toner

Abstract

To provide a toner that has good charge rising properties and can form stable images even in a low printing rate intermittent mode in a low temperature and low humidity environment.SOLUTION: A toner has toner particles and silica fine particles A. (I) A peak derived from boron atoms and a peak derived from a BO structure are detected in the toner particles, and the toner contains dodecylbenzenesulfonic acid or dodecylbenzene sulfonate. (II) Fragment ions corresponding to a dimethylsiloxane structure are observed in the silica fine particles A, and when a silica fine particle titration operation is performed, Sn defined by Sn={(a-b)×c×NA} / (d×e) satisfies the following formula (2). (2) 0.10≤Sn≤0.80. (DDD / SDD) / B is 4.70×10-6 or more and 1.40×10-3 or less, (DCP / SCP) / B is 4.70×10-4 or more and 1.00×10-2 or less, and (DCP / SCP) / (DDD / SDD) is 3.00 or more and 3.00×102 or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a toner used in an image forming method such as electrophotography. [Background technology]

[0002] In recent years, image forming apparatuses such as copiers and printers are being required to operate at higher speeds and with higher image quality as the purposes and environments of use become more diverse. In order to simultaneously achieve higher speeds and higher image quality, the charge rise property of the toner is important. The charge rise property of the toner can be improved by increasing the charge property and fluidity of the toner. For the purpose of improving the chargeability of the toner, Patent Document 1 proposes disposing an external additive having high chargeability and fluidity, such as dimethyldichlorosilane-treated silica, on the surface of the toner. From the viewpoint of durability, approaches to improve gloss and fixability have also been made. For example, Patent Document 2 proposes a toner using borax coupling. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2001-356521 A [Patent Document 2] Patent No. 6059251 Summary of the Invention [Problem to be solved by the invention]

[0004] While the external additives described in Patent Document 1 provide excellent charge build-up, it is difficult to control the charge depending on the usage pattern. For example, when a mode is applied that assumes a usage pattern of a personal printer with a low print rate and a small number of prints at one time (hereinafter, low intermittent print mode), the toner has many opportunities to be charged, so the charge tends to become excessive. This tendency is particularly noticeable in low intermittent print mode in a low temperature and low humidity environment. When the toner becomes excessively chargeable, a sudden drop in charge occurs when it mixes with a toner with a low charge that is supplied to the developing member later, resulting in a phenomenon called "vertical density unevenness" in which part of the image becomes thin in a vertical band shape. Furthermore, in Patent Document 2, the effect of improving the charge rise property is insufficient, and there is still room for improvement, including in performance under low-temperature and low-humidity environments. The present invention has been made in consideration of the above problems, and provides a toner that has excellent charge rise properties and can form stable images even in a low-temperature, low-humidity environment in a low-intermittent printing mode. [Means for solving the problem]

[0005] The present invention provides a toner having toner particles containing a binder resin and silica fine particles A, (I) in a TOF-SIMS measurement of the toner particles, a fragment peak derived from a boron atom and a fragment peak derived from a boron-oxygen structure are detected, the toner contains at least one selected from the group consisting of dodecylbenzenesulfonic acid and dodecylbenzenesulfonate salts, (II) In a measurement of the silica fine particles A by time-of-flight secondary ion mass spectrometry, a fragment ion corresponding to a structure represented by the following formula (1) is observed,

[0006] [ka] (In formula (1), n ​​represents an integer of 1 or more.) When 2.00 g of the silica fine particles were dispersed in a mixture of 25.0 g of ethanol and 75.0 g of a 20% by mass NaCl aqueous solution and titrated with sodium hydroxide, Sn defined as Sn={(ab)×c×NA} / (d×e) satisfies the following formula (2), 0.10≦Sn≦0.80 (2) (In formula (2), a is the titer (L) of the aqueous NaOH solution required to adjust the pH of the mixture in which the silica fine particles are dispersed to 9.0, b is the titer (L) of NaOH solution required to adjust a mixture of 25.0 g of ethanol and 75.0 g of 20% by mass NaCl aqueous solution to pH 9.0, c is the concentration (mol / L) of the NaOH solution used in the titration, NA is Avogadro's number, d is the mass (g) of the silica microparticles, e is the BET specific surface area (nm 2 / g). The solid of the silica fine particles A 29 The area of ​​the peak of the D unit that has a peak top in the range of -25 ppm to -15 ppm in the chemical shift obtained by the Si-NMR DD / MAS method is defined as D. DD The sum of the areas of the peaks of M, D, T, and Q units present in the range of -140 ppm to 100 ppm is defined as S. DD The BET specific surface area of ​​the silica particles is B (m 2 / g), (D DD / S DD ) to B (D DD / S DD ) / B is 4.70×10 -6 Above 1.40 x 10 -3 The following is further: The solid of the silica fine particles A 29 The area of ​​the peak of the D unit that has a peak top in the range of -25 ppm to -15 ppm in the chemical shift obtained by the Si-NMR CP / MAS method is D CPThe sum of the areas of the peaks of M, D, T, and Q units present in the range of -140 ppm to 100 ppm is defined as S. CP When (D CP / S CP ) to B (D CP / S CP ) / B is 4.70×10 -4 End 1.00×10 -2 is as follows: (D CP / S CP ) of (D DD / S DD ) to the ratio value (D CP / S CP ) / (D DD / S DD ) is 3.00 or more 3.00 x 10 2 The present invention relates to a toner characterized in that: Effect of the Invention

[0007] The toner of the present invention has excellent charge build-up properties and can form stable images even in a low-intermittent printing mode in a low-temperature, low-humidity environment. [Brief description of the drawings]

[0008] [Figure 1] FIG. 2 is a diagram showing a configuration of an apparatus used for measuring the amount of triboelectric charge of a toner. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] In the present disclosure, the description of a numerical range such as "XX or more and YY or less" or "XX to YY" means a numerical range including the lower and upper limits, which are the endpoints, unless otherwise specified. When a numerical range is described in stages, the upper and lower limits of each numerical range can be arbitrarily combined.

[0010] [Features of the present invention] In order to improve the charge rising property of the toner, it is effective to make silica fine particles with high chargeability and fluidity present on the toner surface as an external additive. However, simply adding such silica fine particles to the outside will cause excessive chargeability of the toner when used in a low-temperature, low-humidity environment and in a low-intermittent printing mode, resulting in problems of vertical density unevenness. In order to solve the above problem, the present inventors have intensively studied the appropriate control state of the silica fine particle surface and the toner base particle surface. As a result, it was found that by combining silica fine particles that have been properly treated with a surface treatment agent that imparts a dimethylsiloxane structure and in which the amount of surface silanol groups is controlled, with toner particles that have a dodecylbenzenesulfonic acid structure on the surface and further have a BO bond (boron-oxygen bond), it is possible to suppress overcharging while maintaining the high charge rising property of the silica fine particles.

[0011] The detailed configuration of the toner of the present invention having toner particles containing a binder resin and silica fine particles A is as follows. (I) In a TOF-SIMS measurement of the toner particles, a fragment peak derived from a boron atom and a fragment peak derived from a BO structure (boron-oxygen structure) are detected, The toner contains at least one selected from the group consisting of dodecylbenzenesulfonic acid and dodecylbenzenesulfonate salts. (II) In a TOF-SIMS measurement of the silica fine particles A, fragment ions corresponding to a structure represented by the following formula (1) are observed,

[0012] [ka] (In formula (1), n ​​represents an integer of 1 or more.) When 2.00 g of the silica fine particles were dispersed in a mixture of 25.0 g of ethanol and 75.0 g of a 20% by mass NaCl aqueous solution and titrated with sodium hydroxide, Sn defined as Sn={(ab)×c×NA} / (d×e) satisfies the following formula (2), 0.10≦Sn≦0.80 (2) (In formula (2), a is the titer (L) of the NaOH aqueous solution required to adjust the mixed liquid in which the silica fine particles A are dispersed to pH 9.0, b is the titer (L) of NaOH solution required to adjust a mixture of 25.0 g of ethanol and 75.0 g of 20% by mass NaCl aqueous solution to pH 9.0, c is the concentration (mol / L) of the NaOH solution used in the titration, NA is Avogadro's number, d is the mass (g) of the silica microparticles, e is the BET specific surface area (nm 2 / g). The solid of the silica fine particles A 29 The area of ​​the peak of the D unit that has a peak top in the range of -25 ppm to -15 ppm in the chemical shift obtained by the Si-NMR DD / MAS method is defined as D. DD The sum of the areas of the peaks of M, D, T, and Q units present in the range of -140 ppm to 100 ppm is defined as S. DD and the specific surface area of ​​the silica particles is B (m 2 / g), (D DD / S DD ) to B (D DD / S DD ) / B is 4.70×10 -6 Above 1.40 x 10 -3 The following is further: The solid of the silica fine particles A 29 The area of ​​the peak of the D unit that has a peak top in the range of -25 ppm to -15 ppm in the chemical shift obtained by the Si-NMR CP / MAS method is D CP The sum of the areas of the peaks of M, D, T, and Q units present in the range of -140 ppm to 100 ppm is defined as S. CP When (D CP / S CP ) to B (D CP / S CP ) / B is 4.70×10 -4 Above 1.00 x 10-2 is as follows: (D CP / S CP ) of (D DD / S DD ) to the ratio value (D CP / S CP ) / (D DD / S DD ) is 3.00 or more 3.00 x 10 2 It is less than or equal to.

[0013] The present inventors believe that the reason why the above-mentioned effects are obtained by this configuration is as follows.

[0014] First, the toner surface of the present invention has BO bonds and dodecylbenzenesulfonic acid or dodecylbenzenesulfonate. BO bonds are functional groups that are highly adsorbent to moisture, and are considered to retain moisture to a certain extent on the toner surface even in environments with little moisture, such as low temperature and low humidity environments. Furthermore, since dodecylbenzenesulfonic acid or dodecylbenzenesulfonate is water-soluble, it migrates into the moisture retained on the toner surface and becomes mobile on the toner surface containing moisture. Then, the sulfonic acid portion in the dodecylbenzenesulfonic acid structure and the silanol group on the surface of the silica fine particles having the other polarity of the present invention are electrostatically adsorbed. As a result, it is considered that the excess charge of the silica is easily leaked into the surrounding moisture through the dodecylbenzenesulfonic acid or dodecylbenzenesulfonate, and overcharging can be suppressed. In addition, in order to control the adsorption of the sulfonic acid portion and silanol group of dodecylbenzenesulfonic acid or dodecylbenzenesulfonate while maintaining the chargeability and fluidity of silica, it is considered important to appropriately adjust the amount of treatment with the surface treatment agent that imparts a dimethylsiloxane structure and the amount of surface silanol groups.

[0015] The present invention will now be described in further detail.

[0016] In the toner of the present invention, boron atoms are present on the toner surface. Specifically, in a time-of-flight secondary ion mass spectrometry (hereinafter referred to as TOF-SIMS) measurement of the toner, a fragment peak derived from boron atoms is present. TOF-SIMS is a method for analyzing the composition of a sample surface by irradiating the sample with ions and analyzing the mass of secondary ions emitted from the sample. Since the secondary ions are emitted from a region several nm deep from the sample surface, a region several nm deep on the toner surface can be qualitatively measured. The presence or absence of boron atoms is confirmed by TOF-SIMS measurement using sodium tetraborate decahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a standard sample. The measurement data includes boron atoms and BO 2 The peak position due to (a representative structure having a BO bond) is confirmed. Then, the presence or absence of boron atoms and BO bonds can be determined by performing TOF-SIMS measurement of the target toner. If there are no boron atoms or BO bonds, the effect of the present invention cannot be obtained.

[0017] The toner of the present invention has dodecylbenzenesulfonic acid or a salt of dodecylbenzenesulfonate. The measurement of dodecylbenzenesulfonic acid will be described in detail later, but ESI-MS measurement can be used to determine whether it is present near the surface and further the content in the toner. If there is no dodecylbenzenesulfonic acid or a salt of dodecylbenzenesulfonate, the effect of the present invention cannot be obtained, as in the case of BO bonds.

[0018] The toner of the present invention contains silica fine particles A as an external additive. The silica fine particles A are surface-treated, which can be confirmed by TOF-SIMS. In the measurement of the silica fine particles A by TOF-SIMS, it is necessary that fragment ions corresponding to the structure represented by formula (1) are observed. The observation of fragment ions represented by formula (1) indicates that the silica fine particles A are surface-treated with a surface treatment agent that imparts a dimethylsiloxane structure. In addition, since the dimethylsiloxane structure is hydrophobic, the moisture adsorption and chargeability can be controlled by controlling the surface treatment state with the surface treatment agent that imparts the dimethylsiloxane structure.

[0019] [ka] (In formula (1), n ​​is an integer of 1 or more.) As mentioned above, TOF-SIMS is a method for analyzing the composition of a sample surface by irradiating the sample with ions and analyzing the mass of the secondary ions emitted from the sample. Since the secondary ions are emitted from a region several nm deep from the sample surface, it is possible to analyze the structure near the surface of silica microparticles. The mass spectrum of the secondary ions obtained by measurement is a set of fragment ions that reflect the molecular structure of the surface treatment agent for the silica microparticles.

[0020] In the measurement of silica fine particles A by TOF-SIMS, fragment ions corresponding to the structure represented by the above formula (1) are observed. In this disclosure, a structural unit having this structure is defined as a D unit. When fragment ions of a D unit are observed by TOF-SIMS, it means that the silica fine particles have been surface-treated with a surface treatment agent that imparts D units.

[0021] When silica fine particles A are dispersed in a solvent and titrated with sodium hydroxide, the amount of sodium hydroxide required to adjust to the target pH corresponds to the amount of silanol groups on the surface of the silica fine particle substrate and the amount of silanol groups in the surface-treated structure of the silica fine particles. In other words, the amount of Si-OH groups is the value Sn (particles / nm2) calculated from the titration amount of the sodium hydroxide solution. 2 ) This is because the Si-OH groups of the silica microparticle substrate and the Si-OH groups derived from the surface treatment agent undergo a neutralization reaction with sodium hydroxide. Since silanol groups have polarity, it is believed that the chargeability of the silica microparticles is controlled by the content of silanol groups. If the content of silanol groups is low, the chargeability decreases. Also, if the content of silanol groups is excessive, the particles are prone to overcharging.

[0022] Specifically, 2.00 g of silica fine particles A was dispersed in a mixture of 25.0 g of ethanol and 75.0 g of a 20% by mass NaCl aqueous solution, and titration was performed using sodium hydroxide. Sn, defined as Sn={(ab)×c×NA} / (d×e), must satisfy the following formula (2). 0.10≦Sn≦0.80 (2) (In formula (2), a is the titer (L) of the NaOH aqueous solution required to adjust the mixed liquid in which the silica fine particles A are dispersed to pH 9.0, b is the titer (L) of NaOH solution required to adjust a mixture of 25.0 g of ethanol and 75.0 g of 20% by mass NaCl aqueous solution to pH 9.0, c is the concentration (mol / L) of the NaOH solution used in the titration, NA is Avogadro's number, d is the mass (g) of the silica microparticles, e is the BET specific surface area (nm 2 / g).

[0023] Sn can be obtained by the titration procedure described above. If there are silanol groups on the surface of the silica fine particles, they are immediately neutralized by sodium hydroxide, so Sn is thought to correlate with the silanol groups per unit surface area of ​​the silica fine particle surface. When Sn satisfies formula (2), the amount of silanol groups on the surface of the silica fine particle base and in the structure derived from the surface treatment agent of the silica fine particles becomes appropriate, improving the charge rise property. In addition, when Sn satisfies formula (2), adsorption with the sulfonic acid portion of dodecylbenzenesulfonic acid or dodecylsulfonate salt occurs appropriately, making it possible to suppress overcharging.

[0024] Sn is preferably 0.10 or more and 0.50 or less, and more preferably 0.20 or more and 0.50 or less.

[0025] In addition, Sn can be increased by performing the treatment under conditions in which the reaction of the surface treatment agent does not proceed so that the silanol groups on the surface of the silica fine particle substrate remain, or by adding only a small amount of the treatment agent that does not completely cover the surface of the silica fine particle substrate. On the other hand, Sn can be decreased by reducing the silanol groups on the surface of the silica fine particles by surface treating the silica fine particles. It can also be decreased by extending the reaction time or raising the temperature during the surface treatment.

[0026] In the present invention, the surface treatment state of the silica fine particles A ((D DD / S DD ) / B, (D CP / S CP ) / B, (D CP / S CP ) / (D DD / S DD The surface treatment state of silica fine particles A is controlled by 29 Si-NMR Calculated by DD / MAS and CP / MAS methods. With DD / MAS measurement, all Si atoms in the measurement sample are observed, so information on the content of Si atoms in silica microparticles can be obtained. On the other hand, with CP / MAS measurement, measurements are performed while magnetizing via H atoms that exist near Si atoms, so Si atoms that exist near H atoms can be observed with high sensitivity. Si atoms that exist near H atoms have low mobility. In other words, with CP / MAS measurement, information on the presence of Si atoms with low mobility in the measurement sample can be obtained.

[0027] Generally, solid 29 In Si-NMR, four types of peaks can be observed for Si atoms in a solid sample: M unit (formula (3)), D unit (formula (4)), T unit (formula (5)), and Q unit (formula (6)). M unit: (R i )(R j )(R k )SiO 1 / 2 Formula (3) D Unit: (R g )(R h )Si(O 1 / 2 ) 2Formula (4) T unit:R m Si(O 1 / 2 ) 3 Formula (5) Q unit: Si(O 1 / 2 ) 4 Formula (6) (R in Equations (3), (4), and (5) i , R j , R k , R g , R h , R m represents an alkyl group such as a hydrocarbon group having 1 to 6 carbon atoms bonded to silicon, a halogen atom, a hydroxyl group, an acetoxy group, an alkoxy group, or the like.

[0028] In the present disclosure, the silica fine particles A are surface-treated with a surface treatment agent that imparts a dimethylsiloxane structure, and the portion derived from the surface treatment agent is also referred to as "silica fine particles A." The silica fine particles A before surface treatment are also referred to as "silica fine particle substrate." The Q unit indicates a peak corresponding to the Si atoms in the silica fine particle substrate before surface treatment. The BET specific surface area of ​​the silica fine particles after surface treatment is defined as B(m 2 The M unit, D unit and T unit each show a peak corresponding to the structure of the surface treatment agent for the silica fine particles A represented by the above formulas (3) to (5). 29 They can be identified by the chemical shift values ​​in the Si-NMR spectrum. Q units appear at chemical shifts of -130 ppm to -85 ppm, T units at -65 ppm to -51 ppm, D units at -25 ppm to -15 ppm, and M units at 10 ppm to 25 ppm, and they can be quantified by their integral values.

[0029] Solid silica fine particles A 29 The area of ​​the peak of the D unit that has a peak top in the range of -25 ppm to -15 ppm in the chemical shift obtained by the Si-NMR DD / MAS method is defined as D. DD The sum of the areas of the peaks of M, D, T, and Q units present in the range of -140 ppm to 100 ppm is defined as S. DD The specific surface area of ​​the silica particles is B (m2 / g). In this case, (D DD / S DD ) to B (D DD / S DD ) / B is 4.70×10 -6 Above 1.40 x 10 -3 The following is the result.

[0030] (D DD / S DD ) / B means the amount of Si atoms per unit surface area constituting the D unit relative to the amount of Si atoms in the entire silica fine particle. Here, in the TOF-SIMS measurement, a fragment corresponding to the structure represented by the above formula (1) is observed, and the solid 29 In Si-NMR measurement, silica fine particles having a peak at the D unit indicate that they have been surface-treated with a compound that imparts a dimethylsiloxane structure.

[0031] That is, (D DD / S DD ) / B represents the amount of dimethylsiloxane on the surface of the silica particles per unit surface area. (D DD / S DD The smaller the ratio of (D) / B, the less the amount of dimethylsiloxane on the surface of the silica fine particles, and the less the fluidity of the external additive is hindered. However, it becomes difficult to control the amount of silanol on the surface of the silica fine particle substrate. DD / S DD The larger the ) / B, the greater the amount of dimethylsiloxane on the surface of the silica particles, which inhibits flowability as an external additive.

[0032] Specifically, (D DD / S DD ) / B is 4.70×10 -6 If the amount of the surface treatment agent relative to the silica particles is small, the amount of the surface treatment agent relative to the silica particles will be small. CP / S CP ) / B becomes difficult to control. DD / S DD ) / B is 1.40×10 -3 If the content exceeds 100%, the amount of dimethylsiloxane becomes excessive, and the toner fluidity decreases. DD / S DD) / B is 5.00 x 10 -6 Above 1.40 x 10 -3 Less than or equal to 5.00 x 10 is preferred -6 More than 6.70 x 10 -4 The following is more preferred:

[0033] (D DD / S DD ) / B can be controlled by adjusting the amount of the surface treatment agent used in the surface treatment of the silica fine particle substrate.

[0034] On the other hand, the solid of silica fine particles A 29 The area of ​​the peak of the D unit that has a peak top in the range of -25 ppm to -15 ppm in the chemical shift obtained by the Si-NMR CP / MAS method is D CP The sum of the areas of the peaks of M, D, T, and Q units present in the range of -140 ppm to 100 ppm is defined as S. CP The specific surface area of ​​the silica particles is B (m 2 / g). In this case, (D CP / S CP ) to B (D CP / S CP ) / B is 4.70×10 -4 Above 1.00 x 10 -2 The following is the result.

[0035] (D CP / S CP ) / B means the amount of Si atoms with low mobility per unit surface area constituting the D unit relative to the amount of Si atoms with low mobility in the silica fine particles. Here, in the TOF-SIMS measurement, a fragment corresponding to the structure represented by the above formula (1) is observed, and the solid 29 In Si-NMR CP / MAS measurements, silica particles with a peak at the D unit indicate that compounds with dimethylsiloxane structures are present on the surface in a state of low mobility, which is considered to mean that compounds with dimethylsiloxane structures are chemically or physically fixed to the surface of the silica particle substrate.

[0036] That is, (DCP / S CP ) / B represents the amount of dimethylsiloxane adhering to the surface of the silica fine particles per unit surface area. The present inventors believe that the dimethylsiloxane adhering to the surface of the silica fine particles is an important factor in the chargeability of the silica fine particles. DD / S DD ) / B includes dimethylsiloxane that adheres poorly to the surface of silica particles, in addition to the dimethylsiloxane that adheres poorly to the surface of silica particles. Dimethylsiloxane that adheres poorly to the surface of silica particles not only contributes little to charge control, but also has a large fluidity inhibiting effect. For this reason, we believe it is important to control the absolute amount and abundance ratio of dimethylsiloxane that adheres to the surface of silica particles, which has a relatively small fluidity inhibiting effect and a large contribution to charge control.

[0037] (D CP / S CP ) / B is 4.70×10 -4 If the surface treatment of the silica particles is below this value, a large number of silanol groups remain on the surface of the silica particle substrate, causing overcharging. CP / S CP ) / B is 1.00×10 -2 If the amount of dimethylsiloxane adhering to the surface of the silica fine particles is greater than 100%, the amount of silanol groups on the surface of the silica fine particle substrate will be too small, and the chargeability will decrease. CP / S CP ) / B is 4.70 x 10 -4 More than 9.80 x 10 -3 Less than or equal to 1.10×10 is preferable. -3 More than 9.80 x 10 -3 The following is more preferred:

[0038] (D CP / S CP ) / B can be controlled by adjusting the reaction time and temperature during the surface treatment of the silica fine particle substrate with a specific surface treatment agent. It can also be controlled by adjusting the amount of the surface treatment agent. DD / S DD) / B's control range is difficult to reconcile.

[0039] From the above findings, (D CP / S CP ) of (D DD / S DD It is important to control the ratio of (D CP / S CP ) / (D DD / S DD ) represents the ratio of dimethylsiloxane that is attached to the surface of the silica fine particles among the dimethylsiloxane present on the surface of the silica fine particles. Specifically, (D CP / S CP ) / (D DD / S DD ) is 3.00 or more 3.00 x 10 2 The following is the result. CP / S CP ) / (D DD / S DD By setting the above range, the amount of dimethylsiloxane that contributes to charge control can be made appropriate.

[0040] The effect of the present invention can be achieved only when the silica fine particles A, the surface state of which is controlled, are externally disposed on the toner surface having the above-mentioned BO bond, dodecylbenzenesulfonic acid or dodecylbenzenesulfonate.

[0041] [Preferable Configuration] A preferred configuration of the present invention will be described below.

[0042] In the toner of the present invention, the content (mass basis) of dodecylbenzenesulfonic acid or dodecylbenzenesulfonate is preferably 10 ppm or more and 1000 ppm or less relative to the toner. If it is 10 ppm or more, the adsorption action to the silanol group of the silica fine particles is sufficiently exerted, and overcharging can be suppressed, so this is preferable. More preferably, it is 20 ppm or more. On the other hand, although a compound such as dodecylbenzenesulfonic acid tends to affect the chargeability when contained in a large amount in the toner, if it is 1000 ppm or less, the desired chargeability can be obtained, so this is preferable. More preferably, it is 800 ppm or less.

[0043] The amount of boron atoms present in the toner of the present invention (mass basis) is preferably 0.1 ppm or more and 100 ppm or less, since the chargeability can be appropriately controlled. The amount of boron atoms in the toner can be measured by ICP-MS measurement, as described later. More preferably, the amount of boron atoms is 0.1 ppm or more and 25 ppm or less, even more preferably, the amount of boron atoms is 0.1 ppm or more and 10 ppm or less, and even more preferably, the amount of boron atoms is 0.1 ppm or more and 2.0 ppm or less.

[0044] The number-average particle diameter of the primary particles of the silica fine particles A is preferably 5 nm or more and 50 nm or less, and more preferably 5 nm or more and 15 nm or less. By externally adding the silica fine particles A having a particle diameter in this range to the toner particles, the charge rise property of the toner becomes good.

[0045] The content of the silica fine particles A is preferably 0.2 parts by mass or more and 3.0 parts by mass or less, more preferably 0.2 parts by mass or more and 2.0 parts by mass or less, and even more preferably 0.2 parts by mass or more and 1.5 parts by mass or less, relative to 100 parts by mass of the toner particles. By setting the content of the silica fine particles A in the above range, the charge rise property of the toner becomes good.

[0046] The BET specific surface area of ​​silica particle A is 15m 2 / g or more 300m 2 / g or less, and 2 / g or more 300m 2 / g or less is more preferable, and 20m 2 / g or more 280m 2 It is more preferable that the molecular weight is not more than 1 / g.

[0047] In the toner of the present invention, the amount of boron and (D CP / S CP The ratio of the amount of boron atoms present in the toner (mass basis) I / B is also an important factor. B [ppm], the content S of silica fine particles A in the toner A [Parts by mass], and (D CP / S CP It is preferable that the relationship of (a) / B satisfies the following formula (7). Equation (7) 2.6×10 -5 ≦{(D CP / S CP ) / B}×S A / I B ≦3.6×10 -3

[0048] When the charge amount is in the above range, the toner has excellent charge rising property and can solve the unevenness of density in the vertical direction. -4 More preferably, it is 4.3×10 -4 More preferably, the upper limit is 2.4×10 -3 More preferably, it is 2.0×10 -3 The following is the result.

[0049] In addition, the content (mass basis) of dodecylbenzenesulfonic acid or dodecylbenzenesulfonate salts D [ppm] and (D CP / S CP It is also preferable to adjust the ratio of the amount of dodecylbenzenesulfonic acid or dodecylbenzenesulfonate salt in the toner (mass basis) D [ppm] and the amount of silica fine particles A in the toner (mass basis) S [ppm]. A [Parts by mass], and (D CP / S CP It is preferable that the relationship of (a) / B satisfies the following formula (8). Equation (8) 7.7×10 3 ≦D / {(D CP / S CP ) / B}×S A ≦1.9×10 6

[0050] When the charge amount is in the above range, the toner has excellent charge rising property and can solve the unevenness in density in the vertical direction, which is preferable. More preferably, the charge amount is 1.5×10 4 More than 7.7 x 10 5 The following is the result.

[0051] The toner of the present invention preferably contains titanium compound particles B having a major axis of 300 nm to 3000 nm and an aspect ratio of 5.0 to 50.0. The titanium compound particles B are classified as external additives having a large particle size and low resistance, and have a needle-like structure. The use of titanium compound particles B is preferable because it suppresses overcharging in a low intermittent printing mode in a low humidity environment, suppresses toner deterioration during long-term use, and improves image density maintenance during long-term use. The content of the titanium compound particles B is preferably 0.1 parts by mass to 10 parts by mass relative to 100 parts by mass of toner particles.

[0052] As long as the above conditions are satisfied, there is no particular limitation on the titanium compound particles B. For example, titanium oxide easily satisfies the above conditions, and rutile-type titanium oxide is one of the preferred forms.

[0053] In the toner of the present invention, it is preferable to control the ratio of the amount of boron to the titanium compound particles B. Specifically, the amount of boron atoms present (based on mass) I B It is preferable that the relationship between the content T [ppm] of the titanium compound particles B and the content T [parts by mass] of the titanium compound particles B satisfies the following formula (9). Equation (9) 5.0×10 -2 ≦T / I B <=8.3

[0054] The above range is preferable because it is possible to solve unevenness in density in the vertical direction and maintain a high image density maintenance rate during long-term use, and more preferably, it is 0.5 or more and 5.0 or less.

[0055] In order to optimize the chargeability, it is also preferable to use titanium oxide (titanium compound particle C) that does not fall under the category of titanium compound particle B in addition to titanium compound particle B. The titanium compound particle C preferably has a particle size of 20 nm or more and 250 nm or less.

[0056] The toner of the present invention preferably has a polyester resin on the surface layer of the toner particles, because the polyester resin is likely to retain moisture in a low humidity environment, and, together with the presence of a BO bond, tends to suppress overcharging.

[0057] Furthermore, the surface layer made of the polyester resin preferably has a thickness of 300 nm to 700 nm. By having a thickness, the moisture can be sufficiently retained, and the overcharge suppression effect tends to be improved.

[0058] [Toner components and toner manufacturing method] Each component constituting the toner and the method for producing the toner will be described in more detail.

[0059] <Binding resin> The toner particles contain a binder resin, and the content of the binder resin is preferably 50% by mass or more of the total amount of the resin components in the toner particles.

[0060] The binder resin is not particularly limited, but examples thereof include styrene-acrylic resin, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, mixed resins or composite resins thereof. Styrene-acrylic resin and polyester resin are preferred because they are inexpensive, easily available, and have excellent low-temperature fixing properties. Polyester resin is more preferred.

[0061] The polyester resin can be obtained by selecting and combining suitable polycarboxylic acids, polyols, hydroxycarboxylic acids, etc., and synthesizing them using a known method such as an ester exchange method or a polycondensation method. Preferably, the polyester resin contains a condensation polymer of a dicarboxylic acid and a diol.

[0062] Polycarboxylic acids are compounds containing two or more carboxy groups in one molecule. Among them, dicarboxylic acids are compounds containing two carboxy groups in one molecule and are preferably used.

[0063] Examples of the acid include oxalic acid, succinic acid, glutaric acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, suberic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, o-phenylenediacetic acid, diphenylacetic acid, diphenyl-p,p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracenedicarboxylic acid, and cyclohexanedicarboxylic acid.

[0064] Examples of polyvalent carboxylic acids other than the dicarboxylic acids include trimellitic acid, trimesic acid, pyromellitic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, pyrene tricarboxylic acid, pyrene tetracarboxylic acid, itaconic acid, glutaconic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, etc. These may be used alone or in combination of two or more.

[0065] A polyol is a compound containing two or more hydroxyl groups in one molecule. Among them, a diol is a compound containing two hydroxyl groups in one molecule, and is preferably used.

[0066] Specifically, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, and 1,14-eicosanediol. Examples of bisphenols include dimethyl ether glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-butenediol, neopentyl glycol, polytetramethylene glycol, hydrogenated bisphenol A, bisphenol A, bisphenol F, bisphenol S, and alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols.

[0067] Among these, preferred are alkylene glycols having from 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and their combined use with alkylene glycols having from 2 to 12 carbon atoms. Examples of alkylene oxide adducts of bisphenol A include the compounds represented by the following formula (A).

[0068] [ka] (In formula (A), each R is independently an ethylene or propylene group, each of x and y is an integer of 0 or more, and the average value of x+y is 0 or more and 10 or less.)

[0069] The alkylene oxide adduct of bisphenol A is preferably a propylene oxide adduct and / or an ethylene oxide adduct of bisphenol A. More preferably, it is a propylene oxide adduct. The average value of x+y is preferably 1 or more and 5 or less.

[0070] Examples of trihydric or higher alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, hexamethylolmelamine, hexaethylolmelamine, tetramethylolbenzoguanamine, tetraethylolbenzoguanamine, sorbitol, trisphenol PA, phenol novolac, cresol novolac, alkylene oxide adducts of the above trihydric or higher polyphenols, etc. These may be used alone or in combination of two or more.

[0071] Examples of the styrene-acrylic resin include homopolymers made of the following polymerizable monomers, copolymers obtained by combining two or more of these, and mixtures thereof.

[0072] Styrenic monomers such as styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene and p-phenylstyrene; (Meth)acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dimethyl phosphate ethyl (meth)acrylate, diethyl phosphate ethyl (meth)acrylate, dibutyl phosphate ethyl (meth)acrylate and 2-benzoyloxyethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid, maleic acid; Vinyl ether monomers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketone monomers such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; Polyolefins such as ethylene, propylene, and butadiene.

[0073] The styrene acrylic resin may use a polyfunctional polymerizable monomer as required. Examples of the polyfunctional polymerizable monomer include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2,2'-bis(4-((meth)acryloxydiethoxy)phenyl)propane, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

[0074] In order to control the degree of polymerization, it is also possible to further add a known chain transfer agent and a polymerization inhibitor. Examples of the polymerization initiator for obtaining the styrene-acrylic resin include organic peroxide-based initiators and azo-based polymerization initiators.

[0075] Examples of the organic peroxide initiator include benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, bis(4-t-butylcyclohexyl)peroxydicarbonate, 1,1-bis(t-butylperoxy)cyclododecane, t-butylperoxymaleic acid, bis(t-butylperoxy)isophthalate, methyl ethyl ketone peroxide, tert-butylperoxy-2-ethylhexanoate, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and tert-butylperoxypivalate.

[0076] Examples of the azo polymerization initiator include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobismethylbutyronitrile, and 2,2'-azobis-(methyl isobutyrate).

[0077] Furthermore, a redox initiator, which is a combination of an oxidizing substance and a reducing substance, can also be used as the polymerization initiator.

[0078] Oxidizing substances include inorganic peroxides such as hydrogen peroxide, persulfates (sodium, potassium and ammonium salts) and oxidizing metal salts such as tetravalent cerium salts.

[0079] Examples of reducing substances include reducing metal salts (divalent iron salts, monovalent copper salts, and trivalent chromium salts), ammonia, lower amines (amines having from 1 to 6 carbon atoms, such as methylamine and ethylamine), amino compounds such as hydroxylamine, reducing sulfur compounds such as sodium thiosulfate, sodium hydrosulfite, sodium hydrogensulfite, sodium sulfite, and sodium formaldehyde sulfoxylate, lower alcohols (having from 1 to 6 carbon atoms), ascorbic acid or a salt thereof, and lower aldehydes (having from 1 to 6 carbon atoms).

[0080] The polymerization initiator is selected with reference to its 10-hour half-life temperature and is used alone or in combination. The amount of polymerization initiator added varies depending on the desired degree of polymerization, but is generally 0.5 to 20.0 parts by mass per 100.0 parts by mass of polymerizable monomer.

[0081] In the toner of the present invention, a configuration in which the binder resin is a styrene acrylic resin and the shell layer is a polyester resin is preferable because it has excellent charge rise properties.

[0082] <Release agent> The toner may contain a known wax as a releasing agent.

[0083] Specific examples include petroleum waxes and derivatives thereof, such as paraffin wax, microcrystalline wax, and petrolatum, montan wax and derivatives thereof, hydrocarbon waxes produced by the Fischer-Tropsch process and derivatives thereof, polyolefin waxes and derivatives thereof, such as polyethylene, natural waxes and derivatives thereof, such as carnauba wax and candelilla wax, and derivatives thereof. Derivatives also include oxides, block copolymers with vinyl monomers, and graft modified products.

[0084] Other examples include alcohols such as higher aliphatic alcohols, fatty acids such as stearic acid and palmitic acid or their acid amides, esters and ketones, hydrogenated castor oil and its derivatives, vegetable waxes and animal waxes. These can be used alone or in combination.

[0085] Among these, polyolefin, Fischer-Tropsch hydrocarbon wax, or petroleum wax is preferably used since it tends to improve the developability and transferability. An antioxidant may be added to these waxes within a range that does not affect the effects of the toner. In addition, from the viewpoint of phase separation with respect to the binder resin or crystallization temperature, higher fatty acid esters such as behenyl behenate and dibehenyl sebacate are suitable examples.

[0086] The content of the release agent is preferably 1.0 part by mass or more and 30.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

[0087] The melting point of the release agent is preferably from 30° C. to 120° C., and more preferably from 60° C. to 100° C. By using a release agent having the above-mentioned thermal characteristics, the release effect is efficiently exerted and a wider fixing area is secured.

[0088] <Plasticizer> The toner particles may contain a crystalline plasticizer in order to improve sharp melting properties. The plasticizer is not particularly limited, and any of the known plasticizers used in toners such as those described below can be used.

[0089] Specifically, the esters include esters of monohydric alcohols and aliphatic carboxylic acids, such as behenyl behenate, stearyl stearate, and palmityl palmitate, or esters of monohydric carboxylic acids and aliphatic alcohols; esters of dihydric alcohols and aliphatic carboxylic acids, such as ethylene glycol distearate, dibehenyl sebacate, and hexanediol dibehenate, or esters of dihydric carboxylic acids and aliphatic alcohols; esters of trihydric alcohols and aliphatic carboxylic acids, such as glycerin tribehenate, or esters of trihydric carboxylic acids and aliphatic alcohols; and pentaerythritol tetrastearate. esters of tetrahydric alcohols and aliphatic carboxylic acids, such as stearate and pentaerythritol tetrapalmitate, or esters of tetrahydric carboxylic acids and aliphatic alcohols; esters of hexahydric alcohols and aliphatic carboxylic acids, such as dipentaerythritol hexastearate and dipentaerythritol hexapalmitate, or esters of hexahydric carboxylic acids and aliphatic alcohols; esters of polyhydric alcohols and aliphatic carboxylic acids, such as polyglycerin behenate, or esters of polyhydric carboxylic acids and aliphatic alcohols; natural ester waxes, such as carnauba wax and rice wax. These may be used alone or in combination.

[0090] <Coloring agent> The toner particles may contain a colorant. Known pigments and dyes can be used as the colorant. Pigments are preferred as the colorant because they have excellent weather resistance.

[0091] Cyan colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specific examples include the following: CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66.

[0092] Magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254, and CI Pigment Violet 19.

[0093] Yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following: CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185, 191, and 194.

[0094] Examples of black colorants include those toned to black using the above yellow, magenta and cyan colorants, as well as carbon black and magnetic materials.

[0095] These colorants can be used alone or in mixture, or in the form of a solid solution. The colorant is preferably used in an amount of 1.0 to 20.0 parts by mass per 100.0 parts by mass of the binder resin. When using a magnetic material and applying the manufacturing method in an aqueous medium described below, a hydrophobic treatment can be performed in order to stably contain the magnetic material in the resin. The use of a magnetic material is preferable from the viewpoint of improving the durability of the toner particles.

[0096] <Charge control agents and charge control resins> The toner particles may contain a charge control agent or a charge control resin. Any known charge control agent can be used as the charge control agent, and a charge control agent that has a high triboelectric charging speed and can stably maintain a constant triboelectric charge amount is particularly preferred. Furthermore, when the toner particles are produced by a suspension polymerization method, a charge control agent that has low polymerization inhibition and is substantially free of solubilized matter in an aqueous medium is particularly preferred.

[0097] Examples of toners that control the toner to be negatively charged include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic and dicarboxylic acid-based metal compounds, aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, calixarenes, and charge control resins.

[0098] The charge control resin may be a polymer or copolymer having a sulfonic acid group, a sulfonate group, or a sulfonate ester group. As the polymer having a sulfonic acid group, a sulfonate group, or a sulfonate ester group, a polymer containing a sulfonic acid group-containing acrylamide monomer or a sulfonate group-containing methacrylamide monomer in a copolymerization ratio of 2% by mass or more is preferable, and a polymer containing a sulfonic acid group-containing methacrylamide monomer in a copolymerization ratio of 5% by mass or more is more preferable.

[0099] The charge control resin preferably has a glass transition temperature (Tg) of 35° C. or more and 90° C. or less, a peak molecular weight (Mp) of 10,000 or more and 30,000 or less, and a weight average molecular weight (Mw) of 25,000 or more and 50,000 or less. When used, it is possible to impart preferable triboelectric charging characteristics without affecting the thermal characteristics required for the toner particles. Furthermore, when the charge control resin contains a sulfonic acid group, for example, the dispersibility of the charge control resin itself in the polymerizable monomer composition and the dispersibility of the colorant are improved, and the coloring power, transparency, and triboelectric charging characteristics can be further improved.

[0100] These charge control agents or charge control resins may be added alone or in combination of two or more. The amount of the charge control agent or charge control resin added is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, more preferably 0.5 parts by mass or more and 10.0 parts by mass or less, relative to 100.0 parts by mass of the binder resin.

[0101] <Toner manufacturing method> The method for producing the toner is not particularly limited, and any known method such as a pulverization method, a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, a dispersion polymerization method, etc. Any manufacturing method can be applied to obtain the toner of the present invention.

[0102] To obtain a structure having a BO bond on the toner surface, a compound having a BO bond can be used and oriented on the surface in an aqueous medium, or attached to the toner particles in an external addition process described below. Any compound can be used as the compound having a BO bond, but boric acid compounds are preferred because they are easy to handle. Examples of boric acid compounds include sodium tetraborate, borax, and ammonium borate.

[0103] In order to arrange dodecylbenzenesulfonic acid or a dodecylbenzenesulfonate on the toner surface, the compound may be added. In order to quantitatively control the content of the dodecylbenzenesulfonic acid structure, it may be possible to add the compound in an external addition step, which will be described later, after the production of the toner particles. As the dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate may be preferably used.

[0104] <External addition process> In the external addition step, silica fine particles treated with a treatment agent that imparts a dimethylsiloxane structure to the toner particles and other external additives are added thereto.

[0105] Examples of the treatment agent for imparting a dimethylsiloxane structure to the surface of silica fine particles include chlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, t-butyldimethylchlorosilane, and vinyltrichlorosilane; Examples of the siloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, and octamethyltrisiloxane.

[0106] Among these, dimethyldichlorosilane and octamethylcyclotetrasiloxane are preferably used since they facilitate the attainment of the surface state of the silica fine particles of the present invention. Dimethyldichlorosilane is particularly preferred since it facilitates the control of the amount of silanol groups on the surface of the silica fine particle substrate.

[0107] Specific examples of other external additives include inorganic fine particles other than silica, and resin fine particles such as vinyl resin, polyester resin, silicone resin, etc. These external additives are preferably added by applying a shear force in a dry state, for example.

[0108] As described above, it is preferable to contain titanium compound particles B having a major axis of 300 nm or more and 3000 nm or less and an aspect ratio of 5.0 or more and 50.0 or less. Furthermore, it is also preferable to use titanium oxide (titanium compound particles C) that does not fall under the category of titanium compound particles B in addition to titanium compound particles B.

[0109] [Methods for measuring each physical property] Next, the methods for measuring the various physical properties according to the present invention will be described.

[0110] <Measuring method for fragment peaks derived from boron atoms and BO structures> The detection of fragment peaks originating from boron atoms and BO structures in the toner was carried out by using TOF-SIMS.

[0111] To measure the fragment ions on the toner surface using TOF-SIMS, TRIFT-IV manufactured by ULVAC-PHI, Inc. The analysis conditions are as follows: Sample preparation: Depositing toner particles onto an indium sheet Primary ion: Au ion Acceleration voltage: 30 kV Charge neutralization mode: On Measurement mode: Positive Raster: 200μm Measurement time: 60s

[0112] From the obtained mass profile of secondary ion mass / secondary ion charge number (m / z), it is confirmed whether or not fragment ions derived from boron atoms are observed. In the present invention, the presence or absence of a BO bond is judged based on the presence or absence of a mass profile of BO2, taking into account the balance of peak intensity.

[0113] <Determining the presence of dodecylbenzenesulfonic acid or dodecylbenzenesulfonate salts in toner> The presence or absence of dodecylbenzenesulfonic acid or dodecylbenzenesulfonate salts is determined by analysis using the MS / MS (mass-mass spectrometry) method with a tandem mass spectrometer directly connected to a liquid chromatograph ESI / MS analyzer.

[0114] The MS / MS method is a mass spectrometry technique that allows the detection of fragments with smaller molecular weights by measuring fragments extracted in a first analytical system using a second analytical system, making it easy to perform structural analysis of a sample.

[0115] Dissolution condition A: At 25° C., 10 times the mass of the toner is used in methanol (JIS K8891 equivalent), and the toner is stirred for 10 hours at a rotor speed of 200 rpm using a stirring device. Centrifugation condition A: Rotation is performed for 30 minutes at 25° C., a rotation radius of 10.1 cm, and a rotation speed of 3,500 rpm. The sample is prepared by using a toner under the above-mentioned elution condition A, and then separated into a solid content and a supernatant liquid under the above-mentioned centrifugation condition A.

[0116] The supernatant obtained by the above adjustment is supplied to the measuring device described below, and liquid chromatograph ESI / MS analysis is performed under the analytical condition B described below. A mass spectrometry spectrum of the anions is obtained, and it is confirmed that a peak is detected at m / z=325. In addition, the ion detected as a peak at m / z=325 is supplied as a precursor ion to a tandem mass spectrometer, and an MS / MS spectrum is obtained under the analytical condition B. Measurement device: Ultimate3000 (Thermo Fisher Scientific) Mass spectrometer: LCQ Fleet (manufactured by Thermo Fisher Scientific) Analysis condition B: Under the following conditions, the ionized material is detected as anion under the capillary voltage: -35 V, tube lens voltage: -110 V, and the ion detected at m / z = 325 is selected as a precursor ion, and the ion that is collision-induced dissociated in an inert gas: He with a collision energy of 35 eV is detected. Ionization method: Electrospray Ionization (ESI) Sheath Gas: 10 (arb. unit.) Aux Gas: 5 (arb. unit.) Spray voltage: 5kV Capillary temperature: 275℃ Mobile phase: Methanol (JISK8891 standard equivalent) Column: Not used (no stationary phase) Flow rate: 1ml / min Injection volume: 10μl Chromatogram detector: UV detector MS acquisition time: 5min MS measurement range: 50-1500 m / z Collision inert gas: He (helium) Collision energy: 35 eV

[0117] <Quantitative Determination of Dodecylbenzenesulfonic Acid or Dodecylbenzenesulfonate in Toner> The amount of dodecylbenzenesulfonic acid or dodecylbenzenesulfonate in the toner is determined by subjecting the methanol extract in the toner to LC / MS measurement under the following conditions: A calibration curve is created using sodium dodecylbenzenesulfonate as a standard, and then the amount is determined. (LC / MS analysis conditions) Model: Agilent 6130Quadropole LC / MS (Agilent Technologies) Eluent: Methanol Column: ZORBAX Eclipse Plus C18 (1.8 μm, 100 × 4.6 mm I.D.) (Agilent Technologies) Flow rate: 1.0mL / min Column temperature: 30℃

[0118] <Measurement of the amount of boron atoms present in toner> The content of boron atoms on the surface of the toner particles is measured by an inductively coupled plasma mass spectrometer (ICP-MS (manufactured by Agilent Technologies)).

[0119] For pretreatment, a 6.0 mol / L aqueous solution of nitric acid is prepared using 60% nitric acid (Kanto Chemical, Ultrapur standard) and ultrapure water. 5.00 g of 6.0 mol / L nitric acid is added to 50.0 mg of toner and stirred to prepare a toner-containing solution sample. After leaving it for 120 minutes, it is filtered using filter paper with a pore size of 1 μm to prepare a toner cake, and then 10.00 g of ultrapure water is added to the toner cake as washing water to separate the toner from the toner-containing solution sample. Ultrapure water is added to the filtrate solution sample until the total weight becomes 50.00 g to prepare a solution sample for boron atom measurement.

[0120] As a blank solution sample, ultrapure water was added to 5.00 g of 6.0 mol / L nitric acid aqueous solution to make a total of 50.00 g, and a solution sample with a known boron atom content was prepared, and a calibration curve was created. The boron atom content on the toner surface was measured by quantifying the boron atoms contained in the boron atom measurement sample.

[0121] <Silica fine particle solid 29 Si-NMR DD / MAS and CP / MAS measurements (D DD / S DD ) / B, (D CP / S CP ) / B, (D CP / S CP ) / (D DD / S DD ) Calculation method> Silica fine particle solid 29 The Si-NMR measurement is performed by separating the silica particles from the toner surface. 29 The Si-NMR measurements are described.

[0122] (Method for separating silica fine particles from toner surface) When the silica fine particles separated from the surface of the toner are used as a measurement sample, the silica fine particles are separated from the toner by the following procedure.

[0123] Add 1.6 kg of sucrose (Kishida Chemical) to 1 L of ion-exchanged water and dissolve it in a hot water bath to prepare a concentrated sucrose solution. Place 31 g of the concentrated sucrose solution and 6 mL of Contaminon N (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) in a centrifuge tube to prepare a dispersion. Add 10 g of toner to this dispersion, and break up the toner clumps with a spatula or the like.

[0124] The centrifuge tube is placed in an Iwaki Sangyo KM Shaker (model: V.SX) and shaken for 20 minutes at 350 reciprocations per minute. After shaking, the solution is transferred to a glass tube (50 mL) for a swing rotor and centrifuged at 3,500 rpm for 30 minutes.

[0125] After centrifugation, the toner particles are present in the top layer in the glass tube, and the inorganic fine particle mixture containing silica fine particles is present in the lower aqueous solution. The upper and lower aqueous solutions are separated and dried, and the toner particles are obtained from the upper layer and the inorganic fine particle mixture is obtained from the lower layer. The obtained toner particles are used to measure the abundance ratio of the structure of formula (9) described below. The above centrifugation process is repeated until the amount of inorganic fine particle mixture obtained from the lower layer is 10 g or more in total.

[0126] Next, 10 g of the obtained inorganic fine particle mixture is dispersed in a dispersion liquid containing 100 mL of ion-exchanged water and 6 mL of Contaminon N. The obtained dispersion liquid is transferred to a glass tube (50 mL) for a swing rotor, and centrifuged in a centrifuge at 3500 rpm for 30 minutes.

[0127] After centrifugation, the silica particles are present in the top layer of the glass tube, and other inorganic particles are present in the aqueous solution in the lower layer. The aqueous solution in the upper layer is collected and centrifuged repeatedly as necessary. After sufficient separation, the dispersion is dried and the silica particles are collected.

[0128] Next, the solid silica particles recovered from the toner particles are 29 The Si-NMR measurement is carried out under the measurement conditions shown below.

[0129] (solid 29 DD / MAS measurement conditions for Si-NMR measurement) solid 29 The DD / MAS measurement conditions for Si-NMR measurement are as follows: Equipment: JNM-ECX5002 (JEOL RESONANCE) Temperature: room temperature Measurement method: DD / MAS method 29 Si 45° Sample tube: Zirconia 3.2mmφ Sample: Powdered material filled into test tube Sample rotation speed: 10kHz Delay time: 180s Accumulation count: 2000 Calibration standard: DSS (sodium 3-(trimethylsilyl)-1-propanesulfonate)

[0130] After the above measurements, the solid 29 From the Si-NMR spectrum, multiple silane components having different substituents and bonding groups are separated into the following peaks of M units, D units, T units, and Q units by curve fitting.

[0131] Curve fitting is performed using EXcalibur for Windows (registered trademark) version 4.2 (EX series), software for JNM-EX400 manufactured by JEOL Ltd. Click "1D Pro" from the menu icon to load the measurement data. Next, select "Curve fitting function" from "Command" on the menu bar to perform curve fitting. Curve fitting is performed for each component so that the difference (composite peak difference) between the composite peak obtained by combining the peaks obtained by curve fitting and the peak of the measurement result is minimized. M unit: (R i )(R j )(R k )SiO 1 / 2 Formula (3) D Unit: (R g )(R h )Si(O 1 / 2 ) 2 Formula (4) T unit:R m Si(O 1 / 2 ) 3 Formula (5) Q unit: Si(O 1 / 2 ) 4 Formula (6) (R in Equations (3), (4), and (5) i , R j , R k , R g , R h , R m represents an alkyl group such as a hydrocarbon group having 1 to 6 carbon atoms bonded to silicon, a halogen atom, a hydroxyl group, an acetoxy group, an alkoxy group, or the like.

[0132] After peak separation, the integral value D of the D unit that exists in the chemical shift range of -25ppm to -15ppm DD and the sum of all integral values ​​of M, D, T, and Q units in the range of -140ppm to 100ppm, S DD The BET specific surface area B (m 2 / g) and calculate the ratio (D DD / S DD ) / B.

[0133] (solid 29 CP / MAS measurement conditions for Si-NMR measurement) solid 29 The CP / MAS measurement conditions for Si-NMR measurement are as follows: Equipment: JNM-ECX5002 (JEOL RESONANCE) Temperature: room temperature Measurement method: CP / MAS method 29 Si 45° Sample tube: Zirconia 3.2mmφ Sample: Powdered material filled into test tube Sample rotation speed: 10kHz Delay time: 5s Accumulation count: 12000 Contact time: 10 ms Calibration standard: DSS (sodium 3-(trimethylsilyl)-1-propanesulfonate) After the above measurements, the solid 29 From the Si-NMR spectrum, a plurality of silane components having different substituents and bonding groups are subjected to peak separation into the above-mentioned M units, D units, T units, and Q units by curve fitting in the same manner as above.

[0134] After peak separation, the integral value D of the D unit that exists in the chemical shift range of -25ppm to -15ppm CP and the sum of all integral values ​​of M, D, T, and Q units in the range of -140ppm to 100ppm, S CP The BET specific surface area B (m 2 / g) and calculate the ratio (D CP / S CP ) / B.

[0135] <Measuring method for fragment ions on the surface of silica fine particles using time-of-flight secondary ion mass spectrometry (TOF-SIMS)> The TOF-SIMS measurement of the silica fine particles is performed using the silica fine particles separated from the toner by the above-mentioned method for separating the silica fine particles from the toner surface.

[0136] To measure fragment ions on the surface of silica particles using TOF-SIMS, TRIFT-IV manufactured by ULVAC-PHI, Inc. is used.

[0137] The analysis conditions are as follows. Sample preparation: Attaching silica particles to an indium sheet Primary ion: Au ion Acceleration voltage: 30 kV Charge neutralization mode: On Measurement mode: Positive Raster: 200μm Measurement time: 60s

[0138] From the obtained mass profile of secondary ion mass / secondary ion charge number (m / z), it is confirmed whether fragment ions corresponding to the structure shown in formula (1) are observed. For example, if the surface treatment agent is polydimethylsiloxane or cyclic siloxane, fragment ions are observed at positions such as m / z = 147, 207, and 221.

[0139] <Method for measuring the BET specific surface area of ​​silica particles> The BET specific surface area of ​​silica microparticles is measured using the following procedure. The measurement device used is the "Automatic Specific Surface Area / Porosity Distribution Measurement Device TriStar3000 (Shimadzu Corporation)," which uses the constant volume gas adsorption method as its measurement method. The measurement conditions are set and the measurement data is analyzed using the dedicated software "TriStar3000 Version 4.00" that comes with the device. In addition, a vacuum pump, nitrogen gas piping, and helium gas piping are connected to the device. Nitrogen gas is used as the adsorption gas, and the value calculated by the BET multipoint method is taken as the BET specific surface area.

[0140] The BET specific surface area is calculated as follows. First, nitrogen gas is adsorbed onto the silica fine particles, and the equilibrium pressure P (P a ) and the nitrogen adsorption amount of the magnetic material V a (mol g -1 ) is measured. Then, the equilibrium pressure P(P a ) to the saturated vapor pressure of nitrogen P o (P a ) is the relative pressure P r The horizontal axis is the nitrogen adsorption amount V a (mol g -1 Next, the amount of monolayer adsorption V, which is the amount of adsorption required to form a monolayer on the surface of the silica fine particles, is obtained. m (mol g -1 ) is calculated by applying the BET formula below. P r / V a (1-P r )=1 / (V m ×C)+(C-1)×P r / (V m ×C) (Here, C is the BET parameter, which varies depending on the type of sample to be measured, the type of adsorbed gas, and the adsorption temperature.)

[0141] The BET formula is to set the X axis to P r , Y axis is P r / V a (1-P r ), then the slope is (C-1) / (V m ×C), with the intercept being 1 / (Vm × C) (This straight line is called the BET plot).

[0142] Slope of the line = (C-1) / (V m ×C) Line intercept = 1 / (V m ×C) P r The measured value of and P r / V a (1-P r ) on a graph and draw a line using the least squares method to calculate the slope and intercept of the line. Using these values ​​to solve the above simultaneous equations for the slope and intercept, we get V m and C can be calculated. Furthermore, the V calculated above m and the molecular occupancy cross section of the nitrogen molecule (0.162 nm 2 ) and the BET specific surface area S (m 2 / g) is calculated. S=V m ×N×0.162×10 -18 (Here, N is Avogadro's number (mol -1 )

[0143] Specifically, measurements using this device are performed in the following procedure.

[0144] Accurately weigh the tared weight of a dedicated glass sample cell (stem diameter 3 / 8 inch, volume 5 mL) that has been thoroughly washed and dried. Then, use a funnel to place 0.1 g of silica particles into this sample cell. Place the sample cell containing the silica particles in a "pretreatment device VacuPrep 061 (Shimadzu Corporation)" connected to a vacuum pump and nitrogen gas piping, and continue vacuum degassing at 23°C for 10 hours.

[0145] During vacuum degassing, the valve is adjusted to gradually degas the silica particles so that they are not sucked into the vacuum pump. The pressure inside the cell gradually decreases as the cell is degassed, eventually reaching 0.4 Pa (approximately 3 mTorr).

[0146] After the vacuum degassing is completed, nitrogen gas is gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell is removed from the pretreatment device. The mass of this sample cell is then precisely weighed, and the exact mass of the silica particles is calculated from the difference with the tare weight. During this weighing, the sample cell is covered with a rubber stopper to prevent the silica particles in the sample cell from being contaminated by moisture in the air.

[0147] Next, a special isothermal jacket is attached to the sample cell containing the silica particles. A special filler rod is inserted into the sample cell, and the sample cell is set in the analysis port of the device. The isothermal jacket is a cylindrical member with a porous inner surface and an impermeable outer surface that can suck up liquid nitrogen to a certain level by capillary action.

[0148] Next, the free space of the sample cell including the connecting device is measured. The free space is calculated by measuring the volume of the sample cell at 23°C using helium gas, then measuring the volume of the sample cell after cooling it with liquid nitrogen in the same manner using helium gas, and converting it from the difference between these volumes. In addition, the saturated vapor pressure P o (P a ) is the P o A separate automated measurement is performed using a tube.

[0149] Next, the inside of the sample cell is evacuated and then cooled with liquid nitrogen while continuing the vacuum evacuation. Nitrogen gas is then gradually introduced into the sample cell to adsorb nitrogen molecules onto the silica particles. At this time, the equilibrium pressure P(P a ) is measured at regular intervals to obtain an adsorption isotherm, which is then converted into a BET plot.

[0150] The relative pressure P r The points are set to 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30, for a total of six points. A straight line is drawn using the least squares method for the obtained measurement data, and V is calculated from the slope and intercept of the straight line. m Calculate this Vm Using this value, the BET specific surface area of ​​the silica fine particles is calculated as described above.

[0151] <Method for measuring the Si-OH content of silica particles> The Si-OH amount of the silica fine particles can be determined by the following method using the silica fine particles separated from the toner by the above-mentioned method for separating the silica fine particles from the toner surface.

[0152] Mix 25.0 g of ethanol and 75.0 g of 20% by mass sodium chloride aqueous solution to prepare sample solution 1. Also, weigh out 2.00 g of silica microparticles into a glass bottle and add a mixed solvent of 25.0 g of ethanol and 75.0 g of 20% by mass sodium chloride aqueous solution to prepare sample solution 2. Stir sample solution 2 with a magnetic stirrer for 5 minutes or more to disperse the silica microparticles.

[0153] Next, for each of sample solutions 1 and 2, measure the pH change of the sample solution while dropping 0.1 mol / L sodium hydroxide solution at 0.01 mL / min. Record the titer (L) of the sodium hydroxide solution when the pH reaches 9.0. 2 Amount of Si-OH per Sn (pieces / nm 2 ) can be calculated. Sn = {(ab) × c × NA} / (d × e) a: NaOH titration amount (L) of sample solution 2 b: NaOH titration amount (L) of sample solution 1 c: Concentration of the NaOH solution used in the titration (mol / L) NA: Avogadro's number d: Mass of silica particles (g) e: BET specific surface area of ​​silica particles (nm 2 / g: specific surface area (m 2 / g)

[0154] <Method for measuring the number-average particle size of primary particles of silica fine particles A> The number-average particle diameter of the silica fine particles is measured from a secondary electron image obtained by observing the toner surface with a scanning electron microscope (SEM).

[0155] (Method of Obtaining Secondary Electron Image of Toner) Equipment used: Carl Zeiss Microscopy ULTRA PLUS Acceleration voltage: 1.0 kV WD: 2.5mm Aperture Size: 30.0μm Detection signal: SE2 (secondary electrons) Magnification: 50,000x Resolution: 1024 x 768 pixels Pretreatment: Toner is scattered on carbon tape (Pt deposition is not performed)

[0156] From the obtained secondary electron image, the longest diameter of 100 primary particles of the silica fine particles on the surface of the toner particle is measured, and the arithmetic average value is taken as the number average particle diameter of the silica fine particles.

[0157] The silica fine particles and the titanium compound particles are distinguished by element mapping using SEM-EDX.

[0158] <Identification of titanium compound particles B in toner> The major axis (maximum diameter) and aspect ratio of titanium compound particles B are measured using a scanning electron microscope (for example, scanning electron microscope "S-4800" (product name; manufactured by Hitachi, Ltd.)). In a field of view magnified up to 50,000 times, only external additives with major axes of 300 nm to 3000 nm were selected and observed, and the major axis and minor axis of primary particles of 100 external additives were measured and calculated at random. Those with an aspect ratio of 5.00 to 50.0 were defined as titanium compound particles B (external additive B). The aspect ratio was calculated by dividing the major axis by the minor axis.

[0159] <Identification of titanium compound particles C in toner> The major axis (maximum diameter) of the titanium compound particles C was measured using a scanning electron microscope (e.g., scanning electron microscope "S-4800" (product name; manufactured by Hitachi, Ltd.)). Only external additives with major axes of 20 nm to 250 nm were selected and observed in a field of view magnified up to 50,000 times, and the major axes of the primary particles of 100 external additives were measured at random.

[0160] Furthermore, by combining elemental analysis using energy dispersive X-ray spectrometry (EDS), it is possible to determine whether or not the substance is titanium oxide.

[0161] Using a scanning electron microscope "S-4800" (product name; manufactured by Hitachi), the toner is observed at a maximum magnification of 50,000 times. The focus is set on the surface of the toner particles, and the external additive to be identified is observed. An EDS analysis is performed on the external additive to be identified, and it is possible to determine whether it is titanium oxide or not from the element peak.

[0162] <Measurement of weight average particle size (D4) of toner or toner particles> The weight-average particle size (D4) of the toner or toner particles is measured with an effective measurement channel count of 25,000 channels using a precision particle size distribution measuring device using a pore electrical resistance method equipped with a 100 μm aperture tube, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), and the accompanying dedicated software for setting measurement conditions and analyzing measurement data, "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.), and the measurement data is analyzed and calculated.

[0163] The electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter).

[0164] Before carrying out the measurements and analyses, the dedicated software is set up as follows.

[0165] In the "Change Standard Measurement Method (SOM) screen" of the dedicated software, set the total count number in the control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. In addition, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the aperture tube flush after measurement.

[0166] In the "Pulse to particle size conversion setting screen" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm to 60 μm.

[0167] The specific measurement method is as follows. (1) Pour about 200 ml of the electrolyte solution into a 250 ml round-bottom glass beaker made exclusively for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, remove dirt and air bubbles from inside the aperture tube using the "Aperture Tube Flush" function of the dedicated software. (2) Approximately 30 ml of the above-mentioned aqueous electrolyte solution is placed in a 100 ml flat-bottom glass beaker, and approximately 0.3 ml of a solution prepared by diluting "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, with a pH of 7, manufactured by Wako Pure Chemical Industries, Ltd.) three times by weight with ion-exchanged water is added as a dispersant. (3) A predetermined amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.) that has two oscillators with an oscillation frequency of 50 kHz built in with a phase shift of 180 degrees and an electrical output of 120 W, and approximately 2 ml of the Conaminon N is added to this water tank. (4) The beaker (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolyte solution in the beaker is maximized. (5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, about 10 mg of toner or toner particles is added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10°C or higher and 40°C or lower. (6) Using a pipette, add the electrolytic solution (5) in which the toner or toner particles are dispersed to the round-bottom beaker (1) placed in the sample stand, and adjust the measurement concentration to about 5%. Then, measurements are continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software that comes with the device, and the weight-average particle size (D4) is calculated. Note that when the dedicated software is set to Graph / Volume%, the "Average diameter" on the Analysis / Volume Statistics (Arithmetic Mean) screen is the weight-average particle size (D4).

[0168] [Configuration included in the embodiment of the present invention] The disclosure of this embodiment includes the following configuration. (Configuration 1) A toner having toner particles containing a binder resin and silica fine particles A, (I) in a TOF-SIMS measurement of the toner particles, a fragment peak derived from a boron atom and a fragment peak derived from a boron-oxygen structure are detected, the toner contains at least one selected from the group consisting of dodecylbenzenesulfonic acid and dodecylbenzenesulfonate salts, (II) In a TOF-SIMS measurement of the silica fine particles A, fragment ions corresponding to the structure represented by the above formula (1) are observed, When 2.00 g of the silica fine particles were dispersed in a mixture of 25.0 g of ethanol and 75.0 g of a 20% by mass NaCl aqueous solution and titrated with sodium hydroxide, Sn defined as Sn={(ab)×c×NA} / (d×e) satisfies the following formula (2), 0.10≦Sn≦0.80 (2) (In formula (2), a is the titer (L) of the NaOH aqueous solution required to adjust the mixed liquid in which the silica fine particles A are dispersed to pH 9.0, b is the titer (L) of NaOH solution required to adjust a mixture of 25.0 g of ethanol and 75.0 g of 20% by mass NaCl aqueous solution to pH 9.0, c is the concentration (mol / L) of the NaOH solution used in the titration, NA is Avogadro's number, d is the mass (g) of the silica microparticles, e is the BET specific surface area (nm 2 / g). The solid of the silica fine particles A 29 The area of ​​the peak of the D unit that has a peak top in the range of -25 ppm to -15 ppm in the chemical shift obtained by the Si-NMR DD / MAS method is defined as D. DD The sum of the areas of the peaks of M, D, T, and Q units present in the range of -140 ppm to 100 ppm is defined as S. DD The BET specific surface area of ​​the silica particles is B (m 2 / g), (D DD / S DD ) to B (D DD / S DD ) / B is 4.70×10 -6 Above 1.40 x 10 -3 The following is further: The solid of the silica fine particles A 29 The area of ​​the peak of the D unit that has a peak top in the range of -25 ppm to -15 ppm in the chemical shift obtained by the Si-NMR CP / MAS method is D CP The sum of the areas of the peaks of M, D, T, and Q units present in the range of -140 ppm to 100 ppm is defined as S. CP When (D CP / S CP ) to B (D CP / S CP ) / B is 4.70×10 -4 Above 1.00 x 10 -2 is as follows: (D CP / S CP ) of (D DD / S DD ) to the ratio value (D CP / S CP ) / (D DD / S DD ) is 3.00 or more 3.00 x 10 2 A toner characterized in that: (Configuration 2) The toner according to Configuration 1, wherein the content (by mass) of the dodecylbenzenesulfonic acid or a dodecylbenzenesulfonate salt is 10 ppm or more and 1000 ppm or less with respect to the toner. (Configuration 3) The toner according to configuration 1 or 2, wherein the amount (by mass) of boron atoms present in the toner measured by inductively coupled plasma mass spectrometry (ICP-MS) is 0.1 ppm or more and 100 ppm or less. (Configuration 4) The toner according to any one of Configurations 1 to 3, wherein the number average particle size of the primary particles of the silica fine particles A is 5 nm or more and 50 nm or less. (Configuration 5) The toner according to any one of Configurations 1 to 4, wherein the content of the silica fine particles A in the toner is 0.2 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the toner particles. (Configuration 6) The BET specific surface area of ​​the silica fine particles A is 15 m 2 / g or more 300m 2 / g or less. (Configuration 7) The amount of boron atoms present in the toner (by mass) I B [ppm] and the content S of silica fine particles A in the toner A [Parts by mass] and (D CP / S CP 7. The toner according to any one of configurations 1 to 6, wherein the relationship between A and B satisfies the following formula (7): 2.6×10 -5 ≦{(D CP / S CP ) / B}×S A / I B ≦3.6×10 -3 (7) (Configuration 8) The content (mass basis) D [ppm] of dodecylbenzenesulfonic acid or dodecylbenzenesulfonate and the content S of silica fine particles A in the toner A [Parts by mass], and (D CP / S CP 8. The toner according to any one of configurations 1 to 7, wherein the relationship of (A) / B satisfies the following formula (8): 7.7×10 3 ≦D / {(D CP / S CP ) / B}×S A ≦1.9×10 6 (8) (Configuration 9) The toner according to any one of Configurations 1 to 8, wherein the toner contains titanium compound particles B having a major axis of 300 nm or more and 3,000 nm or less and an aspect ratio of 5.0 or more and 50.0 or less. (Configuration 10) The amount of boron atoms present in the toner (by mass) I B The toner according to configuration 9, wherein the relationship between the amount of titanium compound B in the toner (ppm) and the amount of titanium compound B in the toner (T) (mass %) satisfies the following formula (9): 5.0×10 -2 ≦T / I B ≦8.3···(9) (Configuration 11) The toner according to any one of Configurations 1 to 10, wherein the toner particles have a polyester resin in a surface layer of the toner particles, and the surface layer has a thickness of 300 nm or more and 700 nm or less. EXAMPLES

[0169] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is in no way limited thereto. Parts used in the formulations of the examples are by weight unless otherwise specified.

[0170] <Manufacture of magnetic body 1> 100 parts of magnetic iron oxide was placed in a high-speed mixer (Fukae Powtec Co., Ltd. LFS-2 type), and while stirring at a rotation speed of 2000 rpm, 8.0 parts of an aqueous solution containing a silane compound was added dropwise over 2 minutes. Then, the mixture was mixed and stirred for 5 minutes.

[0171] Next, in order to increase the adhesion of the silane compound, the mixture was dried at 40°C for 1 hour to reduce the moisture, and then dried at 110°C for 3 hours to promote the condensation reaction of the silane compound.The mixture was then crushed and passed through a sieve with 100 μm openings to obtain magnetic material 1 as a colorant.

[0172] <Production Example of Polyester Resin 1> A reaction apparatus equipped with a stirrer, a thermometer, and an outflow cooler was charged with 20 parts of propylene oxide-modified bisphenol A (2-mol adduct), 80 parts of propylene oxide-modified bisphenol A (3-mol adduct), 20 parts of terephthalic acid, 20 parts of isophthalic acid, and 0.50 parts of tetrabutoxytitanium, and an esterification reaction was carried out at 190°C.

[0173] Thereafter, 1 part of trimellitic anhydride (TMA) was added, and the temperature was raised to 220°C while the pressure inside the system was gradually reduced, and a polycondensation reaction was carried out at 150 Pa to obtain polyester resin 1. The acid value of polyester resin 1 was 12 mgKOH / g, and the softening point was 110°C.

[0174] <Production Example of Silica Fine Particle A1> Untreated fumed silica (BET surface area 300m 2 100 parts of untreated dry silica were sprayed with 15.0 parts of dimethyldichlorosilane using a spray nozzle, and the mixture was allowed to react for 1 hour with heating and stirring to obtain silica fine particles A1. The physical properties of silica fine particles A1 are shown in Table 1.

[0175] <Production Examples of Silica Particles A2 to A5, A9 to A10> Silica fine particles A2 to A5 and A9 to A10 were obtained in the same manner as in the production example of silica fine particles A1, except that the BET specific surface area of ​​the untreated dry silica, the amount of dimethyldichlorosilane added, the reaction temperature and the reaction time were changed as shown in Table 1. The physical properties of silica fine particles A2 to A5 and A9 to A10 are shown in Table 1.

[0176] <Production Example of Silica Microparticle A6> Untreated fumed silica (BET surface area 300m 2 100g) was placed in a reactor and heated to 270°C while being fluidized by stirring. The inside of the reactor was replaced with nitrogen gas, the reactor was sealed, and octamethylcyclotetrasiloxane was sprayed and mixed as a first surface treatment agent using a spray nozzle until the gauge pressure reached 200 kPa. After that, heating and stirring were continued for 1 hour to cause a reaction, and the inside of the reactor was replaced again with a nitrogen atmosphere to obtain silica microparticles A6. The physical properties of silica microparticles A6 are shown in Table 1.

[0177] <Production Examples of Silica Particles A7 to A8> Silica microparticles A7 to A8 were obtained in the same manner as in the production example of silica microparticles A6, except that the BET specific surface area of ​​the untreated dry silica, the gauge pressure when adding octamethylcyclotetrasiloxane, the reaction temperature, and the reaction time were changed as shown in Table 1. The physical properties of silica microparticles A7 to A8 are shown in Table 1.

[0178] <Production Example of Silica Fine Particle A11> Untreated fumed silica (BET surface area 30 m 2 100 parts of untreated dry silica were sprayed with 5.0 parts of dimethyl silicone oil (KF-96-50CS, manufactured by Shin-Etsu Chemical Co., Ltd.) using a spray nozzle, and the mixture was allowed to react for 1 hour with heating and stirring to obtain silica microparticles A11. The physical properties of silica microparticles A11 are shown in Table 1.

[0179] <Production Example of Silica Microparticle A12> Untreated fumed silica (BET specific surface area 20 m 2 1.0 part of hexamethyldisilazane was sprayed onto 100 parts of untreated dry silica using a spray nozzle, and the mixture was allowed to react for 1 hour with heating and stirring to obtain silica fine particles A12. The physical properties of silica fine particles A12 are shown in Table 1.

[0180] <Production Example of Silica Microparticle A13> Untreated fumed silica (BET surface area 30 m 2 The mixture was charged into a reactor and heated to 270° C. in a fluidized state by stirring. The inside of the reactor was conditioned under a nitrogen gas atmosphere, and 1.5 parts of hexamethyldisilazane was sprayed onto 100 parts of untreated dry silica using a spray nozzle. Heating and stirring were continued for 1 hour to carry out the reaction, thereby carrying out the coating treatment.

[0181] After the treatment, the inside of the reactor was replaced with a nitrogen atmosphere and heated to 300°C. Subsequently, 5.0 parts of dimethyl silicone oil (KF-96-50CS manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed to 100 parts of untreated dry silica, and the mixture was reacted by heating and stirring for 1 hour to obtain silica microparticles A13. The physical properties of silica microparticles A13 are shown in Table 1.

[0182] [Table 1]

[0183] <Production Example of Titanium Compound Particles B (External Additive B)> Titanium compound particles B were produced as follows. Metatitanic acid obtained by the sulfuric acid method was mixed with a 50% NaOH aqueous solution to obtain TiO 2 The mixture was heated at 95°C for 2 hours. After thorough washing, 31%-HCl was added to the HCl / TiO 2 = 0.26, and heated at the boiling point for 1 hour. After cooling, the solution was neutralized to pH 7 with 1 mol / L-NaOH, washed and dried to produce fine titanium dioxide particles. The specific surface area of ​​the resulting fine titanium dioxide particles was 115 g / m 2 The titanium dioxide fine particles were mixed with 100 parts of NaCl and 100 parts of Na 2 P 2 O 7 10H 225 parts of O were added, mixed in a vibrating ball mill for 1 hour, and the mixture was calcined in an electric furnace at 850°C for 2 hours. The calcined product was placed in pure water and heated at 80°C for 6 hours, and then washed to remove soluble salts. All particles obtained by drying were acicular titanium oxide fine particles (titanium compound particles B) with a minor axis in the range of 0.03 μm to 0.07 μm and a major axis in the range of 0.4 μm to 0.8 μm.

[0184] <Production Example of Toner Particle 1> Toner particles were prepared according to the following procedure.

[0185] (Preparation of First Aqueous Medium) 2.9 parts of sodium phosphate 12-hydrate was added to 353.8 parts of ion-exchanged water and heated to 60°C while stirring using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). After that, an aqueous calcium chloride solution prepared by adding 1.7 parts of calcium chloride dihydrate to 11.7 parts of ion-exchanged water and an aqueous magnesium chloride solution prepared by adding 0.5 parts of magnesium chloride to 15.0 parts of ion-exchanged water were added and stirring was continued to obtain a first aqueous medium containing a dispersion stabilizer.

[0186] (Preparation of Polymerizable Monomer Composition) Styrene 75.0 parts n-Butyl acrylate 25.0 parts 1-6 Hexanediol Diacrylate 0.5 parts ·Magnetic material 1 95.0 parts Polyester resin 1 3.0 parts The above materials were uniformly dispersed and mixed using an attritor (manufactured by Mitsui Miike Chemical Engineering Co., Ltd.), and then heated to 60°C. 15.0 parts of behenyl stearate wax (melting point 68°C) as an ester wax and 8.0 parts of paraffin wax (manufactured by Nippon Seiro Co., Ltd., HNP-9) as a hydrocarbon wax were added, mixed, and dissolved to obtain a polymerizable monomer composition.

[0187] (Preparation of second aqueous medium) 0.6 parts of sodium phosphate 12-hydrate was added to 166.8 parts of ion-exchanged water and heated to 60°C while stirring using a paddle stirring blade, and then an aqueous calcium chloride solution prepared by adding 0.3 parts of calcium chloride dihydrate to 2.3 parts of ion-exchanged water was added and stirring was continued to obtain a second aqueous medium containing a dispersion stabilizer.

[0188] (granulation) The polymerizable monomer composition was added to the first aqueous medium, and the granulation liquid was treated for 1 hour using a Cavitron (manufactured by Eurotech) at a rotor peripheral speed of 29 m / s to uniformly disperse and mix. Further, 7.0 parts of t-butyl peroxypivalate was added as a polymerization initiator, and the mixture was stirred at 60° C. and N 2 The mixture was granulated under atmospheric conditions while being stirred at a peripheral speed of 22 m / s for 10 minutes using a Clearmix (manufactured by M Technique Co., Ltd.) to obtain a granulation liquid containing droplets of the polymerizable monomer composition.

[0189] (Polymerization / Distillation / Drying / External Addition) The granulation liquid was added to the second aqueous medium, and the mixture was reacted at 74°C for 3 hours while stirring with a paddle impeller. After the reaction was completed, the mixture was heated to 98°C and distilled for 3 hours to obtain a reaction slurry. Thereafter, in a cooling step, 0°C water was added to the reaction slurry, and the reaction slurry was cooled from 98°C to 45°C at a rate of 100°C / min, and then further heated and held at 50°C for 3 hours.

[0190] Thereafter, the reaction slurry was allowed to cool to 25° C. After being allowed to cool, hydrochloric acid was added to wash the reaction slurry, followed by filtration and drying to obtain toner particles 1-1 having a weight average particle size of 7.7 μm.

[0191] Thereafter, polyester resin 1 (17 parts) and toner particles 1-1 (100 parts) were externally mixed while heating to 48°C in an FM10C (manufactured by Nippon Coke and Engineering Co., Ltd.) to obtain toner particles 1-2. When the cross section of the toner was observed, a shell was formed by polyester resin 1, and the thickness was 530 nm on average.

[0192] A 1% aqueous solution of sodium tetraborate decahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was sprayed onto the toner particles 1-2 obtained above so that the boron content in the toner was 1.0 ppm. Furthermore, a 1% aqueous solution of sodium dodecylbenzenesulfonate (product name: Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was sprayed onto the toner particles 1-2 obtained above so that the dodecylbenzenesulfonic acid content in the toner was 500 ppm, thereby obtaining toner particles 1.

[0193] Toner particles 1 (100.0 parts) obtained above, silica fine particles A1 (1.0 part), titanium compound particles B (1.0 part), and titanium oxide particles with a particle size of 150 nm (0.20 parts) were externally added and mixed using FM10C (manufactured by Nippon Coke & Engineering Co., Ltd.) The external addition conditions were as follows: the lower blade was set to A0 blade, the gap with the deflector wall was set to 20 mm, the amount of toner particles charged was 2.0 kg, and the rotation speed was 66.6 s. -1 The external addition time was 10 minutes, and the cooling water temperature was 20°C and the flow rate was 10 L / min.

[0194] Thereafter, the mixture was sieved through a mesh having an opening of 200 μm to obtain toner 1.

[0195] <Production Examples of Toner Particles 2 and 3> Toner particles 2 were obtained in the same manner as in the production example of toner particles 1-2, except that the amount of polyester resin 1 added was adjusted so that the shell thickness was 700 nm. In addition, toner particles 3 were obtained by adjusting the shell thickness to 300 nm.

[0196] <Production Examples of Toner Particles 4 to 18> In the production example of toner particle 1, except that polyester resin was not added to toner particle 1-1 and the contents of dodecylbenzenesulfonic acid and boron were changed as shown in Table 2, toner particles 4 to 18 were obtained in the same manner.

[0197] <Toner 1 Manufacturing Example> Toner particles 1 (100.0 parts) obtained above, silica fine particles A1 (1.0 part), titanium compound particles B (1.0 part), and titanium oxide particles with a particle size of 150 nm (0.20 parts) were externally added and mixed using FM10C (manufactured by Nippon Coke & Engineering Co., Ltd.) The external addition conditions were as follows: the lower blade was set to A0 blade, the gap with the deflector wall was set to 20 mm, the amount of toner particles charged was 2.0 kg, and the rotation speed was 66.6 s. -1 The external addition time was 10 minutes, and the cooling water temperature was 20°C and the flow rate was 10 L / min.

[0198] Thereafter, the mixture was sieved through a mesh having an opening of 200 μm to obtain toner 1.

[0199] <Production Examples of Toners 2 to 31> Toners 2 to 31 were obtained in the same manner as in the production example of toner 1, except that the toner particles and the external additive formulation used were changed as shown in Table 2.

[0200] [Table 2-1]

[0201] [Table 2-2]

[0202] Example 1 The following evaluations were carried out using Toner 1. For the evaluation using an actual machine, an HP LaserJet Enterprise M609dn was used after modifying the process speed to 410 mm / sec.

[0203] The evaluation paper was Vitality (Xerox, basis weight 75 g / cm 2 The evaluation results are shown in Table 3.

[0204] <Charge start-up evaluation> Two 50mL plastic bottles with lids were prepared by putting 19.0g of magnetic carrier F813-300 (manufactured by Powder Tech Co., Ltd.) and 1.0g of evaluation toner into them, and the bottles were left to stand in a harsh environment (temperature 40°C, humidity 95% RH) for 30 days.The bottles were then left to stand in a low-temperature, low-humidity environment (temperature 15°C, humidity 10% RH) for one day.Then, the following operations were performed in a high-temperature, high-humidity environment (temperature 32.5°C, humidity 80% RH).

[0205] The mixture was shaken for 2 minutes and 10 minutes at a speed of 4 reciprocations per second using a shaker (YS-LD, manufactured by Yayoi Co., Ltd.) to prepare a two-component developer.

[0206] 0.200 g of the two-component developer for which the amount of triboelectric charge is to be measured is placed in a metal measurement container 2 having a 500 mesh (25 μm opening) screen 3 at the bottom as shown in Figure 1, and then the metal lid 4 is placed on the container. The total mass of the measurement container 2 at this time is measured and taken as W1 (g).

[0207] Next, the suction device 1 (at least the part in contact with the measurement container 2 is an insulator) sucks from the suction port 7, and the air flow control valve 6 is adjusted to set the pressure on the vacuum gauge 5 to 50 mmAq. In this state, the toner is sucked for one minute and removed.

[0208] The potential of the electrometer 9 at this time is V (volts). Here, 8 is a capacitor with a capacity of C (μF). The mass of the entire measuring container after suction is measured and is defined as W2 (g). The amount of triboelectric charge of this toner is calculated by the following formula. Frictional charge (mC / kg) = (C × V) / (W1-W2)

[0209] The calculation was made by dividing "amount of triboelectric charge after shaking for 2 minutes" by "amount of triboelectric charge after shaking for 10 minutes" x 100, and the result was regarded as charge rise property, and evaluation was performed according to the following criteria. A: Charge rise rate is 90% or more B: Charge rise rate is 80% or more but less than 90% C: Charge rise rate is 70% or more but less than 80% D: Charge rise rate is 60% or more but less than 70% E: Charge rise rate is less than 60%

[0210] <Vertical density unevenness and density uniformity evaluation> The image output tester and the toner cartridge filled with the toner to be evaluated were left for more than one day in a low temperature and low humidity environment (temperature 15°C, humidity 10% RH), and then 4,000 sheets of horizontal line patterns were printed using the image output tester in intermittent mode (8 second break after every two sheets printed) with 3-dot horizontal lines printed at 180-dot intervals. Immediately after that, a halftone (30H) image and a full solid black image were output. The 30H image is a halftone image where 256 gradations are expressed in hexadecimal, with 00H being solid white (non-image) and FFH being solid black (full image).

[0211] The halftone images obtained were visually checked for the presence or absence of vertical density unevenness (vertical bands of light density). Furthermore, for the full solid black images obtained, nine points were uniformly selected from the entire image, and the reflection density was measured using a Macbeth densitometer (manufactured by Macbeth) with an SPI filter. The difference between the maximum and minimum values ​​of the nine points was calculated and used as the maximum density difference. The vertical density unevenness and density uniformity were evaluated according to the following criteria. A: No vertical density unevenness was observed, and the maximum density difference was less than 0.04. B: No vertical density unevenness was observed, and the maximum density difference was 0.04 or more and less than 0.08. C: No vertical density unevenness is observed, and the maximum density difference is 0.08 or more. D: Vertical density unevenness is visible, and the maximum density difference is less than 0.15. E: Vertical density unevenness is visible, and the maximum density difference is 0.15 or more.

[0212] <Evaluation of concentration maintenance rate before and after durability> The image output tester and the toner cartridge filled with the toner to be evaluated were left for at least one day in a low temperature and low humidity environment (temperature 15°C, humidity 10% RH), and then 10,000 sheets were printed in intermittent mode (8 second break after every two sheets printed) with a horizontal line pattern of 3 dots printed at 180 dot intervals using the image output tester. Before and after printing the 10,000 sheets, a full solid black image was output, and 9 points were selected evenly from the entire full solid black image obtained, and the reflection density was measured using a SPI filter with a Macbeth densitometer (manufactured by Macbeth Co., Ltd.), which is a reflection density meter.

[0213] {(initial 9-point average density) / (9-point average density after printing 10,000 sheets)}×100 was calculated, and the density maintenance rate before and after durability was evaluated according to the following criteria. A: 96% or more B: 91% or more but less than 95% C: 81% to less than 90% D: 76% or more but less than 81% E: Less than 76%

[0214] [Examples 2 to 26] The evaluation was carried out in the same manner as in Example 1, except that toners 2 to 26 were used. The evaluation results are shown in Table 3.

[0215] [Comparative Examples 1 to 5] The evaluation was carried out in the same manner as in Example 1, except that toners 27 to 31 were used. The evaluation results are shown in Table 3.

[0216] [Table 3]

Claims

1. A toner having toner particles containing a binder resin and silica fine particles A, (I) in a TOF-SIMS measurement of the toner particles, a fragment peak derived from a boron atom and a fragment peak derived from a boron-oxygen structure are detected; the toner contains at least one selected from the group consisting of dodecylbenzenesulfonic acid and dodecylbenzenesulfonate salts, (II) In a TOF-SIMS measurement of the silica fine particles A, fragment ions corresponding to a structure represented by the following formula (1) are observed, 【Chemistry 1】 (In formula (1), n ​​represents an integer of 1 or more.) When 2.00 g of the silica fine particles were dispersed in a mixed liquid of 25.0 g of ethanol and 75.0 g of a 20% by mass NaCl aqueous solution and titrated with sodium hydroxide, Sn defined as Sn={(a-b)×c×NA} / (d×e) satisfies the following formula (2): 0.10≦Sn≦0.80 ... (2) (In formula (2), a is the titration amount (L) of the aqueous NaOH solution required to adjust the mixed liquid in which the silica fine particles A are dispersed to pH 9.0, b is the titer (L) of the aqueous NaOH solution required to adjust a mixture of 25.0 g of ethanol and 75.0 g of a 20% by mass NaCl aqueous solution to pH 9.0; c is the concentration (mol / L) of the NaOH aqueous solution used in the titration, NA is Avogadro's number, d is the mass (g) of the silica fine particles, e is the BET specific surface area (nm 2 / g). The solid of the silica fine particles A 29 In the chemical shift obtained by Si-NMR DD / MAS method, the area of ​​the peak of the D unit having a peak top in the range of -25 ppm to -15 ppm is defined as D DD The sum of the areas of the peaks of M units, D units, T units, and Q units present in the range of -140 ppm to 100 ppm is defined as S DD The BET specific surface area of ​​the silica fine particles is B (m 2 / g), (D DD / S DD ) to B (D DD / S DD ) / B is 4.70 x 10 -6 Above 1.40 x 10 -3 The following is further: The solid of the silica fine particles A 29 In the chemical shift obtained by Si-NMR CP / MAS method, the area of ​​the peak of the D unit having a peak top in the range of -25 ppm to -15 ppm is defined as D CP The sum of the areas of the peaks of M units, D units, T units, and Q units present in the range of -140 ppm to 100 ppm is defined as S CP When (D CP / S CP ) to B (D CP / S CP ) / B is 4.70 x 10 -4 Above 1.00 x 10 -2 is as follows: (D CP / S CP ) of (D DD / S DD ) to the ratio value (D CP / S CP ) / (D DD / S DD ) is 3.00 or more 3.00 x 10 2 A toner characterized in that:

2. 2. The toner according to claim 1, wherein the content (by mass) of the dodecylbenzenesulfonic acid or the dodecylbenzenesulfonate salt is from 10 ppm to 1000 ppm based on the mass of the toner.

3. 3. The toner according to claim 1, wherein the amount of boron atoms present (by mass) in the toner measured by an inductively coupled plasma mass spectrometer (ICP-MS) is 0.1 ppm or more and 100 ppm or less.

4. 3. The toner according to claim 1, wherein the number average particle size of the primary particles of the silica fine particles A is 5 nm or more and 50 nm or less.

5. 3. The toner according to claim 1, wherein the content of the silica fine particles A in the toner is from 0.2 parts by mass to 2.0 parts by mass with respect to 100 parts by mass of the toner particles.

6. The BET specific surface area of ​​the silica fine particles A is 15 m 2 / g or more 300m 2 The toner according to claim 1 or 2, wherein the toner has a molecular weight of 1 / g or less.

7. The amount of boron atoms present in the toner (by mass) I B [ppm] and the content S of the silica fine particles A in the toner A [Parts by mass] and (D CP / S CP 3. The toner according to claim 1, wherein the relationship between A and B satisfies the following formula (7): 2.6×10 -5 ≦{(D CP / S CP ) / B}×S A / I B ≦3.6×10 -3 ・・・(7)

8. The content (mass basis) D [ppm] of dodecylbenzenesulfonic acid or dodecylbenzenesulfonate and the content S of silica fine particles A in the toner A [Parts by mass], and (D CP / S CP 3. The toner according to claim 1, wherein the relationship of (a) / B satisfies the following formula (8): 7.7×10 3 ≦D / {(D CP / S CP ) / B}×S A ≦1.9×10 6 ・・・(8)

9. 3. The toner according to claim 1, wherein the toner contains titanium compound particles B having a major axis of 300 nm or more and 3,000 nm or less and an aspect ratio of 5.0 or more and 50.0 or less.

10. The amount of boron atoms present in the toner (by mass) I B 10. The toner according to claim 9, wherein the relationship between the titanium compound particle B content (ppm) and the content T (mass %) of the titanium compound particle B in the toner satisfies the following formula (9): 5.0×10 -2 ≦T / I B ≦8.3・・・(9)

11. 3. The toner according to claim 1, wherein the toner particles have a surface layer made of a polyester resin, the surface layer having a thickness of 300 nm or more and 700 nm or less.

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