JP7313881B2 - Toner and two-component developer - Google Patents

Description

The present invention relates to a toner used in electrophotography, electrostatic recording, electrostatic printing, and toner jet, and a two-component developer using the toner.

In recent years, with the widespread use of electrophotographic full-color copiers, there is a growing demand for high-speed printing and energy saving. In order to cope with high-speed printing, techniques for melting toner more quickly in the fixing process are being studied. Also, in order to improve productivity, techniques for shortening the time for various controls during one job or between jobs are being studied. Also, as an energy-saving countermeasure, a technology for fixing toner at a lower temperature is being studied in order to reduce power consumption in the fixing process.
In order to cope with high-speed printing and improve the low-temperature fixability of the toner, there is a method of using a binder resin which lowers the glass transition point and softening point of the binder resin of the toner and has a sharp melting property. In recent years, many toners containing crystalline polyester have been proposed as a resin having a sharp melting property. However, the crystalline polyester is a material with problems in terms of charging stability in a high-temperature and high-humidity environment, especially in maintaining charging properties after being left in a high-temperature and high-humidity environment.
Various toners using crystalline vinyl resins have been proposed as other crystalline resins having sharp melting properties.

For example, Patent Document 1 proposes a toner that achieves both low-temperature fixability and heat-resistant storage stability by using an acrylate-based resin having crystallinity in a side chain.
Further, Japanese Patent Application Laid-Open No. 2002-200003 proposes a toner using a binder resin in which an amorphous vinyl resin and a crystalline vinyl resin are chemically bonded.

JP 2014-130243 A JP 2017-58604 A

The toners of the above-mentioned patent documents can achieve both low-temperature fixability and heat-resistant storage stability, and can also somewhat improve charging stability, which has been a weak point of toners using crystalline polyester resins. However, it has been found that toners using these crystalline vinyl resins as binder resins are slow in charging rise.
As a result, when an image with a small print ratio is printed immediately after an image with a large print ratio is printed, the image density gradually fluctuates due to the difference in the amount of charge between the toner existing in the developing machine and the toner newly supplied to the developing machine. This tendency is particularly remarkable in a low humidity environment.
An object of the present invention is to provide a toner that solves the above problems. Specifically, the object of the present invention is to provide a toner that satisfies both low-temperature fixability and heat-resistant storage stability, has charging stability even in a high-temperature and high-humidity environment, and has a quick charging rise that is less likely to cause density fluctuations regardless of the image printing ratio.

A first aspect of the present invention is a toner having toner particles containing a binder resin and inorganic fine particles,
The binder resin contains a polymer A, which is a vinyl polymer ,
The polymer A is
a first monomer unit derived from a first polymerizable monomer that is a vinyl-based monomer and that is a reacted form of the first polymerizable monomer in the main chain of a polymer obtained by polymerizing the vinyl-based monomer; and
A second monomer unit derived from a second polymerizable monomer that is a vinyl-based monomer different from the first polymerizable monomer, and is in the form of a reaction of the second polymerizable monomer in the main chain of the polymer obtained by polymerizing the vinyl-based monomer.
has
The first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms,
The 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,
When the SP value of the first monomer unit is SP ₁₁ (J/cm ³ ) ^0.5 and the SP value of the second monomer unit is SP ₂₁ (J/cm ³ ) ^0.5 , the following formulas (1) and (2) are satisfied,
3.00≦(SP ₂₁ −SP ₁₁ )≦25.00 (1)
21.00≦SP ₂₁ (2)
The content of the polymer A is 50% by mass or more based on the total mass of the binder resin,
The inorganic fine particles are surface-treated with a compound having an alkyl group,
The toner is characterized in that the inorganic fine particles have a volume resistivity of 1.0×10 ⁵ Ω·cm to 1.0×10 ¹³ Ω·cm.
A second aspect of the present invention is a toner having toner particles containing a binder resin and inorganic fine particles,
The binder resin contains a polymer A, which is a vinyl polymer ,
The polymer A is
a first polymerizable monomer that is a vinyl monomer, and
a second polymerizable monomer that is a vinyl-based monomer different from the first polymerizable monomer
is a polymer of a composition containing
The first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms,
The content of the first polymerizable monomer in the composition is 5.0 mol% to 60.0 mol% based on the total number of moles of all polymerizable monomers in the composition,
The content of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of all polymerizable monomers in the composition,
When the SP value of the first polymerizable monomer is SP ₁₂ (J/cm ³ ) ^0.5 and the SP value of the second polymerizable monomer is SP ₂₂ (J/cm ³ ) ^0.5 , the following formulas (3) and (4) are satisfied,
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (3)
18.30≦SP ₂₂ (4)
The content of the polymer A is 50% by mass or more based on the total mass of the binder resin,
The inorganic fine particles are surface-treated with a compound having an alkyl group,
The toner is characterized in that the inorganic fine particles have a volume resistivity of 1.0×10 ⁵ Ω·cm to 1.0×10 ¹³ Ω·cm.

The toner of the present invention achieves both low-temperature fixability and heat-resistant storage stability, has charge stability even in a high-temperature and high-humidity environment, and can provide a toner with a fast charging rise that is less likely to cause density fluctuations regardless of the image printing ratio.

［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。 In the present invention, the descriptions of "XX or more and YY or less" and "XX to YY" that represent numerical ranges mean numerical ranges including the lower and upper limits, which are endpoints, unless otherwise specified.
In the present invention, (meth)acrylic acid ester means acrylic acid ester and/or methacrylic acid ester.
In the present invention, the term "monomer unit" refers to a reacted form of a monomer substance in a polymer, and one unit is defined as one carbon-carbon bond segment in the main chain formed by polymerizing the vinyl-based monomer in the polymer.
A vinyl-based monomer can be represented by the following formula (Z).

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

A first aspect of the present invention is a toner having toner particles containing a binder resin and inorganic fine particles,
The binder resin contains a polymer A having a first monomer unit derived from a first polymerizable monomer and a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer,
The first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms,
The 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,
When the SP value of the first monomer unit is SP ₁₁ (J/cm ³ ) ^0.5 and the SP value of the second monomer unit is SP ₂₁ (J/cm ³ ) ^0.5 , the following formulas (1) and (2) are satisfied,
3.00≦(SP ₂₁ −SP ₁₁ )≦25.00 (1)
21.00≦SP ₂₁ (2)
The inorganic fine particles are surface-treated with a compound having an alkyl group,
The inorganic fine particles have a volume resistivity of 1.0×10 ⁵ Ω·cm to 1.0×10 ¹³ Ω·cm.
A second aspect of the present invention is a toner having toner particles containing a binder resin and inorganic fine particles,
The binder resin contains a polymer A which is a polymer of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer,
The first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms,
The content of the first polymerizable monomer in the composition is 5.0 mol% to 60.0 mol% based on the total number of moles of all polymerizable monomers in the composition,
The content of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of all polymerizable monomers in the composition,
When the SP value of the first polymerizable monomer is SP ₁₂ (J/cm ³ ) ^0.5 and the SP value of the second polymerizable monomer is SP ₂₂ (J/cm ³ ) ^0.5 , the following formulas (3) and (4) are satisfied,
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (3)
18.30≦SP ₂₂ (4)
The inorganic fine particles are surface-treated with a compound having an alkyl group,
The inorganic fine particles have a volume resistivity of 1.0×10 ⁵ Ω·cm to 1.0×10 ¹³ Ω·cm.

The present inventors consider the mechanism by which the effects of the present invention are exhibited as follows.
It is considered that the charging speed of the toner is determined by the speed at which the charge moves from the inorganic fine particles on the toner particle surface to the toner particle surface and the charge is saturated on the entire toner particle. Conventionally, it is known that the use of inorganic fine particles having a low resistivity, such as titanium oxide, increases the transfer speed of electric charge inside the inorganic fine particles, thereby increasing the charging speed of the toner.
However, the inventors of the present invention have found that the use of a crystalline vinyl resin alone as the binder resin does not sufficiently increase the charge rising speed. It is considered that the charge transfer from the inorganic fine particles to the toner particle surface is rate-limiting.

As a result of investigation into changing the composition of the binder resin, it has been found that the presence of a monomer unit having a high SP value in the crystalline vinyl resin slightly improves the rise of charging. It is thought that when the SP value is high, the charge moves faster due to the presence of an electric dipole due to the localization of the charge. However, depending on the composition, low-temperature fixability and heat-resistant storage stability may be deteriorated.
As a result of intensive studies, the present inventors have found that the above problems can be solved by controlling the molar ratio of monomer units derived from a plurality of polymerizable monomers in the binder resin in the toner, the SP value, the difference in the SP value, the resistivity of the inorganic fine particles on the surface of the toner particles, and the surface treatment, within specific ranges, and have arrived at the present invention.

The binder resin is characterized by containing a polymer A having a first monomer unit 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.
Since the first monomer unit is a (meth)acrylic acid ester having an alkyl group having 18 to 36 carbon atoms, the binder resin has crystallinity and low-temperature fixability is improved.
In the first aspect, the content of the first monomer units 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.
Moreover, in the second aspect, the polymer A is a polymer of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer. The content of the first polymerizable monomer in the composition is 5.0 mol % to 60.0 mol % based on the total number of moles of all polymerizable monomers in the composition.
When the content is within the above range, good low-temperature fixability and good charging start-up in a low-humidity environment are obtained. If the content is less than 5.0 mol %, the low-temperature fixability will deteriorate. On the other hand, if the content exceeds 60.0 mol %, the portion occupied by the non-polar portion having a low SP value in the polymer becomes large, so that the rise of charging in a low-humidity environment is lowered. The preferred range is 10.0 mol % to 60.0 mol %, and the more preferred range is 20.0 mol % to 40.0 mol %.

The first polymerizable monomer forming the first monomer unit is at least one selected from the group consisting of (meth)acrylic acid esters having alkyl groups of 18 to 36 carbon atoms.
Examples of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms include (meth)acrylic acid esters having a linear alkyl group having 18 to 36 carbon atoms [stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosa (meth)acrylate , myricyl (meth)acrylate, dodriaconta (meth)acrylate, etc.] and (meth)acrylate esters having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth)acrylate, etc.].
Among these, from the viewpoint of storage stability of the toner, it is preferably at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group having 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 having 18 to 30 carbon atoms, and still more preferably at least one selected from the group consisting of linear stearyl (meth)acrylate and behenyl (meth)acrylate.
A 1st polymerizable monomer may be used individually by 1 type, or may use 2 or more types together.

In the first aspect, the polymer A is characterized by having a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer. When the SP value of the second monomer unit is _SP21 , the following formula (2) is satisfied. It is preferable to satisfy the following formula (2)′, more preferably to satisfy the following formula (2)″.
21.00≦SP ₂₁ (2)
21.00≦SP ₂₁ ≦40.00 (2)′
25.00≦SP ₂₁ ≦30.00 (2)''
Moreover, in the second aspect, when the SP value of the second polymerizable monomer is SP ₂₂ (J/cm ³ ) ^0.5 , the following formula (4) is satisfied. It is preferable to satisfy the following formula (4)′, and it is more preferable to satisfy the following formula (4)″.
18.30≦SP ₂₂ (4)
18.30≦SP ₂₂ ≦30.00 (4)′
21.00≦SP ₂₂ ≦23.00 (4)''
When the SP value of the second monomer unit or the second polymerizable monomer is within the above range, the charge transfer from the inorganic fine particles with low resistivity is rapidly performed, and the charging rise speed is increased.
Here, the SP value is an abbreviation for soluble parameter, and is a value that serves as an index of solubility. A calculation method will be described later.

In the first embodiment, the following formula (1) is satisfied, where the SP value of the first monomer unit is SP ₁₁ (J/cm ³ ) ^0.5 and the SP value of the second monomer unit is SP ₂₁ (J/cm ³ ) ^0.5 . It preferably satisfies formula (1)′, more preferably satisfies formula (1)″, and more preferably satisfies formula (1)′″.
In the second embodiment, the SP value of the first polymerizable monomer is SP ₁₂ (J/cm ³ ) ^0.5 , and the SP value of the second polymerizable monomer is SP ₂₂ (J/cm ³ ) ^0.5 , and the following formula (3) is satisfied. It preferably satisfies formula (3)′, more preferably satisfies formula (3)″, and even more preferably satisfies formula (3)′″.
3.00≦(SP ₂₁ −SP ₁₁ )≦25.00 (1)
3.00≦(SP ₂₁ −SP ₁₁ )≦20.00 (1)′
4.00≦(SP ₂₁ −SP ₁₁ )≦15.00 (1)''
5.00≦(SP ₂₁ −SP ₁₁ )≦15.00 (1)'''
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (3)
0.60≦(SP ₂₂ −SP ₁₂ )≦10.00 (3)′
2.00≦(SP ₂₂ −SP ₁₂ )≦7.00 (3)''
3.00≦(SP ₂₂ −SP ₁₂ )≦7.00 (3)'''
The unit of the SP value in the present invention is (J/m ³ ) ^0.5 , which can be converted to the unit of (cal/cm ³ ) ^0.5 by 1(cal/cm ³ ) ^0.5 =2.045×10 ³ (J/m ³ ) ^0.5 .

By satisfying the above SP value difference, the melting point of the polymer A is maintained without lowering the crystallinity. As a result, both low-temperature fixability and heat-resistant storage stability can be achieved.
In addition, the first monomer units interact with the alkyl groups of the low-resistance inorganic fine particles, and the charge transfer from the low-resistance inorganic fine particles to the polar portion of the second monomer unit is facilitated, thereby improving the charging rise.
This mechanism is inferred as follows.
The first monomer unit is incorporated into the polymer A, and crystallinity is exhibited by the aggregation of the first monomer units. Usually, however, the incorporation of other monomer units inhibits crystallization, making it difficult for the polymer to exhibit crystallinity. This tendency becomes remarkable when the first monomer unit and other monomer units are randomly combined in one molecule of the polymer.

On the other hand, in the present invention, by using a polymerizable monomer in which SP ₂₂ -SP ₁₂ is in the range of the above formula (2), it is believed that the first polymerizable monomer and the second polymerizable monomer are not randomly bonded but can be bonded continuously to some extent during polymerization. As a result, the first monomer units of the polymer A can be aggregated with each other, and even if other monomer units are incorporated, the crystallinity can be improved, and the melting point can be maintained.
In addition, when SP ₂₁ -SP ₁₁ is in the range of the above formula (1), it is thought that the first monomer unit and the second monomer unit in Polymer A can form a clear phase separation state without causing compatibility, and the melting point is maintained without lowering the crystallinity.
Polymer A preferably has a crystalline portion containing a first monomer unit derived from the first polymerizable monomer. Moreover, the polymer A preferably has an amorphous portion containing a second monomer unit derived from the second polymerizable monomer.

In addition, since the first monomer units are continuously bonded to each other, they are likely to interact with the alkyl groups on the surface of the inorganic fine particles with low resistivity, which is thought to improve the adhesion between the inorganic fine particles and the toner particles. In addition, since the second monomer units are also continuously bonded to each other, it is easy to adopt an arrangement that facilitates rapid charge transfer from the low resistivity inorganic fine particles to the high SP value second monomer unit, which is thought to improve the rise of charging.

In the first aspect, the content of the second monomer units 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.
In the second aspect, the content of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of all polymerizable monomers in the composition.
When the content ratio is within the above range, charge transfer from the low-resistance inorganic fine particles to the polar portion of the second monomer unit occurs rapidly. From the viewpoint of charging rise in a low-humidity environment, the content is preferably 40.0 mol % to 95.0 mol %, more preferably 40.0 mol % to 70.0 mol %.

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

Monomers having a urethane group: for example, alcohols having 2 to 22 carbon atoms having an ethylenically unsaturated bond (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, 2-ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate and 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, etc.), 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, etc.), and aromatic diisocyanate compounds (phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl methane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate and xylylene diisocyanate, etc.)], and alcohols having 1 to 26 carbon atoms (methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, heptanol, octanol, 2-ethylhexanol, nona alcohol, 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, nonadecyl alcohol, heneicosanol, behenyl alcohol, erucyl alcohol, etc.) and an isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond [2-isocyanatoethyl (meth)acrylate , 2-(0-[1′-methylpropylideneamino]carboxyamino)ethyl (meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate] by a known method.

A monomer having a urea group: For example, a monomer obtained by reacting an amine having 3 to 22 carbon atoms [primary amine (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amine (di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, cycloxylamine, etc.] with an isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond by a known method.
Carboxy group-containing monomers; for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate.
Among them, 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 preferred are monomers 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. The use of these monomers is preferable because the rise of charging in a low-humidity environment is further improved. Among them, a nitrile group is particularly preferable because it has a high electron-withdrawing property and speeds up charge transfer.

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.
Since vinyl esters are non-conjugated monomers and tend to maintain moderate reactivity with the first polymerizable monomer, they tend to improve the crystallinity of the polymer A, making it easier to achieve both low-temperature fixability and heat-resistant storage stability.
The second polymerizable monomer preferably has an ethylenically unsaturated bond, and more preferably has one ethylenically unsaturated bond.
Moreover, it is preferable that the second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B).

(In the formula, X represents a single bond or an alkylene group having 1 to 6 carbon atoms.
R ¹ is a nitrile group (-C≡N),
amide group (-C(=O)NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)),
hydroxy group,
—COOR ¹¹ (R ¹¹ is 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)),
urethane group (-NHCOOR ¹² (R ¹² is an alkyl group having 1 to 4 carbon atoms)),
a urea group (--NH--C(=O)--N(R ¹³ ) ₂ (each R ¹³ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4)));
—COO(CH ₂ ) ₂ NHCOOR ¹⁴ (R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or —COO(CH ₂ ) ₂ —NH—C(═O)—N(R ¹⁵ ) _{2 (} each R ¹⁵ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4))
is.
Preferably, R ¹ is a nitrile group (-C≡N),
amide group (-C(=O)NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)),
hydroxy group,
—COOR ¹¹ (R ¹¹ is 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 urea group (--NH--C(=O)--N(R ¹³ ) ₂ (each R ¹³ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4)));
—COO(CH ₂ ) ₂ NHCOOR ¹⁴ (R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or —COO(CH ₂ ) ₂ —NH—C(═O)—N(R ¹⁵ ) _{2 (} each R ¹⁵ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4))
is.
R ² is an alkyl group having 1 to 4 carbon atoms, and each R ³ is independently a hydrogen atom or a methyl group. )

The second polymerizable monomer may be used singly or in combination of two or more.
In the present invention, when a plurality of types of monomer units satisfying the requirements of the first monomer unit exist in the polymer A, the value of SP ₁₁ in formula (1) is the weighted average of the SP values of the respective monomer units. For example, a monomer unit A with an SP value of SP ₁₁₁ is included in A mol% based on the number of moles of the entire monomer units that satisfy the requirements of the first monomer unit, and a monomer unit B with an SP _value of SP ₁₁₂ is included in (100-A) mol% based on the number of moles of the entire monomer units that satisfy the requirements of the first monomer unit.
SP ₁₁ = (SP ₁₁₁ ×A+SP ₁₁₂ ×(100−A))/100
is. A similar calculation is made when three or more monomer units satisfying the requirements of the first monomer unit are included. On the other hand, SP ₁₂ also represents an average value calculated from the molar ratio of each first polymerizable monomer.
In the present invention, the second monomer unit corresponds to all monomer units that satisfy SP ₂₁ that satisfies formula (1) with respect to SP ₁₁ calculated by the above method. Similarly, the second polymerizable monomer corresponds to all polymerizable monomers having an SP _{of 22} that satisfies the formula (3) with respect to the SP of ₁₂ calculated by the above method.
That is, when the second polymerizable monomer is two or more polymerizable monomers, SP ₂₁ represents the SP value of the monomer unit derived from each polymerizable monomer, and SP ₂₁ -SP ₁₁ are determined for each monomer unit derived from the second polymerizable monomer. Similarly, SP ₂₂ represents the SP value of each polymerizable monomer, and SP ₂₂ -SP ₁₂ are determined for each second polymerizable monomer.

Polymer A is preferably a vinyl polymer. Examples of vinyl polymers include polymers of monomers containing ethylenically unsaturated bonds. The ethylenically unsaturated bond refers to a carbon-carbon double bond capable of undergoing radical polymerization, and includes, for example, vinyl group, propenyl group, acryloyl group, methacryloyl group and the like.
The acid value Av of the polymer A is preferably 30.0 mgKOH/g or less, more preferably 20.0 mgKOH/g or less. Although the lower limit is not particularly limited, it 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 less likely to be inhibited, and the melting point is well maintained.

The polymer A preferably has a weight average molecular weight (Mw) of 10,000 to 200,000, more preferably 20,000 to 150,000, as measured by gel permeation chromatography (GPC). When Mw is within the above range, it becomes easier to maintain elasticity around room temperature.
Moreover, the melting point of the polymer A is preferably 50° C. or higher and 80° C. or lower, and more preferably 53° C. or higher and 70° C. or lower. When the melting point is 50° C. or higher, the heat-resistant storage stability is improved, and when it is 80° C. or lower, the low-temperature fixability is improved.

Polymer A is a range that does not impair the molar ratio of the first monomer unit derived from the first polymerizable monomer and the second monomer unit derived from the second polymerizable monomer, and the above formula (1) or (3) (i.e., different from the first polymerizable monomer and the second polymerizable monomer).
As the third polymerizable monomer, a monomer that does not satisfy the formula (1) or the formula (3) among the monomers listed in the section of the second polymerizable monomer can be used.
In addition, the following monomers having no nitrile group, amide group, urethane group, hydroxy group, urea group, or carboxy group can also be used.
For example, styrene, styrene such as o-methylstyrene and its derivatives, methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate (meth)acrylic acid esters.
The third polymerizable monomer is preferably at least one selected from the group consisting of styrene, methyl methacrylate and methyl acrylate.
In addition, when these satisfy the formula (1) or formula (3), they can be used as the second polymerizable monomer.

From the viewpoint of easily obtaining the effects of the present invention, the content of the polymer A is preferably 50% by mass or more based on the total mass of the binder resin. It is more preferably 80% by mass to 100% by mass, and more preferably the polymer A as the binder resin.
In addition, it is preferable that the polymer A is present on the surface of the toner particles because the effect of the present invention can be easily obtained.

The binder resin may contain a resin other than the polymer A, if necessary, for the purpose of improving pigment dispersibility.
Examples of resins other than the polymer A used for the binder resin include the following resins.
Styrene and its substituted homopolymers such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene; Styrenic copolymers such as vinyl methyl ketone copolymers and styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic acid resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, cumarone-indene resins, petroleum-based resins, and the like.
Among these, styrenic copolymers and polyester resins are preferred. Also, it is preferably amorphous.

The toner of the present invention is characterized by containing inorganic fine particles having a volume resistivity of 1.0×10 ⁵ Ω·cm to 1.0×10 ¹³ Ω·cm.
When the volume resistivity of the inorganic fine particles is within the above range, the movement of charges in the inorganic fine particles becomes faster, and the charging rise is favorable. If the volume resistivity is less than 1.0×10 ⁵ Ω·cm, the resistivity is too low and the chargeability in a high-temperature and high-humidity environment is lowered. On the other hand, if it exceeds 1.0×10 ¹³ Ω·cm, the charging rise is delayed due to the high resistance. The volume resistivity of the inorganic fine particles is preferably 1.0×10 ⁸ Ω·cm to 7.0×10 ¹² Ω·cm. The volume resistivity can be controlled by the type of inorganic fine particles, the type of surface treatment, the concentration of the surface treatment agent, and the like.

Examples of inorganic fine particles having a volume resistivity of 1.0×10 ⁵ to 1.0×10 ¹³ Ω·cm include the following. metal titanates such as strontium titanate, calcium titanate and magnesium titanate; metal oxides such as titanium oxide, magnesium oxide, zinc oxide and cerium oxide;
Among these, titanium oxide, strontium titanate, calcium titanate, and zinc oxide are preferred. More preferred is strontium titanate. It is relatively easy to control properties such as grain size, resistivity and dielectric constant by adjusting manufacturing conditions. Strontium titanate preferably has a perovskite crystal structure. If strontium titanate has a perovskite crystal structure, the speed of electron transfer with the second monomer unit can be increased.

Strontium titanate, calcium titanate, and magnesium titanate fine particles can be obtained, for example, by a normal pressure heating reaction method. At this time, as a titanium oxide source, a hydrolyzate of a titanium compound is used, and a water-soluble acidic metal compound is used as a metal oxide source. It can be produced by a method of reacting the mixture while adding an alkaline aqueous solution at 60° C. or higher, followed by acid treatment.

The method for producing titanium oxide fine particles is not particularly limited, and examples include titania fine particles produced by a conventionally known sulfuric acid method and chlorine method, and titania fine particles obtained by a gas phase oxidation method in which titanium tetrachloride is reacted with oxygen in a gas phase. The titania fine particles obtained by the sulfuric acid method are more preferable because the number average diameter of the primary particles of the obtained titania fine particles can be easily controlled.
Titania fine particles are preferably used in either of two types of crystal forms, rutile type and anatase type. When it is desired to obtain anatase-type titanium oxide fine particles, it is preferable to add phosphoric acid, a phosphate, a potassium salt, or the like as a rutile transfer inhibitor when calcining metatitanic acid.
Further, when it is desired to obtain rutile-type titanium oxide fine particles, it is preferable to add salts such as lithium salts, magnesium salts, zinc salts and aluminum salts as rutile transfer accelerators when firing metatitanic acid, or seeds such as slurry containing rutile microcrystals.

Methods for producing metal oxide fine particles such as magnesium oxide, zinc oxide, and cerium oxide include a dry method in which metal vapor is oxidized with air to produce zinc oxide, and a wet method in which a metal salt is reacted with an alkali in an aqueous solution to neutralize, washed with water, dried, and then calcined to produce zinc oxide. Among these, those synthesized by the wet method are preferable in that fine particles having a relatively small particle diameter that can be added to the toner surface can be easily obtained.

Furthermore, it is preferable that the inorganic fine particles have a dielectric constant of 20 pF/m to 100 pF/m at 1 MHz. Inorganic fine particles having a dielectric constant within the above range are preferable because charge transfer with the second monomer unit occurs quickly. This is probably because the dielectric constant is derived from intra-atomic or inter-atomic polarization and is closely related to charge transfer.
Methods for controlling the dielectric constant include selection of inorganic fine particles, as well as conditions/operations that change the crystallinity of the particles when producing the inorganic fine particles. For example, methods such as changing the reaction temperature and water pressure in the case of a dry method, changing the pH and temperature in the case of a wet method, and performing ultrasonic treatment or bubbling treatment during crystal formation. More preferably, it is 20 pF/m to 50 pF/m.

Further, the inorganic fine particles are characterized by being surface-treated with a compound having an alkyl group.
Since the inorganic fine particles are surface-treated with a compound having an alkyl group, they can interact with the alkyl groups contained in the polymer A, thereby improving the adhesion and providing an arrangement that facilitates rapid charge transfer from the inorganic fine particles to the second monomer units of the toner particles.

Examples of alkyl group-containing compounds include fatty acids, fatty acid metal salts, silicone oils, silane coupling agents, titanium coupling agents, and aliphatic alcohols.
Among them, at least one compound selected from the group consisting of fatty acids, fatty acid metal salts, silicone oils, and silane coupling agents is preferable because the effect of the present invention can be obtained more easily.
Examples of fatty acids and fatty acid metal salts include lauric acid, stearic acid, behenic acid, lithium laurate, lithium stearate, sodium stearate, zinc laurate, zinc stearate, calcium stearate, and aluminum stearate.
Methods for surface-treating inorganic fine particles with a fatty acid or a metal salt thereof include the following methods. For example, in an Ar gas or N ₂ gas atmosphere, a slurry containing inorganic fine particles is put into a fatty acid sodium aqueous solution to deposit fatty acid on the perovskite crystal surface. Further, for example, a slurry containing inorganic fine particles is put into a fatty acid sodium aqueous solution in an Ar gas or _N2 gas atmosphere, and a desired metal salt aqueous solution is added dropwise while stirring, whereby the fatty acid metal salt can be precipitated and adsorbed on the perovskite crystal surface. For example, aluminum stearate can be adsorbed by using an aqueous sodium stearate solution and aluminum sulfate.

Examples of silicone oils include alkyl-modified silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, and octyl-modified silicone oil.
A known technique can be used as a method of silicone oil treatment. For example, the inorganic fine particles and silicone oil are mixed using a mixer; the silicone oil is sprayed into the inorganic fine particles using a sprayer; or the silicone oil is dissolved in a solvent and then the inorganic fine particles are mixed. The processing method is not limited to this.

Examples of silane coupling agents include hexamethyldisilazane, trimethylsilane, trimethylethoxysilane, isobutyltrimethoxysilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, dimethylethoxysilane, dimethyldimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, cetyltrimethoxysilane, stearyltrimethoxysilane, and the like.

Examples of fatty alcohols include ethanol, n-propanol, 2-propanol, n-butanol, t-butanol, n-octanol, stearyl alcohol, 1-tetracosanol, and the like. As a method for treating the aliphatic alcohol, for example, it may be treated with inorganic fine particles in a vaporized state by heating to a temperature equal to or higher than the boiling point.
Among these compounds, at least one compound selected from the group consisting of compounds having an alkyl group having 4 to 24 carbon atoms (preferably 4 to 18 carbon atoms) is preferable because the interaction with the alkyl group of the first monomer unit is further improved, thereby further improving the charging rise.

When C _x is the number of carbon atoms in the alkyl group of the first polymerizable monomer, and C _y is the number of carbon atoms in the alkyl group of the compound having an alkyl group, C _x /C _y is preferably from 0.8 to 24.0 because the interaction between the alkyl groups becomes stronger. It is more preferably 1.0 to 10.0. When using a plurality of first polymerizable monomers or compounds having an alkyl group, the average carbon number is determined according to the molar ratio.

The number average diameter of the primary particles of the inorganic fine particles is preferably 20 nm to 300 nm. When the number average diameter of the primary particles is within the above range, the inorganic fine particles are more likely to interact with both the first monomer unit and the second monomer unit of the polymer A having a block copolymer-like structure, which is preferable. It is more preferably 20 nm to 200 nm.
Also, the content of the inorganic fine particles 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.

It is preferable that the coverage ratio of the inorganic fine particles of the toner particles is 3 area % to 80 area % because the effect of the present invention can be easily obtained. It is more preferably 10 area % to 80 area %, still more preferably 20 area % to 80 area %. The coverage can be controlled by the amount of inorganic fine particles added, external addition conditions, and the like.

Also, the charge decay rate coefficient of the toner measured in an environment of 30° C. and 80% RH is preferably 3-100, more preferably 3-60. When the charge decay rate coefficient is within the above range, it is preferable because a decrease in charging in a high-temperature and high-humidity environment can be suppressed. The charge decay rate coefficient can be controlled by the type and acid value of the binder resin, the type of the inorganic fine particles, the surface treatment agent for the inorganic fine particles, the coating ratio of the toner particles with the inorganic fine particles, and the like.

Strontium titanate particles can be obtained by the normal pressure heating reaction method, as described above.
(Atmospheric pressure heating reaction method)
As a titanium oxide source, a hydrolyzate of a titanium compound, which is peptized with mineral acid, is used. For example, metatitanic acid obtained by the sulfuric acid method and having an SO ₃ content of preferably 1.0% by mass or less, more preferably 0.5% by mass or less, is peptized by adjusting the pH to 0.8 to 1.5 with hydrochloric acid.
As the strontium oxide source, nitrates, hydrochlorides, and the like can be used, and for example, strontium nitrate and strontium chloride can be used.
As the alkaline aqueous solution, caustic alkali can be used, and sodium hydroxide aqueous solution is particularly preferable.

Factors affecting the particle size of the obtained strontium titanate particles include the mixing ratio of the titanium oxide source and the strontium oxide source during the reaction, the concentration of the titanium oxide source at the initial stage of the reaction, the temperature and addition rate when adding the alkaline aqueous solution, and the like, which can be appropriately adjusted in order to obtain the desired particle size and particle size distribution. In addition, in order to prevent the formation of carbonate during the reaction process, it is preferable to prevent contamination with carbon dioxide by, for example, conducting the reaction in a nitrogen gas atmosphere.
Factors affecting the dielectric constant of the resulting strontium titanate particles include conditions/operations that destroy the crystallinity of the particles. In order to obtain strontium titanate with a low dielectric constant, it is preferable to perform an operation to give energy to disturb the crystal growth in a state where the concentration of the reaction solution is increased. As a specific method, for example, micro-bubbling with nitrogen is added to the crystal growth process.

The mixing ratio of the titanium oxide source and the strontium oxide source during the reaction is preferably 0.9 to 1.4, more preferably 1.05 to 1.20, in terms of SrO/TiO ₂ molar ratio. When the SrO/TiO ₂ molar ratio is 0.9 or more, it becomes difficult for unreacted titanium oxide to remain. The appropriate concentration of the titanium oxide source at the initial stage of the reaction is 0.05 to 1.3 mol/L, preferably 0.08 to 1.0 mol/L as TiO ₂ .
The temperature at which the alkaline aqueous solution is added is preferably about 60°C to 100°C. As for the addition speed of the alkaline aqueous solution, the slower the addition speed is, the larger the metal titanate particles are obtained, and the faster the addition speed is, the smaller the metal titanate particles are obtained. The addition rate of the alkaline aqueous solution is preferably 0.001 to 1.2 equivalents/h, more preferably 0.002 to 1.1 equivalents/h, relative to the charged raw material, and can be appropriately adjusted according to the particle size to be obtained.

(acid treatment)
It is preferable to further acid-treat the metal titanate particles obtained by the atmospheric pressure heating reaction. When synthesizing metal titanate particles by conducting a heating reaction under normal pressure, if the mixing ratio of the titanium oxide source and the strontium oxide source exceeds 1.0 in terms of the molar ratio of SrO/TiO ₂ , the unreacted metal source other than titanium that remains after the reaction may react with carbon dioxide gas in the air to generate impurities such as metal carbonate. Therefore, after the addition of the alkaline aqueous solution, it is preferable to carry out acid treatment in order to remove the unreacted metal source.
In the acid treatment, hydrochloric acid is preferably used to adjust the pH to 2.5 to 7.0, more preferably 4.5 to 6.0. As an acid, besides hydrochloric acid, nitric acid, acetic acid, or the like can be used for the acid treatment.

<Colorant>
A colorant may be used in the toner. Coloring agents include the following.
Examples of black colorants include carbon black; black toned by using a yellow colorant, a magenta colorant and a cyan colorant. A pigment may be used alone as a coloring agent, but it is more preferable to use a dye and a pigment in combination to improve the definition from the viewpoint of image quality of a full-color image.
Examples of magenta toner pigments 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; I. Pigment Violet 19; C.I. 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. I. disperse thread 9;C. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. 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. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of cyan toner pigments include the following. C. I. Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; C.I. I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment having a phthalocyanine skeleton substituted with 1 to 5 phthalimidomethyl groups.
As dyes for cyan toners, C.I. I. There is Solvent Blue 70.
Examples of yellow toner pigments 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, 1 74, 175, 176, 180, 181, 185; I. Bat Yellow 1, 3, 20.
As a yellow toner dye, C.I. I. There is 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.

(wax)
Wax may be used for the toner. Examples of wax include the following.
Hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; waxes mainly composed of fatty acid esters such as carnauba wax; and partially or wholly deoxidized fatty acid esters such as deoxidized carnauba wax.
Furthermore, the following are mentioned. Saturated straight-chain fatty acids such as palmitic acid, stearic acid and montanic acid; Unsaturated fatty acids such as brassic acid, eleostearic acid and valinaric acid; Saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, ceryl alcohol and mericyl alcohol; Polyhydric alcohols such as sorbitol; , carnauvyl alcohol, ceryl alcohol, merisyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide and lauric acid amide; saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide and hexamethylenebisstearic acid amide; Aromatic bisamides such as m-xylene bisstearic acid amide and N,N' distearyl isophthalic acid amide; Aliphatic metal salts (generally referred to as metallic soaps) such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate; Waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; A methyl ester compound having a hydroxyl group obtained by hydrogenation of
The wax content is preferably 2.0 parts by mass to 30.0 parts by mass with respect to 100 parts by mass of the binder resin.

(Charge control agent)
The toner may also contain a charge control agent, if necessary. As the charge control agent contained in the toner, a known charge control agent can be used, but a metal compound of an aromatic carboxylic acid which is colorless, has a high charging speed of the toner, and can stably maintain a constant charge amount is particularly preferable.
Examples of negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylic acid compounds, polymeric compounds having sulfonic acid or carboxylic acid side chains, polymeric compounds having sulfonates or sulfonic acid esters in side chains, polymeric compounds having carboxylates or carboxylic acid esters in side chains, boron compounds, urea compounds, silicon compounds, and calixarene. The charge control agent may be added internally or externally to the toner particles.
The amount of the charge control agent added is preferably 0.2 parts by mass to 10 parts by mass with respect to 100 parts by mass of the binder resin.

(inorganic fine powder)
In addition to the inorganic fine particles described above, the toner may also contain other inorganic fine powders, if necessary. The inorganic fine powder may be added internally to the toner particles, or may be mixed with the toner particles as an external additive. As the external additive, an inorganic fine powder such as silica is preferred. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.
For example, silica fine powder produced by any method such as a wet method of obtaining silica by neutralizing sodium silicate, typified by a sedimentation method and a sol-gel method, or a dry method of obtaining silica in a gas phase, typified by a flame fusion method and an arc method, is preferably used. Among them, fine silica powder produced by a sol-gel method or a flame melting method is more preferable because the number average diameter of primary particles can be easily controlled within a desired range.

As an external additive for improving fluidity, inorganic fine powder having a specific surface area of 50 m ² /g or more and 400 ^{m 2 /} g or less is preferable.
It is preferably an inorganic fine powder with a particle size of ² /g or less. In order to improve fluidity and stabilize durability, inorganic fine particles having a specific surface area within the above range may be used in combination.

<Developer>
The toner can be used as a one-component developer, but in order to further improve dot reproducibility, it is preferable to mix it with a magnetic carrier and use it as a two-component developer because stable images can be obtained over a long period of time. That is, it is preferable that the developer is a two-component developer containing a toner and a magnetic carrier, and the toner is the toner of the present invention.
As the magnetic carrier, for example, iron powder whose surface is oxidized, or unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earths, magnetic substances such as alloy particles thereof, oxide particles, and ferrite, and magnetic substance-dispersed resin carriers (so-called resin carriers) containing a magnetic substance and a binder resin that holds the magnetic substance in a dispersed state can be used.
When the toner is mixed with a magnetic carrier and used as a two-component developer, the carrier mixing ratio at that time is preferably 2% by mass or more and 15% by mass or less, more preferably 4% by mass or more and 13% by mass or less, as the toner concentration in the two-component developer.

<Method for producing toner particles>
The method for producing the toner particles is not particularly limited, and conventionally known production methods such as a suspension polymerization method, an emulsion aggregation method, a melt-kneading method, and a dissolution suspension method can be employed.
The obtained toner particles may be used as a toner as it is. Toner particles may be obtained by mixing the obtained toner particles with inorganic fine particles and, if necessary, other external additives. Toner particles, inorganic fine particles, and other external additives can be mixed using a mixing apparatus such as a double-con mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nauta mixer, Mechanohybrid (manufactured by Nippon Coke Kogyo Co., Ltd.), Nobilta (manufactured by Hosokawa Micron Co., Ltd.).
The external additive is preferably used in an amount of 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.

Methods for measuring various physical properties of toner and raw materials are described below.
<Analysis method>
(Measurement of Volume Resistivity of Inorganic Fine Particles)
The volume resistivity of inorganic fine particles is measured as follows. As a device, Keithley Instruments 6517 Electrometer/High Resistance System is used. Electrodes having a diameter of 25 mm are connected, inorganic fine particles are placed between the electrodes so as to have a thickness of about 0.5 mm, and a load of about 2.0 N is applied to measure the distance between the electrodes.
The resistance value is measured when a voltage of 1,000 V is applied to the inorganic fine particles for 1 minute, and the volume resistivity is calculated using the following formula.
Volume resistivity (Ω cm) = R x L
R: Resistance value (Ω)
L: Distance between electrodes (cm)
(Separation of inorganic fine particles from toner)
The inorganic fine particles can be separated from the toner and measured by the following method.
200 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved in a hot water bath to prepare a concentrated sucrose solution. 31 g of the concentrated sucrose solution and 6 mL of contaminon N (a 10% by mass aqueous solution of a neutral detergent for cleaning precision measuring instruments with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a centrifugation tube to prepare a dispersion. 1 g of toner is added to this dispersion, and clumps of toner are loosened with a spatula or the like.
The centrifuge tube is shaken for 20 minutes at 350 reciprocations per minute in the above shaker. After shaking, the solution is replaced in a swing rotor glass tube (50 mL), and centrifuged at 3500 rpm for 30 minutes in a centrifuge. In the glass tube after centrifugation, toner exists in the uppermost layer, and inorganic fine particles exist in the aqueous solution side of the lower layer. The aqueous solution of the lower layer is collected and centrifuged to separate sucrose and inorganic fine particles, and the inorganic fine particles are collected. If necessary, the centrifugal separation is repeated, and after sufficient separation, the dispersion is dried and the inorganic fine particles are collected.
When a plurality of inorganic fine particles are added, they can be sorted out using a centrifugal separation method or the like.

(Measurement of permittivity)
Using a 284A precision LCR meter (manufactured by Hewlett-Packard), after calibrating at frequencies of 1 kHz and 1 MHz, the complex permittivity at a frequency of 1 MHz is measured. A load of 39,200 kPa (400 kg/cm ² ) is applied to the inorganic fine particles to be measured for 5 minutes to form a disk-shaped measurement sample having a diameter of 25 mm and a thickness of 1 mm or less (preferably 0.5 to 0.9 mm). This measurement sample is mounted on ARES (manufactured by Rheometric Scientific F.E. Inc.) equipped with a dielectric constant measurement jig (electrode) having a diameter of 25 mm, and a load of 0.49 N (50 g) is applied in an atmosphere at a temperature of 25 ° C. It is obtained by measuring at a frequency of 1 MHz.

(Measurement of Charge Decay Rate Coefficient of Toner)
The charge decay rate coefficient of the toner was measured using an electrostatic diffusion rate measuring device NS-D100 (manufactured by Nanoseeds Co., Ltd.).
First, a sample pan is filled with about 100 mg of toner, and the surface is scraped to make it smooth. The sample pan is irradiated with X-rays for 30 seconds by an X-ray static eliminator to remove static electricity from the toner. Place the neutralized sample pan on the measurement plate. A metal plate is simultaneously placed as a reference for zero correction of the surface potential meter. The measurement plate on which the sample is placed is left in an environment of 30° C. and 80% RH for 1 hour or more before measurement.
Measurement conditions are set as follows.
Charge time: 0.1 second Measurement time: 1800 seconds Measurement interval: 1 second Discharge polarity: -
Electrode: Yes The initial potential was set to -600 V, and the change in surface potential immediately after charging was measured. By fitting the obtained results to the following equation, the charge decay rate coefficient α is obtained.
V _t =V ₀ exp(−αt ^1/2 )
V _t : surface potential (V) at time t
V ₀ : initial surface potential (V)
t: Time (seconds) after charging is applied
α: charge decay rate coefficient

(Number average diameter of primary particles of inorganic fine powder)
The number average diameter of the primary particles of the inorganic fine particles is measured using a Hitachi ultra-high resolution field emission scanning electron microscope (FE-SEM) S-4800 (Hitachi High-Technologies Corporation).
The measurement is performed on the toner after mixing the inorganic fine particles.
The photographing magnification is 50,000 times, and the photographed photograph is further enlarged twice, and from the obtained FE-SEM photograph image, the maximum diameter (major axis diameter) a and the minimum diameter (minor axis diameter) b of the inorganic fine particles are measured, and (a + b) / 2 is the particle diameter of the particle. The particle diameters of 100 randomly selected inorganic fine particles are measured, and the arithmetic average is obtained, which is taken as the number average diameter of the primary particles of the inorganic fine powder.

<Method for measuring content ratio of monomer units derived from various polymerizable monomers in polymer A>
The content of monomer units derived from various polymerizable monomers in the 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: 10500Hz
Accumulated times: 64 times Measurement temperature: 30°C
Sample: Prepared by putting 50 mg of a sample to be measured into a sample tube with an inner diameter of 5 mm, adding deuterated chloroform (CDCl ₃ ) as a solvent, and dissolving it in a constant temperature bath at 40°C.
From the obtained ¹ H-NMR chart, among the peaks attributed to the constituent elements of the monomer units derived from the first polymerizable monomer, a peak independent of the peaks attributed to the constituent elements of the monomer units derived from other monomers is selected, and the integrated value S1 of this peak is calculated. Similarly, from among the peaks attributed to the constituent elements of the monomer units derived from the second polymerizable monomer, a peak independent of the peaks attributed to the constituent elements of the monomer units derived from others is selected, and the integrated value S2 of this peak is calculated.
Furthermore, when a third polymerizable monomer is used, from the peaks attributed to the constituent elements of the monomer units derived from the third polymerizable monomer, a peak independent of the peaks attributed to the constituent elements of the monomer units derived from others is selected, and the integrated value S3 of this peak is calculated.
The content ratio of the monomer units derived from the first polymerizable monomer is determined as follows using the integral values S1, S2, and S3. Note that n1, n2, and n3 are the numbers of hydrogen atoms in the constituent elements to which the focused peaks are assigned for each site.
Content ratio (mol%) of monomer units derived from the first polymerizable monomer =
{(S1/n1)/((S1/n1)+(S2/n2)+(S3/n3))}×100
Similarly, the content ratio of monomer units derived from the second polymerizable monomer and the third polymerizable monomer is obtained as follows.
Content ratio (mol%) of monomer units derived from the second polymerizable monomer =
{(S2/n2)/((S1/n1)+(S2/n2)+(S3/n3))}×100
Content ratio (mol%) of monomer units derived from the third polymerizable monomer =
{(S3/n3)/((S1/n1)+(S2/n2)+(S3/n3))}×100
In addition, when a polymerizable monomer containing no hydrogen atom in the constituent elements other than the vinyl group is used in the polymer A, ¹³ C-NMR is used with ¹³ C as the atomic nucleus to be measured, the measurement is performed in the single pulse mode, and ^{the 1} H-NMR is calculated in the same manner.
In addition, when the toner is produced by suspension polymerization, the peaks of the release agent and other resins may overlap and independent peaks may not be observed. As a result, the content ratio of the monomer units derived from various polymerizable monomers in the polymer A may not be calculated. In that case, the polymer A' can be produced by performing the same suspension polymerization without using a release agent or other resin, and the polymer A' can be regarded as the polymer A for analysis.

<Method for calculating SP value>
SP ₁₂ and SP ₂₂ are obtained as follows according to the calculation method proposed by Fedors.
Eng. Sci., 14(2), 147-154 (1974), for ^each polymerizable monomer, the vaporization energy (Δei) (cal/mol) and the molar volume (Δvi) (cm ³ /mol) are determined for atoms or atomic groups in the molecular ^structure . ) to be ^0.5 .
SP ₁₁ and SP ₂₁ are calculated by the same calculation method as above for the atoms or atomic groups in the molecular structure in which the double bond of the polymerizable monomer is cleaved by polymerization.

<Measuring method of melting point>
The melting points of the polymer A and the release agent are measured using DSC Q1000 (manufactured by TA Instruments) under the following conditions.
Heating rate: 10°C/min
Measurement start temperature: 20°C
Measurement end temperature: 180°C
The melting points of indium and zinc are used to correct the temperature of the device detector, and the heat of fusion of indium is used to correct the amount of heat.
Specifically, about 5 mg of a sample is accurately weighed, placed in an aluminum pan, and subjected to differential scanning calorimetry. An empty silver pan is used as a reference.
Let the peak temperature of the maximum endothermic peak in the first heating process be the melting point.
Note that the maximum endothermic peak is the peak at which the endothermic amount is maximum when there are a plurality of peaks.

(Measurement of molecular weight of THF-soluble portion of resin)
The weight average molecular weight (Mw) of the THF-soluble portion of polymer A is measured by gel permeation chromatography (GPC) as follows.
First, the sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of THF-soluble components is about 0.8% by mass. This sample solution is used for measurement 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, 807 (manufactured by Showa Denko)
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, a standard polystyrene resin (for example, trade name "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) was used. Use a molecular weight calibration curve.

<Method for measuring acid value>
The acid value is mg of potassium hydroxide required to neutralize the acid contained in 1 g of sample. The acid value of polymer A in the present invention is measured according to JIS K 0070-1992, and specifically, it is measured according to the following procedure.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), and ion-exchanged water is added to make 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. After leaving it for 3 days in an alkali-resistant container so as not to come into contact with carbon dioxide gas, etc., it is filtered to obtain a potassium hydroxide solution. The resulting potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution is obtained by taking 25 mL of 0.1 mol/L hydrochloric acid in an Erlenmeyer flask, adding several drops of the phenolphthalein solution, titrating with the potassium hydroxide solution, and determining the amount of the potassium hydroxide solution required for neutralization. The 0.1 mol/L hydrochloric acid used is prepared according to JIS K 8001-1998.
(2) Operation (A) Main Test A 2.0 g sample of pulverized polymer A is precisely weighed in a 200 mL Erlenmeyer flask, 100 mL of a mixed solution of toluene/ethanol (2:1) is added, and dissolved over 5 hours. Next, a few drops of the phenolphthalein solution are added as an indicator, and the potassium hydroxide solution is used for titration. The end point of titration is when the light red color of the indicator continues for about 30 seconds.
(B) Blank test Titration is performed in the same manner as described above except that no sample is used (that is, only a mixed solution of toluene/ethanol (2:1) is used).
(3) Calculate the acid value by substituting the obtained result into the following formula.
A = [(CB) x f x 5.61]/S
Here, A: acid value (mgKOH/g), B: added amount of potassium hydroxide solution in blank test (mL), C: added amount of potassium hydroxide solution in final test (mL), f: factor of potassium hydroxide solution, S: mass of sample (g).

(Method for measuring coverage of external additive)
The coverage of the external additive is calculated by analyzing a surface image of the toner particles taken with a Hitachi ultra-high-resolution field emission scanning electron microscope (SEM; S-4800, Hitachi High-Technologies Corporation) using image analysis software (Image-Pro Plus ver.5.0, Nippon Roper Co., Ltd.).
Inorganic fine particles present on the surface of the toner particles are observed with the above SEM.
When observing, a place where the surface of the toner particles is as flat as possible is selected.
binarize an image in which only the inorganic fine particles are extracted from the surface of the toner particles,
It is calculated as a ratio of the area occupied by the inorganic fine particles to the area of the toner particle surface. A similar operation is performed for 10 toner particles, and their arithmetic mean value is obtained.

(Weight Average Particle Diameter (D4) of Toner Particles)
The weight-average particle diameter (D4) of the toner particles was measured using a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with an aperture tube of 100 μm and employing the pore electrical resistance method, and dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data. Then, measure with 25,000 effective measurement channels, analyze the measurement data, and calculate.
The electrolytic aqueous solution used for the measurement can be prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of about 1% by mass, such as "ISOTON II" (manufactured by Beckman Coulter, Inc.).
Before performing measurement and analysis, the dedicated software is set as follows.
In the "change standard measurement method (SOM) screen" of the dedicated software, set the total count number in control mode to 50000 particles, set the number of measurements to 1, and set the Kd value to the value obtained using "standard particle 10.0 μm" (manufactured by Beckman Coulter, Inc.). By pressing the threshold/noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the flash of aperture tube after measurement.
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 or more and 60 μm or less.

A specific measuring method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is placed in a 250 ml round-bottom glass beaker exclusively for Multisizer 3, set on a sample stand, and stirred with a stirrer rod counterclockwise at 24 rotations/sec. Then, remove the dirt and air bubbles inside the aperture tube using the dedicated software's "Flush Aperture Tube" function.
(2) Place about 30 ml of the electrolytic aqueous solution in a 100 ml flat-bottomed glass beaker, and add about 0.3 ml of a diluted solution obtained by diluting "Contaminon N" (a 10% by weight aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, made by Wako Pure Chemical Industries, Ltd.) as a dispersing agent with ion-exchanged water.
(3) Put a predetermined amount of ion-exchanged water in a water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W and two oscillators with an oscillation frequency of 50 kHz built in with a phase shift of 180 degrees.
(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 level of the electrolytic aqueous solution in the beaker is maximized.
(5) While the electrolytic aqueous solution in the beaker in (4) above is being irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water in the water tank is appropriately adjusted to 10°C or higher and 40°C or lower.
(6) The electrolytic aqueous solution of (5) above, in which the toner is dispersed, is dripped into the round-bottomed beaker of (1) above set in the sample stand, and adjusted so that the measured concentration is about 5%. The measurement is continued until the number of measured particles reaches 50,000.
(7) Analyze the measurement data with the dedicated software attached to the apparatus, and calculate the weight average particle size (D4). The weight average particle diameter (D4) is the "average diameter" on the analysis/volume statistics (arithmetic mean) screen when graph/vol% is set using dedicated software.

The present invention will be specifically described with reference to the following examples. However, these do not limit the present invention at all. Unless otherwise specified, "parts" in the following prescriptions are all based on mass. In addition, Example 43 is hereinafter referred to as Reference Example 43.

<Production example of strontium titanate fine particles>
Metatitanic acid obtained by the sulfuric acid method was deironized and bleached, then adjusted to pH 9.0 with an aqueous sodium hydroxide solution, subjected to desulfurization, neutralized to pH 5.8 with hydrochloric acid, filtered and washed with water. Water was added to the washed cake to obtain a slurry of 1.5 mol/L as TiO ₂ , and then hydrochloric acid was added to adjust the pH to 1.5 for deflocculation.
The desulfurized and deflocculated metatitanic acid was collected as TiO ₂ and put into a 3 L reactor. After adding an aqueous solution of strontium chloride to the peptized metatitanic acid slurry so that the SrO/TiO2 molar ratio was 1.15, the _TiO2 concentration was adjusted to 0.8 mol/L. Next, after heating to 90 ° C. while stirring and mixing, 444 mL of a 10 mol / L sodium hydroxide aqueous solution was added over 45 minutes while performing micro-bubbling of nitrogen gas at 600 ml / min, and then stirring was performed at 95 ° C. for 1 hour while performing micro-bubbling of nitrogen gas at 400 ml / min.
After that, the reaction slurry was stirred while cooling water at 10° C. was flown through the jacket of the reaction vessel, and was rapidly cooled to 15° C. Hydrochloric acid was added until the pH reached 2.0, and stirring was continued for 1 hour. After the obtained precipitate was washed by decantation, 5.0% by mass of sodium stearate based on the solid content was added as an aqueous solution dissolved in water, and the mixture was kept stirring for 2 hours, and then hydrochloric acid was added to adjust the pH to 6.5.
Next, the cake obtained by filtration and washing was left in the air at 120° C. for 10 hours, and then pulverized by a jet mill until aggregates disappeared to obtain strontium titanate (inorganic fine particles 1). Inorganic fine particles 1 showed a diffraction peak of strontium titanate in powder X-ray diffraction measurement, and had a perovskite crystal structure. Physical properties are shown in Table 1.

<Production example of calcium titanate fine particles>
Calcium titanate fine particles (inorganic fine particles 2) were obtained in the same manner as in Production Example of Strontium Titanate Particles 1, except that strontium chloride was replaced with calcium chloride and nitrogen gas microbubbling was not performed. Physical properties are shown in Table 1.

<Production Example 1 of Zinc Oxide Fine Particles>
200 parts of zinc oxide was added to an aqueous hydrochloric acid solution consisting of 500 parts of 35 mass % hydrochloric acid and 700 parts of purified water to completely dissolve the zinc oxide to prepare an aqueous zinc chloride solution. Separately, an aqueous ammonium bicarbonate solution was prepared by dissolving 460 parts of ammonium carbonate in 3000 parts of purified water. The zinc chloride aqueous solution was added to the ammonium bicarbonate aqueous solution over 60 minutes to form a precipitate. Thereafter, the precipitate was thoroughly washed, separated from the liquid phase, and dried at 130° C. for 5 hours.
The dry powder was then pulverized in an agate mortar. The powder thus prepared was heated to 500° C. at a rate of 200° C./hour while supplying a mixed gas of 0.21 L/min of nitrogen gas and 0.09 L/min of hydrogen gas. After maintaining the mixture for 2 hours and allowing it to cool to room temperature, 5.0% by mass of sodium stearate in the form of an aqueous solution dissolved in water with respect to the obtained zinc oxide fine particles was added, and the mixture was kept stirring for 2 hours. Then, hydrochloric acid was added to adjust the pH to 6.5, and the mixture was kept stirring for 1 hour to deposit stearic acid on the surface of the zinc oxide fine particles.
Next, the cake obtained by filtration and washing was dried in the air at 120° C. for 10 hours, and then pulverized by a jet mill until aggregates disappeared to obtain zinc oxide fine particles (inorganic fine particles 3). Physical properties are shown in Table 1.

<Production Example 1 of Titanium Oxide Fine Particles>
A hydrous titanium oxide slurry obtained by thermally hydrolyzing an aqueous solution of titanyl sulfate was neutralized to pH 7 with aqueous ammonia, filtered, and washed with water to obtain a cake. The average primary particle size of this sol was 7 nm.
Also, ilmenite ore containing 50% by mass of TiO ₂ equivalent was used as a starting material, and this raw material was dried at 150 ° C. for 2 hours, and then sulfuric acid was added and dissolved to obtain a TiOSO ₄ aqueous solution. This was concentrated, and after adding 4.0 parts of the anatase titania sol as a seed to 100 parts of TiO ₂ equivalent, hydrolysis was performed at 120° C. to obtain a slurry of TiO(OH) ₂ containing impurities.
This slurry was repeatedly washed with water at pH 5-6 to sufficiently remove sulfuric acid, FeSO ₄ and impurities. Then, a slurry of high-purity metatitanic acid [TiO(OH) ₂ ] was obtained.
After the metatitanic acid was heat-treated at 270° C. for 6 hours, it was sufficiently pulverized to obtain titanium oxide microparticles of anatase type crystals having a BET specific surface area of 50 m ² /g and a number average particle diameter of 50 nm.
Next, 5.0% by mass of sodium stearate was added to the above anatase-type titanium oxide fine particles as an aqueous solution dissolved in water, and the mixture was kept stirring for 2 hours. Then, hydrochloric acid was added to adjust the pH to 6.5, and stirring was continued for 1 hour.
Next, the cake obtained by filtration and washing was dried in the air at 120° C. for 10 hours, and pulverized by a jet mill until the aggregates of titanium fine particles disappeared, to obtain titanic acid fine particles 1 (inorganic fine particles 4). Physical properties are shown in Table 1.

<Production Example 2 of Titanium Oxide Fine Particles>
In Production Example 1 of Titanium Oxide Fine Particles, after adding an aqueous solution in which sodium stearate was dissolved, an aluminum sulfate aqueous solution was added with stirring to deposit aluminum stearate on the surfaces of the titanium oxide fine particles. Next, the cake obtained by filtering and washing is
After drying in the atmosphere at 20° C. for 10 hours, pulverization treatment by a jet mill was performed until the aggregates of titanium fine particles disappeared, to obtain titanic acid fine particles 2 (inorganic fine particles 5). Physical properties are shown in Table 1.

<Production Example 3 of Titanium Oxide Fine Particles>
Titanium oxide fine particles 3 (inorganic fine particles 6) were produced in the same manner as in Production Example 1 of titanium oxide fine particles, except that an aqueous solution in which sodium laurate was dissolved was used instead of an aqueous solution in which sodium stearate was dissolved. Physical properties are shown in Table 1.

<Production Example 4 of Titanium Oxide Fine Particles>
In Production Example 1 of Titanium Oxide Fine Particles, the following operations were carried out after the anatase-type titanium oxide fine particles were obtained. Hydrochloric acid was added to the dispersion of anatase-type titanium oxide fine particles to adjust the pH to 6.5, 0.5 part of octyl-modified silicone oil (FZ-3196; manufactured by Dow Corning) was added to 100 parts of the anatase-type titanium oxide fine particles, and stirring was continued for 1 hour.
Next, the cake obtained by filtration and washing was dried in the air at 120° C. for 10 hours, and pulverized by a jet mill until the aggregates of titanium fine particles disappeared, to obtain titanic acid fine particles 4 (inorganic fine particles 7). Physical properties are shown in Table 1.

<Production Example 5 of Titanium Oxide Fine Particles>
Titanium oxide fine particles 5 (inorganic fine particles 8) were produced in the same manner as in Production Example 1 of titanium oxide fine particles, except that an aqueous solution in which sodium behenate was dissolved was used instead of an aqueous solution in which sodium stearate was dissolved. Physical properties are shown in Table 1.

<Production Example 6 of Titanium Oxide Fine Particles>
In Production Example 1 of Titanium Oxide Fine Particles, the following operations were carried out after the anatase-type titanium oxide fine particles were obtained. A dispersion of anatase-type titanium oxide fine particles was adjusted to 50° C., hydrochloric acid was added to adjust the pH to 2.5, 5 parts of stearyltrimethoxysilane was added to 100 parts of the solid content, and stirring was continued for 6 hours.
Then, a sodium hydroxide solution was added to adjust the pH to 6.5, and the mixture was stirred for 1 hour, filtered and washed, and the obtained cake was dried in the atmosphere at 120° C. for 10 hours. After that, pulverization treatment by a jet mill was performed until the aggregates of titanium fine particles disappeared, and titanium oxide fine particles 6 (inorganic fine particles 9) were obtained. Physical properties are shown in Table 1.

<Production Example 7 of Titanium Oxide Fine Particles>
Titanium oxide fine particles 7 (inorganic fine particles 10) were obtained in the same manner as in Preparation Example 6 of titanium oxide fine particles, except that octyltrimethoxysilane was used instead of stearyltrimethoxysilane. Physical properties are shown in Table 1.

<Production Example 8 of Titanium Oxide Fine Particles>
Titanium oxide fine particles 8 (inorganic fine particles 11) were obtained in the same manner as in Preparation Example 6 of titanium oxide fine particles, except that isobutyltrimethoxysilane was used instead of stearyltrimethoxysilane. Physical properties are shown in Table 1.

<Production Example 9 of Titanium Oxide Fine Particles>
In Production Example 1 of Titanium Oxide Fine Particles, the following operations were carried out after the anatase-type titanium oxide fine particles were obtained. Anatase-type titanium oxide fine particles and a 20/80% by volume mixed solution of 1-tetracosanol/n-hexane were charged into an autoclave. It was heated at 240° C. for 1 hour under a pressure of 2.8 MPa. After that, the cake obtained by filtering and washing was dried in the air at 120° C. for 10 hours. After that, pulverization treatment by a jet mill was performed until aggregates of titanium oxide fine particles disappeared, and titanium oxide fine particles 9 (inorganic fine particles 12) were obtained. Physical properties are shown in Table 1.

<Production Example 10 of Titanium Oxide Fine Particles>
Titanium oxide fine particles 10 (inorganic fine particles 13) were obtained in the same manner as in Production Example 9 of titanium oxide fine particles, except that n-butanol was used instead of 1-tetracosanol. Physical properties are shown in Table 1.

<Production Example 11 of Titanium Oxide Fine Particles>
Titanium oxide fine particles 11 (inorganic fine particles 14) were obtained in the same manner as in Production Example 9 of titanium oxide fine particles, except that n-octocosanol was used instead of 1-tetracosanol. Physical properties are shown in Table 1.

<Production Example 12 of Titanium Oxide Fine Particles>
Titanium oxide fine particles 12 (inorganic fine particles 15) were obtained in the same manner as in Preparation Example 9 of titanium oxide fine particles, except that n-propanol was used instead of 1-tetracosanol. Physical properties are shown in Table 1.

<Production Example 2 of Zinc Oxide Fine Particles>
In Production Example 1 of zinc oxide microparticles, the zinc oxide microparticles before addition of the sodium stearate aqueous solution were used, and production was carried out by the following method.
An autoclave was charged with fine particles of zinc oxide and a mixed solution of 20/80% by volume of n-propanol/n-hexane. It was heated at 240° C. for 1 hour under a pressure of 2.8 MPa. After that, the cake obtained by filtering and washing was dried in the air at 120° C. for 10 hours. After that, pulverization treatment by a jet mill was performed until aggregates of zinc oxide fine particles disappeared, and zinc oxide fine particles 2 (inorganic fine particles 16) were obtained.

<Production Example 13 of Titanium Oxide Fine Particles>
Titanium oxide fine particles 13 (inorganic fine particles 17) were obtained in the same manner as in Production Example 12 of titanium oxide fine particles, except that the ratio of the mixed solution of n-propanol/n-hexane was changed to 5/95. Physical properties are shown in Table 1.

<Production Example 14 of Titanium Oxide Fine Particles>
Titanium oxide fine particles 14 (inorganic fine particles 18) were obtained in the same manner as in Production Example 1 of titanium oxide fine particles, except that the treatment with the aqueous sodium stearate solution was not performed. Physical properties are shown in Table 1.

<Production example of antimony-doped tin oxide fine particles>
Antimony-doped tin oxide fine particles (inorganic fine particles 19) were obtained in the same manner as in Production Example 12 of titanium oxide fine particles, except that antimony-doped tin oxide fine particles (SN-100P; manufactured by Ishihara Sangyo Co., Ltd.) were used instead of the anatase-type titanium oxide fine particles. Physical properties are shown in Table 1.

<Production example of silica fine particles>
Silica microparticles (inorganic microparticles 20) were obtained in the same manner as in Preparation Example 12 of titanium oxide microparticles, except that silica microparticles prepared by the following method were used instead of the anatase-type titanium oxide microparticles. Physical properties are shown in Table 1.
As a combustion furnace, a double-tube hydrocarbon-oxygen mixed burner capable of forming an inner flame and an outer flame was used. A two-fluid nozzle for slurry injection was grounded at the center of the burner, and the raw material silicon compound was introduced. A hydrocarbon-oxygen combustible gas was injected from around the two-fluid nozzle to form an inner flame and an outer flame, which are reducing atmospheres.
By controlling the amount and flow rate of the combustible gas and oxygen, the atmosphere, temperature, flame length, etc. were adjusted. Silica fine particles were formed from the silicon compound in the flame, and were further fused until a desired particle size was obtained. Then, after cooling, silica fine particles were obtained by collecting with a bag filter or the like.

表中の体積抵抗率の記載に関し、例えば「１．０Ｅ＋１０」は、「１．０×１０^１０」を意味する。
表１中の略号は以下の通り。
ＡＴＯ：アンチモンドープ酸化スズ

Regarding the description of volume resistivity in the table, for example, "1.0E+10" means "1.0×10 ¹⁰ ".
Abbreviations in Table 1 are as follows.
ATO: antimony-doped tin oxide

<Production example of polymer 1>
Solvent: Toluene 100.0 parts Monomer composition 100.0 parts (The monomer composition is a mixture of the following behenyl acrylate, methacrylonitrile, and styrene in the following proportions)
- 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 (manufactured by NOF Corporation: Perbutyl PV) 0.5 parts The above materials were put into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen inlet tube under a nitrogen atmosphere. While stirring the inside of the reaction vessel at 200 rpm, the mixture was heated to 70° C. and a polymerization reaction was carried out for 12 hours to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Subsequently, after the solution was cooled to 25° C., the solution was poured into 1000.0 parts of methanol with stirring to precipitate the methanol-insoluble matter. The resulting methanol-insoluble matter was separated by filtration, washed with methanol, and vacuum-dried at 40° C. for 24 hours to obtain Polymer 1. Polymer 1 had a weight average molecular weight of 68400, a melting point of 62° C. and an acid value of 0.0 mgKOH/g.
When the polymer A1 was analyzed by NMR, it contained 28.9 mol % of behenyl acrylate-derived monomer units, 53.8 mol % of methacrylonitrile-derived monomer units, and 17.3 mol % of styrene-derived monomer units. The SP values of the monomers and the monomer units derived from the monomers were calculated.

<Preparation of monomer having urethane group>
50.0 parts of methanol was charged into the reactor. After that, 5.0 parts of Karenz MOI [2-isocyanatoethyl methacrylate] (Showa Denko KK) was added dropwise at 40° C. while stirring. After the dropwise addition was completed, the mixture was stirred for 2 hours while maintaining the temperature at 40°C. Then, a monomer having a urethane group was prepared by removing unreacted methanol with an evaporator.

<Preparation of monomer having urea group>
A reaction vessel was charged with 50.0 parts of dibutylamine. After that, 5.0 parts of Karenz MOI [2-isocyanatoethyl methacrylate] was added dropwise at room temperature while stirring. After the dropwise addition was completed, the mixture was stirred for 2 hours. Then, a monomer having a urea group was prepared by removing unreacted dibutylamine with an evaporator.

<Production Examples of Polymers 2 to 27>
Polymers 2 to 27 were obtained in the same manner as in Production Example of Polymer 1, except that the respective monomers and parts by weight were changed as shown in Table 2. Physical properties are shown in Tables 3-5.

表２～５中の略号は以下の通り。
ＢＥＡ：ベヘニルアクリレート
ＢＭＡ：ベヘニルメタクリレート
ＳＡ：ステアリルアクリレート
ＭＹＡ：ミリシルアクリレート
ＯＡ：オクタコサアクリレート
ＨＡ：ヘキサデシルアクリレート
ＭＮ：メタクリロニトリル
ＡＮ：アクリロニトリル
ＨＰＭＡ：メタクリル酸２ヒドロキシプロピル
ＡＭ：アクリルアミド
ＵＴ：ウレタン基を有する単量体
ＵＲ：ウレア基を有する単量体
ＡＡ：アクリル酸
ＶＡ：酢酸ビニル
ＭＡ：アクリル酸メチル
Ｓｔ：スチレン
ＭＭ：メタクリル酸メチル

Abbreviations in Tables 2 to 5 are as follows.
BEA: Behenyl acrylate BMA: Behenyl methacrylate SA: Stearyl acrylate MYA: Myrisyl acrylate OA: Octacosa acrylate HA: Hexadecyl acrylate MN: Methacrylonitrile AN: Acrylonitrile HPMA: Dihydroxypropyl methacrylate AM: Acrylamide UT: Monomer having urethane group UR: Monomer having urea group AA: Acrylic acid VA: Vinyl acetate MA: Methyl acrylate St: Styrene MM: methyl methacrylate

(Synthesis example 1 of amorphous resin other than polymer A)
An autoclave was charged with 50 parts of xylene, purged with nitrogen, and heated to 185° C. while stirring and sealed. A mixed solution of 95 parts of styrene, 5 parts of n-butyl acrylate, 5 parts of di-t-butyl peroxide, and 20 parts of xylene was continuously added dropwise for 3 hours while controlling the internal temperature of the autoclave at 185° C. for polymerization. Further, the mixture was maintained at the same temperature for 1 hour to complete the polymerization, and the solvent was removed to obtain an amorphous resin 1 which is not the polymer A. The obtained resin had a weight average molecular weight (Mw) of 3500, a softening point (Tm) of 96°C, and a glass transition temperature (Tg) of 58°C.

<Production Example of Polymer Fine Particle 1 Dispersion>
- Toluene (manufactured by Wako Pure Chemical Industries, Ltd.) 300 parts - Polymer 1 100 parts The above materials were weighed, mixed, and dissolved at 90°C.
Separately, 5.0 parts of sodium dodecylbenzenesulfonate and 10.0 parts of sodium laurate were added to 700 parts of ion-exchanged water and dissolved by heating at 90°C. Next, the above toluene solution and the aqueous solution are mixed together, and an ultra-high speed stirrer T.I. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primix). Furthermore, emulsification was performed at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). Thereafter, toluene was removed using an evaporator, and the concentration was adjusted with deionized water to obtain an aqueous dispersion (polymer fine particle 1 dispersion) having a polymer fine particle 1 concentration of 20% by mass.
The 50% particle diameter (D50) based on volume distribution of the polymer fine particles 1 was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso) and found to be 0.40 μm.

<Production Example of Polymer Fine Particles 2 to 27 Dispersion>
Emulsification was carried out in the same manner as in Production Example of Polymer Fine Particle 1 Dispersion, except that each polymer was changed as shown in Table 6, to obtain Polymer Fine Particle 2 to 27 Dispersions. Physical properties are shown in Table 6.

<Production Example of Amorphous Resin Fine Particles 1 Dispersion Not Polymer A>
- 300 parts of tetrahydrofuran (manufactured by Wako Pure Chemical Industries) - 100 parts of amorphous resin 1 which is not polymer A - 0.5 parts of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) The above materials were weighed, mixed and dissolved.
Next, 20.0 parts of 1 mol/L ammonia water was added, and the ultra-high-speed stirrer T.I. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primix). Further, 700 parts of ion-exchanged water was added at a rate of 8 g/min to precipitate amorphous resin fine particles other than the polymer A. Thereafter, tetrahydrofuran was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (amorphous resin fine particle 1 dispersion) having a concentration of 20% by mass of amorphous resin fine particles 1 other than polymer A.
The volume distribution-based 50% particle size (D50) of the amorphous resin fine particles 1 that are not the polymer A was 0.13 μm.

<Production Example of Release Agent (Aliphatic Hydrocarbon Compound) Fine Particle Dispersion>
・ Aliphatic hydrocarbon compound HNP-51 (manufactured by Nippon Seiro) 100 parts ・ Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) 5 parts ・ Ion-exchanged water 395 parts Weigh the above materials and put them in a mixing container with a stirring device. The conditions for distributed processing were as follows.
・Rotor outer diameter 3cm
・Clearance 0.3mm
・Rotor speed 19000r/min
・Screen rotation speed 19000r/min
After the dispersion treatment, the mixture was cooled to 40° C. under the conditions of a rotor rotation speed of 1000 r/min, a screen rotation speed of 0 r/min, and a cooling rate of 10° C./min, thereby obtaining an aqueous dispersion (release agent (aliphatic hydrocarbon compound) fine particle dispersion) having a release agent (aliphatic hydrocarbon compound) fine particle concentration of 20% by mass.
The 50% particle size (D50) based on volume distribution of the releasing agent (aliphatic hydrocarbon compound) fine particles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso) and found to be 0.15 μm.

<Production of Colorant Fine Particle Dispersion>
- Colorant 50.0 parts (Cyan pigment made by Dainichiseika: Pigment Blue 15:3)
Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) 7.5 parts Ion-exchanged water 442.5 parts The above materials were weighed, mixed, dissolved, and dispersed for about 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Co., Ltd.) to obtain an aqueous dispersion (colorant fine particle dispersion) in which the colorant was dispersed and the concentration of the colorant fine particles was 10% by mass.
The 50% particle size (D50) based on volume distribution of the fine 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 Particle 1>
Polymer fine particle 1 dispersion liquid 500 parts Release agent (aliphatic hydrocarbon compound fine particle dispersion liquid) 50 parts Coloring agent fine particle dispersion liquid 80 parts Ion-exchanged water 160 parts The above materials were placed in a round stainless steel flask and mixed. Subsequently, homogenizer Ultra Turrax T50 (manufactured by IKA) was used to disperse at 5000 r/min for 10 minutes. After adjusting the pH to 3.0 by adding a 1.0% nitric acid aqueous solution, the mixture was heated to 58° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. The volume average particle size of the formed aggregated particles was appropriately confirmed using Coulter Multisizer III, and when aggregated particles having a weight average particle size (D4) of about 6.00 μm were formed, a 5% aqueous sodium hydroxide solution was used to adjust the pH to 9.0. After that, the mixture was heated to 75° C. while stirring was continued. Then, the aggregated particles were fused by holding at 75° C. for 1 hour.
Thereafter, the temperature was lowered to 50° C. and held for 3 hours to promote crystallization of the polymer.
Then, it was cooled to 25° C., filtered and separated into solid and liquid, and then washed with ion-exchanged water. After washing, the particles were dried using a vacuum dryer to obtain toner particles 1 having a weight average particle size (D4) of about 6.1 μm.

<Production Example 2 of Toner Particles>
- Monomer composition 100.0 parts (monomer composition is a mixture of behenyl acrylate, methacrylonitrile, and styrene in the ratio shown below)
(Behenyl acrylate 67.0 parts (28.9 mol%))
(Methacrylonitrile 22.0 parts (53.8 mol%))
(Styrene 11.0 parts (17.3 mol%))
・Colorant Pigment Blue 15:3 6.5 parts ・Di-t-butyl salicylic acid aluminum 1.0 parts ・Paraffin wax 10.0 parts (manufactured by Nippon Seiro Co., Ltd.: HNP-51)
- A mixture of 100.0 parts of toluene was prepared. The above mixture was put into an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed at 200 rpm for 2 hours using zirconia beads with a diameter of 5 mm to obtain a raw material dispersion.
On the other hand, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (12-hydrate) were added to a container equipped with a high-speed stirring device Homomixer (manufactured by Primix) and a thermometer, and the temperature was raised to 60°C while stirring at 12000 rpm. A calcium chloride aqueous solution prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12000 rpm for 30 minutes while maintaining the temperature at 60°C. 10% Hydrochloric acid was added thereto to adjust the pH to 6.0 to obtain an aqueous medium containing a dispersion stabilizer.
Subsequently, the raw material dispersion was transferred to a container equipped with a stirrer and a thermometer, and heated to 60° C. while being stirred at 100 rpm. There, 8.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) was added as a polymerization initiator, and the mixture was stirred at 100 rpm for 5 minutes while maintaining the temperature at 60°C.
Stirring was continued at 12,000 rpm for 20 minutes with the high-speed stirring device while maintaining the temperature at 60° C. to obtain a granulation liquid. The granulation liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen inlet tube, and heated to 70° C. under a nitrogen atmosphere while being stirred at 150 rpm. A polymerization reaction was carried out at 150 rpm for 10 hours while maintaining the temperature at 70°C. Thereafter, the reflux condenser was removed from the reaction vessel, and the temperature of the reaction solution was raised to 95° C., followed by stirring at 150 rpm for 5 hours while maintaining the temperature at 95° C. to remove toluene, thereby obtaining a toner particle dispersion.
The obtained toner particle dispersion was cooled to 20° C. while being stirred at 150 rpm, and diluted hydrochloric acid was added until the pH reached 1.5 while stirring to dissolve the dispersion stabilizer. The solid content was separated by filtration, thoroughly washed with deionized water, and vacuum-dried at 40° C. for 24 hours to obtain toner particles 2 .

<Toner Particle Production Example 3>
[Preparation of Fine Particle Dispersion Liquid 1]
In the reaction container with a stirring rod and a thermometer, 683.0 water water, sodium salt (Eleminol RS -30, Sanyo -karako manufactured by Sanyo Kosen Co., Ltd.), 130.0 stains, 138.0 methacrylate, 138.0 parts, acrylic acid -n -n -buchil A white suspension was obtained when the 184.0 portions and 1.0 ammonium perconate were prepared and the mixture was stirred for 15 minutes in 400 revolutions / minutes. The system temperature was raised to 75° C. by heating, and the reaction was carried out for 5 hours.
Further, 30.0 parts of a 1% aqueous ammonium persulfate solution was added, and the mixture was aged at 75° C. for 5 hours to obtain a fine particle dispersion liquid 1 of a vinyl polymer. The volume average particle diameter of the fine particle dispersion liquid 1 was 0.15 μm.
[Preparation of colorant dispersion]
C. I. Pigment Blue 15:3 100.0 parts Ethyl acetate 150.0 parts Glass beads (1 mm) 200.0 parts The above materials were placed in a heat-resistant glass container and dispersed for 5 hours using a paint shaker.
[Preparation of Wax Dispersion 1]
Paraffin wax (manufactured by Nippon Seiro Co., Ltd.: HNP-51) 20.0 parts Ethyl acetate 80.0 parts The above ingredients were placed in a sealable reaction vessel and heated at 80°C with stirring. Then, the system was cooled to 25° C. over 3 hours while gently stirring at 50 rpm to obtain a milky white liquid.
This solution was put into a heat-resistant container together with 30.0 parts by mass of glass beads with a diameter of 1 mm, dispersed for 3 hours with a paint shaker (manufactured by Toyo Seiki), and the glass beads were removed with a nylon mesh to obtain wax dispersion 1.
[Preparation of oil phase 1]
Polymer (A1) 100.0 parts Ethyl acetate 85.0 parts The above materials were placed in a beaker and stirred at 3000 rpm for 1 minute using Disper (manufactured by Tokushu Kika).
Wax dispersion 1 (solid content 20%) 50.0 parts Colorant dispersion 1 (solid content 40%) 12.5 parts Ethyl acetate 5.0 parts Further, the above ingredients were placed in a beaker and stirred at 6000 rpm for 3 minutes using Disper (manufactured by Tokushu Kika Co., Ltd.) to prepare oil phase 1.
[Preparation of aqueous phase 1]
Fine particle dispersion liquid 1 15.0 parts Sodium dodecyldiphenyl ether disulfonate aqueous solution (ELEMINOL MON7, manufactured by Sanyo Chemical Industries, Ltd.) 30.0 parts Ion-exchanged water 955.0 parts The above materials were placed in a beaker and stirred at 3000 rpm for 3 minutes using a Disper (manufactured by Tokushu Kika) to prepare an aqueous phase 1.
[Production of Toner Particles]
The oil phase 1 was added to the water phase 1 and dispersed for 10 minutes at 10000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.). After that, the solvent was removed for 30 minutes at 30° C. under reduced pressure of 50 mmHg. Next, filtration was performed, and the operations of filtration and re-dispersion in ion-exchanged water were repeated until the conductivity of the slurry reached 100 μS, thereby removing the surfactant and obtaining a filter cake.
Toner particles 3 were obtained by vacuum-drying the filter cake and then subjecting it to air classification.

<Toner Particle Production Example 4>
・Polymer 1 100 parts ・Aliphatic hydrocarbon compound HNP-51 (manufactured by Nippon Seiro Co., Ltd.) 10 parts ・C.I. I. Pigment Blue 15:3 6.5 parts 3,5-di-t-butylsalicylic acid aluminum compound 0.5 parts The above materials were mixed using a Henschel mixer (FM-75 type, manufactured by Nippon Coke Kogyo Co., Ltd.) at a rotation speed of 20 s ^-1 and a rotation time of 5 min, and then kneaded at a discharge temperature of 135 ° C. with a twin-screw kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.) set at a temperature of 120 ° C. The resulting kneaded material was cooled at a cooling rate of 15° C./min and coarsely pulverized to 1 mm or less by a hammer mill to obtain a coarsely pulverized material. The coarsely crushed material obtained was finely pulverized with a mechanical pulverizer (T-250, manufactured by Freund Turbo Co., Ltd.).
Further, classification was carried out using Faculty F-300 (manufactured by Hosokawa Micron Corporation), and toner particles 4 were obtained. The operating conditions were a classification rotor rotation speed of 130 s ^-1 and a dispersing rotor rotation speed of 120 s ^-1 .

<Toner Production Example 1>
・Toner particles 1 100 parts ・Strontium titanate fine particles 1 0.5 parts
⁻¹ and mixing at a rotation time of 10 min to obtain Toner 1. Table 8 shows the constituent materials of Toner 1.
The weight average particle size (D4) of Toner 1 was 6.1 μm. Table 9 shows the physical properties of Toner 1.

<Production Examples of Toner Particles 5 to 32>
Toner Particles 5 to 32 were obtained in the same manner as in Production Example of Toner Particle 1 except that the formulation of Polymer 1 was changed as shown in Table 7. For toner particles 24 and 25, the dispersion liquid of fine polymer particles 1 and the dispersion liquid of amorphous resin fine particles 1 other than polymer A were mixed so that the amounts shown in Table 7 were obtained.

<Toner Production Examples 2 to 55>
Toners 2 to 55 were produced in the same manner as in Toner Production Example 1 except that the toner particles and inorganic fine particles were changed to those shown in Table 7.
Table 8 shows the physical properties of toners 2 to 55 obtained.

<Manufacturing Example of Magnetic Carrier 1>
・Magnetite with a number average particle diameter of 0.30 μm (magnetization intensity of 65 Am ² /kg under a magnetic field of 1000/4π (kA/m)) ・Magnetite with a number average particle diameter of 0.50 μm (magnetization intensity of 65 Am ² /kg under a magnetic field of 1000/4π (kA/m)) 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)) per 100 parts of each of the above materials Trimethoxysilane) was added, and the mixture was mixed and stirred at high speed in a container at 100° C. or higher to treat each fine particle.
・Phenol: 10% by mass
Formaldehyde solution:; 6% by mass (40% by mass formaldehyde, 10% by mass methanol, 50% by mass water)
- Magnetite treated with the above silane compound: 58% by mass
- Magnetite treated with the above silane compound: 26% by mass
100 parts of the above materials, 5 parts of a 28% by mass aqueous ammonia solution, and 20 parts of water were placed in a flask, heated to 85° C. for 30 minutes while being stirred and mixed, and polymerized for 3 hours to cure the resulting phenolic resin. After that, the hardened phenol resin was cooled to 30° C., water was added, the supernatant was removed, and the precipitate was washed with water and air-dried. Next, this was dried at a temperature of 60° C. under reduced pressure (5 mmHg or less) to obtain a magnetic material-dispersed spherical magnetic carrier 1 . The volume-based 50% particle size (D50) was 34.2 μm.

<Production example of two-component developer 1>
8.0 parts of toner 1 was added to 92.0 parts of magnetic carrier 1, and the mixture was mixed with a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain two-component developer 1.
<Production Examples of Two-Component Developers 2 to 55>
Two-component developers 2 to 55 were obtained in the same manner as in the production example of two-component developer 1, except that the toner was changed as shown in Table 9.

<Evaluation of charge rising property>
The evaluation of the charge rising property was carried out by measuring the change in density when images having different image printing ratio densities were output. After an image with a low image ratio is output to saturate the charge of the toner in the developing device, an image with a high image ratio is output. Then, the charged toner in the developing device and the toner newly supplied to the developing device are charged differently, resulting in a change in density.
A toner having a fast charging rise has a small change in density because the charging is saturated immediately after being supplied into the developing device. On the other hand, toner with a slow rise in charge takes a long time from being supplied into the developing device until the charge is saturated.
Using Canon's full-color copier imagePress C800 as an image forming apparatus, the two-component developer to be evaluated was placed in the cyan developing device of the image forming apparatus, and the toner to be evaluated was placed in the cyan toner container to perform the evaluation described later.
The modified point is to remove the mechanism for discharging the magnetic carrier, which has become excessive inside the developing device, from the developing device. Plain paper GF-C081 (A4, basis weight 81.4 g/m ² , marketed by Canon Marketing Japan Inc.) was used as evaluation paper.
Adjustment was made so that the amount of toner on the paper in the FFh image (solid image) was 0.45 mg/cm ² . FFh is a value representing 256 gradations in hexadecimal, where 00h is the first gradation (white background portion) of the 256 gradations, and FF is the 256th gradation (solid portion) of the 256 gradations.
First, an image output test was performed on 1000 sheets with an image ratio of 1%. During continuous paper feeding of 1000 sheets, paper was fed under the same developing conditions and transfer conditions (without calibration) as those for the first sheet.
After that, an image output test of 1000 sheets was performed with an image ratio of 80%. During continuous paper feeding of 1000 sheets, paper was fed under the same developing conditions and transfer conditions (without calibration) as those for the first sheet.
The image density of the 1000th print with an image ratio of 1% was defined as the initial density, and the density of the 1000th image with an image ratio of 80% was measured and evaluated according to the following evaluation criteria. Also, the evaluation results are shown in the table.
The above tests were conducted under normal temperature and normal humidity environment (N/N; temperature 23° C., relative humidity 50%) and normal temperature and low humidity environment (N/L; temperature 23° C., relative humidity 5%).
(1) Measurement of Image Density Change Using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite), the density of the 1000th image in printing at an initial density and an image ratio of 80% was measured and ranked according to the following criteria. Table 8 shows the evaluation results. It was judged that the effects of the present invention were obtained when C or higher was obtained.
(Density difference)
A: less than 0.02 BB: 0.02 or more and less than 0.04 B: 0.04 or more and less than 0.06 C: 0.06 or more and less than 0.10 D: 0.10 or more

[Charge retention rate in high temperature and high humidity environment]
The triboelectrification amount of the toner was calculated by collecting the toner on the electrostatic latent image carrier by suction using a metal cylindrical tube and a cylindrical filter.
Specifically, the triboelectric charge amount of the toner on the electrostatic latent image bearing member was measured by a Faraday-Cage. A Faraday cage is a coaxial double cylinder in which the inner and outer cylinders are insulated. If a charged body with an electric charge of Q is placed in this inner cylinder, it will be as if a metal cylinder with an electric charge of Q exists due to electrostatic induction. The amount of this induced charge was measured with an electrometer (Kesley 6517A, manufactured by Kessley), and the charge amount Q (mC) divided by the toner mass M (kg) in the inner cylinder was taken as the triboelectric charge amount of the toner (Q/M).
Triboelectric charge amount of toner (mC/kg)=Q/M
First, the evaluation image was formed on the electrostatic latent image carrier, and before being transferred to the intermediate transfer member, the rotation of the electrostatic latent image carrier was stopped, the toner on the electrostatic latent image carrier was collected by suction with a metal cylindrical tube and a cylindrical filter, and [initial Q/M] was measured.
Subsequently, after leaving the developing device in the evaluation machine for two weeks in a high temperature and high humidity (H/H) environment (30° C. and 80% RH), the same operation as before leaving was performed, and the charge amount Q/M (mC/kg) per unit mass on the electrostatic latent image bearing member after leaving was measured. Taking the above initial Q/M per unit mass on the electrostatic latent image carrier as 100%, the Q/M retention rate per unit mass on the electrostatic latent image carrier after standing ([Q/M after standing]/[initial Q/M]×100) was calculated and judged according to the following criteria. It was judged that the effects of the present invention were obtained when C or higher was obtained.
(Evaluation criteria)
A: Maintenance rate is 95% or more B: Maintenance rate is 90% or more and less than 95% BB: Maintenance rate is 85% or more and less than 90% C: Maintenance rate is 80% or more and less than 85% D: Maintenance rate is less than 80%

<Evaluation of Low Temperature Fixability of Toner>
Paper: GFC-081 (81.0 g/m ² ) (Canon Marketing Japan Inc.) Amount of toner on paper: 0.50 mg/cm ²
(Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power)
Evaluation image: Place a 2 cm x 5 cm image in the center of the above A4 paper Test environment: Low temperature and low humidity environment: temperature 15 ° C. / humidity 10% RH (hereinafter "L / L")
Fixing temperature: 130°C
Process speed: 377mm/sec
The image for evaluation was printed out to evaluate the low-temperature fixability. The value of the rate of image density reduction was used as an evaluation index for low-temperature fixability. The rate of image density reduction is determined by first measuring the image density at the center using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). Next, a load of 4.9 kPa (50 g/cm ² ) is applied to the portion where the image density has been measured, and the fixed image is rubbed (five reciprocations) with Silbon paper, and the image density is measured again. Then, the rate of decrease in image density before and after rubbing was calculated using the following formula. The reduction rate of the obtained image density was evaluated according to the following evaluation criteria. It was judged that the effects of the present invention were obtained when C or higher was obtained.
Decrease rate of image density = (image density before rubbing - image density after rubbing) / image density before rubbing x 100
(Evaluation criteria)
A: Image density decrease rate of less than 3.0% B: Image density decrease rate of 3.0% or more and less than 5.0% C: Image density decrease rate of 5.0% or more and less than 15.0% D: Image density decrease rate of 15.0% or more

[Toner blocking property (heat resistant storage stability)]
Blocking resistance was evaluated to evaluate stability during storage. About 5 g of toner was placed in a 100 ml resin cup and allowed to stand for 10 days in an environment of 50° C. and 20% humidity.
As a measuring device, a digital display type vibration meter "Digivibro MODEL 1332A" (manufactured by Showa Sokki Co., Ltd.) was connected to the side of the shaking table of "Powder Tester" (manufactured by Hosokawa Micron Co., Ltd.). A sieve with an opening of 38 μm (400 mesh), a sieve with an opening of 75 μm (200 mesh), and a sieve with an opening of 150 μm (100 mesh) were stacked in this order on the vibrating table of the powder tester. The measurement was performed in the following manner under the environment of 23° C. and 60% RH.
(1) The amplitude of vibration of the vibration table was previously adjusted so that the displacement value of the digital display type vibration meter was 0.60 mm (peak-to-peak).
(2) The toner left for 10 days as described above was left in an environment of 23° C. and 60% RH for 24 hours.
(3) After vibrating the sieve for 15 seconds, the mass of the toner remaining on each sieve was measured, and the aggregation degree was calculated based on the following formula.
Aggregation degree (%) = {(sample mass (g) on sieve with mesh size of 150 µm) / 5 (g)} x 100
+ {(Sample mass (g) on a sieve with an opening of 75 μm) / 5 (g)} × 100 × 0.6
+ {(Sample mass (g) on sieve with mesh opening of 38 μm) / 5 (g)} × 100 × 0.2
The evaluation criteria are as follows.
A: The degree of aggregation is less than 20% B: The degree of aggregation is 20% or more and less than 25%.
C: Degree of aggregation is 25% or more and less than 35%.
D: Aggregation degree is 35% or more.
It was judged that the effects of the present invention were obtained when C or higher was obtained.

Claims (18)

A toner having toner particles containing a binder resin and inorganic fine particles,
The binder resin contains a polymer A, which is a vinyl polymer ,
The polymer A is
a first monomer unit derived from a first polymerizable monomer that is a vinyl-based monomer and that is a reacted form of the first polymerizable monomer in the main chain of a polymer obtained by polymerizing the vinyl-based monomer; and
A second monomer unit derived from a second polymerizable monomer that is a vinyl-based monomer different from the first polymerizable monomer, and is in the form of a reaction of the second polymerizable monomer in the main chain of the polymer obtained by polymerizing the vinyl-based monomer.
has
The first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms,
The 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,
When the SP value of the first monomer unit is SP ₁₁ (J/cm ³ ) ^0.5 and the SP value of the second monomer unit is SP ₂₁ (J/cm ³ ) ^0.5 , the following formulas (1) and (2) are satisfied,
3.00≦(SP ₂₁ −SP ₁₁ )≦25.00 (1)
21.00≦SP ₂₁ (2)
The content of the polymer A is 50% by mass or more based on the total mass of the binder resin,
The inorganic fine particles are surface-treated with a compound having an alkyl group,
A toner, wherein the inorganic fine particles have a volume resistivity of 1.0×10 ⁵ Ω·cm to 1.0×10 ¹³ Ω·cm. A toner having toner particles containing a binder resin and inorganic fine particles,
The binder resin contains a polymer A, which is a vinyl polymer ,
The polymer A is
a first polymerizable monomer that is a vinyl monomer, and
a second polymerizable monomer that is a vinyl-based monomer different from the first polymerizable monomer
is a polymer of a composition containing
The first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms,
The content of the first polymerizable monomer in the composition is 5.0 mol% to 60.0 mol% based on the total number of moles of all polymerizable monomers in the composition,
The content of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of all polymerizable monomers in the composition,
When the SP value of the first polymerizable monomer is SP ₁₂ (J/cm ³ ) ^0.5 and the SP value of the second polymerizable monomer is SP ₂₂ (J/cm ³ ) ^0.5 , the following formulas (3) and (4) are satisfied,
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (3)
18.30≦SP ₂₂ (4)
The content of the polymer A is 50% by mass or more based on the total mass of the binder resin,
The inorganic fine particles are surface-treated with a compound having an alkyl group,
A toner, wherein the inorganic fine particles have a volume resistivity of 1.0×10 ⁵ Ω·cm to 1.0×10 ¹³ Ω·cm. 2. The toner according to claim 1, wherein the content of the second monomer units in the polymer A is 40.0 mol % to 95.0 mol % based on the total number of moles of all monomer units in the polymer A. 3. The toner according to claim 2, wherein the content of the second polymerizable monomer in the composition is 40.0 mol % to 95.0 mol % based on the total number of moles of all polymerizable monomers in the composition. The toner according to any one of claims 1 to 4, wherein the first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group having 18 to 36 carbon atoms. The toner according to any one of claims 1 to 5, wherein the second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B).

(In the formula (A), X represents a single bond or an alkylene group having 1 to 6 carbon atoms,
R ¹ is −C≡N ,
- C(=O)NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms ),
hydroxy group,
—COOR ¹¹ (R ¹¹ is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms),
- NHCOOR ¹² (R ¹² is an alkyl group having 1 to 4 carbon atoms ),
- NH-C(=O)-N(R ¹³ ) ₂ (each R ¹³ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms ),
—COO(CH ₂ ) ₂ NHCOOR ¹⁴ (R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or —COO(CH ₂ ) ₂ —NH—C(=O)—N(R ¹⁵ ) ₂ (each R ¹⁵ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)
and R ³ is a hydrogen atom or a methyl group. )
(In formula (B), R ² is an alkyl group having 1 to 4 carbon atoms, and R ³ is a hydrogen atom or a methyl group.) The toner according to any one of claims 1 to 6, wherein the second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B).

(In the formula (A), X represents a single bond or an alkylene group having 1 to 6 carbon atoms,
R ¹ is −C≡N ,
- C(=O)NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms ),
hydroxy group,
—COOR ¹¹ (R ¹¹ is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms),
- NH-C(=O)-N(R ¹³ ) ₂ (each R ¹³ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms ),
—COO(CH ₂ ) ₂ NHCOOR ¹⁴ (R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or —COO(CH ₂ ) ₂ —NH—C(=O)—N(R ¹⁵ ) ₂ (each R ¹⁵ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)
and R ³ is a hydrogen atom or a methyl group. )
(In formula (B), R ² is an alkyl group having 1 to 4 carbon atoms, and R ³ is a hydrogen atom or a methyl group.) The polymer A has a third monomer unit derived from a third polymerizable monomer different from the first polymerizable monomer and the second polymerizable monomer,
8. The toner according to any one of claims 1 to 7, wherein the third polymerizable monomer is at least one selected from the group consisting of styrene, methyl methacrylate and methyl acrylate. 9. The toner according to any one of claims 1 to 8, wherein the toner particles have a coverage ratio of the inorganic fine particles of 3 area % to 80 area %. The toner according to any one of claims 1 to 9 , wherein the compound having an alkyl group is at least one compound selected from the group consisting of compounds having an alkyl group having 4 to 24 carbon atoms. The toner according to any one of claims 1 to 10 , wherein the compound having an alkyl group is at least one compound selected from the group consisting of silane coupling agents, fatty acid metal salts, and silicone oils. The toner according to any one of claims 1 to 11 , wherein the inorganic fine particles are strontium titanate. The toner according to any one of claims 1 to 12 , wherein the inorganic fine particles are strontium titanate having a perovskite crystal structure. The toner according to any one of claims 1 to 13 , wherein the toner has a charge decay rate coefficient of 3 to 100 measured in an environment of 30°C and 80% RH. The toner according to any one of claims 1 to 14 , wherein the inorganic fine particles have a dielectric constant at 1 MHz of 20 pF/m to 100 pF/m. The toner according to any one of claims 1 to 15 , wherein C _x /C _y is 0.8 to 24.0, where C _x is the number of carbon atoms in the alkyl group of the first polymerizable monomer and C _y is the number of carbon atoms in the alkyl group of the compound having an alkyl group. The toner according to any one of claims 1 to 16 , wherein the polymer A is a vinyl polymer. 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 17 .