JP7654476B2 - toner - Google Patents

Description

The present invention relates to a toner used in electrophotography, electrostatic recording, electrostatic printing, toner jet, etc.

In recent years, as full-color electrophotographic copiers have become more widespread, there has been a demand for additional performance improvements, such as energy saving performance, shorter recovery time from sleep mode, and compatibility with a wide variety of media, in addition to higher speed and higher image quality.
Specifically, as a toner that meets the demand for energy saving, a toner that can be fixed at a lower temperature and has excellent low-temperature fixability is required in order to reduce power consumption in the fixing step.
The toner described in Patent Document 1 uses a crystalline vinyl resin having sharp melting properties as the main binder, and therefore has excellent low-temperature fixing properties.
Moreover, the toners described in Patent Documents 2 and 3 have a matrix domain structure, and a crystalline resin having sharp melting properties forms the matrix, thereby enabling excellent low-temperature fixability.
On the other hand, embossed paper, one of the many types of media, has an uneven surface, which makes it difficult for the toner to be transferred to the recesses during the transfer process, and this makes it easy for image density differences to occur between the recesses and the protrusions. Therefore, there is a demand for a toner with excellent emboss transferability that does not cause image density differences even on embossed paper.

JP 2014-130243 A JP 2014-59489 A JP 2014-142632 A

The toner described in Patent Document 1 uses a crystalline resin with high molecular mobility, which causes charge diffusion and leakage to members such as a drum and an intermediate transfer belt (ITB), resulting in a low charge amount for each toner particle. As a result, the electric field driving force becomes small, and the emboss transferability, which has been required in recent years, may be poor.
In addition, the toners described in Patent Documents 2 and 3 have a toner surface made of different materials, crystalline resin and amorphous resin, so that electric charges are trapped at the interface, leading to insufficient charge diffusion and a high charge amount at the contact surface. As a result, the electrostatic adhesion to the above-mentioned members is high, and the emboss transferability, which has been required in recent years, is sometimes poor.
The present invention has been made in consideration of the above problems, and provides a toner that exhibits excellent low-temperature fixing property and also excellent emboss transferability.

The present invention relates to toner particles containing a binder resin having a first resin and a second resin, and a toner having fine particles on the surface of the toner particles,
the first resin is a crystalline resin and the second resin is an amorphous resin;
a cross section of the toner observed by a transmission electron microscope has a matrix domain structure composed of a matrix containing the first resin and a domain containing the second resin, and the first resin occupies 35 area % or more and 70 area % or less of a total area of the matrix and the domain;
The first resin has a first monomer unit represented by the following formula (1):

［式（１）中、Ｒ_Z1は、水素原子又はメチル基を表し、Ｒ¹は、炭素数１８～３６のアルキル基を表す。］
該第一のモノマーユニットの割合が、該結晶性樹脂の全モノマーユニットの総質量に対して４０．０質量％以上８０．０質量％以下であり、
該微粒子がケイ素含有微粒子であって、²⁹Ｓｉ－ＮＭＲ測定で得られるチャートにおいて、該ケイ素含有微粒子由来の全ピーク面積をＡ、Ｓｉ－ＯＨ由来の面積をＢとしたとき、下記式（２）を満たすことを特徴とするトナーに関する。
Ｂ／Ａ≧１．０％ ・・・（２）

[In formula (1), _R represents a hydrogen atom or a methyl group, and ^R represents an alkyl group having 18 to 36 carbon atoms.]
a ratio of the first monomer unit to the total mass of all monomer units of the crystalline resin is 40.0 mass% or more and 80.0 mass% or less;
The toner is characterized in that the fine particles are silicon-containing fine particles, and in a chart obtained by ^29Si -NMR measurement, when the total peak area derived from the silicon-containing fine particles is A and the area derived from Si-OH is B, the following formula (2) is satisfied:
B/A≧1.0%...(2)

According to the present invention, a toner with excellent low-temperature fixing properties and embossing transferability can be obtained.

In the present invention, the expressions "xx or more and xx or less" or "xx to xx" that express a numerical range refer to a numerical range including the lower and upper limit endpoints, unless otherwise specified.

In the present invention, (meth)acrylic acid ester means an acrylic acid ester and/or a methacrylic acid ester.

In the present invention, a "monomer unit" refers to one section of a carbon-carbon bond in the main chain of a polymer formed by polymerization of a vinyl monomer. A vinyl monomer can be represented by the following formula (Z).

［式（Ｚ）中、Ｒ_Z1は、水素原子、又はアルキル基（好ましくは炭素数１～３のアルキル基であり、より好ましくはメチル基）を表し、Ｒ_Z2は、任意の置換基を表す。］

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

In the present invention, a crystalline resin refers to a resin that shows a clear endothermic peak in differential scanning calorimetry (DSC) measurements.

The following describes in detail how to implement the present invention.

The present invention relates to toner particles containing a binder resin having a first resin and a second resin, and a toner having fine particles on the surface of the toner particles,
the first resin is a crystalline resin and the second resin is an amorphous resin;
a cross section of the toner observed by a transmission electron microscope has a matrix domain structure composed of a matrix containing the first resin and a domain containing the second resin, and the first resin occupies 35 area % or more and 70 area % or less of a total area of the matrix and the domain;
The first resin has a first monomer unit represented by the following formula (1):

［式（１）中、Ｒ_Z1は、水素原子又はメチル基を表し、Ｒ¹は、炭素数１８～３６のアルキル基を表す。］

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

a ratio of the first monomer unit to the total mass of all monomer units of the crystalline resin is 40.0 mass% or more and 80.0 mass% or less;
The toner is characterized in that the fine particles are silicon-containing fine particles, and when the total peak area derived from the silicon-containing fine particles is A and the area derived from Si-OH is B in a chart obtained by ^29Si -NMR measurement, the toner satisfies the following formula (2):
B/A≧1.0%...(2)

The toner of the present invention can provide a toner that combines low-temperature fixability and emboss transferability.

As a result of extensive research, the inventors discovered that the above problems can be solved by controlling the matrix domain structure of the crystalline resin and amorphous resin of the toner particles, the area occupied by the crystalline resin, the monomer unit and its amount used in the crystalline resin, and the amount of Si-OH in the fine particles on the surface of the toner particles within specific ranges, which led to the present invention.

The inventors speculate that the reason for solving the above problem is as follows.

The transferability of toner is determined by the magnitude relationship between the electric field driving force caused by the electric field and the adhesive force with members such as a drum or intermediate transfer belt (ITB), and toner can be transferred when the electric field driving force exceeds the adhesive force. The reason why emboss transferability is poor is that when there is a large gap with a member such as the recesses of embossed paper, the electric field driving force is smaller and the transferability of the toner is poor. Also, while the electric field driving force is largely dependent on the amount of charge possessed by a single toner particle, the adhesive force is largely dependent on the amount of charge on the contact surface with the member, i.e., the uniformity of the charge. Therefore, simply increasing the amount of charge of the toner in order to increase the electric field driving force will not lead to improved emboss transferability, as the adhesive force will also increase at the same time.

The inventors have discovered that by having a matrix domain structure consisting of a matrix containing a crystalline resin and a domain containing an amorphous resin, and by controlling the electrostatic charge of the crystalline resin and the external additive, it is possible to obtain an excellent low-temperature fixing property, a reduced adhesion force while maintaining the electric field driving force, and excellent emboss transferability.

In the present invention, it is necessary that the matrix domain structure is composed of a matrix containing a crystalline resin and a domain containing an amorphous resin, and that the area ratio of the matrix containing the first resin to the total area of the matrix and domain combined is 35 area % or more and 70 area % or less.

The first resin has a first monomer unit represented by the following formula (1):

［式（１）中、Ｒ_Z1は、水素原子又はメチル基を表し、Ｒ¹は、炭素数１８～３６のアルキル基を表す。］
第一のモノマーユニットの割合が、結晶性樹脂の全モノマーユニットの総質量に対して４０．０質量％以上８０．０質量％以下であることが必要である。

[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 proportion of the first monomer unit is required to be 40.0% by mass or more and 80.0% by mass or less based on the total mass of all monomer units of the crystalline resin.

Furthermore, in the present invention, the fine particles present on the surface of the toner particles are silicon-containing fine particles, and in a chart obtained by ^29Si -NMR measurement, when the total peak area attributable to the silicon-containing fine particles is A and the area attributable to Si-OH is B, it is necessary that B/A is 1.0% or more.

By satisfying these requirements, the charging ability of the crystalline resin and the fine particles present on the toner surface become similar, realizing uniform charging and reducing the electrostatic adhesion force to the above-mentioned members. On the other hand, the charge amount per toner particle can be maintained because the charge is trapped at the interface between the crystalline resin and the amorphous resin present inside the toner particle, so the electric field driving force can be maintained. As a result, a toner was obtained that has excellent low-temperature fixing properties, can reduce the electrostatic adhesion force to the above-mentioned members while maintaining the electric field driving force, and also has excellent emboss transfer properties.

Next, each component of the present invention will be described in detail.

<Matrix domain structure>
Of the total area of the matrix and domains of the toner cross section, the area ratio of the matrix containing the first resin, which is a crystalline resin, is 35 area% or more and 70 area% or less, preferably 40 area% or more and 60 area% or less. When the area ratio of the matrix satisfies the above range, the balance between the uniform charging property of the toner surface by the crystalline resin and the fine particles and the charge trapping by the interface between the crystalline resin and the amorphous resin is good, and the emboss transferability is improved. The above area ratio can be controlled by the ratio of the crystalline resin forming the matrix and the amorphous resin forming the domain.

The specific methods for observing the cross section of the toner and the matrix domain structure will be described later.

<First Resin>
The first monomer unit represented by the above formula (1) contained in the first resin as a binder resin is derived from a first polymerizable monomer which is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having a carbon number of 18 to 36. When the first resin has the first monomer unit represented by the above formula (1), the charging ability becomes similar to that of the fine particles used, and the emboss transferability becomes good.

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

Among these, from the viewpoint of low-temperature fixing property, it is preferable to use at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 36 carbon atoms. More preferably, it is at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 30 carbon atoms. Even more preferably, it is at least one selected from the group consisting of linear behenyl (meth)acrylate. The polymerizable monomer derived from the first monomer unit represented by the above formula (1) may be used alone or in combination of two or more kinds.

The content of the first monomer unit in the first resin is 40.0% by mass or more and 80.0% by mass or less, preferably 50.0% by mass or more and 70.0% by mass or less, based on the total mass of all monomer units of the crystalline resin. When the content of the first monomer unit in the first resin satisfies the above range, the charging ability becomes closer to that of the fine particles used, and the emboss transferability becomes good.

When the crystalline resin has monomer units derived from two or more types of (meth)acrylic acid esters having alkyl groups with 18 to 36 carbon atoms, the content of the first monomer unit represents the mass ratio of the total of these.

When the SP value (J/ ^cm3 ) ^0.5 of the first monomer unit is taken as SP1, SP1 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.

Here, the SP value is an abbreviation for solubility parameter, and is a value that serves as an index of solubility. The calculation method will be described later.

In the present invention, the unit of the SP value is (J/cm ³ ) ^0.5 , but it can be converted to a unit of (cal/cm ³ ) ^0.5 by 1 (cal/cm ³ ) ^0.5 = 0.4888 × (J/cm ³ ) ^0.5 .

The first resin preferably has a second monomer unit different from the first monomer unit in the first resin, and when the SP value of the second monomer unit is SP2 (J/ ^cm3 ) ^0.5 , it is preferable that the following relational expression (5) is satisfied, and more preferably the following relational expression (5)' is satisfied.
21.00 (J/ ^cm3 ) ^0.5 ≦SP2...(5)
25.00 (J/cm ³ ) ^0.5 ≦SP2...(5)'

The first monomer units are incorporated into the polymer, and the first monomer units aggregate together to form domains, thereby exhibiting crystallinity. Normally, when other monomer units are incorporated, crystallization is easily inhibited, making it difficult for the polymer to exhibit crystallinity.

This tendency becomes more pronounced when the first monomer unit and other monomer units are randomly bonded within a single polymer molecule.

On the other hand, when SP1 and SP2 are within the above-described ranges, it is believed that the first monomer unit and the second monomer unit in the crystalline resin are not miscible with each other and can form a clearly separated phase state, making it easier to maintain the melting point without reducing crystallinity.

Specific examples of the second polymerizable monomer that forms the second monomer unit include the polymerizable monomers listed below. Preferably, a polymerizable monomer that can form a monomer unit represented by the following formula (6) or (7) is used.

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

Monomers having 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 (acrylic acid, methacrylic acid, etc.) 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 by a known method.

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

（式（６）中、Ｘは単結合又は炭素数１～６のアルキレン基を示し、
Ｒ³は、
ニトリル基（－Ｃ≡Ｎ）、アミド基（－Ｃ（＝Ｏ）ＮＨＲ²⁰（Ｒ²⁰は水素原子、若しくは炭素数１～４のアルキル基を表す。））、
ヒドロキシ基、－ＣＯＯＲ³¹（Ｒ³¹は水素原子、炭素数１～６のアルキル基若しくは炭素数１～６のヒドロキシアルキル基を表す。）、
ウレア基（－ＮＨ－Ｃ（＝Ｏ）－Ｎ（Ｒ³³）₂（Ｒ³³はそれぞれ独立して、水素原子若しくは炭素数１～６のアルキル基を表す。））、
－ＣＯＯ（ＣＨ₂）₂ＮＨＣＯＯＲ³⁴（Ｒ³⁴は炭素数１～４のアルキル基を表す。）、又は
－ＣＯＯ（ＣＨ₂）₂－ＮＨ－Ｃ（＝Ｏ）－Ｎ（Ｒ³⁵）₂（Ｒ³⁵はそれぞれ独立して、水素原子若しくは炭素数１～６のアルキル基を表す。）
を表し、
Ｒ⁴は、水素原子又はメチル基を表す。）

In formula (6), X represents a single bond or an alkylene group having 1 to 6 carbon atoms.
^R3 is
A nitrile group (-C≡N), an amide group (-C(=O) ^NHR20 ( ^R20 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)),
a hydroxy group, -COOR ³¹ (wherein R ³¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms);
a urea group (-NH-C(=O)-N( ^R33 ) ₂ (each ^R33 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms);
-COO( _CH2 ) _2NHCOOR34 ( ^{wherein R34 represents} an alkyl group having 1 to 4 carbon atoms), or -COO( _CH2 ) _2- NH-C(=O)-N( ^R35 ) ₂ (wherein ^R35 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
represents
^R4 represents a hydrogen atom or a methyl group.

（式（７）中、Ｒ⁵は、炭素数１～４のアルキル基を表し、
Ｒ⁶は、水素原子又はメチル基を表す。）

(In formula (7), R ⁵ represents an alkyl group having 1 to 4 carbon atoms,
^R6 represents a hydrogen atom or a methyl group.

Among these, it is preferable to use a monomer having a nitrile group, an amide group, a hydroxy group, or a urea group. More preferably, it is a monomer having at least one functional group selected from the group consisting of a nitrile group, an amide group, a hydroxy group, and a urea group, and an ethylenically unsaturated bond. Acrylonitrile and methacrylonitrile are particularly preferable.

Also preferably used as the second monomer unit are vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, and vinyl octylate. Among these, vinyl esters are preferred from the viewpoint of low-temperature fixability, since they are non-conjugated monomers and tend to maintain a suitable reactivity with the first polymerizable monomer and tend to increase the crystallinity of the polymer.

The proportion of the second monomer unit in the first resin is preferably 5.0% by mass or more and 40.0% by mass or less, and more preferably 10.0% by mass or more and 30.0% by mass or less.

A third monomer unit derived from a third polymerizable monomer not included in the range of formula (5) above (i.e., different from the first polymerizable monomer and the second polymerizable monomer) may be included, 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, a monomer that does not satisfy the above formula (5) among the monomers exemplified as the second polymerizable monomer can be used.

For example, the following monomers can also be used:

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. Among these, it is preferable that the third polymerizable monomer is styrene from the viewpoint of charge diffusion.

The proportion of the third monomer unit in the first resin is preferably 5.0% by mass or more and 50.0% by mass or less, and more preferably 10.0% by mass or more and 30.0% by mass or less.

<Microparticles>
The fine particles are silicon-containing fine particles, and in ^29Si -NMR, peaks are detected in different shift regions depending on the structure of the functional group that bonds to Si in the constituent compound of the silicon polymer. The structure that bonds to Si can be identified by identifying the position of each peak using a standard sample. Furthermore, the abundance ratio of each constituent compound can be calculated from the obtained peak area. The peak area ratios of the Q unit (tetrafunctional silane) structure, T unit (trifunctional silane) structure, D unit (difunctional silane) structure, and M unit (monofunctional silane) structure that constitute the fine particles can be calculated.

In the present invention, when the total peak area derived from silicon-containing microparticles is A and the area derived from Si-OH is B, B/A must be 1.0% or more. Methods for controlling B/A include the type and amount of monomer used in the microparticles, the temperature and time during the condensation reaction, and the pH of the solution. B/A can be increased by reducing the amount of tetrafunctional silane used. Details of the method for measuring B/A will be described later.

The method for producing silicon-containing microparticles is not particularly limited. For example, a silane compound can be dropped into water, hydrolyzed and condensed with a catalyst, and the resulting suspension can be filtered and dried. The particle size can be controlled by the type of catalyst, the compounding ratio, the reaction start temperature, the dropping time, etc. Examples of acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while examples of basic catalysts include ammonia water, sodium hydroxide, and potassium hydroxide, but are not limited to these.

The number-based primary average particle size of the silicon-containing microparticles is preferably 20 nm or more and 300 nm or less, and more preferably 50 nm or more and 150 nm or less.

Tetrafunctional silanes include tetramethoxysilane, tetraethoxysilane, and tetraisocyanate silane.

Trifunctional silanes include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydrosilane. Examples of such silane include silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

Examples of bifunctional silanes include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, and diethyldimethoxysilane.

Examples of monofunctional silanes include t-butyldimethylchlorosilane, t-butyldimethylmethoxysilane, t-butyldimethylethoxysilane, t-butyldiphenylchlorosilane, t-butyldiphenylmethoxysilane, t-butyldiphenylethoxysilane, chlorodimethylphenylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, triethylmethoxysilane, triethylethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, tripentylmethoxysilane, triphenylchlorosilane, triphenylmethoxysilane, and triphenylethoxysilane.

It is preferable that the surface of the fine particles is treated with a hydrophobic treatment agent. There is no particular limitation on the hydrophobic treatment agent, but it is preferable that the hydrophobic treatment agent is an organosilicon compound.

Examples of hydrophobic treatment agents include alkylsilazane compounds such as hexamethyldisilazane, alkylalkoxysilane compounds such as diethyldiethoxysilane, trimethylmethoxysilane, methyltrimethoxysilane, and butyltrimethoxysilane, fluoroalkylsilane compounds such as trifluoropropyltrimethoxysilane, chlorosilane compounds such as dimethyldichlorosilane and trimethylchlorosilane, siloxane compounds such as octamethylcyclotetrasiloxane, silicone oils, and silicone varnishes.

The fine particles present on the toner surface are silicon-containing fine particles, and in a chart obtained by ^29Si -NMR measurement, when the total peak area derived from the fine particles is A and the area derived from Si-R ² (R ² represents an alkyl group) is C, C/A is preferably 20.0% or more and 45.0% or less. It is more preferably 26.0% or more and 45.0% or less, and even more preferably 30.0% or more and 35.0% or less. When C/A is present in the above range, the relationship with the amount of the alkyl group of the first monomer unit in the crystalline resin described above becomes optimal, the charging ability becomes closer, and the emboss transferability becomes good. Examples of the method for controlling C/A include the type and amount of monomer used for the fine particles, the temperature and time during the condensation reaction, and the pH of the solution. By increasing the amount of bifunctional silane used, C/A can be increased. The details of the method for measuring C/A will be described later.

The content of the silicon-containing microparticles is preferably 0.1 parts by mass or more and 20.0 parts by mass or less, based on 100 parts by mass of the toner particles. It is more preferably 3.0 parts by mass or more and 10.0 parts by mass or less.

<Preferred embodiment of domain portion of matrix domain>
In the cross-sectional observation of the toner particles, the number average diameter of the circle-equivalent diameter of the domain part containing the second resin described below is preferably 20 nm or more and 500 nm or less, more preferably 100 nm or more and 300 nm or less. When the number average diameter of the circle-equivalent diameter of the domain part satisfies the above range, the dispersibility of the domain in the toner is improved, the trapping of the charge at the interface between the crystalline resin and the amorphous resin is promoted, and the emboss transferability is improved. The method for controlling the number average diameter of the circle-equivalent diameter of the domain part includes the relationship between the SP value of the resin of the matrix part and the domain part, the kneading temperature and the screw rotation speed in the melt kneading process, and the stirring rotation speed in the fusion process. When the SP values of the resins of the matrix part and the domain part are close to each other, the compatibility of the matrix part and the domain part is increased, and the number average diameter of the circle-equivalent diameter of the domain part is reduced. In addition, when the screw rotation speed or the stirring rotation speed is increased, the shear force on the resin is increased, and the number average diameter of the circle-equivalent diameter of the domain part is reduced.

In the cross-sectional observation of the toner particle, it is preferable that the area of the domain in the region within 10% of the distance between the contour and the center of gravity of the cross-section from the contour of the cross-section of the toner particle is 10% to 30% of the total area occupied by the domain. It is more preferable that the area of the domain in the region within 10% of the distance between the contour and the center of gravity of the cross-section from the contour satisfies the above range, and while maintaining uniform charging by the crystalline resin and fine particles present on the surface, an interface between the crystalline resin and the amorphous resin exists near the surface, charge trapping is promoted, and emboss transferability is improved. Examples of methods for controlling the area of the domain in the region within 10% of the distance between the contour and the center of gravity of the cross-section from the contour include the presence or absence of a core-shell structure, the type and amount of shell agent added, and the stirring rotation speed and time of the fusion process. Since the first monomer unit described above is highly hydrophobic, the amorphous resin in the domain portion becomes relatively hydrophilic. Because the fusion process is carried out in water, extending the fusion process time and increasing the stirring speed allows the hydrophilic amorphous resin to be positioned near the surface.

Details of the method for measuring the number-average equivalent circle diameter of the domain and the area of the domain within 10% of the distance from the contour to the center of gravity of the cross section will be described later.

<Second Resin>
The binder resin contains a second resin, and the second resin is an amorphous resin.

From the viewpoint of trapping electric charges, the amorphous resin is preferably a polyester resin, a styrene-acrylic resin, or a hybrid resin thereof, and more preferably a styrene-acrylic resin.

As the styrene-acrylic resin, styrene-acrylic resins that are normally used in toners can be preferably used.

Examples of styrene-based monomers include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 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, and p-phenylstyrene. These styrene-based monomers can be used alone or in combination.

Examples of (meth)acrylic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dimethyl phosphate ethyl (meth)acrylate, diethyl phosphate ethyl (meth)acrylate, dibutyl phosphate ethyl (meth)acrylate, and 2-benzoyloxyethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid, and maleic acid. These (meth)acrylic monomers can be used alone or in combination.

As the polyester resin, polyester resins that are normally used in toners can be suitably used. Monomers that can be used in the polyester resin include polyhydric alcohols (dihydric, trihydric or higher alcohols), polycarboxylic acids (dihydric, trihydric 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 such polycarboxylic acids include the following:

Examples of 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, isooctylsuccinic acid, isooctylsuccinic acid, anhydrides of these acids, and lower alkyl esters of these acids. Of these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenylsuccinic acid are preferably used.

Examples of trivalent or higher carboxylic acids, their anhydrides, or 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.

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

These polycarboxylic acids can be used alone or in combination.

<Other resins>
The binder resin may contain a resin other than the first resin and the second resin for the purpose of improving pigment dispersibility or the like, to the extent that the effects of the present disclosure are not impaired.

Examples of such resins include:

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.

<Wax>
The toner particles of the present invention may contain a wax, if necessary. Examples of the wax include the following.

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

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

The wax content is preferably 2.0 parts by mass or more and 30.0 parts by mass or less per 100 parts by mass of the binder resin.

<Coloring Agent>
The toner particles of the present invention may contain a colorant, if necessary. Examples of the colorant include the following.

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

Pigments for magenta toner include the following: C.I. 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: 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; 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; C.I. Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Pigments for cyan toner include the following: C.I. Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; C.I. Bat 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.

Yellow toner pigments include: 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. Vat Yellow 1, 3, 20.
Yellow toner dyes include C.I. Solvent Yellow 162.

These colorants can be used alone or in mixtures, or even in the form of a solid solution. Colorants are selected based on their hue angle, saturation, brightness, light resistance, transparency on overhead projectors, and dispersibility in toner.

The content of the colorant is preferably 0.1 parts by mass or more and 30.0 parts by mass or less per 100 parts by mass of the total amount of the resin components.

<Charge Control Agent>
The toner particles of the present invention may contain a charge control agent, if necessary. By blending a charge control agent, the charge characteristics can be stabilized and the amount of triboelectric charge can be optimally controlled according to the development system.

Any known charge control agent can be used, but metal compounds of aromatic carboxylic acids are particularly preferred, as they are colorless, have a high charging speed for the toner, 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.

The charge control agent may be added internally or externally to the toner particles. The content of the charge control agent is preferably 0.2 parts by mass or more and 10.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 10.0 parts by mass or less, per 100 parts by mass of the binder resin.

<Inorganic fine particles>
In addition to the above-mentioned fine particles, the toner may contain other inorganic fine particles as necessary. The inorganic fine particles may be added internally to the toner particles, or may be mixed with the toner particles as an external additive. When added as an external additive, inorganic fine particles such as titanium oxide fine particles and aluminum oxide fine particles are preferred. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

As an external additive for improving fluidity, inorganic fine particles having a specific surface area of 50 ^m2 /g or more and 400 ^m2 /g or less are preferable. In order to simultaneously improve fluidity and stabilize durability, inorganic fine particles having a specific surface area in the above range may be used in combination.

The inorganic fine particles are preferably present in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of toner particles.

<Developer>
The toner of the present invention can be used as a one-component developer, but is more preferably mixed with a magnetic carrier and used as a two-component developer in that stable images can be obtained over a long period of time.

As magnetic carriers, for example, iron powder with an oxidized surface, unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, and rare earths, alloy particles thereof, oxide particles, magnetic materials such as ferrite, magnetic material-dispersed resin carriers (so-called resin carriers) containing magnetic materials and a binder resin that holds the magnetic materials in a dispersed state, and other commonly known magnetic carriers can be used.

When the toner of the present invention is mixed with a magnetic carrier to be used as a two-component developer, good results are usually obtained when the carrier mixing ratio is, in terms of toner concentration in the two-component developer, preferably 2.0% by mass or more and 15.0% by mass or less, more preferably 4.0% by mass or more and 13.0% by mass or less.

<Toner Manufacturing Method>
The method for producing the toner of the present invention is not particularly limited, and known methods such as a pulverization method, a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, and a dispersion polymerization method can be used.

The procedure for producing toner using the pulverization method is explained below.

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

[Melt kneading process]
Next, the mixed materials are melt-kneaded to disperse the wax in the binder resin. In the melt-kneading process, a batch-type kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used, and single-screw or twin-screw extruders are mainstream due to their advantage of continuous production. For example, a KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), a TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikegai Iron Works Co., Ltd.), a twin-screw extruder (manufactured by KCK Corporation), a Co-Kneader (manufactured by Buss Co., Ltd.), and Kneadex (manufactured by Nippon Coke and Engineering Co., Ltd.) can be mentioned. Furthermore, the resin composition obtained by melt-kneading may be rolled with a two-roller or the like, and cooled with water or the like in a cooling process.

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

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

[Classification process]
Thereafter, as necessary, the mixture is classified using a classifier or sieve such as an inertial classification type Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.) or a centrifugal classification type Turboplex (manufactured by Hosokawa Micron Corporation), TSP Separator (manufactured by Hosokawa Micron Corporation), or Faculty (manufactured by Hosokawa Micron Corporation).

[External addition process]
Furthermore, if necessary, an external additive is added to the surface of the toner particles for external addition. As a method for externally adding an external additive, a method of mixing the classified toner with a predetermined amount of various known external additives and stirring and mixing them using a mixing device such as a double con mixer, a V-type mixer, a drum type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano Hybrid (manufactured by Nippon Coke & Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation) as an external addition device can be mentioned.

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

In the emulsion aggregation method, toner particles are manufactured through a dispersion process in which a fine particle dispersion liquid made of the constituent materials of the toner particles is prepared, an aggregation process in which the fine particles made of the constituent materials of the toner particles are aggregated and the particle size is controlled until it becomes the particle size of the toner particles, a fusion process in which the resin contained in the resulting aggregated particles is fused, a subsequent cooling process, a metal removal process in which the resulting toner is filtered and excess polyvalent metal ions are removed, a filtration/washing process in which the toner particles are washed with ion-exchanged water, etc., and a process in which the washed toner particles are dehydrated and dried, etc.

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

Specifically, the first resin and the second resin are dissolved in an organic solvent capable of dissolving them, and a surfactant or a basic compound is added as necessary. At this time, if the resin is a crystalline resin having a melting point, it may be heated above the melting point to dissolve it. Next, while stirring with a homogenizer or the like, an aqueous medium is slowly added to precipitate the resin microparticles. Thereafter, the solvent is removed by heating or reducing pressure to produce an aqueous dispersion of the resin microparticles.

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

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

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

The 50% particle size (D50) based on volume distribution of the resin microparticles in the aqueous dispersion of resin microparticles is preferably about 0.05 μm to 1.00 μm, and more preferably about 0.05 μm to 0.40 μm. By adjusting the 50% particle size (D50) based on volume distribution to the above range, it becomes easy 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) based on volume distribution, it is recommended to use the Nanotrac UPA-EX150 dynamic light scattering particle size distribution meter (manufactured by Nikkiso).

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

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

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

Among these, nonionic surfactants or anionic surfactants are preferred. A nonionic surfactant and an anionic surfactant may be used in combination. The surfactant may be used alone or in combination of two or more types. The concentration of the surfactant in the aqueous medium is preferably about 0.5% by mass 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% by mass to 30% by mass relative to the total mass of the colorant particle dispersion.

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

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

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

Wax microparticle dispersions can be made 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 (e.g., M Technique's "Clearmix W Motion") or a pressure-discharge type disperser (e.g., Gorin Homogenizer) and then cooling the mixture to below the melting point.

The particle size of the dispersed wax microparticles in the aqueous wax dispersion is preferably 50% particle size (D50) based on volume distribution of about 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 of 1 μm or more exist.

By having the dispersed particle size of the wax microparticle dispersion within the above range, it becomes possible to have the wax finely dispersed in the toner particles, maximizing the seepage effect during fixing and making it possible to obtain good separation properties. The 50% particle size (D50) based on volume distribution of the wax microparticle dispersion dispersed in the 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 liquid, the second resin particle dispersion liquid, and, if necessary, the wax particle dispersion liquid and the colorant particle dispersion liquid, 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 aggregation step, the fine particles contained in the mixed liquid prepared in the mixing step are aggregated to form aggregates of the desired particle size. At this time, an aggregating agent is added and mixed as necessary, and at least one of heating and mechanical power is appropriately applied to form aggregates in which the resin fine particles and, as necessary, the wax fine particles and the colorant fine particles are aggregated. By adjusting the mechanical power, it is possible to control the dispersion state of the first resin and the second resin, the number average diameter of the domains, and the like.

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

Coagulants containing divalent or higher metal ions have high coagulation power and can achieve their intended purpose by adding a small amount. These coagulants can also ionically neutralize the ionic surfactants contained in the resin microparticle dispersion, wax microparticle dispersion, and colorant microparticle dispersion.

As a result, the effects of salting out and ionic crosslinking make it easier for the resin microparticles, wax microparticles, and colorant microparticles to aggregate.

In the aggregation process, new resin particle dispersion may be added after the aggregates are formed, if necessary. By adding new resin particle dispersion and aggregating, a core-shell structure can be realized. The aggregation process is a process for forming aggregates of the toner particle size in an aqueous medium. The weight average particle size of the aggregates produced in the aggregation process is preferably 3 μm to 10 μm. The weight average particle size may be measured using a particle size distribution analyzer (Coulter Multisizer III, manufactured by Coulter) using the Coulter method.

[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 a basic compound that shifts the equilibrium of the acidic polar group of the surfactant to the dissociation side and stabilizes the aggregated particles. Examples of the aggregation terminator include a chelating agent that partially dissociates the ionic bridge between the acidic polar group of the surfactant and the metal ion serving as the aggregating agent and forms a coordinate bond with the metal ion to stabilize the aggregated particles.

After the dispersion state of the aggregated particles in the dispersion liquid has become stable due to the action of the aggregation terminator, the aggregated particles can be fused by heating to a temperature above the glass transition temperature or melting point of the resin.

It is also possible to control the number-average diameter of the domains by adjusting the temperature during fusion. The weight-average particle size of the resulting toner particles is preferably about 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 the particle size are carried out to obtain toner particles.

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

The measurement methods for various physical properties are explained below.

Separation of toner particles and fine particles from toner
The toner particles and fine particles can be separated from the toner by the following method.

200 g of sucrose (Kishida Chemical) is added to 100 mL of ion-exchanged water, and dissolved in a hot water bath to prepare a concentrated sucrose solution. 31 g of the concentrated sucrose solution and 6 mL of Contaminon N (a 10% aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a centrifuge tube to prepare a dispersion. 1 g of toner is added to this dispersion, and the toner clumps are loosened using a spatula or similar.

The centrifuge tube is shaken for 20 minutes in a shaker (Iwaki Sangyo Co., Ltd.'s "KM Shaker" (model: V.SX)) at 350 reciprocations per minute. After shaking, the solution is transferred to a swing rotor glass tube (50 mL) and centrifuged at 3,500 rpm for 30 minutes in a centrifuge. After centrifugation, toner particles are present in the top layer of the glass tube, and fine particles are present in the aqueous solution layer below. The toner particles from the top layer are collected.

<Method of separating each material from toner>
By utilizing the difference in solubility of each material contained in the toner in a solvent, each material can be separated from the toner.
First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23° C., and the soluble matter (second resin) is separated from the insoluble matter (first resin, wax, colorant, inorganic fine particles, etc.).
Second separation: The insoluble matter obtained in the first separation (such as the first resin, wax, colorant, and inorganic fine particles) is dissolved in MEK at 100° C., and the soluble matter (such as the first resin and wax) is separated from the insoluble matter (such as the colorant and inorganic fine particles).
Third separation: The soluble fraction (first resin, wax) obtained in the second separation is dissolved in chloroform at 23° C., and the soluble fraction (first resin) and the insoluble fraction (wax) are separated.

(When a third resin is included)
First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23° C., and the soluble matter (second resin, third resin) is separated from the insoluble matter (first resin, wax, colorant, inorganic fine particles, etc.).
Second separation: The soluble fraction (second resin, third resin) obtained in the first separation is dissolved in toluene at 23° C., and the soluble fraction (third resin) is separated from the insoluble fraction (second resin).
Third separation: The insoluble matter obtained in the first separation (such as the first resin, wax, colorant, and inorganic fine particles) is dissolved in MEK at 100° C., and the soluble matter (such as the first resin and wax) is separated from the insoluble matter (such as the colorant and inorganic fine particles).
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) and the insoluble fraction (wax) are separated.

(Measurement of the Contents of the First Resin and the Second Resin in the Binder Resin in the Toner)
In each of the separation steps, 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 of Identifying Monomer Units Constituting the First, Second, and Third Resins and Measuring Their Content Ratios>
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: 400MHz
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 this is dissolved in a thermostatic chamber at 40° C. to prepare a sample.

From the obtained ^1H -NMR chart, a peak that is independent of the peaks assigned to the components of the first monomer unit and other monomer unit components is selected, and the integral value _S1 of this peak is calculated.

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

Furthermore, in the case where a third monomer unit is present, a peak that is independent of the peaks that are assigned to the components of the other monomer units is selected from the peaks that are assigned to the components of the third monomer unit, 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 S ₁ , S ₂ and S ₃ as follows: Here, n ₁ , n ₂ and n ₃ 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 contents 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 case where the first, second and third resins use, for example, a polymerizable monomer that does not contain hydrogen atoms in any of its constituent elements other than vinyl groups, ^13C -NMR is used, the measurement nucleus is set to ^13C , the measurement is performed in single pulse mode, and calculations are performed in the same manner as ^1H -NMR.

The mole percentage can be converted to mass percentage based on the molecular weight of the monomer unit.

<Measurement of B/A and C/A of fine particles>
The specific conditions for the solid-state ²⁹ Si-NMR measurement are as follows:
Equipment: JNM-ECX5002 (JEOL RESONANCE)
Temperature: Room temperature Measurement method: DDMAS method 29Si 45°
Sample tube: Zirconia 3.2 mm diameter
Sample: Powdered sample filled in test tube Sample rotation speed: 10 kHz
relaxation delay: 180s
Scan: 2000

The peak area derived from the M unit structure is S1, the peak area derived from the D unit structure is S2, the peak area derived from the T unit structure is S3, and the peak area derived from the Q unit structure is S4, and SA = (S1 + S2 + S3 + S4).

(Calculation method of B/A)
From the chart obtained by solid-state ^29Si -NMR, the peak area of the unreacted group (Si-OH) in each unit structure at the following positions is calculated: the peak area of the unreacted group (Si-OH) in the Q4 unit structure is S44, the peak area of the unreacted group (Si-OH) in the Q3 unit structure is S43, the peak area of the unreacted group (Si-OH) in the Q2 unit structure is S42, and the peak area of the unreacted group (Si-OH) in the Q1 unit structure is S41.

The peak area of the unreacted group (Si-OH) in the T3 unit structure is S33, the peak area of the unreacted group (Si-OH) in the T2 unit structure is S32, and the peak area of the unreacted group (Si-OH) in the T1 unit structure is S31.

The peak area of the unreacted group (Si-OH) in the D2 unit structure is S22, and the peak area of the unreacted group (Si-OH) in the D1 unit structure is S21.

The peak area of the unreacted group (Si-OH) in the M1 unit structure is S11.

At this time, the peak area ratio of Si-OH in each unit structure is calculated as follows:

Peak area ratio QB of Si-OH attributable to Q unit structure=(S44/S4)×0+(S43/S4)×1/4+(S42/S4)×1/2+(S41/S4)×3/4,
Peak area ratio TB of Si-OH assigned to T unit structure=(S33/S3)×0+(S32/S3)×1/4+(S31/S3)×1/2,
Peak area ratio DB of Si-OH attributable to D unit structure=(S22/S2)×0+(S21/S2)×1/4,
Peak area ratio of Si-OH assigned to M unit structure MB=S11×0
Q unit structure Q4: -105 ppm to -115 ppm
Q3: -95ppm to -104ppm
Q2: -85ppm to -94ppm
Q1: -75ppm to -84ppm
T unit structure T3: -60 ppm to -70 ppm
T2: -50ppm to -59ppm
T1: -40ppm to -49ppm
D unit structure D2: -15 ppm to -25 ppm
D1: -10ppm to 14-ppm
M unit structure M1: -5 ppm to -9 ppm

From the above formula, calculate B/A = QB + TB + DB + MB.

(Calculation method of C/A)
From the chart obtained by solid-state ²⁹ Si-NMR, the peak area of (Si-R ² ) in each unit structure at the following positions is calculated, where R ² represents an alkyl group.

The peak area of (Si-R ² ) in the Q4 unit structure is S44, the peak area of (Si-R ² ) in the Q3 unit structure is S43, the peak area of (Si-R ² ) in the Q2 unit structure is S42, and the peak area of (Si-R ² ) in the Q1 unit structure is S41.

The peak area of (Si--R ² ) in the T3 unit structure is S33, the peak area of (Si--R ² ) in the T2 unit structure is S32, and the peak area of (Si--R ² ) in the T1 unit structure is S31.

The peak area of (Si--R ² ) in the D2 unit structure is designated as S22, and the peak area of (Si--R ² ) in the D1 unit structure is designated as S21.

The peak area of (Si-R ² ) in the M1 unit structure is designated as S 11. At this time, the peak area ratio of Si-R ² in each unit structure is calculated as follows.
Peak area ratio QC of Si- ^R2 attributed to Q unit structure = (S44/S4) x 0 + (S43/S4) x 0 + (S42/S4) x 0 + (S41/S4) x 0
Peak area ratio of Si-R2 attributed to T unit structure TC=(S33/S3)×1/4+(S32/S3)×1/4+(S31/S3)×1/4
Peak area ratio DC of Si-R2 attributed to D unit structure = (S22/S2) x 1/2 + (S21/S2) x 1/2
Peak area ratio of Si-R2 attributed to M unit structure MC=S11×3/4
Q unit structure Q4: -105 ppm to -115 ppm
Q3: -95ppm to -104ppm
Q2: -85ppm to -94ppm
Q1: -75ppm to -84ppm
T unit structure T3: -60 ppm to -70 ppm
T2: -50ppm to -59ppm
T1: -40ppm to -49ppm
D unit structure D2: -15 ppm to -25 ppm
D1: -10ppm to 14-ppm
M unit structure M1: -5 ppm to -9 ppm

From the above formula, calculate C/A = QC + TC + DC + MC.

<Method for measuring the peak top temperature of the endothermic peak measured by differential scanning calorimetry (DSC) of a crystalline resin>
The peak top temperature of the endothermic peak measured by differential scanning calorimetry (DSC) of the crystalline resin is measured in accordance with ASTM D3418-82 using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments).

The melting points of indium and zinc are used to correct the temperature of the device's detection section, and the heat of fusion of indium is used to correct the amount of heat.

Specifically, about 3 mg of a sample is precisely weighed and placed in an aluminum pan, and measurement is performed under the following conditions using an empty aluminum pan as a reference.
Heating rate: 10° C./min
Measurement start temperature: 30℃
Measurement end temperature: 180°C

Measurements are performed in the measurement range of 30 to 180°C at a heating rate of 10°C/min. The temperature is raised to 180°C once and held for 10 minutes, then cooled to 30°C, and then raised again. During this second heating process, the peak top temperature of the crystalline resin is calculated from the temperature-endothermic curve in the temperature range of 30°C to 80°C.

The peak top temperature of the endothermic peak of the wax (mold release agent) is also measured in the same manner as above.

<Observation of toner cross section, observation of matrix domain structure, measurement of number-average equivalent circle diameter of domain, measurement of domain area in a region within 10% of the distance from the contour to the center of gravity of the cross section>
(Observation of toner cross section, observation of matrix domain structure)
First, a thin piece is prepared as a reference sample of the amount present. The first resin, which is a crystalline resin, is thoroughly dispersed in a visible light curable resin (Aronix LCR Series D800), and then irradiated with short wavelength light to cure. The obtained cured product is cut out with an ultramicrotome equipped with a diamond knife to prepare a thin piece sample of 250 nm. In the same manner, a thin piece sample is also prepared for the second resin, which is an amorphous resin.

In addition, the first resin and the second resin are mixed in a ratio of 30/70 and 70/30 by mass, and melt-kneaded to produce a kneaded product.

These are also similarly dispersed in a visible light curable resin, cured, and then cut out to prepare thin-section samples. Next, the cut-out samples are observed at the cross section of these reference samples using a transmission electron microscope (JEM-2800 electron microscope manufactured by JEOL Ltd.) (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: 20-30
Mapping resolution: 256 x 256

Based on the spectral intensity (average over a 10 nm square area) of each element, (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 calibration curve of (nitrogen element intensity/carbon element intensity) is used for future quantification.

Next, the toner sample is analyzed. After thoroughly dispersing the toner in a visible light curable resin (Aronix LCR Series D800), it is irradiated with short wavelength light and cured. The resulting cured product is cut out using an ultramicrotome equipped with a diamond knife to prepare a 250 nm thin flake sample. The cut sample is then 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 to be mapped are carbon, oxygen, and nitrogen.

The toner particle cross section to be observed is selected as follows. First, the cross-sectional area of the toner particle is calculated from the toner particle cross-sectional image, and the diameter of a circle having an area equal to the cross-sectional area (equivalent circle diameter) is calculated. Only toner particle cross-sectional images in which the absolute value of the difference between this equivalent circle diameter and the weight average particle diameter (D4) of the toner particles is within 1.0 μm are observed. For the domains confirmed in the observed image of the toner particle, (oxygen element intensity/carbon element intensity) and/or (nitrogen element intensity/carbon element intensity) are calculated based on the spectral intensity of each element (average of 10 nm square), and the ratio of the first resin to the second resin is calculated by comparing with the calibration curve. Domains in which the ratio of the second resin is 80% or more are defined as domains of the present disclosure.

When the proportion of toner particle cross sections that form a matrix domain structure is 80% or more by number, the toner particle cross section of the toner being measured is determined to have a matrix domain structure. The matrix domain structure is a state in which domains, which are discontinuous phases, are dispersed in a matrix, which is a continuous phase. Here, the continuous phase refers to the first resin or the second resin being determined to be a continuous phase when 90% or more of the area of the first resin or the area occupied by the second resin exists as a single continuous region in the toner particle cross section.

(Measurement of the number-average diameter of the equivalent circle diameter of the domain)
After identifying the domains confirmed by the observed image, the particle diameter of the domains present on the cross section of the toner particle is obtained by binarization processing. The particle diameter is defined as the circle-equivalent diameter of the domain. This is measured at 10 points per toner particle, and the arithmetic average value of the domain particle diameters of the 10 toner particles is defined as the number-average circle-equivalent diameter of the domain (μm).

(Measurement of the area of the domain within 10% of the distance from the contour to the center of gravity of the cross section)
On the other hand, the area of the domains is calculated by adding up the areas of all the domains present in one toner particle cross-sectional image, and this total area is designated as S1. The total area of the domains of 100 toner particles (i.e., S1+S2...+S100) is calculated, and the arithmetic average value of the 100 domains is designated as the "area of the domain."

Regarding the cross-sectional area of the toner particles, the sum of the cross-sectional areas of the toner particles (for 100 toner particles) calculated from the toner cross-sectional images used to calculate the domain area is calculated, and the arithmetic average value is taken as the "total cross-sectional area of the toner particles." The "total cross-sectional area of the toner particles" minus the [domain area] is taken as the [matrix area]. The area ratio of the matrix to the total area of the matrix and domain combined is taken as [matrix area] / ([domain area] + [matrix area]) x 100.

For the area of the domain in the region within 10% of the distance between the contour and the center of gravity of the cross section from the contour, the toner cross section image used to calculate the area of the domain is used. The contour of the toner particle is along the surface of the toner particle observed in the cross section image. The center of gravity of the toner particle is the center of a circle having an area equal to the cross section area of the toner particle observed in the cross section image. A line is drawn from the center of gravity of the toner particle cross section to a point on the contour of the toner particle cross section. On the line, a position that is 10% of the distance from the contour to the center of gravity of the cross section is identified. Then, this operation is performed for one circumference of the contour of the toner particle cross section, and a boundary line of 10% of the distance between the contour and the center of gravity of the cross section is clearly indicated from the contour of the toner particle cross section. Based on the toner cross section image in which the 10% boundary line is clearly indicated, the area (s1) occupied by the domain existing in the region within 10% of the distance between the contour and the center of gravity of the cross section from the contour of the toner particle cross section in the cross section of the toner particle is measured. The area of the domain within 10% of the distance between the outline of the cross section of the toner particle and the center of gravity of the cross section is calculated using the following formula.

That is, using the domain area S1 calculated above, the area of the domain within 10% of the distance between the contour and the center of gravity of the cross section of the toner particle is calculated as s1/S1 x 100. This is performed for the cross sections of 100 toner particles, and the arithmetic mean value is taken as the area of the domain within 10% of the distance between the contour and the center of gravity of the cross section.

The image processing software "ImageJ" was used for binarization and calculation of the number-average diameter.

<Method for measuring the number-based primary average particle size of fine particles>
The number-based primary average particle size of the fine particles is determined by centrifugal sedimentation. Specifically, 0.01 g of dried fine particles is placed in a 25 ml glass vial, and 0.2 g of 5% Triton solution and 19.8 g of RO water are added to prepare a solution. Next, the probe (the tip of the tip) of the ultrasonic disperser is immersed in the solution, and ultrasonic dispersion is performed for 15 minutes at an output of 20 W to obtain a dispersion. Next, the number-average particle size of the primary particles is measured using this dispersion with a centrifugal sedimentation particle size distribution measuring device DC24000 manufactured by CPS Instruments. The disk rotation speed is set to 18000 rpm, and the true density is set to 1.3 g/ ^cm3 . Before the measurement, the device is calibrated using polyvinyl chloride particles with an average particle size of 0.476 μm.

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

The electrolyte solution used for the measurements is one in which special grade sodium chloride is dissolved in ion-exchanged water to give a concentration of approximately 1% by mass, for example "ISOTON II" (manufactured by Beckman Coulter).

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

In the "Change Standard Measurement Method (SOM) screen" of the dedicated software, set the total count number in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (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, the gain to 2, the electrolyte to ISOTON II, and check the aperture tube flush after measurement.

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

The specific measurement method is as follows.
(1) Pour about 200 mL of the electrolyte solution into a 250 mL round-bottom glass beaker made exclusively for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, remove dirt and air bubbles from inside the aperture tube using the "Aperture Tube Flush" function of the dedicated software.
(2) Approximately 30 mL of the aqueous electrolyte solution is placed in a 100-mL flat-bottom glass beaker, and approximately 0.3 mL of a solution prepared by diluting "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, having a pH of 7, manufactured by Wako Pure Chemical Industries, Ltd.) three times by weight with ion-exchanged water is added as a dispersant.
(3) A predetermined amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) which has two oscillators with an oscillation frequency of 50 kHz built in with a phase shift of 180 degrees and an electrical output of 120 W, and approximately 2 mL of Contaminon N is added to this water tank.
(4) The beaker from (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolyte solution in the beaker is maximized.
(5) In a state where the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, about 10 mg of toner (particles) is added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10°C or higher and 40°C or lower.
(6) Using a pipette, the electrolyte solution (5) in which the toner (particles) is dispersed is dropped into the round-bottom beaker (1) 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 that comes with the device, and the weight-average particle size (D4) is calculated. Note that when the dedicated software is set to Graph/Volume %, the "Average diameter" on the Analysis/Volume Statistics (Arithmetic Mean) screen is the weight-average particle size (D4).

<Method of measuring 50% particle diameter (D50) based on volume distribution of resin particles, wax particles, and colorant particles>
The 50% particle size (D50) based on the volume distribution 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 the measurement sample from clumping, 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 two measurements are taken to calculate 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.

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

<Method of measuring softening point (Tm) of resin>
The softening point of the resin is measured using a constant load extrusion type capillary rheometer "Flow characteristic evaluation device Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual that comes with the device. With this device, a constant load is applied from above the measurement sample by 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 showing the relationship between the piston descent amount and temperature can be obtained.

The softening point is the "melting temperature in the 1/2 method" described in the manual that comes with the "Flow characteristic evaluation device Flow Tester CFT-500D." The melting temperature in the 1/2 method is calculated as follows.

First, find half the difference between the amount of piston descent when the outflow ends (end of outflow, Smax) and the amount of piston descent when the outflow starts (minimum point, Smin) (call this X. X = (Smax - Smin) / 2). Then, the temperature of the flow curve when the amount of piston descent is the sum of X and Smin is the melting temperature in the 1/2 method.

The measurement sample is made 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) in an environment of 25°C, and forming it into a cylindrical shape with a diameter of approximately 8 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: Heating method Starting temperature: 50°C
Reached temperature: 200°C
Measurement interval: 1.0°C
Heating rate: 4.0° C./min
Piston cross-sectional area: 1.000 ^cm2
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheat time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0 mm

The basic configuration and features of the present invention have been described above. The present invention will now be described in detail with reference to examples. However, the present invention is in no way limited to these. Note that parts are by weight unless otherwise specified.

<Production Example of Crystalline Resin 1>
Solvent: toluene 100.0 parts Monomer composition 100.0 parts (the monomer composition is a mixture of behenyl acrylate, acrylonitrile, and styrene in the ratio shown below)
Behenyl acrylate (behenyl acrylate; first polymerizable monomer (carbon number of R ¹ in general formula (1) is 22)): 60.00 parts; acrylonitrile (second polymerizable monomer): 16.00 parts; styrene (third polymerizable monomer): 24.00 parts; polymerization initiator t-butyl peroxypivalate (Perbutyl PV: manufactured by NOF Corp.): 0.5 parts. 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 to carry out a polymerization reaction for 12 hours, and a solution in which the polymer of the monomer composition was dissolved in toluene was obtained. Subsequently, the temperature of the above solution was lowered to 25° C., and then the above solution was charged into 1000.0 parts of methanol while stirring, and the methanol insoluble matter was precipitated. The resulting methanol insoluble matter was filtered off, washed with methanol, and then vacuum dried at 40° C. for 24 hours to obtain a first resin, crystalline resin 1. The peak top temperature of the temperature-endothermic curve of crystalline resin 1 was 62° C.

<Production Examples of Crystalline Resin 2 to Crystalline Resin 13>
In the manufacturing example of crystalline resin 1, the reaction was carried out in the same manner except that the polymerizable monomers and the parts were changed as shown in Table 1, to obtain crystalline resins 2 to 13, which are the first resins.

表１中の略号は以下の通りである。
ＢＥＡ：ベヘニルアクリレート
ＯＡ：オクタコサアクリレート
ＭＹＡ：ミリシルアクリレート
ＳＡ：ステアリルアクリレート
ＨＡ：ヘキサデシルアクリレート
ＡＮ：アクリロニトリル
ＭＮ：メタクリロニトリル
ＡＡ：アクリル酸
Ｓｔ：スチレン

The abbreviations in Table 1 are as follows.
BEA: Behenyl acrylate OA: Octacosaacrylate MYA: Myrisil acrylate SA: Stearyl acrylate HA: Hexadecyl acrylate AN: Acrylonitrile MN: Methacrylonitrile AA: Acrylic acid St: Styrene

<Production Example of Amorphous Resin 1>
50.0 parts of xylene was charged into an autoclave, and after replacing with nitrogen, the temperature was raised to 185°C under stirring in a sealed state. A mixed solution of 75.0 parts of styrene, 25.0 parts of n-butyl acrylate, and 1.0 part of di-tert-butyl peroxide and 20.0 parts of xylene was continuously added dropwise to the autoclave for 3 hours while controlling the temperature inside the autoclave to 185°C, and polymerization was carried out. The temperature was further maintained for 1 hour to complete the polymerization, and the solvent was removed to obtain amorphous resin 1, which is a second resin. The SP value of amorphous resin 1 was 20.1 (J/cm ³ ) ^0.5 and the softening point (Tm) was 100°C.

<Production Example of Amorphous Resin 2>
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)
Terephthalic acid: 11.6 parts (0.07 moles)
Adipic acid: 6.8 parts (0.05 moles)
Titanium tetrabutoxide: 2.0 parts

Next, the atmosphere in the flask was replaced with nitrogen gas, and the temperature was gradually raised while stirring. The mixture was stirred at a temperature of 200°C and reacted for 2 hours while distilling off the water produced. The pressure in the reaction vessel was then lowered to 8.3 kPa and maintained at this temperature for 1 hour, after which it was cooled to 180°C and returned to atmospheric pressure (first reaction step).

Trimellitic anhydride: 8.2 parts (0.04 moles)
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 reducing the temperature (second reaction step), thereby obtaining Amorphous Resin 2, which was a second resin. Amorphous Resin 2 had an SP value of 23.3 (J/ ^cm3 ) ^0.5 and a softening point (Tm) of 105°C.

<Production of toner particles by pulverization method>
<Production Example of Toner Particle 1>
Crystalline resin 1 50.0 parts Amorphous resin 1 50.0 parts Wax 1 5.0 parts (Fischer-Tropsch wax; peak temperature of maximum endothermic peak 90° C.)
Colorant 1 9.0 parts (cyan pigment manufactured by Dainichi Seikagaku Co., Ltd.: Pigment Blue 15:3)
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 for a rotation time of 5 min, and then kneaded at a discharge temperature of 120°C using a twin-screw kneader (PCM-30, manufactured by Ikegai Co., Ltd.) set at a temperature of 110°C. The kneaded product obtained was cooled and coarsely crushed to 1 mm or less using a hammer mill to obtain a coarsely crushed product. The coarsely crushed product obtained was finely crushed using a mechanical crusher (T-250, manufactured by Freund Turbo Co., Ltd.). Classification was further performed using Faculty F-300 (manufactured by Hosokawa Micron Co., Ltd.) to obtain toner particles 1. The classification operation conditions were a classification rotor rotation speed of 130 s ^-1 and a dispersion rotor rotation speed of 120 s ^-1 . The weight average particle size (D4) of the toner particles 1 was about 6.5 μm.

<Production of toner particles by emulsion aggregation method>
<Production Example of Crystalline Resin 1 Fine Particle Dispersion>
Toluene (manufactured by Wako Pure Chemical Industries, Ltd.) 300 parts Crystalline resin 1 100 parts The above materials were weighed, mixed, and dissolved at 100°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 100°C. The toluene solution and the aqueous solution were then mixed and stirred at 7000 rpm using an ultra-high speed stirring device T.K. Robomix (manufactured by Primix). Furthermore, the mixture was emulsified at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo). After that, the toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (crystalline resin 1 fine particle dispersion) with a concentration of 20% by mass of crystalline resin 1 fine particles.

The 50% particle size (D50) based on volume distribution of crystalline resin 1 was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.40 μm (400 nm).

<Production Example of Crystalline Resin 2 to 13 Fine Particle Dispersion>
Except for changing the crystalline materials used in the manufacturing example of the microparticle dispersion of crystalline resin 1, the manufacturing was carried out in the same manner as in the manufacturing example of the microparticle dispersion of crystalline resin 1 to obtain microparticle dispersions of crystalline resins 2 to 13. The 50% particle diameter (D50) based on volume distribution of crystalline resins 2 to 13 was 0.40 μm, the same as that of crystalline resin 1.

<Production Example of Amorphous Resin 1 Fine Particle Dispersion>
Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 300 parts Amorphous resin 1 100 parts Anionic surfactant NEOGEN RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 part 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 stirring device T.K. Robomix (manufactured by Primix). Furthermore, 700 parts of ion-exchanged water was added at a rate of 8 g/min to precipitate amorphous resin 1 fine particles. After that, tetrahydrofuran was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion of amorphous resin 1 fine particles with a concentration of 20% by mass (amorphous resin 1 fine particle dispersion).

The volume-based 50% particle size (D50) of the amorphous resin 1 microparticles was 0.14 μm (140 nm).

<Production Example of Amorphous Resin 2 Fine Particle Dispersion>
In the manufacturing example of the amorphous resin 1 microparticle dispersion, except for changing the amorphous material used, the manufacturing was carried out in the same manner as in the manufacturing example of the amorphous resin 1 microparticle dispersion to obtain the amorphous resin 2 microparticle dispersion. The volume distribution standard 50% particle diameter (D50) of the amorphous resin 2 microparticles was 0.14 μm, which is the same as that of the amorphous resin 1 microparticles.

<Production Example of Wax Particle Dispersion>
Wax 1 100.0 parts (Fischer-Tropsch wax; maximum endothermic peak temperature 90° C.)
Anionic surfactant NEOGEN RK (manufactured by Daiichi Kogyo Seiyaku) 5 parts Ion-exchanged water 395 parts The above materials were weighed and placed in a mixing vessel equipped with a stirrer, then heated to 90°C and circulated through a Clearmix W Motion (manufactured by M Technique) for 60 minutes for dispersion treatment. The conditions for dispersion treatment were as follows:
・Rotor outer diameter: 3cm
・Clearance: 0.3 mm
Rotor speed: 19,000 r/min
Screen rotation speed: 19,000 r/min

After the dispersion process, the mixture was cooled to 40°C under cooling process conditions of a rotor rotation speed of 1000 r/min, a screen rotation speed of 0 r/min, and a cooling rate of 10°C/min to obtain an aqueous dispersion (wax microparticle dispersion) with a wax microparticle concentration of 20% by mass.

The 50% particle size (D50) based on volume distribution of the wax microparticles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.15 μm (150 nm).

<Production Example of Colorant Microparticle Dispersion>
Colorant 1 50.0 parts (cyan pigment manufactured by Dainichi Seikagaku Co., Ltd.: Pigment Blue 15:3)
Anionic surfactant NEOGEN RK (manufactured by Daiichi 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) to obtain an aqueous dispersion of colorant with a concentration of 10% by mass (colorant fine particle dispersion).

The 50% particle size (D50) based on volume distribution of the colorant particles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.20 μm (200 nm).

<Production Example of Toner Particle 2>
Crystalline resin 1 microparticle dispersion 50.0 parts Amorphous resin 1 microparticle dispersion 50.0 parts Wax microparticle dispersion 5.0 parts Colorant microparticle dispersion 9.0 parts Ion exchange water 20.0 parts The above materials were put into a round stainless steel flask and mixed. Then, a homogenizer Ultra Turrax T50 (IKA) was used to disperse the mixture at 5000 r/min for 10 minutes. After adding a 1.0% nitric acid aqueous solution and adjusting the pH to 3.0, the mixture was heated to 58°C in a heating water bath using a stirring blade while appropriately adjusting the rotation speed so that the mixture was stirred. The formed aggregated particles were appropriately confirmed using a Coulter Multisizer III, and the mixture was held until the weight average particle size (D4) was about 6.4 μm. After that, a crystalline resin 1 microparticle dispersion for post-treatment was added, and the mixture was held for another 30 minutes, and then the pH was adjusted to 9.0 using a 5% sodium hydroxide aqueous solution.

After that, the mixture was heated to 75°C while continuing to stir at 500 r/min. The mixture 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, the mixture was cooled to 25°C, filtered and separated into solid and liquid, thoroughly washed with ion-exchanged water, and dried to obtain toner particles 2. The weight average particle size (D4) of toner particles 2 was approximately 6.5 μm.

<Production Examples of Toner Particles 3 to 33>
Toner particles 3 to 33 were obtained by carrying out the same production procedure as in the production example of toner particles 2, except that the materials and the rotation speed, temperature and time in the fusing step were changed as shown in Table 2.

The physical properties of the resulting toner particles 1 to 33 are summarized in Table 3.

<Production Example of Microparticle 1>
[Hydrolysis step]
A 200 ml beaker was charged with 43.2 g of RO water and 0.008 g of acetic acid as a catalyst, and stirred at 50° C. 27.2 g of tetraethoxysilane and 27.2 g of dimethyldimethoxysilane were added thereto and stirred for 1.5 hours to obtain a raw material solution.

[Polycondensation step]
In a 1000 ml beaker, 68.8 g of RO water, 340.0 g of methanol, and 2.0 g of 25% ammonia water were charged and stirred at 30° C. to prepare an alkaline aqueous medium. The raw material solution obtained in the hydrolysis step was added dropwise to this alkaline aqueous medium over 1 minute. The mixture after the dropwise addition of the raw material solution was stirred for 1.5 hours while keeping it at 30° C. to proceed with the polycondensation reaction and obtain a polycondensation reaction liquid.

[Particle formation process]
1000 g of RO water was placed in a 2000 ml beaker, and the polycondensation reaction liquid obtained in the polycondensation step was added dropwise thereto over a period of 10 minutes while stirring at 30° C. As soon as the polycondensation reaction liquid was mixed with the water, it became cloudy, and a dispersion liquid containing fine particles was obtained.

[Hydrophobization process]
27.1 g of hexamethyldisilazane was added as a hydrophobizing agent to the dispersion containing the silicon polymer particles having siloxane bonds obtained in the particulation step, and the mixture was stirred at 60° C. for 2.5 hours. The powder that precipitated at the bottom of the solution after standing for 5 minutes was collected by suction filtration and dried under reduced pressure at 120° C. for 24 hours to obtain microparticles 1. The number average particle size of the primary particles of the obtained microparticles 1 was 0.10 μm (100 nm). The physical properties of the obtained microparticles 1 are shown in Table 4.

<Production Example of Microparticle 2>
Except for changing the stirring temperature in the hydrolysis step to 55° C. and changing the amount of 25% aqueous ammonia used in the polycondensation step to 1.8 g, the same procedure as in the production example of microparticles 1 was repeated to obtain microparticles 2. The physical properties of the obtained microparticles 2 are shown in Table 4.

<Production Example of Microparticle 3>
Except for changing the amount of 25% aqueous ammonia used in the polycondensation step to 1.8 g, the same procedure as in the production example of fine particles 1 was followed to obtain fine particles 3. The physical properties of the obtained fine particles 3 are shown in Table 4.

<Production Example of Microparticle 4>
Except for changing the stirring temperature in the hydrolysis step to 60° C. and changing the amount of 25% ammonia water used in the polycondensation step to 1.5 g, the same procedure as in the production example of microparticles 1 was followed to obtain microparticles 4. The physical properties of the obtained microparticles 4 are shown in Table 4.

<Production Example of Microparticle 5>
Except for changing the stirring temperature in the hydrolysis step to 55° C. and changing the amount of 25% aqueous ammonia used in the polycondensation step to 2.2 g, the same procedure as in the production example of microparticles 1 was repeated to obtain microparticles 5. The physical properties of the obtained microparticles 5 are shown in Table 4.

<Production Example of Microparticle 6>
Except for changing the stirring temperature in the hydrolysis step to 45° C. and changing the amount of 25% aqueous ammonia used in the polycondensation step to 2.4 g, the same procedure as in the production example of microparticles 1 was repeated to obtain microparticles 6. The physical properties of the obtained microparticles 6 are shown in Table 4.

<Production Example of Microparticle 7>
Except for changing the stirring temperature in the hydrolysis step to 65° C. and changing the amount of 25% ammonia water used in the polycondensation step to 1.5 g, the same procedure as in the production example of microparticles 1 was repeated to obtain microparticles 7. The physical properties of the obtained microparticles 7 are shown in Table 4.

<Production Examples of Microparticles 8 to 13>
Fine particles 8 to 13 were obtained in the same manner as in the production example of fine particles 7, except that the materials were changed to those shown in Table 4. The physical properties of the obtained fine particles 8 to 13 are shown in Table 4.

<Production Example of Microparticles 14>
In a 2000 ml beaker, 124.0 g of ethanol, 24.0 g of RO water, and 10.0 g of 28% aqueous ammonia were added, and the temperature of the solution was adjusted to 70° C., and 232.0 g of tetraethoxysilane and 84.0 g of 5.4% aqueous ammonia were added dropwise over 0.5 hours while stirring. After the addition was completed, stirring was continued for another 0.5 hours to carry out hydrolysis, thereby obtaining a dispersion of fine particles 14.

After adding 95.0 g of hexamethyldisilazane to the dispersion liquid obtained in the above process at room temperature, the dispersion liquid was heated to 50 to 60°C and stirred for 3.0 hours, and the powder in the dispersion liquid was collected by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain microparticles 14. The physical properties of the obtained microparticles 14 are shown in Table 4.

<Production Example of Microparticle 15>
A double-tube hydrocarbon-oxygen mixed burner capable of forming an inner flame and an outer flame was used as the combustion furnace. A two-fluid nozzle for injecting slurry was installed in the center of the burner, and the raw material silicon compound (silicon tetrachloride) was introduced. Combustible hydrocarbon-oxygen gas was injected from the periphery of the two-fluid nozzle, forming an inner flame and an outer flame, which were reducing atmospheres.

The atmosphere, temperature, flame length, etc. were adjusted by controlling the amount and flow rate of the combustible gas and oxygen. Fine particles were formed from the silicon compound in the flame, and were then fused until they reached the desired particle size. After cooling, the particles were collected using a bag filter or the like to obtain fine particles 15.

The physical properties of the obtained microparticles 15 are shown in Table 4.

モノマー種
Ｑ：テトラエトキシシラン
Ｔ：トリメトキシメチルシラン
Ｄ：ジメチルジメトキシシラン
Ｍ：トリメチルシラン

Monomer species Q: tetraethoxysilane T: trimethoxymethylsilane D: dimethyldimethoxysilane M: trimethylsilane

<Production Example of Toner 1 (Example 1)>
Toner particles 1 100 parts Fine particles 1 5.0 parts The above materials were mixed in a Henschel mixer FM-10C (manufactured by Mitsui Miike Kakoki) at a rotation speed of 30 s ⁻¹ for a rotation time of 10 minutes to obtain toner 1.

<Production Examples of Toners 2 to 53 (Examples 2 to 47, Comparative Examples 1 to 6)>
Toners 2 to 53 were obtained by carrying out the same production procedure as in the production example of toner 1, except that the materials were changed to those shown in Table 5.

<Production Example of Magnetic Carrier 1>
Magnetite 1 with 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 28% by weight aqueous ammonia, and 20 parts of water were put into a flask, and the temperature was raised to 85°C in 30 minutes while stirring and mixing, and the temperature was maintained at 85°C for 30 minutes, and polymerization reaction was carried out for 3 hours to harden the resulting phenolic resin. The hardened phenolic resin was then cooled to 30°C, and water was added, after which the supernatant liquid was removed, and the precipitate was washed with water and then air-dried. This was then dried at a temperature of 60°C under reduced pressure (5 mmHg or less) to obtain a spherical magnetic carrier 1 of magnetic material dispersion type. The 50% particle size (D50) based on volume was 34.2 μm.

<Production Examples of Two-Component Developers 1 to 53>
Toners 1 to 53 and magnetic carrier 1 were mixed in a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) for 0.5 s ^-1 , 5 minutes so that the toner concentration became 9% by mass, to obtain two-component developers 1 to 53.

<Toner Evaluation>
A modified Canon full-color copier ImagePRESS C800 equipped with an intermediate transfer belt was used as the image forming apparatus, and two-component developer 1 was placed in the developing device of the cyan station. The apparatus was modified so that the fixing temperature, process speed, direct current voltage V _DC of the developer carrier, charging voltage V _D of the electrostatic latent image carrier, and laser power could be freely set. The image output evaluation was performed by outputting an FFh image (solid image) with a desired image ratio, and adjusting V _DC , V _D , and laser power so that the amount of toner on the FFh image on the paper was desired, and then performing the evaluation described below.

FFh is the hexadecimal representation of 256 gradations, with 00h being the first gradation out of 256 gradations (white background) and FFh being the 256th gradation out of 256 gradations (solid area).

The evaluation was based on the following evaluation method, and the results are shown in Table 6.

[Low temperature fixability]
Paper: Mondi color copy paper (300.0 g/ ^m2 )
(Sold by Mondi)
Toner loading on paper: 1.00 mg/cm ² (FFh image)
(Adjusted by DC voltage VDC of developer carrier, charging voltage VD of electrostatic latent image carrier, and laser power)
Evaluation image: A 2 cm x 5 cm image is 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: 170°C
Process speed: 348 mm/sec

The above evaluation image was output, and the low-temperature fixability was evaluated. The value of the image density reduction rate was used as an evaluation index for low-temperature fixability. The image density reduction rate was measured by first measuring the image density at the center using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). Next, a load of 4.9 kPa (50 g/cm ² ) was applied to the portion where the image density was measured, and the fixed image was rubbed (five round trips) with Silbon paper, and the image density was measured again. Then, the image density reduction rate before and after the rub was calculated using the following formula. The obtained image density reduction rate was evaluated according to the following evaluation criteria. If the evaluation was A to F, it was judged to be good.
Image density decrease rate =
(Image density before rubbing−Image density after rubbing)/(Image density before rubbing)×100

(Evaluation Criteria)
A: Image density reduction rate is less than 0.5% B: Image density reduction rate is 0.5% or more and less than 1.0% C: Image density reduction rate is 1.0% or more and less than 2.0% D: Image density reduction rate is 2.0% or more and less than 3.0% E: Image density reduction rate is 3.0% or more and less than 4.0% F: Image density reduction rate is 4.0% or more and less than 5.0% G: Image density reduction rate is 5.0% or more and less than 6.0% H: Image density reduction rate is 6.0% or more

[Embossing transferability]
Paper: Lezac 66 (302.0 g/ ^m2 )
(Embossed paper, sold by Tokai Tokushu Paper Co., Ltd.)
Toner loading on paper: 0.70 mg/ ^cm2 (FFh image)
(The amount of toner on the paper was confirmed in advance using Mondi color copy paper (250.0 g/m ² ) (sold by Mondi), and was adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power.)
Evaluation image: Image arranged on the entire surface of A4 size paper of REZAQ 66 Fixing test environment: Normal temperature and humidity environment (temperature 23°C/humidity 50% RH (hereinafter referred to as N/N))
Fixing temperature: 180°C
Process speed: 173 mm/sec

The above evaluation image was output and the emboss transferability was evaluated. The standard deviation of brightness was used as the evaluation index for the emboss transferability. Using a scanner (product name: CanoScan 9000F, manufactured by Canon Inc.), the image was read at a reading resolution of 1200 dpi with image correction processing OFF, and trimmed to a range of 2,550 x 2,550 pixels (approximately 10.8 x 10.8 cm). Next, a brightness value histogram (vertical axis: frequency (number of pixels), horizontal axis: brightness, brightness value is expressed in the range of 0 to 255) of the above-mentioned image data was obtained. In addition, the brightness standard deviation of the image data was calculated based on the obtained brightness value histogram. If the evaluation was A to P, it was judged to be good. The brightness standard deviation was calculated using the image processing software "ImageJ".

(Evaluation criteria: luminance standard deviation)
A: Less than 2.0 B: 2.0 or more, less than 4.0 C: 4.0 or more, less than 6.0 D: 6.0 or more, less than 8.0 E: 8.0 or more, less than 10.0 F: 10.0 or more, less than 12.0 G: 12.0 or more, less than 14.0 H: 14.0 or more, less than 16.0 I: 16.0 or more, less than 18.0 J: 18.0 or more, less than 20.0 K: 20.0 or more, less than 22.0 L: 22.0 or more, less than 24.0 M: 24.0 or more, less than 26.0 N: 26.0 or more, less than 28.0 O: 28.0 or more, less than 30.0 P: 30.0 or more, less than 32.0 Q: 32.0 or more, less than 34.0 R: 34.0 or more, less than 36.0 S: 36.0 or more, less than 38.0 T: 38.0 or more

Two-component developers 2 to 53 were also evaluated in the same manner as two-component developer 1. The results are shown in Table 6.

Claims (7)

A toner particle containing a binder resin having a first resin and a second resin, and a toner having fine particles on the surface of the toner particle,
the first resin is a crystalline resin and the second resin is an amorphous resin;
a cross section of the toner observed by a transmission electron microscope has a matrix domain structure composed of a matrix containing the first resin and a domain containing the second resin, and the first resin occupies 35 area % or more and 70 area % or less of a total area of the matrix and the domain;
The first resin has a first monomer 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.]
a ratio of the first monomer unit to the total mass of all monomer units of the crystalline resin is 40.0 mass% or more and 80.0 mass% or less;
The toner is characterized in that the fine particles are silicon-containing fine particles, and when the total peak area derived from the silicon-containing fine particles is A and the area derived from Si-OH is B in a chart obtained by ^29Si -NMR measurement, the toner satisfies the following formula (2):
B/A≧1.0%...(2) The toner according to claim 1, wherein the number-average circle-equivalent diameter of the domain portion is 20 nm or more and 500 nm or less when the cross section of the toner particle is observed. The toner according to claim 1 or 2, wherein in a cross section of the toner particle observed by a transmission electron microscope, the area of the domain in a region within 10% of the distance between the contour of the cross section of the toner particle and the center of gravity of the cross section is 10% to 30% of the total area occupied by the domain. The toner according to any one of claims 1 ^{to 3} , wherein the fine particles are silicon-containing fine particles, and when the total peak area attributable to the fine particles is A and the area attributable to Si-R ² (R ² represents an alkyl group) in a chart obtained by 29 Si-NMR measurement is C, the following formula (3) is satisfied:
20.0%≦C/A≦45.0%...(3) The toner according to any one of claims 1 ^{to 4} , wherein the fine particles are silicon-containing fine particles, and when the total peak area attributable to the fine particles is A and the area attributable to Si-R ² (R ² represents an alkyl group) in a chart obtained by 29 Si-NMR measurement is C, the following formula (4) is satisfied:
26.0%≦C/A≦45.0%...(4) The toner according to any one of claims 1 to 5, wherein the number-based primary average particle size of the fine particles is 20 nm or more and 300 nm or less. The toner according to any one of claims 1 to 6, wherein the content of the fine particles per 100 parts by mass of the toner particles is 0.1 parts by mass or more and 20.0 parts by mass or less.