methods for measuring softening temperature

[0198] The softening temperature of a sample is measured using a constantly loaded extrusion-type capillary rheometer, the "Flow characteristic evaluation device Flowtester CFT-500D" (manufactured by Shimadzu Corp.), according to the operating instructions included with the device. With this device, a constant load is applied downwards to the sample using a piston. The sample, which is contained in a cylinder, is heated and melts. The molten sample is extruded from a nozzle at the bottom of the cylinder, and a flow curve showing the relationship between piston drop and temperature can be obtained.

[0199] The temperature at which the outflow began and the piston started to descend is defined as the outflow start temperature, and the "melting temperature in the 1 / 2 method," described in the operating instructions accompanying the "Flow characteristic evaluation device Flowtester CFT-500D," is defined as the softening temperature. The melting temperature in the 1 / 2 method is calculated as follows. First, 1 / 2 of the difference between the piston descent Smax at the time the outflow is complete and the piston descent Smin at the time the outflow began is calculated (this difference is taken as X). X = (Smax - Smin) / 2). Therefore, the temperature on the flow curve when the piston descent is the sum of X and Smin is the melting temperature in the 1 / 2 method.

[0200] A measurement sample is obtained by compression molding 1.0 g of the resin at an ambient temperature of 25 °C using a tablet press (for example, NT-100H, manufactured by NPa System Co., Ltd.) at 10 MPa for 60 seconds to achieve a cylindrical shape with a diameter of approximately 8 mm.

[0201] The measurement conditions for CFT-500D are as follows. Test mode: Temperature rise method Starting temperature: 50 °C Saturation temperature: 200 °C Measurement interval: 1.0 °C Rate of increase: 4.0 °C / min Piston cross-sectional area: 1,000 cm² 2 Test load (piston load): 10.0 kgf (0.9807 MPa) Preheating time: 300 seconds Nozzle hole diameter: 1.0 mm Nozzle length: 1.0 mm Method for measuring the weight-averaged particle diameter (D4) of toner particles

[0202] The weight-averaged particle diameter (D4) of the toner is calculated as follows. A CDA-1000X particle counting analyzer (manufactured by SYSMEX Corp.) is used as the measuring instrument, employing a pore electrical resistance measurement method and incorporating a 100 µm aperture tube. The accompanying CDA-1000X software (manufactured by SYSMEX Corp.) is used to set the measurement conditions and analyze the measurement data.

[0203] The electrolyte solution used for the measurement can be, for example, "Cellpack" (manufactured by Sysmex Corp.). Prior to measurement and analysis, the specialized software was configured as follows: On the "Measurement Conditions Setting" screen of the software, the total count was set to 50,000, the number of repeated measurements was set to 1, and the measurement mode was set to total count (unlimited).

[0204] The specific measurement procedure is as follows. (1) 150 mL of an aqueous electrolyte solution is placed in a special round-bottomed beaker, which is placed on a sample platform, and stirred with a stirring propeller at 500 rpm. The "blank measurement" function of the special software is then activated to start the measurement, and it is confirmed that the count is less than 500. If the count is 500 or more, the beaker and the opening tube are washed repeatedly. (2) The aqueous electrolyte solution: 30 mL are placed in a 100 mL flat-bottomed beaker. To this solution, 0.3 mL of a dilute solution prepared by diluting “Contaminon N” (a 10 wt% aqueous solution of a neutral cleaning agent with pH 7 for washing precision measuring instruments, comprising a non-ionic surfactant, an anionic surfactant, and an organic former, manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water to 3 times its original volume is added as a dispersing agent. (3) An ultrasonic disperser “Ultrasonic Dispersion System Tetra 150” (manufactured by Nikkaki Bios Co., Ltd.), which integrates two oscillators with an oscillation frequency of 50 kHz and phases shifted by 180 degrees, and has an electrical output power of 120 W, is prepared. 3.3 L of deionized water are placed in the water tank of the ultrasonic disperser, and 2 mL of Contaminon N are added to this water tank. (4) The beaker from (2) is inserted into a beaker mounting opening of the ultrasonic disperser, and the ultrasonic disperser is switched on. Then the height of the beaker is adjusted so that the resonance state of the liquid surface of the aqueous electrolyte solution in the beaker is maximized. (5) While the aqueous electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, 10 mg of the toner are gradually added and dispersed. The ultrasonic dispersion treatment is then continued for a further 60 seconds. In addition, the water temperature in the water tank is adjusted to be within a range of 10 °C to 40 °C for the ultrasonic dispersion. (6) The aqueous electrolyte solution in (5), in which the toner is dispersed, is added dropwise using a pipette to the round-bottomed beaker in (1), which has been placed in the sample rack, and the measurement concentration is adjusted to 6%. The measurement is then carried out until the number of sample particles reaches 50,000. (7) The measurement data are analyzed using special software supplied with the device, and the weight-averaged particle diameter (D4) is calculated. Methods for measuring acidity

[0205] An acid value is the mass [mg] of potassium hydroxide required to neutralize the acids contained in 1 g of a sample. That is, the mass [mg] of potassium hydroxide required to neutralize free fatty acids and resin acids contained in 1 g of a sample is referred to as the acid value.

[0206] The acidity level was measured according to JIS K 0070-1992. Specifically, the acidity level is measured using the following procedure. (1) Preparation of the reagent

[0207] 1.0 g of phenolphthalein was dissolved in 90 mL of ethyl alcohol (95 vol%), deionized water was added to make a volume of 100 mL, thus producing a phenolphthalein solution.

[0208] 7 g of special-grade potassium hydroxide were dissolved in 5 mL of water, and ethyl alcohol (95 vol%) was added to bring the volume to 1 L. To prevent contact with carbon dioxide gas and the like, the mixture was placed in an alkali-resistant container and left to stand for 3 days. After standing, the mixture was filtered to obtain a potassium hydroxide solution. The potassium hydroxide solution was stored in an alkali-resistant container. The potency factor of the potassium hydroxide solution was determined based on the amount of potassium hydroxide solution required for neutralization when 25 mL of 0.1 mol / L hydrochloric acid were placed in an Erlenmeyer flask, several drops of phenolphthalein solution were added, and the titration with the potassium hydroxide solution was performed. The above 0.1 mol / L hydrochloric acid was prepared according to JIS K 8001-1998. (2) Procedure(A) Main Test

[0209] 2.0 g of a sample were accurately weighed into a 200 mL Erlenmeyer flask, 100 mL of a mixed toluene / ethanol solution (2:1) were added, and the sample was allowed to dissolve for 5 hours. Subsequently, several drops of phenolphthalein solution were added as an indicator, and the titration was carried out with the potassium hydroxide solution. It should be noted that the endpoint of the titration is reached when the bright red color of the indicator persists for approximately 30 seconds. (B) Blind test

[0210] The titration was carried out using the same procedure as above, except that no sample was added (that is, only a mixed solution of toluene / ethanol (2:1) was used). (3) Calculation of acid value

[0211] The obtained result was inserted into the following expression to calculate the acid value. AV=[(B−A)×f×5.61] / S

[0212] In this expression, AV denotes an acid value [mgKOH / g], A denotes the amount [mL] of potassium hydroxide solution added in the blank experiment, B denotes the amount [mL] of potassium hydroxide solution added in the main experiment, f denotes the factor of aqueous potassium hydroxide solution, and S denotes the mass [g] of a sample. Method for measuring hydroxyl value

[0213] The hydroxyl value is the number of milligrams of potassium hydroxide required to neutralize the acetic acid bound to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value of the binder resin is measured according to JIS K 0070-1992. Specifically, the hydroxyl value of the binder resin is measured using the following procedure. (1) Preparation of reagent

[0214] 25 g of special-grade acetic anhydride are placed in a 100 mL volumetric flask, then pyridine is added to bring the total volume to 100 mL, and the mixture is shaken thoroughly to obtain an acetylation reagent. To prevent contact with moisture, carbon dioxide gas, and the like, the resulting acetylation reagent is stored in a brown bottle.

[0215] 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95 vol%), and ion-exchanged water is added to adjust the volume to 100 mL to obtain a phenolphthalein solution.

[0216] 35 g of special-grade potassium hydroxide are dissolved in 20 mL of water, and ethyl alcohol (95 vol%) is added to adjust the volume to 1 L. The resulting solution is placed in an alkali-resistant container to prevent contact with carbon dioxide gas or the like, allowed to stand for 3 days, and then filtered to obtain a potassium hydroxide solution. The potassium hydroxide solution is stored in an alkali-resistant container. The concentration factor of the potassium hydroxide solution is determined from the amount of potassium hydroxide solution required for neutralization by placing 25 mL of 0.5 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution. The 0.5 mol / L hydrochloric acid is prepared according to JIS K 8001-1998. (2) Procedure(A) Main Test

[0217] 1.0 g of a sample is accurately weighed into a 200 mL round-bottom flask, and 5.0 mL of the acetylation reagent is carefully added using a volumetric pipette. If the sample does not dissolve readily in the acetylation reagent, a small amount of special-grade toluene is added to dissolve the sample.

[0218] A small funnel is placed over the opening of the flask, and approximately 1 cm of the flask base is immersed in a glycerin bath at about 97 °C and heated. In this case, to prevent the temperature of the flask neck from rising due to the heat of the bath, it is preferable to cover the neck of the flask with a piece of heavy paper with a round hole in it.

[0219] After 1 hour, the flask is removed from the glycerol bath and cooled. After cooling, 1 mL of water is added through the funnel and the mixture is shaken to hydrolyze the acetic anhydride. For more complete hydrolysis, the flask is reheated in the glycerol bath for 10 minutes. After cooling, the funnel and flask walls are washed with 5 mL of ethyl alcohol.

[0220] A few drops of phenolphthalein solution are added as an indicator, and titration is carried out using potassium hydroxide solution. It should be noted that the endpoint of the titration is reached when the indicator remains bright red for approximately 30 seconds. (B) Blind trial

[0221] The titration is carried out in the same way as the above procedure, except that no sample is used.

[0222] (3) The result obtained is substituted into the following expression to calculate the hydroxyl number. A=[{(B−C)×28.05×f} / S]+D

[0223] Here, A is the hydroxyl number (mgKOH / g), B is the amount of potassium hydroxide solution added in the blank experiment (mL), C is the amount of potassium hydroxide solution added in the main experiment (mL), f is the potassium hydroxide solution factor, S is the sample (g), and D is the acid number of the sample (mgKOH / g).

[0224] Method for calculating the modification rate with a linear alkyl compound from the molecular chain end of modified amorphous polyester resin or modified crystalline polyester resin

[0225] The modification rate with a linear alkyl compound at the molecular chain ends of a modified amorphous polyester resin or a modified crystalline polyester resin (hereinafter referred to as the resin in the calculation procedure) is calculated using the acid number, hydroxyl number, and molecular weight determined as above. Specifically, the number of moles of terminal functional groups (carboxy group or hydroxyl group remaining without condensation of the linear alkyl compound) per gram of resin is calculated using the following expression. Number of moles of terminal functional groups = (acid number + hydroxyl number) / (1000 × 56.105)

[0226] Next, the number of moles per gram of a resin is calculated from the number-averaged molecular weight Mn of the resin. Number of moles per gram of resin = 1 / Mn

[0227] The number of functional groups in the final product is calculated from the ratio of monomer units in the resin, which is determined by NMR spectroscopy. Specifically, in the case of an ester product of a dicarboxylic acid and a dialcohol, the number of functional groups is 2. If a trivalent or more polyvalent monomer is used, the number of functional groups in the final product can be calculated from the molar ratio. Modification rate with a linear alkyl compound at the molecular chain ends of a resin (mol%) = [1 − (number of moles of terminal functional groups) / (number of moles per gram of resin) × (amount of functional groups)] × 100 Examples

[0228] The following examples and other information illustrate this disclosure. However, the description regarding these examples is not intended to limit the present disclosure. It should be noted that, unless otherwise stated, "part(s)" in the following wording refer to a mass-marketed product.

[0229] Production example of amorphous polyester resin A1 - Bisphenol A / propylene oxide adduct (an average number of moles added of 2.2 mol): 78.0 parts by mass - Terephthalic acid: 20.0 parts by mass - Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass

[0230] The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet tube, and a thermocouple. The interior of the vessel was then purged with nitrogen gas, the temperature was gradually increased while stirring, and the reaction was continued at 200 °C for 2 hours while stirring. After reducing the pressure in the reaction vessel to 8.3 kPa and maintaining it under the same conditions for 1 hour, the reaction vessel was cooled to 160 °C and then returned to atmospheric pressure. - Stearic acid: 2.0 parts by mass

[0231] The aforementioned material was then added, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was initiated while maintaining a temperature of 200 °C. After confirming that the softening temperature had reached the temperature shown in Table 1, the temperature was lowered to stop the reaction and obtain an amorphous polyester resin A1. The physical properties are shown in Table 1.

[0232] Production example of amorphous polyester resins A2 to A14

[0233] Amorphous polyester resins A2 to A14 were obtained in the same manner as in the preparation example for amorphous polyester resin A1, except that the monomers used were modified as listed in Table 1. The composition and physical properties of the obtained amorphous polyester resins A2 to A14 are shown in Table 1.

[0234] The amorphous polyester resins A1 to A14 exhibited a degree of crystallinity of 10% or less when left to stand for 1 week at 30 °C and 80% rH.

[0235] The polyester resins A1 to A11 were modified amorphous polyester resins. Table 1 Amorphous polyester resin A Polymerizable monomer 1 Polymerizable monomer 2 Polymerizable monomer 3 Physical properties Art parts Art parts Art parts Tg °C Softening temperature °C Mn Mw SP value rate of modification 1 BPO-PO 78,0 TPA 20,0 SA 2,0 48 94 2200 6300 10,8 3 2 BPO-PO 78,0 TPA 20,0 BA 2,0 47 94 2200 6300 10,8 2 3 BPO-PO 76,0 TPA 20,0 SA 4,0 47 93 2200 6300 10,8 6 4 BPO-PO 78,0 TPA 21,0 SA 1,0 49 95 2200 6300 10,9 1 5 BPO-PO 74,0 TPA 20,0 SA 6,0 47 92 2200 6300 10,7 8 6 BPO-PO 78,0 TPA 20,0 PA 2,0 48 94 2200 6300 10,8 3 7 BPO-PO 78,0 TPA 20,0 LA 2,0 48 94 2200 6300 10,8 2 8 BPO-PO 78,0 TPA 20,0 SAI 2,0 48 94 2200 6300 10,8 3 9 BPO-PO 78,0 TPA 21,5 SA 0,5 49 97 2200 6300 10,9 1 10 BPO-PO 78,0 TPA 20,0 MA 2,0 49 95 2200 6300 10,8 3 11 BPO-PO 78,0 TPA 20,0 CA 2,0 49 95 2200 6300 10,8 2 12 BPO-PO 80,0 TPA 20,0 - - 52 100 2200 6300 10,8 - 13 BPO-PO 75,0 TPA 18,0 DS 7,0 53 94 2200 6500 10,7 - 14 BPO-PO 80,0 TPA 20,0 - - 59 100 2000 6000 10,9 -

[0236] In Table 1, Tg denotes the glass transition temperature. The unit of SP values ​​is (cal / cm²). 3 ) 0,5 The modification rate is a modification rate (mol%) with a linear alkyl compound at the ends of the molecular chains. The abbreviations in Table 1 are as follows. The numerical values ​​in parentheses refer to the number of carbons in the linear chain alkyl compounds. BPA-PO: Bisphenol-A-propylene oxide adduct (average number of moles added of 2.2 mol) TPA: Terephthalic acid: PA: Palmitic acid (16) SA: Stearic acid (18) BA: Behenic acid (22) LA: Lignoseric acid (24) MA: Myristic acid (14) CA: Cerotic acid (26) SAl: Stearyl alcohol (18) DS: Dodecyl succinic anhydride

[0237] Production example of amorphous polyester resin B1 - Bisphenol-A-propylene oxide adduct (average number of moles added of 2.2 mol): 60.0 parts by mass - Terephthalic acid: 35.0 parts by mass - Trimellitic acid anhydride: 5.0 parts by weight - Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass

[0238] The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet tube, and a thermocouple. The interior of the vessel was then purged with nitrogen gas, the temperature was gradually increased while stirring, and the reaction was continued at 200 °C for 3 hours. Afterward, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was initiated while maintaining a temperature of 200 °C. Upon confirmation that the softening temperature had reached 138 °C, the temperature was lowered to stop the reaction and obtain an amorphous polyester resin, B1. The physical properties are shown in Table 2. Table 2 Amorphous polyester resin B Polymerizable monomer 1 Polymerizable monomer 2 Polymerizable monomer 3 Physical properties Art parts Art parts Art parts Tg°C Mn Mw SP value 1 BPO-PO 60,0 TPA 35,0 TMA 5,0 58 4300 10500 10,8

[0239] In Table 2, Tg denotes the glass transition temperature. The unit of the SP value is (cal / cm²). 3 ) 0,5The abbreviations in Table 2 are as follows. BPA-PO: Bisphenol-A-propylene oxide adduct (average number of moles added of 2.2 mol) TPA: Terephthalic acid: TMA: Trimellitic anhydride

[0240] Production example of crystalline polyester resin 1 - Ethylene glycol: 20.0 parts by mass - Tetradecanoic acid: 74.0 parts by mass - Behenic acid: 6.0 parts by mass - Tin 2-ethylhexanoate: 0.5 parts by mass

[0241] The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet tube, and a thermocouple. The interior of the flask was purged with nitrogen gas, then the temperature was gradually increased while stirring, and the reaction continued while stirring at a temperature of 140 °C for 3 hours.

[0242] The pressure in the reaction vessel was then reduced to 8.3 kPa, and the reaction was continued for 4 hours while maintaining a temperature of 200 °C to obtain a crystalline polyester resin 1. The physical properties are shown in Table 3.

[0243] Preparation Example of Crystalline Polyester Resins 2 to 16: The crystalline polyester resins 2 to 16 were obtained in the same manner as in the preparation example for crystalline polyester resin 1, except that the monomers used were changed as listed in Table 3. The composition and physical properties of the obtained crystalline polyester resins 2 to 16 are listed in Table 3.

[0244] The crystalline polyester resins 1 to 14 and 16 are modified crystalline polyester resins. Table 3 Crystalline polyester resin No. First monomer unit Second monomer unit Third monomer unit Physical properties Art parts Art parts Art parts Melting point °C Mn Mw SP value rate of modification 1 EC 20,0 TDA 74,0 BA 6,0 90 4700 19000 9,8 50 2 EC 20,0 TDA 74,0 SA 6,0 90 4700 19000 9,7 58 3 EC 20,0 TDA 74,0 BA 6,0 88 3900 15000 9,8 37 4 EC 20,0 TDA 74,0 BA 6,0 92 5500 25000 9,8 62 5 EC 20,0 TDA 74,0 BA 6,0 88 3800 13000 9,8 34 6 EC 20,0 TDA 74,0 BA 6,0 92 5600 28000 9,8 73 7 EC 18,0 TDA 74,0 BA 10,0 91 4700 19000 9,5 62 8 EC 26,0 DDA 72,0 BA 2,0 85 4700 19000 10,1 20 9 EC 20,0 TDA 74,0 PA 6,0 90 4700 19000 9,8 66 10 EC 20,0 TDA 74,0 LA 6,0 90 4700 19000 9,9 43 11 EC 20,0 TDA 74,0 BAI 6,0 90 4700 19000 9,8 50 12 EC 20,0 TDA 74,0 BA 6,0 87 2500 9000 9,8 40 13 EC 20,0 TDA 74,0 MA 6,0 90 4700 19000 9,9 66 14 EC 20,0 TDA 74,0 CA 6,0 90 4700 19000 9,9 40 15 EC 22,0 TDA 78,0 - - 88 4700 19000 9,9 - 16 HG 18,0 DDA 82,0 SA 4,0 84 8000 27000 9,7 25

[0245] Table 3 shows the unit of the SP value (cal / cm²).3 ) 0,5 The modification rate is a modification rate (mol%) with a linear alkyl compound at the molecular chain ends.

[0246] The abbreviations in Table 3 are as follows. The numerical values ​​in parentheses denote the number of carbon atoms in a linear chain alkyl compound. EC: Ethylene glycol HG: 1,6-Hexanediol TDA: Tetradecanedioic acid DDA: Dodecanedioic acid PA: Palmitic acid (16) SA: Stearic acid (18) BA: Behenic acid (22) LA: Lignoseric acid (24) MA: Myristic acid (14) CA: Cerotic acid (26) BAI: Behenyl alcohol (22) Production of wax dispersion agents - Low molecular weight polypropene (Biscol 660P, manufactured by Sanyo Chemical Industries, Ltd.) 10.0 parts by mass (0.02 mol; 2.4 mol% relative to the total number of moles of the constituent monomers) - Xylene: 25.0 parts by mass

[0247] The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet tube, and a thermocouple. Next, the interior of the flask was purged with nitrogen gas, and the temperature was gradually increased to 175 °C while stirring. - Styrene: 68.0 parts by mass - Cyclohexyl methacrylate: 5.0 parts by weight - Butyl acrylate: 12.0 parts by mass - Methacrylic acid: 5.0 parts by mass - Xylene: 10.0 parts by mass - Di-t-butylperoxyhexahydroterephthalate: 0.5 part by weight

[0248] The above materials were then added dropwise over a period of 3 hours and stirred for a further 30 minutes. The solvent was then removed by evaporation to obtain a wax dispersion exhibiting a structure in which a vinyl resin component and a hydrocarbon compound had reacted. The resulting wax dispersion had a peak molecular weight (Mp) of 6000 and a softening temperature of 125 °C. Production example of toner particles 1 - Amorphous polyester resin A1: 50.0 parts by weight - Amorphous polyester resin B1: 21.0 parts by weight - Crystalline polyester resin 1:12.0 parts by mass - Wax dispersion agent: 5.0 parts by mass - Fischer-Tropsch wax (hydrocarbon wax, melting point: 90 °C): 5.0 parts by mass - CI Pigment Blue 15: 3: 7.0 parts by mass

[0249] The above material was processed using a Henschel mixer (model FM-75, manufactured by Nihon Coke & Engineering Co., Ltd.) at a speed of 20 s -1The mixture was blended for 5 minutes and then kneaded using a twin-screw mixer (PCM-30, manufactured by Ikegai Corp.) at a screw speed of 250 rpm and an outlet temperature of 130 °C. The resulting kneaded product was rolled and cooled in a drum flaker (MBD 30-30, manufactured by Nihon Coke & Engineering Co., Ltd.). The cooling water temperature was set to 50 °C, and the conditions were adjusted to achieve a post-rolling thickness of 1.0 mm in the resin composition. The post-rolling resin composition was then held at 40 °C to 50 °C for 60 minutes. The resulting resin composition was cooled to room temperature and then coarsely pulverized to a particle size of 1 mm or less using a hammer mill to obtain a coarsely powdered substance.The resulting coarsely pulverized substance was finely pulverized using a mechanical pulverizer (T-250, manufactured by Freund-Turbo Corp.).

[0250] Additionally, classification was performed using a Faculty F-300 (manufactured by Hosokawa Micron Corp.) to obtain a toner particle 1 with a weight-averaged particle diameter of 6.0 µm. The operating conditions were set such that the rotational speed of the classifying rotor was 130 s⁻¹. -1 would be and the rotational speed of the dispersion rotor would be 120 seconds. -1 would be. Production examples of toner particles 2 to 32

[0251] Toner particles 2 to 32 were obtained in the same manner as in the preparation example of toner particles 1, except that the types and mass fractions of the amorphous polyester resin A, the amorphous polyester resin B, and the crystalline polyester resin were changed as listed in Table 4. Table 4 Toner particle no. Amorphous Polyester A Amorphous Polyester B Crystalline polyester SPA-SPC Nr. parts Nr. parts Nr. parts 1 1 50,0 1 21,0 1 12,0 1,0 2 2 50,0 1 21,0 1 12,0 1,0 3 2 50,0 1 21,0 2 12,0 1,1 4 1 50,0 1 21,0 3 12,0 1,0 5 1 50,0 1 21,0 4 12,0 1,0 6 1 50,0 1 21,0 5 12,0 1,0 7 1 50,0 1 21,0 6 12,0 1,0 8 1 50,0 1 21,0 7 12,0 1,3 9 1 55,0 1 23,0 1 5,0 1,0 10 1 45,5 1 19,5 1 18,0 1,0 11 1 56,0 1 24,0 1 3,0 1,0 12 1 41,0 1 17,0 1 25,0 1,0 13 1 50,0 1 21,0 8 12,0 0,7 14 3 50,0 1 21,0 1 12,0 1,0 15 4 50,0 1 21,0 1 12,0 1,1 16 5 37,0 1 16,0 1 12,0 0,9 17 1 50,0 1 21,0 9 12,0 1,0 18 1 50,0 1 21,0 10 12,0 0,9 19 6 50,0 1 21,0 1 12,0 1,0 20 7 50,0 1 21,0 1 12,0 1,0 21 8 50,0 1 21,0 1 12,0 1,0 22 1 50,0 1 21,0 11 12,0 1,0 23 1 50,0 1 21,0 12 12,0 1,0 24 9 50,0 1 21,0 1 12,0 1,1 25 1 50,0 1 21,0 13 12,0 0,9 26 1 50,0 1 21,0 14 12,0 0,9 27 10 50,0 1 21,0 1 12,0 1,0 28 11 50,0 1 21,0 1 12,0 1,0 29 1 50,0 1 21,0 15 12,0 0,9 30 12 50,0 1 21,0 1 12,0 1,0 31 13 50,0 1 21,0 1 12,0 0,9 32 14 50,0 1 21,0 16 12,0 1,2 Production example of toner 1 - Toner particles 1: 100 parts - Silicate particles 1 (pyrogenic silica with a number-averaged diameter of 30 nm, treated with silicone oil): 1.0 parts

[0252] The above materials were processed using a Henschel FM-10C mixer (manufactured by Mitsui Miike Machinery Co., Ltd.) at a speed of 30 s -1 and mixed with a rotation time of 10 minutes to obtain one toner. Manufacturing example of toners 2 to 32

[0253] Toner particles 2 to 32 were obtained by carrying out the production in the same way as in the production example of toner 1, except that toner particles 2 to 32 were used.

[0254] Samples A and B were prepared using toners 1 to 32, and cross-sections were examined. The results are summarized in Table 5. Table 5 Toner No. Toner particle no. Sample A Sample B D B -D A D A S A / W C D B aspect ratio S B / W C 1 1 30 0,2 40 3,5 0,6 10 2 2 25 0,1 30 3,0 0,3 5 3 3 20 0,05 25 2,5 0,2 5 4 4 30 0,1 40 3,5 0,3 10 5 5 30 0,3 40 3,5 0,7 10 6 6 25 0,05 30 3,0 0,2 5 7 7 35 0,4 45 4,0 0,8 10 8 8 50 0,5 70 5,0 0,9 20 9 9 30 0,2 40 3,5 0,5 10 10 10 30 0,2 45 3,5 0,6 15 11 11 25 0,1 30 4,0 0,3 5 12 12 35 0,3 55 3,0 0,7 20 13 13 20 0,05 30 3,5 0,2 10 14 14 20 0,1 40 2,3 0,5 20 15 15 60 0,3 70 5,2 0,5 10 16 16 10 0,1 15 2,2 0,2 5 17 17 80 0,3 100 6,0 0,7 20 18 18 80 0,3 100 6,0 0,7 20 19 19 80 0,3 100 6,0 0,7 20 20 20 80 0,3 100 6,0 0,7 20 21 21 30 0,2 40 3,5 0,6 10 22 22 30 0,2 40 3,5 0,6 10 23 23 8 0,01 15 2,0 0,05 7 24 24 110 0,3 150 8,0 0,8 40 25 25 100 0,3 150 9,0 0,8 50 26 26 100 0,3 150 9,0 0,8 50 27 27 100 0,3 150 9,0 0,8 50 28 28 100 0,3 150 9,0 0,8 50 29 29 150 0,5 200 12,0 0,9 50 30 30 150 0,5 200 12,0 0,9 50 31 31 - - 200 12,0 0,5 - 32 32 - - - - - - Manufacturing example of magnetic core particles 1 - Step 1 (weighing / mixing step) Fe2O3: 62.7 parts by mass MnCO3: 29.5 parts by mass Mg(OH)2: 6.8 parts by mass SrCO3: 1.0 parts by mass

[0255] A ferrite raw material was weighed to obtain the above materials in the above mixing ratio. The mixture was then pulverized and mixed for 5 hours using a dry vibratory mill with stainless steel balls that had a diameter of 1 / 8 inch. - Step 2 (Pre-burning step)

[0256] The resulting pulverized substance was formed into 1 mm square pellets using a roller press. The coarse powder was removed from the pellets using a 3 mm opening vibrating screen, and then the fine powder was removed using a 0.5 mm opening vibrating screen. The powder was then fired in a burner-type furnace at 1000 °C for 4 hours under a nitrogen atmosphere (oxygen concentration: 0.01 vol%), producing pre-fired ferrite. The composition of the resulting calcined ferrite is as follows. (MnO) a (MgO) b (SrO) c (Fe2O3) d

[0257] In the formula above, a = 0.257, b = 0.117, c = 0.007 and d = 0.393. - Step 3 (Powdering step)

[0258] After the pre-fired ferrite was pulverized to about 0.3 mm by a crusher, 30 parts by mass of water, relative to 100 parts by mass of the pre-fired ferrite, were added using zirconium oxide beads with a diameter of 1 / 8 inch, then pulverized by a wet ball mill, and the slurry was pulverized by a wet ball mill using aluminum oxide balls with a diameter of 1 / 16 inch for 4 hours, giving a ferrite slurry (finely pulverized calcined ferrite). - Step 4 (Granulation step)

[0259] To the ferrite slurry, 1.0 parts by mass of ammonium polycarboxylate as a dispersant and 2.0 parts by mass of polyvinyl alcohol as a binder were added, relative to 100 parts by mass of the pre-burned ferrite, and spherical particles were granulated using a spray dryer (manufacturer: Okawara Kakoki, Co., Ltd.). The resulting particles were adjusted for particle size and heated at 650 °C for 2 hours using a rotary kiln to remove organic components of the dispersant and binder. - Step 5 (firing step)

[0260] To control the firing atmosphere, the temperature in an electric furnace under a nitrogen atmosphere (oxygen concentration: 1.00 vol%) was increased from room temperature to 1300 °C in 2 hours, and the particle was fired at a temperature of 1150 °C for 4 hours. Afterwards, the temperature was reduced to 60 °C over 4 hours, the atmosphere was changed from nitrogen to ambient air, and the sample was removed at a temperature of 40 °C or less. - Step 6 (Sorting step)

[0261] After the agglomerated particles were decomposed, the low-magnetic material was cut off by magnetic sorting, and the coarse particles were removed by sieving with a sieve with an opening of 250 µm to obtain magnetic core particles 1 having a 50% grain size (D50) of 37.0 µm based on a volume distribution. Setting of coating resin 1 Cyclohexyl methacrylate monomer: 26.8 parts by weight Methyl methacrylate monomer: 0.2 parts by weight Methyl methacrylate macromonomer: 8.4 parts by mass (Macromonomer with a methacryloyl group at one end, having a weight-averaged molecular weight of 5000) Toluene: 31.3 parts by mass Methyl ethyl ketone: 31.3 parts by mass Azobisisobutyronitrile: 2.0 parts by weight

[0262] Among the above materials, cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone were placed in a four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer. Nitrogen gas was introduced to adequately fill the flask with nitrogen, then the flask was heated to 80 °C, azobisisobutyronitrile was added, and the mixture was heated under reflux for 5 hours to induce polymerization.

[0263] Hexane was injected into the resulting reaction product to precipitate a copolymer. The precipitate was filtered off and then dried under vacuum to obtain a coating resin 1. Thirty parts by mass of the obtained coating resin 1 were dissolved in 40 parts by mass of toluene and 30 parts by mass of methyl ethyl ketone to obtain a polymer solution 1 (solids content: 30 wt%). Production of coating resin solution 1 Polymer solution 1 (resin solids concentration: 30%): 33.3 parts by mass Toluene: 66.4 parts by mass Carbon black (Regal 330, manufactured by Cabot Corp.): 0.3 parts by mass (Primary particle size: 25 nm, nitrogen adsorption specific surface area: 94 m²) 2 / g, and DBP oil absorption: 75 mL / 100 g)

[0264] The above material was dispersed for one hour using a color mixer with 0.5 mm diameter zirconium dioxide beads. The resulting dispersion was filtered through a 5.0 µm membrane filter to obtain a coating resin solution 1. Manufacturing example of a magnetic carrier: 1 resin coating step

[0265] The coating resin solution 1 was placed in a vacuum degassing-type kneader, which was kept at room temperature, such that the amount of resin was 2.5 parts by mass relative to 100 parts by mass of the magnetic core particle 1. After placement, the mixture was stirred at a rotational speed of 30 rpm for 15 minutes, and the solvent was evaporated to a certain level or more (80 wt%). The temperature was then increased to 80 °C while mixing under reduced pressure, toluene was distilled off over 2 hours, and then the mixture was cooled. Low-magnetic-field products were removed from the resulting magnetic carrier by magnetic sorting. The obtained magnetic carrier was then passed through a 70 µm aperture sieve and classified by a compressed air classifier to obtain a magnetic carrier 1 with a 50% particle size (D50) based on a volume distribution of 38.2 µm. Manufacturing example for two-component developer 1

[0266] Toners 1 to 32 and magnetic carrier 1 were each heated at 0.5 s -1 Using a V-mixer (V-10 type: Tokuju Corp.), the mixture was blended for a rotation time of 5 minutes, resulting in a toner concentration of 8.0 mass % to obtain two-component developer 1 to 32. Example 1: Low-temperature fixability

[0267] The evaluation was performed using the two-component developer 1.

[0268] A modified digital commercial printer (imageRUNNER ADVANCE C5560, manufactured by Canon Inc.) was used as an image generation device, and the two-component developer 1 was placed in a cyan developing apparatus. The modification of the apparatus involved a change so that the fixing temperature, the processing speed, and the DC voltage V could be adjusted. DCof the developer carrier element, the charging voltage V D The electrostatic latent image carrier element and the laser power can be freely adjusted. For image output evaluation, a full-frame (FFh) image with a desired aspect ratio was output. DC , V D The laser power was adjusted so that the amount of toner deposited on the FFh image on the paper reached a desired amount, and the low-temperature fixability was evaluated.

[0269] FFh is a hexadecimal value representing 256 levels, where 00h is the first level (white background) of the 256 levels and FFh is the 256th level (filled area) of the 256 levels.

[0270] The evaluation was carried out on the basis of the following evaluation procedures, and the results are shown in Table 6. - Paper: GFC-081 (81.0 g / m²) 2) (commercially available from Canon Marketing Japan Inc.) - Amount of toner deposited on paper: 0.70 mg / cm² 2 (adjusted by the DC voltage V) DC of the developer carrier element, the charging voltage V D of the electrostatic latent image carrier element, and the laser power) - Image for evaluation: A 2 cm × 5 cm image was placed in the center of the A4 sheet. - Test environment: Low temperature and low humidity environment: Temperature 15 °C / humidity 10% RH (hereinafter referred to as "L / L") - Fixing temperature: 140 °C - Process speed: 320 mm / sec.

[0271] The evaluation images were output, and the low-temperature fixability was evaluated. The rate of image density degradation was used as an evaluation index for low-temperature fixability.

[0272] The rate of image density degradation was measured using an X-Rite color reflectance densitometer (Series 500: manufactured by X-Rite Inc.). First, the image density of the center was measured. Next, a load of 4.9 kPa (50 g / cm²) was applied to the area where the image density was measured. The fixed image was then subjected to rubbing (five times back and forth) with lens cleaning paper, and the image density was measured again. Subsequently, the rate of image density degradation before and after rubbing was calculated using the following formula. The resulting rate of image density degradation was evaluated according to the following evaluation criteria. If the evaluation fell within the range of AA to C, the evaluation was considered satisfactory. Rate of image density decrease = [(image density before rubbing) − (image density after rubbing)] / (image density before rubbing) × 100 (evaluation criteria) AA: The rate of image density degradation was less than 1.0%. A: The rate of image density decrease was 1.0% or more and less than 3.0%. B: The rate of image density decrease was 3.0% or more and less than 5.0%. C: The rate of image density decrease was 5.0% or more and less than 8.0%. D: The rate of image density decrease was 8.0% or more. Charge retention properties under high temperature and high humidity conditions - Paper: GFC-081 (81.0 g / m²) 2 ) (Canon Marketing Japan Inc.) - Amount of toner deposited on paper: 0.35 mg / cm² 2 (adjusted by the DC voltage V) DC of the developer carrier element, the charging voltage V D of the electrostatic latent image carrier element, and the laser power) - Image for evaluation: A 2 cm × 5 cm image was placed in the center of the A4 sheet. - Fixation test environment: High temperature and high humidity environment: Temperature 30 °C / Hygiene 80% RH (hereinafter referred to as "H / H") Process speed: 377 mm / sec.

[0273] The triboelectric charge of the toner was calculated by drawing the toner onto and collecting it on the electrostatic latent image carrier element using a cylindrical metal tube and a cylindrical filter. Specifically, the triboelectric charge of the toner on the electrostatic latent image carrier element was measured using a Faraday cage.

[0274] The Faraday cage is a coaxial double cylinder that insulates the inner and outer cylinders. When a charged body with an electric charge Q is introduced into the inner cylinder, it is as if a metal cylinder with an electric charge Q exists due to electrostatic induction. The induced charge was measured by an electrometer (Keithley 6517A, manufactured by Keithley Instruments), and the electric charge Q (mC) was divided by the mass M (kg) of the toner in the inner cylinder (Q / M) and defined as the triboelectric charge of the toner. Triboelectric charge quantity (mC / kg) of the toner = Q / M

[0275] First, the evaluation image was formed on the electrostatic latent image carrier element, and before the image was transferred to the intermediate transfer element, the rotation of the electrostatic latent image carrier element was stopped, the toner on the electrostatic latent image carrier element was vacuumed and collected using a cylindrical metal tube and a cylindrical filter, and the [initial Q / M] was measured.

[0276] The development apparatus was then left to stand in the evaluation apparatus in an H / H environment for two weeks. The same procedure as before the stand period was then performed, and the amount of electrical charge Q / M (mC / kg) per unit mass on the electrostatic latent image carrier element after the stand period was measured. The aforementioned Q / M per unit mass on the initial electrostatic latent image carrier element was taken as 100%, and the charge conservation rate ([Q / M after stand period] / [initial Q / M] × 100) per unit mass on the electrostatic latent image carrier element after the stand period was calculated and determined based on the following criteria. If the evaluation fell within the range A to C, it was considered satisfactory. Evaluation criteria A: Charge conservation rate of 90% or more B: Charge conservation rate of 85% or more and less than 90% C: Charge conservation rate of 80% or more and less than 85% D: Charge conservation rate of less than 80% Resistance to leaf adhesion - Paper: CS-680 (A4 sheet, 68.0 g / m 2 ) (manufactured by Canon Marketing Japan Inc.) - Amount of toner deposited: 1.20 mg / cm² 2 - Evaluation image: A 100 cm 2 The (10 cm × 10 cm) image was placed in the center of the A4 sheet. - Fixation test environment: Low temperature and low humidity environment: 15 °C / 10% RH (hereinafter referred to as "L / L") - Process speed: 320 mm / sec. - Fixing temperature: 140 °C

[0277] Using the image-generating device described above, two fixed images were output under the conditions described above, and the output items were superimposed so that the printed sections of the output items were brought into contact with each other.

[0278] A bundle of paper sheets (CS-680, 500 sheets) was further stacked on top of two sheets of the output items, and the output items and the bundle of paper sheets were left in a constant temperature bath set to 30 °C and 80% RH for one hour, then the temperature in the constant temperature bath was reset to the evaluation conditions described below and left for 10 hours.

[0279] The two dispensing items were then removed from the thermostat container, allowed to cool for one hour, and then examined to see if they adhered when detached. If the rating fell within the range of A to C, it was considered good. Evaluation criteria A: The starting materials did not adhere to each other in a constant temperature bath at 60 °C. B: The starting materials did not adhere to each other in a constant temperature bath at 55 °C. C: The starting materials did not adhere to each other in a constant temperature bath at 50 °C. D: The starting materials adhered to each other in a constant temperature bath at 50 °C and tore when the two starting materials were strongly separated from each other. Resistance to wrinkles - Paper: OK Topcoat Plus - Amount of toner deposited: 1.2 mg / cm² 2 - Image for evaluation: A full image is printed on the entire surface of an A4 sheet. - Fixation test environment: under a normal temperature and humidity environment at 25 °C and 50% RH (hereinafter referred to as "N / N") - Process speed: 132 mm / sec. - Fixing temperature: 150 °C

[0280] A single fixed image was output using the image-generating device described above under the conditions described above.

[0281] The starting article was left in a constant temperature fan set to 50 °C for 72 hours, and then the removed sample was allowed to cool for 1 hour in a N / N environment, and then subjected to a dowsing test.

[0282] A cylindrical mandrel bend tester (manufactured by COTEC Corp.) was used in the mandrel bend tester. A mandrel with a diameter of Φ 2 mm was used. The image is placed in the mandrel tester and folded 180°. A 200 g weight is placed on a sheet of Silbon paper, and the folded section is rubbed. The image is then detached from the paper. The detached portion of the image is read at three positions by PIAS (manufactured by Quality Engineering Associates Inc.), and the area of ​​the bend that remains beneath the folded section is digitized by ImageJ image processing software for calculation.

[0283] An analysis procedure using ImageJ is described. An image to be evaluated is opened in ImageJ and converted to an 8-bit format. Threshold processing is then performed to separate areas where no detachment has occurred from those where detachment has occurred. A detached area was added to the defined area of ​​500 pixels wide × 70 pixels high using rectangle processing, and the analysis was performed. This calculates the (total area) : (area A) of the detached area.

[0284] Next, the defined area is moved to a region where no detachment occurred, and the ratio (total area) : (area B) of this region is calculated. The ratio of the area where no detachment occurred is then digitized as area B / (area A + area B).

[0285] The value obtained as described above was used to indicate the resistance to creasing of printed images, and the value was evaluated according to the following criteria. A rating of A to C was considered good. Evaluation criteria A: The resistance to wrinkles is 90% or more. B: Resistance to wrinkles is less than 90% and 80% or more. C: Resistance to wrinkles is less than 80% and 70% or more. D: The resistance to wrinkles is less than 70%. Examples 2 to 22 and comparative examples 1 to 10

[0286] The evaluation was performed in the same way as in Example 1, except that the two-component developer used in the evaluation was replaced with the two-component developer listed in Table 6. The evaluation results are shown in Table 6. Table 6 Toner No. Two-component developer no. Toner characterization evaluation Low-temperature fixability Charge conservation properties Resistance to leaf adhesion Resistance to wrinkles Example 1 1 1 A B B B Example 2 2 2 A B C B Example 3 3 3 AA C C A Example 4 4 4 A C C B Example 5 5 5 A A A C Example 6 6 6 A C C A Example 7 7 7 B A A C Example 8 8 8 B B A C Example 9 9 9 C A B A Example 10 10 10 A C B C Example 11 11 11 C A B A Example 12 12 12 AA C A C Example 13 13 13 A C C A Example 14 14 14 A C C C Example 15 15 15 B C A C Example 16 16 16 AA A C A Example 17 17 17 C C A C Example 18 18 18 C C A C Example 19 19 19 C C A C Example 20 20 20 C C A C Example 21 21 21 A B B C Example 22 22 22 A B B C Comparative example 1 23 23 AA C D A Comparative example 2 24 24 D D A D Comparative example 3 25 25 D D A D Comparative example 4 26 26 D D A D Comparative example 5 27 27 D D A D Comparative example 6 28 28 D D A D Comparative example 7 29 29 D D A D Comparative example 8 30 30 D D A D Comparative example 9 31 31 AA D D D Comparative example 10 32 32 AA D D A

[0287] While the present disclosure has been described with reference to embodiments, it is to be understood that the present disclosure is not limited to the disclosed embodiments. The scope of the following claims is to be interpreted as broadly as possible to include all such modifications and equivalent structures and functions. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] JP 2004-046095

[0003] JP 2016-110150 [0004, 0008] Cited non-patent literature

[0000] Polym. Eng. Sci., 14(2), 147-154 (1974

[0190]

Claims

[1] Toner comprising a toner particle comprising an amorphous polyester resin and a crystalline polyester resin, wherein the amorphous polyester resin comprises a modified amorphous polyester resin having at least one linear alkyl compound condensed at one end, selected from the group consisting of linear C16-24 aliphatic monocarboxylic acids and linear C16-24 aliphatic monoalcohols; the crystalline polyester resin comprises a modified crystalline polyester resin having at least one linear alkyl compound condensed at one end, selected from the group consisting of linear C16-24 aliphatic monocarboxylic acids and linear C16-24 aliphatic monoalcohols; and when a cross-section of a sample A, obtained by melting the toner at 150 °C and subsequently cooling the toner to 25 °C at a rate of 100 °C / min, is viewed using a transmission electron microscope, and a number mean of the longitudinal axis lengths of the crystals of the crystalline polyester resin viewed on the cross-section is defined as D A (nm) is taken, and when a cross-section of a sample B, obtained by leaving sample A at 50 °C for 72 hours, is examined using a transmission electron microscope, and a number mean of the longitudinal axis lengths of the crystals of the crystalline polyester resin considered in the cross-section is defined as D B (nm) is taken the D A and the D B the following expressions (1) and (2) satisfy: 10 nm≤DA≤100 nm 1 nm ≤ DB − DA ≤ 20 nm [2] Toner according to claim 1, wherein the DA and the D B the following expressions (3) and (4) satisfy: 10 nm≤DA≤50 nm 20 nm ≤ DB ≤ 70 nm [3] Toner according to claim 1 or 2, wherein, when the cross-section of sample B is considered, the crystals of the crystalline polyester resin considered in the cross-section have an average aspect ratio of 2.5 to 5.

0. [4] Toner according to claim 1 or 2, wherein, if an SP value of the modified amorphous polyester resin is used as SP A (cal / cm 3 ) 0,5 is taken, and an SP value of the modified crystalline polyester resin is used as SP C (cal / cm 3 ) 0,5 is taken, the SP A and the SP C satisfy the following expression (5): 0.8≤SPA−SPC≤1.2 [5] Toner according to claim 1 or 2, wherein the crystalline polyester resin has a content ratio W Cexhibits a mass of 5.0 to 20.0%, based on the mass of the toner particle. [6] Toner according to claim 1 or 2, wherein, when a content ratio of the crystalline polyester resin, based on the mass of the toner particle, is considered W C (mass-%) is taken, and an average area ratio of the crystals of the crystalline polyester resin in an area of ​​a viewing region, when viewing the cross-section of sample A using a transmission electron microscope, as S A (area % is taken) the W C and the S A satisfy the following expression (6): 0.1≤SA / WC≤0.6 [7] Toner according to claim 1 or 2, wherein, when a content ratio of the crystalline polyester resin, based on the mass of the toner particle, is considered W C (mass-%) is taken, and an average area ratio of the crystals of the crystalline polyester resin in an area of ​​a viewing region, when viewing the cross-section of sample B using a transmission electron microscope, as S B (area % is taken) the W C and the S B satisfy the following expression (7): 0.3≤SB / WC≤0.8 [8] Toner according to claim 1 or 2, wherein the modified crystalline polyester resin has a weight-averaged molecular weight of 15000 to 25000. [9] Toner according to claim 1 or 2, wherein the linear alkyl compound condensed onto one end of the modified amorphous polyester resin has a larger number of carbon atoms than the linear alkyl compound condensed onto one end of the modified crystalline polyester resin. [10] Toner according to claim 1 or 2, wherein the linear alkyl compound condensed onto one end of the modified amorphous polyester resin is stearic acid, and the linear alkyl compound condensed onto one end of the modified crystalline polyester resin is behenic acid. [11] Toner according to claim 1 or 2, wherein the modified crystalline polyester resin comprises a monomer unit corresponding to ethylene glycol and a monomer unit corresponding to dodecanedioic acid. [12] Toner according to claim 1 or 2, wherein a proportion of ends where the linear alkyl compound is condensed under molecular chain ends of the modified amorphous polyester resin is at least 0.5 mol% and less than 25 mol%, and a proportion of ends where the linear alkyl compound is condensed under molecular chain ends of the modified crystalline polyester resin is 15 to 75 mol%.