JP7621793B2 - Toner, two-component developer, and method for producing toner - Google Patents

Description

This disclosure relates to a toner, a method for producing the toner, and a two-component developer.

In recent years, there has been an increasing demand for energy-saving measures for electrophotographic image forming devices. As a measure to save energy, technology for fixing toner at low temperatures is being considered in order to reduce power consumption in the fixing process.

In order to achieve both low-temperature fixability and heat-resistant storage stability of toner, a method of using a crystalline resin in the toner is being considered. Amorphous resins, which are generally used as binder resins for toners, do not show a clear endothermic peak in differential scanning calorimetry (DSC) measurements. On the other hand, crystalline resins show an endothermic peak in DSC measurements. Crystalline resins have the property that they hardly soften up to their melting point due to the regular arrangement of alkyl groups between or within molecules. Due to this property, the crystals of crystalline resins melt suddenly (sharp melt) at the melting point, which is accompanied by a sudden drop in viscosity.

For this reason, crystalline resins have been attracting attention as materials that have excellent sharp melting properties and that combine low-temperature fixing properties and heat-resistant storage stability of toner. Crystalline vinyl resins are known as one type of crystalline resin. Crystalline vinyl resins are vinyl polymers that have monomer units with long-chain alkyl groups. In other words, crystalline vinyl resins have a main chain skeleton and long-chain alkyl groups as side chains. The long-chain alkyl groups in the side chains are regularly arranged and crystallized, resulting in the resin exhibiting crystallinity.

Patent document 1 proposes a toner containing a crystalline vinyl resin having a monomer unit with a long-chain alkyl group.

JP 2014-130243 A

As a result of the inventors' investigation of the toner described in Patent Document 1, they realized that there was a need for further improvement in the abrasion resistance of the fixed image using the toner, i.e., the abrasion resistance of the toner.

One aspect of the present disclosure is to provide a toner that can have excellent low-temperature fixing properties and excellent abrasion resistance, and a method for producing the toner.

Another aspect of the present disclosure is to provide a two-component developer that can have excellent low-temperature fixing properties and excellent abrasion resistance.

According to one aspect of the present disclosure, there is provided a toner having toner particles containing a resin component and a wax,
The resin component contains a vinyl polymer A and an amorphous polyester P,
The content of the vinyl polymer A in the resin component is 50.0 to 90.0% by mass,
The vinyl polymer A contains a monomer unit A and a monomer unit B,
The monomer unit A is a monomer unit represented by the following formula (A):
When the SP value of the monomer unit B is SP _B (J/cm ³ ) ^0.5 , the SP _B is 21.00 (J/cm ³ ) ^0.5 or more;
the content of the monomer unit A in the vinyl polymer A is 20.0 to 90.0% by mass,
The content of the amorphous polyester P in the resin component is 10.0 to 49.0 mass %,
When the SP value of the vinyl polymer A is SP _A1 (J/cm ³ ) ^0.5 and the SP value of the amorphous polyester P is SP _P1 (J/cm ³ ) ^0.5 , the SP _A1 and the SP _P1 satisfy the following formula (2):
In the cross section of the toner particle,
(i) a domain matrix structure composed of a matrix containing the vinyl polymer A and a domain containing the amorphous polyester P is observed,
(ii) When the area of the wax contained in the domain is _IW and the area of the wax not contained in the domain is _SW ,
The _Iw and the _Sw satisfy the following formula (3):
A toner is provided, which comprises:
3.0 (J/cm ³ ) ^0.5 ≦SP _P1 -SP _A1 ≦8.0 (J/cm ³ ) ^0.5 ...(2)
0.00≦S _W /I _W ≦0.70...(3)

（式（Ａ）中、Ｒ^１はＨ又はＣＨ_３を示し、Ｒ^２は炭素数１８～３６のアルキル基を示す。）

(In formula (A), ^R1 represents H or _CH3 , and ^R2 represents an alkyl group having 18 to 36 carbon atoms.)

This disclosure provides a toner that can have excellent low-temperature fixing properties and excellent abrasion resistance.

1 is a schematic cross-sectional view of a toner particle for explaining a hypothetical mechanism for exerting the effects of the present disclosure. FIG.

When a numerical range is expressed as "xx or more and xx or less" or "xx to xx", it means that the numerical range includes the upper and lower limits, which are the endpoints, unless otherwise specified. When a numerical range is stated in stages, the upper and lower limits of each numerical range can be combined in any way.

(Meth)acrylate means acrylate and/or methacrylate, and (meth)acrylic acid means acrylic acid and/or methacrylic acid.

A monomer unit is a unit that constitutes a polymer, and refers to the reacted form of a monomer (polymerizable monomer). For example, one section of carbon-carbon bonds in the main chain of a polymer formed by polymerization of a vinyl monomer is one monomer unit. A vinyl monomer can be represented by the following formula (Z), and a vinyl monomer unit is a structural unit of a polymer, and is the reacted form of a monomer represented by the following formula (Z). A monomer unit may also be simply referred to as a "unit."

（式（Ｚ）中、Ｒ_Ｚ１は、水素原子、又はアルキル基を表し、Ｒ_Ｚ２は、任意の置換基を表す。）

(In formula (Z), _R represents a hydrogen atom or an alkyl group, and _R represents an arbitrary substituent.)

A crystalline resin is a resin that shows a clear endothermic peak in a differential scanning calorimeter (DSC) measurement using a resin, toner particles, or toner as a measurement sample (differential scanning calorimeter measurement is also referred to as DSC measurement).

The units of S _w and I _w in this disclosure are area %.

<Background to the invention>
The present inventors speculate as follows about the reason why the abrasion resistance of the toner according to Patent Document 1 may be insufficient.

Toners containing polymers having (meth)acrylate units with long-chain alkyl groups tend to exhibit excellent low-temperature fixing properties. The inventors believe that this is because the polymer has long-chain alkyl groups in its side chains, which tend to arrange the long-chain alkyl groups in the side chains in a regular manner, increasing crystallinity.

However, it was discovered that when the above toner contains wax as a release agent, the abrasion resistance of the fixed image may not be sufficient. Specifically, it was discovered that when this toner is used to form an image on high-whiteness thick coated paper that contains a large amount of inorganic fine particles such as calcium carbonate, part of the fixed image may be easily peeled off.

One of the reasons for this peeling is that the above-mentioned polymer and wax may be easily miscible, making it difficult for the wax to seep out sufficiently onto the surface of the fixed image during fixing. This makes it difficult for a wax layer to form on the surface of the fixed image, and increases the frictional force generated between the image and other paper, etc., which is thought to make it easier for parts of the fixed image to peel off.

As a result of further investigation based on the above considerations, it was found that a toner having the above constituent elements can have excellent low-temperature fixing properties and can impart excellent abrasion resistance to fixed images. The hypothesized mechanism and each of the constituent elements are explained in detail below.

<Mechanism by which the effects of the present disclosure are manifested>
The assumed mechanism by which the effects of the present disclosure are realized will be described with reference to FIG.

When the resin component of the toner contains a polymer A having a monomer unit A represented by formula (A) and a monomer unit B satisfying formula (1) in a specific ratio, the polymer A tends to have high crystallinity, making it easier to obtain a toner with excellent low-temperature fixing properties.

By satisfying formula (2), the compatibility between the vinyl polymer A and the amorphous polyester P is appropriately maintained, and a domain matrix structure consisting of a domain 3 containing the polyester P and a matrix 2 containing the polymer A is easily formed in the toner particle 1. As a result, the polymers A tend to aggregate together in the matrix 2, which increases crystallinity and makes it easier to obtain a toner with excellent low-temperature fixing properties.

Furthermore, by satisfying formula (3), the proportion of wax 4 contained in the toner particle 1 that is encapsulated in the domain 3 increases. Wax 4 is considered to be less compatible with polymer A and to be more likely to seep out onto the surface of the image during fixing. As a result, it is considered to be easier to form a wax layer on the surface of the fixed image, making it easier to obtain a toner that can impart excellent abrasion resistance to the fixed image.

<Wax>
The toner particles of the present disclosure contain a wax, and in the cross section of the toner particle,
(i) A domain matrix structure composed of a matrix containing a vinyl polymer A and a domain containing an amorphous polyester P is observed.
(ii) When the area of the wax contained in the domain is _IW and the area of the wax not contained in the domain is _SW ,
_Iw and _Sw satisfy the following formula (3).
0.00≦S _W /I _W ≦0.70...(3)

When the toner particles satisfy the above requirements (i) and (ii), it is believed that the vinyl polymer A and the wax become less compatible with each other, and it has been found that it is easier to obtain a toner that can impart excellent abrasion resistance to fixed images.

When the S _W /I _W is 0.70 or less, a certain percentage or more of the wax contained in the toner particles is encapsulated in the domain. That is, a certain amount or more of the wax contained in the toner particles can be in a state where it is not in contact with the vinyl polymer A. As a result, it is considered that the compatibility between the wax and the vinyl polymer A is suppressed when the toner containing the toner particles is fixed, and a wax layer is easily formed on the surface of the fixed image. Since it is considered that increasing the amount of wax in the toner particles that is not in direct contact with the vinyl polymer A is advantageous for forming a wax layer on the surface of the fixed image, the S _W /I _W is preferably 0.50 or less. More preferably, it is 0.30 or less, further 0.20 or less, and particularly 0.10 or less. There is no particular limit to the lower limit, and the S _W /I _W is 0.00.

That is, it is more preferable that S _W and I _W satisfy the following formula (4).
0.00≦S _W /I _W ≦0.30...(4)
The above-mentioned preferred ranges of S _W and I _W are easily satisfied when the toner is produced by mixing the amorphous polyester P with a wax to obtain a mixture, and then mixing the mixture with the vinyl polymer A. The values of S _W and I _W can be controlled by the amount of the amorphous polyester P, the amount of the wax, etc.

As described above, it is necessary that a certain amount or more of wax that is not in direct contact with the vinyl polymer A is present in the toner particles according to the present disclosure. Therefore, in the present disclosure, the wax contained within the domain is defined as the wax that is in contact only with the domain (wax 4 in FIG. 1). On the other hand, wax 5 in FIG. 1, which is partially in contact with the matrix, is treated as a wax that is not contained within the domain. Details of the vinyl polymer A and the amorphous polyester P will be described later.

<Average long diameter of encapsulated wax>
The average major axis of the wax contained in the domain is preferably 20 to 100 nm. If the average major axis is 20 nm or more, the size of the wax contained in the domain is unlikely to be too small, and a toner having excellent releasability is likely to be obtained. Therefore, it is preferably 20 nm or more, and more preferably 45 nm or more. If it is 100 nm or less, it is presumed that the wax contained in the domain is likely to disperse in the domain, and the wax is likely to bleed out to the toner surface during fixing. Therefore, the average major axis is preferably 100 nm or less, and more preferably 60 nm or less.

The above average major axis can be controlled by the amount of amorphous polyester P, the amount of wax, etc.

<Wax content>
The wax content in the toner particles is preferably 1.0 to 10.0% by mass. If it is 1.0% by mass or more, a sufficient amount of wax is contained in the toner particles, and a toner having excellent releasability is easily obtained. Therefore, it is preferably 1.0% by mass or more, and more preferably 3.0% by mass or more. Furthermore, if it is 10.0% by mass or less, the amount of wax not encapsulated in the domain is unlikely to become excessive, and a toner having excellent low-temperature fixing property and abrasion resistance is easily obtained. Therefore, it is preferably 10.0% by mass or less, and more preferably 7.0% by mass or less.

<Types of wax>
Examples of the wax contained in the toner particles of the present disclosure include the following.

Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, 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. Saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and valinaric 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 bisstearic acid amide; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N' dioleyl adipamide, and N,N' dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bisstearic acid amide and N,N' distearyl isophthalic acid amide; 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.

Among these waxes, it is more preferable to use a hydrocarbon wax such as paraffin wax or Fischer-Tropsch wax, or a fatty acid ester wax such as carnauba wax, since this makes it easier to obtain a toner with excellent abrasion resistance. Hydrocarbon waxes are even more preferable.

<Resin Component>
The resin component is preferably a binder resin. That is, a toner having toner particles containing a binder resin and a wax,
It is preferable that the binder resin contains a vinyl polymer A and an amorphous polyester P, the content of the vinyl polymer A in the binder resin is 50.0 to 90.0% by mass, and the content of the amorphous polyester P in the binder resin is 10.0 to 49.0% by mass.

<Vinyl Polymer A and Monomer Unit A>
The resin component contains a vinyl polymer A having a monomer unit A represented by the above formula (A). That is, the monomer unit A is a vinyl monomer unit.

The monomer unit A of the vinyl polymer A has a long-chain alkyl group (an alkyl group having 18 to 36 carbon atoms) as a side chain of the vinyl polymer A, which makes it easier to obtain a toner with excellent low-temperature fixing properties.

From the viewpoint of improving the low-temperature fixing property of the toner, it is preferable that the vinyl polymer A is a crystalline resin that shows a clear endothermic peak in differential scanning calorimetry (DSC) measurement.

Monomer unit A can be incorporated as a monomer unit of vinyl polymer A by polymerizing (vinyl polymerization) a (meth)acrylic acid ester having an alkyl group with 18 to 36 carbon atoms as a polymerizable monomer.

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, dodriaconta (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 fixability and abrasion resistance of the toner, a (meth)acrylic acid ester having a linear alkyl group having 18 to 36 carbon atoms is preferred. When the carbon number is 18 or more, the crystallinity of the vinyl polymer A is likely to be increased, and a toner having excellent low-temperature fixability is likely to be obtained. In addition, when the carbon number is 36 or less, it is presumed that the compatibility between the vinyl polymer A and the wax is unlikely to be excessively high. Therefore, a (meth)acrylic acid ester having a linear alkyl group having 18 to 36 carbon atoms is preferred, and a (meth)acrylic acid ester having a linear alkyl group having 18 to 30 carbon atoms is more preferred. More preferred are stearyl (meth)acrylate and/or behenyl (meth)acrylate. In the above formula (1), R ² is an alkyl group having 18 to 36 carbon atoms, more preferably an alkyl group having 18 to 30 carbon atoms, and even more preferably an alkyl group having 18 and 22 carbon atoms. In addition, R ² is preferably a linear alkyl group, and R ¹ is preferably H.

The polymerizable monomer (hereinafter also referred to as polymerizable monomer A) that forms monomer unit A and monomer unit A may be used alone or in combination of two or more types.

From the viewpoint of low-temperature fixing property and abrasion resistance of the toner, the content of monomer unit A in vinyl polymer A is 20.0 to 90.0% by mass.

If the content of monomer unit A in vinyl polymer A is 20.0% by mass or more, a toner having excellent low-temperature fixing properties is easily obtained. Therefore, it is 20.0% by mass or more, preferably 30.0% by mass or more, more preferably 40.0% by mass or more, and more preferably 45.0% by mass or more. In addition, if the content is 90.0% by mass or less, it is presumed that the compatibility between vinyl polymer A and wax is unlikely to become excessive. Therefore, it is more preferable that it is 90.0% by mass or less, more preferably 85.0% by mass or less, and even more preferably 75.0% by mass or less.

The content ratio of monomer unit A is the sum of the content ratios of all monomer units represented by the above formula (A). The same applies when multiple polymerizable monomers A are present.

<Monomer Unit B>
The vinyl polymer A contains a monomer unit B, and when the SP value of the monomer unit B is SP _B (J/cm ³ ) ^0.5 , SP _B is 21.00 (J/cm ³ ) ^0.5 or more. The monomer unit B is preferably a vinyl monomer unit.

The unit of the SP value in this disclosure is (J/m ³ ) ^0.5 , but it can be converted to a unit of (cal/cm ^{3 )} 0.5 by 1 (cal/cm ³ ) ^0.5 = 2.045 × 10 ³ (J/m ³ ) ^0.5 .

By containing the monomer unit B having an SP value of 21.00 (J/cm ³ ) ^0.5 or more, the melting point and other physical properties can be controlled without decreasing the crystallinity of the vinyl polymer A. This is preferable because it makes it easier to obtain a toner having excellent low-temperature fixing property.

The mechanism behind this is speculated as follows:

Monomer unit A is incorporated into vinyl polymer A, and as monomer units A aggregate (block) with each other, the crystallinity of vinyl polymer A increases. However, in general, when other monomer units are incorporated, crystallization is inhibited, and the crystallinity of the polymer decreases compared to when no other monomer units are incorporated. This tendency becomes more pronounced when monomer unit A and other monomer units are incorporated randomly in vinyl polymer A.

On the other hand, by using a polymerizable monomer that gives a monomer unit B with an SP value of 21.00 (J/ ^cm3 ) ^0.5 or more, it is believed that polymerizable monomers A can be bonded to each other in a certain degree of continuity during polymerization, rather than polymerizable monomer A and a polymerizable monomer corresponding to monomer unit B (hereinafter also referred to as polymerizable monomer B; specific examples will be described later) bonding randomly. The present inventors believe that this is because the SP value of monomer unit A is sufficiently lower than the SP value of monomer unit B.

As a result, it is believed that the monomer units A in the vinyl polymer A tend to aggregate (block) with each other, and that excellent crystallinity is more likely to be obtained even when the monomer unit B is incorporated. It is also believed that the monomer unit B makes it easier to control the melting point and other physical properties of the vinyl polymer A. That is, it is preferable that the vinyl polymer A has a crystalline portion containing the monomer unit A. It is also preferable that the vinyl polymer A has an amorphous portion containing the monomer unit B. It is also believed that the vinyl polymer A having an amorphous portion containing the monomer unit B makes it less likely that the compatibility between the vinyl polymer A and the wax will become excessive.

Therefore, SP _B is 21.00 (J/cm ³ ) ^0.5 or more, and more preferably 25.00 (J/cm ³ ) ^0.5 or more.

The upper limit of SP _B is not particularly limited, but is preferably 40.00 (J/cm ³ ) ^0.5 or less, and more preferably 30.00 (J/cm ³ ) ^0.5 or less.

In addition, when the SP value of the monomer unit A is SP _A (J/cm ³ ) ^0.5 , it is preferable that SP _A and SP _B satisfy the following formula (1).
3.00 (J/cm ³ ) ^0.5 ≦ (SP _B −SP _A ) ≦15.00 (J/cm ³ ) ^0.5 ...(1)

When the vinyl polymer A contains a plurality of types of monomer units satisfying the requirements for the monomer unit A, the value of SP _A is determined as a weighted average of the SP values of the respective monomer units.

When there are two or more kinds of monomer units B, SP _B represents the SP value of each monomer unit B, and SP _B -SP _A is determined for each monomer unit B.

The content of monomer unit B in vinyl polymer A is preferably 1.0 to 70.0% by mass.

If the content of monomer unit B in vinyl polymer A is 1.0% by mass or more, the compatibility with wax and the melting point of vinyl polymer A can be easily controlled without impairing the crystallinity of the vinyl polymer. Therefore, it is preferably 1.0% by mass or more, more preferably 5.0% by mass or more, and even more preferably 10.0% by mass or more. Also, if the content is 70.0% by mass or less, the crystallinity of vinyl polymer A is less likely to decrease, and a toner with excellent low-temperature fixing properties is easily obtained. Therefore, it is preferably 70.0% by mass or less, more preferably 60.0% by mass or less, more preferably 40.0% by mass or less, and even more preferably 30.0% by mass or less.

Monomer unit B can be incorporated as a monomer unit of vinyl polymer A by polymerizing (vinyl polymerization) the corresponding polymerizable monomer (polymerizable monomer B) as a polymerizable monomer.

The polymerizable monomer B and the monomer unit B may be used alone or in combination of two or more kinds.

The content of monomer unit B is the sum of the content of all monomer units corresponding to monomer unit B.

As the polymerizable monomer B for forming the monomer unit B, for example, among the following, a polymerizable monomer having a corresponding monomer unit SP value of 21.00 (J/cm ³ ) ^0.5 can be used.

Polymerizable monomers having nitrile groups: for example, acrylonitrile, methacrylonitrile, etc.

Polymerizable monomers having a hydroxy group: For example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.

Polymerizable monomers having an amide structure: For example, acrylamide, a polymerizable monomer obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms and an ethylenically unsaturated bond (such as acrylic acid or methacrylic acid).

Polymerizable monomers having a urethane structure: For example, polymerizable monomers obtained by reacting an alcohol having 2 to 22 carbon atoms (2-hydroxyethyl methacrylate, vinyl alcohol, etc.) that has an ethylenically unsaturated bond with an isocyanate having 1 to 30 carbon atoms. Also, polymerizable monomers obtained by reacting an alcohol having 1 to 26 carbon atoms with an isocyanate having 2 to 30 carbon atoms that has an ethylenically unsaturated bond.

Polymerizable monomers having a urea structure: For example, polymerizable monomers obtained by reacting an amine having 3 to 22 carbon atoms with an isocyanate having 2 to 30 carbon atoms and an ethylenically unsaturated bond.

Polymerizable monomers having a carboxyl group: for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate, etc.

It is preferable to use a polymerizable monomer having a nitrile group, an amide structure, a urethane structure, a hydroxy group, a urea structure, or a carboxyl group as described above. More preferably, it is a polymerizable monomer having at least one functional group selected from the group consisting of a nitrile group, an amide structure, a urethane structure, a hydroxy group, a urea structure, and a carboxyl group, and an ethylenically unsaturated bond. The use of these polymerizable monomers is preferable because it is easy to obtain a toner with excellent low-temperature fixing properties. Among them, the nitrile group is preferable because it has high electron-attracting properties, and in the vinyl polymer A, crystalline sites are easily obtained by aggregation (blocking) of the long-chain alkyl groups of the monomer unit A, and the crystallinity of the vinyl polymer A is further increased.

As the polymerizable monomer B, 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 are also preferably used.

In addition, since it is easy to obtain a toner with excellent low-temperature fixing properties, it is preferable that the monomer unit B is at least one monomer unit selected from the group consisting of the monomer unit represented by the following formula (B1) and the monomer unit represented by the following formula (B2).

（式（Ｂ１）及び（Ｂ２）中、
Ｘは、単結合又は炭素数１～６のアルキレン基を示し、
Ｒ^４は、シアノ基（－Ｃ≡Ｎ）、－Ｃ（＝Ｏ）ＮＨＲ^７（Ｒ^７は水素原子、若しくは炭素数１～４のアルキル基））、ヒドロキシ基、－ＣＯＯＲ^８（Ｒ^８は炭素数１～６（好ましくは炭素数１～４）のアルキル基、若しくは炭素数１～６（好ましくは炭素数１～４）のヒドロキシアルキル基）、－ＮＨＣＯＯＲ^９（Ｒ^９は炭素数１～４のアルキル基）、－ＮＨ－Ｃ（＝Ｏ）－ＮＨ（Ｒ^１０）_２（Ｒ^１０はそれぞれ独立して、水素原子若しくは炭素数１～６（好ましくは炭素数１～４）のアルキル基）、－ＣＯＯ（ＣＨ_２）_２ＮＨＣＯＯＲ^１１（Ｒ^１１は炭素数１～４のアルキル基）、又は－ＣＯＯ（ＣＨ_２）_２－ＮＨ－Ｃ（＝Ｏ）－ＮＨ（Ｒ^１２）_２（Ｒ^１２はそれぞれ独立して、水素原子若しくは炭素数１～６（好ましくは炭素数１～４）のアルキル基）を示し、Ｒ^６は、炭素数１～４のアルキル基を示し、Ｒ^３及びＲ^５は、それぞれ独立して、水素原子又はＣＨ_３を示す。）

(In the formulas (B1) and (B2),
X represents a single bond or an alkylene group having 1 to 6 carbon atoms;
R ⁴ is a cyano group (-C≡N), -C(=O)NHR ⁷ (R ⁷ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)), a hydroxy group, -COOR ⁸ (R ⁸ is an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) or a hydroxyalkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms)), -NHCOOR ⁹ (R ⁹ is an alkyl group having 1 to 4 carbon atoms), -NH-C(=O)-NH(R ¹⁰ ) ₂ (R ¹⁰ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms)), -COO(CH ₂ ) ₂ NHCOOR ¹¹ (R ¹¹ is an alkyl group having 1 to 4 carbon atoms), or -COO(CH ₂ ) ₂ -NH-C(=O)-NH(R ¹² ) ₂ (R R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms), R ⁶ represents an alkyl group having 1 to 4 carbon atoms, and R ³ and R ⁵ each independently represent a hydrogen atom or CH ₃ .

<Monomer Unit C>
The vinyl polymer A may contain another monomer unit C not satisfying the above formula (1) within a range that does not impair the preferred content ratio of the monomer unit A and the monomer unit B described above.

The monomer unit C can be incorporated into the vinyl polymer A by polymerizing the corresponding monomer (hereinafter also referred to as polymerizable monomer C) as a polymerizable monomer.

As the polymerizable monomer C, a monomer corresponding to a monomer unit not satisfying the above formula (1) among the monomers listed as the polymerizable monomer B can be used.

In addition, the following polymerizable monomers that do not have the above-mentioned nitrile group, amide structure, urethane structure, hydroxy group, urea structure, or carboxyl group can also be used.

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

In addition, when these are converted into a monomer unit, if the SP value becomes 21.00 (J/cm ³ ) ^0.5 , they can be used as the polymerizable monomer B.

Moreover, the monomer unit C is preferably at least one monomer unit selected from the group consisting of a monomer unit represented by the following formula (C1) and a monomer unit represented by the following formula (C2). These monomer units can be introduced by adding the corresponding monomer during the copolymerization reaction for producing the vinyl polymer A. Among them, the monomer unit C is more preferably a monomer unit represented by the following formula (C1).

（式（Ｃ２）中、Ｒ^１３はＨ又はＣＨ_３を示す。）

(In formula (C2), R ¹³ represents H or CH _3. )

The content of at least one monomer unit C selected from the above group in the vinyl polymer A is preferably 1.0 to 30.0% by mass. If the content is 1.0% by mass or more, the elasticity of the vinyl polymer A is easily maintained appropriately. Therefore, 1.0% by mass or more is preferable, and 5.0% by mass or more is more preferable. Furthermore, if the content of the monomer unit C in the vinyl polymer A is 30.0% by mass or less, the crystallinity of the vinyl polymer A is less likely to decrease, and a toner having excellent low-temperature fixing properties is easily obtained. Therefore, 30.0% by mass or less is preferable, 20.0% by mass or less is more preferable, and 15.0% by mass or less is even more preferable.

<Acid value of vinyl polymer A>
The acid value of the vinyl polymer A is preferably 30.0 mgKOH/g or less. When it is 30.0 mgKOH/g or less, the crystallization of the vinyl polymer A is less likely to be inhibited. It is more preferably 20.0 mgKOH/g or less. There is no particular lower limit, and it is 0 mgKOH/g or more. The acid value of the vinyl polymer A can be adjusted by the type and amount of the monomer unit A to be incorporated, the type and amount of the monomer unit B to be incorporated, and the like.

<Mw of vinyl polymer A>
The vinyl polymer A preferably has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 10,000 to 200,000. More preferably, it is 20,000 to 150,000, more preferably, 20,000 to 100,000, and even more preferably, it is 20,000 to 50,000. When the Mw is within the above range, elasticity at around room temperature is easily maintained. In addition, the vinyl polymer A is preferably a polymer soluble in THF.

<Melting Point of Vinyl Polymer A>
The melting point of the vinyl polymer A is preferably 50° C. to 80° C. When the melting point is 50° C. or higher, a toner having excellent heat-resistant storage stability is easily obtained. Therefore, the melting point is preferably 50° C. or higher, and more preferably 53° C. or higher. When the melting point is 80° C. or lower, a toner having excellent low-temperature fixing property is easily obtained. Therefore, the melting point is preferably 80° C. or lower, and more preferably 70° C. or lower. The melting point of the vinyl polymer A can be adjusted by the type and amount of the monomer unit A to be incorporated, the type and amount of the monomer unit B to be incorporated, and the like.

<Other aspects of vinyl polymer A>
The content of the vinyl polymer A in the resin component is 50.0 to 90.0% by mass. When the content is 50.0% by mass or more, a toner having excellent low-temperature fixing properties is easily obtained. Therefore, the content is 50.0% by mass or more, and more preferably 55.0% by mass or more. When the content is 90.0% by mass or less, the elasticity of the toner is unlikely to become too small, and the amorphous polyester P is easily contained in the resin component. Therefore, the content is preferably 90.0% by mass or less, more preferably 75.0% by mass or less, and even more preferably 65.0% by mass or less.

The vinyl polymer A may be contained in one or more types in the resin component. When multiple types of vinyl polymer A are contained in the resin component, the total content of the polymers corresponding to vinyl polymer A is regarded as the content of vinyl polymer A.

The vinyl polymer A may be part of a hybrid resin (a hybrid resin of vinyl polymer A and a resin other than a vinyl resin) to which another resin such as polyester is bonded. In this case, the content of vinyl polymer A in the hybrid resin is 50% by mass or more. The content is more preferably 80% by mass or more, and more preferably 95% by mass or more. Examples of the bond include a covalent bond.

A domain matrix structure is observed in the cross section of the toner particle, and the matrix contains vinyl polymer A. By containing vinyl polymer A in the matrix, vinyl polymer A is more likely to be present throughout the entire toner particle, making it easier to obtain a toner with excellent low-temperature fixing properties. It is more preferable that the main component of the matrix is vinyl polymer A.

<Amorphous polyester P>
The resin component according to the present disclosure contains an amorphous polyester P, and when the SP value of the vinyl polymer A is SP _A1 (J/cm ³ ) ^0.5 and the SP value of the amorphous polyester P is SP _P1 (J/cm ³ ) ^0.5 , SP _A1 and SP _P1 satisfy the following formula (2).
3.0 (J/cm ³ ) ^0.5 ≦SP _P1 -SP _A1 ≦8.0 (J/cm ³ ) ^0.5 ...(2)
When SP _P1 -SP _A1 is 3.0 or more, the compatibility of the vinyl polymer A and the amorphous polyester P is easily maintained, and a domain matrix structure in which the vinyl polymer A is contained in the matrix and the amorphous polyester P is contained in the domain is easily formed. This makes it easier for the vinyl polymer A to aggregate, and it is easy to obtain a toner having excellent low-temperature fixing properties. In addition, when the amorphous polyester P is easily aggregated, it is easy to form a structure in which the wax is encapsulated in the domain. In addition, when SP _P1 -SP _A1 is 8.0 or less, the compatibility of the vinyl polymer A and the amorphous polyester P is unlikely to become too small, and it is difficult to obtain a toner containing only the vinyl polymer A or a toner containing only the amorphous polyester P, which is preferable. More preferably, SP _P1 -SP _A1 is 5.0 or less.

In addition, it is preferable that SP _A1 satisfies the following formula (7).
19.0 (J/cm ³ ) ^0.5 ≦SP _A1 ≦24.0 (J/cm ³ ) ^0.5 ...(7)
When SP _A1 is in the above range, it is presumed that the vinyl polymer A and the wax are less compatible with each other, and the wax is more likely to bleed onto the toner surface during fixing. As a result, a toner having excellent abrasion resistance is more likely to be obtained, which is preferable.

In addition, it is preferable that SP _P1 satisfies the following formula (8).
23.0 (J/cm ³ ) ^0.5 ≦SP _P1 ≦29.0 (J/cm ³ ) ^0.5 ...(8)

The content of amorphous polyester P in the resin component is 10.0 to 49.0% by mass. If the content is 10.0% by mass or more, the resin component contains a sufficient amount of amorphous polyester P, and it is easy to form a structure in which wax is encapsulated in the domain containing amorphous polyester P. Therefore, it is 10.0% by mass or more, preferably 20.0% by mass or more, and more preferably 35.0% by mass or more. If the content is 49.0% by mass or less, it is easy to obtain a toner in which the main binder and matrix of the toner are vinyl polymer A, and it is easy to obtain a toner with excellent low-temperature fixing properties. Therefore, it is 49.0% by mass or less, and preferably 45.0% by mass or less.

<THF insoluble matter in amorphous polyester P>
The content of the THF insoluble matter contained in the amorphous polyester P is preferably 50% by mass or more. If the content is 50% by mass or more, it is presumed that the compatibility of the amorphous polyester P with the vinyl polymer A and the wax is likely to be reduced, and the above-mentioned domain matrix structure is likely to be formed. Therefore, the content is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 85% by mass or more. There is no particular limit to the upper limit, but it is preferably 95% by mass or less. The content of the THF insoluble matter can be controlled by controlling the molecular weight of the amorphous polyester P.

<Peak Top Molecular Weight of Amorphous Polyester P>
The peak top molecular weight (Mp) of the THF soluble portion of the amorphous polyester P is preferably 10,000 to 250,000. When the Mp is 10,000 or more, it is presumed that the compatibility of the vinyl polymer A and the amorphous polyester P is easily maintained, and a toner having excellent low-temperature fixing property and abrasion resistance is easily obtained. Therefore, the Mp is preferably 10,000 or more, more preferably 80,000 or more, more preferably 100,000 or more, and even more preferably 150,000 or more. In addition, when the Mp is 250,000 or less, the compatibility of the vinyl polymer A and the amorphous polyester P is unlikely to become too small, and a toner containing only the vinyl polymer A or a toner containing only the amorphous polyester P is unlikely to be obtained, which is preferable. Therefore, the Mp is preferably 250,000 or less, and more preferably 210,000 or less.

<Production Example of Amorphous Polyester P>
The amorphous polyester P can be produced by carrying out a polycondensation reaction using a polyhydric alcohol and a polycarboxylic acid (or a polycarboxylic acid derivative) as monomers. Examples of the derivatives of the polycarboxylic acid include the acid anhydrides and acid halides of the polycarboxylic acid, and lower alkyl esters of the polycarboxylic acid. The polyhydric alcohol and the polycarboxylic acid are preferably divalent and/or trivalent.

Polyhydric alcohols as monomers include the following:

Examples of dihydric alcohol components include bisphenol derivatives. Examples include 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, and polyoxypropylene (6)-2,2-bis(4-hydroxyphenyl)propane.

Other alcohol components include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 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.

Among these, it is preferable to use bisphenol derivatives as monomers.

Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene. Of these, glycerol, trimethylolpropane, and pentaerythritol are preferred. These dihydric alcohols and trihydric or higher alcohols may be used alone or in combination.

Polycarboxylic acids as monomers include the following:

Examples of divalent carboxylic acid components 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, n-dodecenylsuccinic acid, or derivatives thereof are preferably used.

Examples of trivalent or higher carboxylic acids include 1,2,4-benzenetricarboxylic 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, and derivatives thereof. Of these, 1,2,4-benzenetricarboxylic acid, i.e., trimellitic acid or derivatives thereof, is particularly preferred. These divalent carboxylic acids and trivalent or higher carboxylic acids and derivatives thereof may be used alone or in combination.

The method for producing the amorphous polyester P of the present disclosure is not particularly limited. For example, the amorphous polyester P can be produced by putting the above-mentioned alcohol monomer and carboxylic acid monomer into a reaction vessel and causing a condensation polymerization reaction. The temperature during polymerization is not particularly limited, but is preferably in the range of 180°C to 290°C. When obtaining the amorphous polyester P by polymerization, for example, a polymerization catalyst such as a titanium-based catalyst, a tin-based catalyst, zinc acetate, antimony trioxide, or germanium dioxide can be used. Among these, it is preferable to obtain the amorphous polyester P by polymerization using a tin-based catalyst.

<Various additives>
In addition to the resin component and wax, the toner may contain, if necessary, one or more additives selected from a colorant, a magnetic material, a charge control agent, a fluidizing agent, and the like.

<Coloring Agent>
The colorants 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 colorants, pigments may be used alone, or dyes and pigments may be used in combination. From the viewpoint of image quality of full-color images, it is preferable to use dyes and pigments in combination.

Magenta colorants include the following:

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.

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; 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.

Cyan colorants 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 pigment with 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, C.I. Solvent Blue 70.

Yellow colorants include the following:

C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; C.I. Vat Yellow 1, 3, 20, C.I. Solvent Yellow 162.

These colorants can be used alone or in mixtures, or even in the form of a solid solution.

The content of the colorant is preferably 0.1 to 30.0 parts by mass relative to the mass of the resin component.

<Charge Control Agent>
The charge control agent is not particularly limited, but is preferably a metal compound of an aromatic carboxylic acid, since it is colorless, the toner can be charged quickly, and a constant charge amount can be stably maintained.

Examples of negative charge control agents include:

Metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds having sulfonic acid or carboxylic acid on the side chain. Polymeric compounds having sulfonate salts or sulfonic acid esters on the side chain. Polymeric compounds having carboxylate salts or carboxylate esters on the side chain. Boron compounds, urea compounds, silicon compounds, calixarenes, etc.

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 to 10.0 parts by mass, and more preferably 0.5 parts by mass to 10.0 parts by mass, per 100 parts by mass of the resin component.

<Inorganic fine particles>
The inorganic fine particles may be added internally to the toner particles, or may be mixed with the toner as an external additive. Examples of the inorganic fine particles include silica fine particles, titanium oxide fine particles, alumina fine particles, and fine particles of their double oxides. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferred for improving flowability and uniform charging.

The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

The content of the external additive is preferably 0.1 to 10.0 parts by mass per 100 parts by mass of the toner particles. A mixer such as a Henschel mixer can be used to mix the toner particles and the external additive.

<Developer>
The toner can be used as a one-component developer, but in order to further improve dot reproducibility and provide stable images over a long period of time, it is preferable to mix the toner with a magnetic carrier and use it as a two-component developer.

Examples of such magnetic carriers include the following:

Iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earths, alloy particles thereof, and oxide particles thereof. Other examples include magnetic materials such as ferrite, and magnetic material-dispersed resin carriers (so-called resin carriers) that contain magnetic materials and binder resins that hold the magnetic materials in a dispersed state.

When the toner is mixed with a magnetic carrier to be used as a two-component developer, the mixing ratio of the magnetic carrier is preferably 2% by mass to 15% by mass, and more preferably 4% by mass to 13% by mass, in terms of the toner concentration in the two-component developer.

<Toner Manufacturing Method>
The toner of the present disclosure may be produced by any method, including a pulverization method, a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, and a dispersion polymerization method.

The toner of the present disclosure is preferably produced by a pulverization method. That is, the method for producing the toner of the present disclosure is
a first melt-kneading step of melt-kneading a material containing the amorphous polyester P and the wax to obtain a first melt-kneaded product;
a first pulverization step of pulverizing the first molten kneaded product to obtain a first powder;
a second melt-kneading step of melt-kneading the first powder and a material containing the vinyl polymer A to obtain a second melt-kneaded product;
The toner manufacturing method preferably includes a second pulverization step of pulverizing the second molten kneaded product to obtain a second powder.

When the manufacturing method is the above-mentioned method, it is possible to adjust the raw materials charged during melt kneading, the temperature, shaft configuration, rotation, kneading area, clearance, and residence time. This is preferable because it allows control of the domain matrix structure, the domain diameter of the amorphous polyester P, and the wax inclusion rate in the domain.

Similarly, the toner of the present disclosure is preferably produced by an emulsion aggregation method.
obtaining a first microparticle dispersion containing an amorphous polyester P and a wax;
obtaining a second fine particle dispersion containing a vinyl polymer A;
The toner manufacturing method preferably includes a step of adding an aggregating agent to the first fine particle dispersion and the second fine particle dispersion to form aggregate particles.

When the manufacturing method is the above-mentioned method, it is possible to adjust the raw materials, solvent ratio, and emulsification conditions when preparing the raw material microparticle dispersion and when forming the aggregate particles. This is preferable because it allows the domain matrix structure, the domain diameter of the amorphous polyester, and the inclusion rate of the wax in the domain to be controlled.

<Crushing method>
The procedure for producing the toner by the pulverization method will be described below.

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

Next, the mixed materials are melt-kneaded to disperse the wax and the like in the resin components. 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 a single-screw or twin-screw extruder is preferably used because of its advantage of being able to produce continuously. Examples include a KTK type twin-screw extruder (manufactured by Kobe Steel, Ltd.), a TEM type 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 a Kneadex (manufactured by Nippon Coke and Engineering Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading may be rolled with a twin roll or the like, and cooled with water or the like in a cooling process.

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

Here, in order to facilitate the inclusion of wax in the domains containing the amorphous polyester P, it is preferable to first melt-knead and pulverize the amorphous polyester P and wax as the first melt-kneading to obtain a first powder. Then, it is preferable to melt-knead and pulverize the first powder and the vinyl polymer A as the second melt-kneading. By carrying out this first melt-kneading, the amorphous polyester P encapsulating the wax and the vinyl polymer A can be melt-kneaded, and the contact points between the vinyl polymer A and the wax can be greatly reduced. As a result, it is easy to obtain a toner in which the wax is encapsulated in the amorphous polyester P.

Then, if necessary, the mixture is classified using a classifier or sieve such as an inertial classification system such as Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal classification system such as Turboplex (manufactured by Hosokawa Micron Corporation), TSP Separator (manufactured by Hosokawa Micron Corporation), or Faculty (manufactured by Hosokawa Micron Corporation).

If necessary, external additives are added to the surface of the toner particles. Methods for adding external additives include blending the classified toner with a predetermined amount of various external additives, and stirring and mixing them using a mixing device such as a double con mixer, V-type mixer, drum mixer, super mixer, Henschel mixer, Nauta mixer, Mechano Hybrid (manufactured by Nippon Coke & Engineering Co., Ltd.), or Nobilta (manufactured by Hosokawa Micron Corporation) as an external additive machine.

<Various measurement methods, etc.>
Various measurement methods are explained below.

<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 portion (amorphous polyester P) is separated from the insoluble portion (vinyl polymer A, wax, colorant, inorganic fine particles, etc.).

Second separation: The insoluble matter obtained in the first separation (vinyl polymer A, wax, colorant, inorganic fine particles, etc.) is dissolved in MEK at 100°C, and the soluble matter (vinyl polymer A, wax) is separated from the insoluble matter (colorant, inorganic fine particles, etc.).

Third separation: The soluble fraction (vinyl polymer A, wax) obtained in the second separation is dissolved in chloroform at 23°C, and the soluble fraction (vinyl polymer A) is separated from the insoluble fraction (wax).

<Method for measuring content of monomer units in polymer>
The content of the monomer units in the polymer is 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.

As an example of the calculation, the content ratio of monomer unit A in vinyl polymer A is shown below.

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

Similarly, from the peaks attributable to the components of the monomer unit B, 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 the monomer unit C is contained, a peak that is independent of the peaks that are assigned to the components of the monomer unit C and other monomer units is selected, and an integral value _S3 of this peak is calculated.

The content of the monomer unit A in the vinyl polymer A is determined using the integral values _S1 , _S2 , and _S3 as follows: Here, _n1 , n2 _{, and n3} are the numbers of hydrogen atoms in the constituent elements to which the peaks of interest for each site belong.
Content (mol %) of monomer unit A in vinyl polymer A=
{(S ₁ /n ₁ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ ))}×100
The contents of the monomer unit B and the monomer unit C are calculated in the same manner.

In the case where the vinyl polymer A uses a polymerizable monomer containing no hydrogen atoms in the constituent elements other than the vinyl group, the measurement is performed in single pulse mode using ¹³ C-NMR with ¹³ C as the measurement nucleus, and the calculation is performed in the same manner using ¹ H-NMR.

In addition, when a toner is used as a measurement sample, the peaks of wax and other resins may overlap, and independent peaks may not be observed. This may result in the inability to calculate the content ratio of various monomer units in vinyl polymer A. In such cases, vinyl polymer A' can be produced by producing an equivalent toner without using wax or other resins, and vinyl polymer A' can be regarded as vinyl polymer A and analyzed.

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

For an atom or atomic group in the molecular structure to be calculated, the evaporation energy (Δei) (cal/mol) and molar volume (Δvi) (cm ³ /mol) are obtained from the table in "Polym. Eng. Sci., 14(2), 147-154 (1974)", and (4.184×ΣΔei/ΣΔvi) ^0.5 is set as the SP value (J/cm ³ ) ^0.5 . SP _A1 and SP _P1 are calculated from the configurations of the monomer units contained in the vinyl polymer A and amorphous polyester P used in the production of the toner.

<Method of preparing a sample of a toner particle cross section>
The cross section of a toner particle is prepared in the following manner.

The toner is spread on a cover glass (Matsunami Glass Co., Ltd., square cover glass No. 1) so that it forms a single layer. Then, using an osmium plasma coater (Filgen, OPC80T), an Os film (5 nm) and a naphthalene film (20 nm) are applied to the toner as a protective film. Next, a PTFE tube (Φ1.5 mm x Φ3 mm x 3 mm) is filled with photocurable resin D800 (JEOL Ltd.), and the above cover glass is gently placed on top of the tube so that the toner is in contact with the photocurable resin D800. In this state, light is irradiated to harden the resin, and then the cover glass and tube are removed to form a cylindrical resin with the toner embedded in the outermost surface. Using an ultrasonic ultramicrotome (Leica, UC7), a cutting speed of 0.6 mm/s was used to cut the length of the toner radius (for example, 4.0 m when the weight average particle size (D4) is 8.0 m) from the outermost surface of the cylindrical resin to expose the cross section of the toner. Next, cutting was performed to a film thickness of 250 nm to prepare a thin sample of the toner cross section. By cutting in this manner, a cross section of the center of the toner can be obtained.

<Method of measuring area I _W of wax contained in domain, area S _W of wax present in matrix, and average major axis of wax contained in domain in cross section of toner particle>
In the cross section of a toner particle, the wax area I _W contained in the domain and the wax area S _W not contained in the domain are measured as follows.

The measurements are carried out by mapping oxygen and nitrogen using a scanning transmission electron microscope HD-2700 (Hitachi High-Tech Science Corporation) and an energy dispersive X-ray analyzer EDAX204B.

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 those toner particle cross-sectional images in which the absolute value of the difference between the equivalent circle diameter and the weight average particle diameter (D4) of the toner is within 1.0 μm are observed.
Acceleration voltage: 20 kV
Magnification: 10,000 times

Specifically, the captured images were binarized and calculated using image processing software Image-Pro Plus 5.1J (MediaCybernetics).

First, the toner particle group was extracted, and the size of each extracted toner particle was counted. Specifically, first, in order to extract the toner particle group to be analyzed, the toner particle group was separated from the background. Next, select "Measurement" - "Count/Size" in Image-Pro Plus5.1J. In "Select Brightness Range" in "Count/Size", the brightness range was set to 50 to 255, and the low-brightness carbon tape part that was reflected as the background was excluded, and the toner particle group was extracted. When extracting, in the extraction options of "Count/Size", 4-connection was selected, the smoothness was set to 5, and "Fill Holes" was checked. By the above operation, toner particles located on all boundaries (outer periphery) of the image and toner particles overlapping with other toner particles were excluded from the calculation. Next, in the measurement items of "Count/Size", "Area and Feret's Diameter (Average)" was selected, and the area selection range was set to a minimum of 100 pixels and a maximum of 10,000 pixels, and the toner particles to be analyzed were extracted. One toner particle was selected from the extracted toner particle group, and the size (number of pixels) js of the part of the toner particle that corresponds to the matrix region was calculated using oxygen or nitrogen mapping dots. Similarly, the size (number of pixels) ji of the part that corresponds to the domain region was calculated.

Next, the size (number of pixels) mi of the portion (corresponding to the wax portion) where the oxygen mapping dots contained within the domain region were not continuous was determined. Similarly, the size (number of pixels) ms of the portion (corresponding to the wax portion) where the oxygen mapping dots not contained within the domain region were not continuous was determined. The wax areas sw and iw were calculated from the obtained ms and mi values and the area of one pixel.

Next, the same process was performed on each toner particle of the extracted toner particle group until the number of selected toner particles reached 100, and the average value of sw and the average value of iw were taken as the values of _Sw and _Iw according to the present disclosure.

If the number of toner particles in one field of view was less than 100, the same procedure was repeated for the toner particle projection images in another field of view.

The average long diameter of the wax contained in the domain is calculated as follows:

In the above operation, the longest distance between the two pixels in the part (corresponding to the wax part) where the oxygen mapping dots are not continuous and contained in the domain area is taken as the long diameter of one wax domain. The average value of these contained in the toner particle is then calculated. This average value is calculated for 20 toner particles, and the arithmetic average of these is taken as the average long diameter of the wax contained therein.

<Method for measuring the content of tetrahydrofuran (THF) insoluble matter>
1.5 g of a sample for measuring THF-insoluble content is precisely weighed (W ₁ g) and placed in a pre-weighed cylindrical filter paper (product name: No. 86R, size 28×100 mm, manufactured by Advantec Toyo Co., Ltd.) and set in a Soxhlet extractor.

Extraction is performed for 18 hours using 200 mL of tetrahydrofuran (THF) as the solvent, with the reflux speed set so that the solvent extraction cycle occurs approximately once every 5 minutes.

After the extraction, the thimble was removed and air-dried, and then vacuum-dried at 40° C. for 8 hours. The mass of the thimble containing the extraction residue was weighed, and the mass of the extraction residue (W ₂ g) was calculated by subtracting the mass of the thimble. The THF-insoluble content was calculated by the following formula (A).
THF insoluble matter (mass %)=( _W2 / _W1 )×100 (A)

<Measurement of weight average molecular weight of amorphous polyester by GPC>
The molecular weight of the THF-soluble portion of the amorphous polyester is measured by gel permeation chromatography (GPC) as follows.

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

When calculating the molecular weight of the sample, a molecular weight calibration curve is used that is created using standard polystyrene resins (e.g., trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500" manufactured by Tosoh Corporation).

<Measurement of molecular weight of polymer A by GPC>
The molecular weight (Mw) of the polymer A is measured by gel permeation chromatography (GPC) as follows.

First, polymer A is dissolved in toluene at 100° C. for 1 hour. The obtained solution is then filtered through a solvent-resistant membrane filter "Maeshoridisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in toluene is about 0.1% by mass. This sample solution is used to perform measurements under the following conditions.
Apparatus: HLC-8121GPC/HT (manufactured by Tosoh Corporation)
Column: TSKgel GMHHR-H HT (7.8 cm ID x 30 cm) in duplicate (manufactured by Tosoh Corporation)
Detector: High temperature RI
Temperature: 135°C
Solvent: toluene Flow rate: 1.0 mL/min
Sample: 0.4 mL of 0.1% sample injected

The molecular weight of the sample is calculated using a molecular weight calibration curve created using monodisperse polystyrene standard samples. The molecular weight is then calculated using a conversion formula derived from the Mark-Houwink viscosity formula to convert it into polyethylene.

The present disclosure will be specifically described below with reference to examples, but these are not intended to limit the present disclosure in any way. In the following formulations, parts are by weight unless otherwise specified.
In the examples, the respective measurement results were obtained by the measurement methods described above.

<Production Example of Polymer A1>
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 (polymerizable monomer A) 67.0 parts (25.3 mol%)
Acrylonitrile (polymerizable monomer B) 22.0 parts (59.5 mol%)
Styrene (polymerizable monomer C) 11.0 parts (15.2 mol%)
Polymerization initiator: t-butyl peroxypivalate (Perbutyl PV, manufactured by NOF Corp.) 0.5 parts

The above solvent and monomer composition were put 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, obtaining a solution in which the polymer of the monomer composition was dissolved in toluene. The solution was then cooled to 25°C, and the solution was then poured into 1000.0 parts of methanol while stirring to precipitate the methanol insoluble matter. The obtained methanol insoluble matter was filtered off, washed with methanol, and vacuum dried at 40°C for 24 hours to obtain polymer A1. The physical properties of polymer A1 are shown in Tables 2 and 3.

<Production Examples of Polymers A2 to A12>
Polymers A2 to A12 were obtained in the same manner as in the production example of polymer A1, except that the polymerizable monomers and the parts thereof were changed as shown in Table 1. The physical properties of polymers A1 to A12 are shown in Tables 2 and 3.

Polymers A1 to A12 were crystalline resins that had clear endothermic peaks in DSC measurements. Polymers A1 to A12 were also soluble in THF.

The abbreviations in Tables 1 to 3 are as follows.
BEA: Behenyl acrylate STA: Stearyl acrylate MYA: Myrisil acrylate HA: Hexadecyl acrylate AN: Acrylonitrile VA: Vinyl acetate AA: Acrylamide St: Styrene *In Table 1, hexadecyl acrylate does not fall under polymerizable monomer A, but is listed in the column for polymerizable monomer A.

※表２において、ヘキサデシルアクリレートに対応するユニットは、モノマーユニットＡに該当しないが、モノマーユニットＡの列に記載している。

* In Table 2, the unit corresponding to hexadecyl acrylate is not a monomer unit A, but is listed in the column for monomer unit A.

<Production Example of Amorphous Polyester P1>
Bisphenol A PO adduct (average number of moles added: 2.0): 37.0 parts (13.6 mol%)
Ethylene glycol: 13.0 parts (35.5 mol%)
Terephthalic acid: 50.0 parts (50.9 mol%)
Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass The above materials were weighed and placed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet tube, and a thermocouple. The atmosphere in the flask was then replaced with nitrogen gas, and the temperature was gradually raised with stirring, and the mixture was allowed to react for 2 hours at 200°C while stirring.

The pressure in the reaction vessel was then lowered to 8.3 kPa, and the reaction was continued for 5 hours while maintaining the temperature at 200°C. Once it was confirmed that the softening point, measured according to ASTM D36-86, had reached 140°C, the temperature was lowered to stop the reaction, yielding amorphous polyester P1. The peak top molecular weight (Mp) of the resulting amorphous polyester P1 was 200,000. The physical properties of amorphous polyester P1 are shown in Table 5.

<Production Examples of Amorphous Polyesters P2 to P27>
Amorphous polyesters P2 to P27 were obtained in the same manner as in Production Example of amorphous polyester P1, except that the types and parts of each polymerizable monomer were changed as shown in Table 4 and the reaction conditions were adjusted so as to obtain the molecular weights (Mp) shown in Table 5. The physical properties of amorphous polyesters P2 to P27 are shown in Table 5.

The abbreviations in Tables 4 and 5 are as follows.
PO2: Bisphenol A propylene oxide adduct (average number of moles added: 2.0)
EO2: Bisphenol A ethylene oxide adduct (average number of moles added: 2.0)
ED: ethylene glycol THM: pentaerythritol TPA: terephthalic acid AA: adipic acid

<Production Example of Toner 1>
Amorphous polyester P1: 40 parts Hydrocarbon wax (HNP-51, manufactured by Nippon Seiro): 5 parts Colorant (cyan pigment, manufactured by Dainichi Seika Chemicals: Pigment Blue 15:3): 10 parts The above materials were mixed using a Henschel mixer (FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 1500 rpm for a rotation time of 3 minutes, and then kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at a temperature of 150° C. The kneaded product obtained was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain coarsely pulverized product 1.

Next, the following materials were mixed using a Henschel mixer (FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 1500 rpm for a rotation time of 5 minutes, and then kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Co., Ltd.) set at a temperature of 120° 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.
・Polymer A1: 60 parts ・Crushed material 1: 55 parts

The resulting coarsely crushed material was finely pulverized using a mechanical grinder (T-250, manufactured by Turbo Kogyo Co., Ltd.). It was then classified using a Faculty grinder (F-300, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions were a classifying rotor rotation speed of 11,000 rpm and a dispersing rotor rotation speed of 7,200 rpm.

Next, the following materials were mixed in a Henschel mixer (FM-75, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 1900 rpm for a rotation time of 10 minutes to obtain Toner 1. The obtained physical properties are shown in Table 6.
Toner particles 1: 100 parts Silica fine particles A: 4 parts of fumed silica surface-treated with hexamethyldisilazane (median diameter (D50) based on number: 120 nm) Small particle size inorganic fine particles: 1 part of titanium oxide fine particles surface-treated with isobutyltrimethoxysilane (median diameter (D50) based on number: 10 nm)

<Production Examples of Toners 3 to 37>
Toners 3 to 37 were obtained in the same manner as in Production Example 1 of Toner 1, except that the type and amount of Polymer A and the type and amount of Amorphous Polyester P were changed as shown in Table 6. The physical properties obtained are shown in Table 6.

The amount of THF insoluble matter in Table 6 is the ratio of the mass of the THF insoluble matter of the amorphous polyester to the total mass of the amorphous polyester contained in the toner.

<Production Example of Polymer A1 Fine Particle Dispersion>
Toluene (manufactured by Wako Pure Chemical Industries, Ltd.): 300 parts Polymer A1: 100 parts The above materials were weighed, mixed, and dissolved at 90° C. to obtain a toluene solution.

Separately, 5.0 parts of sodium dodecylbenzenesulfonate and 10.0 parts of sodium laurate were added to 700 parts of ion-exchanged water and dissolved by heating at 90°C to obtain an aqueous solution.

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). The mixture was then 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 (polymer A1 microparticle dispersion) with a concentration of polymer A1 microparticles of 20% by mass.

The 50% particle size (D50) based on volume distribution of the Polymer A1 microparticles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.10 μm.

<Production Example of Hydrocarbon Wax-Containing Amorphous Polyester P2 Fine Particle Dispersion>
Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.): 300.0 parts Amorphous polyester P2: 100.0 parts Hydrocarbon wax (HNP-51, manufactured by Nippon Seiro Co., Ltd.): 12.5 parts Anionic surfactant NEOGEN RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.): 0.5 parts The above materials were weighed, mixed, and dissolved.

Next, 20.0 parts of 1 mol/L ammonia water was added and stirred at 4000 rpm using an ultra-high speed 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 hydrocarbon wax-containing amorphous polyester P2 microparticles. Thereafter, tetrahydrofuran was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (hydrocarbon wax-containing amorphous polyester P2 microparticle dispersion) with a microparticle concentration of 20% by mass.

The 50% particle size (D50) based on volume distribution of the hydrocarbon wax-containing amorphous polyester P1 microparticles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.10 μm.

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

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.

<Production Example of Toner 2>
Polymer A1 microparticle dispersion: 300 parts Hydrocarbon wax-containing amorphous polyester P2 microparticle dispersion: 225 parts Colorant microparticle dispersion: 50 parts Ion exchange water: 160 parts The above materials are put into a round stainless steel flask, mixed, and then 10 parts of 10% magnesium sulfate aqueous solution are added.Then, using a homogenizer Ultra Turrax T50 (manufactured by IKA Co., Ltd.), the mixture is dispersed at 5000 r/min for 10 minutes.Then, the mixture is heated to 58 ° C. in a heating water bath using a stirring blade while appropriately adjusting the rotation speed so that the mixture is stirred.

The volume average particle size of the formed aggregated particles was appropriately confirmed using a Coulter Multisizer III, and when aggregated particles with a volume average particle size of approximately 6.00 μm were formed, 100 parts of sodium ethylenediaminetetraacetate was added. After that, the mixture was heated to 75°C while continuing to stir. The aggregated particles were then fused by holding at 75°C for 1 hour.

Then, it was cooled to 50°C and held there for 3 hours to promote crystallization of the polymer.

Then, to remove polyvalent metal ions derived from the coagulant, the mixture was washed with a 5% aqueous solution of sodium ethylenediaminetetraacetate while being kept at 50°C.

Then, it was cooled to 25°C, filtered and separated into solid and liquid, and then washed with ion-exchanged water. After washing, it was dried using a vacuum dryer to obtain toner particles 2 with a weight average particle size (D4) of approximately 6.07 μm.

Next, the following materials were mixed in a Henschel mixer (FM-75, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 1900 rpm for a rotation time of 10 minutes to obtain Toner 2. The obtained physical properties are shown in Table 6.
Toner particles 2: 100 parts Silica fine particles A: 4 parts of fumed silica surface-treated with hexamethyldisilazane (median diameter (D50) based on number: 120 nm) Small particle size inorganic fine particles: 1 part of titanium oxide fine particles surface-treated with isobutyltrimethoxysilane (median diameter (D50) based on number: 10 nm)

<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 weight of formaldehyde, 10% by weight of methanol, 50% by weight of water)
Magnetite treated with the above silane compound 1: 58% by mass
Magnetite 2 treated with the above silane compound: 26% by mass
100 parts of the above material, 5 parts of a 28% by mass aqueous ammonia solution, and 20 parts of water were placed in a flask, and the mixture was heated to 85° C. over 30 minutes while stirring and mixing, and then held for 3 hours to cause a polymerization reaction, thereby hardening the resulting phenolic resin.

Then, the hardened phenolic resin was cooled to 30°C, and water was added. The supernatant liquid was removed, and the precipitate was washed with water and then air-dried. This was then dried at 60°C under reduced pressure (5 mmHg or less) to obtain spherical magnetic carrier 1 with dispersed magnetic material. The 50% particle size (D50) based on volume was 34.21 μm.

<Production Example of Two-Component Developer 1>
92.0 parts of the magnetic carrier 1 and 8.0 parts of the toner 1 were mixed in a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain a two-component developer 1.

<Production Examples of Two-Component Developers 2 to 37>
In the production example of two-component developer 1, the same operation was carried out except that the type of toner was changed as shown in Table 7, to obtain two-component developers 2 to 37.

Example 1
Using the above two-component developer 1, toner 1 was evaluated as follows.

<Evaluation of Abrasion Resistance of Toner>
To evaluate the abrasion resistance of the toner, a modified digital commercial printer (product name: imageRUNNER ADVANCE C5560, manufactured by Canon Inc.) was used as the image forming apparatus. The modification of the apparatus was such 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. In addition, the two-component developer was removed from inside the developing unit at the cyan position, and two-component developer 1 was placed in the developing unit.

First, one evaluation image was output under the following conditions.
White paper (product name: Image Coat Gloss 158 (158.0 g/m ² ), Canon Marketing Japan Inc.)
Toner loading on paper: 0.05 mg/ ^cm2
(Adjusted by DC voltage V _DC of developer carrier, charging voltage V _D of electrostatic latent image carrier, and laser power)
Evaluation image: A 3 cm x 15 cm image is placed in the center of the A4 paper. Fixing test environment: Normal temperature and humidity environment (temperature 23°C / humidity 50% RH (hereinafter N/N))
Fixing temperature: 180°C
Process speed: 377 mm/sec

After that, a new evaluation paper was placed on top of the output evaluation image, and a Gakushin-type friction fastness tester (product name: AB-301, manufactured by Tester Sangyo Co., Ltd.) was used to apply a load of 0.5 kgf from above the image portion of the evaluation image, and rubbed back and forth 10 times. After that, the reflectance of the image portion of the evaluation image and the rubbed portion was measured for the new evaluation paper used during the rubbing. The reflectance was also measured for the new evaluation paper that was not used during the rubbing. A reflectometer (product name: REFLECTOMETER MODEL TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.) was used to measure the reflectance.

The difference in reflectance before and after rubbing was calculated using the following formula. The evaluation results are shown in Table 7. A reflectance difference of 2.5% or less was determined to be one in which the effects of the present disclosure were obtained.
Difference in reflectance (%) = reflectance (%) of new evaluation paper that was not used during rubbing - reflectance (%) of the image part of the evaluation image and the rubbed part

<Evaluation of Low-Temperature Fixability of Toner>
Using the image forming apparatus used in the evaluation of the abrasion resistance of the toner, an evaluation image was output under the following conditions.
White paper (product name: GFC-081 (81.0 g/m ² ), Canon Marketing Japan Inc.)
Toner loading on paper: 0.70 mg/ ^cm2
(Adjusted by DC voltage V _DC of developer carrier, charging voltage V _D of electrostatic latent image carrier, and laser power)
Evaluation image: A 2 cm x 5 cm image was placed in the center of the A4 paper. Test environment: Low temperature and low humidity environment: Temperature 15°C / Humidity 10% RH (hereinafter referred to as "L/L")
Fixing temperature: 150°C
Process speed: 377 mm/sec

First, the image density of the image portion of the evaluation image was measured using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite Corporation). Next, Silbon paper was placed on the image portion where the image density was measured, and a load of 4.9 kPa (50 g/cm ² ) was applied from above and rubbed back and forth five times, and the image density of the image portion was measured again.

The rate of decrease in image density before and after friction was calculated using the following formula, and used as an evaluation index for the low-temperature fixability of the toner. The evaluation results are shown in Table 7. When the rate of decrease in image density was 5.5% or less, it was determined that the effects of the present disclosure were obtained.
Image density decrease rate (%)={(image density before friction−image density after friction)/image density before friction}×100

<Examples 2 to 29 and Comparative Examples 1 to 8>
Except for using two-component developers 2 to 37, the evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 7.

1 toner particle 2 matrix containing vinyl polymer A 3 domain containing amorphous polyester P 4 wax contained in domain 5 wax not contained in domain

Claims (15)

A toner having toner particles containing a resin component and a hydrocarbon wax,
The resin component is
(1) A vinyl polymer A which is a vinyl resin containing a monomer unit A represented by the following formula (A) and a monomer unit B having an SP value (SP _B [J/cm ³ ] ^0.5 ) of 21.00 (J/cm ³ ) ^0.5 or more ;
(2) an amorphous polyester P, which is the only component contained as an amorphous polyester in the resin component ; and
Contains
The vinyl polymer A is a crystalline resin,
The content of the vinyl polymer A in the resin component is 50.0 to 90.0% by mass,
the content of the monomer unit A in the vinyl polymer A is 20.0 to 90.0% by mass,
The content of the amorphous polyester P in the resin component is 10.0 to 49.0 mass %,
When the SP value of the vinyl polymer A is SP _A1 (J/cm ³ ) ^0.5 and the SP value of the amorphous polyester P is SP _P1 (J/cm ³ ) ^0.5 , the SP _A1 and the SP _P1 satisfy the following formula (2):
In the cross section of the toner particle,
(i) a domain matrix structure composed of a matrix containing the vinyl polymer A and a domain containing the amorphous polyester P is observed,
(ii) When the area of the wax contained in the domain is _IW and the area of the wax not contained in the domain is _SW ,
The _Iw and the _Sw satisfy the following formula (3):
A toner characterized by:
3.0 (J/cm ³ ) ^0.5 ≦SP _P1 -SP _A1 ≦8.0 (J/cm ³ ) ^0.5 ...(2)
0.00≦S _W /I _W ≦0.70...(3)

(In formula (A), ^R1 represents H or _CH3 , and ^R2 represents an alkyl group having 18 to 36 carbon atoms.) The toner according to claim 1 , wherein the I _w and the S _w satisfy the following formula (4):
0.00≦S _W /I _W ≦0.30...(4) The toner according to claim 1 or 2, wherein the content of the monomer unit B in the vinyl polymer A is 1.0 to 70.0% by mass. The toner according to any one of claims 1 to 3, wherein the monomer unit B is at least one monomer unit selected from the group consisting of a monomer unit represented by the following formula (B1) and a monomer unit represented by the following formula (B2):

(In the formulas (B1) and (B2),
X represents a single bond or an alkylene group having 1 to 6 carbon atoms;
R ⁴ represents a cyano group (-C≡N), -C(=O)NHR ⁷ (R ⁷ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)), a hydroxy group, -COOR ⁸ (R ⁸ is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms), -NHCOOR ⁹ (R ⁹ is an alkyl group having 1 to 4 carbon atoms), -NH-C(=O)-NH(R ¹⁰ ) ₂ (R ¹⁰ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -COO(CH ₂ ) ₂ NHCOOR ¹¹ (R ¹¹ is an alkyl group having 1 to 4 carbon atoms), or -COO(CH ₂ ) ₂ -NH-C(=O)-NH(R ¹² ) ₂ (R ¹² is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms); R ⁶ represents an alkyl group having 1 to 4 carbon atoms, and R ³ and R ⁵ each independently represent a hydrogen atom or CH ₃ . The toner according to any one of claims 1 to 4, wherein the wax content in the toner particles is 1.0 to 10.0% by mass. In the cross section of the toner particle,
6. The toner according to claim 1, wherein the wax contained in the domain has an average major axis of 20 to 100 nm. The toner according to any one of claims 1 to 6, wherein the SP _A1 satisfies the following formula (7):
19.0 (J/cm ³ ) ^0.5 ≦SP _A1 ≦24.0 (J/cm ³ ) ^0.5 ...(7) The toner according to any one of claims 1 to 7, wherein the content of THF-insoluble matter contained in the amorphous polyester P is 50% by mass or more. The vinyl polymer A further has a monomer unit C,
The toner according to any one of claims 1 to 8, wherein the monomer unit C is at least one monomer unit selected from the group consisting of a monomer unit represented by the following formula (C1) and a monomer unit represented by the following formula (C2):

(In formula (C2), R ¹³ represents H or CH _3. ) The toner according to claim 9, wherein the content of the monomer unit C in the vinyl polymer A is 1.0 to 30.0% by mass. The toner according to any one of claims 1 to 10, wherein the peak top molecular weight (Mp) of the THF-soluble portion of the amorphous polyester P is 10,000 to 250,000. The toner according to any one of claims 1 to 11, wherein the acid value of the vinyl polymer A is 30.0 mg KOH/g or less. A two-component developer containing a toner and a magnetic carrier,
A two-component developer, wherein the toner is the toner according to any one of claims 1 to 12. A method for producing the toner according to any one of claims 1 to 12, comprising the steps of:
The manufacturing method comprises:
a first melt-kneading step of melt-kneading a material containing the amorphous polyester P and a wax to obtain a first melt-kneaded product;
A first pulverization step of pulverizing the first molten kneaded product to obtain a first powder;
a second melt-kneading step of melt-kneading the first powder and a material containing the vinyl polymer A to obtain a second melt-kneaded product;
a second pulverization step of pulverizing the second molten kneaded product to obtain a second powder. A method for producing the toner according to any one of claims 1 to 12, comprising the steps of:
The manufacturing method comprises:
obtaining a first fine particle dispersion containing the amorphous polyester P and a wax;
obtaining a second fine particle dispersion containing the vinyl polymer A;
adding an aggregating agent to the first fine particle dispersion and the second fine particle dispersion to form aggregate particles.

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