toner

Abstract

To provide a toner that is excellent in low-temperature fixability and hot offset resistance, and has a wide fixable temperature range and excellent charge stability in both a high-temperature, high-humidity environment and a low-temperature, low-humidity environment.SOLUTION: Toner has toner particles having resin. When a chloroform-soluble portion of the toner particles is subjected to gradient LC analysis using acetonitrile as a poor solvent and chloroform as a good solvent, a peak detected in a range of 50.0 to 75.0% by volume of chloroform in a mobile phase and the peak detected in the range of 75.0 to 95.0% by volume of chloroform in the mobile phase satisfy a specific relation.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This disclosure relates to toner used in electrophotography and electrostatic recording. [Background technology]

[0002] Traditionally, energy conservation has been considered a major technical challenge in electrophotographic equipment, and significant reductions in the amount of heat required for the fuser have been explored. In particular, there is a growing need for so-called "low-temperature fixing" toners, which enable fixing with lower energy consumption.

[0003] One method to enable fixing at low temperatures is to lower the glass transition temperature (Tg) of the binder resin in the toner. However, lowering Tg leads to a decrease in the heat resistance of the toner, so it is considered difficult to achieve both low-temperature fixing and heat resistance with this method.

[0004] As a countermeasure, Patent Documents 1 and 2 describe the study of toners with added plasticizers. Plasticizers can accelerate the softening rate of the binder resin while maintaining the toner's Tg, thus achieving both low-temperature fixability and heat-resistant storage. However, since the toner softens through the step of the plasticizer melting and plasticizing the binder resin, there is a limit to the toner's melting rate, and further improvement in low-temperature fixability is desired.

[0005] Therefore, in order to achieve both improved low-temperature fixation and heat-resistant storage of toner, a method of using crystalline vinyl resin as a binder resin is being considered. Amorphous resins commonly used as binder resins for toner do not show a clear endothermic peak in differential scanning calorimeter (DSC) measurements, but when crystalline resin components are included, an endothermic peak (melting point) appears in DSC measurements.

[0006] Crystalline vinyl resins have the property of hardly softening until their melting point due to the regular arrangement of side chains within the molecule. Furthermore, the crystals melt rapidly above the melting point, resulting in a sharp decrease in viscosity. For this reason, they are attracting attention as materials that have excellent sharp melt properties and can achieve both low-temperature fixation and heat-resistant storage. Typically, crystalline vinyl resins have long-chain alkyl groups as side chains in the main chain skeleton, and the long-chain alkyl groups of the side chains crystallize together to form a crystalline resin.

[0007] Patent Document 3 proposes a method for manufacturing toner containing crystalline vinyl with excellent manufacturing stability by introducing unsaturated groups into crystalline vinyl resin. Furthermore, Patent Document 4 proposes a method for achieving both low-temperature fixing performance and hot offset resistance using a toner that utilizes a polymerizable monomer having a long-chain alkyl group, a crystalline vinyl resin obtained by copolymerizing amorphous polymerizable monomers with different SP values, and an amorphous resin. Furthermore, Patent Document 5 proposes a method for obtaining a toner that is durable in addition to having both low-temperature fixability and hot-off resistance by crosslinking a crystalline vinyl resin and an amorphous resin. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] International Publication No. 2013 / 047296 [Patent Document 2] Japanese Patent Publication No. 2016-066018 [Patent Document 3] Japanese Patent Publication No. 2016-218237 [Patent Document 4] Japanese Patent Publication No. 2021-096463 [Patent Document 5] Japanese Patent Publication No. 2021-036316 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] However, in Patent Documents 3, 4, and 5, there are problems to be improved in obtaining high charging stability in both high-temperature and high-humidity environments and low-temperature and low-humidity environments while achieving both low-temperature fixing properties and hot offset resistance. set It was found that in Patent Document 3, toner is obtained by reacting a polymerizable monomer and a crystalline vinyl resin, but there are problems in charging stability in a low-temperature and low-humidity environment due to a large difference in reactivity between the crystalline resin and the polymerizable monomer. In Patent Documents 4 and 5, while good charging properties are exhibited in a low-temperature and low-humidity environment by introducing a polar group into the crystalline vinyl resin, there are problems from the viewpoint of charge retention under high-temperature and high-humidity conditions. In Patent Document 3, toner is obtained by reacting a polymerizable monomer and a crystalline vinyl resin, but there are problems in charging stability in a low-temperature and low-humidity environment due to a large difference in reactivity between the crystalline resin and the polymerizable monomer. In Patent Documents 4 and 5, while good charging properties are exhibited in a low-temperature and low-humidity environment by introducing a polar group into the crystalline vinyl resin, there are problems from the viewpoint of charge retention under high-temperature and high-humidity conditions. The present disclosure provides a toner having excellent low-temperature fixing properties and hot offset resistance, a wide fixing temperature range, and excellent charging stability in both high-temperature and high-humidity environments and low-temperature and low-humidity environments.

Means for Solving the Problems

[0010] The present disclosure is Conclusion a toner having toner particles having a Contains resin, wherein The binder resin of the toner particles consists solely of vinyl resin. components having a molecular weight of 2000 or less are removed from the soluble components obtained by Soxhlet extraction using a chloroform solvent of the toner particles for 48 hours by recycled HPLC, and the resulting product is used as the chloroform-soluble components of the Conclusion resin extracted from the toner particles, the Conclusion gradient LC analysis of the eluted components when using acetonitrile as a poor solvent and chloroform as a good solvent for the chloroform-soluble components of the resin, and linearly changing the mobile phase from 100% by volume of acetonitrile to 100% by volume of chloroform, when the proportion of chloroform in the mobile phase is in the range of 50.0 to 75.0% by volume, the area of the peak detected using a Corona charged particle detector is SA, and the maximum value is PA, In the mobile phase where the proportion of chloroform is in the range of 75.0 to 95.0 volume%, the area of ​​the peak detected using the Corona charged particle detector is defined as SB, and the maximum value as PB. When the smallest local minimum between PA and PB is denoted as VAB, If the PA and PB exist, The SA, the SB, the PB and the VAB are ,the below described The equations (1) and (2) are satisfied. death, 0.30 ≦ SA / SB ≦ 0.85 (1) 0.25 ≦ VAB / PB ≦ 0.55 (2) In the gradient LC analysis, the resin obtained by extracting components in the mobile phase where the proportion of chloroform is in the range of 50.0 to 75.0 volume percent is designated as resin A, which is the resin component corresponding to PA. In the gradient LC analysis, the resin obtained by extracting components in the mobile phase where the proportion of chloroform is in the range of 75.0 to 95.0 volume percent is defined as resin B, which is the resin component corresponding to PB. In the Soxhlet extraction of the toner particles using chloroform solvent, the insoluble matter obtained after 48 hours of extraction is separated, and the resin component obtained by removing the incineration residue ash from the insoluble matter is defined as resin C. The proportion of resin A in the binder resin contained in the toner particles is defined as MA (mass%). The proportion of resin B in the binder resin contained in the toner particles is defined as MB (mass%). When the proportion of resin C in the binder resin contained in the toner particles is denoted as MC (mass%), The MA, MB, and MC satisfy the following formulas (8), (9), (10), and (11): MA + MB + MC ≦ 100.0 (8) 25.0 ≦ MA ≦ 55.0 (9) 15.0 ≦ MB ≦ 50.0 (10) 3.0 ≦ MC ≦ 30.0 (11) The resin C has a monomer unit (b) represented by the following formula (12): Regarding toner. TIFF0007888369000001.tif40109 [In formula (12), R 2 L represents a hydrogen atom or a methyl group. 2 [where n represents a single bond, ester bond, or amide bond, and n is an integer between 15 and 30.] [Effects of the Invention]

[0011] According to this disclosure, it is possible to provide a toner that has excellent low-temperature fixing properties and resistance to hot offset, a wide fixing temperature range, and excellent electrostatic stability in both high-temperature, high-humidity and low-temperature, low-humidity environments. [Brief explanation of the drawing]

[0012] [Figure 1] An example of the results of gradient LC analysis. [Modes for carrying out the invention]

[0013] In this disclosure, descriptions of numerical ranges such as "XX or greater and YY or less" or "XX to YY" mean a numerical range that includes the lower and upper limits, unless otherwise specified. When numerical ranges are described in steps, the upper and lower limits of each numerical range can be combined in any way. (Meth)acrylic acid ester refers to acrylic acid ester and / or methacrylic acid ester.

[0014] A "monomer unit" refers to the reacted form of a monomer substance in a polymer. For example, one carbon-carbon bond in the main chain of a polymer formed by the polymerization of vinyl monomers is considered one unit. A vinyl monomer can be represented by the following formula (C). [ka]

[0015] [In formula (C), R A R represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), B represents any substituent. Crystalline resins are resins that exhibit a clear endothermic peak in differential scanning calorimeter (DSC) measurements.

[0016] The inventors focused on the polarity distribution of the resin components contained in the toner and found that the above problem can be solved by appropriately controlling the polarity distribution of the resins that make up the toner. To achieve good low-temperature fixing properties for toner using crystalline vinyl resin, it is important to include a certain amount or more of crystalline vinyl resin in the resin within the toner particles. While the polarity of crystalline vinyl resin can be controlled to some extent by the composition of its constituent monomer units, crystalline vinyl resin generally tends to have low polarity because it needs to contain a high proportion of long-chain alkyl structures. To achieve higher sharp-melt properties, higher crystallinity is required, such as by increasing the proportion of longer-chain alkyl units. Such resins tend to have low polarity and low electrical resistance, making it difficult to retain charge.

[0017] Using a crystalline resin exhibiting such charging properties, we considered combining it with an amorphous resin, which is conventionally used to obtain excellent charging properties. Specifically, we considered whether it would be possible to achieve low-temperature fixability with the crystalline resin while obtaining charging stability with the amorphous resin by using a crystalline resin with excellent sharp-melt properties in combination with a resin with a different polarity from the crystalline resin. After diligent research, we obtained the following toner.

[0018] This disclosure relates to a toner having resin-containing toner particles, In Soxhlet extraction of the toner particles using chloroform solvent, components with a molecular weight of 2000 or less are removed from the soluble components obtained by recycled HPLC, and this is used as the chloroform-soluble components of the resin extracted from the toner particles. When chloroform was used as the poor solvent and chloroform as the good solvent for the chloroform-soluble portion of the resin, and the mobile phase was linearly changed from a 100% by volume acetonitrile mobile phase to a 100% by volume chloroform mobile phase, the eluted components were analyzed by gradient LC. When the proportion of chloroform in the mobile phase is in the range of 50.0 to 75.0 volume%, the area of ​​the peak detected using the Corona charged particle detector is defined as SA, and the maximum value is defined as PA. In the mobile phase where the proportion of chloroform is in the range of 75.0 to 95.0 volume%, the area of ​​the peak detected using the Corona charged particle detector is defined as SB, and the maximum value as PB. When the smallest local minimum between PA and PB is denoted as VAB, If the PA and PB exist, The present invention relates to toners in which SA, SB, PB, and VAB satisfy the following formulas (1) and (2). 0.30 ≦ SA / SB ≦ 0.85 (1) 0.25 ≦ VAB / PB ≦ 0.55 (2)

[0019] First, let's explain gradient LC analysis. In gradient LC analysis, unless otherwise specified, the sample used is the chloroform-soluble component of the resin obtained by removing components with a molecular weight of 2000 or less from the soluble component obtained by 48 hours of Soxhlet extraction using chloroform solvent from toner particles using recycled HPLC. For the chloroform-soluble component of the resin extracted from toner particles, acetonitrile is used as the poor solvent and chloroform as the good solvent. The eluted components are analyzed by gradient LC analysis when the mobile phase is linearly changed from a 100% vol. acetonitrile mobile phase to a 100% vol. chloroform mobile phase.

[0020] For chloroform in the mobile phase within the range of 50.0 to 75.0 volume%, the area of ​​the peak detected using the Corona charged particle detector is defined as SA, and the maximum value of the peak is defined as PA. For chloroform in the mobile phase within the range of 75.0 to 95.0 volume%, the area of ​​the peak detected using the Corona charged particle detector is defined as SB, and the maximum value is defined as PB. Furthermore, the smallest local minimum between the maximum values ​​PA and PB is defined as VAB. At this time, PA and PB exist. Also, SA, SB, PB and VAB satisfy the following equations (1) and (2). 0.30 ≦ SA / SB ≦ 0.85 (1) 0.25 ≦ VAB / PB ≦ 0.55 (2)

[0021] As will be explained in more detail later, the signal detected using the Corona charged particle detector, obtained in gradient LC analysis depending on the proportion of chloroform in the mobile phase, indicates high polarity. A higher volume fraction of chloroform indicates a component with lower polarity.

[0022] The peak maximums PA and SA obtained by gradient LC analysis in the range of 50.0–75.0 volume% for chloroform in the mobile phase originate from relatively polar amorphous resin components. On the other hand, in the range of 75.0–95.0 volume% chloroform in the mobile phase, the peak maximums PB and area SB originate from relatively low-polarity crystalline resin components.

[0023] The SA / SB ratio in gradient LC analysis, which is the ratio of the signal area derived from amorphous resin components to the signal area derived from crystalline resin components, indicates the balance between the charge retention properties of amorphous resin components and the charge leakage properties of crystalline resin components. It was found that when the SA / SB is between 0.30 and 0.85, the effect on chargeability becomes significantly apparent. If the SA / SB ratio is less than 0.30, the leakage in high-temperature, high-humidity environments is too high, and the electrostatic stability will decrease during durability testing. Conversely, if the SA / SB ratio is greater than 0.85, sufficient leakage in low-temperature, low-humidity environments will not be achieved, resulting in a significant charge increase during durability testing.

[0024] SA / SB is preferably 0.40 to 0.80, more preferably 0.50 to 0.77, even more preferably 0.60 to 0.75, and even more preferably 0.65 to 0.75. SA / SB can be increased by increasing the proportion of resin components with high polarity in the toner particles. Conversely, SA / SB can be decreased by increasing the proportion of resin components with low polarity in the toner particles.

[0025] SA is preferably 25.0 to 45.0, and more preferably 35.0 to 42.0. SB is preferably 45.0 to 65.0, and more preferably 50.0 to 55.0.

[0026] The smallest minimum value VAB between the maximum values ​​PA and PB is an indicator of the overall extent to which intermediate polar components between amorphous and crystalline resin components exist. We believe that the presence of a certain proportion of the minimum value VAB enables the transfer of charge between the maximum values ​​PA and PB, resulting in a synergistic effect of the properties of each component.

[0027] In particular, controlling charge leakage is crucial for obtaining excellent toner charging characteristics, and VAB is the ratio of the minimum value VAB to the maximum value PB, which originates from the crystalline resin component. When VAB / PB is between 0.25 and 0.55, it indicates that an appropriate amount of resin exhibiting intermediate polarity between low-polarity crystalline resin and high-polarity amorphous resin is contained, and the effect of transferring charge from the amorphous resin component to the crystalline resin component becomes prominent.

[0028] If the VAB / PB ratio is less than 0.25, there is insufficient polarity between amorphous and crystalline resin components, making charge transfer difficult. As a result, charge-up suppression does not occur during durability tests in low-temperature, low-humidity environments. On the other hand, if the VAB / PB ratio is greater than 0.55, charge leakage becomes high, making it impossible to maintain chargeability in high-temperature, high-humidity environments.

[0029] VAB / PB is preferably 0.30 to 0.50, and more preferably 0.35 to 0.45. VAB / PB can be increased by bringing the polarity of the highly polar resin component and the low polar resin component in the toner particles closer together, increasing the amount of resin component produced by the polymerization reaction between the low polar resin with polymerizable functional groups and the polar polymerizable monomer, adding resin components with intermediate polarity in addition to the highly polar and low polar resin components in the toner particles, and reducing the proportion of low polarity resin components. Conversely, VAB / PB can be decreased by separating the polarity of the highly polar and low polarity resin components in the toner particles and increasing the proportion of low polarity resin components.

[0030] PA is preferably 2.0 to 5.0, and more preferably 3.0 to 4.5. PB is preferably 2.0 to 4.0, and more preferably 2.5 to 3.5. VAB is preferably 0.8 to 2.0, and more preferably 1.0 to 1.3.

[0031] Based on the above, by satisfying the aforementioned equations (1) and (2), a toner with excellent low-temperature fixing properties and hot offset resistance can exhibit excellent electrostatic stability even in high-temperature, high-humidity and low-temperature, low-humidity environments.

[0032] Furthermore, in gradient LC analysis, the resin obtained by extracting components in the mobile phase where the proportion of chloroform is in the range of 50.0 to 75.0 volume percent is defined as resin A, which is the resin component corresponding to the maximum value PA. Furthermore, in gradient LC analysis, the resin obtained by extracting components in the mobile phase where the proportion of chloroform is in the range of 75.0 to 95.0 volume% is defined as resin B, which is the resin component corresponding to the maximum value PB. In this case, it is preferable that resin B has monomer unit (a) represented by the following formula (3). [ka]

[0033] [In formula (3), R 1 L represents a hydrogen atom or a methyl group. 1 [where m represents a single bond, ester bond, or amide bond, and m is an integer between 15 and 30.] If the resin component has monomer unit (a), it is preferable for controlling the electrostatic stability because it is easier to induce a maximum value PB in the chloroform volume fraction range of 75.0 to 95.0 volume% in gradient LC analysis. L 1 Preferably, the carbonyl in the ester bond-COO- is R 1 It is bonded to a carbon atom that has [a certain characteristic]. If m is in the range of 15 to 30, the resulting resin B exhibits excellent crystallinity, making it possible to obtain a toner with excellent low-temperature fixation properties. m is preferably between 18 and 24, and more preferably between 20 and 22.

[0034] One method for introducing the monomer unit (a) shown in formula (3) into resin B is to polymerize (meth)acrylic acid esters as follows: For example, (meth)acrylic acid esters having a linear alkyl group with 16 to 31 carbon atoms [stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosyl (meth)acrylate, myricyl (meth)acrylate, dotriacontyl (meth)acrylate, etc.] and (meth)acrylic acid esters having a branched alkyl group with 16 to 31 carbon atoms [2-decyltetradecyl (meth)acrylate, etc.]. The monomers forming the monomer unit (a) may be one type alone or two or more types in combination.

[0035] The content of the monomer unit (a) represented by formula (3) in resin B is preferably 40.0 to 95.0% by mass, more preferably 60.0 to 93.0% by mass, and even more preferably 70.0 to 90.0% by mass. Within this range, a better balance is achieved between low-temperature fixing properties and hot offset resistance.

[0036] Resin B is preferably a vinyl resin. Resin B may also have other monomer units in addition to monomer unit (a). One method for introducing other monomer units is to polymerize the (meth)acrylic acid ester with other vinyl monomers.

[0037] Other vinyl monomers include the following: (Meth)acrylic acid esters such as styrene, α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Monomers containing a urea group: for example, amines with 3 to 22 carbon atoms [primary amines (n-butylamine, t-butylamine, propylamine, and isopropylamine, etc.), secondary amines (di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, and cyclo He Monomers, etc., obtained by reacting xylamine, etc., with isocyanates having 2 to 30 carbon atoms and having an ethylenically unsaturated bond, by known methods. Monomers having a carboxyl group; for example, methacrylic acid, acrylic acid, and 2-carboxyethyl (meth)acrylate. Monomers having a hydroxyl group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. Monomers having an amide group; for example, acrylamide, monomers obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms having an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) by known methods. Among them, it is preferable to use styrene, methacrylic acid, acrylic acid, methyl (meth)acrylate, and t-butyl (meth)acrylate.

[0038] Resin B preferably has a monomer unit derived from styrene represented by the following formula (A). Further, resin B preferably has a monomer unit derived from (meth)acrylic acid represented by the following formula (B).

Chemical formula

[0039] In resin B, the content ratio of the monomer unit derived from styrene is preferably 1.0 to 50.0% by mass, more preferably 10.0 to 30.0% by mass, and even more preferably 15.0 to 25.0% by mass. In resin B, the content ratio of the monomer unit derived from (meth)acrylic acid (preferably methacrylic acid) is preferably 0.5 to 5.0% by mass, more preferably 1.0 to 3.0% by mass, and even more preferably 1.0 to 2.0% by mass.

[0040] The number average molecular weight Mn of resin B is preferably 4000 to 13000, and more preferably 6000 to 9000. The weight average molecular weight Mw of resin B is preferably 10000 to 50000, and more preferably 20000 to 30000.

[0041] Further, when the acid value of resin B is Avb (mgKOH / g), it is preferable that Avb satisfies the following formula (4) 1.5 ≦ Avb ≦ 25.0 ···(4)

[0042] When Avb is 1.5 mgKOH / g or more, the pole with excellent water adsorption property derived from the acid value Because properties can be introduced, moisture adsorption can be moderately promoted, and charge transfer between amorphous and crystalline resin components becomes more likely. As a result, charge buildup in low-temperature, low-humidity environments is more favorably suppressed, and the electrostatic stability is improved. On the other hand, if Avb is 25.0 mgKOH / g or less, compositional variations originating from the acid value can be reduced, thus more effectively suppressing charge leakage from amorphous resin to crystalline resin, resulting in excellent charge stability under high temperature and high humidity conditions. Avb is preferably 3.0 to 25.0, more preferably 5.0 to 20.0, and even more preferably 6.0 to 15.0.

[0043] Next, when the full width at half maximum of the maximum value PA is denoted as HPA (volume %), it is preferable that HPA satisfies the following equation (5). 3.0 ≦ HPA ≦ 10.0 (5)

[0044] HPA represents the compositional distribution of resin A corresponding to PA. If the HPA is 3.0 or higher, the PA shape is not too sharp, which further suppresses charge buildup in low-temperature, low-humidity environments. On the other hand, if the HPA is 10.0 or lower, the compositional distribution is less pronounced, which is superior in terms of maintaining a sufficient amount of charge, resulting in better charge stability in high-temperature, high-humidity environments.

[0045] HPA is more preferably 5.0 to 8.0, and even more preferably 6.0 to 7.5. HPA can be increased by making the compositional distribution of the constituent resins non-uniform. Conversely, HPA can be decreased by making the compositional distribution of the constituent resins uniform. The compositional distribution of a resin obtained using polymerizable monomers can be made uniform by combining polymerizable monomers with similar reactivity, or non-uniform by combining polymerizable monomers with distant reactivity. Reactivity can be altered by the molecular weight and unsaturated groups of each polymerizable monomer. For example, the larger the molecular weight of a polymerizable monomer, the lower the reactivity, and the smaller the molecular weight, the higher the reactivity. Also, if the unsaturated groups of a polymerizable monomer are acrylic groups and methacrylic acid groups, the methacrylic group will have higher reactivity.

[0046] Furthermore, when the acid value of resin A is Ava (mgKOH / g), it is preferable that Ava satisfies the following formula (6). 0.0 ≤ Ava ≤ 3.0 ···(6)

[0047] When a highly leaky crystalline resin such as resin B is present in the toner, a lower acid value for amorphous resin A results in superior charge retention. Therefore, when Ava is within the above range, it provides superior charge stability in high-temperature and high-humidity environments. Ava is more preferably 0.0 to 2.5, even more preferably 0.0 to 2.0, even more preferably 0.0 to 1.0, and particularly preferably 0.0.

[0048] Resin A preferably has monomer units made of styrene and monomer units made of alkyl (meth)acrylate. Resins having monomer units of styrene and monomer units of alkyl (meth)acrylate readily exhibit a maximum PA value in gradient LC analysis when the chloroform volume fraction is in the range of 50.0-75.0%. Furthermore, they are suitable for controlling HPA within the aforementioned range and are preferable for controlling electrostatic stability.

[0049] Resin A consists of a monomer unit made of styrene represented by the following formula (D) and the following formula (E) It is preferable to have monomer units made of alkyl (meth)acrylate represented by . For example, resin A is a copolymer of styrene and alkyl (meth)acrylate having an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6, more preferably 2 to 4). [ka] In formula (E), R 6 R represents a hydrogen atom or a methyl group. 7 represents an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6, more preferably 2 to 4).

[0050] The content of monomer units made of styrene represented by formula (D) in resin A is preferably 40.0 to 90.0% by mass, more preferably 50.0 to 85.0% by mass, even more preferably 60.0 to 80.0% by mass, and even more preferably 65.0 to 75.0% by mass. The content of monomer units of alkyl (meth)acrylate represented by formula (E) in resin A is preferably 10.0 to 60.0% by mass, more preferably 15.0 to 50.0% by mass, even more preferably 20.0 to 40.0% by mass, and even more preferably 25.0 to 35.0% by mass.

[0051] In gradient LC analysis of the chloroform-soluble component of resin extracted from toner particles, the volume fraction of chloroform in the mobile phase when the maximum value PA is expressed is defined as CA (volume %), the volume fraction of chloroform in the mobile phase when the maximum value PB is expressed is defined as CB (volume %), and the volume fraction of chloroform in the mobile phase when the minimum value VAB is expressed is defined as CV (volume %). In this case, it is preferable that CA and CB satisfy the following formula (7). 10.0 ≦ CB-CA ≦ 30.0 (7)

[0052] Equation (7) represents the difference in chloroform volume fraction between the maximum value PA and the minimum value PB, indicating that there is a suitable difference in polarity between resin A and resin B. When the volume fraction difference CB-CA (volume %) is 10.0 or more, there is a sufficient polarity difference between resin A and resin B, which further suppresses toner charge leakage and results in superior charge stability in high-temperature and high-humidity environments. On the other hand, when CB-CA is 30.0 or less, the polarities of resin A and resin B are somewhat similar, making charge transfer easier, which facilitates the suppression of charge buildup in low-temperature and low-humidity environments and results in superior charge stability. CB-CA (volume %) is preferably 12.5 to 25.0, and more preferably 17.0 to 22.0.

[0053] CA (volume %) is preferably 50.0 to 75.0, and more preferably 60.0 to 70.0. The CB (volume %) is preferably 70.0 to 92.0, and more preferably 80.0 to 90.0. The CV (volume %) is preferably 65.0 to 80.0, more preferably 70.0 to It is 80.0.

[0054] The percentage of resin A contained in the toner particles is defined as MA (mass%), and the percentage of resin B contained in the toner particles is defined as MB (mass%). Furthermore, in Soxhlet extraction of toner particles using chloroform solvent, the insoluble components obtained after 48 hours of extraction are separated. The resin component remaining after removing the incineration residue ash from the obtained insoluble components is defined as resin C, and the content ratio of resin C in the resin contained in the toner particles is defined as MC (mass%). In this case, it is preferable that MA (mass%), MB (mass%), and MC (mass%) satisfy the following formulas (8), (9), and (10). MA + MB + MC ≦ 100.0 (8) 25.0 ≦ MA ≦ 55.0 (9) 15.0 ≦ MB ≦ 50.0 (10)

[0055] Formula (8) represents the total amount of resins A, B, and C contained in the toner, and indicates that resins other than resins A, B, and C may also be present. MA+MB+MC is more preferably 60.0 to 90.0, even more preferably 70.0 to 85.0, and even more preferably 75.0 to 80.0. Formula (9) shows the content of resin A among the resins in the toner particles, and formula (10) shows the content of resin B among the resins in the toner particles.

[0056] If the content ratio MA of resin A is 25.0 to 55.0% by mass, the total charge amount as a toner can be satisfied, resulting in superior charging characteristics in high-temperature, high-humidity and low-temperature, low-humidity environments. A more preferable range for MA is 30.0% by mass or more and 50.0% by mass or less, and even more preferable is 35.0% by mass or more and 45.0% by mass or less.

[0057] If the content ratio MB of resin B is 15.0 to 50.0% by mass, it is even better in terms of achieving both low-temperature fixing properties and hot offset resistance. More preferably, MB is 17.5% by mass or more and 45.0% by mass or less, even more preferably 20.0% by mass or more and 40.0% by mass or less, and even more preferably 20.0% by mass or more and 25.0% by mass or less.

[0058] Furthermore, it is preferable that the content ratio MC (mass%) of resin C among the resins contained in the toner particles satisfies the following formula (11). 3.0 ≦ MC ≦ 30.0 (11)

[0059] Resin C is a resin component that does not dissolve in chloroform and is a resin component with a high molecular weight or a cross-linked structure. Such resins make it easier to control hot offset resistance by maintaining the toner elasticity of the toner particles at high temperatures. If the MC is between 3.0% by mass and 30.0% by mass, it is superior in achieving both low-temperature fixing and resistance to hot offset. The amount of MC is more preferably 5.0% by mass or more and 25.0% by mass or less, and even more preferably 10.0% by mass or more and 20.0% by mass or less.

[0060] The content of resin A in the toner can be controlled by the amount of resin A added or the amount of polymerizable monomer that becomes resin A added. Similarly, the content of resin B can be controlled by the amount of crystalline resin that becomes resin B added. Furthermore, the content of resin C can be controlled by the amount of chloroform-insoluble matter in the added resin, or by the amount of polymerizable monomer having two or more reactive groups in its molecule, or macromonomers having unsaturated double bonds, as described later.

[0061] Furthermore, resin C preferably has monomer units (b) represented by the following formula (12). Shii [ka]

[0062] [In formula (12), R 2 L represents a hydrogen atom or a methyl group. 2 [where n represents a single bond, ester bond, or amide bond, and n is an integer between 15 and 30.] L 2 Preferably, the carbonyl in the ester bond-COO- is R 2 It is bonded to a carbon atom having [a specific characteristic]. n is preferably 18 to 24, and more preferably 20 to 22.

[0063] The structure of formula (12) above indicates that resin C has a long-chain alkyl group. By including a long-chain alkyl group with 16 or more carbon atoms in resin C, which is a chloroform-insoluble resin component in toner particles, intermediate behavior occurs during charge transfer between amorphous and crystalline resin components, thereby improving charge stability.

[0064] Preferably, resin A has a glass transition temperature Tga (°C), resin B has a melting point Tmb (°C), and resin C has a melting point Tmc (°C). Furthermore, it is preferable that Tga (°C), Tmb (°C), and Tmc (°C) satisfy the following formulas (13), (14), and (15). 40.0 ≦ Tga ≦ 65.0 (13) 50.0 ≦ Tmb ≦ 75.0 (14) 45.0 ≦ Tmc ≦ 65.0 (15)

[0065] If the glass transition temperature Tga (°C) of resin A is between 40.0°C and 65.0°C, it exhibits superior electrostatic stability and low-temperature fixation in low-temperature, low-humidity environments. More preferably, Tga is between 45.0°C and 55.0°C. If the melting point Tmb (°C) of resin B is between 50.0°C and 75.0°C, it is superior in achieving both suppression of charge-up in low-temperature, low-humidity environments, low-temperature fixing performance, and resistance to hot offset. Tmb is more preferably between 55.0°C and 65.0°C. If the melting point Tmc (°C) of resin C is between 45.0°C and 65.0°C, it exhibits superior static charge retention in high-temperature, high-humidity environments and superior charge-up suppression in low-temperature, low-humidity environments. Tmb is more preferably between 50.0°C and 60.0°C.

[0066] An example of the results of gradient LC analysis is shown in Figure 1. The numbers in parentheses indicate the signs in the figure. Chloroform volume fraction 50.0 volume % The area SA(1), maximum value PA(3), full width at half maximum HPA(6) and volume fraction CA(7) of the maximum value PA(3) up to 75.0 volume percent can be controlled as follows.

[0067] First, the full width at half maximum (FWHM) of the maximum value derived from resin A, HPA(6), and the chloroform volume fraction CA(7) can be controlled by the composition of resin A. Specifically, HPA(6) is derived from resin A. The reaction can be controlled by the differences in reactivity and polarity of the polymerizable monomers that serve as raw materials for the monomer units. The greater the difference in reaction rate or the greater the difference in monomer polarity, the larger the full width at half maximum (HPA(6)). For example, in the case of resins obtained by vinyl polymerization, the larger the molecular weight of the polymerizable monomer, the slower the reaction rate. Also, polymerizable monomers with methacrylic groups introduced in addition to acrylic groups are more reactive.

[0068] The area SA(1) and maximum value PA(3) for chloroform volume fractions of 50.0-75.0%, derived from resin A containing the maximum value PA(3), can be controlled by the total amount of resin A in the toner particles and the full width at half maximum HPA(6). Specifically, this can be controlled by the amount of resin A added when producing the toner particles, or, if polymerization is involved, by the total amount of polymerizable monomers that become resin A.

[0069] The maximum value PB(4), CB(8) and SB(2) of chloroform volume fractions that exhibit the maximum value PB(4), derived from resin B with a chloroform volume fraction of 75.0-95.0%, can be controlled by the composition of resin B and the total amount of resin used when producing toner particles, similar to the aforementioned resin CA(7).

[0070] Furthermore, the minimum value VAB(5), which lies between the maximum values ​​PA(3) and PB(4), can be controlled by the ratio of resin A and resin B in the toner particles and the composition of the resins. In particular, VAB tends to be smaller when the full width at half maximum (FWHM) of resins A and B is small, and larger when the FWHM is large. In addition, adding a resin with intermediate polarity and compositional distribution between resins A and B is effective in increasing the value of VAB. CV(9) is the chloroform volume fraction of the maximum value VAB.

[0071] As resin C having an intermediate polarity and compositional distribution between resin A and resin B, a copolymer of a polymerizable monomer containing a macromonomer, a styrene monomer, or an alkyl (meth)acrylate, which is a resin having a reactive unsaturated double bond, is preferred. Alternatively, a crystalline vinyl resin obtained by copolymerizing a polymerizable monomer having a long-chain alkyl group with a polymerizable monomer having a different polarity from the polymerizable monomer is preferred.

[0072] Macromonomers, which are low-polarity resins having reactive unsaturated double bonds, are preferably macromonomers derived from alkyl acrylates or alkyl methacrylates. The alkyl acrylates or alkyl methacrylates constituting the macromonomers preferably have 12 to 30 carbon atoms in the alkyl portion. Alkyl acrylates or alkyl methacrylates will also be referred to as alkyl (meth)acrylates below.

[0073] The alkyl (meth)acrylates with 12 to 30 carbon atoms in the alkyl portion are preferably lauryl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, nonadecyl (meth)acrylate, icosyl (meth)acrylate, henicosyl (meth)acrylate, behenyl (meth)acrylate, tricosyl (meth)acrylate, tetracosyl (meth)acrylate, pentacosyl (meth)acrylate, hexacosyl (meth)acrylate, heptacosyl (meth)acrylate, octacosyl (meth)acrylate, nonacosyl (meth)acrylate, and triacontyl (meth)acrylate. These monomers can be used in combination to easily adjust the melting point of macromonomers. Using alkyl (meth)acrylates with an alkyl moiety having 12 or more carbon atoms results in good heat resistance and durability. Using alkyl (meth)acrylates with an alkyl moiety having 30 or fewer carbon atoms results in good granulation properties.

[0074] Other monomers may also be reacted. Examples include styrene derivatives 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; vinyl esters such as methylene aliphatic monocarboxylic acid esters, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

[0075] The following are examples of methods for providing polymerizable functional groups at the ends of acrylic resin polymerized using the above monomers. For example, one method involves radical polymerization of the above monomers using a polymerization initiator having a hydroxyl group at the end, such as VA-086 (Wako Pure Chemical Industries), and then modifying the acrylic resin having terminal hydroxyl groups derived from the initiator with polymerizable functional groups that can polymerize with styrene. Another method involves radical polymerization of the monomer using a polymerizable initiator having a carboxyl group at its terminus, such as VA-057 (Wako Pure Chemical Industries), and then modifying the acrylic resin, which has terminus derived from the initiator, with polymerizable functional groups that can polymerize with styrene.

[0076] In addition to the monomers mentioned above, other methods include using vinyl monomers having hydroxyl groups, such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate; or vinyl monomers having carboxyl groups, such as acrylic acid or methacrylic acid, to introduce hydroxyl or carboxyl groups into the polymer, thereby modifying the acrylic resin with polymerizable functional groups that can polymerize with styrene.

[0077] Modification methods include the Schotten-Baumann reaction using acid cloids and the urethane reaction using isocyanates. Specific reagents include acryloyl chloride, methacryloyl chloride, p-styrene sulfonate chloride, 2-acryloyloxyethyl isocyanate, and 2-methacryloyloxyethyl isocyanate. Another modification method involves the epoxy addition reaction between a carboxyl group and a glycidyl group. Specific reagents include (meth)acrylic acid esters having a glycidyl group, such as glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl glycidyl acrylate, 2-hydroxyethyl glycidyl methacrylate, 4-hydroxybutyl glycidyl acrylate, and 4-hydroxybutyl glycidyl methacrylate. Another method involves obtaining macromonomers by high-temperature continuous polymerization, as described in Japanese Patent Publication No. 2002-363203.

[0078] Polymerizable monomer compositions may also contain polymerizable monomers other than styrene. Preferably used polymerizable monomers include styrene derivatives such as 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; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, and dimethylphosphoethyl acrylate. Examples include acrylic polymerizable monomers such as diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate; methacrylic polymerizable monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl phosphate ethyl methacrylate; vinyl esters such as methylene aliphatic monocarboxylic acid esters, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

[0079] Also, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis(4-(acryloxydiethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate Examples include tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis(4-(methacryloxydiethoxy)phenyl)propane, 2,2'-bis(4-(methacryloxypolyethoxy)phenyl)propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether, 4,4'-divinylbiphenyl, and the like.

[0080] Polymerizable monomers used in crystalline vinyl resins obtained by copolymerizing a polymerizable monomer having a long-chain alkyl group with a polymerizable monomer of a different polarity are: Polymerizable monomers having long-chain alkyls include alkyl(meth)acrylates in which the alkyl portion has 12 to 30 carbon atoms (preferably 18 to 26, more preferably 20 to 24), such as lauryl(meth)acrylate, tridecyl(meth)acrylate, myristyl(meth)acrylate, pentadecyl(meth)acrylate, hexadecyl(meth)acrylate, heptadecyl(meth)acrylate, stearyl(meth)acrylate, and nonadecy Preferably, the ingredients are yl(meth)acrylate, icosyl(meth)acrylate, henicosyl(meth)acrylate, behenyl(meth)acrylate, tricosyl(meth)acrylate, tetracosyl(meth)acrylate, pentacosyl(meth)acrylate, hexacosyl(meth)acrylate, heptacosyl(meth)acrylate, octacosyl(meth)acrylate, nonacosyl(meth)acrylate, or triacontyl(meth)acrylate.

[0081] Polymerizable monomers having long-chain alkyl groups and polymerizable monomers with different polarities are Monomers having a nitrile group; for example, acrylonitrile, methacrylonitrile, etc. Monomers having a hydroxyl group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. Monomers having an amide group; for example, acrylamide, monomers obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms having an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) by known methods.

[0082] Monomers having a urethane group: For example, C2-C22 alcohols having an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate, vinyl alcohol) and C1-C30 isocyanates [monoisocyanate compounds (benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate)] (e.g., 2-ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, and 2,6-dipropylphenyl isocyanate), aliphatic diisocyanate compounds (trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate) (e.g., dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate), alicyclic diisocyanate compounds (1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate, etc.), and aromatics. Monomers obtained by reacting aromatic diisocyanate compounds (phenylenedi diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate and xylylene diisocyanate, etc.) with known methods, and Alcohols with 1 to 26 carbon atoms (methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, heptadecanol, stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, linolenic acid Monomers obtained by reacting a carbon monoxide (such as chol, nonadecyl alcohol, heneicosanol, behenyl alcohol, erucyl alcohol, etc.) with a carbon 2-30 isocyanate having an ethylenically unsaturated bond [such as 2-isocyanatoethyl (meth)acrylate, 2-(0-[1'-methylpropyleneneamino]carboxyamino)ethyl (meth)acrylic acid, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, etc.] by known methods.

[0083] Monomers containing a urea group: for example, amines with 3 to 22 carbon atoms [primary amines (n-butylamine, t-butylamine, propylamine, and isopropylamine, etc.), secondary amines (di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, and cyclo He Monomers, etc., obtained by reacting xylamine, etc., with isocyanates having 2 to 30 carbon atoms and having an ethylenically unsaturated bond, by known methods. Monomers having a carboxyl group; for example, methacrylic acid, acrylic acid, and 2-carboxyethyl (meth)acrylate. These are some examples.

[0084] Macromonomers that can form resin C include, more preferably, alkyl (meth)acrylates with 12 to 30 carbon atoms in the alkyl portion (preferably 18 to 26 carbon atoms, more preferably 20 to 24 carbon atoms), styrene-based monomers such as styrene and styrene derivatives, and polymers of monomers having a carboxyl group, and (meth)acrylic acid having a glycidyl group. The resin is a resin to which styrene has been added. The macromonomers that can form resin C are more preferably polymers of alkyl (meth)acrylate, styrene, and (meth)acrylic acid, with the alkyl portion having 12 to 30 carbon atoms (preferably 18 to 26, more preferably 20 to 24), to which glycidyl (meth)acrylate has been added. The number of unsaturated groups in the macromonomer is preferably 0.5 to 3.0, more preferably 1.0 to 2.5. For example, resin C may be a copolymer of such a macromonomer with styrene and an alkyl (meth)acrylate having an alkyl group having 1 to 8 carbon atoms (preferably 1 to 6, more preferably 2 to 4).

[0085] The macromonomers that can form resin C, or the number-average molecular weight Mn of resin C, is preferably 5000 to 10000, and more preferably 6000 to 8000. The macromonomers that can form resin C, or the weight-average molecular weight Mw of resin C, is preferably 15,000 to 50,000, and more preferably 25,000 to 35,000.

[0086] As described above, by arbitrarily controlling the area SA, maximum value PA, full width at half maximum, and volume fraction CA of the component derived from resin A with a chloroform volume fraction of 50.0-75.0%, and the area SB, maximum value PB, volume fraction CB, and minimum value VAB between the maximum values ​​PA and PB of the component derived from resin B with a chloroform volume fraction of 75.0-95.0%, SA / SB and VAB / PB can be controlled.

[0087] Next, the resin in the toner particles will be described. The toner particles contain a resin. The resin is, for example, a binder resin. The resin is preferably a vinyl resin. Resins A, B, and C may be known resins that satisfy formulas (1) and (2), such as known binder resins like vinyl resins, polyester resins, polyurethane resins, and epoxy resins. They may also be hybrid resins in which a vinyl resin and a polyester resin are bonded together. Resins A, B, and C are, for example, binder resins, and preferably contain a vinyl resin, and more preferably are vinyl resins.

[0088] Furthermore, resins A, B, and C may have monomer units composed of the following monomers in addition to the monomer units described above. Acrylic monomers include acrylic acid and methacrylic acid; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate; and other acrylic acid ester monomers or methacrylic acid ester monomers. Aromatic vinyl monomers include styrene derivatives such as o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, and pn-dodecylstyrene; These are some examples.

[0089] Furthermore, a crosslinking agent may be used to control the molecular weight of the resin. As crosslinking agents, difunctional crosslinking agents include divinylbenzene and bis(4-acryloxy Examples include polyethoxyphenyl)propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol #200, #400, and #600 diacrylates, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and those in which the above diacrylates are replaced with dimethacrylate.

[0090] Examples of polyfunctional crosslinking agents include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and its substitution with methacrylate, 2,2-bis(4-methacryloxypolyethoxyphenyl)propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and triallyl trimellitate.

[0091] The toner particles may contain core particles having a resin and a shell covering the core particles. The resin forming the shell is not particularly limited, but from the viewpoint of electrostatic stability, vinyl resin or polyester resin is preferred. More preferably, amorphous polyester resin is preferred. The shell does not necessarily have to cover the entire core, and there may be parts of the core that are exposed.

[0092] <Release agent> The toner may contain a release agent. The release agent is preferably at least one selected from the group consisting of hydrocarbon waxes and ester waxes. Using hydrocarbon waxes and / or ester waxes makes it easier to ensure effective release properties.

[0093] There are no particular limitations on hydrocarbon waxes, but examples include the following: Aliphatic hydrocarbon waxes: low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymers, Fischer-Tropsch waxes, or waxes obtained by oxidation or acid addition of these.

[0094] Ester waxes only need to have at least one ester bond in each molecule, and either natural or synthetic ester waxes may be used. There are no particular limitations on ester waxes, but examples include the following: Esters of monohydric alcohols and monocarboxylic acids, such as behenyl behenate, stearyl stearate, and palmityl palmitate; Esters of divalent carboxylic acids and monoalcohols, such as dibehenyl sebacate; Esters of dihydric alcohols such as ethylene glycol distearate and hexanediol dibehenate with monocarboxylic acids; Esters of trihydric alcohols such as glycerol tribehenate and monocarboxylic acids; Esters of tetrahydric alcohols such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate with monocarboxylic acids; Esters of hexahydritol alcohols such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabéhenate with monocarboxylic acids; Esters of polyfunctional alcohols such as polyglycerin behenates and monocarboxylic acids; natural ester waxes such as carnauba wax and rice wax;

[0095] Among these, esters of hexavalent alcohols and monocarboxylic acids, such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabéhenate, are preferred.

[0096] The release agent may be a hydrocarbon wax or an ester wax alone, or a combination of hydrocarbon wax and an ester wax, or a mixture of two or more types. However, it is preferable to use a hydrocarbon wax alone or two or more types. It is more preferable that the release agent is a hydrocarbon wax.

[0097] The release agent content in the toner particles is preferably 1.0% by mass or more and 30.0% by mass or less, and more preferably 2.0% by mass or more and 25.0% by mass or less. Having the release agent content in the toner particles within this range makes it easier to ensure release properties during fixing. The melting point of the release agent is preferably between 60°C and 120°C. A melting point within this range allows the release agent to melt during fixing and easily seep onto the toner particle surface, thus facilitating release properties. More preferably, the melting point is between 70°C and 100°C.

[0098] <Coloring agent> The toner may contain a colorant. Examples of colorants include known organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, and magnetic particles. Other colorants conventionally used in toners may also be used. Examples of yellow colorants include: condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, CI Pigment Yellows 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, and 180 are preferably used.

[0099] Examples of magenta colorants include: condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolon compounds, thioindigo compounds, and perylene compounds. Specifically, CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254 are preferably used. Examples of cyanide colorants include: copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specifically, CI pigment blues 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66 are preferably used.

[0100] The colorants are selected based on their hue angle, saturation, brightness, lightfastness, OHP transparency, and dispersibility in toner. The coloring agent content is preferably 1.0 part by mass or more and 20.0 parts by mass or less per 100.0 parts by mass of resin. When magnetic particles are used as the coloring agent, their content is preferably 40.0 parts by mass or more and 150.0 parts by mass or less per 100.0 parts by mass of resin.

[0101] <Charge control agent> A charge control agent may be incorporated into the toner particles as needed. Alternatively, the charge control agent may be added externally to the toner particles. By incorporating a charge control agent, the charge characteristics can be stabilized, and the optimal amount of triboelectric charge can be controlled according to the developing system. Known charge control agents can be used, and charge control agents that have a fast charging speed and can stably maintain a constant amount of charge are particularly preferred.

[0102] Examples of charge control agents that control the toner's charge to match the load charge include the following: Organometallic compounds and chelate compounds are effective, and examples include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, and oxycarboxylic acid and dicarboxylic acid-based metal compounds. Examples of substances that control the toner's positive charge include: nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorganosucroses, guanidine compounds, and imidazole compounds. The charge control agent content is preferably 0.01 parts by mass to 20.0 parts by mass, and more preferably 0.5 parts by mass to 10.0 parts by mass, per 100.0 parts by mass of toner particles.

[0103] <External additives> The toner particles can be used as is as toner, or, if necessary, external additives can be mixed in and attached to the surface of the toner particles to create toner. Examples of external additives include inorganic fine particles selected from the group consisting of silica fine particles, alumina fine particles, and titania fine particles, or composite oxides thereof. Examples of composite oxides include silica-aluminum fine particles and strontium titanate fine particles. The content of the external additive is preferably 0.01 parts by mass or more and 8.0 parts by mass or less per 100 parts by mass of toner particles, and more preferably 0.1 parts by mass or more and 4.0 parts by mass or less.

[0104] Next, the method for manufacturing toner will be described in detail. Toner particles may be manufactured by any known method, such as suspension polymerization, emulsification and agglutination, dissolution and suspension, or pulverization, as long as they are within the scope of the present configuration. Among these, suspension polymerization is preferred because it is easier to satisfy the above formulas (1) and (2).

[0105] I will now describe the suspension polymerization method in detail. For example, a polymerizable monomer composition is prepared by mixing each polymerizable monomer that produces resin A, a pre-synthesized resin B (a crystalline resin that will become resin B), a pre-synthesized macromonomer or resin C (a resin that is not needed for chloroform that will become resin C) that can form resin C, and, if necessary, other materials such as a colorant, mold release agent, and charge control agent, and uniformly dissolving or dispersing them. At least a portion of the polymerizable monomer may be mixed with a colorant beforehand. Subsequently, the polymerizable monomer composition is dispersed in an aqueous medium using a stirrer or the like to prepare suspended particles of the polymerizable monomer composition. Then, toner particles are obtained by polymerizing the polymerizable monomers contained in the particles with an initiator or the like. After polymerization is complete, the toner particles should be filtered, washed, and dried by known methods, and external additives may be added as needed to obtain toner.

[0106] As a polymerization initiator, known polymerization initiators can be used. Examples of azo or diazo polymerization initiators include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonnitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobisisobutyronitrile; and peroxide polymerization initiators such as benzoyl peroxide, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutylate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumenehydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide. In addition, known chain transfer agents and polymerization inhibitors may be used.

[0107] The aqueous medium may contain an inorganic or organic dispersion stabilizer. As a dispersion stabilizer, known dispersion stabilizers can be used. Examples of inorganic dispersion stabilizers include phosphates such as hydroxyapatite, tricalcium phosphate, dicalcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; metal hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; sulfates such as calcium sulfate and barium sulfate; calcium metasilicate; bentonite; silica; and alumina.

[0108] On the other hand, examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salts of carboxymethylcellulose, polyacrylic acid and its salts, and starch.

[0109] When using inorganic compounds as dispersion stabilizers, commercially available compounds may be used as is, but in order to obtain finer particles, the inorganic compounds may be generated in an aqueous medium before use. For example, in the case of calcium phosphate such as hydroxyapatite or tricalcium phosphate, it is best to mix the phosphate aqueous solution with the calcium salt aqueous solution under high stirring.

[0110] The aqueous medium may contain a surfactant. Known surfactants can be used as the surfactant. Examples include anionic surfactants such as sodium dodecylbenzene sulfate and sodium oleate; cationic surfactants; amphoteric surfactants; and nonionic surfactants.

[0111] The calculation and measurement methods for various physical properties are described below. <Separation of toner particles from toner> The toner particles obtained by separating them from the external additive using the following method can be used for each analysis. Add 160g of sucrose (manufactured by Kishida Chemical Co., Ltd.) to 100mL of deionized water and dissolve it over a water bath to prepare a concentrated sucrose solution. Place 31g of this concentrated sucrose solution and 6mL of Contaminon N (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) into a centrifuge tube to prepare a dispersion. Add 1g of toner to this dispersion and break up any clumps of toner with a spatula or similar tool.

[0112] The centrifugation tube is placed in an Iwaki Sangyo Co., Ltd. "KM Shaker" (model: V.SX) and shaken for 20 minutes at a rate of 350 strokes per minute. After shaking, the solution is transferred to a 50 mL glass tube for the swing rotor and centrifuged in a centrifuge at 3500 rpm for 30 minutes. In the glass tube after centrifugation, toner particles are present in the uppermost layer, while external additives such as silica microparticles are present in the lower aqueous solution layer. The toner particles from the upper layer are collected, filtered, and washed with 2 liters of deionized water heated to 40°C. The washed toner particles are then removed.

[0113] <Separation of chloroform-soluble and insoluble resins from toner particles, and measurement of their content ratio (MC)> 1.5 g of toner particles are weighed accurately (W1 [g]) and placed in a pre-weighed cylindrical filter paper (product name: No. 86R, size 28 x 100 mm, manufactured by Advantec Toyo Co., Ltd.) and set in a Soxhlet extractor. Extraction is carried out for 18 hours using 200 mL of chloroform as the solvent, at a reflux rate such that the solvent extraction cycle is once every 5 minutes.

[0114] After extraction is complete, the cylindrical filter paper is removed and air-dried, then vacuum-dried at 40°C for 8 hours. The mass of the cylindrical filter paper containing the extraction residue is weighed, and the mass of the extraction residue (W2 [g]) is calculated by subtracting the mass of the cylindrical filter paper. When recovering the chloroform-soluble components, it is possible to recover them by thoroughly removing the chloroform from the soluble components in the chloroform using an evaporator. Next, determine the content of components other than the resin component (W3 [g]) using the following procedure. Accurately weigh 2g of toner particles (Wa [g]) into a pre-weighed 30mL magnetic crucible.

[0115] A magnetic crucible is placed in an electric furnace and heated at approximately 900°C for 3 hours. After cooling in the electric furnace, it is allowed to cool further in a desiccator at room temperature for at least 1 hour. The mass of the crucible containing the incineration residue ash is weighed, and the incineration residue ash (Wb [g]) is calculated by subtracting the mass of the crucible. Then, the mass of incineration residue ash (W3[g]) in sample W1[g] is calculated using the following formula (A). W3 = W1 × (Wb / Wa) ... (A)

[0116] Furthermore, if the toner particles contain a release agent, it is necessary to separate the resin and the release agent. The separation of the resin and the release agent is performed by recycling HPLC, separating components with a molecular weight of 2000 or less as the release agent and components with a molecular weight of 2000 or more as the resin. The measurement method is as follows. First, the chloroform-soluble components are separated using the method described above and dissolved in chloroform. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshoridisk" (manufactured by Tosoh Corporation) with a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of chloroform-soluble components is 1.0 mass%. This sample solution is used for measurement under the following conditions. ·Equipment: LC-Sakura NEXT (manufactured by Nippon Analytical Industry Co., Ltd.) • Columns: JAIGEL2H, 4H (manufactured by Nippon Analytical Engineering Co., Ltd.) • Eluent: Chloroform ·Flow rate: 10.0ml / min Oven temperature: 40.0℃ • Sample injection volume: 1.0 ml To calculate the molecular weight of the sample, a molecular weight calibration curve created using standard polystyrene resin (for example, "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0117] From the molecular weight curve obtained in this way, components with a molecular weight of 2000 or less are repeatedly separated to separate the resin component (Wc) and the mold release agent component (Wd) in the chloroform-soluble portion of the toner particles. Then, the mass (W5) [g] of the resin component in the chloroform-soluble portion (W4) in sample W1 [g] is calculated using the following formula. W4 = W1 - W2 W5 = W4 × (Wc / (Wc + Wd)) In this case, the proportion of chloroform-soluble components in the resin within the toner particles can be calculated using the following formula. Percentage of chloroform-soluble components in the resin of toner particles (mass%) = W5 / {W5+(W2-W3)}×100

[0118] Furthermore, the percentage of resin C (MC) contained in the toner particles can be determined by the following method. The content of components other than resin components (W7 [g]) in the mass (W2 [g]) of the extraction residue, which is the chloroform-insoluble portion of the toner particles, is determined by the following procedure: Accurately weigh (Wa' [g]) 2g of the chloroform-insoluble portion of toner particles into a pre-weighed 30mL magnetic crucible. . A magnetic crucible is placed in an electric furnace and heated at approximately 900°C for 3 hours. After cooling in the electric furnace, it is allowed to cool further in a desiccator at room temperature for at least 1 hour. The mass of the crucible containing the incineration residue ash is weighed, and the incineration residue ash (Wb' [g]) is calculated by subtracting the mass of the crucible. Then, the mass of incineration residue ash (W7[g]) in sample W2[g] is calculated using the following formula (A'). W7=W2×(Wb´ / Wa´) ···(A´) Next, the mass (W8 [g]) of resin C, which is the resin component of the chloroform-insoluble portion of the toner particles after removing the incineration residue ash, is calculated using the following formula. W8 = W2 - W7 Furthermore, MC (mass%) is calculated using the following formula. MC = W8 / (W5 + W8) × 100

[0119] <Method for gradient LC analysis of resins and calculation of the content ratio of resin A and resin B> The resin component (Wc) in the chloroform-soluble portion of the toner particles obtained by the method described above was used as the sample. The sample was adjusted with chloroform to a sample concentration of 0.1% by mass, and the solution was filtered through a 0.45 μm PTFE filter and used for measurement. The gradient polymer LC measurement conditions are shown below. Equipment: UlTIMATE3000 (manufactured by Thermo Fisher Scientific) Mobile phase: A. Chloroform (HPLC), B. Acetonitrile (HPLC) Gradient: 2 min (A / B=0 / 100) → 25 min (A / B=100 / 0) (Note that the gradient of the mobile phase change was made to be a straight line.) Flow rate: 1.0mL / min Injection: 0.1% by mass x 20μL Column: Tosoh TSKgel ODS (4.6mmφ x 150mm x 5μm) Column temperature: 40℃ Detector: Corona Charged Particle Detector (Corona-CAD) (manufactured by Thermo Fisher Scientific)

[0120] For the time-intensity graph obtained from the measurement, the time is converted to the chloroform percentage, and then the area of ​​the peak for the chloroform percentage is calculated. If the signal-to-noise ratio (S / N ratio) of the signal intensity is insufficient, a moving average is taken for the chloroform volume fraction as appropriate to improve the S / N ratio of the signal. Specifically, the results were calculated using the results of smoothing the signal by taking a moving average within the range of 3% chloroform volume fraction.

[0121] Next, SA is defined as the area where the proportion (volume fraction) of chloroform in the mobile phase is 50.0 to 75.0 vol%, PA is the maximum value, HPA is the full width at half maximum of PA, and CA is the volume fraction of PA. Furthermore, SB is defined as the area where the proportion of chloroform in the mobile phase is 75.0 to 95.0 vol%, PB is the maximum value and CB is the chloroform volume fraction of PB, and VAB is the minimum value between PA and PB. For example, in the case of peaks in chloroform concentrations from 5.0% to 95.0% by volume, the area can be calculated by determining the area enclosed by the vertical axis representing 5.0% by volume, the vertical axis representing 95.0% by volume, the intensity curve, and the horizontal axis (intensity 0).

[0122] The contents of resins A and B are determined by recovering the developing solution in the above gradient LC, extracting the developing solution with a chloroform fraction of 50.0 to 75.0 volume% as a chloroform solution of resin A, and extracting the developing solution with a chloroform fraction of 75.0 to 95.0 volume% as a chloroform solution of resin B. The above extraction is repeated until a quantity suitable for analysis is reached. The solvent is removed from the extracted solutions of resin A and resin B to obtain resin A and resin B in the toner, and the composition of resin A and resin B is analyzed. Furthermore, the composition of the entire chloroform-soluble component of the toner particles is analyzed, and the composition ratio of resin A and resin B to the chloroform-soluble component of the toner particles is calculated. Then, by multiplying the content percentage (mass%) of chloroform-soluble component in the resin in the toner particles, calculated using the method described above, by the composition ratio of resin A or resin B, the MA (mass%) and MB (mass%) content percentages of resin A and resin B in the toner particles are calculated.

[0123] <Measurement of the glass transition temperature (Tga) of resin A> The glass transition temperature is measured using a differential scanning calorimetry analyzer "Q2000" (TA Instruments) in accordance with ASTM D3418-82. The temperature correction for the device's detection unit uses the melting points of indium and zinc, while the heat of fusion of indium is used for heat quantity correction. Specifically, 3 mg of resin is accurately weighed, placed in an aluminum pan, and measured under the following conditions using an empty aluminum pan as a reference. Heating rate: 10℃ / min Measurement start temperature: 30℃ Measurement end temperature: 180℃ Measurements are performed within the measurement range of 30 to 180°C at a heating rate of 10°C / min. The temperature is raised to 180°C and held for 10 minutes, then cooled to 30°C, and then heated again. During this second heating process, the specific heat change is obtained in the temperature range of 30 to 100°C. The intersection point of the line midway between the baseline before and after the specific heat change and the differential heat curve is defined as the glass transition temperature (Tg) of the resin.

[0124] <Method for measuring the peak temperature (Tmb, Tmc) of an endothermic peak> The peak temperature of the endothermic peak of the resin is measured using a DSC Q2000 (TA Instruments) under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 20℃ Measurement end temperature: 180℃ The temperature correction for the device's detection section uses the melting points of indium and zinc, while the heat of fusion of indium is used for heat quantity correction. Specifically, 1.0 mg of the sample is accurately weighed, placed in an aluminum pan, and differential scanning calorimetry is performed. An empty silver pan is used as a reference. The heating process involves raising the temperature to 180°C at a rate of 10°C / min. Then, the peak temperature is calculated from each peak.

[0125] <Method for measuring the content ratio of various monomer units in resin> The measurement of the content ratio of various monomer units in resins A, B, and C is performed as follows: 1 The procedure is performed using H-NMR under the following conditions. ·Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) • Measurement frequency: 400MHz • Pulse condition: 5.0 μs • Frequency range: 10500Hz • Total number of times: 64 ·Measurement temperature: 30℃ • Sample: Place 50 mg of the sample to be measured into a sample tube with an inner diameter of 5 mm, add deuterated chloroform (CDCl3) as a solvent, and dissolve in a constant temperature bath at 40°C to prepare the sample.

[0126] The following example uses resin B. obtained 1 From the H-NMR chart, select a peak from among the peaks attributed to the components of monomer unit (a) that is independent of the peaks attributed to the components of other monomer units, and calculate the integral value S1 of this peak. If resin B contains a second monomer unit, similarly, select a peak from among the peaks attributed to the components of the second monomer unit that is independent of the peaks attributed to the components of other monomer units, and calculate the integral value S2 of this peak. Furthermore, if a third and fourth monomer unit is present, a peak independent of the peaks attributed to the components of the other monomer units is selected from the peaks attributed to the components of the third and fourth monomer units, and the integral values ​​S3 and S4 of this peak are calculated.

[0127] The content of monomer unit (a) is determined using the integral values ​​S1, S2, S3, and S4 as follows. Note that n1, n2, n3, and n4 are the number of hydrogen atoms in the constituent element to which the peak of interest belongs for each part. Percentage of monomer unit (a) (mol %) = {(S1 / n1) / ((S1 / n1)+(S2 / n2)+(S3 / n3)+(S4 / n4))}×100 Similarly, the proportions of the second, third, and fourth monomer units are determined as follows. Second monomer unit content (mol%) = {(S2 / n2) / ((S1 / n1)+(S2 / n2)+(S3 / n3)+(S4 / n4))}×100 The content percentage (mol%) of the third monomer unit = {(S3 / n3) / ((S1 / n1)+(S2 / n2)+(S3 / n3)+(S4 / n4))}×100 Percentage of the fourth monomer unit (mol%) = {(S4 / n4) / ((S1 / n1)+(S2 / n2)+(S3 / n3)+(S4 / n4))}×100

[0128] Furthermore, in the case of resins, if polymerizable monomers are used in which components other than vinyl groups do not contain hydrogen atoms, 13 The atomic nuclei were measured using C-NMR. 13 Let C be used, and the measurement will be performed in single-pulse mode. 1 The same calculation is performed using 1H-NMR. Resins A and C can also be measured in the same manner. Furthermore, when toner is manufactured by suspension polymerization, the peaks of the release agent and shell resin may overlap, preventing the observation of independent peaks. This can make it impossible to calculate the content ratio of various units in the binder resin. In such cases, a resin ' can be produced by performing the same suspension polymerization without using the release agent or other resins, and this resin ' can be analyzed as the resin itself.

[0129] <Method for measuring the molecular weight of resins> The molecular weight (weight-average molecular weight Mw, number-average molecular weight Mn) of the THF-soluble components of the resin is measured by gel permeation chromatography (GPC) as follows: First, the sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the resulting solution is filtered through a solvent-resistant membrane filter, "Myshoridisk" (manufactured by Tosoh Corporation), with a pore diameter of 0.2 μm to obtain the sample solution. The sample solution is adjusted so that the concentration of THF-soluble components is 0.8% by mass. This sample solution is then measured under the following conditions. • Equipment: HLC8120 GPC (Detector: RI) (Manufactured by Tosoh Corporation) • Columns: Shodex KF-801, 802, 803, 804, 805, 806, 807 (7 columns, manufactured by Showa Denko) • Eluent: Tetrahydrofuran (THF) ·Flow rate: 1.0ml / min Oven temperature: 40.0℃ • Sample injection volume: 0.10 ml To calculate the molecular weight of the sample, a molecular weight calibration curve created using standard polystyrene resin (for example, "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0130] <Measurement of acid value AVa of resin A and acid value AVb of resin B> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of the binder resin is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure.

[0131] (1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add deionized water to make 100 mL, and obtain a phenolphthalein solution. Dissolve 7 g of special grade potassium hydroxide in 5 mL of water, add ethyl alcohol (95% by volume) to make 1 L. Place in an alkali-resistant container, keeping away from carbon dioxide, etc., and let stand for 3 days. After filtration, obtain a potassium hydroxide solution. Store the obtained potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by taking 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, titrating with the potassium hydroxide solution, and determining the amount of potassium hydroxide solution required for neutralization. The 0.1 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0132] (2) Operation (A) Main examination 2.0 g of the sample is accurately weighed into a 200 mL Erlenmeyer flask, and 100 mL of a toluene / ethanol (2:1) mixture is added. The sample is dissolved over 5 hours. Then, a few drops of the phenolphthalein solution are added as an indicator, and the sample is titrated with the potassium hydroxide solution. The titration endpoint is reached when the indicator turns a pale pink color for approximately 30 seconds. (B) Blank test The titration procedure is the same as described above, except that no sample is used (i.e., only a mixed solution of toluene / ethanol (2:1) is used).

[0133] (3) Substitute the obtained results into the following formula to calculate the acid value. A = [(CB) × f × 5.61] / S Here, A: acid value (mgKOH / g), B: volume of potassium hydroxide solution added in the blank test (mL), C: volume of potassium hydroxide solution added in the main test (mL), f: factor of the potassium hydroxide solution, and S: mass of the sample (g). [Examples]

[0134] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples. In the following formulations, parts are by mass unless otherwise specified.

[0135] (Method for synthesizing additive resin B1) The following materials were added to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. • Toluene 100.0 parts • Monomer composition 100.0 parts (The monomer composition shall be a mixture of the following monomers in the proportions shown below.) (Behenyl acrylate (monomer (a)) 80.0 parts) (Styrene 18.) 5 Department) (methacrylic acid) 1.5 Department) • Polymerization initiator (Wako Pure Chemical Industries: V-65) 0.5 parts The reaction vessel was heated to 70°C while stirring at 200 rpm, and the polymerization reaction was carried out for 12 hours to obtain a solution in which the monomer polymer was dissolved in toluene. Subsequently, the solution was cooled to 25°C, and then added to 1000.0 parts methanol while stirring to precipitate the methanol-insoluble components. The obtained methanol-insoluble components were filtered off, washed with methanol, and then vacuum-dried at 40°C for 24 hours to obtain the additive resin B1.

[0136] (Preparation of additive resins B2 to B25) In the synthesis of additive resin B1, additive resins B2 to B25 were prepared in the same manner as before, except that the amount of monomer composition added was changed to Table 1, and the amount of initiator added and the reaction time were changed so that the molecular weight was as shown in Table 1. [Table 1] In the table, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, Tm is the melting point (°C), and Av is the acid value (mgKOH / g). The abbreviations for monomers in the table are as follows: St: Styrene BEA: Behenyl Acrylate MAA: Methacrylic acid LAA: Lauryl Acrylate STA: Stearyl Acrylate

[0137] (Method for synthesizing additive resin C1) The following materials were added to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. • Toluene 100.0 parts • Monomer composition 100.0 parts (The monomer composition shall be a mixture of the following monomers in the proportions shown below.) (Behenyl acrylate (monomer (a)) 80.0 parts) (Styrene 1 7.5 Department) (Methacrylic acid 0.8 parts) • Polymerization initiator (Wako Pure Chemical Industries: V-65) 0.5 parts The reaction vessel was heated to 70°C while stirring at 200 rpm, and the polymerization reaction was carried out for 12 hours to obtain a solution in which the monomer polymer was dissolved in toluene.

[0138] Furthermore, in order to deactivate the polymerization initiator, the nitrogen inlet tube was removed, the mixture was heated to 85°C, and heated for another 6 hours. Then, 0.05 parts of triethylamine and 1.3 parts of glycidyl methacrylate were added, and the addition reaction was carried out for 5 hours. Next, the above solution was cooled to 25°C, and then added to 1000.0 parts methanol while stirring to precipitate the methanol-insoluble components. The obtained methanol-insoluble components were filtered off, washed with methanol, and then vacuum-dried at 40°C for 24 hours to obtain the additive resin C1.

[0139] (Preparation of additive resins C2-C9) In the preparation of additive resin C2, additive resins C2 to C9 were prepared in the same manner as above, except that the amount of monomer composition added was changed to Table 2 and the amount of glycidyl methacrylate added was changed to match the number of unsaturated groups in Table 2. [Table 2] The abbreviations for monomers in the table are as follows: St: Styrene BEA: Behenyl Acrylate MAA: Methacrylic acid LAA: Lauryl Acrylate STA: Stearyl Acrylate MAN: Methacrylonitrile

[0140] The number of unsaturated groups was determined by the number-average molecular weight (Mn) obtained by the above gel permeation chromatography (GPC) and nuclear magnetic resonance spectroscopy. 1 The molecular weight was determined using the molecular weight (M_NMR) obtained from 1H-NMR. Nuclear magnetic resonance spectroscopy ( 1The measurement conditions for 1H-NMR [400MHz, CDCl3, room temperature (25℃)] were as follows: Measurement equipment: FT NMR spectrometer JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Total number of times: 64 From the integral of the obtained spectrum, the composition ratio of the constituent monomers per unsaturated group can be determined. From the monomer composition ratio and molecular weight, the NMR molecular weight (M_NMR) per unsaturated group can be calculated. Furthermore, the number of unsaturated groups per macromonomer molecule can be calculated using the following formula, based on the number-average molecular weight (Mn) obtained from gel permeation chromatography (GPC) and the NMR molecular weight (M_NMR) obtained from the above NMR. Number of unsaturated groups = GPC number average molecular weight (Mn) / NMR molecular weight (M_NMR)

[0141] [Toner manufacturing by suspension polymerization method] (Manufacturing of toner particles 1) • Styrene 47.0 parts n-butyl acrylate 20.0 parts • Coloring agent: Pigment Blue 15:3 6.5 parts A mixture consisting of the above materials was prepared. The above mixture was placed in an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed using 5 mm diameter zirconia beads at 200 rpm for 2 hours to obtain a dispersion of raw materials.

[0142] Meanwhile, 735.0 parts of deionized water and 16.0 parts of trisodium phosphate (dodecahydrate) were added to a container equipped with a high-speed stirring device homomixer (Primix Corporation) and a thermometer, and the temperature was raised to 60°C while stirring at 12,000 rpm. Then, an aqueous calcium chloride solution, prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of deionized water, was added, and the mixture was stirred at 12,000 rpm for 30 minutes while maintaining the temperature at 60°C. Then, 10% hydrochloric acid was added to adjust the pH to 6.0, obtaining an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.

[0143] Next, the above raw material dispersion was transferred to a container equipped with a stirring device and a thermometer, and the temperature was raised to 60°C while stirring at 100 rpm. ·Additive resin B1 26.0 parts ·Additive resin C1 7.0 parts • Release agent 1 9.0 parts (Release agent 1: DP18 (Dipentaerythritol stearate wax, melting point 79°C, manufactured by Nippon Seiro Co., Ltd.) The above materials were added and stirred at 100 rpm for 30 minutes while maintaining a temperature of 60°C. Then, 9.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) were added as a polymerization initiator and stirred for another minute. The mixture was then added to an aqueous medium being stirred at 15,000 rpm in the high-speed stirring device. Stirring was continued at 15,000 rpm for 20 minutes while maintaining a temperature of 60°C in the high-speed stirring device to obtain a granulated liquid.

[0144] The above granulated liquid is transferred to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube, and nitrogen is introduced. The mixture was heated to 70°C while being stirred at 150 rpm under controlled conditions. The polymerization reaction was carried out at 150 rpm for 12 hours while maintaining the temperature at 70°C to obtain a toner particle dispersion. The obtained toner particle dispersion was cooled to 45°C while being stirred at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45°C. After that, while maintaining stirring, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid components were filtered off, thoroughly washed with deionized water, and then vacuum-dried at 30°C for 24 hours to obtain toner particles 1. The method for producing toner particles 1 is shown in Table 3.

[0145] (Manufacturing of toner particles 2-48 and comparative toner particles 1-7) Toner particles 2-48 and comparative toner particles 1-6 were manufactured in the same manner as in the production of toner particle 1, except that the monomer composition and the amount of added resin were changed as shown in Table 3. The comparative toner particles 7 were manufactured as follows. • Polyester resin: 50.0 parts (Polycondensate of propylene oxide-modified bisphenol A (2-molar adduct), terephthalic acid and trimellitic acid (molar ratio 10.0:10.0:0.3), glass transition temperature Tg = 67 °C, weight average molecular weight Mw = 10500, molecular weight distribution Mw / Mn = 4.72) · Added resin B1: 50.0 parts · Release agent: 9.0 parts (Release agent: DP18 (dipentaerythritol stearic acid ester wax, melting point 79 °C, manufactured by Nippon Seiro Co., Ltd.) · Colorant Pigment Blue 15:3: 6.5 parts After premixing the above materials with a Henschel mixer (manufactured by Nippon Coke Co., Ltd.), they were melt-kneaded using a twin-screw kneading extruder (manufactured by Ikegai Iron Works Co., Ltd.: PCM-30 type). The obtained kneaded product was cooled, coarsely pulverized with a hammer mill, then pulverized with a mechanical pulverizer (manufactured by Turbo Industries Co., Ltd.: T-250), and the obtained finely pulverized powder was classified using a multi-stage classifier utilizing the Coanda effect to obtain comparative toner particles 7.

[0146]

Table 3

[0147] The results of gradient LC analysis for the obtained toner particles 1 - 48 and comparative toner particles 1 - 7 are shown in Table 4, and the analysis results for the separated resins A, B, and C are shown in Table 5.

Table 4

[0148] [Table 5] In the table, "long-chain alkyl" refers to the monomer that forms the monomer unit of the (meth)acrylate alkyl ester containing long-chain alkyl contained in each resin. "Unit (a) content" indicates the content of monomer unit (a) shown in formula (3).

[0149] (Example 1) (Evaluation of toner particles 1) For the above toner particles in a 1:100.0 ratio, silica microparticles (hydrophobized with hexamethyldisilazane, primary particle number average particle size: 10 nm, BET specific surface area: 170 m²) are used as an external additive. 2 2.0 parts of ( / g) were added and mixed at 3000 rpm for 15 minutes using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) to obtain Toner 1. The obtained toner was evaluated according to the evaluation method described below.

[0150] <Toner Evaluation Method> <1> Evaluation of retention A process cartridge filled with toner was left at 25°C and 40% RH for 48 hours. Using an LBP-712Ci modified to operate without the fuser, an unfixed image was printed with an image pattern consisting of 10mm x 10mm squares evenly distributed at 9 points across the entire transfer paper. The amount of toner adhering to the transfer paper was 0.80 mg / cm². 2 The fixing temperature was varied in 5°C increments from 100°C to 220°C, and the lower and upper fixing temperatures were evaluated. The transfer paper used was A4 paper ("Proverbond paper": 105g / m 2 (Made by Fox River Corporation) 。

[0151] For the fuser, an external fuser was used, which was created by removing the fuser unit from the LBP-712Ci and operating it outside the laser beam printer. The external fuser performed the fixing process at a process speed of 320 mm / sec, with the fixing temperature gradually increased in 5°C increments starting from 90°C. The fixed image was visually inspected, and the lowest temperature at which no cold offset occurred was defined as the lower fixing temperature, and the highest temperature at which no hot offset occurred was defined as the upper fixing temperature. A temperature of 160°C or below was considered to indicate excellent low-temperature fixing performance. Furthermore, the difference between the lower fixing temperature and the upper fixing temperature was defined as the fixing latitude, and a fixing latitude of 40°C or more was considered to indicate excellent fixing performance.

[0152] <2> Evaluation of electrostatic stability Durability was evaluated using a commercially available Canon LBP-712Ci printer. The evaluation cartridge was prepared by removing the toner from a commercially available cartridge, cleaning the inside with compressed air, and then filling it with 200g of the toner to be evaluated. After leaving the cartridge in a 25°C, 40% RH environment for 48 hours, it was installed in a cyan station and durability was evaluated.

[0153] As an evaluation of electrostatic stability under high temperature and high humidity conditions, Canon Oce Red Label (80g / m²) was tested at 30°C and 80% RH. 2 Using [a specific method / tool], an initial solid white image was printed, and the fogging density was measured. Subsequently, to evaluate the degree of leakage, 3000 horizontal line pattern images with a print density of 1% were output consecutively, left for more than 12 hours, and then a solid white image was printed, and the fogging density was measured.

[0154] As an evaluation of electrostatic stability under low temperature and low humidity conditions, Canon Oce Red Label (80g / m²) was tested at 15°C and 10% RH. 2 Using [a specific method / tool], an initial solid white image was printed, and the fogging density was measured. Subsequently, to evaluate the ease of charge-up, 3000 consecutive prints of a horizontal line pattern image with a print density of 1% were output, and immediately afterward, a solid white image was printed, and the fogging density was measured.

[0155] For the measurement of the fog density, "REFLECTMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.) was used, and the fog density (%) was calculated from the difference between the whiteness of the white background part of the printed solid white image and the whiteness of the transfer paper. An amber filter was used as the filter. If the fog density was 2.5% or less, it was judged that the charge stability was excellent.

[0156] The evaluation results of Toner 1 are shown in Table 6.

Table 6

[0159] 1. Area with a chloroform volume fraction of 50.0% to 75.0% SA 2. Area with a chloroform volume fraction of 50.0% to 75.0% (SB) 3. Maximum value of chloroform volume fraction between 50.0% and 75.0% PA 4. Chloroform volume fraction: Maximum value between 50.0% and 75.0% (PB) 5. Local minimum VAB between local maximums PA and PB. 6. Half-width of the maximum value PA (HPA) 7. Chloroform volume fraction CA at the maximum value PA 8. Chloroform volume fraction CB at the maximum value PB 9. Chloroform volume fraction CV at the maximum VAB value

Claims

1. A toner having toner particles containing a binder resin, The binder resin of the toner particles consists solely of vinyl resin. In a Soxhlet extraction of the toner particles using chloroform solvent, components with a molecular weight of 2000 or less are removed from the soluble components obtained by recycled HPLC, and this is used as the chloroform-soluble component of the binder resin extracted from the toner particles. When chloroform was used as the poor solvent and chloroform as the good solvent for the chloroform-soluble portion of the binder resin, and the mobile phase was linearly changed from a 100% by volume acetonitrile mobile phase to a 100% by volume chloroform mobile phase, the eluted components were analyzed by gradient LC. In the mobile phase where the proportion of chloroform is in the range of 50.0 to 75.0 volume%, the area of ​​the peak detected using a Corona charged particle detector is defined as SA, and the maximum value as PA. In the mobile phase where the proportion of chloroform is in the range of 75.0 to 95.0 volume%, the area of ​​the peak detected using a Corona charged particle detector is defined as SB, and the maximum value as PB. When the smallest local minimum between PA and PB is denoted as VAB, PA and PB exist, SA, SB, PB, and VAB satisfy the following formulas (1) and (2), 0.30≦SA / SB≦0.85...(1) 0.25 ≦ VAB / PB ≦ 0.55 (2) In the gradient LC analysis, the resin obtained by extracting components in the mobile phase where the proportion of chloroform is in the range of 50.0 to 75.0 volume percent is defined as resin A, which is the resin component corresponding to PA. In the gradient LC analysis, the resin obtained by extracting components in the mobile phase where the proportion of chloroform is in the range of 75.0 to 95.0 volume percent is defined as resin B, which is the resin component corresponding to PB. In the Soxhlet extraction of the toner particles using chloroform solvent, the insoluble matter obtained after 48 hours of extraction is separated, and the resin component obtained by removing the incineration residue ash from the insoluble matter is defined as resin C. The proportion of resin A in the binder resin contained in the toner particles is defined as MA (mass%). The proportion of resin B in the binder resin contained in the toner particles is defined as MB (mass%). The proportion of resin C in the binder resin contained in the toner particles is defined as MC (mass%). At that time, The MA, MB, and MC satisfy the following formulas (8), (9), (10), and (11): MA + MB + MC ≦ 100.0 (8) 25.0≦MA≦55.0...(9) 15.0≦MB≦50.0...(10) 3.0≦MC≦30.0 (11) The resin C has a monomer unit (b) represented by the following formula (12), A toner characterized by the following features. [In formula (12), R2 represents a hydrogen atom or a methyl group, L2 represents a single bond, an ester bond, or an amide bond, and n represents an integer from 15 to 30.]

2. The resin B has a monomer unit (a) represented by the following formula (3): The toner according to claim 1. [In formula (3), R １ L represents a hydrogen atom or a methyl group. １ [where m represents a single bond, ester bond, or amide bond, and m represents an integer between 15 and 30.]

3. The toner according to claim 2, wherein the content of the monomer unit (a) represented by formula (3) in the resin B is 40.0 to 95.0% by mass.

4. When the acid value of resin B is AVb (mgKOH / g), The AVb satisfies the following formula (4): 1.5≦AVb≦25.0...(4) The toner according to claim 2.

5. When the full width at half maximum of the PA is denoted as HPA (volume %), The HPA satisfies the following formula (5): 3.0≦HPA≦10.0...(5) The toner according to any one of claims 1 to 4.

6. When the acid value of resin A is given by AVa (mgKOH / g), The AVa satisfies the following formula (6): 0.0≦AVa≦3.0...(6) The toner according to any one of claims 1 to 4.

7. The toner according to claim 6, wherein the resin A has monomer units made of styrene and monomer units made of alkyl (meth)acrylate.

8. In the gradient LC analysis, the volume fraction of chloroform in the mobile phase when PA is expressed is defined as CA. In the gradient LC analysis, when the volume fraction of chloroform in the mobile phase at the time PB is expressed is denoted as CB, CA and CB satisfy the following formula (7): 10.0≦CB-CA≦30.0...(7) The toner according to any one of claims 1 to 4.

9. The resin A has a glass transition temperature Tga (°C), The resin B has a melting point Tmb (°C), The resin C has a melting point Tmc (°C), The Tga (°C), Tmb (°C), and Tmc (°C) satisfy the following formulas (13), (14), and (15): 40.0≦Tga≦65.0 (13) 50.0≦Tmb≦75.0 (14) 45.0≦Tmc≦65.0...(15) The toner according to claim 1.

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