JP7797189B2 - toner - Google Patents

Description

This disclosure relates to toners used in electrophotography, electrostatic recording, electrostatic printing, and toner jet printing.

In recent years, as electrophotographic full-color copiers have become more widespread, there has been an 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. Furthermore, 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 achieves both low-temperature fixability and heat-resistant storage stability by using an acrylate resin with crystalline side chains. This toner achieves both 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.

JP 2014-130243 A JP 2014-142632 A

This disclosure provides a toner that has excellent low-temperature fixing properties during high-speed printing, and combines hot offset resistance and wrap-around resistance, and is highly durable and less likely to produce image defects even over long periods of use.

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 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 formula (1) described below,
The second monomer unit is a unit represented by 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 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 endothermic heat 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, T1 (°C) is the temperature at which the melt viscosity V1 becomes 1×10 ⁵ Pa·s at an applied pressure of 0.9807 MPa, and T10 (°C) is the temperature at which the melt viscosity V10 becomes 1×10 ⁵ Pa·s at an applied pressure of 9.807 MPa.
T10≧65
T1-T10≦10
The present invention relates to a toner characterized by satisfying the following relationship:

This disclosure makes it possible to provide a toner that has excellent low-temperature fixing properties during high-speed printing, is resistant to both hot offset and wrapping, and is highly durable, making it less likely to produce poorly-formed images even after long-term use.

In this disclosure, unless otherwise specified, the expressions "XX or greater and YY or less" or "XX to YY" representing a numerical range refer to a numerical range including the endpoints, that is, the lower and upper limits.

(Meth)acrylic acid ester means acrylic acid ester and/or methacrylic acid ester.

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

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):

In the formula (Z), Z ₁ represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and Z ₂ represents an arbitrary substituent.

A crystalline resin is a resin that shows a clear endothermic peak in differential scanning calorimetry (DSC) measurements.

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 endothermic heat 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, T1 (°C) is the temperature at which the melt viscosity V1 becomes 1×10 ⁵ Pa·s at an applied pressure of 0.9807 MPa, and T10 (°C) is the temperature at which the melt viscosity V10 becomes 1×10 ⁵ Pa·s at an applied pressure of 9.807 MPa.
T10≧65
T1-T10≦10
The present invention is characterized in that the following relationship is satisfied.

The inventors have found that when a crystalline resin is used as the main component of the binder resin, adding an amorphous resin to impart viscoelasticity in the high-temperature range does not necessarily expand the fixing temperature range. In some cases, they have found that both low-temperature fixing ability and hot offset resistance may be reduced.

Furthermore, under conditions of use that place a heavy load on the toner, 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 that contain amorphous resins, and we have been investigating ways to resolve this issue.

As a result, the inventors discovered that for toners that use a crystalline resin as the main binder resin component and to which an amorphous resin is added, durability is improved if the temperature-viscosity curve of the toner measured with a flow tester changes little even with applied pressure. Based on this finding, they conducted extensive research and arrived at the present invention.

The inventors believe the mechanism by which the effects of the present invention are realized is as follows.

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 domains contain 80% or more of a second resin, which is an amorphous resin. This results in sharp melting properties due to the melting of the crystals when heated, resulting in excellent low-temperature fixability. Conversely, if the crystalline resin is present in the domains 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 benefits due to the melting of the crystalline resin are not obtained, and the benefits of this invention cannot be achieved. Note that 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.

Typically, the resin with a higher blend ratio forms the matrix, while the resin with a lower blend ratio forms the domain. However, because the above-mentioned crystalline resins have a low viscosity after melting, if the toner particle production process involves a step in which the temperature is above 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 low. Examples of such production processes include the kneading process in the melt-kneading method and the fusion process in the emulsion aggregation method.

On the other hand, from the standpoint of hot offset resistance and wrapping resistance, it is preferable for the viscosity of the molten toner to be high. The viscosity of the molten toner can be increased by incorporating an amorphous resin into the toner particles.

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

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 developer are subjected to extremely high stress. If the toner has temperature-viscosity characteristics that 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 adhere to the drum, causing image defects.

Conversely, if the temperature-viscosity characteristics are similar regardless of the amount of external pressure applied, this will not occur and it is thought that the material will be able to exhibit excellent durability.

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

There is no particular upper limit, but considering the heat absorption of typical crystalline resins, a value of 100 (J/g) or less is considered realistic.

In addition, in the present invention, when a toner sample is measured using a flow tester, T1 (°C) is the temperature at which the melt viscosity V1 becomes 1×10 ⁵ Pa·s at an applied pressure of 0.9807 MPa, and T10 is the temperature at which the melt viscosity V10 becomes 1×10 ⁵ Pa·s at an applied pressure of 9.807 MPa. In this case, T1 and T10 are
T10≧65
T1-T10≦10
The above relationship is satisfied.

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 printing periods. If T10 is less than 65, image defects are more likely to occur, resulting in reduced quality.

Furthermore, T1 is the viscosity characteristic at an applied pressure that simulates the fixing process, and the fact that T1 - T10 ≤ 10 indicates that the temperature-viscosity characteristics are not very dependent on the externally applied pressure. This makes it 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 decreases, and the low-temperature fixability effect of the present invention cannot be obtained.

There is no simple method for bringing T1-T10 within the range of the present invention; this can be achieved by controlling the various physical properties of the first and second resins. The inventors' research has shown that when the SP values of the first and second resins are similar, 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 the values within the range of the present invention.

The SP value is a number that represents the polarity of a resin, with a higher value indicating higher polarity. The calculation method will be explained later.

It is preferable for the relationship between the SP value SP1 of the first resin and the SP value SP2 of the second resin to satisfy the relationship SP2 - SP1 ≦ 0.9, as this makes it easier to achieve the T1 - T10 range of the present invention. Even more preferable is SP2 - SP1 ≦ 0.6.

As will be described later, the SP value can be controlled by changing the type and content ratio of the monomer units that make up the first resin and second resin.

In a DSC using the toner of 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, as this makes it easier to control the temperature within the T1-T10 range of the present invention.

Specific examples 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, and the amount of heat absorption ΔH derived from the crystalline resin, which is the first resin in the toner.

Furthermore, the content of the second resin, which is an amorphous resin, as well as the weight average molecular weight Mw, softening point Tm, glass transition temperature Tg, etc. can be controlled.

Another factor is controlling the dispersion state of the domains in the domain matrix structure of the cross section of the toner particle. It is preferable for the number-average diameter of the domains to be in the range of 0.10 μm to 2.00 μm, as this makes it easier to control it within the range of the present invention. It is even more preferable for it to be in the range of 0.10 μm to 1.00 μm.

Examples of methods for controlling the number-average diameter of the domains include controlling the polarity of the first resin and the second resin described above. Furthermore, during toner production, methods include controlling the screw rotation speed and kneading temperature during the kneading process if the melt kneading method is used, or the dispersion diameter of the resin in the resin dispersion if the emulsion aggregation method is used.

The binder resin according to the present invention contains a first resin, which is a crystalline resin.

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.

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

Furthermore, the first resin is preferably a vinyl resin, and further preferably has a first monomer unit represented by the following formula (1). Furthermore, it is preferable that the content of the first monomer unit in the first resin be 20.0% to 80.0% by mass, as this makes it easier to achieve both low-temperature fixability, hot offset resistance, and winding resistance.

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

R is preferably an alkyl group having 18 to 30 carbon atoms. Furthermore, the alkyl group preferably has a linear structure.

The first monomer unit has an alkyl group with 18 to 36 carbon atoms, represented by R, in its side chain, and the presence of this portion makes the first resin more likely to exhibit crystallinity.

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 improved low-temperature fixability.

If the content of the first monomer unit in the first resin is less than 20.0% by mass, crystallinity is unlikely to be achieved, and low-temperature fixability is likely to decrease. 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, a content of 90.0% by mass or less is preferred, and 80.0% by mass or less is even more preferred.

Furthermore, this first resin is preferred because it has a structure with crystallinity in the side chains and therefore has superior charge retention in high-temperature, high-humidity environments compared to crystalline polyester, a well-known conventional crystalline resin.

When the SP value (J/ ^cm3 ) ^0.5 of the first monomer unit is defined as _SP11 , _SP11 is preferably less than 20.00, more preferably 19.00 or less, and even more preferably 18.40 or less. The lower limit is not particularly limited, but is preferably 17.00 or more.

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.

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 [such as 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, and dotriacontyl (meth)acrylate] and (meth)acrylic acid esters having a branched alkyl group having 18 to 36 carbon atoms [such as 2-decyltetradecyl (meth)acrylate].

Of these, from the viewpoint of low-temperature fixability of the toner, at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 36 carbon atoms is preferred. 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 is preferred. Even more preferably, at least one selected from the group consisting of linear stearyl (meth)acrylate and behenyl (meth)acrylate is preferred.

The first monomer unit may be used alone or in combination of two or more types.

The first resin preferably has a second monomer unit that 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):

Furthermore, when the SP value (J/cm ³ ) ^0.5 of the second monomer unit is taken as SP ₂₁ , SP ₂₁ preferably satisfies the following formula (2), and more preferably satisfies the following formula (2)′.
21.00≦SP ₂₁ (2)
21.00≦SP ₂₁ ≦40.00 (2)'

[In formula (3), X represents a single bond or an alkylene group having 1 to 6 carbon atoms,
^R1 is -C≡N,
-C(=O)NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms),
hydroxy groups,
-COOR ¹¹ (R ¹¹ is 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( ^R13 ) ₂ (wherein each ^R13 independently represents a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms);
-COO( _CH2 ) _2NHCOOR14 ( ^R14 is an alkyl group ^having 1 to 4 carbon atoms),
Or,
-COO( _CH2 ) _2- NH-C(=O)-N( ^R15 ) _{2 (} wherein each ^R15 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms),
^R2 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.

When the first resin contains the second monomer unit, charge polarization occurs due to the highly polar functional group, which increases the viscosity when the toner melts, making it easier to improve winding resistance, which is preferable.

Examples of the second polymerizable monomer that forms the second monomer unit include the following. Furthermore, the second polymerizable monomer may be used alone or in combination of two or more types.

Monomers containing nitrile groups; for example, acrylonitrile, methacrylonitrile, etc.

Monomers containing a hydroxy group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.

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 using a known method.

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 using a known method.

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

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 preferable are monomers 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 prone to the aforementioned charge polarization, and increase the viscosity when the toner melts, which tends to improve winding resistance.

The second polymerizable monomer may be 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 octoate.

Vinyl esters are non-conjugated monomers that tend to maintain a moderate level of 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.

The second polymerizable monomer preferably has an ethylenically unsaturated bond, and more preferably has one ethylenically unsaturated bond.

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. The upper limit 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.

In addition, it is preferable to select the second monomer unit as a monomer unit that satisfies SP ₂₁ shown in the above formula (2).

The first resin may also contain a third monomer unit that is outside 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.

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

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.

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

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

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. The upper limit 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.

The first resin is preferably a vinyl polymer. Examples of vinyl polymers include polymers of monomers containing ethylenically unsaturated bonds. An ethylenically unsaturated bond refers to a carbon-carbon double bond capable of radical polymerization, and examples include vinyl groups, propenyl groups, acryloyl groups, and methacryloyl groups.

From the viewpoint of improving chargeability under high temperature and high humidity conditions, the acid value AVa of the first resin, which is a crystalline resin, is preferably 50.0 mgKOH/g or less, and more preferably 30.0 mgKOH/g or less. There is no particular lower limit, but it is preferably 0 mgKOH/g or more. From the viewpoint of improving charge rise, it is preferably 0.5 mgKOH/g or more, and more preferably 1.0 mgKOH/g or more.

From the viewpoint of improving chargeability under high temperature and high humidity conditions, the hydroxyl value OHVa of the first resin, which is a crystalline resin, is preferably 50.0 mgKOH/g or less, and more preferably 30.0 mgKOH/g or less. There is no particular lower limit, but it is preferably 0 mgKOH/g or more. From the viewpoint of improving charge rise, it is preferably 0.5 mgKOH/g or more, and more preferably 1.0 mgKOH/g or more.

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 15,000 or more and 200,000 or less, and more preferably 20,000 or more and 100,000 or less. 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 near room temperature and reduces the likelihood of image defects during long-term printing.

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

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.

From the viewpoint of making it easier to obtain 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. The upper limit is preferably 80% by mass or less, and even more preferably 70% by mass or less.

The binder resin according to the present invention contains a second resin, which is an amorphous resin.

Amorphous resins that are well known in the art can be used. Examples include the following:

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 resin.

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

Furthermore, when a resin containing the aforementioned first monomer unit 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, resulting in a strong interaction and making it easier to control the T1-T10 range of the present invention. 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.

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. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

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.

When a vinyl resin is used as the second resin, examples of suitable resins include polymers of polymerizable monomers containing ethylenically unsaturated bonds. An ethylenically unsaturated bond refers to a carbon-carbon double bond capable of undergoing radical polymerization, and examples include vinyl, propenyl, acryloyl, and methacryloyl groups.

Examples of polymerizable monomers include the following:

Styrenic monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-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 esters thereof, 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.

Furthermore, 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.

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

Examples of polymerizable monomers include the following:

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 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 alkenylsuccinate half ester, methyl fumarate 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, their acid anhydrides, and their monoesters.

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

Examples of cross-linkable polymerizable monomers include the following:

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; multifunctional crosslinking agents.

Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene.

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.

Vinyl resins include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-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-chloro acrylate. Preferably, the polymer is a polymer of a polymerizable monomer containing at least one selected from the group consisting of ethyl, 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.

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 approximately 0.5% to 5.0% by mass, as this facilitates control of the softening point, as described below.

Among the polymerizable monomers mentioned above, 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 domains containing the second resin, which is an amorphous resin.

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, and more preferably 90.0% by mass or less.

[In formula (5), ^R5 represents a hydrogen atom or a methyl group, and Ph represents a phenyl group. The phenyl group may have a substituent.]

The monomer unit represented by formula (5) contains a phenyl group, which improves charge retention, particularly in high-temperature, high-humidity environments.

Furthermore, when the first resin, in addition to the second resin, contains a monomer unit represented by the above formula (5), interactions due to π electrons are likely to occur between the phenyl groups contained in both the first resin and the second resin. As a result, it is easy to control the number-average diameter of the domains within the above numerical range. Furthermore, charge retention in high-temperature, high-humidity environments is further improved.

The vinyl resin may be a resin produced using a polymerization initiator. From the standpoint of efficiency, it is recommended that the polymerization initiator be used in an amount of 0.05 to 10 parts by mass per 100 parts by mass of polymerizable monomer.

Polymerization initiators include the following:

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), methylethyl Ketone peroxides such as ketone peroxide, acetylacetone 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, and decanoyl peroxide. 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 peroxyisobutyrate, 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.

The polyester resin can be suitably selected from those typically used in toner. Monomers used in such polyester resins include polyhydric alcohols (divalent, trivalent or higher alcohols), polycarboxylic acids (divalent, trivalent or higher carboxylic acids), their acid anhydrides, or their lower alkyl esters.

Examples of such polyhydric alcohols include:

Dihydric alcohols include the following bisphenol derivatives:

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.

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.

These polyhydric alcohols can be used alone or in combination.

Examples of polycarboxylic acids include the following:

Divalent carboxylic acids include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, 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 preferred.

Examples of trivalent or higher carboxylic acids, their anhydrides, and their lower alkyl esters include the following:

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, their acid anhydrides, or their lower alkyl esters.

Among these, 1,2,4-benzenetricarboxylic acid (trimellitic acid) or its derivatives such as acid anhydride are preferred because they are inexpensive and the reaction is easy to control.

These polycarboxylic acids can be used alone or in combination.

There are no particular restrictions on the method for producing polyester resin, 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 polyester resin. The polymerization temperature is not particularly limited, but is preferably in the range of 180°C to 290°C. Polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, and germanium dioxide can be used when polymerizing polyester resin.

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

The acid value AVi of the second resin, which is an amorphous resin, is preferably 50.0 mgKOH/g or less, and more preferably 30.0 mgKOH/g or less, from the viewpoint of improving chargeability under high temperature and high humidity conditions. There is no particular lower limit, but it is preferably 0 mgKOH/g or more. From the viewpoint of improving charge rise, it is preferably 0.5 mgKOH/g or more, and more preferably 1.0 mgKOH/g or more.

From the viewpoint of improving chargeability under high temperature and high humidity conditions, the hydroxyl value OHVi of the second resin, which is an amorphous resin, is preferably 50.0 mgKOH/g or less, and more preferably 30.0 mgKOH/g or less. There is no particular lower limit, but it is preferably 0 mgKOH/g or more. From the viewpoint of improving charge rise, it is preferably 0.5 mgKOH/g or more, and more preferably 1.0 mgKOH/g or more.

The weight-average molecular weight (Mw) of the tetrahydrofuran (THF)-soluble portion of the amorphous second resin, as 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. Having the weight-average molecular weight (Mw) of the THF-soluble portion within the above range makes it easier to maintain elasticity at around room temperature.

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

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. Satisfying this relationship is preferable because it makes it easier to control T10 - T1 within the range of the present invention.

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 making it easier to control T1-T10 within the range of the present invention, it is preferably 110°C or higher.

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

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.

The toner particles may contain a colorant. Examples of such colorants include the following:

Black colorants include carbon black; and black toned with a yellow colorant, a magenta colorant, and a cyan colorant. While a pigment may be used alone as a colorant, it is preferable to use a dye and a pigment together to improve the clarity of the colorant and to improve the image quality of full-color images.

Examples of pigments for magenta toner include:

C.I. 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; C.I. Pigment Violet 19; C.I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

Dyes for magenta toner include the following:

Oil-soluble dyes such as C.I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. Disperse Red 9; C.I. Solvent Violet 8, 13, 14, 21, 27; and C.I. Disperse Violet 1; basic dyes such as C.I. 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 C.I. Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

Examples of pigments for cyan toner include:

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

An example of a dye for cyan toner is C.I. Solvent Blue 70.

Pigments for yellow toner include the following:

C.I. 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; C.I. Bat Yellow 1, 3, 20.

An example of a dye for yellow toner is C.I. Solvent Yellow 162.

The colorant content is preferably 0.1 to 30.0 parts by weight per 100 parts by weight of binder resin.

The toner particles may contain wax. Examples of such waxes include:

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 fully deoxidized fatty acid esters such as deoxidized carnauba wax.

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 alcohols, 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 alcohols, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric 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 obtained by grafting aliphatic hydrocarbon waxes with 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 with hydroxy groups obtained by hydrogenating vegetable oils and fats.

The wax content is preferably 2.0 to 30.0 parts by mass per 100 parts by mass of binder resin.

Furthermore, if the toner contains wax, then, where Tp is the maximum endothermic peak temperature of the first resin and Tw is the maximum endothermic peak temperature of the wax, it is preferable that the relationship 10≦Tw-Tp≦45 is satisfied, and it is even more preferable that the relationship 20≦Tw-Tp≦40 is satisfied. Wax generally has a lower molecular weight than the first resin, and tends to have a lower viscosity after melting than the first resin. When heated, wax melts more slowly than crystalline resins, which is preferable because it prevents low-viscosity components from adhering to the image carrier, etc., and makes it easier to prevent image defects from occurring.

The toner particles may contain a charge control agent. Any known charge control agent can be used, but 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.

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 salts or sulfonate esters on the side chain, polymeric compounds having carboxylate salts or carboxylate esters on the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes. Charge control agents may be added internally or externally to the toner particles.

The content of the charge control agent is preferably 0.2 to 10.0 parts by weight per 100 parts by weight of the binder resin.

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.

As an external additive for improving fluidity, inorganic fine particles having a specific surface area of 50 m ² /g to 400 m ² /g are preferred, and for improving durability, inorganic fine particles having a specific surface area of 10 m ² /g to 50 m ² /g are preferred.

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

The content of the external additive is preferably 0.1 to 10.0 parts by weight per 100 parts by weight of toner particles. To mix the toner particles and the external additive, a known mixer such as a Henschel mixer may be used.

Toner can be used as a one-component developer, but to further improve dot reproducibility, it is preferable to mix it with a magnetic carrier and use it as a two-component developer, as this will produce stable images over a long period of time. In other words, it is preferable for the toner to be a two-component developer containing a toner and a magnetic carrier, and for the toner to be the toner described above.

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.

When toner is mixed with a magnetic carrier to be used as a two-component developer, the toner content in the two-component developer is preferably approximately 2% to 15% by weight, and more preferably approximately 4% to 13% by weight.

There are no particular restrictions on the method for producing toner particles, and conventionally known production methods such as suspension polymerization, emulsion aggregation, melt-kneading, and dissolution-suspension methods can be used.

The following explanation uses the melt-kneading method as an example, but is not limited to this.

First, in the raw material mixing process, the materials that make up 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, and charge control agent, are weighed out in predetermined amounts, blended, and mixed. Examples of mixing equipment include a double-con mixer, V-type mixer, drum mixer, super mixer, Henschel mixer, Nauta mixer, and Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.).

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-screw or twin-screw extruders are the mainstream due to their advantage of continuous production. Examples include the KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), the TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), the PCM kneader (manufactured by Ikegai Iron Works), the twin-screw extruder (manufactured by KCK Corporation), the Co-Kneader (manufactured by Buss Co., Ltd.), and the Kneedex (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.

The dispersion state of the first and second resins, the number-average diameter of the domains, etc. can be controlled by adjusting the kneading temperature during the melt-kneading process and the screw rotation speed.

The cooled resin composition is then pulverized to the desired particle size in a pulverization process. In this process, the resin composition is coarsely pulverized using a pulverizer such as a crusher, hammer mill, or feather mill, and then further pulverized 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 type pulverizer.

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

Next, we will explain how to produce toner particles using the emulsion aggregation method.

Toner particles are produced using the emulsion aggregation method through a series of steps: a dispersion process to create a fine particle dispersion made from the constituent materials of toner particles; an aggregation process to aggregate the fine particles made from 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 the toner particles with ion-exchange water or the like; and a drying process to remove moisture from the washed toner particles.

<Step of Preparing 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.

Specifically, the first resin and the second resin are dissolved in an organic solvent capable of dissolving them, and a surfactant or basic compound is added as needed. If the resin is a crystalline resin with a melting point, it can be heated above the melting point to dissolve it. Next, while stirring using a homogenizer or the like, an aqueous medium is slowly added to precipitate resin microparticles. The solvent is then removed by heating or reducing pressure to produce an aqueous dispersion of resin microparticles.

The organic solvent used to dissolve the resin can be any solvent that can dissolve the resin, but it is preferable to use an organic solvent that forms a homogeneous phase with water, such as toluene, in order to prevent the generation of coarse particles.

The surfactant is not particularly limited, but examples 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. Surfactants may be used alone or in combination of two or more.

Basic compounds include inorganic bases such as sodium hydroxide and potassium hydroxide; and organic bases such as ammonia, triethylamine, trimethylamine, dimethylaminoethanol, and diethylaminoethanol. Basic compounds may be used alone or in combination.

Furthermore, the volume-based 50% particle size (D50) of the resin microparticles in the aqueous dispersion of resin microparticles is preferably approximately 0.05 μm to 1.00 μm, and more preferably approximately 0.05 μm to 0.40 μm. By adjusting the volume-based 50% particle size (D50) within the above range, it becomes easier to obtain toner particles with a weight-average particle size of 3 μm to 10 μm, which is an appropriate size for toner particles.

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

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

The dispersion can be prepared by mixing the colorant, aqueous medium, and dispersant using a known mixer such as a stirrer, emulsifier, or disperser. Known dispersants such as surfactants and polymer dispersants can be used as the dispersant.

While both surfactants and polymeric dispersants can be removed in the cleaning process described below, surfactants are preferred from the standpoint of cleaning efficiency.

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.

Of these, nonionic surfactants or anionic surfactants are preferred. Nonionic surfactants and anionic surfactants may also be used in combination. These surfactants may be used alone, or two or more types may be used in combination. The concentration of the surfactant in the aqueous medium is preferably approximately 0.5% to 5% by mass.

There are no particular restrictions on the content of colorant particles in the colorant particle dispersion, but it is preferably 1% to 30% by mass relative to the total mass of the colorant particle dispersion.

In addition, from the perspective 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) on a volume basis of 0.50 μm or less. For the same reason, it is also preferable that the 90% particle size (D90) on a volume basis of 2 μm or less. The 50% particle size (D50) on a volume basis 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).

Known mixers such as stirrers, emulsifiers, and dispersers used to disperse 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.

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

A wax microparticle dispersion can be produced by adding wax to an aqueous medium containing a surfactant, heating the mixture to above the melting point of the wax, dispersing the wax into particles using a homogenizer with strong shearing capabilities (such as the Clearmix W Motion manufactured by M Technique) or a pressure-discharge disperser (such as the Gaulin Homogenizer manufactured by Gaulin), and then cooling the mixture to below the melting point.

The dispersed particle size of the wax microparticle dispersion in the aqueous wax dispersion is preferably such that the 50% particle size (D50) on a volume basis is approximately 0.03 μm to 1.0 μm, and more preferably 0.10 μm to 0.50 μm. It is also preferable that no coarse particles larger than 1 μm are present.

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

<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.

<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.

If necessary, a flocculant containing a divalent or higher metal ion may be used.

Flocculants containing divalent or higher metal ions have high flocculating power, making it possible to achieve the intended purpose by adding only a small amount. These flocculants can also ionically neutralize the ionic surfactants contained in resin particle dispersions, wax particle dispersions, and colorant particle dispersions. As a result, the effects of salting out and ionic crosslinking make it easier to aggregate resin particles, wax particles, and colorant particles.

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

<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.

After the dispersion state of the aggregated particles in the dispersion liquid has stabilized due to the action of the aggregation terminator, the resin can be heated to a temperature above its glass transition temperature or melting point to fuse the aggregated particles.

The number-average diameter of the domains can also be controlled by adjusting the temperature during fusion. The weight-average particle size of the resulting toner particles is preferably approximately 3 μm to 10 μm.

<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 particle size may be carried out to obtain toner particles.

The resulting toner particles may be used as is. Alternatively, the resulting toner particles may be mixed with inorganic fine particles and, if necessary, other external additives to obtain a toner. Mixing of the toner particles with the inorganic fine particles and other external additives can be performed using a mixing device such as a double con mixer, V-type mixer, drum mixer, super mixer, Henschel mixer, Nauta mixer, Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), or Nobilta (manufactured by Hosokawa Micron Corporation).

The methods for measuring various physical properties of toner and raw materials are explained below.

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

After thoroughly dispersing the first resin, which is a crystalline resin, in a visible light-curable resin (Aronix LCR Series D800), it is cured by irradiating it with short-wavelength light. The resulting cured product is cut using an ultramicrotome equipped with a diamond knife to prepare 250 nm thin flake samples. Thin flake samples are also prepared in the same manner for the second resin, which is an amorphous resin.

The first resin and the second resin were also mixed by mass in ratios of 0/100, 30/70, 70/30, and 100/0 to produce melt-kneaded mixtures. These were then similarly dispersed in a visible light-curable resin, cured, and then cut out to produce thin flake samples.

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

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 nitrogen atoms, the subsequent quantification is performed using the calibration curve of (nitrogen element intensity/carbon element intensity). If a third resin is included, a calibration curve can be created in the same manner.

Next, the toner sample is analyzed.

After thoroughly dispersing the toner in a visible light-curing resin (Aronix LCR Series D800), it is cured by irradiating it with short-wavelength light. The resulting cured product is cut using an ultramicrotome equipped with a diamond knife to prepare 250 nm thin slice samples.

Next, the cut-out thin sample is observed using a transmission electron microscope (JEOL JEM-2800 electron microscope) (TEM-EDX). Cross-sectional images of the toner particles are obtained, and elemental mapping is performed using EDX. The elements mapped are carbon, oxygen, and nitrogen.

The cross-section of the toner particle to be observed is selected as follows: First, the cross-sectional area of the toner particle is determined from the cross-sectional image of the toner particle, and then the diameter of a circle having an area equal to that cross-sectional area (equivalent circle diameter) is determined. 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 considered for analysis.

For the matrix/domains confirmed in the cross-sectional image, the (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 a 10 nm square), and by comparing this 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.

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. The arithmetic mean value of the obtained domain particle sizes is taken as the "number-average diameter of the domain (μm)."

On the other hand, the area of the domains is determined 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 flake-like sample in which toner has been 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-like sample, multiple flake-like samples are used and the process is continued until the number of toner particle cross-sectional images reaches 100.

To determine the cross-sectional area of a toner particle, the total cross-sectional area of 100 toner particles obtained from the toner particle cross-sectional images used to determine the domain area is calculated, and the arithmetic mean value is taken as the "cross-sectional area of a toner particle."

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

Image Pro PLUS (manufactured by Nippon Roper Co., Ltd.) was used for binarization processing and calculation of number-average diameter.

<Method for separating materials 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.

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

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) is separated from the insoluble matter (colorant, inorganic fine particles, etc.).

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) and the insoluble matter (first resin, wax, colorant, inorganic fine particles, etc.) are separated.
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 (first resin, wax, colorant, inorganic fine particles, etc.) obtained in the first separation 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.
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 Contents of First Resin and Second Resin in Binder Resin of 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.

<Method for identifying and measuring the content ratio of monomer units constituting the first, second, and third resins>
The monomer units constituting the first, second and third resins are identified and their content ratios are measured by ¹ H-NMR under the following conditions.
Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400 MHz
Pulse condition: 5.0 μs
Frequency range: 10,500 Hz
Number of measurements: 64 Measurement temperature: 30°C
Sample: 50 mg of a measurement sample is placed in a sample tube with an inner diameter of 5 mm, deuterated chloroform (CDCl ₃ ) is added as a solvent, and the sample is dissolved in a thermostatic bath at 40°C.

From the obtained ^1H -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.

Similarly, a peak independent of the peaks attributable to the constituent elements of the second monomer unit is selected from the peaks attributable to the constituent elements of the other monomer units, and the integral value _S2 of this peak is calculated.

Furthermore, when a third monomer unit is present, a peak that is independent of the peaks that are assigned to the constituent elements of the third monomer unit is selected from the peaks that are assigned to the constituent elements of the other monomer units, and the integral value _S3 of this peak is calculated.

The content ratio of the first monomer unit is determined using the above 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 peaks of interest for each site belong.

Content of first monomer unit (mol %)=
{(S ₁ /n ₁ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ ))}×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%)=
{(S ₂ /n ₂ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ ))}×100
Content of third monomer unit (mol%)=
{(S ₃ /n ₃ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ ))}×100

In addition, in the first, second and third resins, for example, when a polymerizable monomer that does not contain hydrogen atoms in components other than vinyl groups is used, ^13C -NMR is used, the measurement nucleus is set to ^13C , the measurement is performed in single pulse mode, and calculation is performed in the same manner as ^1H -NMR.

Mole % can be converted to mass % based on the molecular weight of the monomer unit.

<Method of calculating SP value>
The SP value is calculated in the following manner according to the calculation method proposed by Fedors.

For each polymerizable monomer, the evaporation energy (Δei) (cal/mol) and molar volume (Δvi) (cm 3 /mol) for each atom or atomic group in the molecular structure are determined from the table in "Polym. Eng. Sci., 14( ² ), 147-154 (1974)", and (4.184 × ΣΔei/ΣΔvi) ^0.5 is defined as the SP value (J/cm ³ ) ^0.5 .

For example, _SP21 can be calculated by the same method as above for an atom or atomic group in the molecular structure of a polymerizable monomer in which the double bond is cleaved by polymerization. That is, _SP21 can be calculated by dividing the vaporization energy of the monomer unit by the molar volume.

The SP value of the entire resin is calculated by taking the arithmetic average of the SP values of each polymerizable monomer based on their mass ratios.

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

First, a resin or the like is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in THF is approximately 0.8% by mass. This sample solution is used for measurements under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: 7 columns of Shodex KF-801, 802, 803, 804, 805, 806, and 807 (manufactured by Showa Denko K.K.)
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0mL/min
Oven temperature: 40.0°C
Sample injection volume: 0.10 mL

When calculating the molecular weight of the sample, a molecular weight calibration curve created 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) is used.

<Method for measuring melting points, endothermic peaks and endothermic amounts of toner, resin, etc.>
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.
Temperature increase rate: 10°C/min
Measurement start temperature: 20℃
Measurement end temperature: 180°C
The melting points of indium and zinc are used to correct the temperature of the detector, and the heat of fusion of indium is used to correct the amount of heat.

Specifically, approximately 5 mg of sample is precisely weighed and placed in an aluminum pan, and differential scanning calorimetry is performed. An empty silver pan is used as a reference.

The peak temperature of the maximum endothermic peak during the first heating process is taken as the melting point.

The maximum endothermic peak is the peak with the greatest amount of endothermic heat when there are multiple peaks. Furthermore, the amount of endothermic heat of the maximum endothermic peak is calculated.

The assignment of each peak can be determined by performing DSC measurements on each material separated from the toner described above.

<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.

(1) Preparation of Reagents 1.0 g of phenolphthalein was dissolved in 90 mL of ethyl alcohol (95% by volume), and ion-exchanged water was added to make the total volume 100 mL to obtain a phenolphthalein solution.

Dissolve 7 g of special-grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Place in an alkali-resistant container to avoid contact with carbon dioxide and other gases, 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. Use 0.1 mol/L hydrochloric acid prepared in accordance with JIS-K8001-1998.

(2) Procedure (A) Main Test: 2.0 g of the crushed sample is accurately weighed into a 200 mL Erlenmeyer flask, and 100 mL of a toluene/ethanol (2:1) mixed solution is added and dissolved over 5 hours. Next, a few drops of the phenolphthalein solution are added as an indicator, and the sample is titrated with the potassium hydroxide solution. The endpoint of the titration is when the light red color of the indicator persists for approximately 30 seconds.
(B) Blank Test: A titration is carried out in the same manner as above, except that no sample is used (i.e., only a mixed solution of toluene/ethanol (2:1) is used).

(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 (mg KOH/g), B is the amount (mL) of potassium hydroxide solution added for the blank test, C is the amount (mL) of potassium hydroxide solution added for the main test, f is the factor of the potassium hydroxide solution, and S is the mass (g) of the sample.

<Method for measuring softening point (Tm) of resin, T1 and T10 of toner>
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" (manufactured by Shimadzu Corporation) in accordance with 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 a die at the bottom of the cylinder, and a flow curve can be obtained that shows the relationship between the piston's descending distance and temperature.

The softening point is the "melting temperature using the 1/2 method" listed in the manual included with the "Flow Property Evaluation Device Flow Tester CFT-500D." The melting temperature using the 1/2 method is calculated as follows:

First, find half the difference between the amount of piston descent when outflow ends (end of outflow, Smax) and the amount of piston descent when outflow begins (minimum point, Smin) (this is 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 according to the 1/2 method.

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

Specific measurement procedures should be performed according to the manual provided with the device.

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

The melt viscosity was also determined according to the manual provided with the device.

In the measurement under an applied pressure of 0.9807 MPa, the temperature at which the melt viscosity V1 reached 1× ¹⁰ Pa·s was defined as T1. In addition, when the same measurement was performed under the above measurement conditions but with a test load of 100.0 kgf (applied pressure of 9.807 MPa), the temperature at which the melt viscosity V10 reached 1× ¹⁰ Pa·s was defined as T10.

In the above analysis, the temperature at which the melt viscosity becomes 1 x ¹⁰⁵ Pa·s was calculated based on a plot of the melt viscosity in the temperature range above the temperature at which the measurement sample started to flow (flow initiation temperature Tfb), and the calculated value was rounded to one decimal place to determine T1 and T10 in the present invention.

<Method for measuring weight average particle size (D4) of toner (particles)>
The weight average particle diameter (D4) of the toner (particles) is measured with an effective number of measurement channels of 25,000 using a precision particle size distribution measuring device using a capillary electrical resistance method, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), equipped with a 100 μm aperture tube, 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, and the weight average particle diameter (D4) is calculated by analyzing the measurement data.

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

Before performing measurements and analysis, configure the dedicated software as follows:

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

In the dedicated software's "Pulse to particle size conversion setting screen," set the bin spacing 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.

The specific measurement method is as follows.
(1) Pour approximately 200 mL of the 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 aqueous electrolyte solution is placed in a 100 mL flat-bottom glass beaker, and approximately 0.3 mL of a dilution obtained by diluting "Contaminon N" (a 10% by mass aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) three times by mass with ion-exchanged water is added thereto as a dispersant.
(3) A predetermined amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) that has two built-in oscillators with an oscillation frequency of 50 kHz and an electrical output of 120 W, with a phase difference of 180 degrees, and approximately 2 mL of Contaminon N is added to this water tank.
(4) Set the beaker from (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 the electrolyte solution in the beaker from (4) is being irradiated with ultrasonic waves, 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, the water temperature in the water tank is appropriately adjusted to be between 10°C and 40°C.
(6) Using a pipette, the electrolytic solution prepared in (5) above, in which the toner particles have been dispersed, is dropped into the round-bottom beaker prepared in (1) above, which is placed in the sample stand, and the measurement concentration is adjusted to about 5%. Then, measurements are continued until the number of particles measured reaches 50,000.
(7) The measurement data is analyzed using the dedicated software provided with the device to calculate the weight-average particle size (D4). 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).

<Method for measuring the 50% particle diameter (D50) based on volume of resin particles, wax particles, and colorant particles>
The volume-based 50% particle size (D50) of each fine 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.

To prevent aggregation of the measurement sample, a dispersion of the measurement sample is poured into an aqueous solution containing Family Fresh (manufactured by Kao Corporation) and stirred. After stirring, the measurement sample is poured into the above device and measured twice to determine the average value.

The measurement conditions are: measurement time 30 seconds, sample particle refractive index 1.49, dispersion medium water, dispersion medium refractive index 1.33.

Measure the volumetric particle size distribution of the measurement sample, and from the measurement results, the particle diameter at which the cumulative volume from the small particle diameter side in the cumulative volume distribution is 50% is taken as the volume-based 50% particle diameter (D50) of each microparticle.

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

<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 (Perbutyl PV manufactured by NOF Corporation)]
The above materials were charged into 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, to obtain a solution in which a polymer of the monomer composition was dissolved in toluene.

Then, the temperature of the solution was lowered to 25°C, and the solution was poured into 1,000.0 parts of methanol with stirring to precipitate the methanol-insoluble matter. The resulting methanol-insoluble matter was filtered off, washed with methanol, and vacuum-dried at 40°C for 24 hours to obtain First Resin 1 (Crystalline Resin 1). The physical properties are shown in Tables 2 and 3.

<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.

<Production Example of First Resin 13 (Crystalline Resin 13)>
1,6-hexanediol: 39.7 parts (100.0 mol% based on the total number of moles of polyhydric alcohols)
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)
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.

The pressure inside the reactor was then reduced to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200°C.

Then, the pressure inside the reaction vessel was reduced to 5 kPa or less, and the mixture was reacted at 200°C for 3 hours to obtain a first resin 13 (crystalline resin 13).

<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 Tables 1 and 2. Their physical properties are shown in Tables 2 and 3.

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: Styrene acrylate HO: Hexanediol AA: Adipic acid DDA: Dodecanedioic acid DDO: Dodecanediol EG: Ethylene glycol

<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.

A mixed solution of 79.0 parts of styrene, 17.0 parts of n-butyl acrylate, 3.1 parts of divinylbenzene, 0.9 parts of acrylic acid, 1.0 part of di-tert-butyl peroxide, and 20.0 parts of xylene was continuously added dropwise to the autoclave over a period of 3 hours while controlling the temperature inside the autoclave at 185°C, and polymerization was allowed to occur.

The mixture was then maintained at the same temperature for another hour to complete the polymerization, and the solvent was removed to obtain Second Resin 1 (Amorphous Resin 1). 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.

<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 for Second Resin 1 (Amorphous Resin 1), except that the monomers and the parts by mass thereof were changed as shown in Table 4. Their physical properties are shown in Table 5.

<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 mol% 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 mole % 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.

Furthermore, the pressure inside the reaction vessel was reduced to 8.3 kPa and maintained at that level for 1 hour, after which the reaction 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 part 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, and the reaction was stopped by lowering the temperature (second reaction step), thereby obtaining a second resin 11. The monomers and the parts by mass are shown in Table 4, and the physical properties are shown in Table 5.

<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 mol% based on the total number of moles of polyhydric alcohol)
Terephthalic acid: 8.0 parts (0.05 moles; 28.0 mol% based on the total number of moles of polycarboxylic acids)
Adipic acid: 8.0 parts (0.06 moles; 32.0 mole% 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 tube, and a thermocouple. The flask was then purged with nitrogen gas, and the temperature was gradually increased while stirring. The mixture was stirred at 230°C and allowed to react for 2 hours while distilling off the resulting water. The mixture was then allowed to react 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% relative to the total number of moles of polycarboxylic acid) of fumaric acid were added. The mixture was allowed to react for 8 hours under a reduced pressure of 0.5 to 2.5 kPa, after which the mixture was removed 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.

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

<Production Example of Block Copolymer 1>
(Production Example 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 alcohol)
Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane: 33.8 parts (0.09 moles; 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-Dodecenyl succinic acid: 9.9 parts (0.01 mole; 21.4 mol% based on the total number of moles of polycarboxylic acids)
Adipic acid: 4.3 parts (0.01 mole; 21.2 mol% based on the total number of moles of polycarboxylic acids)
Dibutyltin oxide: 1.0 part Nitrogen gas was introduced into the vessel, and the vessel was heated while maintaining an inert atmosphere. A condensation polymerization reaction was then carried out at 150°C for 12 hours, and the pressure was then gradually reduced to 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.

(Production Example of Polymer for Crystalline Resin Block)
Solvent: toluene 100.0 parts, stearyl acrylate 100.0 parts, polymerization initiator 0.5 parts [t-butyl peroxypivalate (Perbutyl PV manufactured by NOF Corporation)]
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 1,000.0 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.

(Synthesis of Block Copolymer)
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.
27 parts of amorphous resin block polymer, 73 parts of crystalline resin block polymer, 150 parts of 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 a methanol-insoluble fraction. The resulting methanol-insoluble fraction was filtered, washed with methanol, and dried to obtain block copolymer 1.

<Production Example of Hybrid Resin 1>
60.0 parts of the first resin 7 and 40.0 parts of the second resin 12 were mixed and fed to a twin-screw kneader (Kurimoto Iron Works, S5KRC kneader) at 40 kg/h. At the same time, 4.0 parts of t-butylperoxyisopropyl monocarbonate as a radical reaction initiator was fed at 0.4 kg/h. The mixture was kneaded and extruded at 100 rpm at 160 ° C for 5 minutes to carry out the reaction. Furthermore, nitrogen was flowed from the vent to remove the organic solvent while mixing. The mixture obtained by mixing was cooled to obtain Hybrid Resin 1.

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

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 this aqueous solution were then mixed and stirred at 7,000 rpm using an ultra-high-speed stirring device, T.K. Robomix (manufactured by Primix). The mixture was then 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 with a concentration of 20% by mass (first resin 1 microparticle dispersion).

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

<Production Example of Second Resin 1 Fine Particle Dispersion>
Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 300 parts Second resin 1 100 parts Anionic surfactant NEOGEN RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 0.5 parts The above materials were weighed, mixed, and dissolved.

Next, 20.0 parts of 1 mol/L ammonia water was added and stirred at 4000 rpm using an ultra-high speed stirrer T.K. Robomix (manufactured by Primix). Furthermore, 700 parts of ion-exchanged water was 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).

The volume-based 50% particle size (D50) of the second resin 1 microparticles was 0.14 μm.

<Production Example of Wax Microparticle Dispersion>
Hydrocarbon wax 1 100 parts (Fischer-Tropsch wax; DSC: peak temperature of maximum endothermic peak 92°C)
The above materials were weighed and placed in a mixing vessel equipped with a stirrer, heated to 90°C, and circulated through a Clearmix W Motion (M Technique) for 60 minutes to carry out a dispersion treatment. The dispersion treatment conditions were as follows:
Rotor outer diameter: 3cm
・Clearance: 0.3 mm
Rotor rotation speed: 19,000 r/min
Screen rotation speed: 19,000 r/min
After the dispersion treatment, the mixture was cooled to 40°C under cooling treatment 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, thereby obtaining an aqueous dispersion (wax microparticle dispersion) with a concentration of wax (hydrocarbon compound) microparticles of 20% by mass.

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), and was found to be 0.15 μm.

<Production Example of Colorant Particle Dispersion>
Colorant 1 50.0 parts (cyan pigment manufactured by Dainichiseika Chemicals: Pigment Blue 15:3)
Anionic surfactant NEOGEN RK (manufactured by Dai-ichi Kogyo Seiyaku) 7.5 parts Ion-exchanged water 442.5 parts The above materials were weighed, mixed, dissolved, and dispersed for about 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain an aqueous dispersion of colorant particles having a concentration of 10% by mass (colorant particle dispersion) in which the colorant was dispersed.

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

The following materials were added to a round stainless steel flask and mixed: 300 parts of first resin 1 microparticle dispersion, 200 parts of second resin 1 microparticle dispersion, 65 parts of colorant microparticle dispersion, 50 parts of wax microparticle dispersion, and 160 parts of ion-exchanged water. The mixture was then dispersed at 5,000 rpm for 10 minutes 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.

The mixture was then heated to 75°C while continuing to stir. It was then held at 75°C for 1 hour to fuse the aggregated particles.

The resin was then cooled to 50°C and held there for 3 hours to promote crystallization.

Then, it was cooled to 25°C, filtered and separated into solid and liquid, and then washed with ion-exchanged water.

After washing, the particles were dried using a vacuum dryer to obtain toner particles 1 with a weight average particle size (D4) of approximately 6.0 μm.

<Production Example of Toner Particles 2>
First Resin 1 60 parts Second Resin 1 40 parts Hydrocarbon Wax 1 10.0 parts Colorant 1 6.5 parts The above materials were mixed using a Henschel mixer (FM-75, manufactured by Nippon Coke & Engineering Co., Ltd.) at a rotation speed of 20 s ^-1 and a rotation time of 3 min, and then kneaded at a screw rotation speed of 250 rpm and a discharge temperature of 125 ° C. in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at a temperature of 120 ° C. The resulting kneaded mixture was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized product. The obtained coarsely pulverized product was finely pulverized using a mechanical pulverizer (T-250, manufactured by Freund Turbo Corporation).

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 and a dispersion rotor rotation speed of 120 s ⁻¹ .

<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.

Hydrocarbon wax 2 is a petroleum wax with a melting point of 78°C.

Example 1 (Production Example of Toner 1)
Toner particles 1 100 parts Silica fine particles 1 0.5 parts (hydrophobized silica fine particles with a number average particle size of 15 nm)
Silica fine particles 2 1.0 parts (hydrophobized silica fine particles with a number average particle size of primary particles of 80 nm)
The above materials were mixed in a Henschel mixer FM-10C (manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 50 s ⁻¹ for a rotation time of 10 minutes 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%.

Examples 2 to 31 (Toners 2 to 31 Production Examples), Comparative Examples 1 to 9 (Toners 32 to 40)
Toners 2 to 40 were obtained in the same manner 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 obtained are shown in Table 7.

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 no sea-island structure was observed in Toner 33, so the proportion of crystalline resin in the matrix and the proportion of amorphous resin in the domain could not be calculated.

Although Toner 35 uses a single resin, a sea-island structure, likely due to microphase separation, was observed.

<Production Example of Magnetic Carrier 1>
Magnetite 1 having a number average particle size of 0.30 μm (magnetization strength of 65 Am ² /kg under a magnetic field of 1000/4π (kA/m))
Magnetite 2 with a number average particle size of 0.50 μm (magnetization strength of 65 Am ² /kg under a magnetic field of 1000/4π (kA/m))
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 mass
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% by mass
Magnetite 2 treated with the above silane compound: 26% by 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 while stirring and mixing, and maintained at that temperature. A polymerization reaction was carried out for 3 hours, and the resulting phenolic resin was cured.

The hardened phenolic resin was then cooled to 30°C, and more water was added. The supernatant was then removed, and the precipitate was washed with water and air-dried.

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

<Production 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.

<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.

Evaluations were carried out using each of the above two-component developers 1 to 40.

The image forming device used was a modified Canon ImagePRESS C810 digital commercial printing printer, with a two-component developer loaded into the cyan developer unit. The device was modified to allow for flexible settings of the fixing temperature, process speed, developer carrier DC voltage VDC, electrostatic latent image carrier charging voltage VD, and laser power.

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

Evaluation was based on the following evaluation method, and the results are shown in Table 9.

[Low temperature fixability]
・Paper: GFC-081 (81.0g/m ² )
(Sold by Canon Marketing Japan Inc.)
Toner amount on paper: 0.80 mg/cm ²
(Adjusted by DC voltage VDC of the developer carrier, charging voltage VD of the electrostatic latent image carrier, and laser power)
Evaluation image: A 2 cm x 5 cm image was placed in the center of the A4 paper. Test environment: Low temperature and low humidity environment: temperature 15°C/humidity 10% RH (hereinafter referred to as "L/L")
Fixing temperature: 140°C
Process speed: 400 mm/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.

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

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

(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

[Hot offset resistance]
・Paper: CS-064 (64.0g/m ² )
(Sold by Canon Marketing Japan Inc.)
Toner amount on paper: 0.08 mg/cm ²
(Adjusted by DC voltage VDC of the developer carrier, charging voltage VD of the electrostatic latent image carrier, and laser power)
Evaluation image: A 2 cm x 20 cm image was placed on the long edge of the A4 paper in the paper feed direction, with a 2 mm margin from the leading edge of the paper. Test environment: Normal temperature and low humidity environment: temperature 23°C/humidity 5% RH (hereinafter referred to as "N/L")
Fixing temperature: 140°C, increasing in 5°C increments Process speed: 400 mm/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.

(Evaluation criteria)
A: 165°C or higher B: 155°C or higher but lower than 165°C C: 145°C or higher but lower than 155°C D: Lower than 145°C

[Winding resistance]
・Paper: CS-064 (64.0g/m ² )
(Sold by Canon Marketing Japan Inc.)
Toner amount on paper: 0.80 mg/cm ²
(Adjusted by DC voltage VDC of the developer carrier, charging voltage VD of the electrostatic latent image carrier, and laser power)
Evaluation image: A 2 cm x 20 cm image was placed on the long edge of the A4 paper in the paper feed direction, with a 2 mm margin from the leading edge of the paper. Test environment: High temperature and high humidity environment: temperature 30°C/humidity 80% RH (hereinafter referred to as "H/H")
Fixing temperature: 140°C, increasing in 5°C increments Process speed: 400 mm/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.

(Evaluation criteria)
A: 165°C or higher B: 155°C or higher but lower than 165°C C: 145°C or higher but lower than 155°C D: Lower than 145°C

[Image evaluation after durability testing]
The toner loading on the paper in the FFh image (solid image) was adjusted to 0.45 mg/ ^cm2 . FFh is a value representing 256 gradations in hexadecimal, with 00h being the first gradation (white background) of the 256 gradations and FF being the 256th gradation (solid area) of the 256 gradations.

First, an image output test of 5,000 sheets was conducted in a normal temperature and humidity environment (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 place stress on the toner inside the developing unit. During the continuous printing of 5,000 sheets, the sheets were fed under the same development and transfer conditions (no calibration) as the first sheet.

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.

One solid image was then printed and evaluated according to the following evaluation criteria. A rank of C or higher was deemed to demonstrate the effects of the present invention. The evaluation results are also shown in the table.

(Evaluation criteria)
AA: No visible image defects are observed. A: Slight white spots and streaks are visible to the naked eye. B: Slight white spots and streaks are visible to the naked eye over the entire image. C: Slight white spots and streaks are visible to the naked eye over the entire image. D: Slight white spots and streaks are visible to the naked eye over the entire image.

[Chargeability (charge retention) under high temperature and high 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.

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 the inner and outer cylinders insulated. If a charged body with a charge amount Q is placed inside this inner cylinder, electrostatic induction occurs, just as if a metal cylinder with a charge amount Q were present. This induced charge amount was measured using an electrometer (Kesley 6517A, manufactured by Kesley), and the charge amount Q (mC) divided by the toner mass M (kg) in the inner cylinder (Q/M) was determined as the amount of triboelectric charge of the toner.
Triboelectric charge of toner (mC/kg) = Q/M

First, an evaluation image used for winding resistance was formed on the electrostatic latent image carrier. Before it 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 collected by suction using a metal cylindrical tube and a cylindrical filter, and the [initial Q/M] was measured.

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

(Evaluation criteria)
A: Maintenance rate is 90% or more. B: Maintenance rate is 85% or more but less than 90%. C: Maintenance rate is 70% or more but less than 85%. D: Maintenance rate is less than 70%.

Claims (8)

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):
[In formula (1), R _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):
[In formula (3), X represents a single bond,
R ¹ represents —C≡N or —COOH;
R2 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 endothermic heat 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, T1 (°C) is the temperature at which the melt viscosity V1 becomes 1×10 ⁵ Pa·s at an applied pressure of 0.9807 MPa, and T10 (°C) is the temperature at which the melt viscosity V10 becomes 1×10 ⁵ Pa·s at an applied pressure of 9.807 MPa.
T10≧65
T1-T10≦10
A toner characterized by satisfying the relationship: 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/ ^cm3 ) ^0.5
2. The toner according to claim 1, which satisfies the relationship: 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: 3. The toner according to claim 1, wherein the third monomer unit is a styrene monomer unit. 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: The toner according to any one of claims 1 to 5, wherein the first resin contains 20.0% to 80.0% by mass of the first monomer unit. 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):
[In formula (5), ^R5 represents a hydrogen atom or a methyl group, and Ph represents an unsubstituted phenyl group or a substituted phenyl group.] 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: