JP2019219641A - Toner and two-component developer - Google Patents

Abstract

To provide a toner that achieves both low-temperature fixability and heat-resistant storage property, has charge stability even in a high-temperature and high-humidity environment, and reduces the likelihood of the occurrence of a variation in density regardless of an image printing ratio.SOLUTION: A toner includes 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 selected from a (meth)acrylic ester with an alkyl group having 18 to 36 carbon atoms; the content ratio of the first and second monomer units is within a specific range; the SP value of the first monomer unit and the SP value of the second monomer unit satisfy a specific relationship; the inorganic fine particles are surface-treated with a compound having an alkyl group; the volume resistivity of the inorganic fine particles is within a specific range.SELECTED DRAWING: None

Description

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

In recent years, with the widespread use of electrophotographic full-color copying machines, demands for high-speed printing and energy saving are increasing. In order to cope with high-speed printing, a technique for melting a toner more quickly in a fixing process is being studied. Further, in order to improve productivity, a technique for reducing the time of various controls during one job or between jobs is being studied. Further, as an energy saving measure, a technique of fixing the toner at a lower temperature to reduce the power consumption in the fixing step is being studied.
In order to cope with high-speed printing and improve the low-temperature fixability of the toner, there is a method in which the glass transition point and softening point of the binder resin of the toner are lowered, and a binder resin having a sharp melt property is used. In recent years, many toners containing a crystalline polyester have been proposed as a resin having a further sharp melt property. However, crystalline polyester is a material having a problem in terms of charging stability in a high-temperature and high-humidity environment, particularly, maintaining chargeability after being left in a high-temperature and high-humidity environment.
Various toners using a crystalline vinyl resin as another crystalline resin having a sharp melt property have been proposed.

For example, Patent Literature 1 proposes a toner that achieves both low-temperature fixing property and heat-resistant storage property by using an acrylate resin having crystallinity in a side chain.
Patent Document 2 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 toner disclosed in the above-mentioned patent document can achieve both low-temperature fixability and heat-resistant storage stability, and can improve charge stability, which is a weak point of a toner using a crystalline polyester resin, to some extent. However, it has been found that toners using these crystalline vinyl resins as a binder resin have a slow rise in charging.
As a result, when an image with a small printing ratio is printed immediately after an image with a large printing ratio is printed, the charge amount of the toner existing in the developing device and the toner supplied to the developing device are different. It was found that the image density gradually changed. This tendency is remarkable especially in a low humidity environment.
An object of the present invention is to provide a toner that solves the above problems. Specifically, the aim is to provide a toner that has both low-temperature fixability and heat-resistant storage stability, has charge stability even in a high-temperature, high-humidity environment, and has a fast charge rise that is less likely to cause a density change regardless of the image printing ratio. is there.

A first aspect of the present invention is a toner having toner particles and inorganic fine particles containing a binder resin,
The binder resin is a first monomer unit derived from a first polymerizable monomer, and a second monomer derived from a second polymerizable monomer different from the first polymerizable monomer. Containing a polymer A having a monomer unit,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate 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 formula is used. Satisfy (1) and (2),
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 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.
Further, a second aspect of the present invention is a toner having toner particles and inorganic fine particles containing a binder resin,
The binder resin, a first polymerizable monomer, and a polymer A of a composition containing a second polymerizable monomer different from the first polymerizable monomer, a polymer A Contains
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The content ratio of the first polymerizable monomer in the composition is from 5.0 mol% to 60.0 mol% based on the total number of moles of all the polymerizable monomers in the composition. Yes,
The content ratio 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 the polymerizable monomers in the composition. Yes,
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 When 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 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 provides a toner that has both low-temperature fixability and heat-resistant storage stability, has charge stability even in a high-temperature, high-humidity environment, and has a fast charge rise that is less likely to cause a density change regardless of an image printing ratio. Can be.

［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, description of “XX or more and YY or less” or “XX to YY” representing a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.
In the present invention, the (meth) acrylate means an acrylate and / or a methacrylate.
In the present invention, the “monomer unit” refers to a reacted form of a monomer substance in a polymer, and one section of a carbon-carbon bond in a main chain of a polymer of a vinyl monomer in the polymer is defined as one unit.
The vinyl monomer can be represented by the following formula (Z).

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

A first aspect of the present invention is a toner having toner particles and inorganic fine particles containing a binder resin,
The binder resin is a first monomer unit derived from a first polymerizable monomer, and a second monomer derived from a second polymerizable monomer different from the first polymerizable monomer. Containing a polymer A having a monomer unit,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate 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 formula is used. Satisfy (1) and (2),
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.
Further, a second aspect of the present invention is a toner having toner particles and inorganic fine particles containing a binder resin,
The binder resin, a first polymerizable monomer, and a polymer A of a composition containing a second polymerizable monomer different from the first polymerizable monomer, a polymer A Contains
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The content ratio of the first polymerizable monomer in the composition is from 5.0 mol% to 60.0 mol% based on the total number of moles of all the polymerizable monomers in the composition. Yes,
The content ratio 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 the polymerizable monomers in the composition. Yes,
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 When 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 have considered the mechanism by which the effects of the present invention are exhibited as follows.
It is considered that the rising speed of the charging of the toner is determined by the speed at which the charge moves from the inorganic fine particles on the surface of the toner particle to the surface of the toner particle, and the charge saturates the entire toner particle. Conventionally, it has been known that the use of inorganic fine particles having a low resistivity, such as titanium oxide, can increase the speed of charge transfer inside the inorganic fine particles and increase the toner charging rise speed.
However, in the study of the present inventors, it has been found that when a crystalline vinyl resin is used as the binder resin, the charge rising speed alone does not sufficiently increase. It was considered that the charge transfer from the inorganic fine particles to the surface of the toner particles was rate-determining.

As a result of studying changing the composition of the binder resin, it has been found that the rise of charging is slightly improved by the presence of a monomer unit having a high SP value in the crystalline vinyl resin. It was considered that the higher the SP value, the faster the charge transfer due to the presence of the electric dipole due to the charge localization. However, depending on the composition, the low-temperature fixability and the heat-resistant storage stability may decrease.
As a result of extensive studies by the present inventors, the molar ratio of monomer units derived from a plurality of polymerizable monomers of the binder resin in the toner, the SP value, the difference in the SP value, and the inorganic fine particles on the surface of the toner particles It has been found that the above-mentioned problems can be solved by controlling the resistivity and the surface treatment to specific ranges.

The binder resin has a first monomer unit derived from a first polymerizable monomer that is at least one selected from the group consisting of (meth) acrylates having an alkyl group having 18 to 36 carbon atoms. It is characterized by containing polymer A having.
When the first monomer unit is a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms, the binder resin has crystallinity and the low-temperature fixability is improved.
Further, in the first embodiment, the content ratio of the first monomer unit in the polymer A is from 5.0 mol% to 60.0 mol% based on the total number of moles of all the monomer units in the polymer A. It is characterized by being.
In the second embodiment, the polymer A is a polymer containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer. It is united. The content ratio of the first polymerizable monomer in the composition is from 5.0 mol% to 60.0 mol% based on the total number of moles of all the polymerizable monomers in the composition. .
When the content is in the above range, the low-temperature fixing property and the rise of charging in a low-humidity environment are improved. When the content is less than 5.0 mol%, the low-temperature fixability is reduced. On the other hand, if the content exceeds 60.0 mol%, the non-polar portion having a low SP value occupies a large portion in the polymer, so that the rise of charging in a low humidity environment is reduced. Preferably, it is 10.0 mol% to 60.0 mol%, and a more preferable 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 a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms.
Examples of the (meth) acrylate having an alkyl group having 18 to 36 carbon atoms include, for example, a (meth) acrylate having a linear alkyl group having 18 to 36 carbon atoms [stearyl (meth) acrylate, (meth) acrylate). ) Nonadecyl acrylate, eicosyl (meth) acrylate, heneicosanyl (meth) acrylate, behenyl (meth) acrylate, lignoseryl (meth) acrylate, seryl (meth) acrylate, octacosa (meth) acrylate, (meth) And a (meth) acrylic ester having a branched alkyl group having 18 to 36 carbon atoms [such as 2-decyltetradecyl (meth) acrylate].
Of these, from the viewpoint of storage stability of the toner, it is preferably at least one selected from the group consisting of (meth) acrylates having a linear alkyl group having 18 to 36 carbon atoms, and more preferably It is at least one selected from the group consisting of (meth) acrylates having a straight-chain alkyl group having 18 to 30 carbon atoms, and more preferably straight-chain stearyl (meth) acrylate and (meth) acryl. It is at least one selected from the group consisting of behenyl acid.
As the first polymerizable monomer, one type may be used alone, or two or more types may be used in combination.

In the first embodiment, the polymer A has a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer. When the SP value of the second monomer units and the SP _21, and satisfies the following formula (2). It is preferable that the following formula (2) ′ is satisfied, and it is more preferable that the following formula (2) ″ is satisfied.
21.00 ≦ SP ₂₁ (2)
21.00 ≦ SP ₂₁ ≦ 40.00 (2) ′
25.00 ≦ SP ₂₁ ≦ 30.00 (2) ″
In the second embodiment, when the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 , the following formula (4) is satisfied. It is preferable that the following formula (4) ′ is satisfied, and it is more preferable that the following formula (4) ″ is satisfied.
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, charge transfer from the inorganic fine particles having low resistivity is performed quickly, and the rising speed of charging is increased.
Here, the SP value is an abbreviation of a solubility parameter, and is a value serving as an index of solubility. The calculation method will be described later.

In the first embodiment, the SP value of the first monomer unit is set to SP ₁₁ (J / cm ³ ) ^0.5, and the SP value of the second monomer unit is set to SP ₂₁ (J / cm ³ ) ^0.5 . In this case, the following formula (1) is satisfied. Preferably, expression (1) ′ is satisfied, more preferably expression (1) ″ is satisfied, and it is more preferable that expression (1) ″ ″ is satisfied.
In the second embodiment, the SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ). cm ³ ) When ^0.5 , the following formula (3) is satisfied. Preferably, expression (3) ′ is satisfied, more preferably expression (3) ″ is satisfied, and more preferably expression (3) ″ ″ is satisfied.
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 , and 1 (cal / cm ³ ) ^0.5 = 2.045 × 10 ³ (J / m ³ ) ^0.5 . cal / cm ³ ) It can be converted to a unit of ^0.5 .

By satisfying the SP value difference, the melting point is maintained without lowering the crystallinity of the polymer A. Thereby, both low-temperature fixability and heat-resistant storage stability are achieved.
Further, the interaction between the first monomer unit and the alkyl group 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 are likely to occur. Improve.
This mechanism is speculated as follows.
The first monomer unit is incorporated into the polymer A, and expresses crystallinity by assembling the first monomer units. However, in general, crystallization is inhibited when another monomer unit is incorporated. Therefore, it becomes difficult for the polymer to exhibit crystallinity. This tendency becomes remarkable when the first monomer unit and other monomer units are randomly bonded 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 falls within the range of the above formula (2), the first polymerizable monomer and the second polymerizable monomer are used during polymerization. It is considered that the monomers do not bind at random but can be bound to some extent continuously. Thereby, in the polymer A, it is considered that the first monomer units can be assembled with each other, and the crystallinity can be increased even when other monomer units are incorporated, so that the melting point can be maintained. .
Further, when SP ₂₁ -SP ₁₁ is within the range of the above formula (1), the first monomer unit and the second monomer unit form a clear phase-separated state in the polymer A without being compatible with each other. It is thought that the melting point can be maintained without lowering the crystallinity.
The polymer A preferably has a crystalline site containing the first monomer unit derived from the first polymerizable monomer. Further, the polymer A preferably has an amorphous portion including a second monomer unit derived from the second polymerizable monomer.

  In addition, since the first monomer units are continuously bonded to each other, it is easy to interact with the alkyl group on the surface of the low-resistivity inorganic fine particles, so that the adhesion between the inorganic fine particles and the toner particles is considered to be improved. Can be In addition, since the second monomer units are also continuously bonded to each other, it is easy to take an arrangement in which charge transfer from the inorganic fine particles having a low resistivity to the second monomer unit having a high SP value easily occurs. We believe that the rise of charging is improved.

In the first embodiment, 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 the monomer units in the polymer A. It is characterized by being.
In the second embodiment, the content ratio of the second polymerizable monomer in the composition is 20.0 mol% based on the total number of moles of all the polymerizable monomers in the composition. ~ 95.0 mol%.
When the content ratio is within the above range, the charge transfer from the low-resistance inorganic fine particles to the polar portion of the second monomer unit occurs promptly. From the viewpoint of rising charge 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 forming the second monomer unit, for example, a polymerizable monomer satisfying the formula (1) or the formula (3) among the following can be used. As the second polymerizable monomer, one type may be used alone, or two or more types may be used in combination.
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, an amine having 1 to 30 carbon atoms and a carboxylic acid having 2 to 30 carbon atoms having an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) are reacted by a known method. Monomer.

A monomer having a urethane group: for example, an alcohol having an ethylenic unsaturated bond and having 2 to 22 carbon atoms (such as 2-hydroxyethyl methacrylate and vinyl alcohol) and an isocyanate having 1 to 30 carbon atoms [monoisocyanate compound (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, 2,6-dipropylphenyl isocyanate, etc.) Aromatic diisocyanate compounds (trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 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, hydrogenated And tetramethylxylylene diisocyanate) Group diisocyanate compounds (phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-toluidine diisocyanate, 4,4 -Diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenediisocyanate, xylylene diisocyanate, etc.) and a C1-C26 alcohol (methanol , Ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecyl alcohol , Lauryl alcohol, dodecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, heptadecanol, stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, nonadecyl alcohol, hen Eicosanol, behenyl alcohol, erucyl alcohol, etc.) and an isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond [2-isocyanatoethyl (meth) acrylate, (meth) acrylic acid 2- (0- [1 '-Methylpropylideneamino] carboxyamino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate and 1,1- (bis (meth) acryloyloxymethyl) e Monomers such as the Le isocyanate] was reacted by a known method.

Monomers having a urea group: for example, amines having 3 to 22 carbon atoms [primary amines (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines (dinalethylamine, dinormalpropylamine, diamine) A normal butylamine, etc.), aniline, cycloxylamine, etc.] and an isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond by a known method.
Monomers having a carboxy group; 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 preferably, it is a monomer having at least one functional group selected from the group consisting of a nitrile group, an amide group, a urethane group, a hydroxy group, and a urea group, and an ethylenically unsaturated bond. 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 accelerates charge transfer.

As the second polymerizable monomer, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, pivalic acid Vinyl esters such as vinyl and vinyl octylate are also preferably used.
Vinyl esters are non-conjugated monomers, and the reactivity with the first polymerizable monomer is easily maintained at an appropriate level. Therefore, the crystallinity of the polymer A is easily improved, and the low-temperature fixability and heat-resistant storage stability are improved. More compatible.
The second polymerizable monomer preferably has an ethylenically unsaturated bond, and more preferably has one ethylenically unsaturated bond.
Further, 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),
An 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 (preferably 1 to 4) carbon atoms or a hydroxyalkyl group having 1 to 6 (preferably 1 to 4) carbon atoms),
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 (R ¹³ is each independently a hydrogen atom or an alkyl group having 1 to 6 (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 (R ¹⁵ is Each independently represents a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms)
It is.
Preferably, R ¹ is a nitrile group (—C≡N),
An 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 (preferably 1 to 4) carbon atoms or a hydroxyalkyl group having 1 to 6 (preferably 1 to 4) carbon atoms),
A urea group (—NH—C (＝ O) —N (R ¹³ ) ₂ (R ¹³ is each independently a hydrogen atom or an alkyl group having 1 to 6 (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 (R ¹⁵ is Each independently represents a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms)
It is.
R ² is an alkyl group having 1 to 4 carbon atoms, and R ³ is each independently a hydrogen atom or a methyl group. )

As the second polymerizable monomer, one type may be used alone, or two or more types may be used in combination.
In the case where the monomer unit satisfying the above requirements of the first monomer unit in the polymer A in the present invention are multiple types exist, the value of the SP ₁₁ in the formula (1) is the weighted average SP value of each monomer unit Value. For example, the monomer unit A having an SP value of SP ₁₁₁ is contained in an amount of A mol% based on the total number of moles of the monomer units satisfying the requirements of the first monomer unit, and the monomer unit B having an SP value of SP ₁₁₂ is included in the first monomer unit. The SP value (SP ₁₁ ) when containing (100-A) mol% based on the number of moles of the entire monomer unit satisfying the requirement of
SP ₁₁ = (SP ₁₁₁ × A + SP ₁₁₂ × (100−A)) / 100
It is. The same calculation is performed when three or more monomer units satisfying the requirements of the first monomer unit are included. Meanwhile, SP ₁₂ similarly represent the average value calculated in molar ratio of each of the first polymerizable monomer.
In the present invention, the second monomer unit corresponds to all monomer units satisfying SP ₂₁ satisfying the formula (1) with respect to SP ₁₁ calculated by the above method. Similarly, the second polymerizable monomer, any polymerizable monomer corresponds with SP ₂₂ satisfying the formula (3) with respect to SP ₁₂ calculated by the above method.
That is, when said second polymerizable monomer is 2 or more polymerisable monomers, SP ₂₁ denotes a SP value of the monomer units derived from each of the polymerizable monomer, SP ₂₁ -SP ₁₁ is determined for each monomer unit derived from the second polymerizable monomer. Similarly, _{SP 22} denotes a SP value of each of the polymerizable _monomer, SP 22 _{-SP 12} is determined for each of the second polymerizable monomer.

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

Further, the polymer A preferably has a weight average molecular weight (Mw) of a soluble portion of tetrahydrofuran (THF) measured by gel permeation chromatography (GPC) of 10,000 or more and 200,000 or less, and 20,000 or more and 150,000 or less. More preferably, there is. When Mw is within the above range, elasticity near room temperature can be easily maintained.
Further, the melting point of the polymer A is preferably from 50 ° C. to 80 ° C., and more preferably from 53 ° C. to 70 ° C. When the melting point is 50 ° C. or more, the heat-resistant storage stability becomes good, and when it is 80 ° C. or less, the low-temperature fixability becomes good.

Polymer A, the first monomer unit derived from the first polymerizable monomer described above, the range not to impair the molar ratio of the second monomer unit derived from the second polymerizable monomer, the above A third polymerizable monomer that is not included in any of formulas (1) and (3) (that is, different from the first polymerizable monomer and the second polymerizable monomer) It may include a third monomer unit derived therefrom.
As the third polymerizable monomer, among the monomers listed in the section of the second polymerizable monomer, a monomer that does not satisfy the formula (1) or the formula (3) may be used. it can.
Further, 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 such as styrene and o-methylstyrene and derivatives thereof, methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2- (meth) acrylic acid-2- (Meth) acrylic esters such as ethylhexyl.
The third polymerizable monomer is preferably at least one selected from the group consisting of styrene, methyl methacrylate, and methyl acrylate.
When these satisfy the formula (1) or the 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 it is further preferable that the binder resin is the polymer A.
Further, it is preferable that the polymer A is present on the surface of the toner particles in that the effect of the present invention is 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 the resin other than the polymer A used for the binder resin include the following resins.
Styrenes such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene and their substituted homopolymers; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene -Acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether Styrene copolymers such as copolymers, styrene-vinyl methyl ketone copolymers, styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenolic resins, phenolic resins modified with natural resins, maleic acid resins modified with natural resins, acrylic Resin, methacrylic Resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone - indene resins, petroleum resins, and the like.
Of these, styrene copolymers and polyester resins are preferred. Further, 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 in the above range, the movement of the charges in the inorganic fine particles becomes faster, and the rising of the charging becomes good. When the volume resistivity is less than 1.0 × 10 ⁵ Ω · cm, the chargeability in a high-temperature and high-humidity environment decreases because the resistivity is too low. On the other hand, when it exceeds 1.0 × 10 ¹³ Ω · cm, the rise of charging is delayed due to 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 the inorganic fine particles, the type of the surface treatment, the concentration of the surface treatment agent, and the like.

Examples of the 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 preferably, strontium titanate is used. For these, it is relatively easy to control characteristics such as particle diameter, resistivity, and dielectric constant depending on manufacturing conditions. Strontium titanate preferably has a perovskite crystal structure. When strontium titanate has a perovskite-type crystal structure, the speed of electron transfer with the second monomer unit can be increased.

  The strontium titanate, calcium titanate, and magnesium titanate fine particles can be obtained, for example, by a normal pressure heating reaction method. At this time, a mineral acid peptized product of a hydrolyzate of a titanium compound is used as a titanium oxide source, and a water-soluble acidic metal compound is used as a metal oxide source. The reaction can be carried out by adding an aqueous alkali solution to the mixture at 60 ° C. or higher, followed by acid treatment.

The method for producing the titanium oxide fine particles is not particularly limited, and is obtained by a gas phase oxidation method in which titanium dioxide fine particles produced by a conventionally known sulfuric acid method and chlorine method and titanium tetrachloride are reacted with oxygen in a gas phase as a raw material. Obtained titania fine particles. 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.
As the titania fine particles, both of two kinds of crystal types, rutile type and anatase type, are preferably used. 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 baking metatitanic acid.
Further, when it is desired to obtain rutile-type titanium oxide fine particles, when baking metatitanic acid, as a rutile transfer accelerator, salts such as lithium salts, magnesium salts, zinc salts and aluminum salts, and a slurry containing rutile microcrystals It is preferable to add a seed such as

  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 generate zinc oxide, and a method in which a metal salt is neutralized by reacting with an alkali in an aqueous solution. , Washing with water, drying, and firing to produce zinc oxide. Among them, those synthesized by a wet method are preferable in that fine particles having a relatively small particle diameter that can be added to the toner surface are easily obtained.

Further, the dielectric constant of the inorganic fine particles at 1 MHz is preferably 20 pF / m to 100 pF / m. 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 presumably because the dielectric constant is derived from intra-atomic or inter-atomic polarization, and is closely related to charge transfer.
As a method of controlling the dielectric constant, in addition to the selection of the inorganic fine particles, conditions / operations for changing the crystallinity of the particles at the time of producing the inorganic fine particles may be mentioned. Examples of the method include a method of changing pH and temperature, and a method of 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 surface-treated with a compound having an alkyl group.
Since the inorganic fine particles are surface-treated with the compound having an alkyl group, the inorganic fine particles can interact with the alkyl group contained in the polymer A, thereby improving the adhesion, and the second monomer unit of the inorganic fine particles to the toner particles. Can be arranged so that the charge transfer to the substrate easily occurs.

Examples of the compound having an alkyl group include fatty acids, metal salts of fatty acids, silicone oil, silane coupling agents, titanium coupling agents, and aliphatic alcohols.
Among them, at least one compound selected from the group consisting of a fatty acid, a metal salt of a fatty acid, a silicone oil, and a silane coupling agent is preferable because the effects of the present invention can be more easily obtained.
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, aluminum stearate and the like.
The following methods are available for surface-treating the inorganic fine particles with a fatty acid or a metal salt thereof. For example, under an atmosphere of Ar gas or N ₂ gas, a slurry containing inorganic fine particles can be put into an aqueous solution of fatty acid sodium to precipitate fatty acids on the perovskite crystal surface. Further, for example, under a Ar gas or N ₂ gas atmosphere, a slurry containing inorganic fine particles is placed in an aqueous solution of fatty acid sodium, and a desired metal salt aqueous solution is added dropwise with stirring, so that the fatty acid metal salt is deposited on the perovskite-type crystal surface. It can be deposited and adsorbed. For example, if an aqueous solution of sodium stearate and aluminum sulfate are used, aluminum stearate can be adsorbed.

Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, and alkyl-modified silicone oil such as octyl-modified silicone oil.
Known techniques can be used for the method of treating the silicone oil. For example, the inorganic fine particles and the silicone oil are mixed using a mixer; the silicone oil is sprayed into the inorganic fine particles using a sprayer; or the silicone fine particles are mixed after dissolving the silicone oil in a solvent. Method. 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 can be mentioned.

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

When the first polymerizable monomer an alkyl group of carbon number _{C x} of the carbon atoms in the alkyl group of the compound having an alkyl group with _{C y,} with C x / _{C y} is 0.8 to 24.0 This is preferable because the interaction between the alkyl groups becomes stronger. More preferably, it is 1.0 to 10.0. When a plurality of first polymerizable monomers or compounds having an alkyl group are used, the average number of carbon atoms is determined according to the molar ratio.

The number average diameter of the primary particles of the inorganic fine particles is preferably from 20 nm to 300 nm. It is preferable that the number average diameter of the primary particles be within the above range, since the inorganic fine particles easily interact with both the first monomer unit and the second monomer unit of the polymer A having a block copolymer-like structure. More preferably, it is 20 nm to 200 nm.
Further, the content of the inorganic fine particles is preferably from 0.1 part by mass to 10.0 parts by mass with respect to 100 parts by mass of the toner particles.

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

  Further, the charge decay rate coefficient of the toner measured in a 30 ° C. and 80% RH environment is preferably 3 to 100, and more preferably 3 to 60. It is preferable that the charge decay rate coefficient be within the above-mentioned range, since 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 the acid value of the binder resin, the type of the inorganic fine particles, the surface treating agent of the inorganic fine particles, the coverage of the toner particles with the inorganic fine particles, and the like.

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

Factors that affect 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 beginning of the reaction, the temperature and the rate of addition of the alkaline aqueous solution. And the like, and can be appropriately adjusted in order to obtain a desired particle size and particle size distribution. Note that it is preferable to prevent carbon dioxide gas from being mixed, for example, by reacting in a nitrogen gas atmosphere in order to prevent generation of carbonate in the reaction process.
Factors affecting the dielectric constant of the resulting strontium titanate particles include conditions / operations that disrupt the crystallinity of the particles. In order to obtain strontium titanate having a low dielectric constant, it is preferable to perform an operation of giving energy that disturbs the crystal growth in a state where the concentration of the reaction solution is increased. Adding bubbling.

The mixing ratio of the titanium oxide source and strontium oxide source during the reaction, a molar ratio of SrO / TiO _2, preferably 0.9 to 1.4, 1.05 to 1.20 is more preferable. When the SrO / TiO ₂ molar ratio is 0.9 or more, unreacted titanium oxide hardly remains. The concentration of the titanium oxide source of the initial reaction, 0.05~1.3mol / L as TiO _2, is preferably 0.08~1.0mol / L is suitable.
The temperature at which the aqueous alkali solution is added is preferably about 60C to 100C. As for the addition rate of the alkaline aqueous solution, the slower the addition rate, the larger the metal titanate particles having a larger particle diameter can be obtained, and the higher the addition rate, the smaller the metal titanate particles having a smaller particle diameter. The addition rate of the aqueous alkali solution is preferably 0.001 to 1.2 equivalents / h, more preferably 0.002 to 1.1 equivalents / h, based on the charged raw material, and depends on the particle diameter to be obtained. It can be adjusted appropriately.

(Acid treatment)
It is preferable that the metal titanate particles obtained by the atmospheric pressure heating reaction are further subjected to an acid treatment. When performing a normal pressure heating reaction to synthesize metal titanate particles, if the mixing ratio of the titanium oxide source and the strontium oxide source exceeds 1.0 in a molar ratio of SrO / TiO ₂ , the mixture remains after the reaction. An unreacted metal source other than titanium may react with carbon dioxide gas in the air to generate impurities such as metal carbonates. Therefore, it is preferable to perform an acid treatment after the addition of the alkaline aqueous solution to remove the unreacted metal source.
In the acid treatment, the pH is preferably adjusted to 2.5 to 7.0, more preferably 4.5 to 6.0, using hydrochloric acid. As the acid, nitric acid, acetic acid and the like can be used for the acid treatment in addition to hydrochloric acid.

<Colorant>
A colorant may be used for the toner. Examples of the coloring agent include the following.
Examples of the black colorant include carbon black, which is toned to black using a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment together to improve the sharpness from the viewpoint of the image quality of a full-color image.
Examples of the pigment for magenta toner include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment Violet 19; I. Butt Red 1, 2, 10, 13, 15, 23, 29, 35.
The 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; I. Disperse Red 9; 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; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

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

(wax)
Wax may be used for the toner. Examples of the wax include the following.
Hydrocarbon waxes such as microcrystalline wax, paraffin wax and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; fatty acid esters such as carnauba wax Waxes obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax.
Further, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and vinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, seryl alcohol And polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid and montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol; Esters with alcohols such as seryl alcohol and melisyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide and lauric acid amide; methylene bisstearic acid amide, ethylene biamide Saturated fatty acid bisamides such as capric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N'dioleyl adipamide, N, N Unsaturated fatty acid amides such as 'dioleyl sebacic amide; aromatic bisamides such as m-xylene bisstearic acid amide, N, N' distearylisophthalic acid amide; calcium stearate, calcium laurate, zinc stearate And aliphatic metal salts such as magnesium stearate (commonly referred to as metallic soaps); waxes obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylic acid; behenin It ’s like acid monoglyceride And methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils; partial esters of such fatty acids with polyhydric alcohols.
The content of the wax 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 contain a charge control agent as needed. As the charge control agent contained in the toner, known ones can be used. In particular, a metal compound of an aromatic carboxylic acid which is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable.
As the negative charge control agent, a salicylic acid metal compound, a naphthoic acid metal compound, a dicarboxylic acid metal compound, a high molecular compound having a sulfonic acid or a carboxylic acid as a side chain, a sulfonate or a sulfonic acid ester compound having a side chain. Examples include a high-molecular-weight compound, a high-molecular-weight compound having a carboxylate or a carboxylic acid ester in its side chain, a boron compound, a urea compound, a silicon compound, and calixarene. The charge control agent may be added internally or externally to the toner particles.
The addition amount of the charge control agent 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 above-mentioned inorganic fine particles, the toner may contain other inorganic fine powders as necessary. The inorganic fine powder may be internally added 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 preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.
For example, any method such as a precipitation method, a wet method of obtaining silica by neutralizing sodium silicate represented by a sol-gel method, a dry method of obtaining silica in a gas phase represented by a flame melting method or an arc method, and the like. Is preferably used. Among them, silica fine powder produced by a sol-gel method or a flame melting method is more preferable because the number average diameter of the primary particles can be easily controlled to a desired range.

As the external additive for improving the fluidity, the ratio is ^50m 2 / g or more 400 meters ² / g or less of the inorganic fine powder is preferably surface area, for durability stabilization has a specific surface area of ^{10 m} 2 / g or more 50m
It is preferably an inorganic fine powder of ² / g or less. In order to improve fluidity and stabilize durability, inorganic fine particles having a specific surface area in the above range may be used in combination.

<Developer>
Although the toner can be used as a one-component developer, it can be used as a two-component developer by mixing with a magnetic carrier to further improve dot reproducibility. It is preferable in that respect. That is, it is a two-component developer containing a toner and a magnetic carrier, and the toner is preferably the toner of the present invention.
As the magnetic carrier, for example, iron powder with oxidized surface, or unoxidized iron powder, iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, metal particles such as rare earth, A magnetic material such as alloy particles, oxide particles, and ferrite, and a magnetic material-dispersed resin carrier (a so-called resin carrier) containing a magnetic material and a binder resin holding the magnetic material in a dispersed state are generally known. Can be used.
When the toner is mixed with a magnetic carrier and used as a two-component developer, the carrier mixture ratio at that time is preferably 2% by mass or more and 15% by mass or less, more preferably 2% by mass or less and 15% by mass or less, as the toner concentration in the two-component developer. When the content is 4% by mass or more and 13% by mass or less, usually good results can be obtained.

<Method for producing toner particles>
The method for producing the toner particles is not particularly limited, and a conventionally known production method 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 they are. Toner particles may be obtained by mixing the obtained toner particles with inorganic fine particles and, if necessary, other external additives. The mixing of the toner particles with the inorganic fine particles and other external additives can be performed using a double-con mixer, a V-type mixer, a drum-type mixer, a super-mixer, a Henschel mixer, a Nauta mixer, a mechano hybrid (manufactured by Nippon Coke Industry Co., Ltd.), A mixing device such as Hosokawa Micron Co., Ltd.) can be used.
The external additive is preferably used in an amount of 0.1 to 10.0 parts by mass based on 100 parts by mass of the toner particles.

Methods for measuring various physical properties of the toner and the raw materials will be described below.
<Analysis method>
(Measurement of volume resistivity of inorganic fine particles)
The volume resistivity of the inorganic fine particles is measured as follows. As the device, a Keithley Instruments 6517 type electrometer / high resistance system is used. An electrode having a diameter of 25 mm is connected, inorganic fine particles are placed between the electrodes so as to have a thickness of about 0.5 mm, and a distance between the electrodes is measured with a load of about 2.0 N applied.
The resistance value when a voltage of 1,000 V is applied to the inorganic fine particles for one minute is measured, and the volume resistivity is calculated using the following equation.
Volume resistivity (Ω · cm) = R × L
R: resistance value (Ω)
L: distance between electrodes (cm)
(Separation of inorganic fine particles from toner)
Inorganic fine particles can be separated from the toner and measured by the following method.
200 g of sucrose (manufactured by Kishida Chemical) is added to 100 mL of ion-exchanged water and dissolved in a water bath to prepare a concentrated sucrose solution. In a centrifuge tube, 31 g of the sucrose concentrated solution and 6 mL of a 10% by mass aqueous solution of a neutral detergent for washing a precision measuring instrument having a pH of 7 consisting of contaminone N (a nonionic surfactant, an anionic surfactant and an organic builder). , Manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a dispersion. 1 g of the toner is added to the dispersion, and the lump of the toner is loosened with a spatula or the like.
The tube for centrifugation is shaken with the above-mentioned shaker at the condition of 350 reciprocations per minute for 20 minutes. After shaking, the solution is replaced with a glass tube for a swing rotor (50 mL), and centrifugation is performed with a centrifuge at 3500 rpm for 30 minutes. In the glass tube after the centrifugation, toner is present in the uppermost layer, and inorganic fine particles are present in the lower aqueous solution side. The aqueous solution in the lower layer is collected and centrifuged to separate sucrose and inorganic fine particles, and collect the inorganic fine particles. If necessary, centrifugation is repeated, and after sufficient separation, the dispersion is dried to collect inorganic fine particles.
When a plurality of inorganic fine particles are added, the fine particles can be sorted by using a centrifugal separation method or the like.

(Measurement of dielectric constant)
After calibrating at a frequency of 1 kHz and 1 MHz using a 284A Precision LCR meter (manufactured by Hewlett-Packard), the complex permittivity at a frequency of 1 MHz is measured. A load of 39200 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 was mounted on an ARES (manufactured by Rheometric Scientific F.E.) equipped with a dielectric constant measuring jig (electrode) having a diameter of 25 mm, and 0.49 N (50 g) in an atmosphere at a temperature of 25 ° C. Under a load of 1 MHz 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 Nano Seeds).
First, a sample pan is filled with about 100 mg of toner, and is rubbed to smooth the surface. The sample pan is irradiated with X-rays for 30 seconds by an X-ray remover to remove the charge of the toner. The sample pan from which the charge has been removed is placed on the measurement plate. For zero correction of the surface electrometer, the metal plate is simultaneously mounted as Reference. 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.
The 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. The obtained result is fitted to the following equation to determine the charge decay rate coefficient α.
_{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 particles)
The number average diameter of the primary particles of the inorganic fine particles is measured by 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 was set to 50,000 times, and the photographed image was further enlarged to 2 times. From the obtained FE-SEM photograph image, the maximum diameter (major axis diameter) a and the minimum diameter (minor axis diameter) of the inorganic fine particles were obtained. b is measured, and (a + b) / 2 is defined as the particle size of the particle. The particle diameters of 100 randomly selected inorganic fine particles are measured and an arithmetic average is obtained, which is defined 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 measurement of the content ratio of the monomer units derived from various polymerizable monomers in the polymer A is performed by ¹ H-NMR under the following conditions.
Measurement device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0 μs
Frequency range: 10500Hz
Number of integration: 64 times Measurement temperature: 30 ° C
Sample: 50 mg of a measurement sample is placed in a sample tube having an inner diameter of 5 mm, and chloroform (CDCl ₃ ) is added as a solvent and dissolved in a 40 ° C. thermostat.
From the obtained ¹ H-NMR chart, among the peaks attributed to the components of the monomer unit derived from the first polymerizable monomer, the peaks attributed to the components of the monomer unit derived from the other are Selects an independent peak and calculates the integrated value S1 of this peak. Similarly, from the peaks attributed to the components of the monomer unit derived from the second polymerizable monomer, select a peak independent of the peak attributed to the components of the monomer units derived from the other , The integrated value S2 of this peak is calculated.
Furthermore, when the third polymerizable monomer is used, from the peak attributed to the component of the monomer unit derived from the third polymerizable monomer, the component of the monomer unit derived from the other Is selected, and an integrated value S3 of this peak is calculated.
The content ratio of the monomer unit derived from the first polymerizable monomer is determined as follows using the integrated values S1, S2, and S3. In addition, n1, n2, and n3 are the numbers of hydrogen in the constituent elements to which the peaks focused on each part belong.
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 the monomer units derived from the second polymerizable monomer and the third polymerizable monomer is determined 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 unit derived from third polymerizable monomer =
{(S3 / n3) / ((S1 / n1) + (S2 / n2) + (S3 / n3))} × 100
When a polymerizable monomer containing no hydrogen atom in the constituents other than the vinyl group is used in the polymer A, the measured nuclei are set to ¹³ C by ¹³ C-NMR, and the single pulse mode is used. , And similarly calculated by ¹ H-NMR.
Further, when the toner is manufactured by a suspension polymerization method, the peaks of the release agent and other resins may overlap, and an independent peak may not be observed. As a result, the content of monomer units derived from various polymerizable monomers in the polymer A may not be calculated. In this case, by performing the same suspension polymerization without using a release agent or another resin, the polymer A ′ can be manufactured, and the polymer A ′ can be analyzed as the polymer A.

<Method of calculating SP value>
SP ₁₂ and SP ₂₂ are obtained as follows in accordance with the calculation method proposed by Fedors.
For each polymerizable monomer, the evaporation energy (Δei) from the table described in “polym. Eng. Sci., 14 (2), 147-154 (1974)” with respect to the atom or atomic group in the molecular structure. ) (Cal / mol) and molar volume (Δvi) (cm ³ / mol) are determined, and (4.184 × ΣΔei / ΣΔvi) ^0.5 is defined as SP value (J / cm ³ ) ^0.5 .
Note that SP ₁₁ and SP ₂₁ are calculated by the same calculation method as described above for the atoms or atomic groups of the molecular structure in which the double bond of the polymerizable monomer is cleaved by polymerization.

<Measurement 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 temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of the calorific value uses the heat of fusion of indium.
Specifically, about 5 mg of a sample is precisely weighed, placed in an aluminum pan, and subjected to differential scanning calorimetry. An empty silver pan is used as a reference.
The peak temperature of the maximum endothermic peak in the first heating process is defined as the melting point.
Note that the maximum endothermic peak is a peak at which the amount of endotherm becomes maximum when there are a plurality of peaks.

(Measurement of molecular weight of THF soluble component of resin)
The weight average molecular weight (Mw) of the THF-soluble portion of the polymer A is measured by gel permeation chromatography (GPC) as follows.
First, a sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Maisho Disc” (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 the component soluble in THF is about 0.8% by mass. The measurement is performed under the following conditions using this sample solution.
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 KK)
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 ml / 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-20, 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation).

<Method of measuring acid value>
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of the polymer A in the present invention is measured according to JIS K 0070-1992. Specifically, the acid value is measured according to the following procedure.
(1) Preparation of reagent Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add ion-exchanged water to make 100 mL, and 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 the container in an alkali-resistant container for 3 days so as not to be exposed to carbon dioxide or the like, the mixture is filtered to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 mL of 0.1 mol / L hydrochloric acid was placed in an Erlenmeyer flask, and a few drops of the phenolphthalein solution were added. Determined from the amount of potassium solution. As the 0.1 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test A 2.0 g sample of the pulverized polymer A was precisely weighed in a 200 mL Erlenmeyer flask, and 100 mL of a mixed solution of toluene / ethanol (2: 1) was added and dissolved for 5 hours. . Next, several drops of the phenolphthalein solution are added as an indicator, and titration is performed using the potassium hydroxide solution. Note that the end point of the titration is when the light red color of the indicator continues for about 30 seconds.
(B) Blank test The 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) The obtained result is substituted into the following equation to calculate an acid value.
A = [(CB) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (mL) of potassium hydroxide solution in blank test, C: addition amount (mL) of potassium hydroxide solution in main test, f: potassium hydroxide Solution factor, S: mass (g) of sample.

(Method of measuring external additive coverage)
The coverage of the external additive can be determined by measuring the 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.).
The inorganic fine particles present on the surface of the toner particles are observed with the SEM device.
At the time of observation, a portion where the toner particle surface is as flat as possible is selected.
Binarization is performed on the image obtained by extracting only inorganic fine particles on the toner particle surface,
It is calculated as the ratio of the area occupied by the inorganic fine particles to the area of the toner particle surface. The same operation is performed on ten toner particles, and the arithmetic mean value thereof is obtained.

(Weight average particle diameter of toner particles (D4))
The weight average particle diameter (D4) of the toner particles was measured using a precision particle size distribution analyzer “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electric resistance method equipped with an aperture tube of 100 μm. Using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) for setting conditions and analyzing measurement data, measurement was performed with 25,000 effective measurement channels, and the measurement data was measured. Is analyzed and calculated.
As the electrolytic aqueous solution used for the measurement, a solution prepared by dissolving a special grade sodium chloride in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter) can be used.
Before performing the 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 the control mode to 50,000 particles, set the number of measurements to 1, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained by using the following method. The threshold and the noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, and the electrolytic solution is set to ISOTON II, and a check is made in the flash of the aperture tube after the measurement.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to a logarithmic particle size, the particle size bin is set to a 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.

The specific measuring method is as follows.
(1) Approximately 200 ml of the aqueous electrolytic solution is put into a 250 ml round bottom beaker made of glass exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 revolutions / second. Then, the dirt and air bubbles in the aperture tube are removed by the “flash aperture tube” function of the dedicated software.
(2) About 30 ml of the aqueous electrolytic solution is put into a 100 ml flat bottom beaker made of glass, into which "contaminone N" (a precise measurement of pH 7 comprising a nonionic surfactant, an anionic surfactant, and an organic builder) is used as a dispersant. About 0.3 ml of a diluent obtained by diluting a 10% by mass aqueous solution of a neutral detergent for washing the container (manufactured by Wako Pure Chemical Industries, Ltd.) three times with ion-exchanged water.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in a state shifted by 180 degrees, and are placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetra 150” (manufactured by Nikkaki Bios) having an electric output of 120 W. A predetermined amount of ion-exchanged water is charged, and about 2 ml of the contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the aqueous electrolytic solution in the beaker is maximized.
(5) While irradiating ultrasonic waves to the electrolytic aqueous solution in the beaker of (4), about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. The ultrasonic dispersion is appropriately adjusted so that the water temperature in the water tank is 10 ° C. or more and 40 ° C. or less.
(6) The electrolytic aqueous solution of (5) in which the toner is dispersed is dropped into the round bottom beaker of (1) installed in the sample stand using a pipette, and the measured concentration is adjusted to about 5%. . Then, measurement is performed until the number of particles to be measured reaches 50,000.
(7) Analyze the measured data with the dedicated software attached to the device, and calculate the weight average particle size (D4). The “average diameter” on the analysis / volume statistical value (arithmetic average) screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

  The present invention will be specifically described with reference to the following examples. However, they do not limit the invention in any way. Unless otherwise specified, all “parts” in the following formulations are based on mass.

<Example of manufacturing strontium titanate fine particles>
After meta-titanic acid obtained by the sulfuric acid method was subjected to deiron bleaching treatment, an aqueous sodium hydroxide solution was added to adjust the pH to 9.0, desulfurization treatment was performed, and then neutralized to pH 5.8 with hydrochloric acid, followed by filtration and water washing. Water was added to the washed cake to make TiO ₂ into a slurry of 1.5 mol / L, and then hydrochloric acid was added to adjust the pH to 1.5 and peptization was performed.
The metatitanic acid subjected to desulfurization and deflocculation was collected as TiO ₂ and charged into a 3 L reaction vessel. The該解glue metatitanic acid slurry, strontium chloride aqueous solution, after addition to a 1.15 SrO / TiO2 molar ratio was adjusted to TiO ₂ concentration 0.8 mol / L. Next, after heating to 90 ° C. while stirring and mixing, 444 mL of a 10 mol / L aqueous sodium hydroxide solution was added over 45 minutes while performing microbubbling of nitrogen gas at 600 ml / min. The mixture was stirred at 95 ° C. for 1 hour while bubbling was performed at 400 ml / min.
Thereafter, the reaction slurry was stirred while flowing cooling water at 10 ° C. into the jacket of the reaction vessel, 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 mass% of sodium stearate based on the solid content was added as an aqueous solution dissolved in water, and the mixture was kept under stirring for 2 hours, and then hydrochloric acid was added. The pH was adjusted to 6.5, and the stirring and holding were continued for 1 hour to precipitate stearic acid on the surface of strontium titanate.
Next, the cake obtained by filtration and washing was subjected to a crushing treatment by a jet mill until the aggregates disappeared after the cake obtained at 120 ° C. for 10 hours to obtain strontium titanate (inorganic fine particles 1). The inorganic fine particles 1 showed a diffraction peak of strontium titanate by X-ray powder diffraction measurement, and had a perovskite-type crystal structure. Table 1 shows the physical properties.

<Production example of calcium titanate fine particles>
Calcium titanate fine particles (inorganic fine particles 2) were obtained in the same manner as in the production example of the strontium titanate particles 1 except that calcium chloride was used instead of strontium chloride and that nitrogen gas was not microbubbled. . Table 1 shows the physical properties.

<Production example 1 of zinc oxide fine particles>
200 parts of zinc oxide was added to an aqueous hydrochloric acid solution comprising 500 parts of 35% by mass hydrochloric acid and 700 parts of purified water to completely dissolve the zinc oxide to prepare an aqueous zinc chloride solution. On the other hand, 460 parts of ammonium carbonate was dissolved in 3000 parts of purified water to separately prepare an aqueous solution of ammonium bicarbonate. The zinc chloride aqueous solution was added to the ammonium bicarbonate aqueous solution over 60 minutes to form a precipitate. Thereafter, the precipitate was sufficiently washed, separated from the liquid phase, and dried at 130 ° C. for 5 hours.
Next, the dried powder was crushed in an agate mortar. The held powder was heated to 500 ° C. at 200 ° C./hour while supplying a mixed gas of nitrogen gas 0.21 L / min and hydrogen gas 0.09 L / min. After holding for 2 hours as it is and then allowed to cool to room temperature, 5.0 mass% of sodium stearate was added to the obtained zinc oxide fine particles as an aqueous solution dissolved in water, and stirring and holding were continued for 2 hours. After that, the pH was adjusted to 6.5 by adding hydrochloric acid, and the stirring and holding were continued for 1 hour to precipitate 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 subjected to a crushing treatment with a jet mill until the aggregates disappeared to obtain zinc oxide fine particles (inorganic fine particles 3). Table 1 shows the physical properties.

<Production example 1 of titanium oxide fine particles>
The hydrous titanium oxide slurry obtained by thermally hydrolyzing the aqueous solution of titanyl sulfate is neutralized to pH 7 with aqueous ammonia, and the cake obtained by filtration and washing is deflocculated with titanium oxide of the cake to give anatase-type titania sol. Obtained. The average primary particle size of this sol was 7 nm.
Further, ilmenite ore containing 50% by mass of TiO ₂ equivalent is used as a starting material, and after drying this material at 150 ° C. for 2 hours, sulfuric acid is added to dissolve the TiOSO ₄ aqueous solution. Obtained. This was concentrated, and 4.0 parts of the anatase-type titania sol were added as seeds to 100 parts of TiO ₂ equivalent, and then hydrolyzed at 120 ° C. to obtain a slurry of TiO (OH) ₂ containing impurities. Got.
This slurry was repeatedly washed with water at pH 5 to 6 to sufficiently remove sulfuric acid, FeSO ₄ and impurities. Then, a slurry of high-purity metatitanic acid [TiO (OH) ₂ ] was obtained.
After heat-treating the metatitanic acid at 270 ° C. for 6 hours, it was sufficiently pulverized to obtain titanium oxide fine particles of anatase type crystals having a BET specific surface area of 50 m ² / g and a number average particle size of 50 nm.
Next, 5.0 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 stirred and maintained for 2 hours. And kept stirring for 1 hour.
Next, the cake obtained by filtration and washing is dried in the air at 120 ° C. for 10 hours, and is subjected to a crushing treatment by a jet mill until the aggregates of titanium fine particles are eliminated, and the titanium oxide fine particles 1 (inorganic fine particles 4) are removed. Obtained. Table 1 shows the physical properties.

<Production example 2 of titanium oxide fine particles>
In Production Example 1 of titanium oxide fine particles, an aqueous solution in which sodium stearate was dissolved was added, and then an aqueous solution of aluminum sulfate was added with stirring to precipitate aluminum stearate on the surface of the titanium oxide fine particles. Next, the cake obtained by filtration and washing is
The powder was dried in an air atmosphere at 20 ° C. for 10 hours and subjected to a crushing treatment by a jet mill until the aggregates of the titanium fine particles disappeared, thereby obtaining fine particles of titanic oxide 2 (inorganic fine particles 5). Table 1 shows the physical properties.

<Production example 3 of titanium oxide fine particles>
Titanium oxide fine particles 3 (inorganic fine particles 6) were prepared in the same manner as in Production Example 1 of titanium oxide fine particles except that an aqueous solution of sodium laurate was used instead of the aqueous solution of sodium stearate. ) Got. Table 1 shows the physical properties.

<Production example 4 of titanium oxide fine particles>
In Production Example 1 of titanium oxide fine particles, the following operation was performed after obtaining anatase type titanium oxide fine particles. Hydrochloric acid was added to the dispersion of the anatase-type titanium oxide fine particles to adjust the pH to 6.5, and 0.5 part of octyl-modified silicone oil (FZ-3196; Dow Corning Co., Ltd.) was added to 100 parts of the anatase-type titanium oxide fine particles. Was added and stirring and holding were continued for 1 hour.
Next, the cake obtained by filtration and washing is dried in the air at 120 ° C. for 10 hours, and subjected to a crushing treatment by a jet mill until the aggregates of the titanium fine particles are eliminated, to remove the titanic oxide fine particles 4 (inorganic fine particles 7). Obtained. Table 1 shows the physical properties.

<Example 5 of producing titanium oxide fine particles>
Titanium oxide fine particles 5 (inorganic fine particles 8) were prepared in the same manner as in Production Example 1 of titanium oxide fine particles except that an aqueous solution of sodium behenate was used instead of the aqueous solution of sodium stearate. ) Got. Table 1 shows the physical properties.

<Production example 6 of titanium oxide fine particles>
In Production Example 1 of titanium oxide fine particles, the following operation was performed after obtaining anatase type titanium oxide fine particles. The dispersion of the anatase-type titanium oxide fine particles was adjusted to 50 ° C., and the pH was adjusted to 2.5 with hydrochloric acid. Was.
Next, a sodium hydroxide solution was added to adjust the pH to 6.5, and the mixture was kept under stirring and maintained for 1 hour, and then filtered and washed, and the obtained cake was dried in the air at 120 ° C. for 10 hours. Thereafter, crushing treatment was performed by a jet mill until the aggregates of titanium fine particles disappeared to obtain titanium oxide fine particles 6 (inorganic fine particles 9). Table 1 shows the physical properties.

<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 Production Example 6 of titanium oxide fine particles except that octyltrimethoxysilane was used instead of stearyltrimethoxysilane. Table 1 shows the physical properties.

<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 Production Example 6 of titanium oxide fine particles except that isobutyltrimethoxysilane was used instead of stearyltrimethoxysilane. Table 1 shows the physical properties.

<Production example 9 of titanium oxide fine particles>
In Production Example 1 of titanium oxide fine particles, the following operation was performed after obtaining anatase type titanium oxide fine particles. Into the autoclave, a 20/80% by volume mixed solution of anatase-type titanium oxide fine particles and 1-tetracosanol / n-hexane was charged. It heated at 240 degreeC under the pressure of 2.8 Mpa for 1 hour. Thereafter, the cake obtained by filtration and washing was dried in the air at 120 ° C. for 10 hours. Thereafter, crushing treatment was performed by a jet mill until the aggregates of the titanium oxide fine particles disappeared to obtain titanium oxide fine particles 9 (inorganic fine particles 12). Table 1 shows the physical properties.

<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. Table 1 shows the physical properties.

<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. Table 1 shows the physical properties.

<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 Production Example 9 of titanium oxide fine particles except that n-propanol was used instead of 1-tetracosanol. Table 1 shows the physical properties.

<Production Example 2 of zinc oxide fine particles>
In Preparation Example 1 of zinc oxide fine particles, the zinc oxide fine particles before the addition of the aqueous solution of sodium stearate were used and manufactured by the following method.
Into the autoclave, a mixed solution of zinc oxide fine particles and a 20/80% by volume of n-propanol / n-hexane was charged. It heated at 240 degreeC under the pressure of 2.8 Mpa for 1 hour. Thereafter, the cake obtained by filtration and washing was dried in the air at 120 ° C. for 10 hours. Thereafter, a crushing treatment was performed by a jet mill until the aggregates of the 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. . Table 1 shows the physical properties.

<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 solution of sodium stearate was not performed. Table 1 shows the physical properties.

<Production example of antimony-doped tin oxide fine particles>
Antimony-doped tin oxide fine particles (inorganic fine particles) were prepared 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) were used instead of anatase-type titanium oxide fine particles. 19) was obtained. Table 1 shows the physical properties.

<Production example of silica fine particles>
In Example 12 of producing titanium oxide fine particles, silica fine particles (inorganic fine particles 20) were obtained in the same manner except that silica fine particles manufactured by the following method were used instead of anatase type titanium oxide fine particles. Table 1 shows the physical properties.
As a combustion furnace, a hydrocarbon / oxygen mixed burner having a double tube structure capable of forming an internal flame and an external flame was used. A two-fluid nozzle for slurry injection was grounded at the center of the burner, and a silicon compound as a raw material was introduced. A hydrocarbon-oxygen flammable gas was injected from around the two-fluid nozzle to form an internal flame and an external flame as a reducing atmosphere.
The atmosphere, temperature, flame length, etc. were adjusted by controlling the amounts and flow rates of combustible gas and oxygen. Silica fine particles were formed from the silicon compound in the flame, and the silica particles were fused to a desired particle size. Thereafter, 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 the 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: 100.0 parts of toluene-100.0 parts of monomer composition (The monomer composition is a mixture of the following behenyl acrylate, methacrylonitrile, and styrene in the ratio shown below)
-Behenyl acrylate (first monomer) 67.0 parts (28.9 mol%)
-Methacrylonitrile (second monomer) 22.0 parts (53.8 mol%)
・ Styrene (third monomer) 11.0 parts (17.3 mol%)
0.5 parts of polymerization initiator t-butyl peroxypivalate (manufactured by NOF CORPORATION: perbutyl PV) 0.5 parts of the above-mentioned materials in a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet. I put it in. The polymerization reaction was carried out for 12 hours by heating to 70 ° C. while stirring the inside of the reaction vessel at 200 rpm to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Subsequently, after the temperature of the solution was lowered to 25 ° C., the solution was poured into 1000.0 parts of methanol with stirring to precipitate a methanol-insoluble component. The obtained methanol-insoluble matter was separated by filtration, further washed with methanol, and vacuum-dried at 40 ° C. for 24 hours to obtain a 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 mg KOH / g.
When the polymer A1 was analyzed by NMR, the monomer unit derived from behenyl acrylate was 28.9 mol%, the monomer unit derived from methacrylonitrile was 53.8 mol%, and the monomer unit derived from styrene was 17.3 mol%. Was included. The SP value of the monomer and the monomer unit derived from the monomer was calculated.

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

<Preparation of monomer having urea group>
50.0 parts of dibutylamine was charged to the reaction vessel. Thereafter, 5.0 parts of Karenz MOI [2-isocyanatoethyl methacrylate] was added dropwise at room temperature under stirring. After completion of the dropwise addition, stirring was performed 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>
Reactions were carried out in the same manner as in Production Example 1 of Polymer 1 except that the monomers and parts by mass were changed as shown in Table 2, and Polymers 2 to 27 were obtained. Physical properties are shown in Tables 3 to 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: myristyl acrylate OA: octacosa acrylate HA: hexadecyl acrylate MN: methacrylonitrile AN: acrylonitrile HPMA: 2-hydroxypropyl methacrylate AM: acrylamide UT: urethane group Monomer having 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)
The autoclave was charged with 50 parts of xylene and purged with nitrogen, and then heated to 185 ° C. in a sealed state with stirring. 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 dropped and polymerized continuously for 3 hours while controlling the temperature in the autoclave at 185 ° C. Was. Further, the temperature was kept at the same temperature for 1 hour to complete the polymerization, the solvent was removed, and amorphous resin 1 which was not polymer A was obtained. The weight average molecular weight (Mw) of the obtained resin was 3,500, the softening point (Tm) was 96 ° C., and the glass transition temperature (Tg) was 58 ° C.

<Production Example of Polymer Fine Particle 1 Dispersion>
-300 parts of toluene (manufactured by Wako Pure Chemical Industries)-100 parts of polymer 1 The above materials were weighed and 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-mentioned toluene solution and the aqueous solution were mixed, and an ultra-high-speed stirring device 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 type dispersing machine Nanomizer (manufactured by Yoshida Kikai Kogyo). Thereafter, toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (dispersion of polymer fine particles 1) having a concentration of polymer fine particles 1 of 20% by mass.
The 50% particle size (D50) based on the volume distribution of the polymer fine particles 1 was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.40 μm.

<Production example of dispersion liquid of polymer fine particles 2 to 27>
Emulsification was carried out in the same manner as in Production Example 1 of Polymer Fine Particle Dispersion except that each polymer was changed as shown in Table 6, to obtain Polymer Fine Particles 2 to 27. Table 6 shows the physical properties.

<Production Example of Amorphous Resin Fine Particle 1 Dispersion Not Polymer A>
・ 300 parts of tetrahydrofuran (manufactured by Wako Pure Chemical) ・ 100 parts of amorphous resin 1 which is not polymer A ・ 0.5 part of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) 0.5 parts of the above materials are weighed, mixed and dissolved I let it.
Then, 20.0 parts of 1 mol / L aqueous ammonia was added, and the ultrahigh-speed stirring device T.P. 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 is removed using an evaporator, the concentration is adjusted with ion-exchanged water, and an aqueous dispersion of amorphous resin fine particles 1 other than polymer A at a concentration of 20% by mass (amorphous resin fine particle 1 dispersion). I got
The 50% particle size (D50) based on the volume distribution of the amorphous resin fine particles 1 other than the polymer A was 0.13 μm.

<Production example of release agent (aliphatic hydrocarbon compound) fine particle dispersion>
・ 100 parts of aliphatic hydrocarbon compound HNP-51 (manufactured by Nippon Seiwa) ・ 5 parts of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) ・ 395 parts of ion-exchanged water The above materials are weighed and mixed with a stirrer. After being charged into the container, the mixture was heated to 90 ° C. and circulated through Clearmix W Motion (manufactured by M Technique) to perform a dispersion treatment for 60 minutes. The conditions of the distributed processing were as follows.
・ Rotor outer diameter 3cm
・ Clearance 0.3mm
・ Rotor rotation speed 19000r / min
・ Screen rotation speed 19000r / min
After the dispersion treatment, the mixture is cooled to 40 ° C. under a cooling treatment condition 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, whereby the release agent (aliphatic hydrocarbon compound) fine particles are removed. An aqueous dispersion (release agent (aliphatic hydrocarbon compound) fine particle dispersion) having a concentration of 20% by mass was obtained.
The 50% particle size (D50) based on the volume distribution of the release agent (aliphatic hydrocarbon compound) fine particles was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.). It was 15 μm.

<Manufacture of colorant fine particle dispersion>
・ Colorant 50.0 parts (Cyan pigment manufactured by Dainichi Seika: Pigment Blue 15: 3)
・ 7.5 parts of anionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) ・ 442.5 parts of ion-exchanged water The above materials are weighed, mixed and dissolved, and a high pressure impact disperser Nanomizer (Yoshida Kikai Kogyo) is used. The mixture was dispersed for about 1 hour to obtain an aqueous dispersion (colorant fine particle dispersion) having a colorant fine particle concentration of 10% by mass.
The 50% particle size (D50) based on the volume distribution of the colorant fine particles was measured using a dynamic light scattering type 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>
-500 parts of polymer fine particle 1 dispersion liquid-50 parts of a release agent (aliphatic hydrocarbon compound fine particle dispersion liquid)-80 parts of colorant fine particle dispersion liquid-160 parts of ion exchange water 160 parts of each of the above materials in a round stainless steel flask Charged and mixed. Subsequently, the mixture was dispersed at 5000 r / min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). A 1.0% aqueous nitric acid solution was added to adjust the pH to 3.0, and then the mixture was stirred at 58 ° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. Until heated. The volume average particle size of the formed aggregated particles is appropriately checked using a Coulter Multisizer III. When the aggregated particles having a weight average particle size (D4) of about 6.00 μm are formed, 5% sodium hydroxide is formed. The pH was adjusted to 9.0 using an aqueous solution. Then, it heated to 75 degreeC, continuing stirring. Then, the particles were kept at 75 ° C. for 1 hour to fuse the aggregated particles.
Thereafter, the temperature was cooled to 50 ° C. and maintained for 3 hours to promote crystallization of the polymer.
Thereafter, the mixture was cooled to 25 ° C., filtered and solid-liquid separated, and then washed with ion-exchanged water. After completion of the washing, the particles were dried using a vacuum drier to obtain toner particles 1 having a weight average particle diameter (D4) of about 6.1 μm.

<Production Example 2 of Toner Particle>
-Monomer composition 100.0 parts (The monomer composition is a mixture of the following behenyl acrylate, methacrylonitrile, and styrene in the ratio shown below)
(Behenyl acrylate 67.0 parts (28.9 mol%))
(22.0 parts (53.8 mol%) of methacrylonitrile)
(Styrene 11.0 parts (17.3 mol%))
-Colorant Pigment Blue 15: 3 6.5 parts-Aluminum t-butylsalicylate 1.0 part-Paraffin wax 10.0 parts (Nippon Seiro Co., Ltd .: HNP-51)
A mixture consisting of 100.0 parts of toluene was prepared. The mixture was charged into an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed at 200 rpm for 2 hours using zirconia beads having 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 (decahydrate) were added to a vessel equipped with a high-speed stirrer homomixer (manufactured by Primix) and a thermometer, followed by stirring at 12000 rpm. While heating, the temperature was raised to 60 ° C. An aqueous solution of calcium chloride in which 9.0 parts of calcium chloride (dihydrate) was dissolved in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12,000 rpm for 30 minutes while maintaining the temperature at 60 ° C. There, 10% hydrochloric acid was added 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 stirring at 100 rpm. Then, 8.0 parts of t-butyl peroxypivalate (manufactured by NOF CORPORATION: Perbutyl PV) as a polymerization initiator was added thereto, and the mixture was stirred at 100 rpm for 5 minutes while maintaining the temperature at 60 ° C. Into an aqueous medium stirred at 12000 rpm.
While maintaining the temperature at 60 ° C., stirring was continued at 12,000 rpm for 20 minutes with the high-speed stirring device to obtain a granulated liquid. The granulated 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. while stirring at 150 rpm under a nitrogen atmosphere. The polymerization reaction was performed at 150 rpm for 10 hours while maintaining 70 ° C. Thereafter, the reflux condenser was removed from the reaction vessel, the temperature of the reaction solution was raised to 95 ° C., and the mixture was stirred at 150 rpm for 5 hours while maintaining the temperature at 95 ° C. to remove toluene, thereby obtaining a toner particle dispersion.
After cooling the obtained toner particle dispersion to 20 ° C. while stirring at 150 rpm, dilute hydrochloric acid was added to dissolve the dispersion stabilizer until the pH reached 1.5 while maintaining the stirring. The solid content was separated by filtration, sufficiently washed with ion-exchanged water, and vacuum-dried at 40 ° C. for 24 hours to obtain toner particles 2.

<Example 3 of toner particle production>
[Preparation of fine particle dispersion liquid 1]
683.0 parts of water, 11.0 parts of sodium salt of methacrylic acid EO adduct sulfate ester (Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.) and 130.0 parts of styrene Then, 138.0 parts of methacrylic acid, 184.0 parts of n-butyl acrylate, and 1.0 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to obtain a white suspension. The mixture was heated to a temperature in the system of 75 ° C. and reacted for 5 hours.
Further, 30.0 parts of a 1% aqueous solution of ammonium persulfate was added, and the mixture was aged at 75 ° C. for 5 hours to obtain a fine particle dispersion 1 of a vinyl polymer. The volume average particle size of the fine particle dispersion 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 are put into a heat-resistant glass container, dispersed with a paint shaker for 5 hours, and glass with a nylon mesh. The beads were removed to obtain a colorant dispersion 1.
[Preparation of wax dispersion 1]
Paraffin wax (Nippon Seiro Co., Ltd .: HNP-51): 20.0 parts Ethyl acetate: 80.0 parts Then, the system was cooled to 25 ° C. over 3 hours while gently stirring the system 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 having a diameter of 1 mm, and dispersed for 3 hours with a paint shaker (manufactured by Toyo Seiki), and the glass beads were removed with a nylon mesh. Obtained.
[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 a disper (manufactured by Tokushu Kika Co., Ltd.).
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 materials were placed in a beaker and dispersed (manufactured by Tokushu Kika Co., Ltd.). ) Was stirred at 6000 rpm for 3 minutes to prepare an oil phase 1.
[Preparation of aqueous phase 1]
Fine particle dispersion liquid 1 15.0 parts Sodium dodecyl diphenyl ether disulfonate aqueous solution (Eleminol MON7, manufactured by Sanyo Chemical Industry Co., Ltd.) 30.0 parts Ion-exchanged water 955.0 parts The mixture was stirred at 3000 rpm for 3 minutes to prepare an aqueous phase 1.
[Production of toner particles]
The oil phase 1 was put into the water phase 1, and dispersed by a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at 10,000 rpm for 10 minutes. Thereafter, the solvent was removed at 30 ° C. under a reduced pressure of 50 mmHg for 30 minutes. Next, filtration was performed, and the operation of filtering and redispersing in ion-exchanged water was repeated until the conductivity of the slurry became 100 μS, thereby removing the surfactant and obtaining a filter cake.
After the filter cake was vacuum dried, toner particles 3 were obtained by performing air classification.

<Example 4 of toner particle production>
100 parts of polymer 1 10 parts of aliphatic hydrocarbon compound HNP-51 (manufactured by Nippon Seiro) I. Pigment Blue 15: 3 6.5 parts · 3,5-di-t-butylsalicylate aluminum compound 0.5 part The above materials were rotated using a Henschel mixer (Model FM-75, manufactured by Nippon Coke Industry Co., Ltd.). After mixing at 20 s ^-1 and a rotation time of 5 min, the mixture was kneaded at a discharge temperature of 135 ° C. by a twin-screw kneader (PCM-30, manufactured by Ikegai Co., Ltd.) set at a temperature of 120 ° C. The obtained kneaded material was cooled at a cooling rate of 15 ° C./min, and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely crushed material. The obtained crushed material was finely pulverized with a mechanical pulverizer (T-250, manufactured by Freund Turbo Co., Ltd.).
Classification was further performed using Faculty F-300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles 4. The operating conditions were as follows: the classification rotor rotation speed was 130 s ^-1 , and the dispersion rotor rotation speed was 120 s ^-1 .

<Production Example 1 of Toner>
-100 parts of toner particles 1-0.5 parts of strontium titanate fine particles 1 0.5 parts The above materials were rotated at a rotation speed of 30 seconds with a Henschel mixer FM-10C type (manufactured by Mitsui Miike Kakoki Co., Ltd.).
^-1 and a rotation time of 10 minutes to obtain a toner 1. Table 8 shows constituent materials of the toner 1.
The weight average particle diameter (D4) of Toner 1 was 6.1 μm. Table 9 shows the physical properties of Toner 1.

<Production Example of Toner Particles 5 to 32>
Except that the formulation of the polymer 1 was changed as shown in Table 7, toner particles 5 to 32 were obtained in the same manner as in the production example of the toner particles 1. In the toner particles 24 and 25, the dispersion of the polymer fine particles 1 and the dispersion of the amorphous resin fine particles 1 other than the polymer A were mixed so as to have the amounts shown in Table 7.

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

<Example of manufacturing magnetic carrier 1>
A magnetite having a number average particle diameter of 0.30 μm and a magnetization intensity of 65 Am ² / kg under a magnetic field of 1000 / 4π (kA / m); a number average particle diameter of 0.50 μm and a (1000 / 4π (kA / m) ) Magnetite having a magnetization strength of 65 Am ² / kg under a magnetic field 4.0 parts of a silane compound (3- (2-aminoethylaminopropyl) trimethoxysilane) was added to 100 parts of each of the above materials. High-speed mixing and stirring were performed at 100 ° C. or higher in a container to treat each fine particle.
・ Phenol: 10% by mass
Formaldehyde solution: 6% by mass (formaldehyde 40% by mass, methanol 10% by mass, water 50% by mass)
-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 material, 5 parts of a 28% by mass aqueous ammonia solution, and 20 parts of water are placed in a flask, and the temperature is raised and maintained at 85 ° C. for 30 minutes while stirring and mixing, and a polymerization reaction is performed for 3 hours to produce a phenol resin. Was cured. Thereafter, the cured phenol resin was cooled to 30 ° C., water was further 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 carrier-dispersed spherical magnetic carrier 1. The 50% particle size (D50) on a volume basis 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 mixed with a V-type mixer (V-20, manufactured by Seishin Enterprise) to obtain two-component developer 1.
<Production Examples of Two-Component Developers 2 to 55>
Production was performed in the same manner as in the production example of the two-component developer 1 except that the toner was changed as shown in Table 9, and two-component developers 2 to 55 were obtained.

<Evaluation of charging startability>
The evaluation of the charge rising property was performed by measuring a change in density when images having different image print ratio densities were output. After an image with a low image ratio is output and the charge of the toner in the developing device is saturated, an image with a high image ratio is output. Then, a density change occurs due to a difference in charge between the charged toner in the developing device and the toner newly supplied to the developing device.
The toner whose charge rises quickly is saturated immediately after the toner is supplied into the developing device, and therefore the change in density is small. On the other hand, it takes a long time from the supply of the toner into the developing device to the saturation of the charge of the toner whose charge rises slowly, so that the charge amount of the entire toner decreases and the density changes.
Using a full color copying machine imagePress C800 made by Canon as an image forming apparatus, the two-component developer to be evaluated is put into a cyan developing device of the image forming apparatus, and the toner to be evaluated is put into a cyan toner container, and the evaluation described later is performed. went.
The modification is that the mechanism for discharging the excess magnetic carrier inside the developing device from the developing device is removed. As the evaluation paper, plain paper GF-C081 (A4, basis weight 81.4 g / m ² , sold by Canon Marketing Japan Inc.) was used.
Adjustment was performed so that the amount of toner applied to the paper in the FFh image (solid image) was 0.45 mg / cm ² . FFh is a value in which 256 gradations are displayed in hexadecimal, 00h is the first gradation of 256 gradations (white background), and FF is 256th gradation of 256 gradations (solid part). .
First, an image output test was performed on 1,000 sheets at an image ratio of 1%. During the continuous feeding of 1000 sheets, the sheet was passed under the same developing conditions and transfer conditions (without calibration) as the first sheet.
Thereafter, an image output test was performed on 1,000 sheets at an image ratio of 80%. During the continuous feeding of 1000 sheets, the sheet was passed under the same developing conditions and transfer conditions (without calibration) as the first sheet.
The density of the 1000th image in printing at an image ratio of 1% was used as the initial density, and the density of the 1000th image in printing at an image ratio of 80% was measured, and evaluated according to the following evaluation criteria. The evaluation results are shown in the table.
The above test was performed under a normal temperature and normal humidity environment (N / N; temperature 23 ° C., relative humidity 50%) and a normal temperature and low humidity environment (N / L; temperature 23 ° C., relative humidity 5%).
(1) Measurement of Change in Image Density 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. , Based on the following criteria. Table 8 shows the evaluation results. C and above were judged to have obtained the effects of the present invention.
(Concentration 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 maintenance rate under high temperature and high humidity environment]
The toner on the electrostatic latent image carrier was suctioned and collected using a metal cylindrical tube and a cylindrical filter to calculate the triboelectric charge amount of the toner.
Specifically, the triboelectric charge amount of the toner on the electrostatic latent image carrier was measured by a Faraday-Cage. The Faraday cage is a coaxial double cylinder in which the inner cylinder and the outer cylinder are insulated. Assuming that a charged body having a charge amount Q is placed in this inner cylinder, it is as if a metal cylinder having a charge amount Q is present by electrostatic induction. The amount of the induced charge was measured with an electrometer (Kesley 6517A, manufactured by Kesley), and the value obtained by dividing the charge Q (mC) by the mass M (kg) of the toner in the inner cylinder (Q / M) was the frictional charge of the toner. Amount.
Toner triboelectric charge (mC / kg) = Q / M
First, the evaluation image is formed on the electrostatic latent image carrier, and before being transferred to the intermediate transfer member, the rotation of the electrostatic latent image carrier is stopped, and the toner on the electrostatic latent image carrier is The sample was collected by suction using a cylindrical tube and a cylindrical filter, and [initial Q / M] was measured.
Subsequently, after leaving the developing unit in the evaluation machine for 2 weeks in a high-temperature and high-humidity (H / H) environment (30 ° C., 80% RH), the same operation as before the standing was performed. The charge amount per unit mass Q / M (mC / kg) on the image carrier was measured. The initial Q / M per unit mass on the electrostatic latent image carrier is 100%, and the maintenance rate of Q / M per unit mass on the electrostatic latent image carrier after standing ([ [Q / M] / [initial Q / M] × 100), and the judgment was made based on the following criteria. C and above were judged to have obtained the effects of the present invention.
(Evaluation criteria)
A: Retention rate is 95% or more B: Retention rate is 90% or more and less than 95% BB: Retention rate is 85% or more and less than 90% C: Retention rate is 80% or more and less than 85% D: Retention 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 DC voltage VDC of developer carrier, charging voltage VD of electrostatic latent image carrier, and laser power)
Evaluation image: An image of 2 cm × 5 cm is placed at the center of the 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 evaluation image was output, and the low-temperature fixability was evaluated. The value of the image density reduction rate was used as an evaluation index for low-temperature fixability. First, the image density at the center is measured using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). Next, a load of 4.9 kPa (50 g / cm ² ) was applied to the portion where the image density was measured, and the fixed image was rubbed (five reciprocations) with silbon paper, and the image density was measured again. Then, the decrease rate of the image density before and after the rubbing was calculated using the following equation. The obtained image density reduction rate was evaluated according to the following evaluation criteria. C and above were judged to have obtained the effects of the present invention.
Image density reduction rate = (image density before rubbing−image density after rubbing) / image density before rubbing × 100
(Evaluation criteria)
A: Image density reduction rate of less than 3.0% B: Image density reduction rate of 3.0% or more and less than 5.0% C: Image density reduction rate of 5.0% or more and less than 15.0% D: Image density Reduction rate of 15.0% or more

[Blocking property of toner (heat-resistant storage property)]
An evaluation of blocking resistance was performed to evaluate the stability during storage. About 5 g of the toner is placed in a 100 ml resin cup and left for 10 days in an environment of a temperature of 50 ° C. and a humidity of 20%. Then, the cohesion degree of the toner is measured as follows, and evaluated according to the following criteria. Was.
As a measuring device, a device in which a digital display type vibrometer "Digi Vibro MODEL 1332A" (manufactured by Showa Sokki Co., Ltd.) was connected to the side of the shaking table of "Powder Tester" (manufactured by Hosokawa Micron Corporation) was used. Then, a sieve having a mesh size of 38 μm (400 mesh), a sieve having a mesh size of 75 μm (200 mesh), and a sieve having a mesh size of 150 μm (100 mesh) were set in this order on a vibration table of the powder tester from below. The measurement was performed as follows in a 23 ° C., 60% RH environment.
(1) The vibration width of the vibration table was adjusted in advance so that the displacement value of the digital display type vibrometer was 0.60 mm (peak-to-peak).
(2) The toner left for 10 days as described above was left in advance in an environment of 23 ° C. and 60% RH for 24 hours, and 5 g of the toner was precisely weighed and gently placed on a 150 μm sieve at the uppermost stage. Was.
(3) After the sieve was vibrated for 15 seconds, the mass of the toner remaining on each sieve was measured, and the degree of aggregation was calculated based on the following equation.
Cohesion degree (%) = {(mass of sample on sieve with mesh size of 150 μm (g)) / 5 (g)} × 100
+ {(Sample mass (g) on sieve with mesh size of 75 μm) / 5 (g)} × 100 × 0.6
+ {(Mass of sample (g) on sieve with mesh size of 38 μm) / 5 (g)} × 100 × 0.2
The evaluation criteria are as follows.
A: Cohesion degree is less than 20% B: Cohesion degree is 20% or more and less than 25%.
C: Aggregation degree is 25% or more and less than 35%.
D: Aggregation degree is 35% or more.
C and above were judged to have obtained the effects of the present invention.

Claims (19)

A toner having toner particles and inorganic fine particles containing a binder resin,
The binder resin is a first monomer unit derived from a first polymerizable monomer, and a second monomer derived from a second polymerizable monomer different from the first polymerizable monomer. Containing a polymer A having a monomer unit,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate 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 formula is used. Satisfy (1) and (2),
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,
A toner 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 toner having toner particles and inorganic fine particles containing a binder resin,
The binder resin, a first polymerizable monomer, and a polymer A of a composition containing a second polymerizable monomer different from the first polymerizable monomer, a polymer A Contains
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The content ratio of the first polymerizable monomer in the composition is from 5.0 mol% to 60.0 mol% based on the total number of moles of all the polymerizable monomers in the composition. Yes,
The content ratio 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 the polymerizable monomers in the composition. Yes,
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 When 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,
A toner 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 content ratio of the second monomer unit 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. The toner according to 1.   The content ratio 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 the polymerizable monomers in the composition. The toner according to claim 2.   The said 1st polymerizable monomer is at least one selected from the group which consists of a (meth) acrylic acid ester which has a C18-C36 linear alkyl group. The toner according to claim 1. 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 a nitrile group (—C≡N),
An 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 or a hydroxyalkyl group having 1 to 6 carbon atoms),
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 (R ¹³ is each 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 (R ¹⁵ is Each 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 the 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 a nitrile group (—C≡N),
An 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 or a hydroxyalkyl group having 1 to 6 carbon atoms),
A urea group (—NH—C (＝ O) —N (R ¹³ ) ₂ (R ¹³ is each 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 (R ¹⁵ is Each 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 the 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,
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.   The toner according to any one of claims 1 to 8, wherein the content of the polymer A is 50% by mass or more based on the total mass of the binder resin.   The toner according to claim 1, wherein a coverage of the toner particles by the inorganic fine particles is 3 area% to 80 area%.   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 compounds having an alkyl group having 4 to 24 carbon atoms.   The toner according to any one of claims 1 to 11, wherein the compound having an alkyl group is at least one compound selected from the group consisting of a silane coupling agent, a fatty acid metal salt, and a silicone oil.   The toner according to claim 1, wherein the inorganic fine particles are strontium titanate.   The toner according to any one of claims 1 to 13, wherein the inorganic fine particles are strontium titanate having a perovskite crystal structure.   15. The toner according to claim 1, wherein the toner has a charge decay rate coefficient of 3 to 100 measured in a 30 ° C. and 80% RH environment.   The toner according to any one of claims 1 to 15, wherein the inorganic fine particles have a dielectric constant at 1 MHz of 20 pF / m to 100 pF / m. The number of carbon atoms in the alkyl group of the first polymerizable monomer and C _x, when the number of carbon atoms in the alkyl group of the compound having the alkyl group was C _y, is C x _/ C _y 0.8~24 17. The toner according to any one of claims 1 to 16, wherein   The toner according to any one of claims 1 to 17, 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 18.