toner

Abstract

To provide a toner that is excellent in low temperature fixability during high-speed printing, achieves both hot offset resistance and winding resistance, and has satisfactory durability in which an image defect hardly occurs even after a long-term endurance use.SOLUTION: A toner has a toner particle containing a binder resin having a first resin and a second resin. The first resin is a crystalline resin. The second resin is an amorphous resin. In observation of the cross section of the toner particle, the toner particle has a domain-matrix structure comprising a matrix containing 80% or more of the first resin, and domains containing 80% or more of the second resin. In differential scanning calorimetry (DSC) of the toner, an endothermic quantity ΔH(J / g) derived from the first resin satisfies the relationship of ΔH≥3. In flow tester measurement with the toner as a sample, when T1(°C) is a temperature at which the melt viscosity V1 at an impressed pressure of 0.9807 MPa becomes 1×105 Pa s, and T10(°C) is a temperature at which the melt viscosity V10 at an impressed pressure of 9.807 MPa becomes 1×105 Pa s, the T1 and the T10 satisfy the relationships of T10≥65 and T1-T10≤10.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to toners used in electrophotography, electrostatic recording, electrostatic printing, and toner jet methods. [Background technology]

[0002] In recent years, as electrophotographic full-color copiers have become more widespread, there has been an ever-increasing demand for faster printing and energy conservation. To accommodate this high-speed printing, technologies that melt toner more quickly in the fixing process are being investigated. In addition, to improve productivity, technologies that shorten the time required for various controls during a job and between jobs are being investigated. Furthermore, as an energy-saving measure, technologies that fix toner at lower temperatures are being investigated in order to reduce power consumption in the fixing process. It is known that a toner having a binder resin mainly composed of a crystalline resin having sharp melting properties has superior low-temperature fixing properties compared to a toner having an amorphous resin as its main component. Many toners containing crystalline polyester as a resin having sharp melting properties have been proposed. However, crystalline polyester has been a material that has issues in terms of charge stability in high-temperature, high-humidity environments, particularly in terms of maintaining chargeability after being left in such environments. As another crystalline resin having sharp melting properties, various toners using crystalline vinyl resins have been proposed. For example, Patent Document 1 proposes a toner that combines low-temperature fixability and heat-resistant storage stability by using an acrylate resin with crystalline side chains. This toner combines low-temperature fixability and heat-resistant storage stability, and also improves to some extent the charging stability that was a weakness of toners that use crystalline polyester resins. However, it has been found that toners that use crystalline vinyl resins as binder resins are prone to hot offset and wrapping because their viscosity is too low in the high-temperature range, and that the temperature range in which they can be fixed is narrow. Therefore, in order to increase the viscosity of the toner after it has melted, the addition of an amorphous resin to a crystalline resin has been investigated. For example, Patent Document 2 proposes a toner using a binder resin that combines a crystalline vinyl resin and an amorphous resin. Although this toner has a certain degree of fixation range, further improvement is required. In addition, there are issues with durability, such as low-temperature fixability during high-speed printing and a tendency for image defects such as image streaks to occur during long-term printing, and improvements are required. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-130243 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-142632 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a toner that has excellent low-temperature fixability during high-speed printing, and that is both hot offset resistant and winding resistant, and that is highly durable and less likely to produce poor images even after long-term use. [Means for solving the problem]

[0005] The present invention provides a toner having toner particles containing a binder resin having a first resin and a second resin, The first resin , crystalline vinyl It is a resin, the first resin has a first monomer unit, a second monomer unit, and a third monomer unit; The first monomer unit is a unit represented by the formula (1) described below, The second monomer unit is a unit represented by the formula (3) described below, the third monomer unit is a styrene monomer unit, a methyl methacrylate unit, or a methyl acrylate unit; The second resin , a vinyl resin It is an amorphous resin, In the cross-sectional observation of the toner particles, the toner particles were found to have a thickness of 80 mm. mass% or more of the matrix and the second resin. mass % or more of a domain matrix structure, In differential scanning calorimetry (DSC) of the toner, the amount of heat absorption ΔH (J / g) attributed to the first resin is ΔH≧3 Fulfilling the relationship, In a flow tester measurement using the toner as a sample, the melt viscosity V1 at an applied pressure of 0.9807 MPa was 1×10 5 The temperature at which the melt viscosity becomes Pa·s is T1 (°C), and the melt viscosity V10 at an applied pressure of 9.807 MPa is 1×10 5 When the temperature at which the viscosity becomes Pa·s is T10 (℃), T1 and T10 are T10≧65 T1-T10≦10 The present invention relates to a toner characterized by satisfying the following relationship: [Effects of the Invention]

[0006] According to the present disclosure, it is possible to provide a toner that has excellent low-temperature fixing properties during high-speed printing, and that is compatible with hot offset resistance and winding resistance, and that is highly durable and less likely to produce image defects even after long-term use. DETAILED DESCRIPTION OF THE INVENTION

[0007] In the present disclosure, unless otherwise specified, the expressions "XX or more and YY or less" and "XX to YY" representing a numerical range mean a numerical range including the endpoints, that is, the lower limit and the upper limit.

[0008] The (meth)acrylic acid ester means an acrylic acid ester and / or a methacrylic acid ester.

[0009] When numerical ranges are stated in stages, the upper and lower limits of each numerical range can be combined in any way.

[0010] A "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 formed by polymerizing a vinyl monomer is considered to be one unit. A vinyl monomer can be represented by the following formula (Z):

[0011] [ka]

[0012] In the formula (Z), Z1 represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and Z2 represents an arbitrary substituent.

[0013] A crystalline resin refers to a resin that shows a clear endothermic peak in differential scanning calorimetry (DSC) measurement.

[0014] The present invention provides a toner having toner particles containing a binder resin having a first resin and a second resin, the first resin is a crystalline resin; the second resin is an amorphous resin, When a cross section of the toner particle is observed, the toner particle has a domain matrix structure composed of a matrix containing 80% or more of the first resin and a domain containing 80% or more of the second resin, In differential scanning calorimetry (DSC) of the toner, the amount of heat absorption ΔH (J / g) attributed to the first resin is ΔH≧3 Fulfilling the relationship, In a flow tester measurement using the toner as a sample, the melt viscosity V1 at an applied pressure of 0.9807 MPa was 1×10 5 The temperature at which the melt viscosity becomes Pa·s is T1 (°C), and the melt viscosity V10 at an applied pressure of 9.807 MPa is 1×10 5 When the temperature at which the viscosity becomes Pa·s is T10 (℃), T1 and T10 are T10≧65 T1-T10≦10 The present invention is characterized in that the following relationship is satisfied.

[0015] The present inventors have found that when a crystalline resin is used as the main component of the binder resin, the fixing temperature range does not necessarily expand even if an amorphous resin is added to impart viscoelasticity in the high temperature range, and that in some cases both low temperature fixability and hot offset resistance may deteriorate.

[0016] Furthermore, under conditions of use where the toner is subjected to stress, such as during long printing periods, the crystalline resin component tends to migrate and adhere to the drum, resulting in poor image quality. This phenomenon occurs more noticeably with toners containing amorphous resins, and we have been investigating ways to resolve this issue.

[0017] As a result, the present inventors have found that in a toner in which a crystalline resin is used as the main component of the binder resin and an amorphous resin is added, if the temperature-viscosity curve of the toner measured by a flow tester changes little even with applied pressure, durability is improved. Based on this finding, the present inventors have conducted extensive research and have arrived at the present invention.

[0018] The present inventors believe that the mechanism by which the effects of the present invention are manifested is as follows.

[0019] In the domain-matrix structure of the cross section of a toner particle, the matrix contains 80% or more of a first resin, which is a crystalline resin, and the domain contains 80% or more of a second resin, which is an amorphous resin. When heated, the toner exhibits sharp melting properties due to the melting of the crystals, thereby exhibiting excellent low-temperature fixability. Conversely, if the crystalline resin is present in the domain and the amorphous resin is present in the matrix, the melting properties of the entire toner are dominated by the properties of the amorphous resin, which is the matrix, and the low-temperature fixability effect due to the melting of the crystalline resin is not obtained, and the effects of the present invention cannot be achieved. Even when only one type of crystalline resin and one type of amorphous resin are used, the above proportions do not necessarily add up to 100% due to the presence of compatible components.

[0020] Usually, the resin with a larger amount forms the matrix, and the resin with a smaller amount forms the domain. However, since the crystalline resin has a low viscosity after melting, if the toner particle production process involves a step in which the temperature is equal to or higher than the melting point of the crystalline resin, the matrix may be composed of the crystalline resin even if the blending mass ratio of the crystalline resin is small. Examples of such production processes include the kneading process in the melt-kneading method and the fusion process in the emulsion aggregation method.

[0021] On the other hand, from the viewpoint of hot offset resistance and winding resistance, it is preferable that the viscosity of the molten toner is high. The viscosity of the molten toner can be increased by adding an amorphous resin to the toner particles.

[0022] However, as mentioned above, simply adding an amorphous resin does not necessarily expand the fixing temperature range, and in some cases, under conditions where stress is applied to the toner, such as long-term printing, the crystalline resin components in the toner may migrate and fuse to the drum, causing image defects.

[0023] During printing, toner is subjected to stress due to friction between the cleaning member and the drum. At this time, it is thought that some toner particles in the developing unit are subjected to extremely high stress. If the toner has properties such that its temperature-viscosity characteristics change significantly depending on the amount of external pressure applied, toner particles subjected to extremely high stress, even in the same temperature environment, will lose viscosity, melt and stick to the drum, causing image defects.

[0024] Conversely, if the temperature-viscosity characteristics are similar regardless of the magnitude of externally applied pressure, this will not occur and it is believed that excellent durability can be exhibited.

[0025] In the present invention, in differential scanning calorimetry (DSC) using a toner as a sample, the amount of heat absorption ΔH (J / g) derived from the first resin is ΔH≧3 As described above, in the present invention, excellent low-temperature fixability requires a decrease in viscosity due to melting of crystals. If ΔH is less than 3 (J / g), the crystallinity is insufficient, and the low-temperature fixability is reduced.

[0026] Although there is no particular upper limit, a value of 100 (J / g) or less is considered realistic in view of the heat absorption of typical crystalline resins.

[0027] In addition, the present invention is characterized in that, in a flow tester measurement using a toner sample, the melt viscosity V1 at an applied pressure of 0.9807 MPa is 1×10 5 The temperature at which the melt viscosity becomes Pa·s is T1 (°C), and the melt viscosity V10 at an applied pressure of 9.807 MPa is 1×10 5 When the temperature at which the thermal conductivity becomes Pa·s is T10, T1 and T10 are as follows: T10≧65 T1-T10≦10 The above relationship is satisfied.

[0028] By satisfying the relationship T10≧65, toner particles can be prevented from fusing to other components even when subjected to great stress, and image defects can be suppressed even during long-term printing. If T10 is less than 65, image defects are more likely to occur, resulting in reduced quality.

[0029] Furthermore, T1 is the viscosity characteristic at an applied pressure simulating the fixing process, and T1 - T10 ≦ 10 indicates that the temperature-viscosity characteristic is not significantly dependent on the externally applied pressure. Therefore, it is possible to achieve both excellent low-temperature fixability and suppression of image defects during long-term printing. If T1 - T10 exceeds 10, the low-temperature fixability deteriorates, and the low-temperature fixability effect of the present invention cannot be obtained.

[0030] The method for bringing T1-T10 into the range of the present invention is not easily determined, but can be achieved by controlling the various physical property values ​​of the first resin and the second resin. The inventors' studies have found that when the SP values ​​of the first resin and the second resin are close to each other and when the softening point and weight average molecular weight of the second resin are larger than those of the first resin, it tends to be easier to control T1-T10 into the range of the present invention.

[0031] The SP value is a numerical value that represents the polarity of a resin, and the higher the value, the higher the polarity. The calculation method will be described later.

[0032] The relationship between the SP value SP1 of the first resin and the SP value SP2 of the second resin preferably satisfies the relationship SP2-SP1≦0.9, since this facilitates achieving the T1-T10 range of the present invention. More preferably, SP2-SP1≦0.6.

[0033] As will be described later, the SP value can be controlled by changing the types and content ratios of the monomer units constituting the first resin and the second resin.

[0034] In a DSC analysis using the toner according to the present invention as a sample, it is preferable that the maximum endothermic peak temperature Tp (°C) derived from the first resin satisfies the relationship 45≦Tp≦70. It is also preferable that the relationship between the glass transition temperature Tg of the second resin and the maximum endothermic peak temperature Tp of the first resin is Tg≦Tp. Furthermore, when the softening point Tm of the second resin and the maximum endothermic peak temperature Tp of the first resin are taken as the temperature, it is preferable that the relationship Tp≦Tm-30 is satisfied, since this makes it easier to control the temperature within the T1-T10 range of the present invention.

[0035] Specifically, this can include controlling the content of the first resin, which is a crystalline resin, the weight average molecular weight Mw, the softening point Tm, the temperature of the maximum endothermic peak, the amount of heat absorption ΔH derived from the crystalline resin, which is the first resin in the toner, and the like.

[0036] Further, the content of the amorphous resin as the second resin, the weight average molecular weight Mw, the softening point Tm, the glass transition temperature Tg, and the like may be controlled.

[0037] Another factor is controlling the dispersion state of the domains in the domain matrix structure of the cross section of the toner particle. If the number average diameter of the domains is in the range of 0.10 μm to 2.00 μm, it is easy to control it within the range of the present invention, so it is preferable. It is more preferably 0.10 μm to 1.00 μm.

[0038] Examples of a method for controlling the number-average diameter of the domains include controlling the polarity of the first resin and the second resin described above, or controlling the screw rotation speed and kneading temperature in the kneading step in the case of a melt kneading method, or the dispersion diameter of the resin in the resin dispersion in the case of an emulsion aggregation method during toner production.

[0039] The binder resin according to the present invention contains a first resin, and the first resin is a crystalline resin.

[0040] The crystalline resin may be any known crystalline resin. Examples include crystalline polyester, crystalline vinyl resin, crystalline polyurethane, and crystalline polyurea. Other examples include ethylene copolymers such as ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid copolymer, and ethylene-acrylic acid copolymer.

[0041] Among these, crystalline polyester resins and crystalline vinyl resins are preferred from the viewpoint of low-temperature fixability.

[0042] Furthermore, the first resin is preferably a vinyl resin, and further preferably has a first monomer unit represented by the following formula (1): The content of the first monomer unit in the first resin is preferably 20.0% by mass to 80.0% by mass, since this makes it easier to achieve low-temperature fixability, hot offset resistance, and winding resistance all at the same time.

[0043] [ka] [In formula (1), R Z1 represents a hydrogen atom or a methyl group, and R represents an alkyl group having 18 to 36 carbon atoms.]

[0044] The R is preferably an alkyl group having a carbon number of 18 to 30. The alkyl group preferably has a linear structure.

[0045] The first monomer unit has an alkyl group having 18 to 36 carbon atoms represented by R on the side chain, and the presence of this portion makes it easier for the first resin to exhibit crystallinity.

[0046] When the content of the first monomer unit in the first resin is 20.0% by mass to 100.0% by mass, the first resin has crystallinity, which contributes to improving low-temperature fixability.

[0047] If the content of the first monomer unit in the first resin is less than 20.0% by mass, crystallinity is unlikely to be exhibited, and low-temperature fixability is likely to be reduced. The content is preferably 40.0% by mass or more, and more preferably 50.0% by mass or more. There is no particular upper limit, but when other monomer units described below are contained, it is preferably 90.0% by mass or less, and more preferably 80.0% by mass or less.

[0048] Furthermore, the first resin is preferred because it has a structure with crystallinity in the side chain and therefore has excellent charge retention properties in a high-temperature, high-humidity environment compared to crystalline polyester, which is a well-known conventional crystalline resin.

[0049] The SP value (J / cm) of the first monomer unit 3 ) 0.5 ,SP 11 Then, SP 11is preferably less than 20.00, more preferably 19.00 or less, and even more preferably 18.40 or less. There is no particular limitation on the lower limit, but it is preferably 17.00 or more.

[0050] The first monomer unit represented by formula (1) is preferably a monomer unit derived from at least one (first polymerizable monomer) selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms.

[0051] Examples of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms include (meth)acrylic acid esters having a linear alkyl group having 18 to 36 carbon atoms [stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosyl (meth)acrylate, myricyl (meth)acrylate, dotriacontyl (meth)acrylate, etc.] and (meth)acrylic acid esters having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth)acrylate, etc.].

[0052] Among these, from the viewpoint of low-temperature fixability of the toner, it is preferably at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 36 carbon atoms. It is more preferably at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 30 carbon atoms. It is even more preferably at least one selected from the group consisting of linear stearyl (meth)acrylate and behenyl (meth)acrylate.

[0053] The first monomer unit may be used alone or in combination of two or more kinds.

[0054] The first resin preferably has a second monomer unit which is different from the first monomer unit and is at least one selected from the group consisting of a monomer unit represented by the following formula (3) and a monomer unit represented by the following formula (4):

[0055] In addition, the SP value of the second monomer unit (J / cm 3 ) 0.5 SP 21 Then, SP 21 It is preferable that the following formula (2) is satisfied, and it is more preferable that the following formula (2)' is satisfied. 21:00≦SP 21 (2) 21:00≦SP 21 ≦40.00 (2)'

[0056] [ka] [In formula (3), X represents a single bond or an alkylene group having 1 to 6 carbon atoms, R 1 is -C≡N, -C(=O)NHR 10 (R 10 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), hydroxy groups, -COOR 11 (R 11 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4), or a hydroxyalkyl group having 1 to 6 carbon atoms (preferably 1 to 4), -NH-C(=O)-N(R 13 )2(R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms, -COO(CH2)2NHCOOR 14 (R 14 is an alkyl group having 1 to 4 carbon atoms), Or, -COO(CH2)2-NH-C(=O)-N(R 15 )2(R 15each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 2 represents a hydrogen atom or a methyl group. In formula (4), R 3 represents an alkyl group having 1 to 4 carbon atoms, and R 4 represents a hydrogen atom or a methyl group.

[0057] When the first resin contains the second monomer unit, polarization of charge occurs due to the presence of a highly polar functional group, which has the effect of increasing the viscosity when the toner is melted, and this is preferable because it tends to improve the winding resistance.

[0058] Examples of the second polymerizable monomer that forms the second monomer unit include the following: The second polymerizable monomer may be used alone or in combination of two or more.

[0059] Monomers having a nitrile group; for example, acrylonitrile, methacrylonitrile, etc.

[0060] Monomers having a hydroxy group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.

[0061] Monomers having an amide group: for example, acrylamide, a monomer obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms (such as acrylic acid or methacrylic acid) having an ethylenically unsaturated bond by a known method.

[0062] Monomers having a urea group: for example, monomers obtained by reacting an amine having 3 to 22 carbon atoms [primary amines (such as normal butylamine, t-butylamine, propylamine, and isopropylamine), secondary amines (such as di-normal ethylamine, di-normal propylamine, and di-normal butylamine), aniline, and cycloxylamine] with an isocyanate having 2 to 30 carbon atoms and an ethylenically unsaturated bond by a known method.

[0063] Monomers having a carboxy group; for example, methacrylic acid, acrylic acid, and 2-carboxyethyl (meth)acrylate.

[0064] Among these, it is preferable to use a monomer having a nitrile group, an amide group, a urethane group, a hydroxy group, or a urea group. More preferably, it is a monomer having an ethylenically unsaturated bond and at least one functional group selected from the group consisting of a nitrile group, an amide group, a urethane group, a hydroxy group, and a urea group. The use of these monomers further improves the charge build-up in low-humidity environments. Among these, nitrile groups are particularly preferable because they have high electron-withdrawing properties, are likely to cause the aforementioned charge polarization, and increase the viscosity when the toner is melted, which tends to improve winding resistance.

[0065] As the second polymerizable monomer, at least one vinyl ester selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, and vinyl octylate may be used.

[0066] Vinyl esters are non-conjugated monomers and tend to maintain a moderate reactivity with the first polymerizable monomer, which makes it easier to improve the crystallinity of the first resin and more likely to achieve both low-temperature fixability and heat-resistant storage stability.

[0067] The second polymerizable monomer preferably has an ethylenically unsaturated bond, more preferably has one ethylenically unsaturated bond.

[0068] The content of the second monomer unit in the first resin is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and even more preferably 5.0% by mass or more, and the upper limit thereof is preferably 70.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 20.0% by mass or less.

[0069] The second monomer unit is SP represented by the above formula (2).21 It is preferable to select a monomer unit that satisfies the following.

[0070] Furthermore, the first resin may have a third monomer unit that is not included in the SP value range of the first monomer unit and the second monomer unit, as long as the mass ratio of the first monomer unit and the second monomer unit described above is not impaired.

[0071] As the third polymerizable monomer constituting the third monomer unit, it is preferable to select, for example, one that does not satisfy formula (2) as a monomer unit from among the monomers listed in the section on the second polymerizable monomer. Note that if formula (2) is satisfied, it can be used as the second polymerizable monomer.

[0072] Furthermore, the following monomers which do not have the above-mentioned nitrile group, amide group, urethane group, hydroxy group, urea group, or carboxy group can also be used.

[0073] For example, styrene and derivatives thereof such as styrene and o-methylstyrene, (meth)acrylic acid esters such as methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0074] The third polymerizable monomer is preferably at least one selected from the group consisting of styrene, methyl methacrylate, and methyl acrylate, and more preferably styrene from the viewpoint of charge retention.

[0075] The content of the third monomer unit derived from the third polymerizable monomer in the first resin is preferably 10.0% by mass or more, more preferably 15.0% by mass or more, and even more preferably 20.0% by mass or more, and the upper limit thereof is preferably 70.0% by mass or less, more preferably 50.0% by mass or less, and even more preferably 40.0% by mass or less.

[0076] The first resin is preferably a vinyl polymer. Examples of the vinyl polymer include polymers of monomers containing an ethylenically unsaturated bond. The ethylenically unsaturated bond refers to a carbon-carbon double bond capable of radical polymerization, such as a vinyl group, a propenyl group, an acryloyl group, or a methacryloyl group.

[0077] The acid value AVa of the first resin, which is a crystalline resin, is preferably 50.0 mgKOH / g or less, more preferably 30.0 mgKOH / g or less, from the viewpoint of improving chargeability under high temperature and high humidity conditions. The lower limit is not particularly limited, but is preferably 0 mgKOH / g or more, and from the viewpoint of improving charge rise, is preferably 0.5 mgKOH / g or more, more preferably 1.0 mgKOH / g or more.

[0078] The hydroxyl value OHVa of the first resin, which is a crystalline resin, is preferably 50.0 mgKOH / g or less, more preferably 30.0 mgKOH / g or less, from the viewpoint of improving chargeability under high temperature and high humidity conditions. The lower limit is not particularly limited, but is preferably 0 mgKOH / g or more, and from the viewpoint of improving charge rise, is preferably 0.5 mgKOH / g or more, more preferably 1.0 mgKOH / g or more.

[0079] The weight average molecular weight (Mw) of the tetrahydrofuran (THF) soluble portion of the first resin, which is a crystalline resin, measured by gel permeation chromatography (GPC) is preferably from 15,000 to 200,000, more preferably from 20,000 to 100,000. Having the weight average molecular weight (Mw) of the THF soluble portion within the above range is preferable because it makes it easier to maintain elasticity at around room temperature and reduces the likelihood of image defects during long-term printing.

[0080] The melting point of the first resin, which is a crystalline resin, is preferably 40° C. or higher and 80° C. or lower, more preferably 45° C. or higher and 70° C. or lower, from the viewpoints of heat-resistant storage stability and low-temperature fixability.

[0081] The SP value SP1 of the first resin is preferably 18.0 or more, more preferably 18.6 or more, and even more preferably 19.2 or more.

[0082] From the viewpoint of easily obtaining a domain matrix structure, the content of the first resin, which is a crystalline resin, in the binder resin is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, and the upper limit thereof is preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0083] The binder resin according to the present invention contains a second resin, and the second resin is an amorphous resin.

[0084] As the amorphous resin, known amorphous resins can be used, for example, the following:

[0085] Polyvinyl chloride, phenolic resin, natural resin modified phenolic resin, natural resin modified maleic acid resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum-based resin, vinyl-based resin.

[0086] When a crystalline polyester resin is used as the first resin, it is preferable to use an amorphous polyester resin as the second resin, since the SP values ​​of the first resin and the second resin are close to each other, resulting in a strong interaction, and making it easier to control the T1-T10 within the range of the present invention.

[0087] Furthermore, when a resin containing the first monomer unit described above is used as the first resin, using a vinyl resin as the second resin is preferable because the SP values ​​of the first and second resins are close to each other, resulting in a strong interaction and making it easier to control the T1-T10 within the range of the present invention.Furthermore, this is also preferable from the viewpoint of making it easier to form a domain matrix structure compared to when a polyester resin is used as the first resin.

[0088] The content of the second resin, which is an amorphous resin, in the binder resin is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and particularly preferably 30% by mass or more, with the upper limit being preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0089] In the toner particles of the present invention, the content W1 of the first resin and the content W2 of the second resin are 0.2≦W2 / W1≦4.0 It is preferable that the relationship be satisfied, and it is more preferable that the relationship be satisfied: 0.3≦W2 / W1≦3.0.

[0090] When a vinyl resin is used as the second resin, for example, the second resin may be a polymer of a polymerizable monomer containing an ethylenically unsaturated bond, which refers to a carbon-carbon double bond capable of radical polymerization, such as a vinyl group, a propenyl group, an acryloyl group, or a methacryloyl group.

[0091] Examples of the polymerizable monomer include the following.

[0092] Styrenic monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene; acrylic acid and acrylic acid esters such as acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate; α-methylene aliphatic monocarboxylic acids and their esters, such as methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate; Also, acrylonitrile, methacrylonitrile, acrylamide, etc.

[0093] Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate, and polymerizable monomers having a hydroxy group such as 4-(1-hydroxy-1-methylbutyl)styrene and 4-(1-hydroxy-1-methylhexyl)styrene can be used alone or in combination.

[0094] In addition to the above, various polymerizable monomers capable of vinyl polymerization may be used in combination with the vinyl resin as needed.

[0095] Examples of the polymerizable monomer include the following.

[0096] Unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate, and vinyl benzoate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; vinylnaphthalenes; unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, and benzoic acid. unsaturated dibasic acid anhydrides such as alkenylsuccinic anhydride; half esters of unsaturated basic acids such as methyl maleate half ester, ethyl maleate half ester, butyl maleate half ester, methyl citraconic acid half ester, ethyl citraconic acid half ester, butyl citraconic acid half ester, methyl itaconic acid half ester, methyl alkenylsuccinic acid half ester, methyl fumaric acid half ester, and methyl mesaconic acid half ester; unsaturated basic acid esters such as dimethylmaleic acid and dimethylfumaric acid; acid anhydrides of α,β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid; anhydrides of such α,β-unsaturated acids and lower fatty acids; and polymerizable monomers having a carboxy group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides thereof, and monoesters thereof.

[0097] Furthermore, the vinyl resin may be a polymer crosslinked with a crosslinkable polymerizable monomer as exemplified below, if necessary.

[0098] Examples of the crosslinkable polymerizable monomer include the following.

[0099] Aromatic divinyl compounds; diacrylate compounds linked by alkyl chains; diacrylate compounds linked by alkyl chains containing ether bonds; diacrylate compounds linked by chains containing aromatic groups and ether bonds; polyester-type diacrylates; polyfunctional crosslinkers.

[0100] Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene.

[0101] Examples of diacrylate compounds linked by alkyl chains include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and compounds in which the acrylate in the above compounds is replaced with methacrylate.

[0102] Vinyl resins include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, and 2-chloroethyl acrylate. , phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-(1-hydroxy-1-methylbutyl)styrene, and 4-(1-hydroxy-1-methylhexyl)styrene.

[0103] The vinyl resin may also be a copolymer of at least one polymerizable monomer selected from the above group and at least one crosslinkable polymerizable monomer selected from the group consisting of divinylbenzene, divinylnaphthalene, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and neopentyl glycol dimethacrylate. The content of the crosslinkable polymer in the monomer is preferably about 0.5% to 5.0% by mass, since this facilitates control of the softening point, as described below.

[0104] Among the above-mentioned polymerizable monomers, styrene-based monomers, acrylic acid ester-based monomers, and methacrylic acid ester-based monomers are preferred. A combination of styrene and n-butyl acrylate is preferred. Furthermore, the number of carbon atoms in the alkyl group bonded to the ester moiety of the acrylic acid ester-based monomer or methacrylic acid ester-based monomer can also be used to control the number-average diameter of the domains containing the second resin, which is an amorphous resin.

[0105] The second resin, which is an amorphous resin, preferably has a monomer unit represented by the following formula (5). When the second resin has a monomer unit represented by the following formula (5), the content of the monomer unit of the following formula (5) in the second resin is preferably 30.0% by mass or more, more preferably 50.0% by mass or more, and even more preferably 70.0% by mass or more. The upper limit is preferably 95.0% by mass or less, more preferably 90.0% by mass or less.

[0106] [ka] [In formula (5), R 5represents a hydrogen atom or a methyl group, and Ph represents a phenyl group. The phenyl group may have a substituent.]

[0107] The monomer unit represented by the formula (5) has a phenyl group, and therefore improves the charge retention particularly in a high-temperature, high-humidity environment.

[0108] Furthermore, when the first resin contains the monomer unit represented by formula (5) in addition to the second resin, phenyl groups contained in both the first and second resins are more likely to interact with each other due to π electrons. As a result, it is easier to control the number-average diameter of the domains within the above-mentioned range. Furthermore, charge retention in high-temperature, high-humidity environments is further improved.

[0109] The vinyl resin may be a resin produced using a polymerization initiator. From the viewpoint of efficiency, the polymerization initiator is preferably used in an amount of 0.05 to 10 parts by mass per 100 parts by mass of the polymerizable monomer.

[0110] Examples of the polymerization initiator include the following.

[0111] 2,2'-Azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis(1-cyclohexanecarbonitrile), 2-carbamoylazoisobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis(2-methylpropane), methyl ethyl ketone peroxide, acetonitrile Ketone peroxides such as ethyl acetone peroxide and cyclohexanone peroxide, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α,α'-bis(tert-butylperoxyisopropyl)benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-Trimethylhexanoyl peroxide, benzoyl peroxide, m-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxy Diisobutyrate, tert-butyl peroxyneodecanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, tert-amyl peroxy-2-ethylhexanoate, di-tert-butyl peroxyhexahydroterephthalate, di-tert-butyl peroxyazelate.

[0112] The polyester resin may be a polyester resin that is normally used in toner. Monomers that can be used for the polyester resin include polyhydric alcohols (dihydric, trihydric or higher alcohols), polycarboxylic acids (dihydric, trihydric or higher carboxylic acids), acid anhydrides thereof, or lower alkyl esters thereof.

[0113] Examples of the polyhydric alcohol include the following:

[0114] Examples of dihydric alcohols include the following bisphenol derivatives:

[0115] Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(3.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(2.0)-polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(6)-2,2-bis(4-hydroxyphenyl)propane, etc.

[0116] Other polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

[0117] These polyhydric alcohols can be used alone or in combination.

[0118] Examples of polycarboxylic acids include the following:

[0119] Examples of dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, anhydrides of these acids, and lower alkyl esters thereof. Of these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenylsuccinic acid are preferably used.

[0120] Examples of trivalent or higher carboxylic acids, acid anhydrides thereof, or lower alkyl esters thereof include the following.

[0121] 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empol trimer acid, acid anhydrides thereof, or lower alkyl esters thereof.

[0122] Among these, 1,2,4-benzenetricarboxylic acid (trimellitic acid) or its derivatives such as acid anhydride are preferably used because they are inexpensive and the reaction can be easily controlled.

[0123] These polycarboxylic acids can be used alone or in combination.

[0124] The method for producing the polyester resin is not particularly limited, and known methods can be used. For example, the aforementioned polyhydric alcohol and polycarboxylic acid are simultaneously charged and polymerized via an esterification reaction or transesterification reaction and a condensation reaction to produce the polyester resin. The polymerization temperature is not particularly limited, but is preferably in the range of 180°C to 290°C. For polymerization of the polyester resin, for example, a polymerization catalyst such as a titanium-based catalyst, a tin-based catalyst, zinc acetate, antimony trioxide, or germanium dioxide can be used.

[0125] The polyester resin used as the amorphous resin is preferably one that has been polycondensed using at least one of a titanium-based catalyst and a tin-based catalyst.

[0126] The acid value AVi of the second resin, which is an amorphous resin, is preferably 50.0 mgKOH / g or less, more preferably 30.0 mgKOH / g or less, from the viewpoint of improving chargeability under high temperature and high humidity conditions. The lower limit is not particularly limited, but is preferably 0 mgKOH / g or more, and from the viewpoint of improving charge rise, it is preferably 0.5 mgKOH / g or more, more preferably 1.0 mgKOH / g or more.

[0127] The hydroxyl value OHVi of the second resin, which is an amorphous resin, is preferably 50.0 mgKOH / g or less, more preferably 30.0 mgKOH / g or less, from the viewpoint of improving chargeability under high temperature and high humidity conditions. The lower limit is not particularly limited, but is preferably 0 mgKOH / g or more, and from the viewpoint of improving charge rise, it is preferably 0.5 mgKOH / g or more, more preferably 1.0 mgKOH / g or more.

[0128] The weight average molecular weight (Mw) of the tetrahydrofuran (THF) soluble portion of the second resin, which is an amorphous resin, measured by gel permeation chromatography (GPC) is preferably 20,000 or more and 1,000,000 or less, and more preferably 50,000 or more and 150,000 or less. When the weight average molecular weight (Mw) of the THF soluble portion is within the above range, elasticity at around room temperature can be easily maintained.

[0129] From the viewpoint of hot offset resistance, it is preferable that the content of tetrahydrofuran (THF) insoluble matter in the second resin is 3% by mass or more.

[0130] Furthermore, when the weight-average molecular weight Mw1 of the tetrahydrofuran (THF)-soluble portion of the first resin measured by gel permeation chromatography (GPC) is taken as the weight-average molecular weight Mw2 of the THF-soluble portion of the first resin measured by GPC, it is preferable that the relationship Mw2 / Mw1 ≧ 1.5 is satisfied. More preferably, Mw2 / Mw1 ≧ 2.0 is satisfied. When this relationship is satisfied, it is easy to control T10 - T1 within the range of the present invention, which is preferable.

[0131] The softening point Tm of the second resin, which is an amorphous resin, is preferably 100° C. or higher from the viewpoint of suppressing image defects. The upper limit is preferably 160° C. or lower, more preferably 140° C. or lower, and even more preferably 130° C. or lower. Furthermore, from the viewpoint of easily controlling T1-T10 within the range of the present invention, the softening point Tm is preferably 110° C. or higher.

[0132] The binder resin may contain a resin other than the first resin, the second resin, and the third resin to the extent that the effects of the present disclosure are not impaired, for the purpose of improving pigment dispersibility, etc. Examples of such resins include the following.

[0133] Polyvinyl chloride, phenolic resin, natural resin modified phenolic resin, natural resin modified maleic acid resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum-based resin.

[0134] The toner particles may contain a colorant, such as the following:

[0135] Examples of black colorants include carbon black and those toned to black using a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, a pigment may be used alone, but it is preferable to use a dye and a pigment in combination to improve the clarity from the viewpoint of the image quality of a full-color image.

[0136] Examples of pigments for magenta toner include the following:

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

[0138] Examples of dyes for magenta toner include the following:

[0139] Solvent dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, 27; and CI Disperse Violet 1; and basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0140] Examples of pigments for cyan toner include the following:

[0141] CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; CI Vat Blue 6; CI Acid Blue 45, copper phthalocyanine pigments with 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.

[0142] An example of a dye for cyan toner is CI Solvent Blue 70.

[0143] Examples of pigments for yellow toner include the following:

[0144] CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Bat Yellow 1, 3, 20.

[0145] An example of a yellow toner dye is CI Solvent Yellow 162.

[0146] The content of the colorant is preferably 0.1 to 30.0 parts by mass with respect to 100 parts by mass of the binder resin.

[0147] The toner particles may contain wax. Examples of the wax include the following:

[0148] Hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or their block copolymers; waxes whose main component is fatty acid esters such as carnauba wax; partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.

[0149] Further examples include saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and parinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylene saturated fatty acid bisamides such as m-xylenebisstearamide; unsaturated fatty acid amides such as ethylenebisoleamide, hexamethylenebisoleamide, N,N'-dioleyl adipamide, and N,N'-dioleyl sebacamide; aromatic bisamides such as m-xylenebisstearamide and N,N'-distearyl isophthalamide; fatty metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having hydroxy groups obtained by hydrogenating vegetable oils and fats.

[0150] The content of the wax is preferably 2.0 parts by mass to 30.0 parts by mass with respect to 100 parts by mass of the binder resin.

[0151] Furthermore, when the toner contains a wax, the maximum endothermic peak temperature Tp of the first resin and the maximum endothermic peak temperature Tw of the wax preferably satisfy the relationship 10≦Tw−Tp≦45, and more preferably satisfy the relationship 20≦Tw−Tp≦40. Generally, wax has a lower molecular weight than the first resin, and tends to have a lower viscosity after melting than the first resin. When heated, the wax melts more slowly than the crystalline resin, which is preferable because it prevents low-viscosity components from adhering to the image carrier, etc., and makes it easier to prevent image defects.

[0152] The toner particles may contain a charge control agent. Although known charge control agents can be used as the charge control agent, metal compounds of aromatic carboxylic acids are particularly preferred because they are colorless, can charge the toner quickly, and can stably maintain a constant charge amount.

[0153] Examples of negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds having sulfonic acid or carboxylic acid on the side chain, polymeric compounds having sulfonate or sulfonate ester on the side chain, polymeric compounds having carboxylate or carboxylate ester on the side chain, boron compounds, urea compounds, silicon compounds, and calixarene. The charge control agent may be added internally or externally to the toner particles.

[0154] The content of the charge control agent is preferably 0.2 parts by mass to 10.0 parts by mass with respect to 100 parts by mass of the binder resin.

[0155] The toner may contain an external additive. For example, an external additive may be added to toner particles to form a toner. As the external additive, inorganic fine particles such as silica fine particles, titanium oxide fine particles, and aluminum oxide fine particles are preferred.

[0156] As an external additive to improve fluidity, 2 / g~400m 2 / g of inorganic fine particles are preferred, and for improved durability, a specific surface area of ​​10 m 2 / g~50m2 / g of inorganic fine particles is preferred.

[0157] In order to improve both the fluidity and durability of the toner, inorganic fine particles having a specific surface area within the above range may be used in combination.

[0158] The content of the external additive is preferably 0.1 to 10.0 parts by mass with respect to 100 parts by mass of toner particles. A known mixer such as a Henschel mixer may be used to mix the toner particles and the external additive.

[0159] The toner can be used as a one-component developer, but in order to further improve dot reproducibility, it is preferable to mix the toner with a magnetic carrier and use it as a two-component developer, since this allows stable images to be obtained over a long period of time. That is, it is preferable that the toner is a two-component developer containing a toner and a magnetic carrier, and the toner is the toner described above.

[0160] Examples of magnetic carriers include commonly known ones such as iron powder or surface-oxidized iron powder; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, or oxide particles thereof; magnetic materials such as ferrite; and magnetic material-dispersed resin carriers (so-called resin carriers) containing the magnetic material and a binder resin that holds the magnetic material in a dispersed state.

[0161] When the toner is mixed with a magnetic carrier and used as a two-component developer, the toner content in the two-component developer is preferably about 2% by mass to 15% by mass, and more preferably about 4% by mass to 13% by mass.

[0162] The method for producing the toner particles is not particularly limited, and any of the conventionally known production methods such as suspension polymerization, emulsion aggregation, melt-kneading, and dissolution suspension methods can be used.

[0163] Hereinafter, the melt-kneading method will be described as an example, but the method is not limited thereto.

[0164] First, in the raw material mixing process, predetermined amounts of materials constituting the toner particles, such as a first resin and a second resin or a binder resin containing the first resin and the second resin, and, if necessary, other components such as wax, colorant, charge control agent, etc., are weighed, blended, and mixed. Examples of mixing devices include a double cone mixer, V-type mixer, drum mixer, super mixer, Henschel mixer, Nauta mixer, and Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.).

[0165] Next, the mixed materials are melt-kneaded to disperse the other components in the binder resin containing the first and second resins. In the melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. Single- or twin-screw extruders are commonly used due to their advantage of continuous production. Examples include a KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), a TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikegai Iron Works), a twin-screw extruder (manufactured by KCK Corporation), a Ko-Kneader (manufactured by Buss Co., Ltd.), and a Kneadex (manufactured by Nippon Coke and Engineering Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading may be rolled using a twin roll or the like and cooled with water or the like in a cooling process.

[0166] The state of dispersion of the first resin and the second resin, the number-average diameter of the domains, and the like can be controlled by adjusting the kneading temperature in the melt-kneading step, the number of revolutions of the screw, and the like.

[0167] The cooled resin composition is then pulverized to a desired particle size in a pulverization step, which may involve coarse pulverization using a pulverizer such as a crusher, hammer mill, or feather mill, followed by further pulverization using a pulverizer such as a Kryptron System (Kawasaki Heavy Industries), a Super Rotor (Nisshin Engineering), a Turbo Mill (Turbo Kogyo), or an air jet pulverizer.

[0168] Thereafter, if necessary, the mixture may be classified using a classifier or sieve such as an inertial classification type Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal classification type Turboplex (manufactured by Hosokawa Micron Corporation), a TSP Separator (manufactured by Hosokawa Micron Corporation), or a Faculty (manufactured by Hosokawa Micron Corporation) to obtain toner particles.

[0169] Next, the case where toner particles are produced by the emulsion aggregation method will be described.

[0170] In the emulsion aggregation method, toner particles are manufactured through a series of steps, including a dispersion process to prepare a fine particle dispersion made up of the constituent materials of toner particles, an aggregation process to aggregate the fine particles made up of the constituent materials of toner particles and control the particle size until the particle size reaches that of toner particles, a fusion process to fuse the resin contained in the resulting aggregated particles, a subsequent cooling process, a metal removal process to filter the resulting toner and remove excess polyvalent metal ions, a filtration and washing process to wash with ion-exchanged water or the like, and a process to remove moisture from the washed toner particles and dry them.

[0171] <Step of preparing a resin particle dispersion (dispersion step)> The resin particle dispersion can be prepared by a known method, but is not limited to these methods. Examples of known methods include emulsion polymerization, self-emulsification, phase inversion emulsification in which a resin is emulsified by adding an aqueous medium to a resin solution dissolved in an organic solvent, and forced emulsification in which a resin is forcibly emulsified by high-temperature treatment in an aqueous medium without using an organic solvent.

[0172] Specifically, the first resin and the second resin are dissolved in an organic solvent capable of dissolving them, and a surfactant or a basic compound is added as needed. If the resin is a crystalline resin having a melting point, it may be dissolved by heating above the melting point. Subsequently, an aqueous medium is slowly added while stirring with a homogenizer or the like to precipitate resin microparticles. The solvent is then removed by heating or decompression to produce an aqueous dispersion of resin microparticles.

[0173] Any organic solvent can be used to dissolve the resin as long as it can dissolve the resin. However, it is preferable to use an organic solvent that forms a homogeneous phase with water, such as toluene, from the viewpoint of suppressing the generation of coarse powder.

[0174] The surfactant is not particularly limited, but examples thereof include anionic surfactants such as sulfate ester salts, sulfonate salts, carboxylate salts, phosphate esters, and soap-based surfactants; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. The surfactants may be used alone or in combination of two or more.

[0175] Examples of the basic compound include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as ammonia, triethylamine, trimethylamine, dimethylaminoethanol, and diethylaminoethanol. The basic compound may be used alone or in combination of two or more.

[0176] Furthermore, the volume-based 50% particle diameter (D50) of the resin fine particles in the aqueous dispersion of resin fine particles is preferably about 0.05 μm to 1.00 μm, and more preferably about 0.05 μm to 0.40 μm. By adjusting the volume-based 50% particle diameter (D50) within the above range, it becomes easy to obtain toner particles with a weight average particle diameter of 3 μm to 10 μm, which is appropriate for toner particles.

[0177] To measure the 50% particle size (D50) on a volume basis, it is recommended to use a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso).

[0178] <Preparation of Colorant Particle Dispersion> The colorant particle dispersion can be prepared by the following known methods, but is not limited to these methods.

[0179] The colorant, the aqueous medium, and the dispersant can be mixed using a known mixer such as a stirrer, an emulsifier, or a disperser. The dispersant used here can be a known surfactant or polymer dispersant.

[0180] Both surfactants and polymer dispersants can be removed in the washing step described below, but surfactants are preferred from the viewpoint of washing efficiency.

[0181] Examples of surfactants include anionic surfactants such as sulfate ester salts, sulfonate salts, phosphate esters, and soap-based surfactants; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols.

[0182] Among these, nonionic surfactants or anionic surfactants are preferred. A nonionic surfactant and an anionic surfactant may also be used in combination. The surfactant may be used alone or in combination of two or more. The concentration of the surfactant in the aqueous medium is preferably about 0.5% by mass to 5% by mass.

[0183] The content of the colorant particles in the colorant particle dispersion is not particularly limited, but is preferably 1% by mass to 30% by mass relative to the total mass of the colorant particle dispersion.

[0184] From the viewpoint of dispersibility of the colorant in the final toner particles, the dispersed particle size of the colorant microparticles in the aqueous dispersion of the colorant is preferably a 50% particle size (D50) based on volume of 0.50 μm or less. For the same reason, it is also preferable that the 90% particle size (D90) based on volume is 2 μm or less. The 50% particle size (D50) based on volume of the colorant microparticles dispersed in the aqueous medium can be measured using a dynamic light scattering particle size distribution analyzer (Nanotrac UPA-EX150, manufactured by Nikkiso).

[0185] Known mixers such as stirrers, emulsifiers, and dispersers used when dispersing a colorant in an aqueous medium include ultrasonic homogenizers, jet mills, pressure homogenizers, colloid mills, ball mills, sand mills, and paint shakers. These may be used alone or in combination.

[0186] <Preparation of wax particle dispersion> The wax particle dispersion can be prepared by the following known methods, but is not limited to these methods.

[0187] Wax microparticle dispersions can be produced by adding wax to an aqueous medium containing a surfactant, heating the mixture above the melting point of the wax, dispersing the mixture into particles using a homogenizer with strong shearing capabilities (e.g., M Technique's "Clearmix W Motion") or a pressure-discharge disperser (e.g., Gaulin Homogenizer) and then cooling the mixture below the melting point.

[0188] The volume-based 50% particle size (D50) of the dispersed particle of the wax microparticle dispersion in the aqueous wax dispersion is preferably about 0.03 μm to 1.0 μm, more preferably 0.10 μm to 0.50 μm, and preferably no coarse particles of 1 μm or larger are present.

[0189] By having the dispersed particle size of the wax particle dispersion within the above range, it is possible to finely disperse the wax in the toner particles, maximize the exudation effect during fixing, and obtain good separability. The 50% particle size (D50) on a volume basis of the wax particle dispersion dispersed in an aqueous medium can be measured using a dynamic light scattering particle size distribution analyzer (Nanotrac UPA-EX150: manufactured by Nikkiso).

[0190] <Mixing process> In the mixing step, a mixed liquid is prepared by mixing the first resin particle dispersion, the second resin particle dispersion, and, if necessary, the wax particle dispersion and the colorant particle dispersion, etc. This may be carried out using a known mixing device such as a homogenizer or a mixer.

[0191] <Step of forming aggregate particles (aggregation step)> In the aggregating step, the fine particles contained in the mixed solution prepared in the mixing step are aggregated to form aggregates of a desired particle size. At this time, an aggregating agent is added and mixed as needed, and at least one of heat and mechanical power is appropriately applied to form aggregates in which the resin fine particles and, as needed, the wax fine particles and colorant fine particles are aggregated.

[0192] As the flocculant, a flocculant containing a divalent or higher metal ion may be used as necessary.

[0193] A flocculant containing a divalent or higher metal ion has a high flocculating force, and the purpose can be achieved by adding a small amount. These flocculants can also ionically neutralize the ionic surfactants contained in the resin particle dispersion, wax particle dispersion, and colorant particle dispersion. As a result, the effects of salting out and ionic crosslinking make it easy to aggregate the resin particle, wax particle, and colorant particle.

[0194] The aggregation step is a step of forming aggregates of the same size as toner particles in an aqueous medium. The weight-average particle size of the aggregates produced in the aggregation step is preferably 3 μm to 10 μm. The weight-average particle size may be measured using a particle size distribution analyzer (Coulter Multisizer III, manufactured by Coulter) using the Coulter method.

[0195] <Fusion process> In the fusion step, an aggregation terminator may be added to the dispersion containing the aggregates obtained in the aggregation step under stirring in the same manner as in the aggregation step. Examples of the aggregation terminator include basic compounds that shift the equilibrium of the acidic polar group of the surfactant toward the dissociation side and stabilize the aggregated particles. Also included are chelating agents that partially dissociate the ionic bridge between the acidic polar group of the surfactant and the metal ion serving as the aggregating agent, thereby forming a coordinate bond with the metal ion and stabilizing the aggregated particles.

[0196] After the dispersion state of the aggregated particles in the dispersion liquid has become stable due to the action of the aggregation terminator, the aggregated particles may be fused by heating to a temperature equal to or higher than the glass transition temperature or melting point of the resin.

[0197] It is also possible to control the number average diameter of the domains by adjusting the temperature during fusion.The weight average particle diameter of the obtained toner particles is preferably about 3 μm to 10 μm.

[0198] <Filtration process, washing process, drying process, classification process> Thereafter, a filtration step for filtering out the solid content of the toner particles, and if necessary, a washing step, a drying step, and a classification step for adjusting the particle size are carried out to obtain toner particles.

[0199] The obtained toner particles may be used as they are. The obtained toner particles may be mixed with inorganic fine particles and, if necessary, other external additives to obtain a toner. The toner particles, inorganic fine particles, and other external additives may be mixed using a mixing device such as a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation).

[0200] The methods for measuring various physical properties of the toner and raw materials are described below.

[0201] <Cross-section observation of toner particles, measurement of domain matrix structure> First, a thin section is prepared as a reference sample for the abundance.

[0202] The first resin, a crystalline resin, was thoroughly dispersed in a visible light-curable resin (Aronix LCR Series D800), and then cured by irradiating it with short-wavelength light. The resulting cured product was cut using an ultramicrotome equipped with a diamond knife to prepare 250 nm thin flake samples. Similarly, thin flake samples were also prepared for the second resin, an amorphous resin.

[0203] In addition, the first resin and the second resin are mixed at ratios of 0 / 100, 30 / 70, 70 / 30, and 100 / 0 by mass, and melt-kneaded to prepare kneaded products. These are also dispersed in a visible light-curable resin, cured, and then cut out to prepare thin flake samples.

[0204] Next, the cross sections of the cut samples were observed using a transmission electron microscope (JEOL JEM-2800) (TEM-EDX), and elemental mapping was performed using EDX. The elements to be mapped were carbon, oxygen, and nitrogen. The mapping conditions are as follows: Accelerating voltage: 200 kV Electron beam irradiation size: 1.5 nm Live time limit: 600 seconds Dead time: 20~30sec Mapping resolution: 256 x 256

[0205] Based on the spectral intensity of each element (average over a 10 nm square area), (oxygen element intensity / carbon element intensity) and (nitrogen element intensity / carbon element intensity) are calculated, and a calibration curve is created for the mass ratio of the first resin to the second resin. If the monomer unit of the first resin contains a nitrogen atom, the subsequent quantification is performed using the calibration curve of (nitrogen element intensity / carbon element intensity). If a third resin is contained, a calibration curve can be created in the same way.

[0206] The toner samples are then analyzed.

[0207] After thoroughly dispersing the toner in a visible light curable resin (Aronix LCR Series D800), the resin is cured by irradiating it with short wavelength light. The cured product is then cut into 250 nm thin slice samples using an ultramicrotome equipped with a diamond knife.

[0208] Next, the cut-out thin sample is observed using a transmission electron microscope (JEOL JEM-2800 electron microscope) (TEM-EDX). A cross-sectional image of the toner particle is obtained, and element mapping is performed using EDX. The elements to be mapped are carbon, oxygen, and nitrogen.

[0209] The cross-section of the toner particle to be observed is selected as follows: First, the cross-sectional area of ​​the toner particle is calculated from the cross-sectional image of the toner particle, and then the diameter of a circle having the same area as that cross-sectional area (equivalent circle diameter) is calculated. Only cross-sectional images of toner particles where the absolute value of the difference between this equivalent circle diameter and the weight-average particle diameter of the toner (D4) is within 1.0 μm are to be analyzed.

[0210] For the matrix / domain confirmed by the cross-sectional image, (oxygen element intensity / carbon element intensity) and / or (nitrogen element intensity / carbon element intensity) are calculated based on the spectral intensity of each element (average of 10 nm square), and by comparing with the calibration curve, the proportion of the first resin in the matrix and the proportion (%) of the second resin in the domain are calculated. Note that, since the calibration curve is created on a mass basis, the calculated proportions are on a mass basis.

[0211] After identifying the domains confirmed in the observed image, the particle size of the domains present in the toner particle cross-sectional image is determined by binarization processing. The particle size is taken as the major axis of the domain. This is measured at 10 points per toner particle, and the same measurement is performed on 10 toner particles, and the arithmetic mean value of the obtained domain particle size is taken as the "number-average diameter of the domain (μm)."

[0212] On the other hand, the area of ​​the domains is calculated by adding up the areas of all domains composed of the second resin present in the cross-sectional image of one toner particle, and this total area is designated as S1. Similar measurements are performed on 100 toner particles present in a thin flake sample in which toner is dispersed, and the total area of ​​the domains (i.e., S1 + S2... + S100) is calculated, and the arithmetic mean value is designated as the "domain area." Note that if there are 100 or fewer measurable toner particle cross-sectional images in one flake sample, multiple thin flake samples are used and the measurement is continued until the number of toner particle cross-sectional images reaches 100.

[0213] Regarding the cross-sectional area of ​​the toner particle, the total cross-sectional areas of 100 toner particles obtained from the toner particle cross-sectional images used to calculate the domain area is calculated, and the arithmetic mean value is taken as the "cross-sectional area of ​​the toner particle."

[0214] Then, [domain area] / [cross-sectional area of ​​toner particle]×100 is defined as the ratio of the domain area to the cross-sectional area of ​​the toner particle (domain area ratio (%)).

[0215] The binarization process and calculation of the number-average diameter are carried out using Image Pro PLUS (manufactured by Nippon Roper Co., Ltd.).

[0216] <Method for separating each material from toner> The materials contained in the toner can be separated from the toner by utilizing the difference in solubility in the solvent of each material.

[0217] First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23°C, and the soluble matter (second resin) is separated from the insoluble matter (first resin, wax, colorant, inorganic fine particles, etc.).

[0218] Second separation: The insoluble matter obtained in the first separation (first resin, wax, colorant, inorganic fine particles, etc.) is dissolved in MEK at 100°C, and the soluble matter (first resin, wax) and the insoluble matter (colorant, inorganic fine particles, etc.) are separated.

[0219] Third separation: The soluble matter (first resin, wax) obtained in the second separation is dissolved in chloroform at 23°C, and the soluble matter (first resin) is separated from the insoluble matter (wax). (When a third resin is included) First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23°C, and the soluble matter (second resin, third resin) is separated from the insoluble matter (first resin, wax, colorant, inorganic fine particles, etc.). Second separation: The soluble fraction (second resin, third resin) obtained in the first separation is dissolved in toluene at 23°C, and the soluble fraction (third resin) is separated from the insoluble fraction (second resin). Third separation: The insoluble matter obtained in the first separation (first resin, wax, colorant, inorganic fine particles, etc.) is dissolved in MEK at 100°C, and the soluble matter (first resin, wax) is separated from the insoluble matter (colorant, inorganic fine particles, etc.). Fourth separation: The soluble fraction (first resin, wax) obtained in the third separation is dissolved in chloroform at 23°C, and the soluble fraction (first resin) is separated from the insoluble fraction (wax). (Measurement of the Contents of the First Resin and the Second Resin in the Binder Resin of the Toner) In each separation step, the masses of the soluble and insoluble components are measured to calculate the contents of the first resin and the second resin in the binder resin in the toner.

[0220] <Method for identifying and measuring the content ratio of monomer units constituting the first, second, and third resins> The identification and content ratio of the monomer units constituting the first, second and third resins are 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: 5.0 μs Frequency range: 10500Hz Accumulation count: 64 times Measurement temperature: 30℃ Sample: 50 mg of the measurement sample is placed in a sample tube with an inner diameter of 5 mm, deuterated chloroform (CDCl3) is added as a solvent, and the sample is dissolved in a thermostatic bath at 40°C.

[0221] obtained 1 From the H-NMR chart, a peak that is independent of the peaks that are assigned to the components of the first monomer unit is selected from the peaks that are assigned to the components of the other monomer units, and the integral value S1 of this peak is calculated.

[0222] Similarly, a peak that is independent of the peaks that are attributed to the constituent elements of the second monomer unit is selected from the peaks that are attributed to the constituent elements of the other monomer units, and the integral value S2 of this peak is calculated.

[0223] Furthermore, when a third monomer unit is present, a peak that is independent of the peaks attributable to the constituent elements of the third monomer unit is selected from the peaks attributable to the constituent elements of the other monomer units, and the integral value S3 of this peak is calculated.

[0224] The content ratio of the first monomer unit is determined using the above-mentioned integral values ​​S1, S2, and S3 as follows: where n1, n2, and n3 are the numbers of hydrogen atoms in the constituent elements to which the peak of interest for each site belongs.

[0225] Content of first monomer unit (mol%)= {(S1 / n1) / ((S1 / n1)+(S2 / n2)+(S3 / n3))}×100 Similarly, the content ratios of the second monomer unit and the third monomer unit are determined as follows. Content of second monomer unit (mol%)= {(S2 / n2) / ((S1 / n1)+(S2 / n2)+(S3 / n3))}×100 Content of third monomer unit (mol%)= {(S3 / n3) / ((S1 / n1)+(S2 / n2)+(S3 / n3))}×100

[0226] In the case where, for example, a polymerizable monomer in which a component other than a vinyl group does not contain a hydrogen atom is used in the first, second, and third resins, 13 using C-NMR, the measurement nucleus is 13 set to C, and measurement is performed in the single pulse mode, 1 and calculated in the same manner as H-NMR.

[0227] Based on the molecular weight of the monomer unit, it can be converted from mol% to mass%.

[0228] <Calculation method of SP value> The SP value is obtained as follows according to the calculation method proposed by Fedors.

[0229] For each polymerizable monomer, for the atoms or atomic groups in the molecular structure, the evaporation energy (Δei) (cal / mol) and the molar volume (Δvi) (cm 3 / mol) are obtained from the table described in "polym.Eng.Sci., 14(2), 147-154(1974)", and (4.184×ΣΔei / ΣΔvi) 0.5 is taken as the SP value (J / cm 3 ) 0.5 and used as such.

[0230] For example, SP 21 is calculated by the same calculation method as described above for the atoms or atomic groups in the molecular structure in the state where the double bond of the polymerizable monomer has been cleaved by polymerization. That is, SP 21 may be obtained by dividing the evaporation energy of the monomer unit by the molar volume.

[0231] The SP value of the entire resin is obtained by calculating the weighted average of the SP values of the respective polymerizable monomers based on the mass ratio.

[0232] <Method for measuring the weight average molecular weight (Mw) of resins, etc. using gel permeation chromatography (GPC)> The weight average molecular weight (Mw) of a tetrahydrofuran (THF) soluble component such as a resin is measured using gel permeation chromatography (GPC) as follows.

[0233] First, resins and other materials are dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (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 THF-soluble components is approximately 0.8% by mass. This sample solution is used for measurements under the following conditions. Apparatus: HLC8120 GPC (detector: RI) (Tosoh Corporation) Column: Shodex KF-801, 802, 803, 804, 805, 806, 807 (7 columns, manufactured by Showa Denko Co., Ltd.) Eluent: tetrahydrofuran (THF) Flow rate: 1.0mL / min Oven temperature: 40.0℃ Sample injection volume: 0.10 mL

[0234] To calculate the molecular weight of the sample, a molecular weight calibration curve prepared using standard polystyrene resins (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) was used.

[0235] <Measuring methods for melting points of toners, resins, etc., as well as endothermic peaks and endothermic amounts> The melting points of the toner and resin, as well as the endothermic peak and endothermic amount, are measured using a DSC Q1000 (manufactured by TA Instruments) under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 20℃ Measurement end 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.

[0236] Specifically, approximately 5 mg of sample is weighed out and placed in an aluminum pan for differential scanning calorimetry, with an empty silver pan used as a reference.

[0237] The peak temperature of the maximum endothermic peak in the first heating process is taken as the melting point.

[0238] The maximum endothermic peak is the peak with the largest endothermic amount when there are multiple peaks. Furthermore, the endothermic amount of the maximum endothermic peak is determined.

[0239] The assignment of each peak can be determined by performing DSC measurement on each material separated from the toner.

[0240] <Method for measuring acid value> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of sample. The acid value is measured in accordance with JIS-K0070-1992, specifically, by the following procedure.

[0241] (1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), and add ion-exchanged water to make 100 mL to obtain a phenolphthalein solution.

[0242] 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 and leave for 3 days, then filter to obtain potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined 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 to determine the amount of potassium hydroxide solution required for neutralization. The 0.1 mol / L hydrochloric acid used is prepared in accordance with JIS-K8001-1998.

[0243] (2) Operation (A) Main test 2.0 g of the crushed sample was accurately weighed into a 200 mL Erlenmeyer flask, and 100 mL of a toluene / ethanol (2:1) mixture was added and allowed to dissolve for 5 hours. Next, several drops of the phenolphthalein solution were added as an indicator, and the solution was titrated with the potassium hydroxide solution. The endpoint of the titration was determined when the indicator's light red color persisted for approximately 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).

[0244] (3) The obtained results are substituted into the following formula to calculate the acid value. A=[(CB)×f×5.61] / S where 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).

[0245] <Method for measuring resin softening point (Tm), toner T1 and T10> The softening point of the resin and the T1 and T10 of the toner are measured using a constant-load extrusion type capillary rheometer, "Flow Property Evaluation Device Flow Tester CFT-500D" (Shimadzu Corporation), according to the manual that comes with the device. With this device, a constant load is applied from above the measurement sample using a piston, while the measurement sample filled in a cylinder is heated and melted, and the molten measurement sample is extruded from the die at the bottom of the cylinder, allowing a flow curve to be obtained that shows the relationship between the piston's descent amount and temperature.

[0246] The softening point is the "melting temperature in the 1 / 2 method" described in the manual attached to the "Flow Tester CFT-500D, a flow property evaluation device." The melting temperature in the 1 / 2 method is calculated as follows.

[0247] First, calculate half the difference between the amount of piston descent when the outflow ends (end of outflow, Smax) and the amount of piston descent when the outflow starts (lowest point, Smin) (this is called X; X = (Smax - Smin) / 2). Then, the temperature on the flow curve when the amount of piston descent is the sum of X and Smin is the melting temperature in the 1 / 2 method.

[0248] The measurement sample is prepared by compressing approximately 1.0 g of resin at 25°C using a tablet press (e.g., NT-100H, manufactured by NPA Systems Co., Ltd.) at approximately 10 MPa for approximately 60 seconds to form a cylindrical sample with a diameter of approximately 10 mm.

[0249] The specific procedures for measurement are carried out according to the manual that comes with the device.

[0250] The measurement conditions for the CFT-500D are as follows: Test mode: Temperature rising method Starting temperature: 40℃ Achieved temperature: 200℃ Measurement interval: 1.0℃ Heating rate: 4.0℃ / min Piston cross-sectional area: 1.000cm 2 Test load (applied pressure): 10.0 kgf (0.9807 MPa) Preheat time: 300 seconds Die hole diameter: 1.0mm Die length: 1.0mm

[0251] The melt viscosity was also determined according to the manual attached to the apparatus.

[0252] In measurements under an applied pressure of 0.9807 MPa, the melt viscosity V1 was 1 x 10 5 The temperature at which the melt viscosity V10 reached 1×10 Pa·s was defined as T1. When the same measurement was performed under the above measurement conditions with a test load of 100.0 kgf (applied pressure of 9.807 MPa), the melt viscosity V10 reached 1×10 5 The temperature at which the value becomes Pa·s is defined as T10.

[0253] In the above analysis, the melt viscosity was calculated based on the plot of the melt viscosity in the temperature range above the temperature at which the sample started to flow (flow initiation temperature Tfb). 5 The temperatures at which the values ​​become Pa·s were calculated, and the values ​​were rounded off to one decimal place to determine T1 and T10 in the present invention.

[0254] <Method for measuring weight average particle size (D4) of toner (particles)> The weight average particle size (D4) of the toner (particles) is measured with an effective number of 25,000 measurement channels using a precision particle size distribution measuring device, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), which is equipped with a 100 μm aperture tube and uses the narrow hole electrical resistance method, and the accompanying dedicated software, "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.), for setting measurement conditions and analyzing measurement data. The weight average particle size (D4) of the toner (particles) is measured with an effective number of measurement channels of 25,000, and the measurement data is analyzed and calculated.

[0255] The aqueous electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass, such as "ISOTON II" (manufactured by Beckman Coulter).

[0256] Before performing measurements and analysis, the dedicated software is set up as follows.

[0257] In the "Change Standard Measurement Method (SOM)" screen of the dedicated software, set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value obtained using "Standard Particles 10.0 μm" (Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush aperture tube after measurement."

[0258] In the dedicated software's "Pulse to particle size conversion setting screen," set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less.

[0259] The specific measurement method is as follows. (1) Pour approximately 200 mL of electrolyte solution into a 250 mL round-bottom glass beaker made specifically for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "Aperture Tube Flush" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Approximately 30 mL of the electrolyte solution is placed in a 100 mL flat-bottom glass beaker, and approximately 0.3 mL of a diluted solution prepared by diluting "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.) three times by weight with ion-exchanged water is added as a dispersant. (3) A specified amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser, "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.), which has two built-in oscillators with an oscillation frequency of 50 kHz and a phase difference of 180 degrees and an electrical output of 120 W, and approximately 2 mL of Contaminon N is added to this water tank. (4) Set the beaker (2) in the beaker fixing hole of the ultrasonic disperser, operate the ultrasonic disperser, and adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized. (5) While ultrasonic waves are irradiating the electrolyte solution in the beaker from (4), approximately 10 mg of toner (particles) is added little by little to the electrolyte solution and dispersed. The ultrasonic dispersion process is then continued for another 60 seconds. During the ultrasonic dispersion process, the water temperature in the water tank is appropriately adjusted to be between 10°C and 40°C. (6) Using a pipette, add the electrolytic solution (5) containing dispersed toner particles to the round-bottom beaker (1) placed in the sample stand, and adjust the measurement concentration to approximately 5%. Then, measure the number of particles measured until it reaches 50,000. (7) The measurement data is analyzed using the dedicated software that comes with the device, and the weight-average particle size (D4) is calculated. Note that when the dedicated software is set to Graph / Volume %, the "Average diameter" on the Analysis / Volume Statistics (Arithmetic Mean) screen is the weight-average particle size (D4).

[0260] <Method for measuring the 50% particle diameter (D50) of resin particles, wax particles, and colorant particles by volume> The volume-based 50% particle size (D50) of each particle is measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) Specifically, the measurement is performed according to the following procedure.

[0261] To prevent the sample from agglomerating, a dispersion of the sample is placed in an aqueous solution containing Family Fresh (Kao Corporation) and stirred. After stirring, the sample is poured into the above-mentioned device and measured twice to obtain the average value.

[0262] The measurement conditions are as follows: measurement time is 30 seconds, the refractive index of the sample particles is 1.49, the dispersion medium is water, and the refractive index of the dispersion medium is 1.33.

[0263] The volume particle size distribution of the measurement sample is measured, and the particle size at which the cumulative volume from the small particle diameter side in the cumulative volume distribution is 50% is defined as the volume-based 50% particle size (D50) of each fine particle. [Example]

[0264] The present disclosure will be specifically explained by the following examples, which, however, are not intended to limit the present disclosure in any way. Examples 23 to 31 are reference examples. Unless otherwise specified, all "parts" in the following formulations are by mass.

[0265] <Production Example of First Resin 1 (Crystalline Resin 1)> Solvent: toluene 100.0 parts Monomer composition 100.0 parts (The monomer composition is a mixture of behenyl acrylate, acrylonitrile, acrylic acid, and styrene in the ratios shown below.) Behenyl acrylate 58.0 parts Acrylonitrile 10.0 parts Acrylic acid 2.0 parts Styrene 30.0 parts Polymerization initiator 0.5 parts [t-Butyl peroxypivalate (NOF Corporation: Perbutyl PV)] The above 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. The reaction vessel was heated to 70°C while stirring at 200 rpm, and a polymerization reaction was carried out for 12 hours, yielding a solution in which a polymer of the monomer composition was dissolved in toluene.

[0266] The solution was then cooled to 25°C, and poured into 1000 parts of methanol with stirring to precipitate the methanol-insoluble matter. The resulting methanol-insoluble matter was filtered, washed with methanol, and vacuum-dried at 40°C for 24 hours to obtain a first resin 1 (crystalline resin 1). The physical properties are shown in Tables 2 and 3.

[0267] <Production Examples of First Resins 2 to 12 (Crystalline Resins 2 to 12)> First resins 2 to 12 (crystalline resins 2 to 12) were obtained by carrying out the reaction in the same manner as in the production example of first resin 1 (crystalline resin 1), except that the monomers and the mass parts thereof were changed as shown in Table 1-1. The physical properties are shown in Tables 2 and 3.

[0268] [Table 1-1]

[0269] <Production Example of First Resin 13 (Crystalline Resin 13)> 1,6-Hexanediol: 39.7 parts (100.0 mol% of the total number of moles of polyhydric alcohol) Adipic acid: 29.4 parts (60.0 mol% based on the total number of moles of polycarboxylic acids) Dodecanedioic acid: 30.9 parts (40.0 mol% based on the total number of moles of polycarboxylic acids) Tin 2-ethylhexanoate: 0.5 parts The above materials were weighed and placed in a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. After the atmosphere in the flask was replaced with nitrogen gas, the temperature was gradually raised with stirring, and the mixture was allowed to react for 3 hours at 140°C with stirring.

[0270] Next, the pressure inside the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200°C.

[0271] Thereafter, the pressure inside the reaction vessel was reduced to 5 kPa or less, and the mixture was reacted at 200° C. for 3 hours, thereby obtaining a first resin 13 (crystalline resin 13).

[0272] <Production Examples of First Resins 14 to 17 (Crystalline Resins 14 to 17)> First resins 14 to 17 were obtained in the same manner as in the production example for first resin 13, except that the alcohol component and carboxylic acid component were changed to the monomers shown in Table 1-2. The physical properties are shown in Tables 2 and 3.

[0273] [Table 1-2]

[0274] [Table 2-1]

[0275] [Table 2-2]

[0276] [Table 3]

[0277] The abbreviations in Tables 1 and 2 are as follows: BEA: Behenyl acrylate STA: stearyl acrylate MYA: Myricyl acrylate UDA: Undecyl acrylate HA: hexadecyl acrylate AN: Acrylonitrile AA: acrylic acid St: styrene HO: Hexanediol AA: Adipic acid DDA: Dodecanedioic acid DDO: Dodecanediol EG: Ethylene glycol

[0278] <Production Example of Second Resin 1 (Amorphous Resin 1)> An autoclave was charged with 50.0 parts of xylene, and after replacing the atmosphere with nitrogen, the autoclave was heated to 185°C in a sealed state with stirring.

[0279] A mixed solution of 79.0 parts of styrene, 17.0 parts of n-butyl acrylate, 3.1 parts of divinylbenzene, and 0.9 parts of acrylic acid, as well as 1.0 part of di-tert-butyl peroxide and 20.0 parts of xylene, was continuously added dropwise to the autoclave for 3 hours while controlling the temperature inside the autoclave at 185°C, and polymerization was carried out.

[0280] The temperature was maintained for another hour to complete the polymerization, and the solvent was removed to obtain a second resin 1 (amorphous resin 1). The second resin 1 (amorphous resin 1) had a weight average molecular weight (Mw) of 60,000, a softening point (Tm) of 140°C, an acid value of 15.0 mgKOH / g, and a hydroxyl value of 0.0 mgKOH / g.

[0281] <Production Examples of Second Resins 2 to 10 (Amorphous Resins 2 to 10)> Second resins 2 to 10 (amorphous resins 2 to 10) were obtained by carrying out the reaction in the same manner as in the production example of second resin 1 (amorphous resin 1), except that the monomers and the parts by mass thereof were changed as shown in Table 4. The physical properties are shown in Table 5.

[0282] <Production Example of Second Resin 11 (Amorphous Resin 11)> 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. Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane: 73.4 parts (0.19 moles; 100.0 mole % based on the total number of moles of polyhydric alcohol) Terephthalic acid: 11.6 parts (0.07 moles; 82.0 mole % based on the total number of moles of polycarboxylic acids) Adipic acid: 6.8 parts (0.05 moles; 14.0 moles based on the total number of moles of polycarboxylic acids) Titanium tetrabutoxide: 2.0 parts Next, the atmosphere in the flask was replaced with nitrogen gas, and the temperature was gradually raised with stirring, and the mixture was stirred at a temperature of 200°C and reacted for 2 hours while distilling off the water produced.

[0283] Furthermore, the pressure inside the reaction vessel was reduced to 8.3 kPa and maintained at that level for 1 hour, after which the vessel was cooled to 180° C. and returned to atmospheric pressure (first reaction step). Trimellitic anhydride: 8.2 parts (0.04 moles; 6.0 mole % based on the total number of moles of polycarboxylic acids) tert-butylcatechol (polymerization inhibitor): 0.1 parts The above materials were then added, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 150°C. The reaction was stopped by lowering the temperature (second reaction step), thereby obtaining a second resin 11. The monomers and the mass parts are shown in Table 4, and the physical properties are shown in Table 5.

[0284] <Production Example of Second Resin 12> 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. Polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 70.0 parts (0.17 moles; 100.0 mole% based on the total number of moles of polyhydric alcohols) Terephthalic acid: 8.0 parts (0.05 moles; 28.0 mole% based on the total number of moles of polycarboxylic acids) Adipic acid: 8.0 parts (0.06 moles; 32.0 moles based on the total number of moles of polycarboxylic acids) Titanium tetrabutoxide: 2.5 parts The above materials were weighed and placed in a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet, and a thermocouple. The atmosphere in the flask was then replaced with nitrogen gas, and the temperature was gradually increased while stirring. The mixture was stirred at 230°C and reacted for 2 hours while distilling off the resulting water. The mixture was then reacted for 5 hours under a reduced pressure of 2.5 kPa, after which the temperature was lowered to 180°C. One part of tert-butylcatechol was added as a polymerization inhibitor, and 8 parts (0.01 mol; 40.0 mol% based on the total number of moles of polycarboxylic acid) of fumaric acid were added. The mixture was reacted for 8 hours under a reduced pressure of 0.5 to 2.5 kPa, and then removed from the vessel to obtain a second resin 12. The monomers and mass parts are shown in Table 4, and the physical properties are shown in Table 5.

[0285] [Table 4]

[0286] The abbreviations in Table 4 are as follows: St: styrene MMA: methyl methacrylate BA: n-butyl acrylate OA: n-octyl acrylate DVB: Divinylbenzene DDA: Dodecyl acrylate AA: acrylic acid BPO-PO: Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane BPO-EO: Polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane TPA: Terephthalic acid TMA: Trimellitic acid ADA: Adipic acid

[0287] [Table 5]

[0288] <Production Example of Block Copolymer 1> (Example of production of polymer for amorphous resin block) 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. Polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 36.0 parts (0.09 moles; 50.0 mol% based on the total number of moles of polyhydric alcohols) Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane: 33.8 parts (0.09 mole; 50.0 mol% based on the total number of moles of polyhydric alcohol) Terephthalic acid: 16.0 parts (0.10 moles; 55.4 mol% based on the total number of moles of polycarboxylic acids) n-Dodecenylsuccinic acid: 9.9 parts (0.01 mole; 21.4 mole % based on the total number of moles of polycarboxylic acids) Adipic acid: 4.3 parts (0.01 mole; 21.2 mole% based on the total number of moles of polycarboxylic acids) Dibutyltin oxide: 1.0 parts Nitrogen gas was introduced into the vessel, and the vessel was heated to an inert atmosphere. A condensation polymerization reaction was then carried out at 150°C for 12 hours, followed by gradual pressure reduction at 210°C to synthesize a polymer for amorphous resin blocks. The weight-average molecular weight of the resulting polymer was measured to be 41,000. The glass transition temperature (Tg) was 50°C, the softening point (Tm) was 100°C, and the acid value was 10 mgKOH / g.

[0289] (Example of production of polymer for crystalline resin block) Solvent: toluene 100.0 parts Stearyl acrylate 100.0 parts Polymerization initiator 0.5 parts [t-Butyl peroxypivalate (NOF Corporation: Perbutyl PV)] Chain transfer agent 3.0 parts [2-Cyano-2-propyl dodecyl trithiocarbonate] The above 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. The reaction vessel was heated to 70°C while stirring at 200 rpm, and a polymerization reaction was carried out for 12 hours, yielding a solution in which a polymer of the monomer composition was dissolved in toluene. The solution was then cooled to 25°C, and then poured into 1,000 parts of methanol while stirring, resulting in the precipitation of methanol-insoluble matter. The resulting methanol-insoluble matter was filtered, washed with methanol, and dried to obtain a polymer for crystalline resin blocks. The weight-average molecular weight of the resulting polymer was measured to be 50,000. The melting point was 63°C.

[0290] (Synthesis of block copolymers) 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. Amorphous resin block polymer 27 parts Crystalline resin block polymer 73 parts 150 parts toluene After stirring and dissolving under a nitrogen atmosphere, 2.7 parts of dicyclocarbodiimide (DCC) and 0.17 parts of dimethylaminopyridine (DMAP) were added and reacted at 50°C for 2 hours. The above solution was poured into 1000.0 parts of methanol with stirring to precipitate the methanol-insoluble matter. The resulting methanol-insoluble matter was filtered, washed with methanol, and dried to obtain block copolymer 1.

[0291] <Production example of hybrid resin 1> First Resin 7 60.0 parts Second Resin 12 40.0 parts The mixture was mixed and fed into a twin-screw kneader (Kurimoto Iron Works, S5KRC kneader) at 40 kg / h. At the same time, 4.0 parts of t-butylperoxyisopropyl monocarbonate was fed at 0.4 kg / h as a radical reaction initiator, and the mixture was kneaded and extruded at 100 rpm for 5 minutes at 160°C to carry out the reaction. Nitrogen was then passed through the vent to remove the organic solvent while mixing. The mixture was cooled to obtain Hybrid Resin 1.

[0292] <Production Example of Toner Particle 1> <Production Example of First Resin 1 Fine Particle Dispersion> Toluene (Wako Pure Chemical Industries, Ltd.) 300 parts 100 parts of First Resin The above materials were weighed, mixed and dissolved at 90°C.

[0293] Separately, 5.0 parts of sodium dodecylbenzenesulfonate and 10.0 parts of sodium laurate were added to 700 parts of ion-exchanged water and dissolved by heating at 90°C. The toluene solution and the aqueous solution were then mixed and stirred at 7000 rpm using an ultra-high-speed stirring device TK Robomix (manufactured by Primix). Furthermore, the mixture was emulsified at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo). The toluene was then removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion of first resin 1 microparticles at a concentration of 20% by mass (first resin 1 microparticle dispersion).

[0294] The volume-based 50% particle size (D50) of the fine particles of the first resin 1 was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.40 μm.

[0295] <Production Example of Second Resin 1 Fine Particle Dispersion> Tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) 300 parts 100 parts of second resin 0.5 parts anionic surfactant Neogen RK (Dai-ichi Kogyo Seiyaku) The above materials were weighed, mixed and dissolved.

[0296] Next, 20.0 parts of 1 mol / L ammonia water was added and stirred at 4000 rpm using an ultra-high speed stirrer TK Robomix (manufactured by Primix). 700 parts of ion-exchanged water were then added at a rate of 8 g / min to precipitate second resin 1 microparticles. After that, tetrahydrofuran was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion of second resin 1 microparticles with a concentration of 20% by mass (second resin 1 microparticle dispersion).

[0297] The volume-based 50% particle size (D50) of the second resin 1 fine particles was 0.14 μm.

[0298] <Production example of wax particle dispersion> 100 parts hydrocarbon wax (Fischer-Tropsch wax; DSC: maximum endothermic peak temperature 92°C) 5 parts anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) 395 parts ion-exchanged water The above materials were weighed and placed in a mixing vessel equipped with a stirrer, then heated to 90°C and circulated through a Clearmix W Motion (M Technique) for 60 minutes to perform a dispersion process. The dispersion process conditions were as follows: Rotor outer diameter: 3cm Clearance: 0.3mm Rotor speed: 19000 r / min Screen rotation speed: 19000 r / min After the dispersion process, the mixture was cooled to 40°C under cooling conditions of a rotor rotation speed of 1000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10°C / min, to obtain an aqueous dispersion (wax microparticle dispersion) with a concentration of 20% by mass of wax (hydrocarbon compound) microparticles.

[0299] The volume-based 50% particle size (D50) of the wax (hydrocarbon compound) microparticles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.15 μm.

[0300] <Production example of colorant particle dispersion> Colorant 1 50.0 parts (Cyan pigment manufactured by Dainichi Seika: Pigment Blue 15:3) 7.5 parts anionic surfactant Neogen RK (Dai-ichi Kogyo Seiyaku) 442.5 parts ion-exchanged water The above materials were weighed, mixed, dissolved, and dispersed for approximately 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain an aqueous dispersion (colorant particle dispersion) containing dispersed colorant particles with a concentration of 10% by mass.

[0301] The volume-based 50% particle size (D50) of the colorant fine particles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.20 μm.

[0302] 300 parts of First Resin 1 fine particle dispersion 200 parts of second resin 1 fine particle dispersion Colorant particle dispersion 65 parts Wax microparticle dispersion 50 parts 160 parts ion-exchanged water The above materials were placed in a round stainless steel flask and mixed. Subsequently, the mixture was dispersed for 10 minutes at 5,000 rpm using an Ultra-Turrax T50 homogenizer (manufactured by IKA). After adding a 1.0% aqueous nitric acid solution and adjusting the pH to 3.0, the mixture was heated to 58°C in a heated water bath using a stirring blade while adjusting the rotation speed appropriately to stir the mixture. The formed aggregated particles were appropriately confirmed using a Coulter Multisizer III. When aggregated particles with a weight-average particle size (D4) of approximately 6.00 μm were formed, the pH was adjusted to 9.0 using a 5% aqueous sodium hydroxide solution.

[0303] Thereafter, the mixture was heated to 75° C. while continuing to stir, and then maintained at 75° C. for 1 hour to fuse the aggregated particles.

[0304] Thereafter, the resin was cooled to 50°C and held at this temperature for 3 hours to promote crystallization of the resin.

[0305] Thereafter, the mixture was cooled to 25°C, filtered and separated into solid and liquid, and then washed with ion-exchanged water.

[0306] After the washing was completed, the particles were dried using a vacuum dryer to obtain toner particles 1 having a weight average particle size (D4) of about 6.0 μm.

[0307] <Production Example of Toner Particle 2> 160 parts of First Resin 1 / 40 of the second resin Hydrocarbon wax 1 10.0 parts 6.5 parts colorant 1 The above materials were mixed in a Henschel mixer (FM-75 model, manufactured by Nippon Coke & Engineering Co., Ltd.) at a rotation speed of 20 s -1 After mixing for 3 minutes, the mixture was kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at 120°C with a screw rotation speed of 250 rpm and a discharge temperature of 125°C. The resulting kneaded mixture was cooled and coarsely crushed to 1 mm or less using a hammer mill. The resulting coarsely crushed product was then finely crushed using a mechanical crusher (T-250, manufactured by Freund Turbo Corporation).

[0308] Further, classification was carried out using Faculty F-300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles 1 having a weight average particle size of about 6.0 μm. The operating conditions were a classification rotor rotation speed of 130 s -1 , distributed rotor rotation speed 120s -1 It was decided.

[0309] <Production Examples of Toner Particles 3 to 40> Toner particles 3 to 40 were obtained by carrying out the same production procedure as in the production example of toner particle 1, except that the resin, wax, and the amount added thereof used were changed to those shown in Table 6.

[0310] The hydrocarbon wax 2 is a petroleum wax with a melting point of 78°C.

[0311] [Table 6]

[0312] Example 1 (Production Example of Toner 1) 100 parts of toner particles Silica fine particles 1 0.5 parts (Hydrophobic silica particles with a number-average primary particle size of 15 nm) Silica fine particles 2 1.0 parts (Hydrophobic silica particles with a number-average primary particle size of 80 nm) The above materials were mixed in a Henschel mixer FM-10C (Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 50 s -1 The mixture was mixed for 10 minutes at a rotation time to obtain Toner 1. The physical properties are shown in Table 7. In the toner particles, the proportion of the crystalline resin 1 in the matrix was 86%, and the proportion of the amorphous resin 1 in the domain was 86%.

[0313] [Examples 2 to 31 (Production Examples of Toners 2 to 31), Comparative Examples 1 to 9 (Toners 32 to 40)] Toners 2 to 40 were obtained by carrying out the same production procedure as in the production example of Toner 1, except that the toner particles were changed to those shown in Table 7. The physical properties of Toners 2 to 40 thus obtained are shown in Table 7.

[0314] In each toner particle, the proportion of crystalline resin in the matrix was 82 to 94% and the proportion of amorphous resin in the domain was 82 to 94% by mass. Note that for Toner 33, no sea-island structure was observed, so the proportion of crystalline resin in the matrix and the proportion of amorphous resin in the domain could not be calculated.

[0315] Although a single resin was used in Toner 35, a sea-island structure was observed, which was probably due to microphase separation.

[0316] [Table 7-1]

[0317] [Table 7-2]

[0318] <Magnetic Carrier 1 Manufacturing Example> Number average particle size: 0.30 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) of magnetite 1 Number average particle size: 0.50 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) magnetite2 To 100 parts of each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and the mixture was mixed and stirred at high speed in a container at 100° C. or higher to treat each of the fine particles. Phenol: 10% by weight Formaldehyde solution: 6% by mass (40% by mass of formaldehyde, 10% by mass of methanol, 50% by mass of water) Magnetite treated with the above silane compound 1:58 mass% Magnetite treated with the above silane compound 2: 26 mass% 100 parts of the above material, 5 parts of a 28% by mass aqueous ammonia solution, and 20 parts of water were placed in a flask, and the mixture was heated to 85°C over 30 minutes and held at that temperature while stirring and mixing. A polymerization reaction was carried out for 3 hours, and the resulting phenolic resin was cured.

[0319] Thereafter, the cured phenolic resin was cooled to 30°C, and water was further added thereto. The supernatant was then removed, and the precipitate was washed with water and then air-dried.

[0320] This was then dried under reduced pressure (5 mmHg or less) at a temperature of 60° C. to obtain magnetic material dispersed spherical magnetic carrier 1. The volume-based 50% particle size (D50) of magnetic carrier 1 was 34.2 μm.

[0321] <Manufacturing example of two-component developer 1> To 92.0 parts of magnetic carrier 1, 8.0 parts of toner 1 were added and mixed in a V-type mixer (V-20, manufactured by Seishin Enterprises) to obtain two-component developer 1.

[0322] <Production examples of two-component developers 2 to 40> Two-component developers 2 to 40 were obtained by carrying out the same production procedure as in the production example of two-component developer 1, except that the toner was changed as shown in Table 8.

[0323] [Table 8]

[0324] The above two-component developers 1 to 40 were each used for evaluation.

[0325] The image forming device used was a modified Canon imagePRESS C810 digital commercial printing printer, with a two-component developer placed in the cyan developer unit. The device was modified so that the fixing temperature, process speed, developer carrier DC voltage VDC, electrostatic latent image carrier charging voltage VD, and laser power could be freely set.

[0326] In particular, evaluations were conducted at high process speeds to demonstrate superior performance in high-speed printing compared to conventional methods. Furthermore, image output evaluations were conducted by printing an FFh image (solid image) with the desired image ratio, adjusting VDC, VD, and laser power so that the toner coverage on the FFh image on paper was as desired, and then conducting the evaluations described below. FFh is the hexadecimal representation of 256 gradations, with 00h representing the first gradation (white background) of the 256 gradations and FFh representing the 256th gradation (solid area).

[0327] The evaluation was carried out based on the following evaluation methods, and the results are shown in Table 9.

[0328] [Low temperature fixability] ·Paper: GFC-081 (81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner amount on paper: 0.80mg / cm 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) Evaluation image: Place a 2cm x 5cm image in the center of the A4 paper. Test environment: Low temperature and low humidity: 15°C / 10%RH (hereinafter referred to as "L / L") Fixing temperature: 140℃ Process speed: 400mm / sec The above evaluation image was output, and the low-temperature fixability was evaluated. The value of the image density decrease rate was used as an evaluation index for the low-temperature fixability.

[0329] The image density reduction rate was measured using an X-Rite color reflection densitometer (500 series, manufactured by X-Rite Corporation) by first measuring the image density at the center. Next, the area where the image density was measured was subjected to pressure of 4.9 kPa (50 g / cm). 2 The fixed image is rubbed (five times back and forth) with Silbon paper under a load of 1000 kJ / cm2, and the image density is measured again.

[0330] The rate of decrease in image density before and after rubbing was calculated using the following formula: The rate of decrease in image density obtained was evaluated according to the following evaluation criteria. Image density reduction rate=(image density before friction−image density after friction) / (image density before friction)×100

[0331] (Evaluation criteria) AA: Image density reduction rate less than 1.0% A: Image density reduction rate: 1.0% or more and less than 3.0% B: Image density reduction rate: 3.0% or more and less than 5.0% C: Image density reduction rate: 5.0% or more and less than 8.0% D: Image density reduction rate 8.0% or more

[0332] [Hot offset resistance] ·Paper:CS-064(64.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner amount on paper: 0.08mg / cm 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) Evaluation image: A 2cm x 20cm image placed on the long edge of the A4 paper with a 2mm margin from the leading edge of the paper. Test environment: Normal temperature and low humidity: Temperature 23°C / Humidity 5% RH (hereinafter referred to as "N / L") Fixing temperature: 140°C, increasing in 5°C increments Process speed: 400mm / sec The above evaluation image was output, and the hot offset resistance was evaluated according to the following criteria at the highest fixing temperature at which no hot offset occurred.

[0333] (Evaluation criteria) A: 165℃ or higher B: 155℃ or higher and lower than 165℃ C: 145℃ or higher and lower than 155℃ D: Less than 145°C

[0334] [Wrapping resistance] ·Paper:CS-064(64.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner amount on paper: 0.80mg / cm 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) Evaluation image: A 2cm x 20cm image placed on the long edge of the A4 paper with a 2mm margin from the leading edge of the paper. Test environment: High temperature and humidity: 30°C / 80%RH (hereinafter referred to as "H / H"). Fixing temperature: 140°C, increasing in 5°C increments Process speed: 400mm / sec The above evaluation image was output, and the anti-winding property was evaluated according to the following criteria at the highest fixing temperature at which no winding occurred.

[0335] (Evaluation criteria) A: 165℃ or higher B: 155℃ or higher and lower than 165℃ C: 145℃ or higher and lower than 155℃ D: Less than 145°C

[0336] [Image evaluation after durability] The amount of toner on the paper in a FFh image (solid image) is 0.45 mg / cm 2 FFh is the 256 gradations expressed in hexadecimal, with 00h being the first gradation of the 256 gradations (white background) and FF being the 256th gradation of the 256 gradations (solid area).

[0337] First, an image output test of 5,000 sheets was conducted under normal temperature and humidity conditions (N / N; temperature 23°C, relative humidity 50%) with an image printing ratio of 2%. The low image printing ratio of 2% was intended to put stress on the toner inside the developing unit. During the continuous printing of 5,000 sheets, the sheets were passed under the same development and transfer conditions (without calibration) as the first sheet.

[0338] After that, an image output test of 3,000 sheets was carried out with an image ratio of 80%. The purpose of increasing the image printing ratio to 80% was to increase the contact opportunity between the drum and cleaning member and the toner. During the continuous paper feed of 3,000 sheets, the paper was fed under the same development and transfer conditions (without calibration) as the first sheet. The evaluation paper was GFC-081 (81.0 g / m 2 ) (sold by Canon Marketing Japan Inc.) was used.

[0339] Thereafter, one solid image was printed and evaluated according to the following evaluation criteria. A rank of C or higher was judged to demonstrate the effects of the present invention. The evaluation results are also shown in the table below.

[0340] (Evaluation criteria) AA: No visible image defects are observed A: There are some slight white spots and streaks that are visible to the naked eye. B: Minor white spots and streaks visible to the naked eye are visible throughout the image. C: Visually visible white spots and streaks are observed in some areas D: Visually visible white spots and streaks are visible throughout the image

[0341] [Chargeability (charge retention) under high temperature and humidity conditions] The toner on the electrostatic latent image bearing member was collected by suction using a metal cylindrical tube and a cylindrical filter, and the amount of triboelectric charge of the toner was calculated.

[0342] Specifically, the amount of triboelectric charge of the toner on the electrostatic latent image carrier was measured using a Faraday cage. A Faraday cage is a coaxial double cylinder with an insulated inner and outer cylinder. If a charged body with a charge Q is placed inside this inner cylinder, electrostatic induction will create the same effect as if a metal cylinder with a charge Q were present. This induced charge was measured using an electrometer (Kesley 6517A, manufactured by Kesley), and the amount of charge Q (mC) divided by the mass M (kg) of the toner in the inner cylinder (Q / M) was determined as the amount of triboelectric charge of the toner. Toner triboelectric charge (mC / kg) = Q / M

[0343] First, an evaluation image used for winding resistance was formed on an electrostatic latent image carrier, and before the image was transferred to the intermediate transfer member, the rotation of the electrostatic latent image carrier was stopped, and the toner on the electrostatic latent image carrier was sucked and collected using a metal cylindrical tube and a cylindrical filter, and the [initial Q / M] was measured.

[0344] Next, the developer was left in the evaluation machine in a high temperature and humidity (H / H) environment (32°C, 80% RH) for two weeks, and then the same operations as before leaving were performed to measure the charge amount Q / M (mC / kg) per unit mass on the electrostatic latent image carrier after leaving it. The Q / M per unit mass on the electrostatic latent image carrier before leaving it was defined as [initial Q / M], and the Q / M per unit mass on the electrostatic latent image carrier after leaving it was defined as [Q / M after leaving it], and the maintenance rate was calculated as ([Q / M after leaving it] / [initial Q / M] x 100) and evaluated according to the following criteria.

[0345] (Evaluation criteria) A: Retention rate is over 90% B: Retention rate is between 85% and 90% C: Retention rate is between 70% and 85% D: Retention rate is less than 70%

[0346] Table 9

Claims

1. A toner having toner particles containing a binder resin having a first resin and a second resin, the first resin is a crystalline vinyl resin; the first resin has a first monomer unit, a second monomer unit, and a third monomer unit; The first monomer unit is a unit represented by the following formula (1): 【Chemistry 1】 [In formula (1), R Z1 represents a hydrogen atom or a methyl group, and R represents an alkyl group having 18 to 36 carbon atoms.] The second monomer unit is a unit represented by the following formula (3): 【Chemistry 2】 [In formula (3), X represents a single bond, R 1 represents —C≡N or —COOH; R 2 represents a hydrogen atom or a methyl group. the third monomer unit is a styrene monomer unit, a methyl methacrylate unit, or a methyl acrylate unit; the second resin is an amorphous resin that is a vinyl-based resin, When a cross section of the toner particle is observed, the toner particle has a domain matrix structure composed of a matrix containing 80% by mass or more of the first resin and a domain containing 80% by mass or more of the second resin, In differential scanning calorimetry (DSC) of the toner, the amount of heat absorption ΔH (J / g) derived from the first resin is ΔH≧3 Fulfilling the relationship, In a flow tester measurement using the toner as a sample, the melt viscosity V1 at an applied pressure of 0.9807 MPa was 1×10 5 The temperature at which the viscosity becomes Pa s is T1 (°C), and the melt viscosity V10 at an applied pressure of 9.807 MPa is 1 x 10 5 When the temperature at which the viscosity becomes Pa s is T10 (°C), T1 and T10 are T10≧65 T1-T10≦10 A toner characterized by satisfying the relationship:

2. When the SP value of the first resin is SP1 and the SP value of the second resin is SP2, the SP1 and the SP2 satisfy the following conditions: SP2-SP1≦0.9 (J / cm 3 ) 0.5 2. The toner according to claim 1, which satisfies the relationship:

3. The SP1 and the SP2 are 0.0 (J / cm 3 ) 0.5 ≦SP2-SP1 ≦0.5 (J / cm 3 ) 0.5 The toner according to claim 2, which satisfies the relationship:

4. The toner according to claim 1, wherein the third monomer unit is a styrene monomer unit.

5. In a DSC measurement using the toner as a sample, the maximum endothermic peak temperature Tp (°C) attributable to the first resin is 45≦Tp≦70 3. The toner according to claim 1, wherein the following relationship is satisfied:

6. 6. The toner according to claim 1, wherein the first resin contains the first monomer unit in an amount of 20.0% by mass to 80.0% by mass.

7. 7. The toner according to claim 1, wherein the second resin contains 30.0% by mass to 95.0% by mass of a monomer unit represented by the following formula (5): 【Transformation 3】 [In formula (5), R 5 represents a hydrogen atom or a methyl group, and Ph represents an unsubstituted phenyl group or a substituted phenyl group.

8. When the content of the first resin in the toner particles is W1 and the content of the second resin is W2, W1 and W2 are 0.2≦W2 / W1≦4.0 8. The toner according to claim 1, wherein the following relationship is satisfied:

Images