toner

Abstract

A toner that exhibits excellent low-temperature fixing and static charge retention, suppresses paper adhesion immediately after fixing, and maintains good bending resistance even during long-term storage. [Solution] A toner having toner particles containing an amorphous polyester resin and a crystalline polyester resin, wherein the amorphous polyester resin contains a modified amorphous polyester resin in which a linear alkyl compound of a specific number of carbon atoms is condensed at the end, and the crystalline polyester resin contains a modified crystalline polyester resin in which a linear alkyl compound of a specific number of carbon atoms is condensed at the end, and the average number of crystals D of the major axis length of the crystals of the crystalline polyester resin observed in the cross-section of sample A obtained by melting the toner at 150°C and cooling it to 25°C. A (nm) and the average number of major axis lengths of the crystals of the crystalline polyester resin observed in the cross-section of sample B, which is obtained by leaving sample A at 50°C for 72 hours. B (nm) satisfies a specific relationship.

Description

[Technical Field]

[0001] This disclosure relates to toner used in electrophotographic, electrostatic recording, and electrostatic printing methods. [Background technology]

[0002] In recent years, electrophotographic devices such as full-color printers and full-color copiers have been increasingly expected to offer added value such as high productivity, high image quality, and high stability. To achieve high productivity, it is crucial to melt the toner more quickly during the fixing process. Specifically, there is a demand for toners that can be fixed at lower temperatures and have excellent low-temperature fixing properties.

[0003] Patent Document 1 discloses a toner that uses crystalline polyester as the binder resin, as a toner with excellent low-temperature fixing properties. Crystalline polyester has higher sharp melt properties compared to amorphous polyester and acts as a plasticizer for amorphous polyester, making it an effective material for low-temperature fixing of toner. However, if the compatibility between crystalline polyester and amorphous polyester is increased to improve low-temperature fixability, the crystalline polyester may not crystallize in the toner, which can lead to a decrease in charge retention. Therefore, Patent Document 2 discloses a manufacturing method that promotes the crystallization of crystalline polyester by annealing the toner in order to achieve both low-temperature fixability and charge retention. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2004-046095 [Patent Document 2] Japanese Patent Publication No. 2016-110150 [Overview of the project] [Problems that the invention aims to solve]

[0005] In toners containing crystalline resins with low-temperature fixing properties, the molten toner constituting the fixed image often maintains a miscible state between the binder resin and the plasticizer. As a result, the heat resistance of the toner decreases, making it easier for the fixed image to adhere to the back of the printed paper or to other fixed images, which can lead to image defects. This image defect is called paper adhesion. Especially in the case of double-sided printing, the fixed image areas inevitably come into contact with each other, making image loss even more likely than in single-sided printing. Therefore, there is a need for toner that can achieve both low-temperature fixing properties and resistance to paper adhesion.

[0006] On the other hand, if a fixed image printed using toner containing crystalline resin is stored for a long period of time, the crystalline resin may gradually anneal and crystallize, potentially causing needle-shaped crystalline domains with a large aspect ratio to appear in the fixed image. When crystalline resin crystallizes, it becomes brittle, making the image more susceptible to cracking when bent, which can lead to image loss. According to the inventors' research, the toner described in Patent Document 2 achieves both low-temperature fixation and charge retention by annealing in the toner state, but crystallization slows down after fixation. As a result, the paper discharge adhesion resistance decreases, and crystallization progresses during long-term storage, reducing bending resistance.

[0007] This disclosure provides a toner that exhibits excellent low-temperature fixing and charge retention properties, suppresses paper adhesion immediately after fixing, and maintains its bending resistance even during long-term storage. [Means for solving the problem]

[0008] This disclosure relates to a toner having toner particles containing an amorphous polyester resin and a crystalline polyester resin, The amorphous polyester resin contains a modified amorphous polyester resin in which at least one linear alkyl compound selected from the group consisting of linear aliphatic monocarboxylic acids having 16 to 24 carbon atoms and linear aliphatic monoalcohols having 16 to 24 carbon atoms is condensed at the terminal. The crystalline polyester resin contains a modified crystalline polyester resin in which at least one linear alkyl compound selected from the group consisting of linear aliphatic monocarboxylic acids having 16 to 24 carbon atoms and linear aliphatic monoalcohols having 16 to 24 carbon atoms is condensed at the terminal. Sample A, obtained by melting the toner at 150°C and then cooling it to 25°C at 100°C / min, was observed in cross-section using a transmission electron microscope, and the average number of major axis lengths of the crystalline polyester resin crystals observed in the cross-section was calculated as D. A (nm) Regarding sample B, which is obtained by leaving sample A at 50°C for 72 hours, sample B is observed in cross-section using a transmission electron microscope, and the average number of major axis lengths of the crystals of the crystalline polyester resin observed in the cross-section is D. B When set to (nm), The D A and D B The following relates to toner that satisfies equations (1) and (2) below. 10nm≦D A ≤100nm ···(1) 1nm ≤ D B -D A ≤20nm ···(2) [Effects of the Invention]

[0009] According to this disclosure, it is possible to provide a toner that exhibits excellent low-temperature fixing properties and charge retention, suppresses paper adhesion immediately after fixing, and maintains its bending resistance even during long-term storage. [Modes for carrying out the invention]

[0010] In this disclosure, descriptions of numerical ranges such as "XX or greater and YY or less" or "XX to YY" mean a numerical range that includes the lower and upper limits, unless otherwise specified. When numerical ranges are described in steps, the upper and lower limits of each numerical range can be any combination. In addition, in this disclosure, a description such as "at least one selected from the group consisting of XX, YY, and ZZ" means any of the following: 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. Note that if XX is a group, multiple values ​​may be selected from XX, and the same applies to YY and ZZ.

[0011] Furthermore, a monomer unit refers to the reacted form of monomer substances within a polymer. Crystalline polyester resins are resins whose main skeleton is crystalline, and in which an endothermic peak is observed in differential scanning calorimetry (DSC).

[0012] This disclosure relates to a toner having toner particles containing an amorphous polyester resin and a crystalline polyester resin, The amorphous polyester resin contains a modified amorphous polyester resin in which at least one linear alkyl compound selected from the group consisting of linear aliphatic monocarboxylic acids having 16 to 24 carbon atoms and linear aliphatic monoalcohols having 16 to 24 carbon atoms is condensed at the terminal. The crystalline polyester resin contains a modified crystalline polyester resin in which at least one linear alkyl compound selected from the group consisting of linear aliphatic monocarboxylic acids having 16 to 24 carbon atoms and linear aliphatic monoalcohols having 16 to 24 carbon atoms is condensed at the terminal. Sample A, obtained by melting the toner at 150°C and then cooling it to 25°C at 100°C / min, was observed in cross-section using a transmission electron microscope, and the average number of major axis lengths of the crystalline polyester resin crystals observed in the cross-section was calculated as D. A (nm) Regarding sample B, which is obtained by leaving sample A at 50°C for 72 hours, a transmission electron microscope was used. Then, the sample B was observed in cross-section, and the number average value of the long axis lengths of the crystals of the crystalline polyester resin observed in the cross-section was defined as D B (nm), and this D A and this D B relate to the toner and satisfy the following formulas (1) and (2). 10 nm ≤ D A ≤ 100 nm ···(1) 1 nm ≤ D B - D A ≤ 20 nm ···(2)

[0013] The present inventors have intensively studied a toner that exhibits excellent low-temperature fixing properties and charge retention properties, suppresses paper discharge adhesion immediately after fixing, and is less likely to have reduced bending resistance even during long-term storage. As a result, the present inventors have found that the above problems can be solved by the toner. First, it is important to maintain a microcrystalline state with little change in the crystal domains when the toner is melted and then rapidly cooled and after annealing. Regarding the mechanism by which the effects of the present disclosure are exhibited, the present inventors consider it as follows.

[0014] The step of melting the toner at 150°C and then rapidly cooling it to 25°C at 100°C / min to obtain sample A mimics the cooling rate after melting of the toner during fixing, and by giving the same change to the toner, the state of the fixed matter immediately after fixing can be observed. Therefore, it is considered that a toner in which the crystalline polyester resin crystallizes and satisfies formula (1) becomes hard even immediately after fixing, and the paper discharge adhesion property becomes good.

[0015] Furthermore, the step of leaving sample A at 50°C for 72 hours to obtain sample B is a test that accelerates the evaluation of the fixed material after a long period of time, during which it reaches a sufficiently transient state. Therefore, satisfying equation (2) indicates that the change in the size of the crystal domains after being left at 50°C for 72 hours is very small, that is, that the change in the size of the crystal domains is very small in the fixed material after a long period of time.

[0016] Therefore, satisfying equations (1) and (2) means that the crystalline domains remain largely unchanged even after a long period of time and are in a microcrystalline state. When the fixed material is bent immediately after fixing and after a long period of time, the small size of the crystalline domains makes it less likely for cracks to initiate, thus improving bending resistance. Thus, it is believed that the material crystallizes immediately after rapid cooling, forming microcrystals with small crystalline domains, and that the crystalline domains hardly enlarge even after a long period of time, making it possible to achieve both paper adhesion resistance and bending resistance.

[0017] Furthermore, in the toner, the amorphous polyester resin and crystalline polyester resin each contain a modified amorphous polyester resin and a modified crystalline polyester resin, respectively, in which a linear aliphatic monocarboxylic acid or linear aliphatic monoalcohol of a specific chain length is condensed at the ends. In other words, the ends of the amorphous polyester resin and the crystalline polyester resin are modified with a linear alkyl compound of a specific length. It is thought that the alkyl chains at the ends of the modified amorphous polyester resin and the alkyl chains at the ends of the modified crystalline polyester resin interact with each other, making the crystalline domain smaller. Therefore, it is believed that crystallization occurs in a microcrystalline state that satisfies equation (2) when sufficiently transient, further improving the paper adhesion resistance and bending resistance.

[0018] The number of carbon atoms in the terminal alkyl chains of the modified amorphous polyester resin and the modified crystalline polyester resin are close within the above range, which strengthens their interaction and is thought to produce a eutectic-like effect.

[0019] The preferred embodiment of the toner will be described in detail below. The toner particles contain amorphous polyester resin and crystalline polyester resin. The toner particles contain amorphous polyester resin and crystalline polyester resin as a binder resin, for example. From the viewpoint of low-temperature fixation, the binder resin is preferably mainly composed of polyester resin. Main component means that its content is 50% by mass or more. The content ratio of polyester resin, including amorphous polyester resin and crystalline polyester resin, in the binder resin is, for example, 50 to 100% by mass, preferably 80 to 100% by mass, and more preferably 90 to 100% by mass. In addition, the toner particles may contain resins other than amorphous polyester resin and crystalline polyester resin to an extent that does not impair the effects of this disclosure.

[0020] (Amorphous polyester resin) The amorphous polyester resin contains a modified amorphous polyester resin in which at least one linear alkyl compound selected from the group consisting of linear aliphatic monocarboxylic acids having 16 to 24 carbon atoms and linear aliphatic monoalcohols having 16 to 24 carbon atoms is condensed at the terminal. That is, the modified amorphous polyester resin contains a polyester chain having monomer units corresponding to the linear alkyl compound at its terminal. The modified amorphous polyester resin preferably has a main chain of a condensed polymer of an alcohol mainly composed of an aromatic diol and a carboxylic acid.

[0021] An alcohol primarily composed of aromatic diols means that, excluding the monoalcohols that condense and become the molecular chain ends as described later, the aromatic diol content in the total alcohols constituting the modified amorphous polyester resin is 50% by mass or more.

[0022] The aromatic diol used in the modified amorphous polyester resin is not particularly limited, but examples include bisphenol derivatives represented by the following formula (A) and diols represented by the following formula (B). The aromatic diol is preferably a bisphenol derivative represented by formula (A). [ka]

[0023] In the formula, R represents an ethylene group or a propylene group, x and y are integers greater than or equal to 1, and the average value of x + y is between 2 and 7.

[0024] [ka]

[0025] Examples of bisphenol derivatives represented by the above formula (A) are as follows: 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, etc.

[0026] Furthermore, the following are examples of alcohols other than the bisphenol derivatives represented by formula (A) or the diols represented by formula (B) above. 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-hexanetetrol, 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, etc.

[0027] These alcohols can be used individually or in combination of two or more. As described above, the main component of the alcohol is preferably an aromatic diol. Furthermore, in the alcohol, the content of the aromatic diol in the total alcohol constituting the modified amorphous polyester resin, excluding monoalcohols that condense to the ends of the modified amorphous polyester resin to form linear alkyl groups at the molecular chain ends, is preferably 80 to 100% by mass, and more preferably 90 to 100% by mass.

[0028] Examples of carboxylic acids used in the modified amorphous polyester resin include the following polycarboxylic acids. Divalent carboxylic acids 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, and malonic acid. Of these, at least one divalent carboxylic acid selected from the group consisting of maleic acid, fumaric acid, and terephthalic acid is preferred.

[0029] Examples of carboxylic acids with a valency of 3 or higher include: 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalentricarboxylic acid, 1,2,4-naphthalentricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empoletrimeric acid, and their acid anhydrides or lower alkyl esters. Of these, 1,2,4-benzenetricarboxylic acid (i.e., trimellitic acid) or its derivatives are preferred because they are inexpensive and easy to control the reaction.

[0030] These divalent carboxylic acids and trivalent or higher carboxylic acids can be used individually or in combination of two or more. The main component of the carboxylic acid constituting the modified amorphous polyester resin is preferably a dicarboxylic acid. Here, the main component means that the content of dicarboxylic acid in the total carboxylic acid constituting the modified amorphous polyester resin is 50% by mass or more. In the carboxylic acid, the content of dicarboxylic acid in the total carboxylic acid constituting the modified amorphous polyester resin, excluding monocarboxylic acid which condenses to the ends of the modified amorphous polyester resin to form linear alkyl groups at the end of the molecular chain, is preferably 80 to 100% by mass, and more preferably 90 to 100% by mass.

[0031] The amorphous polyester resin preferably includes a modified amorphous polyester resin in which at least one linear alkyl compound selected from the group consisting of linear alkyl monocarboxylic acids having 16 to 24 carbon atoms and linear alkyl monoalcohols having 16 to 24 carbon atoms is condensed at the terminal.

[0032] The modified amorphous polyester resin may have molecular chain ends formed by the condensation of linear alkyl compounds of multiple chain lengths, and may also contain molecular chain ends formed by the condensation of linear alkyl compounds outside the above range, to the extent that it does not impair the effects of the present disclosure. Preferably, 90% by mass or more of the terminally modified linear alkyl compounds are in the range of 16 to 24 carbon atoms, and more preferably, 100% by mass are in the range of 16 to 24 carbon atoms.

[0033] If a carboxyl group is present at the molecular chain end of the amorphous polyester resin before the linear alkyl compound condenses, a condensation reaction with a linear aliphatic monoalcohol occurs. On the other hand, if a hydroxyl group is present at the molecular chain end of the amorphous polyester resin before the linear alkyl compound condenses, a condensation reaction with a linear aliphatic monocarboxylic acid occurs.

[0034] Therefore, when a linear alkyl compound is condensed at the end of a molecular chain, the end of the chain is formed by the removal of a hydrogen atom from the hydroxyl group of a linear aliphatic monoalcohol, or by the removal of the -OH group from the carboxyl group of a linear aliphatic monocarboxylic acid. In this case, the linear alkyl group refers to the alkyl group included in the group formed by the removal of a hydrogen atom from the hydroxyl group of a linear aliphatic monoalcohol, or the group formed by the removal of the -OH group from the carboxyl group of the linear aliphatic monocarboxylic acid. Furthermore, if the modified amorphous polyester resin has branched chains, the molecular chain ends also include the ends of those branched chains.

[0035] Examples of linear aliphatic monocarboxylic acids having 16 to 24 carbon atoms include: palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), nonadesylic acid, arachidic acid (eicosanoic acid), henicosylic acid, behenic acid (docosanoic acid), tricosanoic acid, and tetracosanoic acid.

[0036] On the other hand, examples of linear aliphatic monoalcohols with 16 to 24 carbon atoms include: palmityl alcohol (hexadecanol), heptadecanol, stearyl alcohol (octadecanol), nonadecanol, arachidyl alcohol (icosanol), heneicosanol, behenyl alcohol, lignoceryl alcohol, tricosanol, and tetracosanol.

[0037] If the number of carbon atoms is less than 16, the interaction between linear alkyl groups is insufficient, preventing the modified crystalline polyester resin from being constrained by the modified amorphous polyester resin. This results in larger crystalline domains in the crystalline polyester resin, leading to reduced low-temperature fixation properties for the toner and decreased bending resistance after long-term storage of the fixed material. Furthermore, if the number of carbon atoms is too short, crystallization becomes difficult, and the nucleating effect is lost. This slows down crystallization, reducing the toner's charge retention and the paper adhesion resistance of the fixed material.

[0038] On the other hand, if the number of carbon atoms is longer than 24, the mobility of the linear alkyl group becomes too high, preventing the modified amorphous polyester resin from constraining the linear alkyl group of the modified crystalline polyester resin, resulting in larger crystalline domains. Consequently, the low-temperature fixability of the toner decreases, and the bending resistance of the fixed material after long-term storage decreases. The number of carbon atoms in the linear alkyl compound condensed at the ends of the modified amorphous polyester resin is preferably 18 to 22, and more preferably 18 to 20.

[0039] The end-modified amorphous polyester resin may have crystallinity derived from the terminal linear alkyl group. A modified amorphous polyester resin is defined as one in which the degree of crystallinity is 10% or less when left at 30°C and 80% RH for one week.

[0040] Crystallinity was measured using an X-ray diffractometer MiniFlex600 (manufactured by Rigaku Corporation). The powdered sample was placed on an anti-reflective sample plate and measured under the following conditions. X-ray source: CuKα ray Output: 40kV, 15mA Slit dimensions: DS=0.625°, SS=8mm, RS=13mm Detector: D / teX Ultra Scanning method: 2θ-θ continuous scan Measurement range (2θ): 5~60° Step width (2θ): 0.02° From the measurement results, background noise was subtracted, peak separation was performed, and the percentage obtained by dividing the sum of the integrated intensities originating from the crystal by the sum of the integrated intensities of all peaks was defined as the degree of crystallinity.

[0041] The modified amorphous polyester resin can be produced according to conventional polyester synthesis methods. For example, the carboxylic acid monomer and the alcohol monomer are subjected to an esterification or transesterification reaction. Subsequently, the desired polyester resin can be obtained by carrying out a condensation polymerization reaction under reduced pressure or by introducing nitrogen gas according to a conventional method.

[0042] However, if the linear aliphatic monocarboxylic acid or linear aliphatic monoalcohol that forms the molecular chain end is present simultaneously during the reaction between the carboxylic acid monomer and the alcohol monomer, the linear alkyl compound will form the molecular chain end. Therefore, it may act like an end cap, potentially causing the molecular chain to become extremely short. For this reason, it is preferable to add the linear alkyl compound to the reaction system after the reaction between the carboxylic acid monomer and the alcohol monomer has proceeded.

[0043] The above esterification or transesterification reactions can be carried out using conventional esterification or transesterification catalysts such as sulfuric acid, titanium butoxide, dibutyltin oxide, tin 2-ethylhexanoate, manganese acetate, or magnesium acetate, as needed.

[0044] Furthermore, the above condensation polymerization reaction can be carried out using conventional polymerization catalysts, such as known catalysts like titanium butoxide, dibutyltin oxide, tin 2-ethylhexanoate, tin acetate, zinc acetate, tin disulfide, antimony trioxide, and germanium dioxide. The polymerization temperature and catalyst amount are not particularly limited and can be determined as appropriate.

[0045] The percentage of the molecular chain ends of the modified amorphous polyester resin to which linear alkyl compounds are condensed (modification rate) 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%. When the modification rate of the molecular chain ends of the modified amorphous polyester resin is 1 mol% or more, it can interact more sufficiently with the terminal alkyl of the modified crystalline polyester resin. On the other hand, when 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 polyester interacting with the modified amorphous polyester is appropriately maintained, making it easier to make the crystalline domains smaller.

[0046] The above modification rate indicates the proportion of the ends (carboxyl groups and hydroxyl groups) of the polyester resin to which a linear alkyl compound is condensed. The above modification rate indicates that the polyester molecular chains contained in the modified amorphous polyester resin include polyester molecular chains to which a linear alkyl compound is condensed at the molecular chain ends in the proportion described above. In other words, modified amorphous The polyester resin may be a mixture of polyester molecular chains in which linear alkyl compounds are condensed at the molecular chain ends and polyester molecular chains in which linear alkyl compounds are not condensed at the molecular chain ends.

[0047] The glass transition temperature (Tg) of the modified amorphous polyester resin, as measured by a differential scanning calorimetry analyzer, is preferably 40.0°C to 60.0°C, and more preferably 45.0°C to 52.0°C. When Tg is within the above range, it is easier to achieve both low-temperature fixation and blocking resistance.

[0048] The number-average molecular weight Mn of the modified amorphous polyester resin is preferably 1500 to 10000 or 2000 to 4000. The weight-average molecular weight Mw of the modified amorphous polyester resin is preferably 2000 to 20000, 3000 to 10000 or 3000 to 8000.

[0049] The amorphous polyester resin may further contain amorphous polyester resin B, which is different from the modified amorphous polyester resin. Amorphous polyester resin B can be a condensation polymer of an alcohol other than the monoalcohol and monocarboxylic acid in the modified amorphous polyester resin described above, and a carboxylic acid.

[0050] The alcohol preferably contains an aromatic diol. The aromatic diol content in the total alcohol constituting amorphous polyester resin B is preferably 80 to 100% by mass, and more preferably 90 to 100% by mass. 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.

[0051] The glass transition temperature (Tg) of amorphous polyester resin B, as measured by a differential scanning calorimetry analyzer, is preferably 50.0°C to 70.0°C, and more preferably 50.0°C to 65.0°C. The number-average molecular weight Mn of amorphous polyester resin B is preferably 2000 to 10000 or 2500 to 6000. The weight-average molecular weight Mw of amorphous polyester resin B is preferably 2000 to 20000 or 5000 to 15000.

[0052] Examples of the content of modified amorphous polyester resin in amorphous polyester resin include 50-95% by mass and 60-80% by mass. Examples of amorphous polyester resin content include 5-50% by mass and 20-40% by mass.

[0053] Examples of the content of modified amorphous polyester resin, based on the mass of toner particles, include 20.0-80.0% by mass, 30.0-70.0% by mass, and 40.0-60.0% by mass. Examples of amorphous polyester resin B content, based on the mass of toner particles, include 5.0-40.0% by mass, 10.0-30.0% by mass, and 15.0-25.0% by mass.

[0054] (Crystalline polyester) The toner particles contain a crystalline polyester resin. The crystalline polyester resin contains a modified crystalline polyester resin in which at least one linear alkyl compound selected from the group consisting of linear aliphatic monocarboxylic acids having 16 to 24 carbon atoms and linear aliphatic monoalcohols having 16 to 24 carbon atoms is condensed at the end. That is, the modified crystalline polyester resin contains linear a The material contains a polyester chain having monomer units corresponding to the kill compound at its terminals. The crystalline polyester resin is, for example, a resin whose main skeleton is crystalline and which preferably has a weight-average molecular weight of 5000 or more.

[0055] Monomers used in modified crystalline polyester resins include polyhydric alcohols (dihydric or trihydric or higher alcohols), polyhydric carboxylic acids (dihydric or trihydric or higher carboxylic acids), their acid anhydrides, or their lower alkyl esters. In modified crystalline polyester resins, the structure other than the condensed terminals of the linear alkyl compound is preferably a condensed polymer of aliphatic dicarboxylic acid and aliphatic diol.

[0056] The following polyhydric alcohol monomers can be used in modified crystalline polyester resins. The polyhydric alcohol monomers are not particularly limited, but they are preferably linear (more preferably straight-chain) aliphatic diols. Examples 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. Among these, linear aliphatic and α,ω-diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol are particularly preferred examples.

[0057] Other polyhydric alcohol monomers besides those listed above can also be used. Examples of dihydric alcohol monomers among these polyhydric alcohol monomers include aromatic alcohols such as polyoxyethylene-bisphenol A and polyoxypropylene-bisphenol A; and 1,4-cyclohexanedimethanol. Examples of trihydric or higher polyhydric alcohol monomers among these polyhydric alcohol monomers include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; and aliphatic alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.

[0058] The following polycarboxylic acid monomers can be used in modified crystalline polyester resins. While the polycarboxylic acid monomer is not particularly limited, it is preferably a linear (more preferably linear) aliphatic dicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superiric acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, and also include hydrolyzed acid anhydrides or lower alkyl esters of these acids.

[0059] Other polycarboxylic acids besides the polycarboxylic acid monomers mentioned above can also be used. Among the other polycarboxylic acid monomers, divalent carboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecylsuccinic acid and n-dodecenylsuccinic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. These also include their acid anhydrides or lower alkyl esters.

[0060] Furthermore, among other carboxylic acid monomers, the polycarboxylic acids with a valency of 3 or higher are 1,2 Examples include aromatic carboxylic acids such as 4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalentricarboxylic acid, 1,2,4-naphthalentricarboxylic acid, and pyromellitic acid, as well as aliphatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, and 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane. Derivatives such as acid anhydrides or lower alkyl esters of these compounds are also included.

[0061] The aliphatic dicarboxylic acid is preferably a linear aliphatic dicarboxylic acid having 2 to 16 carbon atoms (preferably 8 to 14). The aliphatic diol is preferably a linear aliphatic diol having 2 to 16 carbon atoms (preferably 2 to 6). The content of monomer units polymerized from linear aliphatic dicarboxylic acids having 2 to 16 carbon atoms (preferably 8 to 14) in the modified crystalline polyester resin is preferably 8% to 45% by mass, and more preferably 20% to 35% by mass. The content of monomer units polymerized from linear aliphatic diols having 2 to 16 carbon atoms (preferably 2 to 6) in the modified crystalline polyester resin is preferably 15% to 50% by mass, and more preferably 25% to 45% by mass.

[0062] The crystalline polyester resin contains a modified crystalline polyester resin in which at least one linear alkyl compound selected from the group consisting of linear aliphatic monocarboxylic acids having 16 to 24 carbon atoms and linear aliphatic monoalcohols having 16 to 24 carbon atoms is condensed at the end. Preferably, the crystalline polyester resin contains a modified crystalline polyester resin having molecular chain ends condensed with one or more linear alkyl compounds selected from the group consisting of linear alkyl monocarboxylic acids having 16 to 24 carbon atoms and linear alkyl monoalcohols having 16 to 24 carbon atoms.

[0063] The modified crystalline polyester resin may have molecular chain ends formed by the condensation of linear alkyl compounds of multiple chain lengths, and may also contain molecular chain ends formed by the condensation of linear alkyl compounds outside the above range, to the extent that it does not impair the effects of the present disclosure. Preferably, 90% by mass or more of the terminally modified linear alkyl compounds are in the range of 16 to 24 carbon atoms, and more preferably, 100% by mass are in the range of 16 to 24 carbon atoms.

[0064] Examples of linear aliphatic monocarboxylic acids having 16 to 24 carbon atoms include: palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), nonadesylic acid, arachidic acid (eicosanoic acid), henicosylic acid, behenic acid (docosanoic acid), tricosanoic acid, and tetracosanoic acid.

[0065] On the other hand, examples of linear aliphatic monoalcohols with 16 to 24 carbon atoms include: palmityl alcohol (hexadecanol), heptadecanol, stearyl alcohol (octadecanol), nonadecanol, arachidyl alcohol (icosanol), heneicosanol, behenyl alcohol, lignoceryl alcohol, tricosanol, and tetracosanol.

[0066] If the number of carbon atoms is less than 16, the interaction between linear alkyl groups is insufficient, and the modified crystalline polyester resin is not constrained by the terminal alkyl groups of the modified amorphous polyester resin, resulting in larger crystalline domains in the crystalline polyester resin. Consequently, the low-temperature fixing performance of the toner decreases, and the bending resistance of the fixed material after long-term storage decreases. Furthermore, if the number of carbon atoms is too short, crystallization becomes difficult, and the nucleating effect is lost, resulting in delayed crystallization and decreased toner charge retention and paper discharge adhesion resistance of the fixed material.

[0067] On the other hand, if the number of carbon atoms is longer than 24, the mobility of the linear alkyl group becomes too high, and the linear alkyl group of the modified amorphous polyester resin cannot restrain the modified crystalline polyester resin, causing the crystalline domain to become larger. As a result, the low-temperature fixing performance of the toner decreases, and the fixed product The bending resistance decreases after long-term storage.

[0068] Modified crystalline polyester resins can be produced according to conventional polyester synthesis methods. For example, a crystalline polyester resin can be obtained by esterifying or transesterifying the aforementioned dicarboxylic acid and diol, followed by a polycondensation reaction under reduced pressure or by introducing nitrogen gas, according to conventional methods. Subsequently, the desired modified crystalline polyester resin can be obtained by further adding the above-mentioned linear alkyl compound and carrying out an esterification reaction.

[0069] The above esterification or transesterification reactions can be carried out using conventional esterification or transesterification catalysts such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, or magnesium acetate, as needed.

[0070] Furthermore, the above polycondensation reaction can be carried out using conventional polymerization catalysts, such as known catalysts like titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, and germanium dioxide. The polymerization temperature and catalyst amount are not particularly limited and can be determined as appropriate.

[0071] In esterification, transesterification, or polycondensation reactions, methods such as charging all monomers at once to increase the strength of the resulting modified crystalline polyester resin, or first reacting divalent monomers and then adding trivalent or higher monomers to reduce the amount of low molecular weight components, may be used.

[0072] In the synthesis of crystalline polyester resins, including modified crystalline polyester resins, it is preferable to condense and polymerize at least one selected from the group consisting of linear aliphatic monocarboxylic acids and linear aliphatic monoalcohols (preferably the linear aliphatic monocarboxylic acids), as well as aliphatic diols and aliphatic dicarboxylic acids.

[0073] In the modified crystalline polyester resin, the proportion of monomer units polymerized from aliphatic diols is preferably 30 to 50 mol%, more preferably 35 to 45 mol%. In the modified crystalline polyester resin, the proportion of monomer units polymerized from aliphatic dicarboxylic acids is preferably 5 to 45 mol%, more preferably 10 to 35 mol%. Furthermore, the proportion of at least one selected from the group consisting of the above-mentioned linear aliphatic monocarboxylic acids and linear aliphatic monoalcohols (preferably the above-mentioned linear aliphatic monocarboxylic acids) is preferably 15 to 60 mol%, more preferably 20 to 30 mol%.

[0074] The total content of monomer units consisting of linear alkyl compounds at the molecular chain ends of the modified crystalline polyester resin is preferably 1.0 to 30.0% by mass, more preferably 2.0 to 25.0% by mass, and even more preferably 4.0 to 12.0% by mass.

[0075] In the modified crystalline polyester resin, the proportion of monomer units polymerized with aliphatic diols is preferably 10 to 40% by mass, more preferably 15 to 25% by mass. In the modified crystalline polyester resin, the proportion of monomer units polymerized with aliphatic dicarboxylic acids is preferably 40 to 85% by mass, more preferably 60 to 80% by mass. Examples of the content of modified crystalline polyester resin in crystalline polyester resin include 50-100% by mass, 80-100% by mass, and 90-100% by mass. The crystalline polyester resin may also be a modified crystalline polyester resin.

[0076] The percentage of crystalline polyester resin (e.g., modified crystalline polyester resin) based on the mass of toner particles W C It is preferably 3.0 to 25.0% by mass, and 5.0 to 2 It is more preferable that the amount is 0.0% by mass, and even more preferable that it is 5.0 to 18.0% by mass. The above range is preferable from the viewpoint of achieving a higher level of compatibility between low-temperature fixability, static charge retention, paper discharge adhesion resistance, and bending resistance. The melting point of the modified crystalline polyester is preferably 60 to 105°C, more preferably 65 to 100°C, and even more preferably 70 to 95°C.

[0077] 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 Mw is 10,000 or higher, compatibility with the modified amorphous polyester resin decreases, and crystallization becomes faster, which tends to improve charge retention and paper discharge adhesion resistance. When Mw is 30,000 or lower, the modified crystalline polyester resin is more easily constrained by the terminal alkyl of the modified amorphous polyester resin, the crystalline domains become smaller, and low-temperature fixation and bending resistance tend to improve. The number-average molecular weight of the modified crystalline polyester resin is preferably 1000 to 10000 or 2000 to 7000.

[0078] The proportion of the molecular chain ends of the modified crystalline polyester resin to which linear alkyl compounds are condensed (modification rate) 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%. Within this range, the interaction between the terminal alkyls of the modified crystalline polyester resin and the modified amorphous polyester resin is strengthened, the modified crystalline polyester resin becomes more constrained, the crystalline domains become smaller, and the low-temperature fixation and bending resistance tend to improve.

[0079] The above modification rate indicates the proportion of the ends (carboxyl groups and hydroxyl groups) of the polyester resin to which a linear alkyl compound is condensed. The above modification rate indicates that the polyester molecular chains contained in the modified crystalline polyester resin include polyester molecular chains to which a linear alkyl compound is condensed at the molecular chain ends in the proportion of the above modification rate. In other words, the modified crystalline polyester resin may be a mixture of polyester molecular chains to which a linear alkyl compound is condensed at the molecular chain ends and polyester molecular chains to which a linear alkyl compound is not condensed at the molecular chain ends.

[0080] The toner is melted at 150°C, and then cooled to 25°C at 100°C / min to obtain sample A. Sample A is observed in cross-section using a transmission electron microscope (TEM), and the average number of crystals of the crystalline polyester resin observed in the cross-section is defined as D. A Let's call it (nm). Furthermore, sample A is left at 50°C for 72 hours to obtain sample B. Sample B is observed in cross-section using a transmission electron microscope (TEM), and the average number of major axis lengths of the crystals of the crystalline polyester resin observed in the cross-section is D. B Let's call it (nm). At this time, D A and D B It is necessary that the following equations (1) and (2) are satisfied. 10nm≦D A ≤100nm ···(1) 1nm ≤ D B -D A ≤20nm ···(2)

[0081] As described above, the process of melting the toner and then cooling it to 25°C at 100°C / min to obtain sample A simulates the temperature change of the fixed material during fixing. At this time, the crystalline polyester resin crystallizes and satisfies equation (1), resulting in good resistance to paper adhesion. Furthermore, it is necessary for equation (2) to be satisfied after being left at 50°C for 72 hours. Satisfying equation (2) means that crystal growth is suppressed to between 1 nm and 20 nm, resulting in good bending resistance.

[0082] D A It is preferable that the wavelength is between 10 nm and 50 nm. B While satisfying the above formula (2), it is preferable that the wavelength is, for example, 15 nm or more and 100 nm or less, and 20 nm or more and 70 nm or less. That is, D A and D B However, it is preferable that the following equations (3) and (4) are satisfied. stomach. 10nm≦D A ≤50nm ···(3) 20nm≦D B ≤70nm ···(4) Also, DB -D A Preferably, the wavelength is 1 to 12 nm or 3 to 12 nm.

[0083] D A Means for achieving the above range include using a modified crystalline polyester resin and a modified amorphous polyester resin in which a linear alkyl compound is condensed at the terminal. A To reduce the amount, it is best to increase the modification rate of either the modified crystalline polyester resin or the modified amorphous polyester resin, or both. Also, D A To increase the yield, it is advisable to lower the modification rate of either the modified crystalline polyester resin or the modified amorphous polyester resin, or both.

[0084] D B -D A Means for bringing the range to the above range include using a modified crystalline polyester resin and a modified amorphous polyester resin in which a linear alkyl compound is condensed at the terminal, and reducing the weight-average molecular weight Mw of the modified amorphous polyester resin (for example, to less than 10,000). B -D A To reduce this, it is advisable to bring the alkyl chain lengths of the linear alkyl compounds condensed at the ends of the modified crystalline polyester resin and the modified amorphous polyester resin closer together. Also, D B -D A To increase the size, it is best to increase the length of the alkyl chain.

[0085] Also, D B To reduce this, it is advisable to increase the modification rate of the modified amorphous polyester resin. B To increase the value, it is best to lower the modification rate of the modified amorphous polyester resin.

[0086] From the viewpoint of low-temperature fixation, when sample B is observed in cross-section, the average aspect ratio of the crystalline polyester resin crystals observed in the cross-section is preferably 2.0 to 8.0, and more preferably 2.5 to 5.0. Furthermore, to reduce the average aspect ratio, it is advisable to increase the modification rate of the modified amorphous polyester resin. To increase the average aspect ratio, it is advisable to decrease the modification rate of the modified amorphous polyester resin.

[0087] The SP value of the modified amorphous polyester resin is determined by SP A (cal / cm 3 ) 0.5 The SP value of the modified crystalline polyester resin is then set to SP C (cal / cm 3 ) 0.5 Let's assume that SP A -SP C For example, it is 0.7 to 1.3. A I understand SP C It is preferable that the following formula (5) is satisfied, in terms of compatibility and ease of crystallization. SP A -SP C A range of 0.9 to 1.1 is more preferable. 0.8≦SP A -SP C ≤1.2 ···(5)

[0088] The percentage of crystalline polyester resin (e.g., modified crystalline polyester resin) based on the mass of the toner particles is W. C (Assuming mass%). Furthermore, in cross-sectional observation of sample A by transmission electron microscope (TEM), the average area ratio of the crystalline polyester resin crystals in the observed area is S. A (Assuming area percentage) A / W C For example, this is 0.05 to 0.5. C and S A It is preferable that the following equation (6) is satisfied. 0.1≦S A / W C ≤0.4 ···(6)

[0089] Furthermore, the content ratio of crystalline polyester resin (e.g., modified crystalline polyester resin) based on the mass of the toner particles is defined as W C(Assuming mass%). In cross-sectional observation of sample B by transmission electron microscope (TEM), the average area ratio of the crystals of the crystalline polyester resin in the area of ​​the observation range is S. B (Assuming area percentage) B / W C For example, W is between 0.2 and 1.0. C and S B It is preferable that the following equation (7) is satisfied. 0.3 ≤ S B / W C ≤0.8 ···(7)

[0090] The above S A / W C A value of 0.1 or higher results in better paper adhesion resistance during paper ejection. S B / W C A value of 0.8 or less results in better bending resistance. S A To reduce this, it is best to lower the modification rate of the modified crystalline polyester resin. A To increase this, it is advisable to increase the modification rate of the modified crystalline polyester resin. Also, S B To reduce this, it is advisable to either increase the modification rate of the modified amorphous polyester resin or decrease the modification rate of the modified crystalline polyester resin. B To increase this, it is advisable to either lower the modification rate of the modified amorphous polyester resin or increase the modification rate of the modified crystalline polyester resin.

[0091] It is preferable that the number of carbon atoms in the linear alkyl compound condensed at the end of the modified crystalline polyester resin is greater than the number of carbon atoms in the linear alkyl compound condensed at the end of the modified amorphous polyester resin. A shorter number of carbon atoms in the linear alkyl compound modifying the ends of the amorphous polyester allows the amorphous polyester resin to interact rapidly with the crystalline polyester resin during compatibility. As a result, crystallization is further accelerated, and the static charge retention and paper discharge adhesion resistance are improved.

[0092] The difference between the number of carbon atoms in the linear alkyl compound condensed at the end of the modified amorphous polyester resin and the number of carbon atoms in the linear alkyl compound condensed at the end of the modified crystalline polyester resin is preferably 1 to 6 or 2 to 4.

[0093] Preferred combinations of modified amorphous polyester resin and modified crystalline polyester resin include the following: It is particularly preferable that the linear alkyl compound condensed at the end of the modified amorphous polyester resin is stearic acid, and that the linear alkyl compound condensed at the end of the modified crystalline polyester resin is behenic acid. With this combination, the crystalline polyester resin and the amorphous polyester resin interact at a higher level, allowing the crystalline polyester resin to crystallize more rapidly in a finer dispersion state.

[0094] Furthermore, it is preferable that the modified crystalline polyester resin has monomer units corresponding to ethylene glycol and monomer units corresponding to dodecanedioic acid. More preferably, the structure of the modified crystalline polyester resin other than the terminals is a condensed polymer of ethylene glycol and dodecanedioic acid.

[0095] Because the modified crystalline polyester resin has monomer units corresponding to ethylene glycol, linear alkyl compounds are modified at the ends of regions with high ester group concentrations. The high ester group concentration makes the crystalline polyester resin more likely to resemble the amorphous polyester resin, thus increasing the interaction between the terminal alkyl groups of the modified crystalline polyester resin and the modified amorphous polyester resin. Furthermore, the modified crystalline polyester resin, by having monomer units corresponding to dodecanediic acid, allows for faster crystallization and a suitable melting point.

[0096] (Release agent) 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, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; waxes mainly composed of fatty acid esters such as carnauba wax; and deoxidized fatty acid esters such as deoxidized carnauba wax, which have been partially or completely deoxidized.

[0097] Furthermore, the following can be mentioned: palmitic acid, stearic acid, montanic acid, etc. Saturated linear fatty acids; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinalic 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 with 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; methylenebisstearate amide, ethylenebiscaprate amide, ethylenebislaurate amide, and hexamethylenebisstearate amide Saturated fatty acid bisamides such as; unsaturated fatty acid amides such as ethylenebisoleamide, hexamethylenebisoleamide, N,N'dioleyladipamide, and N,N'dioleylsebacamide; aromatic bisamides such as m-xylenebisstearamide and N,N'distearylisophthalamide; fatty acid metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes with vinyl monomers such as styrene or acrylic acid; partially esterified fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils.

[0098] Among these release agents, hydrocarbon-based waxes such as paraffin wax and Fischer-Tropsch wax are preferred from the viewpoint of low-temperature fixation. The release agent content is preferably 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the binder resin. Here, the binder resin refers to, for example, the sum of the crystalline polyester resin and the amorphous polyester resin.

[0099] (Dispersant) If the toner particles contain a release agent, it is preferable that the toner particles also contain a dispersant in order to disperse the wax in the resin. While known dispersants can be used, if the wax contains a hydrocarbon-based wax, it is preferable that the dispersant contains a polymer having a structure in which a vinyl-based resin component and a hydrocarbon compound have reacted, in order to disperse the wax in the resin. Among these, a graft polymer in which vinyl monomers are graft-polymerized onto a polyolefin is preferred.

[0100] When this polymer is included, the compatibility between the wax and the resin is promoted, making it less likely to cause problems such as poor static charge and contamination of components due to poor wax dispersion. Furthermore, the dispersant content is preferably 1.0 part by mass or more and 15 parts by mass or less per 100 parts by mass of the binder resin. When the content is within this range, the dispersion state of the wax in the amorphous resin tends to become uniform. 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-based and polypropylene-based polyolefins are particularly preferred. Multiple types of these may be used.

[0101] Examples of monomers having vinyl groups include the following: Styrene-based units 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, pn-dodecylstyrene, and styrene derivatives thereof. Amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; acrylonitrile, methacrylo A vinyl-based unit containing an N atom, such as nitriles, acrylamide, or acrylic or methacrylic acid derivatives. 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 acid anhydride, itaconic acid anhydride, and alkenyl succinic acid anhydride; methyl maleate half ester, ethyl maleate half ester, butyl maleate half ester, methyl citraconic acid half ester, ethyl citraconic acid half ester, butyl citraconic acid half ester, methyl itaconic acid half ester, methyl alkenyl succinate half ester, f Half-esters of unsaturated dibasic acids such as methyl malate half-ester and methyl mesaconate half-ester; 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 acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, anhydrides of the α,β-unsaturated acid and lower fatty acids; vinyl units containing carboxyl groups such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, their acid anhydrides, and their monoesters. Acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate, and vinyl units containing a hydroxyl group such as 4-(1-hydroxy-1-methylbutyl)styrene and 4-(1-hydroxy-1-methylhexyl)styrene. Ester units consisting of 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 consisting of methacrylic acid esters 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, which are α-methylene aliphatic monocarboxylic acid esters. Multiple units of these may be used.

[0102] Dispersants can be obtained by known methods, such as the reactions of these polymers with each other or the reactions of monomers from one polymer with those from the other polymer.

[0103] (Coloring agent) Toner particles may contain colorants. Examples of colorants include the following: Examples of black colorants include carbon black and black colorants prepared by mixing yellow, magenta, and cyan colorants. While pigments may be used alone as colorants, using dyes and pigments in combination is preferable from the standpoint of full-color image quality to improve clarity.

[0104] The following are examples of pigments used for magenta toner: CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0105] Examples of dyes for magenta toner include: oil-soluble dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, 27; CI Disperse Violet 1; and basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

[0106] Examples of pigments for cyan toner include: CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; CI Bat Blue 6; CI Acid Blue 45; and copper phthalocyanine pigments in which one to five phthalimidomethyl groups are substituted onto the phthalocyanine skeleton. CI Solvent Blue 70 is a dye used for cyan toner.

[0107] The following pigments are used for yellow toner: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Bat Yellow 1, 3, 20. CI Solvent Yellow 162 is a dye used for yellow toner.

[0108] The coloring agent content is preferably 0.1 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the binder resin.

[0109] (Charge control agent) The toner may contain a charge control agent as needed. While known charge control agents can be used in the toner, aromatic carboxylic acid metal compounds that are colorless, have a fast charging speed for the toner, and can stably maintain a constant charge are particularly preferred.

[0110] Examples of negative charge control agents include salicylate metal compounds, naphthoate metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid as a side chain, polymer compounds having sulfonate salts or sulfonic acid esters as a side chain, polymer compounds having carboxylate salts or carboxylic acid esters as a side chain, boron compounds, urea compounds, silicon compounds, and calixarenes. Examples of positive charge control agents include quaternary ammonium salts, polymer compounds having the aforementioned quaternary ammonium salts as a side chain, guanidine compounds, and imidazole compounds. The charge control agent may be added internally or externally to the toner particles. The amount of charge control agent added is preferably 0.05 parts by mass or more and 10 parts by mass or less per 100 parts by mass of binder resin.

[0111] (Inorganic fine particles) The toner may also contain inorganic fine particles as needed. The inorganic fine particles may be added internally to the toner particles or mixed with the toner particles as an external additive. As external additives, inorganic fine powders such as silica, titanium dioxide, and aluminum oxide are preferred. The inorganic fine powders are preferably hydrophobized with a hydrophobic agent such as a silane compound, silicone oil, or a mixture thereof. As an external additive for improving fluidity, it has a specific surface area of ​​50 m². 2 / g or more 400m 2 Inorganic fine powders of less than / g are preferred. For durability and stability, a specific surface area of ​​10 m² is desirable. 2 / g or more 50m 2 Inorganic fine powders of less than / g are preferred. To achieve both improved fluidity and stable durability, inorganic fine powders with a specific surface area within the above range may be used in combination. It is preferable that the external additive is used in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of toner particles. The toner particles and the external additive can be mixed using a known mixer such as a Henschel mixer.

[0112] (Developer) Toner can be used as a one-component developer, but it is preferable to mix it with a magnetic carrier and use it as a two-component developer to further improve dot reproduction and to supply stable images over a long period of time. When toner is mixed with a magnetic carrier and used as a two-component developer, the mixing ratio of the magnetic carrier in the two-component developer is preferably 2% to 15% by mass, and more preferably 4% to 13% by mass or less, as the toner concentration in the two-component developer.

[0113] (Magnetic carrier) As magnetic carriers, generally known ones can be used, such as iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, strontium, and rare earth elements, their alloy particles, and their oxide particles; magnetic materials such as ferrite and magnetite; magnetic material dispersion resin carriers (so-called resin carriers) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state; and magnetic carriers in the form of ferrite or magnetite particles having voids filled with resin.

[0114] As a magnetic carrier, the above-mentioned magnetic material may be used directly, or a magnetic material may be used in which the above-mentioned magnetic material is used as a core and its surface is coated with resin. From the viewpoint of improving the chargeability of the toner, it is preferable to use a magnetic material as a magnetic carrier in which the above-mentioned magnetic material is used as a core and its surface is coated with resin.

[0115] The resin used to coat the core is not particularly limited, and any known resin can be selected and used as long as it does not impair the toner properties. Examples include (meth)acrylic resins, silicone resins, urethane resins, polyethylene, polyethylene terephthalate, polystyrene, phenolic resins, or copolymer polymers and polymer mixtures containing these. In particular, (meth)acrylic resins or silicone resins are preferred from the viewpoint of electrostatic properties and preventing foreign matter from adhering to the carrier surface. (Meth)acrylic resins having alicyclic hydrocarbon groups such as cyclohexyl, cycloheptyl, cyclooctyl, cyclopentyl, cyclobutyl, or cyclopropyl groups are particularly preferred because they make the surface (coated film surface) of the resin coating layer covering the surface of the magnetic material smooth, and can suppress the adhesion of toner-derived components such as binders, release agents, and external additives.

[0116] (Manufacturing method) The method for producing toner particles is not particularly limited, and known methods such as grinding, suspension polymerization, dissolution-suspension, emulsification-coagulation, and dispersion polymerization can be used. The following describes an example of a toner manufacturing procedure using the grinding method.

[0117] In the raw material mixing process, predetermined amounts of materials constituting the toner particles, such as crystalline polyester resin, amorphous polyester resin, and, if necessary, other components such as mold release agents, colorants, and charge control agents, are weighed, blended, and mixed. Examples of mixing equipment include double-con mixers, V-type mixers, drum-type mixers, super mixers, Henschel mixers, Nauta mixers, and Mechanohybrid (manufactured by Nippon Coke Industries Co., Ltd.).

[0118] Next, the mixed materials are melt-kneaded to disperse wax and other substances in the binder resin. The mixing and dispensing temperature can be adjusted as appropriate depending on the binder resin and colorant used, but generally 100 to 180°C is preferred. In this melt-kneading process, a pressurized kneader, a Banbury mixer, etc. Single-screw or twin-screw extruders are the mainstream due to their advantage of being able to be used in continuous production, whether as a push-type or continuous-type mixer.

[0119] Examples include the KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), the TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), the PCM kneader (manufactured by Ikegai Iron Works Co., Ltd.), the twin-screw extruder (manufactured by KCK Co., Ltd.), the Co-kneader (manufactured by Buss Co., Ltd.), and the Nidex (manufactured by Nippon Coke Industries Co., Ltd.). Furthermore, the resin composition obtained by melt kneading may be rolled with two rolls or the like and cooled with water or the like in a cooling process.

[0120] Next, the cooled resin composition is pulverized to the desired particle size in a pulverization process. In the pulverization process, for example, it is coarsely pulverized using a pulverizer such as a crusher, hammer mill, or feather mill, and then further finely pulverized using a fine pulverizer such as a Kryptron system (manufactured by Kawasaki Heavy Industries), Super Rotor (manufactured by Nisshin Engineering Co., Ltd.), Turbo Mill (manufactured by Freund Turbo), or an air jet type pulverizer.

[0121] Subsequently, the material is classified as needed using classifiers and sieving machines such as the inertial classifier Elbow Jet (manufactured by Nippon Steel Mining Co., Ltd.), the centrifugal classifier Turboplex (manufactured by Hosokawa Micron Corporation), TSP separator (manufactured by Hosokawa Micron Corporation), and Faculty (manufactured by Hosokawa Micron Corporation) to obtain the classified product (toner particles).

[0122] Toner particles may be used as toner as is, or, if necessary, external additives may be added to the surface of the toner particles to form toner. Methods for externally adding external additives include mixing toner particles with a predetermined amount of various known external additives and stirring and mixing them using a mixing device such as a double-con mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nauta mixer, Mechanohybrid (manufactured by Nippon Coke Industries Co., Ltd.), or Novilta (manufactured by Hosokawa Micron Corporation) as an external additive machine.

[0123] Next, we will describe the methods for measuring each physical property. [Measurement of average crystal area ratio, average number of major axis lengths, and average aspect ratio of crystalline polyester resin] (Evaluation of the dispersion state of crystalline polyester resins in samples A and B using TEM) Cross-sectional observation of samples A and B using a transmission electron microscope (TEM) and evaluation of the crystal structure of the crystalline polyester resin can be performed as follows. The preparation procedures for samples A and B are as follows.

[0124] Sample A is prepared using the following procedure. Using an osmium plasma coater (filgen, OPC80T), an Os film (5 nm) and a naphthalene film (20 nm) are applied to the toner as protective films, and then embedded in photocurable resin D800 (JEOL). Then, sample A is prepared using a differential scanning calorimeter "DSC7020" (Hitachi High-Tech Corporation). The sample in an aluminum pan is introduced into the apparatus set to 25°C, the temperature is raised to 150°C at 10°C / min, and the temperature is maintained for 5 minutes to melt the toner, and then it is cooled to 25°C at 100°C / min to obtain sample A. Sample A was collected, removed from the aluminum pan, and observed in cross-section using the method described below. The average number of crystals in the crystalline polyester resin along their major axis length was measured. A , average area ratio S A Measure it.

[0125] Furthermore, sample B is prepared using sample A prepared by the method described above, and using a forced-air constant-temperature incubator "DFN600" (manufactured by Yamato Scientific Co., Ltd.). Sample A is placed in the apparatus set to 50°C, left for 72 hours, and then retrieved to obtain sample B. The obtained sample B is observed in cross-section using the method described later, and the average number of crystals in the long axis length of the crystalline polyester resin is measured D. B , average aspect ratio, average area ratio S B Measure it.

[0126] By staining the cross-section of sample A or sample B with ruthenium, the crystalline polyester resin is obtained as a clear contrast. The crystalline polyester resin is stained less strongly than the organic components that make up the inside of the toner. This is thought to be because the penetration of the dyeing material into the crystalline polyester resin is weaker than that of the organic components inside the toner due to differences in density, etc. Because the amount of ruthenium atoms differs depending on the intensity of staining, areas that are strongly stained have a large amount of these atoms, preventing electron beams from passing through and appearing black in the observed image, while areas that are weakly stained allow electron beams to pass through easily and appear white in the observed image.

[0127] Sample A or Sample B is prepared using an ultrasonic ultramicrotome (Leica, UC7) at a cutting speed of 1 mm / s to create a sample cross-section with a film thickness of 60 nm (or 70 nm). The obtained cross-sections were stained using a vacuum electron staining system (filgen, VSC4R1H) in a RuO4 gas atmosphere at 500 Pa for 15 minutes, and then observed using a TEM (JEOL, JEM2800) in STEM mode. The STEM probe size was 1 nm, and images were acquired at a size of 1024 × 1024 pixels.

[0128] For the obtained image, binarization (threshold value: 120 / 255 levels) is performed using the image processing software "Image-Pro Plus" (manufactured by Media Cybernetics). Since the crystal domains can be extracted by binarization, their sizes are measured. When observing the cross-sections of 20 randomly selected samples, the lengths of the major and minor axes of the crystal domains of the crystalline polyester resin for which the length can be measured are measured for all samples. From the measured lengths, the number average value D A , the number average value D B , and the average aspect ratio are calculated.

[0129] Also, the average area ratio (S A , S B ) of the crystals of the crystalline polyester resin in the cross-sections of Sample A and Sample B is calculated. From the 20 sample cross-sections where the major diameter of the cross-section is 3.0 μm or more among the randomly selected sample cross-sections above, the area ratio is calculated. Regarding the measurement range, a range that does not protrude beyond the embedding resin in the cross-section (within 100 nm from the interface with the embedding resin) is selected, and the total area ratio of the domains of the crystalline polyester resin within the selected range in the area of the selected observation range is calculated, and the arithmetic mean value of the 20 cross-sections is adopted.

[0130] (Separation of each material from the toner) The separation of materials from the toner can be carried out by utilizing the difference in solubility in solvents. An example is shown below. First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23°C to separate the soluble component (amorphous polyester resin) and the insoluble component (crystalline polyester resin, wax, wax dispersant, colorant, inorganic particles, etc.). Second separation: The insoluble component (crystalline polyester resin, wax, wax dispersant, colorant, inorganic particles, etc.) obtained in the first separation is dissolved in MEK at 100°C to separate the soluble component (crystalline polyester resin, wax, wax dispersant) and the insoluble component (colorant, inorganic particles). Third separation: The soluble components (crystalline polyester resin, wax, wax dispersant) obtained in the second separation are dissolved in chloroform at 23°C, and the soluble components (crystalline polyester resin) and insoluble components (wax, wax dispersant) are separated.

[0131] Based on the mass of each material, such as crystalline polyester resin, separated by the above separation method, the content of each material can be calculated. Furthermore, amorphous polyester resin can be separated into modified amorphous polyester resin and amorphous polyester resin B by known means such as GPC, depending on the molecular weight.

[0132] (Calculation of monomer unit content ratio in modified amorphous polyester resin and modified crystalline polyester resin) The content of constituent monomers in modified amorphous polyester resin and modified crystalline polyester resin is calculated using NMR and the following method. Weigh out 5 mg of the resin to be measured and dissolve it in deuterated THF or deuterated chloroform. 1 1H-NMR measurements are performed, and the composition ratio is calculated from the integrated values ​​of each peak. The specific instrument conditions are as follows.

[0133] (Measurement conditions) Measuring device JNM-ECA400FT-NMR(JEOL) Measured radionuclides: 1 H Solvent: Deuterated THF or deuterated chloroform Measurement frequency: 400MHz Pulse width: 5.0 μs Frequency range: 10500Hz Total number of times: 64 Measurement temperature: room temperature

[0134] (Measurement of the glass transition temperature (Tg) of resins) The glass transition temperature (Tg) is measured using a differential scanning calorimetry analyzer "Q2000" (TA Instruments) in accordance with ASTM D3418-82. The temperature correction for the instrument's detection unit uses the melting points of indium and zinc, and the heat of fusion of indium is used for heat quantity correction. Specifically, 3 mg of resin or toner is accurately weighed and placed in an aluminum pan. An empty aluminum pan is used as a reference, and measurements are taken at a heating rate of 10°C / min within the measurement temperature range of 30 to 200°C. During the measurement, the temperature is raised to 200°C once, then lowered to 30°C, and then raised again. During this second heating process, the specific heat change is obtained in the temperature range of 40°C to 100°C. The intersection point of the line midway between the baseline before and after the specific heat change and the differential heat curve is defined as the glass transition temperature of the resin.

[0135] (Measurement of the melting point of modified crystalline polyester resin) The melting point of modified crystalline polyester resin is measured using a differential scanning calorimetry analyzer "Q2000" (TA Instruments) in accordance with ASTM D3418-82. The temperature correction for the device's detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. Specifically, 3 mg of the sample is accurately weighed, placed in an aluminum pan, and measured under the following conditions using an empty aluminum pan as a reference: Heating rate: 10°C / min Measurement start temperature: 30℃ Measurement end temperature: 180℃ Measurements are taken within the range of 30 to 180°C at a heating rate of 10°C / min. The temperature is raised to 180°C and held for 10 minutes, then cooled to 30°C, and then heated again. During this second heating process, the temperature at which the temperature-endothermic curve reaches its maximum endothermic peak in the range of 30 to 100°C is defined as the melting point.

[0136] (SP value calculation method) For the sp values of the modified amorphous polyester resin and the modified crystalline polyester resin, they are calculated according to the calculation method proposed by Fedors. For the atoms or atomic groups in the molecular structure, the evaporation energy (Δei) (cal / mol) and the molar volume (Δvi) ( cm 3 / mol) are obtained from the table described in "Polym. Eng. Sci., 14(2), 147-154(1974)", and (ΣΔei / ΣΔvi) 0.5 is taken as the SP value (cal / cm 3 ). 0.5 That is to say.

[0137] (Measurement of the molecular weight of amorphous polyester resin such as the weight average molecular weight of the modified amorphous polyester resin by GPC) The molecular weight distribution of the THF-soluble component of the amorphous polyester resin is measured by gel permeation chromatography (GPC) as follows. First, the resin is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Maechory Disk" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of the components soluble in THF is 0.8% by mass. Using this sample solution, measurements are carried out under the following conditions. Apparatus: HLC8120GPC (Detector: RI) (manufactured by Tosoh Corporation) Column: 7-connected Shodex KF-801, 802, 803, 804, 805, 806, 807 (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 For the calculation of the molecular weight of the sample, a molecular weight calibration curve prepared using a standard polystyrene resin (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0138] (Molecular weight measurement of modified crystalline polyester resin, including weight-average molecular weight (Mw), by GPC) First, the 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 membrane filter, "Maeshori Disc" (manufactured by Tosoh Corporation), with a pore diameter of 0.2 μm to obtain the sample solution. The sample solution is adjusted so that the concentration of THF-soluble components is 0.8% by mass. This sample solution is then used for measurement under the following conditions. Equipment: HLC-8121GPC / HT (manufactured by Tosoh Corporation) Column: TSKgelGMHHR-HHT 7.8cm I.D x 30cm 2-row (manufactured by Tosoh Corporation) Detector: High-temperature radioisotope detector Temperature: 135℃ Solvent: o-dichlorobenzene (with 0.05% ionol added) Flow rate: 1.0ml / min Sample: Inject 0.4 ml of 0.1% sample. Measurements are taken under the above conditions, and the molecular weight of the sample is calculated using a molecular weight calibration curve prepared with monodisperse polystyrene standard samples. Furthermore, the molecular weight is calculated by converting it to polyethylene using a conversion formula derived from the Mark-Houwink viscosity equation.

[0139] (Method for measuring softening temperature) The softening temperature of the sample is measured using a constant-load extrusion type capillary rheometer, the "Flow Characteristics Evaluation Device Flow Tester CFT-500D" (manufactured by Shimadzu Corporation), according to the manual included with the device. With this device, a constant load is applied from the top of the sample by a piston, the sample filled in the cylinder is heated and melted, and the molten sample is extruded from a die at the bottom of the cylinder. A flow curve showing the relationship between the piston descent amount and temperature can be obtained. The temperature at which outflow begins and the piston starts to descend is defined as the outflow start temperature, and the "melting temperature in the 1 / 2 method" described in the manual for the "Flow Characteristics Evaluation Device Flow Tester CFT-500D" is defined as the softening temperature. The melting temperature in the 1 / 2 method is calculated as follows: First, half of the difference between the piston descent amount Smax at the end of outflow and the piston descent amount Smin at the start of outflow is determined (let this be X. X = (Smax - Smin) / 2). Then, the temperature at which the piston descent amount in the flow curve is the sum of X and Smin is the melting temperature in the 1 / 2 method.

[0140] The sample used for measurement is a cylindrical shape with a diameter of approximately 8 mm, obtained by compressing 1.0 g of resin at 10 MPa for 60 seconds in a tablet molding compressor (e.g., NT-100H, manufactured by NPA Systems Co., Ltd.) at 25°C. The measurement conditions for the CFT-500D are as follows: Test mode: Temperature increase method Starting temperature: 50℃ Achieved temperature: 200℃ Measurement interval: 1.0℃ Heating rate: 4.0℃ / min Piston cross-sectional area: 1,000 cm² 2 Test load (piston load): 10.0 kgf (0.9807 MPa) Preheating time: 300 seconds Die hole diameter: 1.0mm Die length: 1.0mm

[0141] (Method for measuring the weight-average particle size (D4) of toner particles) The weight-average particle size (D4) of the toner is calculated as follows. The measuring device used is the "CDA-1000X" particle counting analyzer (manufactured by Sysmex Corporation), which employs the pore electrical resistance method and is equipped with a 100 μm aperture tube. The included dedicated software, "CDA-1000X" (manufactured by Sysmex Corporation), is used to set the measurement conditions and analyze the measurement data. For the electrolytic aqueous solution used for measurement, for example, "Cellpack" (manufactured by Sysmex Corporation) can be used. Before performing the measurement and analysis, the dedicated software was configured as follows: In the "Measurement Condition Settings" screen of the dedicated software, the total count was set to 50,000, the number of repeated measurements to 1, and the measurement mode to total count (unlimited). The specific measurement method is as follows:

[0142] (1) Place 150 ml of electrolytic solution into a dedicated glass round-bottom beaker, set it on the sample stage, and stir with the stirring propeller at 500 rpm. Then, click "Blank Check Measurement" in the dedicated software to start the measurement and confirm that the count is less than 500. If the count is 500 or more, repeat the washing of the beaker and aperture tube. (2) Place 30 ml of the electrolytic aqueous solution into a 100 ml flat-bottomed glass beaker. Add 0.3 ml of a diluted solution of "Contaminon N" (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted three times by mass with deionized water as a dispersant. (3) Prepare an ultrasonic disperser "UltrasonicDispensionSystemTetra150" (manufactured by Nikko Bios Co., Ltd.) with an electrical output of 120W, which incorporates two oscillators with an oscillation frequency of 50kHz and a phase shift of 180 degrees. Add 3.3L of deionized water to the water tank of the ultrasonic disperser, and add 2ml of Contaminon N to this water tank. (4) Set the beaker from (2) into the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the beaker so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker is maximized. Adjust the height of the marker. (5) While irradiating the electrolytic aqueous solution in the beaker described in (4) with ultrasound, add 10 mg of toner in small amounts and disperse it. Continue the ultrasonic dispersion treatment for another 60 seconds. During ultrasonic dispersion, adjust the water temperature in the tank to be between 10°C and 40°C as appropriate. (6) Using a pipette, the electrolytic aqueous solution (5) containing the dispersed toner is dropped into the round-bottom beaker (1) placed in the sample stand, and the concentration is adjusted to 6%. The measurement is then continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software attached to the device, and the weight-average particle size (D4) is calculated.

[0143] (Method for measuring acid value) The acid value is the mass [mg] of potassium hydroxide required to neutralize the acid contained in 1g of a sample. In other words, the acid value is the mass [mg] of potassium hydroxide required to neutralize the free fatty acids and resin acids contained in 1g of a sample. The acid value was measured in accordance with JIS K0070-1992. Specifically, the measurement was performed according to the following procedure.

[0144] (1) Preparation of reagents 1.0 g of phenolphthalein was dissolved in 90 mL of ethyl alcohol (95% by volume), and deionized water was added to make a total volume of 100 mL to obtain a phenolphthalein solution. 7 g of special grade potassium hydroxide was dissolved in 5 mL of water, and ethyl alcohol (95 vol%) was added to make 1 L. The solution was placed in an alkali-resistant container to prevent contact with carbon dioxide, etc., and left for 3 days. After standing, the solution was filtered to obtain potassium hydroxide solution. The obtained potassium hydroxide solution was stored in an alkali-resistant container. The factor of the potassium hydroxide solution was determined by placing 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, titrating with the potassium hydroxide solution, and determining the amount of potassium hydroxide solution required for neutralization. The 0.1 mol / L hydrochloric acid used was prepared in accordance with JIS K8001-1998.

[0145] (2) Operation (A) Main examination 2.0 g of the sample was weighed accurately in a 200 mL Erlenmeyer flask, and 100 mL of a toluene / ethanol (2:1) mixture was added. The sample was dissolved over 5 hours. Then, a few drops of the phenolphthalein solution were added as an indicator, and the sample was titrated with the potassium hydroxide solution. The titration endpoint was defined as the indicator turning pale pink for 30 seconds. (B) Blank test The titration was performed in the same manner as described above, except that no sample was added (i.e., only a toluene / ethanol (2:1) mixed solution was used).

[0146] (3) Calculation of acid value The acid value was calculated by substituting the obtained results into the following formula. AV = [(BA) × f × 5.61] / S In the above formula, AV represents the acid value [mgKOH / g], A represents the amount of potassium hydroxide solution added in the blank test [mL], B represents the amount of potassium hydroxide solution added in the main test [mL], f represents the factor of the potassium hydroxide solution, and S represents the mass of the sample [g].

[0147] (Method for measuring hydroxyl value) The hydroxyl value is the number of milligrams of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl groups when acetylating 1 g of a sample. The hydroxyl value of the binder resin is specified in JIS K0070-199. The measurement is performed in accordance with section 2, but specifically, it is performed according to the following procedure.

[0148] (1) Preparation of reagents Place 25g of special grade acetic anhydride into a 100ml volumetric flask, add pyridine to bring the total volume to 100ml, and shake thoroughly to obtain the acetylation reagent. Store the obtained acetylation reagent in a brown bottle, keeping it away from moisture, carbon dioxide, etc. Dissolve 1.0 g of phenolphthalein in 90 ml of ethyl alcohol (95 vol%), add deionized water to make a total volume of 100 ml, and obtain a phenolphthalein solution. Dissolve 35 g of special grade potassium hydroxide in 20 ml of water and add ethyl alcohol (95 vol%) to make 1 L. Place the solution in an alkali-resistant container, taking care not to allow it to come into contact with carbon dioxide, etc., and leave it for 3 days. After that, filter the solution to obtain potassium hydroxide solution. Store the obtained potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by taking 25 ml of 0.5 mol / l hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, titrating with the potassium hydroxide solution, and determining the amount of potassium hydroxide solution required for neutralization. The 0.5 mol / l hydrochloric acid used is prepared in accordance with JIS K8001-1998.

[0149] (2) Operation (A) Main examination Accurately weigh 1.0 g of the sample into a 200 ml round-bottom flask, and precisely add 5.0 ml of the acetylation reagent to it using a volumetric pipette. If the sample is difficult to dissolve in the acetylation reagent, add a small amount of special grade toluene to dissolve it. Place a small funnel over the mouth of the flask and immerse about 1 cm of the bottom of the flask in a glycerin bath at approximately 97°C and heat. At this time, it is preferable to cover the base of the flask's neck with a piece of cardboard with a round hole cut out to prevent the temperature of the flask's neck from rising due to the heat of the bath.

[0150] After 1 hour, remove the flask from the glycerin bath and allow it to cool. After cooling, add 1 ml of water from the funnel and shake to hydrolyze the acetic anhydride. To further complete hydrolysis, heat the flask again in the glycerin bath for 10 minutes. After cooling, wash the funnel and the walls of the flask with 5 ml of ethyl alcohol. Add a few drops of the phenolphthalein solution as an indicator, and titrate with the potassium hydroxide solution. The titration endpoint is reached when the indicator remains faintly pink for approximately 30 seconds. (B) Blank test Perform the titration in the same manner as described above, except that no sample is used.

[0151] (3) Substitute the obtained results into the following formula to calculate the hydroxyl value. A = [{(BC) × 28.05 × f} / S] + D Here, A: hydroxyl value (mgKOH / g), B: amount of potassium hydroxide solution added in the blank test (ml), C: amount of potassium hydroxide solution added in the main test (ml), f: factor of the potassium hydroxide solution, S: sample (g), D: acid value of the sample (mgKOH / g).

[0152] (Method for calculating the modification rate of modified amorphous polyester resin or modified crystalline polyester resin due to linear alkyl compounds at the molecular chain ends) The degree of modification by linear alkyl compounds at the molecular chain ends of a modified amorphous polyester resin or a modified crystalline polyester resin (hereinafter referred to as "resin" in the calculation method) is calculated using the acid value, hydroxyl value, and molecular weight obtained above. Specifically, the number of moles of terminal functional groups (carboxyl groups or hydroxyl groups remaining without condensation of linear alkyl compounds) per 1 g of resin is calculated using the following formula. Number of moles of terminal functional groups = (acid value + hydroxyl value) / (1000 × 56.105)

[0153] Next, the number of moles per gram of resin is calculated from the number-average molecular weight (Mn) of the resin. Number of moles in 1g of resin = 1 / Mn The amount of terminal functional groups is calculated from the ratio of each monomer unit in the resin determined by the above NMR. Specifically, for ester products of dicarboxylic acids and dialcohols, the amount of functional groups is set to 2. If monomers with a valency of 3 or higher are used, the amount of terminal functional groups can be calculated based on their molar ratio. Degradation rate (mol%) due to linear alkyl compounds at the molecular chain ends of the resin = [1 - number of moles of terminal functional groups / (number of moles per gram of resin × amount of functional groups)] × 100 [Examples]

[0154] The present disclosure will be explained below with reference to examples, etc. However, the description of these examples is not intended to limit the present disclosure. In the following formulations, parts are by mass unless otherwise specified.

[0155] <Example of manufacturing amorphous polyester resin A1> • Bisphenol A propylene oxide adduct (average number of moles added: 2.2 mol): 78.0 parts by mass Terephthalic acid: 20.0 parts by mass Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass The above materials were weighed into a reaction vessel equipped with a condenser, stirrer, nitrogen inlet tube, and thermocouple. Next, the flask was purged with nitrogen gas, and the temperature was gradually increased while stirring. The reaction was carried out at 200°C for 2 hours while stirring. Furthermore, the pressure in the reaction vessel was reduced to 8.3 kPa and maintained for 1 hour, after which it was cooled to 160°C and returned to atmospheric pressure. Stearic acid: 2.0 parts by mass Subsequently, the above materials were added, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was allowed to proceed while maintaining the temperature at 200°C. After confirming that the softening temperature reached the temperature shown in Table 1, the temperature was lowered to stop the reaction, and amorphous polyester resin A1 was obtained. The physical properties are shown in Table 1.

[0156] <Manufacturing examples of amorphous polyester resins A2 to A14> In the example of producing amorphous polyester resin A1, the reaction was carried out in the same manner except that the monomers used were changed as shown in Table 1, to obtain amorphous polyester resins A2 to A14. The composition and physical properties of the obtained amorphous polyester resins A2 to A14 are shown in Table 1. Amorphous polyester resins A1 to A14 exhibited a crystallinity of 10% or less after being left at 30°C and 80% RH for one week. Furthermore, amorphous polyester resins A1 to A11 are modified amorphous polyester resins.

[0157] [Table 1]

[0158] In Table 1, Tg represents the glass transition temperature. The unit of SP value is (cal / cm²). 3 ) 0.5 The denaturation rate is the denaturation rate (mol%) due to linear alkyl compounds at the molecular chain ends. The abbreviations in Table 1 are as follows. The numerical values in parentheses are the number of carbon atoms in the linear alkyl compound. BPA-PO: Propylene oxide adduct of bisphenol A (average number of added moles: 2.2 mol) TPA: Terephthalic acid PA: Palmitic acid (16) SA: Stearic acid (18) BA: Behenic acid (22) LA: Lignoceric acid (24) MA: Myristic acid (14) CA: Cerotic acid (26) SAl: Stearyl alcohol (18) DS: Dodecyl succinic anhydride

[0159] <Production Example of Amorphous Polyester Resin B1> · Propylene oxide adduct of bisphenol A (average number of added moles: 2.2 mol) : 60.0 parts by mass · Terephthalic acid: 35.0 parts by mass · Trimellitic anhydride: 5.0 parts by mass · Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass e The above materials were weighed into a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen inlet pipe, and a thermocouple. Next, the inside of the flask was replaced with nitrogen gas, and then the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 200°C. Then, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was continued while maintaining the temperature at 200°C. After confirming that the softening temperature reached 138°C, the temperature was lowered to stop the reaction, and amorphous polyester resin B1 was obtained. The physical properties are shown in Table 2.

[0160]

Table 2

[0161] In Table 2, Tg represents the glass transition temperature. The unit of the SP value is (cal / cm 3 ) 0.5 is. The abbreviations in Table 2 are as follows. BPA-PO: Propylene oxide adduct of bisphenol A (average number of moles added: 2.2 mol) TPA: Terephthalic acid TMA: Trimellitus anhydride

[0162] <Example of manufacturing crystalline polyester resin 1> • Ethylene glycol: 20.0 parts by mass Tetradecanedioic acid: 74.0 parts by mass ·Behenic acid: 6.0 parts by mass • Tin 2-ethylhexanoate: 0.5 parts by mass The above materials were weighed into a reaction vessel equipped with a condenser, stirrer, nitrogen inlet tube, and thermocouple. After replacing the inside of the flask with nitrogen gas, the temperature was gradually increased while stirring, and the reaction was carried out for 3 hours at a temperature of 140°C while stirring. Subsequently, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200°C to obtain crystalline polyester resin 1. The physical properties are shown in Table 3.

[0163] <Examples of manufacturing crystalline polyester resins 2-16> In the example of producing crystalline polyester resin 1, the reaction was carried out in the same manner except that the monomer used was changed as shown in Table 3, to obtain crystalline polyester resins 2 to 16. The composition and physical properties of the obtained crystalline polyester resins 2 to 16 are shown in Table 3. Crystalline polyester resins 1-14 and 16 are modified crystalline polyester resins.

[0164] [Table 3]

[0165] In Table 3, the unit of SP value is (cal / cm). 3 ) 0.5 The denaturation rate is the denaturation rate (mol%) due to linear alkyl compounds at the molecular chain ends. The abbreviations in Table 3 are as follows. The numbers in parentheses represent the number of carbon atoms in the linear alkyl compound. EG: Ethylene glycol HG:1,6-Hexanediol TDA: Tetradecane dioxide DDA: Dodecane dioxide PA: Palmitic acid (16) SA: Stearic acid (18) BA: Behenic acid (22) LA: Lignoceric acid (24) MA: Myristic acid (14) CA: Cerotic acid (26) BAl: Behenyl alcohol (22)

[0166] <Example of wax dispersant manufacturing method> • Low molecular weight polypropylene (Viscol 660P, manufactured by Sanyo Chemical Industries, Ltd.): 10.0 parts by mass (0.02 moles; 2.4 mol% of the total number of moles of constituent monomers) Xylene: 25.0 parts by mass The above materials were weighed into a reaction vessel equipped with a condenser, stirrer, nitrogen inlet tube, and thermocouple. Next, the flask was purged with nitrogen gas, and the temperature was gradually raised to 175°C while stirring.

[0167] Styrene: 68.0 parts by mass Cyclohexyl methacrylate: 5.0 parts by mass Butyl acrylate: 12.0 parts by mass Methacrylic acid: 5.0 parts by mass Xylene: 10.0 parts by mass • Di-t-butyl peroxyhexahydroterephthalate: 0.5 parts by mass Subsequently, the above materials were added dropwise over 3 hours, and the mixture was stirred for a further 30 minutes. Next, the solvent was removed by distillation to obtain a wax dispersant having a structure in which vinyl resin components and hydrocarbon compounds reacted. The obtained wax dispersant had a peak molecular weight of Mp6000 and a softening temperature of 125°C.

[0168] <Example of toner particle manufacturing> Amorphous polyester resin A1: 50.0 parts by mass Amorphous polyester resin B1: 21.0 parts by mass · Crystalline polyester resin 1: 12.0 parts by mass · Wax dispersant: 5.0 parts by mass · Fischer-Tropsch wax (hydrocarbon wax, melting point: 90 °C): 5.0 parts by mass · C.I. Pigment Blue 15:3: 7.0 parts by mass Using a Henschel mixer (FM-75 type, manufactured by Nippon Coke Industry Co., Ltd.), the above materials were mixed at a rotation speed of 20 s -1 and a rotation time of 5 minutes, and then kneaded with a twin-screw kneader (PCM-30 type, manufactured by Ikegai Corporation) set at a temperature of 130 °C at a screw rotation speed of 250 rpm and a discharge temperature of 130 °C. The obtained kneaded product was rolled and cooled by a drum flaker (MBD30-30, manufactured by Nippon Coke). The temperature of the cooling water was set at 50 °C, and the conditions were set so that the thickness of the resin composition after rolling was 1.0 mm. Thereafter, the resin composition after rolling was held at 40 to 50 °C for ½ hour. The obtained resin composition was cooled to room temperature and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized product. The obtained coarsely pulverized product was finely pulverized with a mechanical pulverizer (T-250, manufactured by Freund Turbo Co., Ltd.). Furthermore, using a Faculity F-300 (manufactured by Hosokawa Micron Corporation), classification was performed to obtain toner particles 1 having a weight average particle diameter of 6.0 μm. The operating conditions were a classification rotor rotation speed of 130 s -1 and a dispersion rotor rotation speed of 120 s -1 as described above.

[0169] <Production Example of Toner Particles 2 to 32> In the production example of toner particles 1, toner particles 2 to 32 were obtained in the same manner except that the types and parts by mass of the amorphous polyester resin A, amorphous polyester resin B, and crystalline polyester resin were changed as described in Table 4.

[0170]

Table 4

[0171] <Production Example of Toner 1> · 100 parts of toner particles 1 • Silica particles 1 (fumed silica with an average number-average diameter of 30 nm, treated with silicone oil) 1.0 part The above ingredients were mixed in a Henschel FM-10C mixer (manufactured by Mitsui Miike Chemical Machinery) at a rotation speed of 30 seconds. -1 The mixture was then mixed for a rotation time of 10 minutes to obtain toner 1.

[0172] <Manufacturing examples for toners 2-32> In the example of manufacturing toner 1, the manufacturing process was carried out in the same manner except that toner particles 2 to 32 were used, and toners 2 to 32 were obtained. Samples A and B were prepared using toners 1-32, and the results of cross-sectional observations are shown together in Table 5.

[0173] [Table 5]

[0174] <Example of manufacturing magnetic core particle 1> • Process 1 (Weighing and Mixing Process): 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 The ferrite raw materials were weighed to achieve the above composition ratio. Then, they were ground and mixed for 5 hours using a dry vibratory mill with 1 / 8-inch diameter stainless steel beads.

[0175] • Process 2 (Calibration Process): The obtained pulverized material was processed into 1 mm cube pellets using a roller compactor. These pellets were then subjected to a vibrating sieve with a 3 mm mesh size to remove coarse powder, followed by a vibrating sieve with a 0.5 mm mesh size to remove fine powder. Finally, the pellets were calcined in a burner-type calcination furnace under a nitrogen atmosphere (oxygen concentration 0.01 vol%) at a temperature of 1000°C for 4 hours to produce calcined ferrite. The composition of the obtained calcined ferrite is as follows. (MnO) a (MgO) b (SrO) c (Fe2O3)d In the above equation, a=0.257, b=0.117, c=0.007, d=0.393

[0176] • Process 3 (Grinding process): After crushing the calcined ferrite to approximately 0.3 mm using a crusher, 30 parts by mass of water were added to 100 parts by mass of calcined ferrite using 1 / 8-inch diameter zirconia beads, and the mixture was ground in a wet ball mill for 1 hour. The resulting slurry was then ground in a wet ball mill using 1 / 16-inch diameter alumina beads for 4 hours to obtain a ferrite slurry (finely ground calcined ferrite).

[0177] ·Process 4 (granulation process): To a ferrite slurry, 1.0 part by mass of ammonium polycarboxylate was added as a dispersant and 2.0 parts by mass of polyvinyl alcohol was added as a binder per 100 parts by mass of calcined ferrite. The mixture was then granulated into spherical particles using a spray dryer (manufacturer: Okawara Chemical Machinery). After adjusting the particle size of the resulting particles, they were heated in a rotary kiln at 650°C for 2 hours to remove the organic components of the dispersant and binder.

[0178] • Process 5 (Baking Process): To control the firing atmosphere, the product was heated in an electric furnace under a nitrogen atmosphere (oxygen concentration 1.00 vol%) from room temperature to 1300°C in 2 hours, and then fired at 1150°C for 4 hours. After that, the temperature was cooled to 60°C over 4 hours, the atmosphere was changed from nitrogen to air, and the product was removed at a temperature of 40°C or lower.

[0179] • Process 6 (sorting process): After crushing the aggregated particles, low-magnetic-force particles were cut by magnetic separation, and coarse particles were removed by sieving with a 250 μm mesh sieve to obtain magnetic core particles 1 with a 50% particle size (D50) of 37.0 μm based on volume distribution.

[0180] <Preparation of coating resin 1> 26.8 parts by mass of cyclohexyl methacrylate monomer 0.2 parts by mass of methyl methacrylate monomer 8.4 parts by mass of methyl methacrylate macromonomer (A macromonomer with a weight-average molecular weight of 5000, having a methacryloyl group at one end.) Toluene 31.3 parts by mass 31.3 parts by mass of methyl ethyl ketone 2.0 parts by mass of azobisisobutyronitrile Of the above materials, cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone were added to a four-necked separable flask equipped with a reflux condenser, thermometer, nitrogen inlet tube, and stirrer. After introducing nitrogen gas to create a sufficient nitrogen atmosphere, the mixture was heated to 80°C, azobisisobutyronitrile was added, and polymerization was carried out under reflux for 5 hours. Hexane was injected into the resulting reaction product to precipitate the copolymer. After filtering off the precipitate, it was vacuum-dried to obtain coating resin 1. 30 parts by mass of the obtained coating resin 1 was dissolved in 40 parts by mass of toluene and 30 parts by mass of methyl ethyl ketone to obtain polymer solution 1 (solid content 30% by mass).

[0181] <Preparation 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 (Regal330; manufactured by Cabot) 0.3 parts by mass (Primary particle size 25nm, nitrogen adsorption specific surface area 94m2 / g, DBP oil absorption 75ml / 100g) The above materials were dispersed using 0.5 mm diameter zirconia beads in a paint shaker for 1 hour. The resulting dispersion was filtered through a 5.0 μm membrane filter to obtain coating resin solution 1.

[0182] <Manufacturing example of magnetic carrier 1> (Resin coating process): In a vacuum-degassed kneader maintained at room temperature, coating resin solution 1 was added in a ratio of 2.5 parts by mass of resin component per 100 parts by mass of magnetic core particles 1. After addition, the mixture was stirred at a rotation speed of 30 rpm for 15 minutes. After the solvent had evaporated to a certain extent (80% by mass), the temperature was raised to 80°C while mixing under reduced pressure, and toluene was removed by distillation over 2 hours, followed by cooling. The obtained magnetic carriers were separated for low magnetic force by magnetic separation, passed through a sieve with an opening of 70 μm, and then classified in an air classifier to obtain magnetic carrier 1 with a volume distribution-based 50% particle size (D50) of 38.2 μm.

[0183] <Example of manufacturing a two-component developer 1> Each of the toners (1-32) and magnetic carrier (1) was mixed in a V-type mixer (V-10 model: Tokuju Seisakusho Co., Ltd.) for 0.5 seconds to achieve a toner density of 8.0% by mass. -1 The mixture was then mixed for a rotation time of 5 minutes to obtain two-component developers 1 to 32.

[0184] <Example 1> [Low temperature fixation] The evaluation was performed using the two-component developer 1 described above. As the image forming apparatus, a modified Canon imageRUNNER ADVANCE C5560 digital commercial printer was used, and a two-component developer 1 was placed in the cyan developer unit. The modifications to the apparatus included allowing free setting of the fixing temperature, process speed, DC voltage VDC of the developer carrier, charging voltage VD of the electrostatic latent image carrier, and laser power. For image output evaluation, a solid-tone image (FFh image) with the desired image ratio was output, and the VDC, VD, and laser power were adjusted so that the amount of toner on the FFh image on the paper was as desired, and the low-temperature fixing performance was evaluated. FFh is a hexadecimal value representing 256 gradations, where 00h is the first gradation (white area) of the 256 gradations, and FFh is the 256th gradation (solid area).

[0185] The evaluation was conducted based on the following evaluation method, and the results are shown in Table 6. ·Paper: GFC-081 (81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) • Toner amount on paper: 0.70 mg / cm² 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) • Evaluation image: Place a 2cm x 5cm image in the center of the A4 paper shown above. • Test environment: Low temperature and low humidity environment: Temperature 15°C / Humidity 10%RH (hereinafter referred to as "L / L") Fixing temperature: 140℃ Process speed: 320 mm / sec

[0186] The above evaluation images were output, and the low-temperature fixability was assessed. The value of the image density reduction rate was used as the evaluation index for low-temperature fixability. Image density degradation rate is measured by the X-Rite color reflectance densitometer (500 series: X-Rite Corporation). First, the image density of the central part was measured using a (manufactured) device. Next, 4.9 kPa (50 g / cm³) was applied to the area where the image density was measured. 2 The image was fixed using Silbon paper with a load of ) applied and rubbed (5 times back and forth), and the image density was measured again. The percentage decrease in image density before and after friction was calculated using the following formula. The obtained percentage decrease in image density was evaluated according to the following evaluation criteria. An evaluation of AA to C was considered good. Image density reduction rate = (Image density before friction - Image density after friction) / (Image density before friction) × 100 (Evaluation Criteria) AA: Image density reduction rate less than 1.0% A: Image density reduction rate of 1.0% or more and less than 3.0% B: Image density reduction rate of 3.0% or more and less than 5.0% C: Image density reduction rate of 5.0% or more and less than 8.0% D: Image density reduction rate of 8.0% or more

[0187] [Static resistance under high temperature and high humidity conditions] ·Paper: GFC-081 (81.0g / m 2 (Canon Marketing Japan Inc.) • Amount of toner on paper: 0.35 mg / cm² 2 (DC voltage V of the developer carrier) DC , the charging voltage V of the electrostatic latent image carrier D (and adjusted by laser power) • Evaluation image: Place a 2cm x 5cm image in the center of the A4 paper shown above. • Fixation test environment: High temperature and high humidity environment: Temperature 30°C / Humidity 80%RH (hereinafter referred to as "H / H") Process speed: 377 mm / sec The amount of triboelectric charge on the toner on the electrostatic latent image carrier was calculated by collecting the toner using a metal cylindrical tube and a cylindrical filter. Specifically, the amount of triboelectric charge on the toner on the electrostatic latent image carrier was measured using a Faraday cage.

[0188] A Faraday cage is a coaxial double-cylinder structure where the inner and outer cylinders are insulated from each other. If a charged object with charge Q is placed inside the inner cylinder, electrostatic induction will cause it to behave as if a metal cylinder with charge Q were present. The amount of this induced charge was measured using an electrometer (Kessley 6517A, manufactured by Kessley), and the amount of charge Q (mC) divided by the mass of toner M (kg) inside the inner cylinder (Q / M) was defined as the amount of triboelectric charge on the toner. The amount of triboelectric charge on toner (mC / kg) = Q / M First, the evaluation image described above was formed on the electrostatic latent image carrier. Before it was transferred to the intermediate transfer medium, the rotation of the electrostatic latent image carrier was stopped, and the toner on the electrostatic latent image carrier was collected by suction using a metal cylindrical tube and a cylindrical filter, and the [initial Q / M] was measured. Subsequently, the developer was left inside the evaluation unit in an H / H environment for two weeks. After that, the same operations as before were performed, and the charge amount Q / M (mC / kg) per unit mass on the electrostatic latent image carrier was measured. The initial Q / M per unit mass on the electrostatic latent image carrier was set to 100%, and the charge retention rate per unit mass on the electrostatic latent image carrier after standing ([Q / M after standing] / [Initial Q / M] × 100) was calculated and judged according to the following criteria. An evaluation of A to C was considered good. (Evaluation Criteria) A: Static electricity retention rate of 90% or higher B: Static charge retention rate is 85% or more but less than 90% C: Static retention rate is 80% or more but less than 85% D: Static charge retention rate is less than 80%

[0189] [Paper ejection adhesion resistance] ·Paper: CS-680 (A4 paper, 68.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) • Toner coverage: 1.20 mg / cm² 2 • Evaluation image: 100cm in the center of the A4 paper shown above. 2 Place an image (10cm x 10cm) • Fixation test environment: Low temperature and low humidity environment, 15℃ / 10%RH (hereinafter referred to as "L / L") Process speed: 320 mm / sec Fixing temperature: 140℃ Using the image forming apparatus described above, two fixed images were output under the above conditions, and the output images were superimposed so that the printed parts of the output images were in contact with each other. A stack of paper (CS-680, 500 sheets) was placed on top of the two printed materials, and the printed materials and paper stack were placed in a constant temperature chamber set to 30°C and 80%RH. After leaving it for 1 hour, the temperature of the constant temperature chamber was reset to the evaluation conditions described below, and it was left for 10 hours. Next, the two printed objects were removed from the constant temperature bath and allowed to cool for one hour. After that, the two printed objects were peeled apart, and their adhesion was evaluated. A rating of A to C was considered satisfactory. (Evaluation Criteria) A: At a constant temperature of 60°C, the printed parts do not adhere to each other. B: At a constant temperature of 55°C, the printed objects do not adhere to each other. C: At a constant temperature of 50°C, the printed parts do not adhere to each other. D: Under constant temperature conditions of 50°C, the printed objects adhere to each other, and when pulled apart forcefully, the printed objects tear.

[0190] [Bending resistance] • Paper: OK Top Coat Plus • Toner coverage: 1.2 mg / cm² 2 • Evaluation image: A solid color image covering the entire A4 sheet of paper shown above. • Fixation test environment: Normal temperature and humidity environment, 25°C / 50%RH (hereinafter referred to as "N / N") • Process speed: 132 mm / sec Fixing temperature: 150℃ Using the image forming apparatus described above, one fixed image was output under the above conditions.

[0191] The output material was placed in a forced-air constant-temperature incubator set to 50°C and left for 72 hours. After that, the removed sample was allowed to cool in an N / N environment for 1 hour, and then a mandrel test was performed. A cylindrical mandrel bending tester (manufactured by Cortec Co., Ltd.) was used for the mandrel testing apparatus. A mandrel with a diameter of Φ2 mm was used. The image was placed in the mandrel testing apparatus and folded 180°. The folded portion was rubbed with a 200g weight placed on a piece of lens tissue to peel the image off the paper. Three points on the peeled portion of the image were read using PIAS (manufactured by QEA), and the area of ​​the portion of the folded area that did not peel off was quantified and calculated using the image processing software ImageJ.

[0192] This section explains the ImageJ analysis method. The image to be evaluated is opened in ImageJ and converted to 8-bit. Next, a Threshhold process is performed to separate the areas where peeling has occurred from those where it has not. A Rectangle process is used to place the peeled area within a specified range of 500 pixels wide x 70 pixels high and perform the analysis to calculate the TotalArea (area A) of the peeled area. Next, the specified area was moved to the area where no peeling had occurred, and the TotalArea: Area B of the area where no peeling had occurred was calculated. Subsequently, the area ratio of the area where no peeling occurred was quantified by Area B / (Area A + Area B). The values ​​obtained above were used to indicate the bending resistance of the printed image, and were evaluated according to the following criteria. A rating of A to C was considered good. (Evaluation Criteria) A: Bending resistance of 90% or more B: Bending resistance is less than 90% but 80% or more. C: Bending resistance less than 80% or more than 70% D: Bending resistance of 70% or more

[0193] <Examples 2-22 and Comparative Examples 1-10> In Example 1, the evaluation was carried out in the same manner except that the two-component developer used for evaluation was changed to one of the two-component developers listed in Table 6. The evaluation results are shown in Table 6.

[0194] [Table 6]

[0195] This disclosure relates to the following configuration. (Composition 1) A toner having toner particles containing amorphous polyester resin and crystalline polyester resin, The amorphous polyester resin contains a modified amorphous polyester resin in which at least one linear alkyl compound selected from the group consisting of linear aliphatic monocarboxylic acids having 16 to 24 carbon atoms and linear aliphatic monoalcohols having 16 to 24 carbon atoms is condensed at the terminal. The crystalline polyester resin contains a modified crystalline polyester resin in which at least one linear alkyl compound selected from the group consisting of linear aliphatic monocarboxylic acids having 16 to 24 carbon atoms and linear aliphatic monoalcohols having 16 to 24 carbon atoms is condensed at the terminal. Sample A, obtained by melting the toner at 150°C and then cooling it to 25°C at 100°C / min, was observed in cross-section using a transmission electron microscope, and the average number of major axis lengths of the crystalline polyester resin crystals observed in the cross-section was calculated as D. A (nm) Regarding sample B, which is obtained by leaving sample A at 50°C for 72 hours, sample B is observed in cross-section using a transmission electron microscope, and the average number of major axis lengths of the crystals of the crystalline polyester resin observed in the cross-section is D. B When set to (nm), The DA and D B A toner characterized in that it satisfies the following formulas (1) and (2). 10nm≦D A ≤100nm ···(1) 1nm ≤ D B -D A ≤20nm ···(2) (Configuration 2) The aforementioned D A and the aforementioned D B However, the toner described in Configuration 1 satisfies the following equations (3) and (4). 10nm≦D A ≤50nm ···(3) 20nm≦D B ≤70nm ···(4) (Composition 3) The toner according to configuration 1 or 2, wherein when the sample B is observed in cross-section, the average aspect ratio of the crystals of the crystalline polyester resin observed in the cross-section is 2.5 to 5.0. (Composition 4) The SP value of the modified amorphous polyester resin is determined by SP A (cal / cm 3 ) 0.5 The SP value of the modified crystalline polyester resin is then set to SP C (cal / cm 3 ) 0.5 In that case, the SP A I understand SP C A toner described in any of configurations 1 to 3, which satisfies the following formula (5). 0.8≦SP A -SP C ≤1.2 ···(5) (Composition 5) The content ratio W of the crystalline polyester resin based on the mass of the toner particles C However, the toner is 5.0 to 20.0% by mass, as described in one of the configurations 1 to 4. (Composition 6) The content ratio of the crystalline polyester resin based on the mass of the toner particles is W C (Assuming mass %) In cross-sectional observation of sample A using a transmission electron microscope, the average area ratio of the crystals of the crystalline polyester resin in the area of ​​the observation range is S. A When expressed as (area %), The W C and S A A toner described in any of configurations 1 to 5, which satisfies the following formula (6). 0.1≦S A / W C ≤0.6 ···(6) (Composition 7) The content ratio of the crystalline polyester resin based on the mass of the toner particles is W C (Assuming mass %) In cross-sectional observation of sample B using a transmission electron microscope, the average area ratio of the crystals of the crystalline polyester resin in the area of ​​the observation range is S. B When expressed as (area %), The W C and S B A toner described in any of configurations 1 to 6, which satisfies the following formula (7). 0.3 ≤ S B / W C ≤0.8 ···(7) (Composition 8) The toner according to any one of configurations 1 to 7, wherein the weight-average molecular weight Mw of the modified crystalline polyester resin is 15,000 to 25,000. (Composition 9) The number of carbon atoms in the linear alkyl compound condensed at the end of the modified amorphous polyester resin is greater than the number of carbon atoms in the linear alkyl compound condensed at the end of the modified amorphous polyester resin. The toner according to any one of configurations 1 to 8, wherein the linear alkyl compound condensed at the end of the modified crystalline polyester resin has a large number of carbon atoms. (Composition 10) The linear alkyl compound condensed at the end of the modified amorphous polyester resin is stearic acid. The toner according to any one of configurations 1 to 9, wherein the linear alkyl compound condensed at the end of the modified crystalline polyester resin is behenic acid. (Composition 11) The toner according to any one of configurations 1 to 10, wherein the modified crystalline polyester resin has monomer units corresponding to ethylene glycol and monomer units corresponding to dodecanedioic acid. (Composition 12) The proportion of the molecular chain ends of the modified amorphous polyester resin to which the linear alkyl compound is condensed is 0.5 mol% or more and less than 25 mol%, The toner according to any one of configurations 1 to 11, wherein the proportion of the molecular chain ends of the modified crystalline polyester resin to which the linear alkyl compound is condensed is 15 to 75 mol%.

Claims

1. A toner having toner particles containing amorphous polyester resin and crystalline polyester resin, The amorphous polyester resin contains a modified amorphous polyester resin in which at least one linear alkyl compound selected from the group consisting of linear aliphatic monocarboxylic acids having 16 to 24 carbon atoms and linear aliphatic monoalcohols having 16 to 24 carbon atoms is condensed at the terminal. The crystalline polyester resin contains a modified crystalline polyester resin in which at least one linear alkyl compound selected from the group consisting of linear aliphatic monocarboxylic acids having 16 to 24 carbon atoms and linear aliphatic monoalcohols having 16 to 24 carbon atoms is condensed at the terminal. Sample A, obtained by melting the toner at 150°C and then cooling it to 25°C at 100°C / min, was observed in cross-section using a transmission electron microscope, and the average number of major axis lengths of the crystals of the crystalline polyester resin observed in the cross-section was given as D. Ａ (nm) Regarding sample B, which is obtained by leaving sample A at 50°C for 72 hours, sample B is observed in cross-section using a transmission electron microscope, and the average number of major axis lengths of the crystals of the crystalline polyester resin observed in the cross-section is D. Ｂ When set to (nm), The D Ａ and D Ｂ A toner characterized in that it satisfies the following formulas (1) and (2). 10nm≦D Ａ ≦100nm ・・・(1) 1nm≦D Ｂ -D Ａ ≦20nm ・・・(2)

2. Said D Ａ and said D Ｂ satisfy the following formulas (3) and (4), the toner according to claim 1. 10nm≦D Ａ ≦50nm ・・・(3) 20nm≦D Ｂ ≦70nm ・・・(4)

3. The toner according to claim 1 or 2, wherein when the sample B is observed in cross-section, the average aspect ratio of the crystals of the crystalline polyester resin observed in the cross-section is 2.5 to 5.

0.

4. The SP value of the modified amorphous polyester resin is SP Ａ (cal / cm ３ ) ０．５ The SP value of the modified crystalline polyester resin is set to SP Ｃ (cal / cm ３ ) ０．５ When this happens, the SP Ａ and the SP Ｃ The toner according to claim 1 or 2, wherein the following formula (5) is satisfied. 0.8≦SP Ａ -SP Ｃ ≦1.2 ・・・(5)

5. The content ratio W of the crystalline polyester resin based on the mass of the toner particles Ｃ The toner according to claim 1 or 2, wherein the amount is 5.0 to 20.0% by mass.

6. The content ratio of the crystalline polyester resin based on the mass of the toner particles is W Ｃ (As mass%), In cross-sectional observation of sample A using a transmission electron microscope, the average area ratio of the crystals of the crystalline polyester resin in the area of ​​the observation range is S. Ａ (Assuming area percentage), The W Ｃ and S Ａ The toner according to claim 1 or 2, wherein the following formula (6) is satisfied. 0.1≦S Ａ / W Ｃ ≦0.6 ・・・(6)

7. The content ratio of the crystalline polyester resin based on the mass of the toner particles is W Ｃ (As mass%), In cross-sectional observation of sample B using a transmission electron microscope, the average area ratio of the crystals of the crystalline polyester resin in the area of ​​the observation range is S. Ｂ (Assuming area percentage), The W Ｃ and S Ｂ The toner according to claim 1 or 2, wherein the following formula (7) is satisfied. 0.3≦S Ｂ / W Ｃ ≦0.8 ・・・(7)

8. The weight-average molecular weight Mw of the modified crystalline polyester resin is 15,000 to 25,000. A toner according to claim 1 or 2.

9. The number of carbon atoms in the linear alkyl compound condensed at the end of the modified amorphous polyester resin is greater than the number of carbon atoms in the linear alkyl compound condensed at the end of the modified amorphous polyester resin. The toner according to claim 1 or 2, wherein the linear alkyl compound condensed at the ends of the modified crystalline polyester resin has a large number of carbon atoms.

10. The linear alkyl compound condensed at the end of the modified amorphous polyester resin is stearic acid. The toner according to claim 1 or 2, wherein the linear alkyl compound condensed at the end of the modified crystalline polyester resin is behenic acid.

11. The toner according to claim 1 or 2, wherein the modified crystalline polyester resin has monomer units corresponding to ethylene glycol and monomer units corresponding to dodecanedioic acid.

12. The proportion of the molecular chain ends of the modified amorphous polyester resin into which the linear alkyl compound is condensed is 0.5 mol% or more and less than 25 mol%, The toner according to claim 1 or 2, wherein the proportion of the molecular chain ends of the modified crystalline polyester resin to which the linear alkyl compound is condensed is 15 to 75 mol%.

Images