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] The present disclosure relates to toners used in electrophotography and electrostatic recording. [Background technology]

[0002] Conventionally, energy saving has been considered as a major technical issue in electrophotographic devices, and a significant reduction in the amount of heat required for fixing devices has been considered. In particular, there is an increasing need for toners that can be fixed with less energy, that is, so-called "low-temperature fixing properties."

[0003] One method for enabling fixation at low temperatures is to lower the glass transition temperature (Tg) of the binder resin in the toner. However, lowering the Tg leads to a decrease in the heat-resistant storage stability of the toner, and it is considered difficult to achieve both low-temperature fixability and heat-resistant storage stability of the toner with this method.

[0004] As a countermeasure, toners to which a plasticizer has been added are being considered in Patent Documents 1 and 2. The plasticizer can increase the softening speed of the binder resin while maintaining the Tg of the toner, and can achieve both low-temperature fixability and heat-resistant storage stability. However, since the toner softens through the steps of melting the plasticizer and plasticizing the binder resin, there is a limit to the melting speed of the toner, and further improvement in low-temperature fixability is desired.

[0005] Therefore, in order to achieve both further low-temperature fixability and heat-resistant storage stability of the toner, a method of using a crystalline vinyl resin as a binder resin has been investigated. Amorphous resins that are generally used as binder resins for toners do not show a clear endothermic peak in differential scanning calorimeter (DSC) measurements, but when they contain a crystalline resin component, an endothermic peak (melting point) appears in DSC measurements.

[0006] Crystalline vinyl resins have the property that they hardly soften up to the melting point due to the regular arrangement of side chains in the molecule. In addition, the crystals melt suddenly at the melting point, and the viscosity drops rapidly. For this reason, they are attracting attention as a material that has excellent sharp melting properties and is compatible with low-temperature fixing properties and heat-resistant storage properties. Usually, crystalline vinyl resins have long-chain alkyl groups as side chains in the main chain skeleton, and become crystalline resins when the long-chain alkyl groups in the side chains crystallize with each other.

[0007] Patent Document 3 proposes a method for producing a toner containing a crystalline vinyl, which has excellent production stability, by introducing an unsaturated group into a crystalline vinyl resin. Furthermore, Patent Document 4 proposes a method for achieving both low temperature fixing ability and hot offset resistance by using a toner that uses an amorphous resin and a crystalline vinyl resin obtained by copolymerizing a polymerizable monomer having a long-chain alkyl group and an amorphous polymerizable monomer having a different SP value. Furthermore, Patent Document 5 proposes a method for obtaining a toner having excellent durability in addition to achieving both low-temperature fixing ability and hot offset resistance by crosslinking a crystalline vinyl resin with an amorphous resin. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] International Publication No. 2013 / 047296 [Patent Document 2] JP 2016-066018 A [Patent Document 3] JP 2016-218237 A [Patent Document 4] Patent Publication No. 2021-096463 [Patent Document 5] Patent Publication No. 2021-036316 Summary of the Invention [Problem to be solved by the invention]

[0009] However, Patent Documents 3, 4, and 5 reveal that there is a problem to be solved in obtaining high charging stability in both a high-temperature, high-humidity environment and a low-temperature, low-humidity environment while achieving both low-temperature fixing ability and hot-off resistance. In Patent Document 3, a toner is obtained by reacting a polymerizable monomer with a crystalline vinyl resin, but due to a large difference in reactivity between the crystalline resin and the polymerizable monomer, there is a problem with the charge stability in a low-temperature, low-humidity environment. In Patent Documents 4 and 5, a polar group is introduced into the crystalline vinyl resin, which exhibits good chargeability in a low-temperature, low-humidity environment, but has a problem in terms of charge retention in a high-temperature, high-humidity environment. The present disclosure provides a toner that has 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 problem]

[0010] The present disclosure provides a toner having toner particles having a resin, the toner particles are subjected to Soxhlet extraction using a chloroform solvent for 48 hours, and components having a molecular weight of 2000 or less are removed by recycling HPLC from the soluble fraction obtained, which is defined as the chloroform-soluble fraction of the resin extracted from the toner particles; Acetonitrile was used as a poor solvent and chloroform was used as a good solvent for the chloroform-soluble portion of the resin. The mobile phase was changed linearly from 100% acetonitrile by volume to 100% chloroform by volume. The eluted components were analyzed by gradient LC. The area of ​​the peak detected by using a Corona charged particle detector in a range of 50.0 to 75.0% by volume of chloroform in the mobile phase is designated as SA, and the maximum value is designated as PA. The area of ​​the peak detected by using a Corona charged particle detector in the mobile phase in which the ratio of chloroform in the mobile phase is in the range of 75.0 to 95.0% by volume is designated as SB, and the maximum value is designated as PB. When the minimum value existing between the PA and the PB is VAB, The PA and the PB are present, The toner relates to a toner in which the SA, the SB, the PB and the VAB satisfy the following formulas (1) and (2). 0.30 ≦ SA / SB ≦ 0.85 (1) 0.25 ≦ VAB / PB ≦ 0.55 (2) Effect of the Invention

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

[0012] [Figure 1] Example results of gradient LC analysis. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] In the present disclosure, the description of a numerical range such as "XX or more and YY or less" or "XX to YY" means a numerical range including the lower and upper limits, which are the endpoints, unless otherwise specified. When a numerical range is described in stages, the upper and lower limits of each numerical range can be arbitrarily combined. The (meth)acrylic acid ester means an acrylic acid ester and / or a methacrylic acid ester.

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

[0015] [In formula (C), R A represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group); RB represents an optional substituent.] The crystalline resin refers to a resin that shows a clear endothermic peak in a differential scanning calorimeter (DSC) measurement.

[0016] The present inventors have focused on the polarity distribution of the resin component contained in the toner, and have found that the above-mentioned problems can be solved by appropriately controlling the polarity distribution of the resin constituting the toner. In order to obtain low-temperature fixing properties of a toner using a crystalline vinyl resin, it is important to include a certain amount of crystalline vinyl resin in the resin in the toner particles. The polarity of the crystalline vinyl resin can be controlled to a certain extent by the composition of the monomer units that constitute the crystalline vinyl resin, but since the crystalline vinyl resin generally needs to contain a high proportion of long-chain alkyl structures, the polarity tends to be low. In order to obtain even sharper melting properties, high crystallinity is required, for example by increasing the content ratio of longer long-chain alkyl units. Such resins tend to have low polarity and low electrical resistance, making it difficult to retain a charge.

[0017] The inventors considered combining a crystalline resin exhibiting such charging characteristics with a conventionally used amorphous resin in order to obtain excellent charging properties. Specifically, the inventors considered whether a crystalline resin having excellent sharp melting properties could be used in combination with a resin having a different polarity from that of the crystalline resin, thereby obtaining low-temperature fixing properties from the crystalline resin while obtaining charging stability from the amorphous resin. As a result of extensive investigations, the inventors have obtained the following toner.

[0018] The present disclosure provides a toner having toner particles having a resin, the toner particles are subjected to Soxhlet extraction using a chloroform solvent for 48 hours, and components having a molecular weight of 2000 or less are removed by recycling HPLC from the soluble fraction obtained, which is defined as the chloroform-soluble fraction of the resin extracted from the toner particles; Acetonitrile was used as a poor solvent and chloroform was used as a good solvent for the chloroform-soluble portion of the resin. The mobile phase was changed linearly from 100% acetonitrile by volume to 100% chloroform by volume. The eluted components were analyzed by gradient LC. The area of ​​the peak detected by using a Corona charged particle detector in a range of 50.0 to 75.0% by volume of chloroform in the mobile phase is designated as SA, and the maximum value is designated as PA. The area of ​​the peak detected by using a Corona charged particle detector in the mobile phase in which the ratio of chloroform in the mobile phase is in the range of 75.0 to 95.0% by volume is designated as SB, and the maximum value is designated as PB. When the minimum value existing between the PA and the PB is VAB, The PA and the PB are present, The toner relates to a toner in which the SA, the SB, the PB and the VAB satisfy the following formulas (1) and (2). 0.30 ≦ SA / SB ≦ 0.85 (1) 0.25 ≦ VAB / PB ≦ 0.55 (2)

[0019] First, gradient LC analysis will be described. In gradient LC analysis, unless otherwise specified, the sample is the chloroform-soluble resin fraction obtained by removing components with a molecular weight of 2000 or less by recycling HPLC from the soluble fraction obtained by extracting toner particles for 48 hours using a Soxhlet extraction method with a chloroform solvent. Acetonitrile is used as a poor solvent and chloroform is used as a good solvent for the chloroform-soluble resin fraction extracted from the toner particles, and the eluted components are analyzed by gradient LC when the mobile phase is changed linearly from 100% acetonitrile by volume to 100% chloroform by volume.

[0020] The area of ​​the peak detected by the Corona charged aerosol detector in the mobile phase with a chloroform content of 50.0 to 75.0% by volume is designated SA, and the maximum value of the peak is designated PA. The area of ​​the peak detected by the Corona charged aerosol detector in the mobile phase with a chloroform content of 75.0 to 95.0% by volume is designated SB, and the maximum value is designated PB. The smallest minimum value between the maximum value PA and the maximum value PB is designated VAB. In this case, PA and PB exist, and 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)

[0021] As will be described in detail later, the signal obtained according to the proportion of chloroform in the mobile phase in gradient LC analysis, detected using a Corona charged aerosol detector, indicates the degree of polarity. The higher the volume fraction of chloroform, the lower the polarity of the component.

[0022] The maximum value PA and area SA of the peak obtained by gradient LC analysis in the range of 50.0 to 75.0 volume % of chloroform in the mobile phase are derived from the amorphous resin component having a relatively high polarity. On the other hand, when the proportion of chloroform in the mobile phase is in the range of 75.0 to 95.0% by volume, the maximum value PB and area SB of the peak are derived from the crystalline resin component having relatively low polarity.

[0023] SA / SB, which is the ratio of the area of ​​the signal derived from the amorphous resin component to the area of ​​the signal derived from the crystalline resin component in gradient LC analysis, indicates the balance between the charge retention property of the amorphous resin component and the charge leakage property of the crystalline resin component. It was found that when SA / SB is 0.30 or more and 0.85 or less, the effect on chargeability is remarkable. If SA / SB is less than 0.30, the leakage is too high in a high-temperature, high-humidity environment, and the charging stability is reduced when a durability test is performed. If SA / SB is more than 0.85, the leakage is not sufficient in a low-temperature, low-humidity environment, and significant charge-up occurs when a durability test is performed.

[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 ratio of resin components having high polarity in the toner particles, and SA / SB can be decreased by increasing the ratio of resin components having low polarity in the toner particles.

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

[0026] The minimum value VAB, which is the smallest of the minimum values ​​between the maximum value PA and the maximum value PB, is an index of the overall amount of intermediate polarity components between the amorphous resin component and the crystalline resin component. It is believed that the presence of a certain proportion of the minimum value VAB enables the transfer of charge between the maximum value PA and the maximum value PB, resulting in a synergistic effect of the characteristics of each component.

[0027] In particular, controlling the leakage of electric charge is important to obtain excellent charging characteristics of the toner, and is the ratio of the minimum value VAB to the maximum value PB derived from the crystalline resin component. When VAB / PB is 0.25 or more and 0.55 or less, it indicates that an appropriate amount of resin showing intermediate polarity between the low polarity crystalline resin and the high polarity amorphous resin is contained, and the effect of transferring electric charge stored in the amorphous resin component to the crystalline resin component is remarkable.

[0028] When VAB / PB is less than 0.25, the amount of intermediate polarity components between the amorphous resin component and the crystalline resin component is too small, making it difficult to exchange charges, and therefore charge-up suppression in a durability test in a low-temperature, low-humidity environment is not achieved.On the other hand, when VAB / PB is greater than 0.55, the charge leakage becomes high, making it impossible to maintain chargeability in a high-temperature, high-humidity environment.

[0029] The VAB / PB is preferably 0.30 to 0.50, and more preferably 0.35 to 0.45. The VAB / PB can be increased by bringing the polarities of the resin components having high polarity and low polarity in the toner particles closer to each other, increasing the resin components produced by the polymerization reaction between a resin having low polarity and a polymerizable monomer having polarity, which has a polymerizable functional group, adding a resin component having a polarity between the resin components having high polarity and low polarity in the toner particles, and decreasing the content ratio of the resin component having low polarity, etc. Also, the VAB / PB can be decreased by separating the polarities of the resin components having high polarity and low polarity in the toner particles and increasing the content ratio of the resin component having low polarity, etc.

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

[0031] From the above, by satisfying the above-mentioned formulas (1) and (2), a toner having excellent low-temperature fixing ability and hot offset resistance can exhibit excellent charging stability even in a high-temperature and high-humidity environment and a low-temperature and low-humidity environment.

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

[0033] [In formula (3), R 1 represents a hydrogen atom or a methyl group, L 1 represents a single bond, an ester bond, or an amide bond, and m represents an integer of 15 to 30. A resin component having the monomer unit (a) is preferred for controlling the charging stability because it is likely to exhibit a maximum value PB in a range where the chloroform volume fraction is 75.0 to 95.0% by volume in gradient LC analysis. L 1 is preferably an ester bond, and more preferably the carbonyl in the ester bond -COO- is R 1 is bonded to the carbon having When m is in the range of 15 to 30, the resulting resin B exhibits excellent crystallinity, so that a toner having excellent low-temperature fixing properties can be obtained. m is preferably in the range of 18 to 24, and more preferably in the range of 20 to 22.

[0034] As a method for introducing the monomer unit (a) represented by formula (3) into resin B, there is a method of polymerizing the following (meth)acrylic acid esters. For example, (meth)acrylic acid esters having a linear alkyl group having 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, myrisyl (meth)acrylate, dotriacontyl (meth)acrylate, etc.] and (meth)acrylic acid esters having a branched alkyl group having 16 to 31 carbon atoms [2-decyltetradecyl (meth)acrylate, etc.] can be mentioned. The monomers forming the monomer unit (a) may be used alone or in combination of two or more.

[0035] The content of the monomer unit (a) represented by formula (3) in the 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 the above range, a better balance between low temperature fixability and hot offset resistance is achieved.

[0036] Resin B is preferably a vinyl resin. Resin B may have other monomer units in addition to the monomer unit (a). As a method for introducing other monomer units, there is a method of polymerizing 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. Monomer having a urea group: for example, a monomer obtained by reacting an amine having 3 to 22 carbon atoms [primary amine (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amine (di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, cycloxylamine, etc.] with an isocyanate having 2 to 30 carbon atoms and an ethylenically unsaturated bond by a known method, etc. Monomers having a carboxy group; for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate. Monomers having a hydroxy group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and the like. 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 (acrylic acid, methacrylic acid, etc.) having an ethylenically unsaturated bond by a known method. Of these, 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 of styrene represented by the following formula (A): Resin B also preferably has a monomer unit of (meth)acrylic acid represented by the following formula (B): [ka] In formula (B), R 3 R represents a hydrogen atom or a methyl group. 3 is preferably a methyl group.

[0039] The content of styrene monomer units in Resin B is preferably from 1.0 to 50.0 mass %, more preferably from 10.0 to 30.0 mass %, and even more preferably from 15.0 to 25.0 mass %. The content of monomer units of (meth)acrylic acid (preferably methacrylic acid) in Resin B is preferably 0.5 to 5.0 mass %, more preferably 1.0 to 3.0 mass %, and even more preferably 1.0 to 2.0 mass %.

[0040] The number average molecular weight Mn of Resin B is preferably 4,000 to 13,000, and more preferably 6,000 to 9,000. The weight average molecular weight Mw of Resin B is preferably 10,000 to 50,000, and more preferably 20,000 to 30,000.

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

[0042] If Avb is 1.5 mgKOH / g or more, it is considered that the water adsorption property is excellent due to the acid value. Since the crystalline resin component can be introduced into the resin, moisture adsorption can be appropriately promoted, and charge transfer between the amorphous resin component and the crystalline resin component can be facilitated. As a result, charge-up in a low-temperature, low-humidity environment is more preferably suppressed, and the charge stability is more excellent. On the other hand, if Avb is 25.0 mgKOH / g or less, composition unevenness due to the acid value can be reduced, so that charge leakage from the amorphous resin to the crystalline resin can be more preferably suppressed, resulting in excellent charging stability under high temperature and high humidity conditions. The Avb is preferably 3.0 or more and 25.0 or less, more preferably 5.0 or more and 20.0 or less, and even more preferably 6.0 or more and 15.0 or less.

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

[0044] HPA represents the distribution of the composition of resin A corresponding to PA. If the HPA is 3.0 or more, the shape of the PA is not too sharp, which is effective in suppressing charge-up in a low-temperature, low-humidity environment.On the other hand, if the HPA is 10.0 or less, the composition distribution is small, which is excellent in terms of maintaining a sufficient charge amount, and therefore, the charge stability is excellent in a high-temperature, high-humidity environment.

[0045] The HPA is more preferably 5.0 or more and 8.0 or less, and further preferably 6.0 or more and 7.5 or less. The HPA can be increased by making the composition distribution of the constituent resins non-uniform. The HPA can be decreased by making the composition distribution of the constituent resins uniform. In the case of a resin obtained using a polymerizable monomer, the composition distribution can be made uniform by combining polymerizable monomers having similar reactivity, and conversely, the composition distribution can be made non-uniform by combining polymerizable monomers having different reactivity. The reactivity can be changed by the molecular weight of each polymerizable monomer, the unsaturated group of the polymerizable monomer, etc. For example, the higher the molecular weight of the polymerizable monomer, the lower the reactivity, and the lower the molecular weight, the higher the reactivity. In addition, if the unsaturated group of the polymerizable monomer is an acrylic group and a methacrylic acid group, the reactivity of the methacrylic group is high.

[0046] In addition, when the acid value Ava (mgKOH / g) of the resin A is taken as the acid value, it is preferable that Ava satisfies the following formula (6): 0.0 ≦ Ava ≦ 3.0 (6)

[0047] When a crystalline resin with high leakability such as resin B is present in the toner, the charge retention is superior when the acid value of the amorphous resin A is lower. Therefore, when Ava is within the above range, the charge stability in a high-temperature and high-humidity environment is superior. Ava is more preferably 0.0 or more and 2.5 or less, even more preferably 0.0 or more and 2.0 or less, even more preferably 0.0 or more and 1.0 or less, and particularly preferably 0.0.

[0048] Resin A preferably has a monomer unit based on styrene and a monomer unit based on an alkyl (meth)acrylate. A resin having a monomer unit of styrene and a monomer unit of (meth)acrylic acid alkyl ester is likely to exhibit a maximum PA value in a range of chloroform volume fraction of 50.0 to 75.0% in gradient LC analysis. Furthermore, it is suitable for controlling HPA within the above-mentioned range, and is preferable for controlling charging stability.

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

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

[0051] In the gradient LC analysis of the chloroform soluble matter of the resin extracted from the toner particles, the volume fraction of chloroform in the mobile phase when the maximum value PA appears is defined as CA (volume %), the volume fraction of chloroform in the mobile phase when the maximum value PB appears is defined as CB (volume %), and the volume fraction of chloroform in the mobile phase when the minimum value VAB appears 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, and indicates that there is a moderate difference in the polarity of resin A and resin B. When the difference in volume fraction CB-CA (volume %) is 10.0 or more, the charge leakage of the toner can be further suppressed and the charge stability in a high-temperature, high-humidity environment is superior because there is a sufficient difference in polarity between resin A and resin B. On the other hand, when CB-CA is 30.0 or less, the polarities of resin A and resin B are relatively close to each other, so that the transfer of charge is more easily performed, the charge-up suppression effect in a low-temperature, low-humidity environment is more easily manifested, and the charge stability is superior. The CB-CA (volume %) is preferably 12.5 to 25.0, and more preferably 17.0 to 22.0.

[0053] The 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 The value is 80.0.

[0054] The content ratio of resin A among the resins contained in the toner particles is represented as MA (mass %), and the content ratio of resin B among the resins contained in the toner particles is represented as MB (mass %). In addition, the toner particles are subjected to Soxhlet extraction using a chloroform solvent, and the insoluble matter obtained by extraction for 48 hours is separated. The resin component of the obtained insoluble matter excluding the incineration ash is defined as resin C, and the content of resin C in the resins 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 formulae (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 resin A, resin B, and resin C contained in the toner, and indicates that resins other than resin A, resin B, and resin C may be contained. 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) represents the content of resin A among the resins in the toner particles, and formula (10) represents 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 of the toner can be satisfied, and therefore the charge characteristics are superior in high temperature and high humidity environments and low temperature and low humidity environments. The range of MA is more preferably 30.0% to 50.0% by mass, and even more preferably 35.0% to 45.0% by mass.

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

[0058] Furthermore, it is preferable that the content ratio MC (mass %) of resin C in 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 is not soluble in chloroform and has a high molecular weight or a crosslinked structure as a resin. Such a resin maintains the toner elasticity of the toner particles at high temperatures, making it easier to control the hot offset resistance. When the MC content is 3.0% by mass or more and 30.0% by mass or less, the toner is excellent in achieving both low temperature fixability and hot offset resistance. The MC is more preferably from 5.0% by mass to 25.0% by mass, and further preferably from 10.0% by mass to 20.0% by mass.

[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. 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 contained in the added resin, or the amount of a polymerizable monomer having two or more reactive groups in the molecule or a macromonomer that is a resin having an unsaturated double bond, as described below.

[0061] Moreover, the resin C preferably has a monomer unit (b) represented by the following formula (12): Shii [ka]

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

[0063] The structure of the above formula (12) indicates that resin C has a long-chain alkyl group. By including a long-chain alkyl group having 16 or more carbon atoms in resin C, which is a resin component in the toner particles that does not dissolve in chloroform, the resin exhibits intermediate behavior during charge transfer that occurs between the amorphous resin component and the crystalline resin component, thereby making it possible to further improve charging stability.

[0064] It is preferable that Resin A has a glass transition point Tga (°C), Resin B has a melting point Tmb (°C), and Resin C has a melting point Tmc (°C). 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] When the glass transition point Tga (°C) of the resin A is 40.0°C or more and 65.0°C or less, the electrostatic charge stability and low-temperature fixability in a low-temperature and low-humidity environment are excellent. Tga is more preferably 45.0°C or more and 55.0°C or less. If the melting point Tmb (°C) of the resin B is 50.0°C or more and 75.0°C or less, the toner is excellent in suppressing charge-up in a low-temperature and low-humidity environment, and in achieving both low-temperature fixing property and hot offset resistance. Tmb is more preferably 55.0°C or more and 65.0°C or less. If the melting point Tmc (°C) of resin C is 45.0°C or more and 65.0°C or less, the charge retention in a high-temperature and high-humidity environment and the charge-up suppression effect in a low-temperature and low-humidity environment are excellent. Tmb is more preferably 50.0°C or more and 60.0°C or less.

[0066] An example of the results of gradient LC analysis is shown in Figure 1. The numbers in parentheses indicate the symbols in the figure. The area SA(1) where the chloroform volume fraction is 50.0 volume percent or more and 75.0 volume percent or less, the maximum value PA(3), the half-width HPA(6) of the maximum value PA(3), and the volume fraction CA(7) can be controlled as follows.

[0067] First, the half-width 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. This can be controlled by the difference in reactivity of the polymerizable monomers that are the raw material for the monomer units that are synthesized, or the difference in polarity of the polymerizable monomers. The greater the difference in reaction rate or the greater the difference in polarity of the monomers, the larger the full width at half maximum HPA(6). For example, in the case of resins obtained by vinyl polymerization, the higher the molecular weight of the polymerizable monomer, the slower the reaction rate. Also, polymerizable monomers with methacrylic groups introduced into them are more reactive than acrylic groups.

[0068] The area SA(1) at a chloroform volume fraction of 50.0 to 75.0% and the maximum value PA(3) derived from the resin A including the maximum value PA(3) can be controlled by the total amount of the resin A in the toner particles and the half-value width HPA(6). Specifically, they can be controlled by the amount of the resin A added when producing the toner particles, or the total amount of the polymerizable monomer that becomes the resin A when polymerization is involved.

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

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

[0071] Resin C, which has intermediate polarity and composition distribution between resin A and resin B, is preferably a copolymer of a macromonomer, which is a resin having a reactive unsaturated double bond, a styrene monomer, and a polymerizable monomer including an alkyl (meth)acrylate ester. Alternatively, a crystalline vinyl resin copolymerized with a polymerizable monomer having a long alkyl chain and a polymerizable monomer having a different polarity from the polymerizable monomer is preferable.

[0072] The macromonomer, which is a low-polarity resin having a reactive unsaturated double bond, is preferably a macromonomer derived from an alkyl acrylate or an alkyl methacrylate. The alkyl acrylate or alkyl methacrylate constituting the macromonomer preferably has an alkyl moiety having 12 to 30 carbon atoms. Hereinafter, the alkyl acrylate or alkyl methacrylate is also referred to as alkyl (meth)acrylate.

[0073] The alkyl (meth)acrylate having an alkyl moiety with 12 to 30 carbon atoms is 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, or triacontyl (meth)acrylate. The combined use of these monomers makes it easier to adjust the melting point of the macromonomer. The use of alkyl (meth)acrylates with alkyl moieties having 12 or more carbon atoms results in good heat resistance and durability. The use of alkyl (meth)acrylates with alkyl moieties having 30 or less carbon atoms results in good granulation properties.

[0074] Monomers other than the above may also be reacted. For example, 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 monocarboxylate, 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 methods can be used to provide a polymerizable functional group at the end of the acrylic resin polymerized using the above monomer: For example, a method can be used in which the above monomer is radically polymerized using a polymerization initiator having a hydroxyl group at the end, such as VA-086 (Wako Pure Chemical Industries), and the acrylic resin having the terminal hydroxyl group derived from the initiator is modified with a polymerizable functional group capable of polymerizing with styrene. Another method is to radically polymerize the above monomer using a polymerization initiator having a carboxyl group at the end, such as VA-057 (Wako Pure Chemical Industries, Ltd.), and modify the acrylic resin having an end derived from the initiator with a polymerizable functional group capable of polymerizing with styrene.

[0076] Further, in addition to the above-mentioned monomers, there can be mentioned a method in which a hydroxyl group or a carboxy group is introduced into the polymer using a vinyl monomer having a hydroxyl group, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate; or a vinyl monomer having a carboxy group, such as acrylic acid or methacrylic acid, to modify the acrylic resin with a polymerizable functional group capable of polymerizing with styrene.

[0077] Modification methods include the Schotten-Baumann reaction using acid chloride and the urethane reaction using isocyanate. Specific reagents include acryloyl chloride, methacryloyl chloride, p-styrenesulfonic acid chloride, 2-acryloyloxyethyl isocyanate, and 2-methacryloyloxyethyl isocyanate. Another modification method is the epoxy addition reaction between carboxyl groups and glycidyl groups. Specific examples of the reagent include (meth)acrylic 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. As another method, there is mentioned a method for obtaining a macromonomer by high-temperature continuous polymerization as disclosed in JP-A-2002-363203.

[0078] The polymerizable monomer composition may be used in combination with a polymerizable monomer other than styrene.As the polymerizable monomer that can be suitably used, 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, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, and dimethyl phosphate ethyl 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 , 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] The polymerizable monomer used in the crystalline vinyl resin obtained by copolymerizing a polymerizable monomer having a long alkyl chain with a polymerizable monomer having a different polarity is: The polymerizable monomer having a long chain alkyl is an alkyl(meth)acrylate having an alkyl moiety with a carbon number of 12 to 30 (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, nonadecyl(meth)acrylate, Preferred are aryl (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.

[0081] The polymerizable monomer having a long alkyl chain and the polymerizable monomer having a different polarity are Monomers having a nitrile group; for example, acrylonitrile, methacrylonitrile, etc. Monomers having a hydroxy group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and the like. 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 (acrylic acid, methacrylic acid, etc.) having an ethylenically unsaturated bond by a known method.

[0082] Monomers having a urethane group: For example, alcohols having 2 to 22 carbon atoms having an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate, vinyl alcohol, etc.) and isocyanates having 1 to 30 carbon atoms [monoisocyanate compounds (benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, diisocyanate, 2-ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, and 2,6-dipropylphenyl isocyanate, etc.), aliphatic diisocyanate compounds (trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, etc.) , dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, etc.), 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 aromatic A monomer obtained by reacting an aromatic diisocyanate compound (such as phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenylether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, and xylylene diisocyanate) by a known method, 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, linoleyl alcohol, and monomers obtained by reacting, by a known method, an isocyanate having 2 to 30 carbon atoms and an ethylenically unsaturated bond [2-isocyanatoethyl (meth)acrylate, 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl (meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, etc.], and the like.

[0083] Monomer having a urea group: for example, a monomer obtained by reacting an amine having 3 to 22 carbon atoms [primary amine (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amine (di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, cycloxylamine, etc.] with an isocyanate having 2 to 30 carbon atoms and an ethylenically unsaturated bond by a known method, etc. Monomers having a carboxy group; for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate. etc.

[0084] The macromonomer capable of forming the resin C is preferably an alkyl(meth)acrylate having an alkyl portion with a carbon number of 12 to 30 (preferably 18 to 26, more preferably 20 to 24), a styrene-based monomer such as styrene or a styrene derivative, and a polymer of a monomer having a carboxyl group, and a (meth)acrylic acid ester having a glycidyl group. The macromonomer capable of forming Resin C is more preferably a resin in which glycidyl (meth)acrylate is added to a polymer of alkyl (meth)acrylate having an alkyl portion with 12 to 30 carbon atoms (preferably 18 to 26, more preferably 20 to 24 carbon atoms), styrene, and (meth)acrylic acid. The number of unsaturated groups in the macromonomer is preferably 0.5 to 3.0, and 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 number average molecular weight Mn of the macromonomer capable of forming the resin C or the resin C is preferably 5,000-10,000, and more preferably 6,000-8,000. The weight average molecular weight Mw of the macromonomer capable of forming the resin C or the resin C is preferably 15,000 to 50,000, and more preferably 25,000 to 35,000.

[0086] By arbitrarily controlling the area SA, maximum value PA, half width and volume fraction CA of the component with a chloroform volume fraction of 50.0 to 75.0% derived from resin A, and the area SB, maximum value PB, volume fraction CB and minimum value VAB between maximum value PA and maximum value PB of the component with a chloroform volume fraction of 75.0 to 95.0% derived from resin B, as described above, 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. Resin A, resin B, and resin C may be any known resin as long as it satisfies formulas (1) and (2), and examples of such known binder resins include vinyl resins, polyester resins, polyurethane resins, and epoxy resins. They may also be hybrid resins in which vinyl resins and polyester resins are combined. Resin A, resin B, and resin C are, for example, binder resins, and preferably contain vinyl resins, and more preferably are vinyl resins.

[0088] Furthermore, in addition to the monomer units described above, resin A, resin B, and resin C may have monomer units based on the following monomers: As acrylic monomers, acrylic acid and methacrylic acid; acrylic acid ester monomers or methacrylic acid ester monomers such as 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, and diethylaminoethyl methacrylate; Examples of 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; etc.

[0089] Furthermore, a crosslinking agent may be used to control the molecular weight of the resin. As a crosslinking agent, divinylbenzene, bis(4-acryloxy) 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 diacrylate (MANDA Nippon Kayaku), and those in which the above diacrylates are replaced with dimethacrylates.

[0090] Examples of polyfunctional crosslinking agents include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylates and those in which the acrylates are replaced with methacrylates, 2,2-bis(4-methacryloxypolyethoxyphenyl)propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and triallyl trimellitate.

[0091] The toner particles may contain a core particle having a resin and a shell that covers the core particle. The resin that forms the shell is not particularly limited, but from the viewpoint of charging stability, a vinyl resin or a polyester resin is preferable. A non-crystalline polyester resin is more preferable. The shell does not necessarily need to cover the entire core, and the core may be partially 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 a hydrocarbon wax and an ester wax. By using a hydrocarbon wax and / or an ester wax, effective releasability can be easily ensured.

[0093] The hydrocarbon wax is not particularly limited, but examples thereof include the following: Aliphatic hydrocarbon waxes: low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymers, Fischer-Tropsch wax, or waxes obtained by oxidizing or adding acids to these.

[0094] The ester wax may be any wax having at least one ester bond in one molecule, and may be either a natural ester wax or a synthetic ester wax. The ester wax is not particularly limited, but examples thereof 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 and monocarboxylic acids, such as ethylene glycol distearate and hexanediol dibehenate; Esters of trihydric alcohols and monocarboxylic acids, such as glycerin tribehenate; Esters of tetrahydric alcohols and monocarboxylic acids, such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate; Esters of hexahydric alcohols and monocarboxylic acids, such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabehenate; Esters of polyfunctional alcohols and monocarboxylic acids, such as polyglycerin behenate; natural ester waxes, such as carnauba wax and rice wax;

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

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

[0097] The content of the release agent in the toner particles is preferably 1.0% by mass or more and 30.0% by mass or less, more preferably 2.0% by mass or more and 25.0% by mass or less. When the content of the release agent in the toner particles is in the above range, releasability during fixing is easily ensured. The melting point of the release agent is preferably 60° C. or more and 120° C. or less. When the melting point of the release agent is in the above range, the release agent melts during fixing and easily seeps out onto the toner particle surface, and the release property is easily exhibited. The melting point is more preferably 70° C. or more and 100° C. or less.

[0098] <Coloring agent> The toner may contain a colorant. Examples of the colorant include known organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, magnetic particles, etc. In addition, colorants that have been used in conventional 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 Yellow 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, benzimidazolone 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 cyan colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specifically, CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66 are preferably used.

[0100] The colorant is selected in consideration of hue angle, chroma, brightness, light resistance, transparency on an OHP sheet, and dispersibility in the toner. The content of the colorant is preferably 1.0 to 20.0 parts by mass per 100.0 parts by mass of the resin. When magnetic particles are used as the colorant, the content is preferably 40.0 to 150.0 parts by mass per 100.0 parts by mass of the resin.

[0101] <Charge control agent> If necessary, a charge control agent may be contained in the toner particles. Alternatively, the charge control agent may be added externally to the toner particles. By blending the charge control agent, it becomes possible to stabilize the charge characteristics and control the amount of triboelectric charge optimally according to the development system. Any known charge control agent can be used as the charge control agent, and a charge control agent that can charge quickly and stably maintain a constant charge amount is particularly preferred.

[0102] Examples of charge control agents that control the toner to be negatively charged include the following: organic metal compounds and chelate compounds are effective, and examples of the charge control agents include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Examples of compounds that control the toner to have a positive charge include nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorgano tin borates, guanidine compounds, and imidazole compounds. The content of the charge control agent is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 10.0 parts by mass or less, relative to 100.0 parts by mass of the toner particles.

[0103] <External additives> The toner particles may be used as they are as a toner, or may be used as a toner by mixing with an external additive, if necessary, and attaching the additive to the surface of the toner particles. The external additive may be an inorganic fine particle selected from the group consisting of silica fine particles, alumina fine particles, and titania fine particles, or a composite oxide thereof, etc. Examples of the composite oxide 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, and more preferably 0.1 parts by mass or more and 4.0 parts by mass or less, based on 100 parts by mass of the toner particles.

[0104] Next, the toner manufacturing method will be described in detail. The toner particles may be manufactured by any known method, such as a suspension polymerization method, an emulsion aggregation method, a dissolution suspension method, or a pulverization method, as long as the toner particles are manufactured within the scope of the present invention. Among these, the suspension polymerization method is preferred because it is easy to satisfy the above formulas (1) and (2).

[0105] The suspension polymerization method will now be described in detail. For example, the polymerizable monomers for forming resin A, previously synthesized resin B (crystalline resin that becomes resin B) and previously synthesized macromonomer capable of forming resin C or resin C (resin not required for chloroform that becomes resin C), and other materials such as colorants, release agents, charge control agents, etc., as necessary, are mixed and uniformly dissolved or dispersed to prepare a polymerizable monomer composition. At least a portion of the polymerizable monomers may be mixed with the colorant in advance. The polymerizable monomer composition is then dispersed in an aqueous medium using a stirrer or the like to prepare suspended particles of the polymerizable monomer composition, and the polymerizable monomer contained in the particles is then polymerized with an initiator or the like to obtain toner particles. After the polymerization is completed, the toner particles are filtered, washed and dried by known methods, and external additives are added as necessary to obtain the toner.

[0106] As the polymerization initiator, a known polymerization initiator can be used. Examples of the polymerization initiator include azo or diazo polymerization initiators such as 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 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 peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide. Furthermore, known chain transfer agents and polymerization inhibitors may be used.

[0107] The aqueous medium may contain an inorganic or organic dispersion stabilizer. As the dispersion stabilizer, a known dispersion stabilizer 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, methyl cellulose, methylhydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salts, and starch.

[0109] When an inorganic compound is used as the dispersion stabilizer, a commercially available product may be used as it is, but in order to obtain finer particles, the inorganic compound may be formed in an aqueous medium and then used. For example, in the case of calcium phosphates such as hydroxyapatite or tricalcium phosphate, an aqueous solution of the phosphate may be mixed with an aqueous solution of the calcium salt under high agitation.

[0110] The aqueous medium may contain a surfactant. As the surfactant, a known surfactant can be used. For example, anionic surfactants such as sodium dodecylbenzene sulfate and sodium oleate, cationic surfactants, amphoteric surfactants, and nonionic surfactants can be mentioned.

[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 the toner particles from the external additives by the following method can be used for each analysis. Add 160 g of sucrose (Kishida Chemical) to 100 mL of ion-exchanged water and dissolve in a hot water bath to prepare a concentrated sucrose solution. Place 31 g of the concentrated sucrose solution and 6 mL of Contaminon N (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) in a centrifuge tube to prepare a dispersion. Add 1 g of toner to this dispersion and break up the toner clumps with a spatula or the like.

[0112] The centrifuge tube is placed in an Iwaki Sangyo KM Shaker (model: V.SX) and shaken for 20 minutes at 350 reciprocations per minute. After shaking, the solution is transferred to a glass tube (50 mL) for a swing rotor and centrifuged at 3,500 rpm for 30 minutes. After centrifugation, the toner particles are in the top layer of the glass tube, and the external additives such as silica particles are in the aqueous solution in the bottom layer. The toner particles in the top layer are collected and filtered, then washed with 2 L of ion-exchanged water heated to 40°C, and the washed toner particles are taken out.

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

[0114] After the extraction is complete, the thimble is removed and air-dried, and then vacuum-dried at 40°C for 8 hours. The mass of the thimble containing the extraction residue is weighed, and the mass of the extraction residue (W2 [g]) is calculated by subtracting the mass of the thimble. In addition, when recovering the chloroform-soluble matter, it is possible to recover it by thoroughly distilling off the chloroform from the soluble matter in chloroform using an evaporator. Next, the content (W3 [g]) of components other than the resin component is calculated by the following procedure: 2 g of toner particles are precisely weighed (Wa [g]) into a pre-weighed 30 mL magnetic crucible.

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

[0116] In addition, when the toner particles contain a release agent, it is necessary to separate the resin from the release agent. The resin and the release agent are separated by recycling HPLC, with the components with a molecular weight of 2000 or less being the release agent and the components with a molecular weight of more than 2000 being the resin. The measurement method is as follows. First, the chloroform-soluble components are separated by the above-mentioned method and dissolved in chloroform. The obtained solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the components soluble in chloroform is 1.0 mass %. Using this sample solution, measurements are performed under the following conditions. ·Equipment: LC-Sakura NEXT (manufactured by Nippon Analytical Industry Co., Ltd.) Column: JAIGEL 2H, 4H (Japan Analytical Industry Co., Ltd.) Eluent: Chloroform ·Flow rate: 10.0ml / min Oven temperature: 40.0℃ Sample injection volume: 1.0ml In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using standard polystyrene resins (e.g., trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500" manufactured by Tosoh Corporation) is used.

[0117] From the molecular weight curve thus obtained, the components with a molecular weight of 2000 or less are repeatedly collected to separate the resin component (Wc) and the 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 the sample W1 [g] is calculated using the following formula. W4=W1-W2 W5 = W4 × (Wc / (Wc + Wd)) In this case, the content of the chloroform soluble matter in the resin of the toner particles can be calculated by the following formula. Content of chloroform soluble matter in the resin of the toner particles (mass%)= W5 / {W5+(W2-W3)}×100

[0118] The content ratio MC (mass %) of resin C in the resins contained in the toner particles is determined by the following method. The content (W7 [g]) of components other than the resin component in the mass (W2 [g]) of the above extraction residue, which is the chloroform insoluble portion of the toner particles, is calculated by the following procedure. 2 g of the chloroform insoluble portion of the toner particles is precisely weighed (Wa' [g]) into a pre-weighed 30 mL magnetic crucible. . The magnetic crucible is placed in an electric furnace and heated to approximately 900°C for 3 hours, allowed to cool in the electric furnace, and then allowed to cool at room temperature in a desiccator for at least 1 hour. The mass of the crucible including the incineration ash is weighed and the mass of the crucible is subtracted to calculate the incineration ash (Wb´ [g]). Then, the mass (W7 [g]) of the incineration ash in the 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 excluding the incineration ash content in the chloroform insoluble matter of the toner particles, is calculated using the following formula. W8=W2-W7 Furthermore, MC (mass%) is calculated by the following formula. MC = W8 / (W5+W8) x 100

[0119] <Gradient LC analysis method for resins and calculation of the content ratio of resin A and resin B> The resin component (Wc) in the chloroform-soluble matter of the toner particles obtained by the above method is used as the sample. The sample is adjusted to a sample concentration of 0.1% by mass with chloroform, and the solution is filtered through a 0.45 μm PTFE filter before being used for measurement. The gradient polymer LC measurement conditions are as follows: Equipment: UlTIMATE3000 (Thermo Fisher Scientific) Mobile phase: A Chloroform (HPLC), B Acetonitrile (HPLC) Gradient: 2min (A / B=0 / 100) → 25min (A / B=100 / 0) (The gradient of the mobile phase change was made linear.) Flow rate: 1.0mL / min Injection: 0.1% by mass x 20μL Column: Tosoh TSKgel ODS (4.6mmφx150mm x 5μm) Column temperature: 40℃ Detector: Corona Charged Aerosol Detector (Corona-CAD) (Thermo Fisher Scientific)

[0120] For the time-intensity graph obtained in the measurement, the time was converted to the percentage of chloroform, and the area of ​​the peak of the percentage of chloroform was then calculated. If the S / N ratio of the signal intensity was insufficient, the moving average was appropriately taken for the chloroform volume fraction to improve the S / N ratio of the signal. Specifically, the moving average was taken in the range of 3% chloroform volume fraction, and the signal was smoothed to calculate the results.

[0121] Next, the area where the ratio (volume fraction) of chloroform in the mobile phase is 50.0 to 75.0% by volume is SA, the maximum value is PA, the half-width of the maximum value PA is HPA, and the volume fraction of the maximum value PA is CA. In addition, the area where the ratio of chloroform in the mobile phase is 75.0 to 95.0% by volume is SB, the maximum value PB and the chloroform volume fraction of the maximum value PB are CB, and the maximum value PA and the minimum value VAB between the maximum value PB. For example, in the case of a peak where the chloroform ratio is 5.0 to 95.0% by volume, the area may be calculated as the area of ​​the range surrounded by the 5.0% by volume vertical axis, the 95.0% by volume vertical axis, the intensity curve, and the horizontal axis (intensity 0).

[0122] Regarding the contents of resin A and resin B, the developing solution in the above gradient LC is recovered, and when the volume fraction of chloroform is 50.0 to 75.0% by volume, the developing solution is extracted as a chloroform solution of resin A, and when the volume fraction of chloroform is 75.0 to 95.0% by volume, the developing solution is extracted as a chloroform solution of resin B. The above extraction is repeated until the amount of extraction reaches a level that can be analyzed. The solvent is removed from the resulting extracted solution 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 content of the toner particles is analyzed, and the composition ratio of resin A and resin B relative to the chloroform-soluble content of the toner particles is calculated. Then, the content ratio (mass%) of the chloroform-soluble content in the resin of the toner particles calculated by the above method is multiplied by the composition ratio of resin A or resin B to calculate MA (mass%) and MB (mass%), which are the content ratios of resin A and resin B in the resin contained in the toner particles.

[0123] <Measurement of glass transition temperature (Tga) of resin A> The glass transition point is measured using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments) in accordance with ASTM D3418-82. The melting points of indium and zinc are used for temperature correction of the device detection section, and the heat of fusion of indium is used for heat correction. Specifically, 3 mg of resin is precisely weighed and placed in an aluminum pan, and measurement is performed under the following conditions using an empty aluminum pan as a reference. Heating rate: 10℃ / min Measurement start temperature: 30℃ End of measurement temperature: 180℃ Measurements are performed in the measurement range of 30 to 180°C at a heating rate of 10°C / min. The temperature is raised to 180°C once and held for 10 minutes, then cooled to 30°C, and then raised again. During this second heating process, the specific heat change is obtained in the temperature range of 30 to 100°C. The point at which the line midway between the baselines before and after the specific heat change appears and the differential thermal curve intersect is the glass transition temperature (Tg) of the resin.

[0124] <Measuring method for endothermic peak temperature (Tmb, Tmc)> The peak temperature of the endothermic peak of the resin is measured using a DSC Q2000 (manufactured by TA Instruments) under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 20℃ End of measurement temperature: 180℃ The melting points of indium and zinc are used to correct the temperature of the detector, and the heat of fusion of indium is used to correct the amount of heat. Specifically, 1.0 mg of sample is precisely weighed and placed in an aluminum pan, and differential scanning calorimetry is performed. An empty silver pan is used as a reference. During the temperature rise process, the temperature is raised to 180°C at a rate of 10°C / min. The peak temperature is then calculated from each peak.

[0125] <Method for measuring the content of various monomer units in resin> The content ratio of various monomer units in Resin A, Resin B, and Resin C was measured by: 1 H-NMR was performed under the following conditions. ·Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0μs Frequency range: 10500Hz Number of times: 64 ·Measurement temperature: 30℃ Sample: 50 mg of the sample to be measured was placed in a sample tube with an inner diameter of 5 mm and diluted with deuterated chloroform (CDCl 3 ) and dissolve in a thermostatic bath at 40°C.

[0126] The following describes Resin B as an example. Obtained 1 From the H-NMR chart, select a peak that is independent of the peaks that are assigned to the components of the monomer unit (a) from the peaks that are assigned to the components of other monomer units, and calculate the integral value S 1 In the case where the resin B contains a second monomer unit, a peak independent of the peaks attributable to the components of the second monomer unit is selected from the peaks attributable to the components of the other monomer units, and the integral value S of this peak is calculated. 2 Calculate. Furthermore, when a third and a fourth monomer unit are contained, a peak that is independent of the peaks that are attributed to the components of the third and fourth monomer units is selected from the peaks that are attributed to the components of the other monomer units, and the integral value S 3 and S 4 Calculate.

[0127] The content of the monomer unit (a) is the integral value S 1 , S 2 , S 3 and S 4 Using the above, it is calculated as follows. Note that n 1 , n 2 , n 3 , n 4 is the number of hydrogens in the component to which the peak of interest for each site is assigned. Content of monomer unit (a) (mol%)= {(S 1 / n 1 ) / ((S 1 / n 1 )+(S 2 / n 2 )+(S3 / n 3 )+(S 4 / n 4 ))}×100 Similarly, the proportions of the second, third and fourth monomer units are determined as follows. Content of second monomer unit (mol%)= {(S 2 / n 2 ) / ((S 1 / n 1 )+(S 2 / n 2 )+(S 3 / n 3 )+(S 4 / n 4 ))}×100 Content of third monomer unit (mol%)= {(S 3 / n 3 ) / ((S 1 / n 1 )+(S 2 / n 2 )+(S 3 / n 3 )+(S 4 / n 4 ))}×100 Content of fourth monomer unit (mol%)= {(S 4 / n 4 ) / ((S 1 / n 1 )+(S 2 / n 2 )+(S 3 / n 3 )+(S 4 / n 4 ))}×100

[0128] In addition, when a polymerizable monomer that does not contain a hydrogen atom in any component other than the vinyl group is used in the resin, 13 Measure nuclei using C-NMR 13 C, and the measurement was performed in single pulse mode. 1 The same calculation is performed by H-NMR. Resin A and Resin C can also be measured in the same manner. In addition, when the toner is manufactured by the suspension polymerization method, the peaks of the release agent and shell resin may overlap, and independent peaks may not be observed. This may result in the inability to calculate the content ratio of each unit in the binder resin. In such a case, a similar suspension polymerization may be performed without using a release agent or other resin to manufacture a resin ', and the resin ' may be analyzed as a resin.

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

[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 a sample. The acid value of the binder resin is measured in accordance with JIS K 0070-1992, and specifically, 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 ion-exchanged water to make 100 mL, and obtain a phenolphthalein solution. Dissolve 7 g of special grade potassium hydroxide in 5 mL of water, and add ethyl alcohol (95% by volume) to make 1 L. Place in an alkali-resistant container to avoid contact with carbon dioxide, etc., leave for 3 days, and then filter to obtain a potassium hydroxide solution. Store the obtained potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is obtained by placing 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding several drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution, and then calculating from the amount of the 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 Test Weigh out 2.0 g of sample into a 200 mL Erlenmeyer flask, add 100 mL of a toluene / ethanol (2:1) mixed solution, and dissolve for 5 hours. Next, add a few drops of the phenolphthalein solution as an indicator, and titrate with the potassium hydroxide solution. The end point of the titration is when the indicator remains a light red color for about 30 seconds. (B) Blank test The titration is carried out in the same manner as above, except that no sample is used (i.e., only the toluene / ethanol (2:1) mixed solution is used).

[0133] (3) The obtained result is substituted into the following formula to calculate the acid value. A = [(CB) × f × 5.61] / S Here, A is the acid value (mgKOH / g), B is the amount of potassium hydroxide solution added for the blank test (mL), C is the amount of potassium hydroxide solution added for the main test (mL), f is the factor of the potassium hydroxide solution, and S is the 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 weight unless otherwise specified.

[0135] (Method of synthesizing additive resin B1) The following materials were placed in a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. Toluene 100.0 parts Monomer composition 100.0 parts (The monomer composition is a mixture of the following monomers in the ratio shown below.) (Behenyl acrylate (monomer (a)) 80.0 parts) (18.0 parts styrene) (Methacrylic acid 2.0 parts) Polymerization initiator (Wako Pure Chemical Industries: V-65) 0.5 parts The inside of the reaction vessel was heated to 70°C while stirring at 200 rpm, and polymerization reaction was carried out for 12 hours, to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Then, the temperature of the solution was lowered to 25°C, and the solution was poured into 1000.0 parts of methanol while stirring, to precipitate the methanol insoluble matter. The obtained methanol insoluble matter was filtered, washed with methanol, and then vacuum dried at 40°C for 24 hours to obtain additive resin B1.

[0136] (Preparation of Additive Resins B2 to B25) Additive Resins B2 to B25 were prepared in the same manner as in the synthesis of Additive Resin B1, except that the amount of monomer composition added was changed to that shown in 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 monomer abbreviations in the table are as follows: St: styrene BEA: Behenyl acrylate MAA: Methacrylic acid LAA: Lauryl acrylate STA: Stearyl acrylate

[0137] (Method of synthesizing additive resin C1) The following materials were placed in a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. Toluene 100.0 parts Monomer composition 100.0 parts (The monomer composition is a mixture of the following monomers in the ratio shown below.) (Behenyl acrylate (monomer (a)) 80.0 parts) (19.2 parts styrene) (Methacrylic acid 0.8 parts) Polymerization initiator (Wako Pure Chemical Industries: V-65) 0.5 parts The inside of the reaction vessel was heated to 70° C. while stirring at 200 rpm to carry out a polymerization reaction for 12 hours, thereby obtaining a solution in which the polymer of the monomer composition was dissolved in toluene.

[0138] Furthermore, in order to deactivate the polymerization initiator, the nitrogen inlet tube was removed, and the mixture was heated to 85°C and further heated for 6 hours, after which 0.05 parts of triethylamine and 1.3 parts of glycidyl methacrylate were added and an addition reaction was carried out for 5 hours. Next, the temperature of the solution was lowered to 25°C, and then the solution was poured into 1000.0 parts of methanol while stirring to precipitate the methanol insoluble matter. The resulting methanol insoluble matter was filtered off, washed with methanol, and vacuum dried at 40°C for 24 hours to obtain additive resin C1.

[0139] (Preparation of Additive Resins C2 to C9) Additive Resins C2 to C9 were prepared in the same manner as Additive Resin C2, except that the amount of monomer composition added was changed to Table 2 and the amount of glycidyl methacrylate added was changed so that the number of unsaturated groups was as shown in Table 2. [Table 2] The monomer abbreviations 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 calculated using the molecular weight (M_NMR) determined by 1 H-NMR. Nuclear magnetic resonance spectroscopy ( 1 H-NMR) [400MHz, CDCl 3 Measurement conditions: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0μs Frequency range: 10500Hz Number of times accumulated: 64 The integral value of the spectrum obtained gives the ratio of the constituent monomers per unsaturated group. The NMR molecular weight (M_NMR) can be calculated as the molecular weight per unsaturated group from the monomer composition ratio and molecular weight. Furthermore, the number of unsaturated groups per macromonomer molecule can be calculated from the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) and the NMR molecular weight (M_NMR) determined by the above NMR, using the following formula. Number of unsaturated groups = GPC number average molecular weight (Mn) / NMR molecular weight (M_NMR)

[0141] [Toner production by suspension polymerization method] (Production of toner particles 1) Styrene 47.0 parts n-Butyl acrylate 20.0 parts Colorant Pigment Blue 15:3 6.5 parts A mixture of the above materials was prepared. The mixture was placed in an attritor (manufactured by Nippon Coke Corporation) and dispersed at 200 rpm for 2 hours using zirconia beads with a diameter of 5 mm to obtain a raw material dispersion.

[0142] On the other hand, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (12-hydrate) were added to a container equipped with a high-speed stirring device homomixer (manufactured by Primix Corporation) and a thermometer, and the temperature was raised to 60 ° C. while stirring at 12000 rpm. An aqueous calcium chloride solution in which 9.0 parts of calcium chloride (2-hydrate) was dissolved in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12000 rpm for 30 minutes while maintaining the temperature at 60 ° C. 10% hydrochloric acid was added thereto to adjust the pH to 6.0, and an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water was obtained.

[0143] Next, the raw material dispersion liquid was transferred to a container equipped with a stirrer 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 ester wax, melting point 79°C, manufactured by Nippon Seiro Co., Ltd.) The above materials were added thereto and stirred at 100 rpm for 30 minutes while maintaining the temperature at 60°C, and then 9.0 parts of t-butyl peroxypivalate (Perbutyl PV, manufactured by NOF Corp.) was added as a polymerization initiator and stirred for another minute, after which the mixture was poured into the aqueous medium being stirred at 15,000 rpm in the high-speed stirring device. Stirring was continued at 15,000 rpm in the high-speed stirring device for 20 minutes while maintaining the temperature at 60°C, to obtain a granulation liquid.

[0144] The granulation liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, and nitrogen was introduced into the reaction vessel. The mixture was heated to 70° C. under stirring at 150 rpm in an atmospheric atmosphere. A 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 stirring at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45°C. Dilute hydrochloric acid was then added while maintaining the stirring until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid content was filtered off, thoroughly washed with ion-exchanged water, and then vacuum-dried at 30°C for 24 hours to obtain toner particle 1. The manufacturing method of toner particle 1 is shown in Table 3.

[0145] (Production of Toner Particles 2 to 48 and Comparative Toner Particles 1 to 7) In the same manner as in the production of toner particles 1, except that the amounts of the monomer compositions and the added resins were changed as shown in Table 3, toner particles 2 to 48 and comparative toner particles 1 to 6 were produced. Comparative toner particles 7 were produced as follows. Polyester resin: 50.0 parts (Propylene oxide modified bisphenol A (2 mole adduct), polycondensate of 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) ·Additive resin B1: 50.0 parts Release agent: 9.0 parts (Release agent: DP18 (dipentaerythritol stearate wax, melting point 79°C, manufactured by Nippon Seiro Co., Ltd.) Colorant Pigment Blue 15:3:6.5 parts The above materials were premixed in a Henschel mixer (manufactured by Nippon Coke Company), and then melt-kneaded using a twin-screw kneading extruder (manufactured by Ikegai Iron Works Co., Ltd.: PCM-30 type). The obtained kneaded material was cooled, coarsely pulverized in a hammer mill, and then pulverized in a mechanical pulverizer (Turbo Kogyo Co., Ltd.: T-250). The obtained finely pulverized powder was classified using a multi-division classifier utilizing the Coanda effect, and comparative toner particles 7 were obtained.

[0146] [Table 3] The monomer abbreviations in the table are as follows: St: styrene BA: n-butyl acrylate EA: Ethyl acrylate MMA: Methyl methacrylate LAA: Lauryl acrylate HDDA: Hexanediol diacrylate BEA: Behenyl acrylate MAA: Methacrylic acid

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

[0148] [Table 5] In the table, the long-chain alkyl group indicates the monomer that forms the monomer unit of the (meth)acrylic acid alkyl ester having the long-chain alkyl group contained in each resin. The "content of unit (a)" indicates the content of the monomer unit (a) represented by formula (3).

[0149] Example 1 (Evaluation of toner particles 1) For the above toner particles, 1:100.0 parts, silica fine particles (hydrophobized with hexamethyldisilazane, number-average particle size of primary particles: 10 nm, BET specific surface area: 170 m) were added as an external additive. 2The mixture was mixed for 15 minutes at 3000 rpm using a Henschel mixer (manufactured by Nippon Coke Corporation) to obtain toner 1. The obtained toner was evaluated according to the following evaluation method.

[0150] <Toner Evaluation Method> <1> Fixation evaluation The process cartridge filled with toner was left for 48 hours at 25°C and 40% RH. Using an LBP-712Ci that had been modified so that it could operate even without the fixing unit, an unfixed image was printed with an image pattern in which 9 10mm x 10mm square images were evenly arranged on the entire transfer paper. The amount of toner on the transfer paper was 0.80mg / cm. 2 The minimum and maximum fixing temperatures were evaluated while changing the fixing temperature in 5°C intervals in the range of 100°C to 220°C. The transfer paper was A4 size paper ("Prover Bond paper": 105g / m 2 (manufactured by Fox River) was used.

[0151] The fixing unit was an external fixing unit that had been removed from the LBP-712Ci and was designed to operate outside the laser beam printer. The fixing temperature of the external fixing unit was raised in 5°C increments from 90°C, and fixing was performed at a process speed of 320mm / sec. The fixed image was visually checked, and the lowest temperature at which cold offset did not occur was defined as the minimum fixing temperature, and the highest temperature at which hot offset did not occur was defined as the maximum fixing temperature. A minimum low temperature temperature of 160°C or less was determined to have excellent low-temperature fixing properties. Furthermore, the difference between the minimum fixing temperature and the maximum fixing temperature was defined as the fixing latitude, and if a fixing latitude of 40°C or more was secured, it was determined to have excellent fixing properties.

[0152] <2> Evaluation of charging stability A commercially available Canon printer LBP-712Ci was used to evaluate durability. The toner in the cartridge was removed, the inside was cleaned with an air blower, and then 200 g of the toner to be evaluated was filled in the cartridge. The cartridge was left for 48 hours in an environment of 25°C and 40% RH, and then installed in the cyan station to evaluate durability.

[0153] To evaluate the charging stability in a high temperature and high humidity environment, a Canon Oce Red Label (80g / m 2 ) was used to print an initial solid white image and measure the fog density. After that, in order to evaluate the degree of leakage, 3000 sheets of horizontal line pattern images with a printing rate of 1% were output continuously, and after leaving it for 12 hours or more, a solid white image was printed and the fog density was measured.

[0154] To evaluate the charging stability in a low temperature and low humidity environment, a Canon Oce Red Label (80g / m 2 ) was used to print an initial solid white image and measure the fog density. Then, in order to evaluate the ease of charge-up, a horizontal line pattern image with a print rate of 1% was output 3000 times in succession, and immediately after that, a solid white image was printed and the fog density was measured.

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

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

[0157] (Examples 2 to 48 and Comparative Examples 1 to 7) For toner particles 2 to 48 and comparative toner particles 1 to 7, silica fine particles were externally added to prepare toners in the same manner as for toner particle 1, and then the toners were evaluated. The evaluation results are shown in Table 5.

[0158] The present disclosure relates to the following configurations. (Configuration 1) A toner having toner particles having a resin, the toner particles are subjected to Soxhlet extraction using a chloroform solvent for 48 hours, and components having a molecular weight of 2000 or less are removed by recycling HPLC from the soluble fraction obtained, which is defined as the chloroform-soluble fraction of the resin extracted from the toner particles; Acetonitrile was used as a poor solvent and chloroform was used as a good solvent for the chloroform-soluble portion of the resin. The mobile phase was changed linearly from 100% acetonitrile by volume to 100% chloroform by volume. The eluted components were analyzed by gradient LC. The area of ​​the peak detected by using a Corona charged particle detector in a range of 50.0 to 75.0% by volume of chloroform in the mobile phase is designated as SA, and the maximum value is designated as PA. The area of ​​the peak detected by using a Corona charged particle detector in the mobile phase in which the ratio of chloroform in the mobile phase is in the range of 75.0 to 95.0% by volume is designated as SB, and the maximum value is designated as PB. When the minimum value existing between the PA and the PB is VAB, The PA and the PB are present, The toner, wherein the SA, the SB, the PB and the VAB satisfy the following formulas (1) and (2): 0.30 ≦ SA / SB ≦ 0.85 (1) 0.25 ≦ VAB / PB ≦ 0.55 (2) (Configuration 2) In the gradient LC analysis, when a resin obtained by extracting a component in which the ratio of chloroform in the mobile phase is in the range of 75.0 to 95.0% by volume is designated as resin B, which is a resin component corresponding to PB, The toner according to embodiment 1, wherein the resin B has a monomer unit (a) represented by the following formula (3): TIFF2024001652000013.tif56153[In formula (3), R 1 represents a hydrogen atom or a methyl group, and L 1 represents a single bond, an ester bond or an amide bond, and m represents an integer of 15 to 30. (Configuration 3) The toner according to Configuration 2, wherein the content of the monomer unit (a) represented by the formula (3) in the resin B is 40.0 to 95.0% by mass. (Configuration 4) The toner according to embodiment 2 or 3, wherein when the acid value of the resin B is AVb (mgKOH / g), the AVb satisfies the following formula (4): 1.5 ≦ AVb ≦ 25.0 (4) (Configuration 5) The toner according to any one of configurations 1 to 4, wherein when the half width of the PA is expressed as HPA (volume %), the HPA satisfies the following formula (5): 3.0 ≦ HPA ≦ 10.0 (5) (Configuration 6) In the gradient LC analysis, a resin obtained by extracting components in which the ratio of chloroform in the mobile phase is in the range of 50.0 to 75.0% by volume is designated as resin A, which is a resin component corresponding to the PA; The toner according to any one of configurations 1 to 5, wherein when the acid value of the resin A is AVa (mg KOH / g), AVa satisfies the following formula (6): 0.0 ≦ AVa ≦ 3.0 (6) (Configuration 7) 7. The toner according to embodiment 6, wherein the resin A has a monomer unit derived from styrene and a monomer unit derived from an alkyl (meth)acrylate ester. (Configuration 8) In the gradient LC analysis, when the volume fraction of chloroform in the mobile phase when the PA is expressed is defined as CA, and when the volume fraction of chloroform in the mobile phase when the PB is expressed is defined as CB, The toner according to any one of configurations 1 to 7, wherein the CA and the CB satisfy the following formula (7): 10.0 ≦ CB-CA ≦ 30.0 (7) (Configuration 9) In the gradient LC analysis, a resin obtained by extracting components in which the ratio of chloroform in the mobile phase is in the range of 50.0 to 75.0% by volume is designated as resin A, which is a resin component corresponding to the PA; The content ratio of the resin A in the resins contained in the toner particles is represented by MA (mass%), In the gradient LC analysis, a resin obtained by extracting components in which the ratio of chloroform in the mobile phase is in the range of 75.0 to 95.0% by volume is designated as resin B, which is a resin component corresponding to PB; The content ratio of the resin B in the resin contained in the toner particles is represented by MB (mass%), In the Soxhlet extraction of the toner particles using a chloroform solvent, the insoluble matter obtained by extraction for 48 hours is separated, and a resin component of the insoluble matter obtained by excluding the incineration ash is designated as Resin C; When the content ratio of the resin C in the resin contained in the toner particles is MC (mass%), The toner according to any one of configurations 1 to 8, wherein the MA, the MB and the MC satisfy the following formulae (8), (9) and (10). MA + MB + MC ≦ 100.0 (8) 25.0 ≦ MA ≦ 55.0 (9) 15.0 ≦ MB ≦ 50.0 (10) (Configuration 10) The toner according to embodiment 9, wherein the MC (% by mass) satisfies the following formula (11): 3.0 ≦ MC ≦ 30.0 (11) (Configuration 11) 11. The toner according to embodiment 9 or 10, wherein the resin C has a monomer unit (b) represented by the following formula (12): TIFF2024001652000014.tif56153 [In formula (12), R 2 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 of 15 to 30. (Configuration 12) The resin A has a glass transition point Tga (°C), the resin B has a melting point Tmb (°C), and the resin C has a melting point Tmc (°C), The toner according to any one of configurations 9 to 11, wherein the Tga (° C.), the Tmb (° C.) and the Tmc (° C.) satisfy the following formulae (13), (14) and (15): 40.0 ≦ Tga ≦ 65.0 (13) 50.0 ≦ Tmb ≦ 75.0 (14) 45.0 ≦ Tmc ≦ 65.0 (15) (Configuration 13) 13. The toner according to any one of configurations 1 to 12, wherein the resin is a vinyl resin. [Explanation of symbols]

[0159] 1 Area SA of chloroform volume fraction 50.0% to 75.0% by volume 2 Area of ​​chloroform volume fraction 50.0% to 75.0% by volume SB 3. Maximum value for chloroform volume fractions of 50.0% to 75.0% by volume PA 4. Maximum value for chloroform volume fraction between 50.0% and 75.0% by volume PB 5. Minimum value VAB between maximum value PA and maximum value PB 6 Half-width of maximum PA HPA 7. Chloroform volume fraction at maximum PA CA 8 Chloroform volume fraction at maximum value PB CB 9 Chloroform volume fraction at maximum VAB CV

Claims

1. A toner having toner particles having a resin, the toner particles are subjected to Soxhlet extraction using a chloroform solvent for 48 hours, and from the soluble matter obtained, components having a molecular weight of 2000 or less are removed by recycling HPLC, and this is defined as the chloroform-soluble matter of the resin extracted from the toner particles; Acetonitrile was used as a poor solvent and chloroform was used as a good solvent for the chloroform-soluble portion of the resin. The mobile phase was changed linearly from 100% by volume of acetonitrile to 100% by volume of chloroform. The eluted components were analyzed by gradient LC. The area of ​​the peak detected by using a Corona charged particle detector in a mobile phase in which the ratio of chloroform in the mobile phase is in the range of 50.0 to 75.0% by volume is defined as SA, and the maximum value is defined as PA. The area of ​​the peak detected by using a Corona charged particle detector in a mobile phase in which the ratio of chloroform in the mobile phase is in the range of 75.0 to 95.0% by volume is defined as SB, and the maximum value is defined as PB. When the smallest minimum value existing between the PA and the PB is VAB, The PA and the PB are present, The toner, wherein the SA, the SB, the PB and the VAB satisfy the following formulas (1) and (2): 0.30≦SA / SB≦0.85...(1) 0.25 ≦ VAB / PB ≦ 0.55 (2)

2. In the gradient LC analysis, when a resin obtained by extracting components in the mobile phase in which the ratio of chloroform is in the range of 75.0 to 95.0% by volume is defined as resin B, which is a resin component corresponding to PB, 2. The toner according to claim 1, wherein the resin B has a monomer unit (a) represented by the following formula (3): [In formula (3), R １ represents a hydrogen atom or a methyl group, L １ represents a single bond, an ester bond or an amide bond, and m represents an integer of 15 to 30.

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

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

5. 5. The toner according to claim 1, wherein when the half width of the PA is defined as HPA (volume %), the HPA satisfies the following formula (5): 3.0≦HPA≦10.0...(5)

6. In the gradient LC analysis, a resin obtained by extracting a component in which the ratio of chloroform in the mobile phase is in the range of 50.0 to 75.0% by volume is designated as resin A, which is a resin component corresponding to PA; 5. The toner according to claim 1, wherein when the acid value of the resin A is AVa (mg KOH / g), AVa satisfies the following formula (6): 0.0≦AVa≦3.0...(6)

7. 7. The toner according to claim 6, wherein the resin A comprises a monomer unit derived from styrene and a monomer unit derived from an alkyl (meth)acrylate ester.

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

9. In the gradient LC analysis, a resin obtained by extracting a component in which the ratio of chloroform in the mobile phase is in the range of 50.0 to 75.0% by volume is designated as resin A, which is a resin component corresponding to PA; The content ratio of the resin A in the resins contained in the toner particles is represented as MA (mass%), In the gradient LC analysis, a resin obtained by extracting a component in which the ratio of chloroform in the mobile phase is in the range of 75.0 to 95.0% by volume is designated as resin B, which is a resin component corresponding to PB; The content ratio of the resin B in the resins contained in the toner particles is defined as MB (mass%), In the Soxhlet extraction of the toner particles using a chloroform solvent, the insoluble matter obtained by extraction for 48 hours is separated, and the resin component of the insoluble matter obtained by excluding the incineration ash is designated as Resin C; When the content ratio of the resin C in the resin contained in the toner particles is MC (mass%), The toner according to any one of claims 1 to 4, wherein the MA, the MB and the MC satisfy the following formulae (8), (9) and (10). MA + MB + MC ≦ 100.0 (8) 25.0≦MA≦55.0...(9) 15.0≦MB≦50.0...(10)

10. The toner according to claim 9 , wherein the MC (% by mass) satisfies the following formula (11): 3.0≦MC≦30.0 (11)

11. The toner according to claim 9 , wherein the resin C has a monomer unit (b) represented by the following formula (12): [In formula (12), R ２ represents a hydrogen atom or a methyl group; L ２ represents a single bond, an ester bond, or an amide bond, and n represents an integer of 15 to 30.

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

13. 5. The toner according to claim 1, wherein the resin is a vinyl resin.

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