JP7599992B2 - toner - Google Patents

Description

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

In recent years, there has been a demand for toners that provide high color stability in printed images during image formation. Specifically, there has been a demand for toners that are less susceptible to change in charge amount in order to stabilize development efficiency even during long-term image output.
For example, in Patent Document 1, an approach is taken to improve the charging stability by using a composite polyester resin in which silicone oil is bonded to a polyester resin.

JP 2002-12657 A

When the copier is operated in an air-conditioned environment, such as after the summer vacation, the charge amount of the toner as described in the above document also decreases, and it was found that further improvement is necessary.
On the other hand, as full-color printers have started to be applied to the printing market, the scratch resistance of printed images is becoming important. When a printed image made of toner that has low adhesion to paper is scratched with a fingernail, the toner may peel off from the paper.
When the above composite polyester is used as the main binder of the toner, the adhesion between the toner and the paper is low due to its low polarity. As a result, "image scratches" occur, and it was found that further improvement is necessary.
The present disclosure provides a toner that has further improved charging stability and excellent image scratch resistance.

、及び－Ｒ^２０ＮＨ_２からなる群から選択されるいずれかの官能基を表し、Ｒ^２０は、単結合又は炭素数１～４のアルキレン基を表し、
平均繰り返し数ｎは１０～８０であり、
該重合体Ａが、下記式（Ｉ）で表される構造を有する第一のモノマーユニット、及び該第一のモノマーユニットとは異なる第二のモノマーユニットを有し、
下記式（Ｉ）中、Ｒ^Ｚ１は、水素原子又はメチル基を表し、Ｒは、炭素数１８～３６のアルキル基を表し、
該重合体Ａ中の該第一のモノマーユニットの含有割合が、該重合体Ａの全モノマーユニ
ットの総モル数を基準として、５．０モル％～６０．０モル％であり、
該重合体Ａ中の該第二のモノマーユニットの含有割合が、該重合体Ａの全モノマーユニットの総モル数を基準として、２０．０モル％～９５．０モル％であり、
該第一のモノマーユニットのＳＰ値をＳＰ１（Ｊ／ｃｍ^３）^０．５とし、該第二のモノマーユニットのＳＰ値をＳＰ２（Ｊ／ｃｍ^３）^０．５とし、該式（Ｂ）で表される構造中の－（Ｓｉ（Ｒ^Ｘ）_２Ｏ）_ｎ－Ｓｉ（Ｒ^Ｘ）_２－で表されるシリコーン部位のＳＰ値をＳＰ３（Ｊ／ｃｍ^３）^０．５としたとき、下記式（１）～（３）を満たすトナーに関する。
ＳＰ１≦１８．４ ・・・（１）
２１．０≦ＳＰ２ ・・・（２）
ＳＰ１－ＳＰ３＜ＳＰ２－ＳＰ１ ・・・（３） The present disclosure provides a toner having toner particles containing a binder resin and a polymer A,
The binder resin contains a polyester resin having a structure represented by the following formula (B):
In the following formula (B), R and ^X each independently represent a hydrogen atom, a methyl group, or a phenyl group.
A represents a polyester moiety;
B is a polyester moiety, or -R ²⁰ OH, -R ²⁰ COOH,

and -R ²⁰ NH ₂ , where R ²⁰ represents a single bond or an alkylene group having 1 to 4 carbon atoms;
The average number of repetitions n is 10 to 80;
The polymer A has a first monomer unit having a structure represented by the following formula (I) and a second monomer unit different from the first monomer unit,
In the following formula (I), ^R represents a hydrogen atom or a methyl group, R represents an alkyl group having 18 to 36 carbon atoms,
a content ratio of the first monomer unit in the polymer A is 5.0 mol % to 60.0 mol % based on the total number of moles of all monomer units in the polymer A,
the content ratio of the second monomer unit in the polymer A is 20.0 mol % to 95.0 mol % based on the total number of moles of all monomer units in the polymer A,
The toner relates to a toner which satisfies the following formulas (1) to (3), where the SP value of the first monomer unit is SP1 (J/cm ³ ) ^0.5 , the SP value of the second monomer unit is SP2 (J/cm ³ ) ^0.5 , and the SP value of the silicone moiety represented by -(Si(R ^x ) ₂ O) _n -Si(R ^x ) ₂ - in the structure represented by formula (B) is SP3 (J/cm ³ ) ^0.5 :
SP1≦18.4...(1)
21.0≦SP2...(2)
SP1-SP3<SP2-SP1...(3)

This disclosure further improves charging stability and provides a toner with excellent image scratch resistance.

［式（Ｚ）中、Ｚ_１は、水素原子、又はアルキル基（好ましくは炭素数１～３のアルキル基であり、より好ましくはメチル基）を表し、Ｚ_２は、任意の置換基を表す。］
結晶性樹脂とは、示差走査熱量計（ＤＳＣ）測定において明確な吸熱ピークを示す樹脂を指す。 The expressions "XX to YY" and "XX to YY" representing a numerical range mean a numerical range including the endpoints, that is, the lower limit and the upper limit, unless otherwise specified.
The (meth)acrylic acid ester means an acrylic acid ester and/or a methacrylic acid ester.
The term "monomer unit" refers to the reacted form of a monomer substance in a polymer, and one section of carbon-carbon bond in the main chain formed by polymerization of a vinyl monomer in a polymer is defined as one unit.
The vinyl monomer can be represented by the following formula (Z).

[In formula (Z), Z ₁ represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and Z ₂ represents an arbitrary substituent.]
The crystalline resin refers to a resin that shows a clear endothermic peak in a differential scanning calorimeter (DSC) measurement.

、及び－Ｒ^２０ＮＨ_２からなる群から選択されるいずれかの官能基を表し、Ｒ^２０は、単結合又は炭素数１～４のアルキレン基を表し、
平均繰り返し数ｎは１０～８０であり、
該重合体Ａが、下記式（Ｉ）で表される構造を有する第一のモノマーユニット、及び該第一のモノマーユニットとは異なる第二のモノマーユニットを有し、
下記式（Ｉ）中、Ｒ^Ｚ１は、水素原子又はメチル基を表し、Ｒは、炭素数１８～３６のアルキル基を表し、
該重合体Ａ中の該第一のモノマーユニットの含有割合が、該重合体Ａの全モノマーユニットの総モル数を基準として、５．０モル％～６０．０モル％であり、
該重合体Ａ中の該第二のモノマーユニットの含有割合が、該重合体Ａの全モノマーユニットの総モル数を基準として、２０．０モル％～９５．０モル％であり、
該第一のモノマーユニットのＳＰ値をＳＰ１（Ｊ／ｃｍ^３）^０．５とし、該第二のモノマーユニットのＳＰ値をＳＰ２（Ｊ／ｃｍ^３）^０．５とし、該式（Ｂ）で表される構造中の－（Ｓｉ（Ｒ^Ｘ）_２Ｏ）_ｎ－Ｓｉ（Ｒ^Ｘ）_２－で表されるシリコーン部位のＳＰ値をＳＰ３（Ｊ／ｃｍ^３）^０．５としたとき、下記式（１）～（３）を満たすトナーに関する。
ＳＰ１≦１８．４ ・・・（１）
２１．０≦ＳＰ２ ・・・（２）
ＳＰ１－ＳＰ３＜ＳＰ２－ＳＰ１ ・・・（３） The present disclosure provides a toner having toner particles containing a binder resin and a polymer A,
The binder resin contains a polyester resin having a structure represented by the following formula (B):
In the following formula (B), R and ^X each independently represent a hydrogen atom, a methyl group, or a phenyl group.
A represents a polyester moiety;
B is a polyester moiety, or -R ²⁰ OH, -R ²⁰ COOH,

and -R ²⁰ NH ₂ , where R ²⁰ represents a single bond or an alkylene group having 1 to 4 carbon atoms;
The average number of repetitions n is 10 to 80;
The polymer A has a first monomer unit having a structure represented by the following formula (I) and a second monomer unit different from the first monomer unit,
In the following formula (I), ^R represents a hydrogen atom or a methyl group, R represents an alkyl group having 18 to 36 carbon atoms,
a content ratio of the first monomer unit in the polymer A is 5.0 mol % to 60.0 mol % based on the total number of moles of all monomer units in the polymer A,
the content ratio of the second monomer unit in the polymer A is 20.0 mol % to 95.0 mol % based on the total number of moles of all monomer units in the polymer A,
The toner relates to a toner which satisfies the following formulas (1) to (3), where the SP value of the first monomer unit is SP1 (J/cm ³ ) ^0.5 , the SP value of the second monomer unit is SP2 (J/cm ³ ) ^0.5 , and the SP value of the silicone moiety represented by -(Si(R ^x ) ₂ O) _n -Si(R ^x ) ₂ - in the structure represented by formula (B) is SP3 (J/cm ³ ) ^0.5 :
SP1≦18.4...(1)
21.0≦SP2...(2)
SP1-SP3<SP2-SP1...(3)

The moiety represented by --(Si(R ^x ) ₂ O) _n --Si(R ^x ) ₂ -- in the structure represented by formula (B), that is, the structure excluding A and B in formula (B), is also referred to as a silicone moiety.
As a result of intensive research, the present inventors have found that the above-mentioned problems can be solved by controlling the molar ratio, SP value, and magnitude relationship of the SP value of the monomer unit represented by formula (I) of polymer A to be added to a polyester resin having a structure represented by formula (B) within specific ranges.
The present inventors speculate as follows about the reason why the above problem has been solved.

The polyester resin having the structure represented by formula (B) is a resin in which a polyester moiety with high polarity is bonded (for example, covalently bonded) to a silicone moiety with low polarity. The silicone moiety has low polarity, which results in good charging stability, but because charge leakage occurs from the polyester moiety with high polarity, further improvement in charging stability was required when the image was left for a long period of time. Furthermore, the silicone moiety has low adhesion to paper, which poses an issue with image scratch resistance.

Therefore, the present inventors have investigated a toner in which a crystalline vinyl resin having a monomer unit with a high SP value is added to a polyester resin having a structure represented by formula (B), and have found that the charging stability is further improved and the image scratch resistance is also improved.
When the first monomer unit of polymer A satisfies the above formula (1): SP1≦18.4, the affinity between the silicone moiety of the polyester resin having the structure represented by formula (B) and the first monomer unit of polymer A is increased.
When the second monomer unit of polymer A satisfies the above formula (2): 21.0≦SP2, the affinity between the polyester moiety of the polyester resin having the structure represented by formula (B) and the second monomer unit of polymer A is increased. Therefore, polymer A functions as a dispersant for the silicone moiety, improving the dispersibility of the silicone moiety in the toner. As a result, the silicone moiety can suppress charge leakage from the polyester moiety, and the charging stability can be improved.
In addition, since polymer A is a crystalline resin, it has a lower viscosity during fixing than polyester resin having the structure represented by formula (B), and precipitates on the surface of the toner particles. Since a silicone moiety with a low surface free energy is present, polymer A can dissolve and spread on paper. When formula (3): SP1-SP3<SP2-SP1 is satisfied, the hydrophobicity of the inside of the toner is increased with respect to the second monomer unit of polymer A, and the second monomer unit of polymer A is easily oriented toward the paper side, so that a pseudo-crosslinked structure can be formed with the paper. As a result, the adhesion between the image and the paper is improved, and the image scratch resistance is improved.

Polymer A has a first monomer unit having a structure represented by the following formula (I) and a second monomer unit different from the first monomer unit. Polymer A has a crystalline portion derived from a long-chain alkyl group present in the first monomer unit.
The first monomer unit is derived from a first polymerizable monomer which is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms.
By adjusting the carbon number to within the above range, the affinity between the polymer A and the silicone moiety of the polyester resin having the structure represented by formula (B) is increased, resulting in good charging stability and image scratch resistance.
The first (or second) monomer unit is, for example, a monomer unit obtained by addition polymerization (vinyl polymerization) of a first (or second) polymerizable monomer.

[In formula (I), ^R represents a hydrogen atom or a methyl group, and R represents an alkyl group having 18 to 36 carbon atoms (preferably a linear alkyl group having 18 to 30 carbon atoms).]

Examples of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms include (meth)acrylic acid esters having a linear alkyl group having 18 to 36 carbon atoms [stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosyl (meth)acrylate, myrisyl (meth)acrylate, dotriacontyl (meth)acrylate, etc.] and (meth)acrylic acid esters having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth)acrylate, etc.].
Among these, from the viewpoint of low temperature fixability, preferably at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 36 carbon atoms, more preferably at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 30 carbon atoms. Even more preferred is at least one selected from the group consisting of linear stearyl (meth)acrylate and behenyl (meth)acrylate, and even more preferred is at least one selected from the group consisting of linear behenyl (meth)acrylate.
The first polymerizable monomer may be used alone or in combination of two or more kinds.

The content of the first monomer unit in polymer A is 5.0 mol % to 60.0 mol %, preferably 20.0 mol % to 40.0 mol %, based on the total number of moles of all monomer units in polymer A.
By ensuring that the content is within the above range, the silicone moiety can be dispersed in the toner, improving the charging stability, and the dissolving and spreading of polymer A during fixing is promoted, improving the image scratch resistance.
The content of the first monomer unit in polymer A is preferably 40.0% by mass to 85.0% by mass, more preferably 50.0% by mass to 80.0% by mass, and further preferably 60.0% by mass to 75.0% by mass.

When the SP value of the first monomer unit in polymer A is taken as SP1 (J/cm ³ ) ^0.5 , the following formula (1) is satisfied. It is further preferred that the following formula (1)' is satisfied.
SP1≦18.4...(1)
18.2≦SP1≦18.4...(1)'
The SP value is an abbreviation for solubility parameter, and is a value that serves as an index of solubility. The calculation method will be described later.
The unit of the SP value is (J/cm ³ ) ^0.5 , but it can be converted to a unit of (cal/cm ³ ) ^0.5 by 1 (cal/cm ³ ) ^0.5 = 2.045 × 10 ³ (J/cm ³ ) ^0.5 .
When the SP value of the first monomer unit is within the above range, the affinity between the first monomer unit and the silicone portion of the polyester resin having the structure represented by formula (B) is increased, resulting in good charging stability and image scratch resistance.

Polymer A also has a second monomer unit different from the first monomer unit. When the SP value of the second monomer unit is SP2 (J/cm ³ ) ^0.5 , the following formula (2) is satisfied. It is further preferred that the following formula (2)′ is satisfied.
21.0≦SP2...(2)
25.0≦SP2≦30.0...(2)'
When the SP value of the second monomer unit is within the above range, the affinity between the second monomer unit and the polyester moiety is increased, the charging stability is improved, and a crosslinked structure can be formed between the paper and the toner, resulting in good image scratch resistance.

Furthermore, when the SP value of the silicone moiety (-(Si(R ^x ) ₂ O) _n -Si(R ^x ) ₂ -) in the polyester resin having the structure represented by formula (B) is taken as SP3 (J/cm ³ ) ^0.5 , the following formula (3) is satisfied.
SP1-SP3<SP2-SP1...(3)
The fact that SP1, SP2, and SP3 satisfy the above formula means that the affinity between the first monomer unit and the silicone moiety is higher than the affinity between the first monomer unit and the second monomer unit. By satisfying the above, the dispersibility of the silicone moiety in the toner is improved, the charging stability is improved, and the melting and spreading of the polymer A during fixing is promoted, resulting in good image scratch resistance.

The content of the second monomer unit in polymer A is 20.0 mol % to 95.0 mol % based on the total number of moles of all monomer units in polymer A. It is preferably 30.0 mol % to 70.0 mol %, and more preferably 40.0 mol % to 60.0 mol %.
When the content ratio is within the above range, the affinity between the second monomer unit and the polyester moiety is increased, improving the charging stability, and the paper and the second monomer unit can form a crosslinked structure, improving the image scratch resistance.
The content of the second monomer unit in polymer A is preferably 10.0% by mass to 50.0% by mass, more preferably 15.0% by mass to 40.0% by mass, and even more preferably 15.0% by mass to 30.0% by mass.

The second monomer unit is preferably at least one selected from the group consisting of a monomer unit represented by the following formula (II) and a monomer unit represented by the following formula (III).

(In formula (II), X represents a single bond or an alkylene group having 1 to 6 carbon atoms.
R ¹ is a nitrile group (-C≡N);
an amide group (-C(=O)NHR ¹⁰ (R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms);
Hydroxy groups,
-COOR ¹¹ (R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4), or a hydroxyalkyl group having 1 to 6 carbon atoms (preferably 1 to 4));
a urethane group (-NHCOOR ¹² (R ¹² represents an alkyl group having 1 to 4 carbon atoms)),
a urea group (-NH-C(=O)-N( ^R13 ) ₂ (wherein each of the two ^R13s independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms));
-COO( _CH2 ) _2NHCOOR14 ^{( R14} represents an alkyl group having 1 to 4 carbon atoms), or -COO( _CH2 ) ₂ -NH-C(=O)-N( ^R15 ) ₂ (two ^R15s each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4).)
^R2 represents a hydrogen atom or a methyl group.
(In formula (III), ^R3 represents an alkyl group having 1 to 4 carbon atoms, and ^R4 represents a hydrogen atom or a methyl group.)

When the second monomer unit contains at least one selected from the group consisting of formulas (II) and (III), the affinity with the polyester moiety is increased, the charging stability is improved, and a crosslinked structure with paper can be formed, resulting in good image scratch resistance.
The second monomer unit may be used alone or in combination of two or more kinds.
When two or more kinds of the first monomer units are used in combination in the polymer A, the content of the monomer units is the sum of the contents of the respective monomer units. The same applies to the second monomer unit.

As the second polymerizable monomer forming the second monomer unit, for example, among the following polymerizable monomers satisfying the formulas (2) and (3) can be used. The second polymerizable monomer may be used alone or in combination of two or more kinds.
Monomers having a nitrile group; for example, acrylonitrile, methacrylonitrile, etc.
Monomers having a hydroxy group: for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.
Monomers having an amide group: for example, acrylamide, monomers obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms (acrylic acid, methacrylic acid, etc.) having an ethylenically unsaturated bond by a known method, and the like.

Monomers having a urethane group; for example, alcohols having 2 to 22 carbon atoms having an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate, vinyl alcohol, etc.) and isocyanates having 1 to 30 carbon atoms [monoisocyanate compounds (benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, diisocyanate, 2-ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, 2,6-dipropylphenyl isocyanate, etc.), aliphatic diisocyanate compounds (trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, , dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate), alicyclic diisocyanate compounds (1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated tetramethylxylylene diisocyanate), and aromatic A monomer obtained by reacting an aromatic diisocyanate compound (such as phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenylether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, etc.) by a known method, and Alcohols having 1 to 26 carbon atoms (methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, heptadecanol, stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and monomers obtained by reacting, by a known method, an isocyanate having 2 to 30 carbon atoms and an ethylenically unsaturated bond [2-isocyanatoethyl (meth)acrylate, 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl (meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, etc.], and the like.

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

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

As the second polymerizable monomer, 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.

The second polymerizable monomer preferably has an ethylenically unsaturated bond, and more preferably has one ethylenically unsaturated bond.
The second polymerizable monomer is more preferably at least one selected from the group consisting of the following formulae (C) and (D).

(In formula (C), X represents a single bond or an alkylene group having 1 to 6 carbon atoms.
R ¹ is a nitrile group (-C≡N);
an amide group (-C(=O)NHR ¹⁰ (R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms);
Hydroxy groups,
-COOR ¹¹ (R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4), or a hydroxyalkyl group having 1 to 6 carbon atoms (preferably 1 to 4));
a urethane group (-NHCOOR ¹² (R ¹² represents an alkyl group having 1 to 4 carbon atoms)),
a urea group (-NH-C(=O)-N( ^R13 ) ₂ (wherein the two ^R13s each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms));
-COO( _CH2 ) _2NHCOOR14 ^{( R14} represents an alkyl group having 1 to 4 carbon atoms), or -COO( _CH2 ) ₂ -NH-C(=O)-N( ^R15 ) ₂ (two ^R15s each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4).)
^R2 represents a hydrogen atom or a methyl group.
(In formula (D), ^R3 represents an alkyl group having 1 to 4 carbon atoms, and ^R4 represents a hydrogen atom or a methyl group.)

When multiple types of monomer units satisfying the requirements for the first monomer unit are present in polymer A, the value of SP1 in formula (3) is a weighted average of the SP values of the respective monomer units. For example, when a polymer contains A mol % of monomer unit A having an SP value of SP ₁₁ based on the total number of moles of monomer units satisfying the requirements for the first monomer unit, and contains (100-A) mol % of monomer unit B having an SP value of SP ₁₂ based on the total number of moles of monomer units satisfying the requirements for the first monomer unit, the SP value (SP1) is
SP1=( _SP11 ×A+ _SP12 ×(100-A))/100
The calculation is similarly performed when three or more monomer units satisfying the requirements for the first monomer unit are contained.
Even when a plurality of second monomer units and/or silicone moieties are present, in the calculation of formula (3), SP2 and/or SP3 are determined in the same manner as SP1.

The polymer A is preferably a vinyl polymer. Examples of the vinyl polymer include polymers of monomers containing an ethylenically unsaturated bond. The ethylenically unsaturated bond refers to a carbon-carbon double bond capable of radical polymerization, and examples of the ethylenically unsaturated bond include a vinyl group, a propenyl group, an acryloyl group, and a methacryloyl group.
The acid value Av of the polymer A is preferably 30.0 mgKOH/g or less, more preferably 20.0 mgKOH/g or less. The lower limit is not particularly limited, but is preferably 0 mgKOH/g or more. When the acid value is 30.0 mgKOH/g or less, the crystallization of the polymer A is not easily inhibited, and the melting point is well maintained.

Furthermore, the weight average molecular weight (Mw) of the tetrahydrofuran (THF) soluble matter of the polymer A measured by gel permeation chromatography (GPC) is preferably from 10,000 to 200,000, more preferably from 20,000 to 150,000. When the Mw is within the above range, the elasticity at around room temperature is easily maintained.
The melting point of the polymer A is preferably from 50° C. to 80° C., and more preferably from 53° C. to 70° C. When the melting point is 50° C. or higher, the charging stability is improved, and when the melting point is 80° C. or lower, the image scratch resistance is improved.

The polymer A may contain a third monomer unit having a third polymerizable monomer not included in the range of either the above formula (1) or (2) (i.e., different from the first polymerizable monomer and the second polymerizable monomer) as a constituent component, within a range that does not impair the molar ratio of the first monomer unit derived from the above-mentioned first polymerizable monomer and the second monomer unit derived from the second polymerizable monomer. The third monomer unit has a structure obtained by addition polymerization of the third polymerizable monomer.
As the third polymerizable monomer, among the monomers listed in the section of the second polymerizable monomer, a monomer not satisfying formula (2) can be used.
In addition, the following monomers which do not have the above-mentioned nitrile group, amide group, urethane group, hydroxy group, urea group, or carboxy group can also be used.
For example, styrene and its derivatives such as styrene, o-methylstyrene, and (meth)acrylic acid esters such as methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.
The third polymerizable monomer is preferably at least one selected from the group consisting of styrene, methyl methacrylate, and methyl acrylate.
When these satisfy the formula (2), they can be used as the second polymerizable monomer.

The content of polymer A is preferably 1.0 parts by mass or more and 10.0 parts by mass or less, and more preferably 3.0 parts by mass or more and 8.0 parts by mass or less, relative to 100 parts by mass of the binder resin. When the content of polymer A is within the above range, the interaction between polymer A and the polyester resin having the structure represented by formula (B) is promoted, and the charging stability and image scratch resistance are improved.

It is particularly preferred that the first monomer unit is a monomer unit derived from behenyl acrylate, that is, in formula (I), it is particularly preferred that R ^Z1 is a hydrogen atom and R is an alkyl group having 22 carbon atoms.
By using behenyl acrylate, the silicone moiety of the polyester resin having the structure represented by formula (B) is dispersed in the toner, improving the charging stability and providing the effect of dissolving and spreading the polymer A during fixing, thereby improving the image scratch resistance.

The polyester resin having the structure represented by formula (B) has a silicone moiety represented by -(Si(R ^x ) ₂ O) _n -Si(R ^x ) ₂ -. That is, the polyester resin having the structure represented by formula (B) has a silicone moiety represented by the following formula (B').
The content of the silicone moiety in the polyester resin having the structure represented by formula (B) is preferably from 0.5% by mass to 5.0% by mass, and more preferably from 2.0% by mass to 4.0% by mass.
By having the content of the silicone moiety within the above range, the dispersibility of the silicone moiety in the toner is improved due to the interaction with polymer A, and the surface free energy during fixing is effectively reduced, thereby promoting the dissolution and spreading of polymer A.

In formula (B'), R 1 ^X and n are the same as those in formula (B). Each of R 1 ^X independently represents a hydrogen atom, a methyl group, or a phenyl group. n is the average number of repetitions of the siloxane unit and represents an integer of 10 to 80 (preferably 20 to 65).
In formulae (B) and (B'), it is preferable that R and ^X are both methyl groups. This increases the affinity with the first monomer unit of polymer A, and improves the charging stability and image scratch resistance.

The binder resin used in the toner will be described.
The binder resin contains a polyester resin having a structure represented by formula (B). In addition to the polyester resin having a structure represented by formula (B), the binder resin may contain other resins.
Examples of other resins include polyester resins, polyurethane resins, epoxy resins, and phenolic resins, as well as hybrid resins in which two or more of these resins are combined.
In the binder resin, the content of the polyester resin having the structure represented by formula (B) is preferably 50% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more. The upper limit is not particularly limited, but is preferably 100% by mass or less. These values can be arbitrarily combined. By using the polyester resin having the structure represented by formula (B) as the main component of the binder resin, it is possible to effectively obtain the above-mentioned interaction with the polymer A.

The polyester resin having the structure represented by formula (B) has a silicone moiety and a polyester moiety represented by formula (B'). The polyester moiety of the polyester resin having the structure represented by formula (B) is preferably an amorphous polyester resin.
The components constituting the polyester moiety of the polyester resin having the structure represented by formula (B) will be described in detail. The following components may be used singly or in combination depending on the type and application.
Examples of the divalent carboxylic acid component constituting the polyester moiety include the following dicarboxylic acids or derivatives thereof.
Benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or their anhydrides or lower alkyl esters; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or their anhydrides or lower alkyl esters; alkenylsuccinic acids or alkylsuccinic acids having an average carbon number of 1 to 50, or their anhydrides or lower alkyl esters; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, or their anhydrides or lower alkyl esters.

On the other hand, examples of the dihydric alcohol component constituting the polyester moiety include the following.
Ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 1,4-cyclohexanedimethanol (CHDM), hydrogenated bisphenol A, bisphenol and derivatives thereof represented by formula (I-1): and diols represented by formula (I-2).

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x+y is 0 or more and 10 or less.)

(In the formula, R' is an ethylene or propylene group, x' and y' are each integers of 0 or more, and the average value of x' + y' is 0 or more and 10 or less.)

The components constituting the polyester moiety may contain, in addition to the above-mentioned divalent carboxylic acid component and divalent alcohol component, a trivalent or higher carboxylic acid component and a trivalent or higher alcohol component.
The trivalent or higher carboxylic acid component is not particularly limited, but examples thereof include trimellitic acid, trimellitic anhydride, pyromellitic acid, etc. Furthermore, the trivalent or higher alcohol component includes trimethylolpropane, pentaerythritol, glycerin, etc.
The polyester moiety may contain, in addition to the above-mentioned compounds, a monovalent carboxylic acid component and a monovalent alcohol component as constituents.Specific examples of the monovalent carboxylic acid component include palmitic acid, stearic acid, arachidic acid, behenic acid, cerotic acid, heptacosanoic acid, montanic acid, melissic acid, lactoseric acid, tetracontanoic acid, and pentacontanoic acid.
Examples of the monohydric alcohol component include behenyl alcohol, ceryl alcohol, melissyl alcohol, and tetracontanol.
The content of the polyester moiety in the polyester resin having the structure represented by formula (B) is preferably from 95.0% by mass to 99.5% by mass, and more preferably from 96.0% by mass to 98.0% by mass.

The components constituting the silicone moiety of the polyester resin having the structure represented by formula (B) are described in detail below. The following components can be used singly or in combination depending on the type and application.
The silicone moiety has the structure represented by the above formula (B'), that is, (-(Si(R ^x ) ₂ O) _n -Si(R ^x ) ₂ -).
As a component for forming a silicone moiety in the polyester resin having the structure represented by formula (B), a silicone oil having a functional group at the end of formula (B') that chemically reacts with polyester can be used. Examples of the functional group that reacts with polyester include a hydroxy group, a carboxy group, an epoxy group, and an amino group.

The functional group at the end of the silicone oil is preferably a hydroxy group or a carboxy group in order to control the reactivity with polyester.
The valence of the functional group of the silicone oil is preferably 1, 2, or 3 or more. By introducing a silicone moiety into the main skeleton of the polyester, the interaction with the polymer A can be controlled, and the charging stability and image scratch resistance can be improved, so it is preferable to use a divalent silicone oil having functional groups at both ends of the silicone oil.
More preferably, it is a silicone oil having a substituent containing a hydroxy group at both ends of the formula (B'). The substituent containing a hydroxy group is, for example,
-(CH ₂ ) _p -O-(CH ₂ ) _q -OH
In the formula, p is an integer of 1 to 3, and q is an integer of 1 to 3.

The method for producing the polyester resin having the structure represented by formula (B) is not particularly limited, and a known method can be used.For example, the above-mentioned divalent carboxylic acid component, divalent alcohol component, and silicone oil having a functional group are polymerized through esterification reaction or ester exchange reaction and condensation reaction to produce the polyester resin having the structure represented by formula (B).
The polymerization temperature is not particularly limited, but is preferably in the range of 180° C. to 290° C. In polymerizing the polyester resin, for example, a polymerization catalyst such as a titanium-based catalyst, a tin-based catalyst, zinc acetate, antimony trioxide, or germanium dioxide can be used.
The softening point of the polyester resin having the structure represented by formula (B) is preferably from 85° C. to 150° C., and more preferably from 100° C. to 150° C. When the softening point of the polyester resin having the structure represented by formula (B) is in the above range, the charging stability is improved and the image scratch resistance is also improved.

The toner may contain wax. Examples of the wax 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 block copolymers thereof; waxes containing fatty acid esters as the main component such as carnauba wax; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.
Among these waxes, from the viewpoint of improving low-temperature fixing property and hot offset resistance, preferred are hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, and fatty acid ester waxes such as carnauba wax.

The wax content is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin.
In addition, in an endothermic curve during temperature rise measured by a differential scanning calorimeter (DSC), the peak temperature (melting point) of the maximum endothermic peak of the wax existing in a temperature range of 30° C. to 200° C. is preferably 50° C. to 140° C., more preferably 60° C. to 105° C.

The toner may contain a colorant. Examples of the colorant include the following.
Examples of black colorants include carbon black, and a mixture of a yellow colorant, a magenta colorant, and a cyan colorant toned to black. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment in combination to improve the clarity of the colorant from the viewpoint of the image quality of a full-color image.
Pigments for magenta toner 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.
Dyes for magenta toner include the following: C.I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. Disperse Red 9; C.I. Solvent Violet 8, 13, 14, 21, 27; C.I. Disperse Violet 1, and basic dyes such as C.I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; C.I. Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of pigments for cyan toner include C.I. Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, and 17; C.I. Bat Blue 6; C.I. Acid Blue 45; and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.
Dyes for cyan toner include C.I. Solvent Blue 70.
Yellow toner pigments include: C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; C.I. Vat Yellow 1, 3, 20.
Yellow toner dyes include C.I. Solvent Yellow 162.
The content of the colorant is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

The toner may contain a charge control agent, if necessary.
Examples of negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds having sulfonic acid or carboxylic acid on the side chain, polymeric compounds having sulfonate or sulfonate ester on the side chain, polymeric compounds having carboxylate or carboxylate ester on the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes. The charge control agent may be added internally or externally to the toner particles.
The amount of the charge control agent added is preferably 0.1 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

The toner may contain inorganic fine particles as required. The inorganic fine particles may be added internally to the toner particles, or may be mixed with the toner particles as an external additive.
As the external additive, inorganic fine particles such as silica, titanium oxide, strontium titanate, and aluminum oxide are preferable. More preferably, low resistance particles such as silica and strontium titanate are preferable from the viewpoint of development stability. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.
As an external additive for improving fluidity, inorganic fine powder having a specific surface area of 50 ^m2 /g or more and 400 ^m2 /g or less is preferable, and for stabilizing durability, inorganic fine powder having a specific surface area of 10 ^m2 /g or more and 50 ^m2 /g or less is preferable. In order to achieve both improvement in fluidity and stabilization of durability, inorganic fine particles having a specific surface area within the above range may be used in combination.
The content of the external additive is preferably 0.1 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the toner particles. The toner particles and the external additive can be mixed using a known mixer such as a Henschel mixer.

The toner can be used as a one-component developer, but it is more preferable to mix the toner with a magnetic carrier and use it as a two-component developer, in that stable images can be obtained over a long period of time.
Examples of magnetic carriers that can be used include generally known magnetic carriers such as surface-oxidized iron powder, unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, and rare earth elements, alloy particles, oxide particles, and magnetic materials such as ferrite, and magnetic material-dispersed resin carriers (so-called resin carriers) that contain a magnetic material and a binder resin that holds the magnetic material in a dispersed state.
When the toner is mixed with a magnetic carrier to be used as a two-component developer, good results are usually obtained when the carrier mixing ratio in this case is, in terms of the toner concentration in the two-component developer, preferably 2% by mass or more and 15% by mass or less, and more preferably 4% by mass or more and 13% by mass or less.

[Production method]
The method for producing the toner particles is not particularly limited, and any of the conventionally known production methods such as an emulsion aggregation method, a melt kneading method, and a dissolution suspension method can be used.
The obtained toner particles may be used as a toner as it is, or an external additive may be mixed (external addition) with the obtained toner particles to obtain a toner.
Examples of the external additive include inorganic fine particles such as silica, alumina, titania, and calcium carbonate, and resin particles such as vinyl resin, polyester resin, and silicone resin. These inorganic fine powders and resin particles function as external additives for charge control, flow aid, cleaning aid, and the like.
Examples of the mixing device include a double con mixer, a V-type mixer, a drum type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.).

Specific examples of the toner production method using the melt-kneading method will be described below, but the present invention is not limited to these.
<Melt kneading method>
First, in the raw material mixing step, predetermined amounts of the binder resin and polymer A, as well as wax, colorant and other additives as required, are weighed out and mixed as toner raw materials.
Examples of devices used for mixing include Henschel mixer (manufactured by Nippon Coke Company); Super mixer (manufactured by Kawata Corporation); Rebocone (manufactured by Okawara Manufacturing Co., Ltd.); Nauta mixer, Turbulizer, Cyclomix (manufactured by Hosokawa Micron Corporation); Spiral Pin Mixer (manufactured by Pacific Machinery Works, Ltd.); and Loedige mixer (manufactured by Matsubo Corporation).

Next, the resulting mixture is melted and kneaded to melt the binder resin and disperse the polymer A and the like therein (melt-kneading step).
Examples of devices used for melt kneading include a TEM type extruder (manufactured by Toshiba Machine Co., Ltd.), a TEX twin screw kneader (manufactured by Japan Steel Works, Ltd.), a PCM kneader (manufactured by Ikegai Iron Works Co., Ltd.), and Kneadex (manufactured by Mitsui Mining Co., Ltd.) etc. Continuous kneaders such as single screw or twin screw extruders are preferred over batch type kneaders because of their advantages such as the ability to perform continuous production.
Next, the resulting molten mixture is rolled using a twin roll or the like, and cooled by water cooling or the like.

The cooled material is then crushed to a desired particle size by first coarsely crushing the material with a crusher, hammer mill, feather mill, or the like, and then finely crushing the material with a Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.) or a Super Rotor (manufactured by Nisshin Engineering, Inc.), to obtain resin particles.
The resin particles thus obtained may be classified into particles of a desired particle size to obtain toner particles. Apparatuses used for classification include Turboplex, Faculty, TSP, and TTSP (manufactured by Hosokawa Micron Corporation); and Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.).

Next, the measurement methods for each physical property will be described.
<Method for measuring the content of each monomer unit in polymer A>
The content ratio of monomer units derived from various polymerizable monomers in polymer A 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.
From the obtained ^1H -NMR chart, a peak independent of peaks attributable to the components of the first monomer unit that originate from other components is selected, and an integral value _S1 of this peak is calculated. Similarly, from the peaks attributable to the components of the second monomer unit that originate from other components is selected, and an integral value _S2 of this peak is calculated.
Furthermore, in the case where a third monomer unit is present, a peak that is independent of the peaks that are attributable to the components of the third monomer unit and that are derived from other monomer unit components is selected from the peaks that are attributable to the components of the third monomer unit, and the integral value _S3 of this peak is calculated.
The content ratio of the first monomer unit is determined using the above integral values S ₁ , S ₂ , and S ₃ as follows: Here, n ₁ , n ₂ , and n ₃ are the numbers of hydrogen atoms in the constituent elements to which the peaks of interest for each site belong.
Content of first monomer unit (mol%)=
{(S ₁ /n ₁ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ ))}×100
Similarly, the contents of the second monomer unit and the third monomer unit are determined as follows.
Content of second monomer unit (mol%)=
{(S ₂ /n ₂ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ ))}×100
Content of third monomer unit (mol%)=
{(S ₃ /n ₃ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ ))}×100
In addition, when a polymerizable monomer containing no hydrogen atoms in components other than vinyl groups is used in polymer A, the measurement nucleus is set to ¹³ C using ¹³ C-NMR, and the measurement is performed in single pulse mode, and the calculation is performed in the same manner using ¹ H-NMR.
Furthermore, when the toner is produced by a suspension polymerization method, the peaks of the release agent and other resins may overlap, and independent peaks may not be observed. This may result in a case where the content ratio of the monomer units derived from various polymerizable monomers in polymer A cannot be calculated. In this case, polymer A' can be produced by performing a similar suspension polymerization without using a release agent or other resin, and polymer A' can be analyzed as polymer A.

<Method of calculating SP value>
The SP values such as SP1 and SP2 are calculated in the following manner according to the calculation method proposed by Fedors.
For each polymerizable monomer, the evaporation energy (Δei) (cal/mol) and molar volume (Δvi) (cm 3 /mol) for the atom or atomic group in the molecular structure are obtained from the table in "Polym. Eng. Sci., 14(2), 147-154 ( ¹⁹⁷⁴ )", and (4.184×ΣΔei/ΣΔvi) ^0.5 is defined as the SP value (J/cm ³ ) ^0.5 .
Incidentally, SP1 and SP2 are calculated by the above-mentioned calculation method for the atoms or atomic groups in the molecular structure in a state in which the double bond of the polymerizable monomer is cleaved by polymerization.

<Measurement of glass transition temperature (Tg) of binder resin and melting peak temperature (melting point) of polymer A>
The Tg and melting point of the resins such as the binder resin and the polymer A are measured in accordance with ASTM D3418-82 using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments).
The melting points of indium and zinc are used for temperature correction of the device detection section, and the heat of fusion of indium is used for heat correction.
Specifically, about 3 mg of resin is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed under the following conditions.
Heating rate: 10° C./min
Measurement start temperature: 30℃
Measurement end temperature: 180°C
Measurements are performed at a temperature rise rate of 10°C/min in the measurement range of 30 to 180°C. The temperature is raised to 180°C once and held for 10 minutes, then cooled to 30°C, and then raised again. During this second temperature rise, a specific heat change is obtained in the temperature range of 30 to 100°C. The intersection of the line midway between the baselines before and after the specific heat change occurs and the differential thermal curve is taken as the glass transition temperature (Tg) of the resin.
Furthermore, the temperature at which the maximum endothermic peak occurs on the temperature-endothermic curve in the temperature range of 40° C. to 90° C. is defined as the melting peak temperature (Tp).

<Method for measuring softening point Tm>
The softening point is measured using a constant load extrusion type capillary rheometer "Flow characteristic evaluation device Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual that comes with the device. With this device, a constant load is applied from above the measurement sample by a piston while the measurement sample filled in a cylinder is heated and melted, and the molten measurement sample is extruded from a die at the bottom of the cylinder, and a flow curve showing the relationship between the piston descent amount and temperature can be obtained.
The "melting temperature in the 1/2 method" described in the manual attached to the "Flow characteristic evaluation device, Flow Tester CFT-500D" is taken as the softening point. The melting temperature in the 1/2 method is calculated as follows. First, 1/2 of the difference between the amount of piston descent Smax at the time when outflow ends and the amount of piston descent Smin at the time when outflow starts is calculated (this is taken as X; X = (Smax - Smin) / 2). Then, the temperature of the flow curve when the amount of piston descent on the flow curve is the sum of X and Smin is the melting temperature Tm (°C) in the 1/2 method.
The measurement sample is prepared by compressing approximately 1.3 g of a sample at approximately 10 MPa for approximately 60 seconds using a tablet molding machine (e.g., NT-100H, manufactured by NPA Systems) in an environment of 25°C to form a cylindrical shape with a diameter of approximately 8 mm.
The measurement conditions for CFT-500D are as follows.
Test mode: Heating method Starting temperature: 50°C
Reached temperature: 200°C
Measurement interval: 1.0°C
Heating rate: 4.0° C./min
Piston cross-sectional area: 1.000 ^cm2
Test load (piston load): 10.0 kgf/ ^cm2 (0.9807 MPa)
Preheat time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0 mm

<Measurement of molecular weight of polymer A by GPC>
The weight average molecular weight (Mw) of the THF-soluble portion of the polymer A is measured by gel permeation chromatography (GPC) as follows.
First, a sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The obtained solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in THF is about 0.8 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
In calculating the molecular weight of the sample, standard polystyrene resins (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-8
A molecular weight calibration curve prepared using "F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, F-14, F-15, F-16, F-17, F-18, F-20, F-21, F-22, F-23, F-24, F-25, F-30, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500" (manufactured by Tosoh Corporation) is used.

<Measurement of Acid Value of Polymer A>
The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of a sample. The acid value of polymer A is measured in accordance with JIS K 0070-1992, and specifically, is measured according to the following procedure.
(1) Preparation of Reagents 1.0 g of phenolphthalein was dissolved in 90 mL of ethyl alcohol (95% by volume), and ion-exchanged water was added to make up to 100 mL to obtain a phenolphthalein solution.
Dissolve 7 g of special grade potassium hydroxide in 5 mL of water, and add ethyl alcohol (95% by volume) to make 1 L. Place in an alkali-resistant container to avoid contact with carbon dioxide, etc., leave for 3 days, then filter to obtain a potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by placing 25 mL of 0.1 mol/L hydrochloric acid in an Erlenmeyer flask, adding several drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution, from the amount of potassium hydroxide solution required for neutralization. The 0.1 mol/L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.
(2) Procedure (A) Main Test 2.0 g of the crushed polymer A sample was precisely weighed into a 200 mL Erlenmeyer flask, and 100 mL of a mixed solution of toluene/ethanol (2:1) was added and dissolved over 5 hours. Then, several drops of the phenolphthalein solution were added as an indicator, and titration was performed using the potassium hydroxide solution. The end point of the titration was when the light red color of the indicator continued for about 30 seconds.
(B) Blank Test: A titration is carried out in the same manner as above, except that no sample is used (i.e., only a mixed solution of toluene/ethanol (2:1) is used).
(3) The obtained result is substituted into the following formula to calculate the acid value.
A=[(CB)×f×5.61]/S
Here, A is the acid value (mg KOH/g), B is the amount of potassium hydroxide solution added for the blank test (mL), C is the amount of potassium hydroxide solution added for the main test (mL), f is the factor of the potassium hydroxide solution, and S is the mass of the sample (g).

<Measurement of weight average particle size (D4) of toner particles>
The weight average particle size (D4) of the toner particles is measured using a precision particle size distribution measuring device by a pore electrical resistance method equipped with a 100 μm aperture tube, “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.), and the accompanying dedicated software for setting measurement conditions and analyzing measurement data, “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.), with an effective measurement channel count of 25,000, and the measurement data is analyzed and calculated.
The aqueous electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of about 1 mass %, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.).
Before carrying out the measurements and analyses, the dedicated software is set up as follows.
In the "Change Standard Measurement Method (SOM) Screen" of the dedicated software, the total count number in the control mode is set to 50,000 particles, the number of measurements is set to 1, and the Kd value is set to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter). The threshold and noise level are automatically set by pressing the threshold/noise level measurement button. In addition, the current is set to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and the aperture tube flush after measurement is checked.
In the "Pulse to particle size conversion setting screen" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Pour about 200 ml of the electrolyte solution into a 250 ml round-bottom glass beaker for use with the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, remove dirt and air bubbles from inside the aperture tube using the "aperture tube flush" function of the dedicated software.
(2) Approximately 30 ml of the aqueous electrolyte solution is placed in a 100 ml flat-bottom glass beaker, and approximately 0.3 ml of a solution prepared by diluting "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, having a pH of 7, manufactured by Wako Pure Chemical Industries, Ltd.) three times by weight with ion-exchanged water is added as a dispersant.
(3) A predetermined amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) having two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees and an electrical output of 120 W, and about 2 ml of the Contaminon N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized.
(5) In a state where the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, about 10 mg of toner particles are added little by little to the electrolyte solution and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. During the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted so as to be 10°C or higher and 40°C or lower.
(6) In the round-bottom beaker (1) placed in the sample stand, the electrolyte solution (5) in which the toner particles are dispersed is dropped using a pipette to adjust the measurement concentration to about 5%. Then, measurements are continued until the number of particles measured reaches 50,000.
(7) The measurement data is analyzed using the dedicated software that comes with the device, and the weight-average particle size (D4) is calculated. Note that when the dedicated software is set to Graph/Volume %, the "Average diameter" on the Analysis/Volume Statistics (Arithmetic Mean) screen is the weight-average particle size (D4).

<Method of separating each material from toner>
By utilizing the difference in solubility of each material contained in the toner in a solvent, each material can be separated from the toner.
First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23° C., and the soluble matter (polyester resin having a structure represented by formula (B)) is separated from the insoluble matter (polymer A, wax, colorant, inorganic fine particles, etc.).
Second separation: The insoluble matter obtained in the first separation (polymer A, wax, colorant, inorganic fine particles, etc.) is dissolved in MEK at 100° C., and the soluble matter (polymer A, wax) and the insoluble matter (colorant, inorganic fine particles, etc.) are separated.
Third separation: The soluble fraction (polymer A, wax) obtained in the second separation is dissolved in chloroform at 23° C., and the soluble fraction (polymer A) and the insoluble fraction (wax) are separated.
Based on the above separation, it is possible to analyze each material and calculate the content of each material.

<Confirmation of the Structure of Polyester Resin Having a Structure Represented by Formula (B)>
The structure of the polyester resin having the structure represented by formula (B) is confirmed by the following method.
The hydrocarbon group and silicone moiety in R 3 ^X of formula (B) are confirmed by ¹³ C-NMR and solid-state ²⁹ Si-NMR.
( ^13C -NMR Measurement Conditions)
Equipment: JEOL RESONANCE JNM-ECX500II
Sample tube: 3.2 mm diameter
Sample: deuterated chloroform solubles of sample for NMR measurement Measurement temperature: room temperature Pulse mode: CP/MAS
Measurement nuclear frequency: 123.25MHz ( ^13C )
Reference substance: Adamantane (external standard: 29.5ppm)
Sample rotation speed: 20 kHz
Contact time: 2 ms
Delay time: 2s
Number of accumulations: 1024 times. In this method, the hydrocarbon group in R X of formula (B) is confirmed based on the presence or absence of a signal due to a methyl group (Si-CH ₃ ) or a phenyl group (Si-C ₆ H ₅ ⁾ bonded to a silicon atom.

The specific measurement conditions for solid-state ^29Si -NMR are as follows.
Equipment: JNM-ECX5002 (JEOL RESONANCE)
Temperature: Room temperature measurement method: DD/MAS method ²⁹ Si 45°
Sample tube: Zirconia 3.2 mm diameter
Sample: Powdered sample filled in test tube Sample rotation speed: 10 kHz
relaxation delay: 180s
Scan: 2000

<Measurement of the content of silicone moieties in polyester resin having a structure represented by formula (B)>
The content of silicone moieties and polymer A in the polyester resin having the structure represented by formula (B) is confirmed by ¹ H-NMR using the above-mentioned device.
( ^1H -NMR Measurement Conditions)
Sample: deuterated chloroform soluble matter Pulse conditions: 5.0 μs
Frequency range: 10,500 Hz
Number of times: 64

The present invention will be specifically described below based on examples. However, the present invention is in no way limited to these. In the following formulations, parts are by weight unless otherwise specified.

<Production Example of Binder Resin P1>
Bisphenol A ethylene oxide (2.2 mol adduct): 50.0 parts by mol Bisphenol A propylene oxide (2.2 mol adduct): 50.0 parts by mol Terephthalic acid: 90.0 parts by mol Trimellitic anhydride: 10.0 parts by mol 97 parts of the above monomer for forming the polyester portion and 3 parts of silicone oil having hydroxy groups at both ends (KF-6001, Shin-Etsu Chemical Co., Ltd.) were mixed together with 500 ppm of titanium tetrabutoxide in a 5-liter autoclave.
A reflux condenser, a water separator, an _N2 gas inlet tube, a thermometer and a stirrer were attached to the autoclave, and a condensation polymerization reaction was carried out at 230° C. while introducing _N2 gas into the autoclave. The reaction time was adjusted so as to obtain a desired softening point, and after the reaction was completed, the mixture was removed from the vessel, cooled and pulverized to obtain a binder resin P1.
The content of the silicone moiety in the binder resin P1 was 3.0% by mass. The physical properties are shown in Table 1.

<Production Examples of Binder Resins P2 to P8>
Binder resins P2 to P8 were obtained in the same manner as in the production example for binder resin P1, except that the amount of silicone oil added was changed so that the content of the silicone moiety would be the value shown in Table 1, and Tm and Tg were changed by adjusting the reaction time.

ＫＦ－６００１により、式（Ｂ）において、Ｒ^Ｘがいずれもメチル基であり、ｎが３８
である構造が得られる。
ＢＰＡ－ＰＯ ビスフェノールＡのプロピレンオキシド付加物（平均付加モル数２．２ｍｏｌ）
ＢＰＡ－ＥＯ ビスフェノールＡのエチレンオキシド付加物（平均付加モル数２．２ｍｏｌ）
ＴＰＡ テレフタル酸
ＴＭＡ 無水トリメリット酸

According to KF-6001, in formula (B), R and ^X are both methyl groups, and n is 38.
A structure is obtained where:
BPA-PO Propylene oxide adduct of bisphenol A (average number of moles added: 2.2 mol)
BPA-EO Ethylene oxide adduct of bisphenol A (average number of moles added: 2.2 mol)
TPA Terephthalic acid TMA Trimellitic anhydride

<Production Example of Polymer A1>
Solvent: toluene 100.0 parts Monomer composition 100.0 parts (the monomer composition is a mixture of behenyl acrylate, methacrylonitrile, and styrene in the ratio shown below)
(Behenyl acrylate (first monomer) 67.0 parts (28.9 mol%))
(Methacrylonitrile (second monomer) 22.0 parts (53.8 mol%))
(Styrene (third monomer) 11.0 parts (17.3 mol %))
Polymerization initiator t-butyl peroxypivalate (Perbutyl PV, manufactured by NOF Corp.) 0.5 parts The above materials were charged into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. The reaction vessel was heated to 70°C while stirring at 200 rpm to carry out a polymerization reaction for 12 hours, and a solution in which the polymer of the monomer composition was dissolved in toluene was obtained. Subsequently, the temperature of the solution was lowered to 25°C, and the solution was added to 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 then vacuum dried at 40°C for 24 hours to obtain polymer A1. The weight average molecular weight of polymer A1 was 68,400, the melting peak temperature (melting point) was 62°C, and the acid value was 0.0 mgKOH/g.
The polymer A1 was analyzed by NMR and found to contain 28.9 mol % of monomer units derived from behenyl acrylate, 53.8 mol % of monomer units derived from methacrylonitrile, and 17.3 mol % of monomer units derived from styrene. The SP values of the monomer units were also calculated.

<Production Examples of Polymers A2 to A17>
Polymers A2 to A17 were obtained by carrying out the reaction in the same manner as in Production Example for Polymer A1, except that the monomers and the mass parts thereof were changed as shown in Table 2. The physical properties are shown in Table 2.

表中、「１ｓｔ」は第一のモノマーユニット（重合性単量体）を、「２ｎｄ」は第二の
モノマーユニット（重合性単量体）を、「３ｒｄ」は第三のモノマーユニット（重合性単量体）を示す。酸価の単位はｍｇＫＯＨ／ｇであり、融点の単位は℃であり、分子量は重量平均分子量である。

In the table, "1st" indicates the first monomer unit (polymerizable monomer), "2nd" indicates the second monomer unit (polymerizable monomer), and "3rd" indicates the third monomer unit (polymerizable monomer). The acid value is in mgKOH/g, the melting point is in °C, and the molecular weight is the weight average molecular weight.

The abbreviations in Table 2 are as follows.
BEA: Behenyl acrylate SA: Stearyl acrylate MYA: Myrisil acrylate OA: Octacosyl acrylate HA: Hexadecyl acrylate MN: Methacrylonitrile AN: Acrylonitrile HPMA: 2-hydroxypropyl methacrylate AM: Acrylamide VA: Vinyl acetate MA: Methyl acrylate St: Styrene MM: Methyl methacrylate

<Production Example of Toner 1>
Binder resin P1 100.0 parts Polymer A1 5.0 parts Fischer-Tropsch wax (peak temperature of maximum endothermic peak 90° C.) 6.0 parts C.I. Pigment Blue 15:3 9.0 parts The raw materials shown in the recipe were mixed using a Henschel mixer (FM75J type, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 20 s ^-1 for a rotation time of 5 min, and then kneaded with a twin-screw kneader (PCM-30 type, manufactured by Ikegai Corporation) set at a temperature of 130° C. and a barrel rotation speed of 200 rpm.
The kneaded product thus obtained was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized product. The coarsely pulverized product thus obtained was finely pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The weight average particle size (D4) of the obtained toner particles 1 was 6.5 μm.
100.0 parts of the obtained toner particles 1 were mixed with 2.0 parts of hydrophobic silica (BET: 200 ^m2 /g) in a Henschel mixer (FM75J type, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 30 s ^-1 for a rotation time of 5 min, and passed through an ultrasonic vibration sieve with an opening of 54 μm to obtain toner 1.

<Production Examples of Toners 2 to 31>
Toners 2 to 31 were obtained in the same manner as in the production example of toner 1, except that the types and amounts of the binder resin and polymer A were changed to those shown in Table 3. The weight average particle size (D4) of the obtained toner particles 2 to 31 was all 6.5 μm.

<Production Example of Magnetic Core Particles>
(Step 1: Weighing and mixing step)
The _ferrite raw materials were weighed so as to _{obtain the} above composition ratio. Then, the materials were pulverized and mixed for 5 hours in a dry vibration mill _using stainless _steel beads having a diameter of 1/8 inch.
(Step 2: Pre-firing step)
The obtained pulverized material was made into pellets of about 1 mm square using a roller compactor. The pellets were passed through a vibrating sieve with 3 mm mesh to remove coarse powder, and then through a vibrating sieve with 0.5 mm mesh to remove fine powder. The pellets were then fired at 1000° C. for 4 hours in a nitrogen atmosphere (oxygen concentration 0.01% by volume) using a burner-type firing furnace to produce calcined ferrite. The composition of the resulting calcined ferrite was as follows:
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393

(Step 3: Crushing step)
The calcined ferrite was crushed to about 0.3 mm using a crusher, and then 30 parts of water was added to 100 parts of the calcined ferrite, and the mixture was crushed in a wet ball mill using zirconia beads with a diameter of 1/8 inch for 1 hour. The obtained slurry was further crushed in a wet ball mill using alumina beads with a diameter of 1/16 inch for 4 hours to obtain a ferrite slurry (finely crushed calcined ferrite).
(Step 4: Granulation step)
To the ferrite slurry, 1.0 part of ammonium polycarboxylate as a dispersant and 2.0 parts of polyvinyl alcohol as a binder were added per 100 parts of the calcined ferrite. The mixture was then granulated into spherical particles using a spray dryer (manufacturer: Okawara Kakoki Co., Ltd.). The resulting particles were adjusted in particle size, and then heated at 650° C. for 2 hours using a rotary kiln to remove the organic components of the dispersant and binder.

(Step 5: Firing step)
In order to control the firing atmosphere, the material was heated from room temperature to 1300° C. in a nitrogen atmosphere (oxygen concentration 1.00% by volume) in an electric furnace over a period of 2 hours, and then fired at a temperature of 1150° C. for 4 hours. The material was then cooled to 60° C. over a period of 4 hours, returned from the nitrogen atmosphere to the air, and taken out at a temperature of 40° C. or less.
(Step 6: Selection step)
After the aggregated particles were crushed, low magnetic particles were removed by magnetic separation, and coarse particles were removed by sieving through a sieve with 250 μm openings, to obtain magnetic core particles 1 having a volume distribution-based median diameter of 37.0 μm.

[Preparation of coating resin]
Cyclohexyl methacrylate 26.8% by mass
Methyl methacrylate 0.2% by mass
Methyl methacrylate macromonomer 8.4% by mass
(Macromonomer having a weight average molecular weight of 5000 and a methacryloyl group at one end)
Toluene 31.3% by mass
Methyl ethyl ketone 31.3% by mass
Azobisisobutyronitrile 2.0% by mass
Of the above materials, cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone were placed in a four-neck separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer.
Nitrogen gas was introduced into the separable flask to replace the inside of the system with nitrogen gas, and then the temperature was raised to 80° C., and azobisisobutyronitrile was added and the mixture was refluxed for 5 hours to polymerize.
Hexane was poured into the obtained reaction product to precipitate a copolymer, and the precipitate was filtered and then vacuum dried to obtain coating resin 1. 30 parts of the obtained coating resin 1 were dissolved in 40 parts of toluene and 30 parts of methyl ethyl ketone to obtain polymer solution 1 (solid content 30 mass %).

[Preparation of coating resin solution]
・Polymer solution 1 (resin solid content concentration 30%) 33.3% by mass
Toluene 66.4% by mass
Carbon black 0.3% by mass
(Primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² /g, DBP oil absorption 75 mL/100 g)
The above materials were dispersed for 1 hour using zirconia beads having a diameter of 0.5 mm in a paint shaker. The resulting dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

[Magnetic Carrier Production Example]
(Resin coating process)
The coating resin solution 1 was added to a vacuum degassing type kneader maintained at room temperature so that the resin component amounted to 2.5 parts per 100 parts of magnetic core particles 1. After the addition, the kneader was rotated at a speed of 30 rpm.
After the solvent had evaporated to a certain extent (80% by mass), the temperature was raised to 80° C. while mixing under reduced pressure, and the toluene was distilled off over 2 hours, followed by cooling.
The obtained magnetic carrier was separated by magnetic separation to separate out low magnetic particles, which were passed through a sieve with openings of 70 μm and then classified by an air classifier to obtain Magnetic Carrier 1 having a volume distribution-based median diameter of 38.2 μm.

<Production Examples of Two-Component Developers 1 to 31>
Each of the toners 1 to 31 and the magnetic carrier 1 (number average particle size 35 μm) were mixed in a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) for 0.5 s ⁻¹ and 5 minutes so that the toner concentration became 9% by mass, and two-component developers 1 to 31 were obtained.

<Toner Evaluation>
A modified Canon full-color copier ImagePRESS C800 was used as the image forming apparatus for evaluation. This image forming apparatus has a photoconductor that forms an electrostatic latent image as an image carrier, and has a developing process in which the electrostatic latent image on the photoconductor is developed into a toner image by a two-component developer. It also has a transfer process in which the developed toner image is transferred to an intermediate transfer body, and then the toner image on the intermediate transfer body is transferred to paper, and a fixing process in which the toner image on the paper is fixed by heat. The image forming apparatus was modified so that the fixing temperature and process speed could be changed.

[Charge Stability Evaluation]
The charge amount of the toner on the electrostatic latent image carrier was measured by a Faraday Cage to evaluate the charging stability.
A Faraday cage is a coaxial double cylinder, with the inner and outer cylinders insulated. If a charged body with a charge Q is placed inside the inner cylinder, electrostatic induction will create the same effect as if a metal cylinder with a charge Q were present. The amount of induced charge was measured with an electrometer (Kessley 6517A, manufactured by Kessley), and the charge Q (mC) divided by the toner mass M (kg) in the inner cylinder (Q/M) was determined as the charge per unit mass.
Paper: CS-680 (68.0 g/m ² ) (Canon Marketing Japan Inc.)
Evaluation image: A 2 cm x 5 cm image is placed in the center of the A4 paper. Amount of toner on the paper: 0.35 mg/ ^cm2
(Adjusted by DC voltage V _DC of developer carrier, charging voltage V _D of electrostatic latent image carrier, and laser power)
Test environment: High temperature and humidity environment (temperature 30°C/humidity 80% RH (hereinafter H/H))
Process speed: 377 mm/s
The two-component developer 1 was charged into the developing device of the cyan station of the image forming apparatus, and evaluation was performed. For stabilization of the evaluation machine, 10 sheets of A4 paper were output using a band chart with an image ratio of 0.1%.
Then, the above-mentioned evaluation image was formed on the electrostatic latent image carrier, and before the image was transferred to the intermediate transfer member, the rotation of the electrostatic latent image carrier was stopped, and the toner on the electrostatic latent image carrier was suctioned and collected by a metal cylindrical tube and a cylindrical filter. At that time, the charge amount Q stored in the capacitor through the metal cylindrical tube and the mass M of the collected toner were measured, and the charge amount Q/M (mC/kg) per unit mass was calculated from the measured charge amount Q/M (mC/kg) on the electrostatic latent image carrier at the beginning.
Next, the developer was left in the evaluation machine in a H/H environment for two weeks, and then the evaluation machine was started and the Q/M (mC/kg) on the electrostatic latent image carrier after the test was measured in the same manner as before the test. The Q/M retention rate on the electrostatic latent image carrier after the test was calculated using the following formula. The Q/M retention rate on the electrostatic latent image carrier after the test was evaluated according to the following evaluation criteria.
Maintenance rate of Q/M on electrostatic latent image carrier after durability test=
{Q/M on electrostatic latent image carrier after durability/Q/M on electrostatic latent image carrier at the beginning}×100
(Evaluation Criteria)
A: Q/M maintenance rate is 95% or more. B: Q/M maintenance rate is 90% or more but less than 95%. C: Q/M maintenance rate is 85% or more but less than 90%. D: Q/M maintenance rate is 80% or more but less than 85%. E: Q/M maintenance rate is 75% or more but less than 80%. F: Q/M maintenance rate is less than 75%.

[Evaluation of image scratch resistance]
Paper: SPLENDLUX 135 (135.0 g/m ² ) (manufactured by Fedrigoni)
Evaluation image: A 2 cm x 15 cm image was placed in the center of the A4 paper. Toner amount on the paper: 0.90 mg/ ^cm2
(Adjusted by DC voltage V _DC of developer carrier, charging voltage V _D of electrostatic latent image carrier, and laser power)
Test environment: Normal temperature and humidity (temperature 23°C, humidity 50% RH (hereinafter N/N))
Process speed: 248 mm/s
The two-component developer 1 was charged into the developing devices of the cyan station and magenta station of the image forming apparatus, and an evaluation was performed. The evaluation image was printed at a fixing temperature of 170°C.
The recording paper on which the evaluation image was formed was subjected to a surface property test using a HEIDON surface property tester manufactured by Shinto Scientific Co., Ltd.
A 200 g weight was placed on the image using a TYPE 14FW, and the image was scratched with a 0.75 mm diameter needle at a speed of 60 mm/min and a length of 30 mm to evaluate image scratch resistance. The area ratio from which the toner peeled off was binarized by image processing.
(Evaluation Criteria)
A: There are no scratches on the image.
B: Image scratches occurred. The toner peeled area ratio is less than 1.0%. C: Image scratches occurred. The toner peeled area ratio is 1.0% to less than 2.0%. D: Image scratches occurred. The toner peeled area ratio is 2.0% to less than 4.0%. E: Image scratches occurred. The toner peeled area ratio is 4.0% to less than 6.0%. F: Image scratches occurred. The toner peeled area ratio is 6.0% or more.

Two-component developers 2 to 31 were also evaluated in the same manner as two-component developer 1. The results are shown in Table 4.

Claims (8)

A toner having toner particles containing a binder resin and a polymer A,
The binder resin contains a polyester resin having a structure represented by the following formula (B):

In formula (B), R and ^X each independently represent a hydrogen atom, a methyl group, or a phenyl group;
A represents a polyester moiety;
B is a polyester moiety, or -R ²⁰ OH, -R ²⁰ COOH,

and -R ²⁰ NH ₂ , where R ²⁰ represents a single bond or an alkylene group having 1 to 4 carbon atoms;
The average number of repetitions n is 10 to 80;
The polymer A has a first monomer unit having a structure represented by the following formula (I) and a second monomer unit different from the first monomer unit,

In formula (I), ^R represents a hydrogen atom or a methyl group, R represents an alkyl group having 18 to 36 carbon atoms,
a content ratio of the first monomer unit in the polymer A is 5.0 mol % to 60.0 mol % based on the total number of moles of all monomer units in the polymer A,
the content ratio of the second monomer unit in the polymer A is 20.0 mol % to 95.0 mol % based on the total number of moles of all monomer units in the polymer A,
A toner characterized in that the following formulas (1) to (3) are satisfied when the SP value of the first monomer unit is SP1 (J/cm ³ ) ^0.5 , the SP value of the second monomer unit is SP2 (J/cm ³ ) ^0.5 , and the SP value of the silicone moiety represented by -(Si(R ^x ) ₂ O) _n -Si(R ^x ) ₂ - in the structure represented by formula (B) is SP3 (J/cm ³ ) ^0.5 :
SP1≦18.4...(1)
21.0≦SP2...(2)
SP1-SP3<SP2-SP1...(3) 2. The toner according to claim 1, wherein the second monomer unit is at least one selected from the group consisting of the following formulae (II) and (III):

In formula (II), X represents a single bond or an alkylene group having 1 to 6 carbon atoms.
^R1 is -C≡N,
-C(=O)NHR ¹⁰ (R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms),
Hydroxy groups,
-COOR ¹¹ (R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms),
-NHCOOR ¹² (R ¹² represents an alkyl group having 1 to 4 carbon atoms);
-NH-C(=O)-N( ^R13 ) ₂ (each of the two ^R13 's independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms),
-COO( _CH2 ) _2NHCOOR14 ^{( R14} represents an alkyl group having 1 to 4 carbon atoms), or -COO( _CH2 ) ₂ -NH-C(=O)-N( ^R15 ) ₂ (two ^R15s each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
^R2 represents a hydrogen atom or a methyl group.
In formula (III), R ³ represents an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group. The toner according to claim 1 or 2, wherein the content of the polymer A is 1.0 part by mass or more and 10.0 parts by mass or less per 100 parts by mass of the binder resin. 4. The toner according to claim 1, wherein in formula (I), R ¹ is a hydrogen atom, and R is an alkyl group having 22 carbon atoms. The toner according to any one of claims 1 to 4, wherein the content of the silicone moiety in the polyester resin having the structure represented by formula (B) is 0.5% by mass or more and 5.0% by mass or less. 6. The toner according to claim 1, wherein in formula (B), R and ^X each represent a methyl group. The toner according to any one of claims 1 to 6, wherein the SP2 satisfies the following formula (2)':
25.0≦SP2≦30.0...(2)' The toner according to any one of claims 1 to 7, wherein the content of the polyester resin having the structure represented by formula (B) in the binder resin is 50% by mass or more.