JP6433175B2 - toner - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic charge image used in an image forming method such as electrophotography or electrostatic printing.

  In recent years, printers and copiers are required to have high speed and low power consumption, and in order to satisfy these demands, improvement of fixing performance of toner itself is also required. That is, it is desired to realize a toner that can be quickly fixed at a low temperature with low energy by being rapidly melted at a lower temperature and that is excellent in low-temperature fixability.

  In order to satisfy these requirements, it is necessary to soften the toner itself. However, when the toner is softened, the problems of heat resistance storage stability and durability decrease simultaneously. Therefore, a toner having a capsule structure composed of core particles excellent in low-temperature fixability and an outer shell formed so as to cover the surface of the core particles has been proposed.

  For example, a polymerized toner having a coating layer in which granular lumps containing a silicon compound are fixed to core particles is disclosed (Patent Document 1).

  Also disclosed is a toner in which resin fine particles are attached to core particles containing crystalline polyester and amorphous polyester to form convex portions on the surface of the core particles (Patent Document 2).

JP 2001-75304 A JP 2012-194314 A

  However, in the toner of Patent Document 1, there is no reduction in heat resistance due to exudation of a release agent or a resin component from a gap between particle lumps containing a silicon compound, and the amount of silane compound deposited on the toner surface and hydrolysis polycondensation are not. It is enough. For this reason, further improvement has been required against the contamination of the members due to toner fusion. Further, in the toner of Patent Document 2, the crystalline polyester is deposited on the surface of the core particle, so that the heat resistant storage stability may be lowered, or the resin fine particles may be buried during printing durability. For this reason, the initial performance cannot be maintained, and further improvement is necessary.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a toner having excellent low-temperature fixability and excellent development durability and heat-resistant storage stability for a long period of time.

  As a result of intensive studies, the present inventors have found that the above-described problem can be solved by adopting the following configuration, and have reached the present invention.

That is, the present invention comprises a core particle,
An outer shell covering the core particles;
A toner having toner particles comprising:
The core particles are
A binder resin,
An organosilicon polymer having a partial structure represented by the following formula (T3);
_{R f -Si-O 3/2 (T3} )
(In the formula (T3), R _f represents a hydrocarbon group.)
Containing
The organosilicon polymer is unevenly distributed on the surface of the core particles;
It said shell is state, and are not formed by a glass transition temperature on the outer surface of the surface portion of the core particles to stick to 50.0 ° C. to 95.0 ° C. of the fine resin particles,
In the NMR chart obtained by ²⁹ Si-NMR measurement of the THF-insoluble matter of the toner particles, it belongs to the structure of the formula (T3) with respect to the total area of all the peaks of the organosilicon polymer shown in the NMR chart. the ratio of the peak area ST3, characterized in der Rukoto 0.40 or more.

  According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixability and excellent in development durability and heat-resistant storage stability for a long period of time.

Is a diagram illustrating an example of a peak processing based on the ²⁹ Si-NMR measurement. It is a figure which shows the structural example of the apparatus used for the measurement of the charge amount of the developing agent using the toner of this invention.

The present invention relates to a toner having toner particles having core particles and an outer shell covering the core particles. In the present invention, the core particles contain a binder resin and an organosilicon polymer having a partial structure represented by the following formula (T3).
_Rf- Si-O3 _{/ 2} (T3)

  Details of the formula (T3) will be described later.

  In the present invention, the organosilicon polymer is unevenly distributed on the surface portion of the core particle, and the outer shell is a resin fine particle having a glass transition temperature of 50.0 ° C. to 95.0 ° C. on the outer surface of the surface portion of the core particle. It is formed by fixing.

  Hereinafter, the present invention will be described in detail. Various toners having a capsule structure in which core particles excellent in low-temperature fixability are coated with an outer shell are known. In particular, a capsule structure formed by using polymer fine particles as core particles and coating the surface of the core particles with resin fine particles is particularly excellent because a uniform layer can be formed. However, when a load is continuously applied to the toner by copying and printing a large number of sheets, a phenomenon occurs in which resin fine particles on the surface of the toner particles are embedded toward the core particles. As a result, the capsule structure is broken and the initial toner characteristics may not be maintained.

  Therefore, as a result of diligent efforts, the present inventor has excessively embedded resin fine particles into the core particles by fixing the resin fine particles with the organosilicon polymer unevenly distributed on the surface of the core particles to form an outer shell. It was found that can be prevented.

The toner of the present invention contains an organosilicon polymer having a partial structure represented by the following formula (T3).
_Rf- Si-O3 _{/ 2} (T3)
In the formula (T3), R _f represents a hydrocarbon group.

  Note that the formula (T3) can be expressed as the following formula (T3 ′).

(In formula (T3 '), * represents a bond with a Si atom contained in another unit.)

Due to the cross-linked structure consisting of siloxane bonds (—O—Si—O—) contained in the formula (T3), the resin fine particles constituting the outer shell are core particles from the region where the organosilicon polymer is unevenly distributed to the inside. Embedding can be suppressed. For this reason, it is thought that durability and heat-resistant storage stability improve. Furthermore, it is considered that the _Rf portion contained in (T3) can improve the affinity with the resin fine particles on the outer surface of the surface portion of the core particle, and the capsule structure becomes stronger.

As the organosilicon polymer having a partial structure of the formula (T3), a compound in which R _f is a linear alkyl group or aryl group is preferable. This is because, when the hydrophobicity of the substituent _Rf is large, the charge amount variation tends to increase in a wide range of environments. In particular, a linear alkyl group or aryl group having 5 or less carbon atoms is preferable because of its excellent environmental stability.

In the present invention, the hydrocarbon group R _f contained in the formula (T3) is particularly preferably an alkyl group having 3 or less carbon atoms, that is, a methyl group, an ethyl group, or a propyl group. This is because the chargeability is good and the fog is good.

From the viewpoint of environmental stability and heat resistant storage stability, the most preferred R _f is a methyl group.

In the toner of the present invention, a sol-gel method is a typical method for producing an organosilicon polymer. In the sol-gel method, a metal alkoxide M (OR) _n (M: metal, O: oxygen, R: hydrocarbon, n: oxidation number of metal) is used as a starting material, and hydrolysis and condensation polymerization are performed in a solvent to form a sol This is a method of synthesizing glass, ceramics, organic-inorganic hybrid, nanocomposite, etc. through a state and a gel state. When this sol-gel method is used, functional materials of various shapes such as surface layers, fibers, bulk bodies, and fine particles can be produced from a liquid phase at a low temperature.

  Specifically, the organosilicon polymer that is unevenly distributed on the surface of the core particle is preferably produced by hydrolytic polycondensation of an organosilicon compound typified by alkoxysilane.

  In particular, when the core particle is produced in an aqueous medium, the organosilicon compound is unevenly distributed on the surface of the core particle due to the hydrophilicity of the hydrophilic substituent such as the silanol group of the organosilicon compound. become. For this reason, it is considered that the organosilicon polymer is unevenly distributed on the surface portion of the core particle with a constant thickness and abundance. Further, it is considered that variation between toners can be suppressed by the organosilicon polymer unevenly distributed on the surface of the core particles. By providing the organosilicon polymer uniformly on the surface of the core particles, the resin fine particles are not embedded unevenly, and the toner performance hardly deteriorates during long-term use, and a toner having excellent heat-resistant storage stability can be obtained.

  In some cases, the core particles constituting the toner of the present invention can be confirmed to be unevenly distributed on the surface of the core particles in cross-sectional observation of the core particles using a transmission electron microscope (TEM). In addition, the surface part of a core particle refers to the area | region between 0 nm-100 nm toward the center (midpoint of a long axis) from the outer surface of a core particle in cross-sectional observation of the core particle by TEM.

The presence state of this organosilicon polymer is controlled by controlling the carbon number of R _f contained in the partial structure of the formula (T3), the temperature at which the core particles are produced, the reaction time, the reaction solvent, and the pH. be able to. In addition, the presence state can be controlled by the amount of the organosilicon polymer.

In the toner of the present invention, the outer shell is formed by fixing resin fine particles having a glass transition temperature of 50.0 ° C. or higher and 95.0 ° C. or lower to the outer surface of the surface portion of the core particles. A uniform and strong layer can be formed by fixing the resin fine particles after producing the core particles. The glass transition temperature of the resin constituting the resin fine particles (hereinafter also referred to as T _g) that is 50 ° C. or more, to the one heat-resistant storage property and durability were excellent. Moreover, inhibition of the low-temperature fixability of the core particles can be reduced when T _g is 95 ° C. or lower. Further, even when inorganic fine powder is externally added, such as a fluidity improver, the adhesion of the inorganic fine powder to the toner particles is improved and the effect of improving the fluidity can be maintained over a long period of time. More preferably, the glass transition temperature of the resin constituting the resin fine particles is 55.0 ° C. or higher and 85.0 ° C. or lower. When the glass transition temperature of the resin constituting the resin fine particles is less than 50.0 ° C., the heat resistance and durability are inferior, and when it exceeds 95 ° C., fixing inhibition occurs and the low-temperature fixability is inferior.

T _g of the resin constituting the resin fine particles mainly monomeric type used for the resin, it is possible to control the ratio.

  In the present invention, various known methods can be used as the method for fixing the resin fine particles to the surface of the core particle. Specifically, a method of mixing the core particles and resin fine particles in a dry manner and fixing them by mechanical treatment, or a method of dispersing the core particles and resin fine particles in an aqueous medium and heating or adding an aggregating agent. Is mentioned. In the present invention, in order to fix the resin fine particles uniformly and densely on the surface of the core particles, it is preferable to fix the resin fine particles to the surface of the core particles by heating in an aqueous medium.

In the present invention, in the chart obtained by measurement of ²⁹ Si-NMR of the THF insoluble content of the toner particles, the peak attributed to the structure of the formula (T3) with respect to the total area of all the peaks of the organosilicon polymer shown in the NMR chart The area ratio ST3 is preferably 0.40 or more.

In the measurement of ²⁹ Si-NMR of the THF-insoluble matter in the toner particles, the strength of the organosilicon polymer is increased by satisfying the requirement that the above ST3 is 0.40 or more. The embedding can be further suppressed, and the effect of being excellent in heat resistant storage stability and member contamination is achieved.

  In the present invention, ST3 can be controlled by monomer species, reaction temperature, reaction time, reaction solvent, and pH.

  In the present invention, the organosilicon polymer is preferably a polymer obtained by polymerizing a polymerizable monomer containing an organosilicon compound represented by the following formula (Z).

In the formula (Z), R ₁ represents an alkyl group having 1 to 5 carbon atoms or an aryl group. In the formula (Z), R ₂ , R ₃ and R ₄ each represent a halogen atom, a hydroxyl group or an alkoxy group.

The hydrocarbon group represented by R ₁ plays a role of improving the affinity between the resin fine particles constituting the toner and the organosilicon polymer. Thereby, a toner having a capsule structure with excellent adhesion between the outer surface of the core particles and the resin fine particles can be obtained. R ₁ is preferably an alkyl group or aryl group having 5 or less carbon atoms. As the carbon number of R ₁ increases, the hydrophobicity increases, and the charge amount variation tends to increase in a wide range of environments. In particular, an alkyl group having 3 or less carbon atoms is preferable from the viewpoint of excellent environmental stability.

In the present invention, examples of the substituent having 3 or less carbon atoms, which is a particularly preferable substituent as the hydrocarbon group R ₁ included in the formula (Z), include a methyl group, an ethyl group, and a propyl group. These substituents improve the chargeability of the toner itself and improve the fog.

From the viewpoints of environmental stability and heat-resistant storage stability, R ₁ is most preferably a methyl group. When R ₁ is a hydrocarbon group having 6 or more carbon atoms, there is a tendency that an aggregate having a weight average particle size (μm) of toner particles of 1/10 or less tends to be formed on the surface of the core particles. There is a possibility that the resin fine particles are not fixed uniformly. On the other hand, when R ₁ is a substituent that is not a hydrocarbon group such as a hydrogen atom, the affinity between the resin fine particles and the organosilicon polymer is reduced, and the adhesion between the outer surface of the core particles and the resin fine particles is poor There is. Further, when R ₁ is a substituent that is not a hydrocarbon group, the hydrophobicity of the organosilicon polymer is weakened, so that the charging stability tends to be poor.

The substituent (halogen atom, hydroxyl group, alkoxy group) defined by any of R ₂ , R ₃ and R ₄ is a substituent that induces a chemical reaction depending on a specific reagent or environment, that is, a reactive group. A cross-linked structure is formed by hydrolysis, addition polymerization or condensation polymerization of these reactive groups. By forming a cross-linked structure caused by the chemical reaction of R ₂ , R ₃ or R _{4 on} the surface of the toner particles, development durability and heat-resistant storage stability are prevented while preventing excessive embedding of resin fine particles forming the outer shell. An excellent toner can be obtained. A methoxy group or an ethoxy group is most preferable as a substituent defined by any one of R ₂ , R ₃ and R ₄ from the viewpoint of mild hydrolyzability at room temperature and from the viewpoint of precipitation and coating properties on the toner surface. The hydrolysis, addition polymerization and condensation polymerization of R _{2 to} R ₄ can be controlled by the reaction temperature, reaction time, reaction solvent and pH.

In order to obtain an organosilicon polymer present on the surface of the core particle, a compound represented by the formula (Z), specifically, a hydrocarbon group R ₁ and three reactive groups (R ₂ , R ₃ and R It is preferable to use one or more organic silicon compounds (hereinafter also referred to as trifunctional silanes) having ₄ ).

  Examples of the formula (Z) include the following. For example, methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane , Methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, Methyldimethoxyhydroxysilane, methylethoxymethoxyhydro Trifunctional methylsilane such as silane, methyldiethoxyhydroxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, Propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltri Trifunctional hexylsilanes such as chlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, Kishishiran, phenyltriethoxysilane, phenyltrichlorosilane, phenyl triacetoxy silane, and a trifunctional phenyl silane and phenyl trihydroxy silane.

  One type of organosilicon compound used for producing the toner of the present invention may be used alone, or two or more types may be used in combination.

  The content of the organosilicon compound having a structure represented by the formula (Z) is preferably 50 mol% or more, more preferably 60 mol% or more, based on the whole organosilicon polymer. When the content of the organosilicon compound having the structure represented by the formula (Z) is 50 mol% or more, the environmental stability of the toner can be further improved.

  Moreover, you may use together the organosilicon compound which has a several reactive group in a different molecule with the organosilicon compound which has a structure of a formula (Z). For example, an organosilicon compound having three reactive groups in one molecule (trifunctional silane), an organosilicon compound having two reactive groups in one molecule (bifunctional silane), or an organosilicon having one reactive group A compound (monofunctional silane) may be used in combination. Examples of the organosilicon compound that may be used in combination include the following. Namely, dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryl Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriemethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3-phenylaminopropyltrime Xysilane, 3-anilinopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Examples include propylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, hexamethyldisilane, tetraisocyanate silane, and methyltriisocyanate silane.

In general, it is known that in the sol-gel reaction, the bonding state of the formed siloxane bond varies depending on the acidity of the reaction medium. Specifically, when the reaction medium is acidic, hydrogen ions are electrophilically added to oxygen contained in a predetermined reactive group (for example, an alkoxy group (—OR group)). Next, the oxygen atom in the water molecule coordinates to the silicon atom. A substitution reaction then forms a hydroxysilyl group. Here, when water is sufficiently present, if at least one H ⁺ is present, this H ⁺ is added to an oxygen atom contained in a reactive group (for example, an alkoxy group (—OR group)). On the other hand, when the content of H ^{+ in} the reaction medium is small, the substitution reaction from the reactive group to the hydroxy group becomes slow. Therefore, if the content of H ⁺ in the reaction medium is appropriately limited, a polycondensation reaction occurs before all of the reactive groups attached to the silane are hydrolyzed, which makes it relatively easy to obtain a one-dimensional linear height. Molecules and two-dimensional polymers are easily generated.

  On the other hand, when the reaction medium is alkaline, hydroxide ions are added to silicon and go through a pentacoordinate intermediate. Therefore, all reactive groups (for example, alkoxy groups (—OR groups)) are easily removed and are easily substituted with silanol groups. In particular, when a silicon compound having three or more reactive groups on the same silane is used, hydrolysis and polycondensation occur three-dimensionally to form an organosilicon polymer having a large number of three-dimensional crosslinks. . The reaction is also completed in a short time. Therefore, in order to form the organosilicon polymer, it is preferable to proceed the sol-gel reaction with the reaction medium being in an alkaline state. Specifically, when producing in an aqueous medium, the pH should be 8.0 or more. preferable. As a result, an organosilicon polymer having higher strength and superior durability can be formed.

  The sol-gel reaction is preferably performed at a reaction temperature of 90 ° C. or more and a reaction time of 5 hours or more.

  By performing this sol-gel reaction at the reaction temperature and reaction time described above, formation of coalesced particles formed by bonding silane compounds in a sol or gel state on the surface of the core particles can be suppressed.

  The addition amount of the organosilicon compound is in the range of 3.0 to 15.0 parts by mass with respect to 100.0 parts by mass of the binder resin or 100.0 parts by mass of the polymerizable monomer constituting the binder resin. Preferably there is. If the amount is less than 3.0 parts by mass, the durability may be inferior. On the other hand, if it exceeds 15.0 parts by mass, the low-temperature fixability may be inferior. More preferably, it is 4.0 to 10.0 parts by mass.

  In the core particles constituting the toner of the present invention, the concentration of silicon element (dSi), the concentration of oxygen element (dO) and the concentration of oxygen element (dO) were determined by measurement using surface X-ray photoelectron spectroscopy (ESCA). The silicon element concentration (dSi) with respect to the total carbon element concentration (dC) is preferably 2.5 atomic% or more, more preferably 5.0 atomic% or more, and even more preferably 10.0 atomic%. ESCA performs elemental analysis of the outermost surface of several nm, and it can be confirmed that the concentration of silicon element is unevenly distributed in the outermost surface layer of the core particle. Here, by adjusting the concentration of silicon element to 2.5 atomic% or more on the surface of the core particle, embedding of the resin fine particles forming the outer shell into the core particle is suppressed, and durability and heat resistance are maintained. Can do.

The silicon concentration in the outermost layer of the core particle by ESCA can be controlled by the structure of R _f in the formula (T3), reaction temperature, reaction time, reaction solvent and pH. It can also be controlled by the content of the organosilicon polymer. In the present invention, the outermost layer of the core particle is a region from 0.0 to 5.0 nm from the surface of the toner particle toward the center of the toner particle (midpoint of the long axis).

  In the present invention, the volume-based median diameter (D50) of the resin fine particles constituting the toner is preferably 30 nm or more and 200 nm or less. The range of 40 nm or more and 170 nm or less is more preferable.

  By being in the above range, the resin fine particles can be more precisely fixed to the core particles.

  Here, if the median diameter (D50) of the resin fine particles is less than 30 nm, the resin fine particles are excessively embedded in the core particles by copying or printing a large number of sheets, which may deteriorate the heat resistance.

  Moreover, when the median diameter (D50) exceeds 200 nm, non-uniform fixation may occur, and the resin fine particles may be easily peeled off from the core particles. The median diameter is a particle diameter defined as a 50% value (central cumulative value) of a cumulative curve of particle size distribution. For example, a laser diffraction / scattering particle size distribution measuring apparatus (LA-) manufactured by HORIBA, Ltd. 920).

  The median diameter (D50) of the resin fine particles can be controlled by the physical properties of the resin constituting the resin fine particles and the production conditions of the resin fine particles. Although various production methods can be considered as production conditions, they are not specifically mentioned, but the physical properties can be controlled by the acid value, the type of functional group, and the molecular weight of the resin constituting the resin fine particles.

  In the toner of the present invention, the coating amount of the outer shell formed from the resin fine particles is preferably 1.0 to 15.0% by mass with respect to the core particle. When the coating amount is within the above range, a dense coating layer can be formed without deteriorating the toner fixing property. More preferably, it is 2.0 mass% or more and 10.0 mass% or less by mass ratio with respect to a core particle.

  In the present invention, the core particles constituting the toner particles preferably contain a polyester resin having a melting point of 55 to 90 ° C.

  When the melting point of the polyester is within the above range, the polyester contained in the toner can maintain a crystalline state even under a high temperature environment, and the polyester contained in the toner is rapidly melted even under a low temperature fixing condition. For this reason, sufficient heat-resistant storage stability as toner and excellent low-temperature fixing performance can be achieved. Further, since the organosilicon polymer is unevenly distributed on the surface of the core particle, direct contact between the polyester resin and the coated resin fine particles forming the outer shell is hindered, and plasticity of the resin fine particles can be suppressed. Here, when the melting point of the polyester is less than 55 ° C., the heat resistant storage stability may be lowered. If the melting point of the polyester exceeds 90 ° C., the low-temperature fixability may be inferior.

  The melting point of the crystalline polyester can be controlled by the types of monomers such as an alcohol component and an acid component constituting the crystalline polyester.

  The addition amount of the polyester resin is in the range of 5.0 parts by mass to 50.0 parts by mass with respect to 100.0 parts by mass of the binder resin or 100.0 parts by mass of the monomer constituting the binder resin. It is preferable. If it is less than 5.0 parts by mass, the low-temperature fixability may be inferior. If the amount exceeds 50.0 parts by mass, the chargeability may decrease due to charge leakage from the crystalline polyester portion, and fog may easily occur. On the other hand, if it exceeds 50.0 parts by mass, the durability is inferior and image defects such as development streaks are likely to occur. The addition amount of the polyester resin is preferably 10.0 parts by mass to 40.0 parts by mass.

  The polyester resin contained in the toner of the present invention is preferably a block polymer having a vinyl polymer portion and a polyester portion.

  This is because by using this block polymer, the block polymer takes a phase separation structure in the toner having a styrene acrylic resin as a binder resin. As a result, the toughness of the styrene acrylic resin is maintained and the durability of the toner is increased.

  In the fixing process, when heat is supplied to the toner, the block polymer instantly dissolves in the styrene acrylic resin starting from the vinyl polymer unit and exhibits a plastic effect. This lowers the softening point of the toner and achieves low temperature fixability. In addition, since the block polymer itself has a vinyl polymer portion, it can have an appropriate viscosity necessary for fixing after melting, so that it acts as a binder resin and synergistically achieves low temperature fixability.

  As the monomer for forming the vinyl polymer portion of the block polymer, known vinyl monomers such as styrene, methyl methacrylate, n-butyl acrylate and the like can be used. Particularly preferred is styrene, which effectively acts as a compatible site with a styrene acrylic resin and exhibits more plasticity when melted.

It is preferable that the weight average molecular weight ( _Mw ) of this vinyl polymer site | part is 4000-15000. When the weight average molecular weight is less than 4000, the vinyl polymer portion is difficult to work as a starting point for compatibility with the styrene acrylic resin, so that the low-temperature fixability may be deteriorated. Furthermore, if the molecular weight is too small, the performance that the vinyl polymer portion should have is not exhibited, and heat resistance and durability may be impaired. On the other hand, when the weight average molecular weight is larger than 15000, the properties of the vinyl polymer portion become too strong, and the sharp melt property due to the polyester portion may be impaired, and the effect on the low-temperature fixability may not be obtained.

  The mass ratio of the polyester moiety and the vinyl polymer moiety contained in the block polymer is preferably in the range of 40:60 to 70:30. When the vinyl polymer portion is excessive (mass ratio is less than 40:60), the properties of the polyester portion are reduced, so that the sharp melt property is impaired and the low-temperature fixability may be deteriorated. On the other hand, when the polyester part is excessive (mass ratio is larger than 70:30), the polyester part has excessively strong characteristics, so that heat resistance is deteriorated and blocking tends to be deteriorated. The mass ratio is more preferably 45:55 to 60:40.

The weight average molecular weight of the block polymer (M _w) is preferably from 20,000 to 45,000, a weight average molecular weight (M _w) and number average molecular weight ratio _{(M n) (M w /} M n) is 1.5 ~ 3.5 is preferred. When the weight average molecular weight is smaller than 20000, the mechanical strength of the block polymer is inferior, so that the durability tends to be low. On the other hand, when the weight average molecular weight is larger than 45,000, the movement of the molecules becomes slow, so that the plastic effect at the time of melting tends to be hardly obtained. The polymerization average molecular weight is more preferably 23,000 to 40,000, still more preferably 25,000 to 37,000.

  A block polymer is defined as a polymer composed of a plurality of linearly connected blocks (a glossary of basic terms of polymer science by the Polymer Nomenclature Committee of the International Association of Applied Chemistry of Polymer Science). The present invention follows the definition.

[Toner Production Method]
Next, a method for producing the toner of the present invention will be described. When the toner of the present invention is produced, at least the steps shown below are included.
(A) Core particle manufacturing process (b) Resin fine particle fixing process

(A) Manufacturing process of core particle When manufacturing the toner of this invention, it is necessary to manufacture the core particle in which the organosilicon polymer is ubiquitous in the surface part. Hereinafter, although an especially preferable example is demonstrated below about the manufacturing process of a core particle, this invention is not necessarily limited to these.

  The core particle is prepared by granulating a polymerizable monomer composition containing a polymerizable monomer, a release agent and a colorant in an aqueous medium and polymerizing the polymerizable monomer. And it is preferable that this polymerizable monomer composition contains an organosilicon compound. In addition, the method demonstrated below is a manufacturing method called a suspension polymerization method.

  The core particles produced by the suspension polymerization method are such that the organosilicon polymer is easily unevenly distributed on the surface of the core particles, has excellent adhesion between the surface layer of the core particles and the inside, heat resistant storage stability, environmental stability and development. Good durability. Hereinafter, the production process of the core particles using the suspension polymerization method will be described in more detail.

  You may add a charge control agent, polar resin, or low molecular weight resin to the said polymerizable monomer composition as needed. Moreover, after completion | finish of a superposition | polymerization process, the produced | generated particle | grains are collect | recovered by washing | cleaning and filtration, and it dries and obtains a core particle. Note that the temperature of the reaction system may be increased in the latter half of the polymerization step. Further, in order to remove unreacted polymerizable monomers or by-products, it is possible to raise the temperature of the reaction system in the latter half of the polymerization process or after the completion of the polymerization process, and to partially distill off the dispersion medium from the reaction system. .

  When producing the core particles using the suspension polymerization method, first, a release agent, a colorant and an organosilicon compound are added to the polymerizable monomer which is the main constituent material of the core particles. Then, these are uniformly dissolved or dispersed using a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser to prepare a polymerizable monomer composition. Next, the prepared polymerizable monomer composition is put into an aqueous medium containing a dispersion stabilizer prepared in advance and suspended using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser. To granulate.

  The polymerization initiator used in the polymerization of the polymerization monomer may be mixed with other additives when preparing the polymerizable monomer composition, and may be polymerized immediately before being suspended in the aqueous medium. You may mix in a monomer composition. Moreover, it can also be added in the state melt | dissolved in the polymerizable monomer or other solvent as needed during granulation or after granulation completion, ie, just before starting a polymerization reaction.

  The suspension after granulation is heated, and the polymerization reaction is carried out with stirring so that the particles of the polymerizable monomer composition in the suspension maintain the particle state and the particles do not float or settle. To complete the core particles.

(B) Fixing step of resin fine particles Next, the resin fine particles are fixed to the surface of the core particles produced by the process (a). As a specific method for fixing the resin fine particles, various known methods can be used. Specifically, the core particles and the resin fine particles are mixed by a dry method and fixed by a mechanical treatment, or the core particles and the resin fine particles are dispersed in an aqueous medium, and then the medium is heated or the flocculant in the medium. Or a method of further adding. In the present invention, a method of fixing the resin fine particles to the surface of the core particles by heating in an aqueous medium is preferable in order to fix the resin fine particles uniformly and densely on the surface of the core particles.

  A particularly preferred example for fixing resin fine particles by this method will be described below.

First, core particles are produced by a suspension polymerization method according to the method (a). At this time, as the dispersion stabilizer, for example, an inorganic dispersant having a significantly different polarity with respect to the core particle such as tricalcium phosphate is used, and the dispersion stabilizer attached to the surface of the core particle is not removed even after the polymerization is completed. Continue stirring as it is.

  Next, an aqueous dispersion of amorphous resin fine particles having an acid value is added to the dispersion containing the core particles with the dispersion stabilizer attached thereto. The resin fine particles preferably have a glass transition temperature higher than that of the core particles. Thereby, resin fine particles adhere electrostatically in a state where the dispersion stabilizer is interposed on the surface of the core particle. Next, this dispersion is heated until the temperature becomes equal to or higher than the glass transition temperature of the core particles.

  Then, while maintaining the temperature of the dispersion within the temperature range from the glass transition temperature of the core particles to the glass transition temperature of the resin fine particles, the dispersion stabilizer is gradually dissolved by slowly adding acid to the dispersion. In this way, the dispersion stabilizer is removed, but at the same time, the resin fine particles come into contact with the surface of the core particle and are fixed (fixed) while maintaining a uniform state.

  After performing the acid addition described above, an alkali is added to the dispersion to adjust to a pH region where the inorganic dispersant contained in the dispersion is re-precipitated, and then heated above the glass transition temperature of the resin fine particles. More preferred. By adjusting the pH and reprecipitating the inorganic dispersant, the surface of the particles to which the resin fine particles are fixed is coated with the inorganic dispersant. Therefore, even when heated above the glass transition temperature of the resin fine particles, the particles aggregate together. Can be suppressed. In addition, the outer shell made of resin fine particles is thereby smoothed to form a more uniform and dense layer.

  The resin fine particles used in this step can be produced using a known method. Specifically, those produced by a method such as an emulsion polymerization method, a soap-free emulsion polymerization method, or a phase inversion emulsification method can be used. Among these production methods, the phase inversion emulsification method is particularly suitable because resin fine particles having a small particle size and a narrow particle size distribution can be easily obtained.

  The method for producing resin fine particles by the phase inversion emulsification method will be specifically described. The resin fine particles produced by using the phase inversion emulsification method are obtained in a form dispersed in a dispersion. First, a resin having desired physical properties prepared in advance is dissolved in an organic solvent in which the resin can be dissolved, and a surfactant, a neutralizing agent, and the like are added as necessary, and mixed with an aqueous medium while stirring. Then, the resin solution causes phase inversion emulsification to form fine particles. The organic solvent in which the resin is dissolved is removed using a method such as heating or decompression after phase inversion emulsification. As described above, a stable aqueous dispersion of resin fine particles having a small particle size and a narrow particle size distribution can be obtained. The material of the resin fine particles may be any material that can be used as a binder resin for toner, and resins such as vinyl resins, polyester resins, epoxy resins, and urethane resins are used. Of these, polyester resins are preferred because they have sharp melt properties and therefore do not obstruct the low-temperature fixability of the core particles. In addition, a combination of a plurality of the above-described resins, a crystallized one, or a hybridized one can be used. Further, a part of the resin may be modified, or a resin having a function such as charging may be used.

  The resin constituting the resin fine particles preferably contains a hydrophilic functional group from the viewpoint of water dispersion stability of the resin fine particles and the chargeability of the toner. The hydrophilic functional group may be appropriately selected depending on the desired toner polarity. In the present invention, a carboxyl group and / or a sulfonic acid group is preferable from the viewpoint of toner production stability. The acid value at this time is preferably 5.0 mgKOH / g or more and 50.0 mgKOH / g or less from the viewpoint of dispersion stability of resin fine particles and charging stability of toner. If it is less than 5.0 mgKOH / g, the adhesion to the dispersion stabilizer is insufficient, and the coverage is lowered, so that there is a concern about deterioration of heat resistance. Further, if it exceeds 50.0 mgKOH / g, the toner charge amount changes particularly in a high-humidity environment, and there is concern about differences in the charging environment.

  For the types and acid values of the hydrophilic functional groups contained in the resin constituting the resin fine particles described above, monomers containing hydrophilic functional groups and other constituent materials are used for the resin constituting the resin fine particles. It is possible to control by things.

  In the toner of the present invention, the weight average particle diameter (D4) is preferably 3.0 μm or more and 8.0 μm or less, and the ratio (D4 / D1) of D4 to the number average particle diameter (D1) is 1.30 or less. preferable.

  As the polymerizable monomer used as a raw material for the binder resin contained in the core particle, a vinyl polymerizable monomer capable of radical polymerization can be used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

  Examples of the monofunctional polymerizable monomer include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and pn. -Butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene Styrene derivatives such as p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl Acrylate, 2-ethylhexylua Acrylic polymerizable monomers such as acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Forms; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n -Octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl Methacrylate, methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate.

  Examples of polyfunctional polymerizable monomers include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and tripropylene. Glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tri Ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxydiethoxy) phenyl) Examples include propane, 2,2′-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

Examples of usage of the polymerizable monomer used as the raw material for the binder resin include those listed below.
(I) A mode in which one type of monofunctional polymerizable monomer is used alone (ii) A mode in which two or more types of monofunctional polymerizable monomers are used in combination (iii) A monofunctional polymerizable monomer (Iv) A mode in which one kind of polyfunctional polymerizable monomer is used alone (v) A mode in which two or more types of polyfunctional polymerizable monomers are used Aspect used in combination

  Upon polymerization of the polymerizable monomer, a polymerization initiator such as a peroxide or an azo compound may be added.

  Examples of peroxide polymerization initiators include the following. That is, t-butyl peroxylaurate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, etc. Peroxyester polymerization initiators; peroxydicarbonate polymerization initiators such as di-n-propyl peroxydicarbonate, di-n-butylperoxydicarbonate, di-n-pentylperoxydicarbonate; Diacyl peroxide polymerization initiators such as tyryl peroxide, diisononanoyl peroxide, di-n-octanoyl peroxide; t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisopropyl monocarbonate, t-butyl Peroxy 2-ethylhe Peroxy monocarbonate polymerization initiators such as sill monocarbonate; dicumyl peroxide, di -t- butyl peroxide, dialkyl peroxide type polymerization initiators such as t- butyl cumyl peroxide and the like.

  Examples of the azo polymerization initiator include the following. That is, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2 ′ -Azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, etc. are mentioned.

  Among these polymerization initiators, peroxide-based polymerization initiators are preferable because there is little residue of decomposition products. Moreover, these polymerization initiators can also use 2 or more types simultaneously as needed. In this case, the preferred amount of the polymerization initiator used is 0.1 or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the polymerizable monomer.

(C) Additive, etc. In order to control the molecular weight of the binder resin constituting the toner particles, a chain transfer agent may be added during the polymerization of the polymerizable monomer. The addition amount of the chain transfer agent is preferably 0.001 to 15.000% by mass of the polymerizable monomer.

  On the other hand, in order to control the molecular weight of the binder resin constituting the toner particles, a crosslinking agent may be added during the polymerization of the polymerizable monomer. The following are mentioned as a crosslinking agent. That is, divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1 , 6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate , Polypropylene glycol diacrylate, polyester diacrylate (MANDA Nippon Kayaku), and the above acrylates Bifunctional crosslinking agents such as those obtained by changing the like.

  A polyfunctional crosslinking agent having three or more functional groups can also be used. For example, the following are mentioned. That is, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and methacrylate thereof, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacryl Examples include phthalate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate and the like.

  The addition amount of the crosslinking agent is preferably 0.001 to 15.000% by mass with respect to the polymerizable monomer.

  The toner of the present invention contains a colorant. As the colorant, known colorants such as various conventionally known dyes and pigments can be used.

  As the black colorant, carbon black, a magnetic material, or a color toned to black using a yellow / magenta / cyan colorant shown below is used. As the colorant for cyan toner, magenta toner, and yellow toner, for example, the following colorants can be used.

  Examples of yellow colorants include pigment-based colorants. Specifically, compounds represented by monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used. More specifically, C.I. I. Pigment yellow 74, 93, 95, 109, 111, 128, 155, 174, 180, 185 and the like.

  As the magenta colorant, monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2,3,5,6,7,23,48: 2,48: 3,48: 4,57: 1,81: 1,122,144,146,150,166,169,177,184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Examples thereof include CI Pigment Bio Red 19.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66, and the like.

  When the toner of the present invention is used as a magnetic toner, the toner particles may contain a magnetic material. In this case, the magnetic material can also serve as a colorant. In the present invention, examples of the magnetic substance that can be contained in the toner include iron oxides such as magnetite, hematite, and ferrite; and iron-based metals such as iron, cobalt, and nickel. Or alloys of these iron-based metals with metals other than iron-based metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, etc. And mixtures thereof.

  The release agent that can be used when producing the toner of the present invention is not particularly limited, and known ones can be used. For example, the following compounds are mentioned. That is, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof Waxes mainly composed of fatty acid esters such as carnauba wax, sazol wax, ester wax and montanic acid ester wax; fatty acid esters such as deoxidized carnauba wax deoxidized partly or entirely; aliphatic hydrocarbons Waxes grafted to vinyl wax using vinyl monomers such as styrene and acrylic acid; partially esterified products of fatty acids such as behenic monoglyceride and polyhydric alcohols; obtained by hydrogenation of vegetable oils and the like Methyl ester compounds having a Dorokishiru group.

  The toner of the present invention may contain a charge control agent. Among them, it is preferable to use a charge control agent that controls the toner particles to be negatively charged. Examples of the charge control agent include the following.

That is, organometallic compounds, chelate compounds, monoazo metal compounds, acetylacetone metal compounds, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, quaternary ammonium salts, calixarene, silicon compounds, nonmetal carboxylic acid compounds and And derivatives thereof. A sulfonic acid resin having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group can also be preferably used.

  Further, as the dispersion stabilizer added to the aqueous medium when producing the core particles contained in the toner, known surfactants, organic dispersants, and inorganic dispersants can be used. Among these, inorganic dispersants can be suitably used because they are less likely to produce ultrafine powder, are less likely to lose stability even when the polymerization temperature is changed, are easy to wash and do not adversely affect the toner. Examples of such inorganic dispersants include the following. That is, polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; inorganics such as calcium metasuccinate, calcium sulfate and barium sulfate Salt: Inorganic oxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite, and alumina can be used. When these inorganic dispersants are used, they may be used as they are in an aqueous medium, but in order to obtain finer particles, they are prepared and used in an aqueous medium using a compound capable of generating inorganic dispersant particles. You can also. For example, in the case of tricalcium phosphate, sodium phosphate aqueous solution and calcium chloride aqueous solution can be mixed under high-speed stirring to produce water-insoluble tricalcium phosphate, which enables more uniform and fine dispersion. Become. These inorganic dispersants can be almost completely removed by adding an acid or an alkali after the polymerization and dissolving. These inorganic dispersants are preferably used alone in an amount of 0.2 to 20.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer, but if necessary, 0.001 A surfactant of 0.100 parts by mass or less may be used in combination. Examples of the surfactant include the following. Sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate.

In the toner of the present invention, it is preferable that inorganic fine powder is externally added to the toner and mixed as a fluidity improver. The inorganic fine powder is preferably hydrophobic. For example, titanium oxide fine powder, silica fine powder, and alumina fine powder are preferably added and used, and silica fine powder is particularly preferred. Inorganic fine powder used in the toner of the present invention, specific surface area by nitrogen adsorption measured by BET method of more than 30 m ² / g, in particular 50m ² / g~400m ² / g good results in the range of Since it can give, it is preferable.

  Furthermore, the toner of the present invention may have an external additive other than the fluidity improver, if necessary. For example, for the purpose of improving cleaning properties, it is also preferable to add fine particles having a primary particle size exceeding 30 nm, more preferably inorganic fine particles or organic fine particles having a primary particle size of 50 nm or more and nearly spherical to the toner. It is. As fine particles used for improving the cleaning property, for example, spherical silica particles, spherical polymethylsilsesquioxane particles, and spherical resin fine particles are preferably used. Still other additives, for example, lubricant powders such as fluororesin powder, zinc stearate powder, polyvinylidene fluoride powder; or abrasives such as cerium oxide powder, silicon carbide powder, strontium titanate powder; anti-caking agent; Conductivity imparting agents such as carbon black powder, zinc oxide powder and tin oxide powder; organic fine particles having opposite polarity and inorganic fine particles can also be added in a small amount as a developability improver. These additives can also be used after hydrophobizing the surface. The external additive as described above may be used in an amount of 0.1 to 5.0 parts by weight (preferably 0.1 to 3.0 parts by weight) with respect to 100.0 parts by weight of the toner.

  The toner of the present invention can be used as it is as a one-component developer or as a two-component developer by mixing with a magnetic carrier. When used as a two-component developer, the average particle size of the carrier to be mixed is preferably 10 μm to 100 μm, and the toner concentration in the developer is preferably 2% by mass to 15% by mass.

[Method for measuring and evaluating properties of toner particles or toner]
The toner evaluation method of the present invention will be described below. An example of evaluation will be described in detail in Examples.

(1) NMR measurement When performing NMR measurement on the toner particles contained in the toner of the present invention, it is necessary to first adjust the THF-insoluble content of the toner particles.

(1-1) Method of Adjusting Toner Particles Insoluble in THF The amount of toner particles insoluble in tetrahydrofuran (THF) can be adjusted as follows. First, 10.0 g of toner is weighed, placed in a cylindrical filter paper (for example, No. 86R, manufactured by Toyo Filter Paper), passed through a Soxhlet extractor, and extracted with 200 ml of THF (extraction solvent) for 20 hours. And what was obtained by vacuum-drying the filtration thing in a cylindrical filter paper for several hours at 40 degreeC is made into the THF insoluble content of the toner particle for NMR measurement.

(1-2) Method for Confirming Presence of Partial Structure of Formula (T3) The presence of the partial structure of Formula (T3) can be confirmed by the method described below. Specifically, the presence or absence of R _f (hydrocarbon group) contained in the formula (T3) may be confirmed by ¹³ C-NMR. Note that the presence of the partial structure of the formula (T3) can be confirmed by ¹ H-NMR, ¹³ C-NMR, and ²⁹ Si-NMR.

Here, the measurement conditions of ¹³ C-NMR (measurement conditions when the sample is fixed) are shown below.
Apparatus: Product made by BRUKER, AVANCE III 500
Probe: 4mm MAS BB / 1H
Measurement temperature: room temperature Sample rotation speed: 6 kHz
Sample: 150 mg of a measurement sample (THF insoluble portion of toner particles for NMR measurement) is placed in a sample tube having a diameter of 4 mm.
Measurement nuclear frequency: 125.77 MHz
Reference substance: Glycine (external standard: 176.03 ppm)
Observation width: 37.88 kHz
Measurement method: CP / MAS
Contact time: 1.75 ms
Repeat time: 4s
Integration count: 2048 times LB value: 50 Hz
If the presence or absence of R _f (hydrocarbon group) included in the formula (T3) is confirmed under the above measurement conditions and a signal can be confirmed, the structure of the formula (T3) can be evaluated as “present”.

(1-3) Confirmation of Partial Structure of Organosilicon Polymer In the toner of the present invention, an organosilicon polymer is particularly contained in the surface portion of the core particles constituting the toner particles. This organosilicon polymer has one of the partial structures represented by the following formulas (X1), (X2), (X3) and (X4). However, this organosilicon polymer is not necessarily provided with all the partial structures represented by the following formulas (X1), (X2), (X3) and (X4).

In the formula (X1), R _i , R _j and R _k each represent an organic group, a halogen atom, a hydroxyl group or an alkoxy group.

In the formula (X2), R _g and R _h each represents an organic group, an aryl group, a halogen atom, a hydroxyl group or an alkoxy group.

In the formula (X3), R _f represents an organic group, an aryl group, a halogen atom, a hydroxyl group or an alkoxy group. )

The partial structures represented by the above formulas (X1), (X2), (X3) and (X4) can be confirmed by ²⁹ Si-NMR. Here, the measurement conditions of ²⁹ Si-NMR (measurement conditions when the sample is fixed) are shown below.

Apparatus: Product made by BRUKER, AVANCE III 500
Probe: 4mm MAS BB / 1H
Measurement temperature: room temperature Sample rotation speed: 6 kHz
Sample: 150 mg of a measurement sample (THF insoluble portion of toner particles for NMR measurement) is placed in a sample tube having a diameter of 4 mm.
Measurement nuclear frequency: 99.36 MHz
Reference substance: DSS (external standard: 1.534 ppm)
Observation width: 29.76 kHz
Measuring method: DD / MAS, CP / MAS
²⁹ Si 90 ° Pulse width: 4.00 μs @ -1 dB
Contact time: 1.75 ms to 10 ms
Repeat time: 30 s (DD / MASS), 10 s (CP / MAS)
Integration count: 2048 times LB value: 50 Hz

(1-4) Ratio of partial structure (T3 structure) represented by formula (T3) in the organosilicon polymer (ST3)
After ²⁹ Si-NMR measurement of the THF-insoluble part of the toner particles, O ₁ that binds to the silicon represented by the above general formula (X4) by curve fitting a plurality of silane components having different substituents and bonding groups in the toner particles. X4 structure in which the number of _{/ 2} is 4.0, X3 structure in which the number of O _1/2 bonded to silicon represented by the above general formula (X3) is 3.0, represented by the above general formula (X2) X2 structure number of O _1/2 bonded to silicon is 2.0, X1 structure number is 1.0 O _1/2 bonded to silicon represented by the general formula (X1), formula (T3 The peak is separated into a T unit structure represented by (), and the mol% of each component is calculated from the area ratio of each peak.

  The curve fitting is performed using EXcalibur for Windows (registered trademark) version 4.2 (EX series) for JNM-EX400 manufactured by JEOL.

Specifically, first, “1D Pro” is clicked from the menu icon to read measurement data. Next, “Curve fitting function” is selected from “Command” on the menu bar, and curve fitting is performed. FIG. 1 is a diagram showing an example of peak processing based on ²⁹ Si-NMR measurement. In FIG. Is a synthetic peak difference obtained by subtracting the synthetic peak (b.) From the measurement result (d.). b. Is a synthetic peak obtained by synthesizing split peaks. c. Is a divided peak obtained by dividing the synthetic peak. d. Is the peak of the measurement result. Here, the peak division is performed such that the peak of the synthetic peak difference (a.), Which is the difference between the synthetic peak (b.) And the measurement result (d.), Is the smallest.
The area of the X1 structure, the area of the X2 structure, the area of the X3 structure, and the area of the X4 structure are obtained, and SX1, SX2, SX3, and SX4 are obtained by the following equations.

In the present invention, the silane monomer is specified by the chemical shift value, and the monomer component is removed from the total peak area in the ²⁹ Si-NMR measurement of the toner particles. The area of the X1 structure, the area of the X2 structure, the area of the X3 structure, and the X4 structure Was the total peak area of the organosilicon polymer.
SX1 + SX2 + SX3 + SX4 = 1.00
SX1 = {area of X1 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
SX2 = {area of X2 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
SX3 = {area of X3 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
SX4 = {area of X4 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}
ST3 = {area of T3 structure / (area of X1 structure + area of X2 structure + area of X3 structure + area of X4 structure)}

Chemical shift value of silicon when any one of R _i , R _j , R _k , R _g , R _h and R _f is specified from the above structures (X1 structure, X2 structure, X3 structure, X4 structure) Is shown below.
X1 structure (R _i = R _j = -OC ₂ H ₅ , R _k = -CH ₃ ): -47 ppm
· X2 Structure _{(R g = -OC 2 H 5} , R h = -CH 3): - 56ppm
· X3 Structure _{(R f = -CH 3):} - 65ppm

In addition, the chemical shift value of silicon in the case of the X4 structure is shown below.
-X4 structure: -108 ppm

(2) Observation of the cross section of the core particle using a transmission electron microscope (TEM) The cross section of the core particle of the present invention can be observed by the following method.

  As a specific method for observing the cross section of the core particles, the toner particles are dispersed in a room temperature curable epoxy resin and then placed in an atmosphere at 40 ° C. for 2 days to cure the epoxy resin. A flaky sample is cut out from the obtained cured product using a microtome equipped with diamond teeth. This sample is magnified by a transmission electron microscope (TEM) to a magnification of 10,000 to 100,000 times, and the cross section of the core particle is observed. In the present invention, the difference between the atomic weights of the binder resin used and the organosilicon polymer is utilized, and the contrast increases when the atomic weight is large. Confirmation of uneven distribution. Further, a ruthenium tetroxide staining method and an osmium tetroxide staining method may be used in order to provide contrast between materials. Further, a TEM bright field image is acquired at an acceleration voltage of 200 kV using an electron microscope Tecnai TF20XT manufactured by FEI. Next, using an EELS detector GIF Tridiem manufactured by Gatan, an EF mapping image at the Si-K end (99 eV) can be obtained by the Three Window method to confirm that the organosilicon polymer is present on the surface layer.

  When the major axis L of the core particle cross section is taken, the midpoint of the major axis L is the center of the core particle, and the region from 0 nm to 100 nm from the outer surface of the core particle cross section to the center is the surface layer portion of the core particle. In Examples described later, the cross-sectional observation of the core particles was measured on 30 arbitrary core particles.

(3) Concentration of silicon element present on the core particle surface (atomic%)
In the present invention, the concentration of silicon element (atomic%) and the concentration of carbon element (atomic%) present on the surface of the core particle were calculated by performing surface composition analysis by ESCA (X-ray photoelectron spectroscopy).

In the present invention, the ESCA apparatus and measurement conditions are as follows.
Device used: Quantum2000 manufactured by ULVAC-PHI
X-ray photoelectron spectrometer measurement conditions: X-ray source Al Kα
X-ray: 100μm 25W 15kV
Raster: 300μm × 200μm
PassEnergy: 58.70 eV StepSize: 0.125 eV
Neutralizing electron gun: 20μA, 1V Ar ion gun: 7mA, 10V
Number of sweeps: Si 15 times, C 10 times

  In the present invention, the surface atomic concentration (atomic%) is calculated from the measured peak intensity of each element using a relative sensitivity factor provided by PHI.

(4) Measuring method of weight average molecular weight (M _w ), number average molecular weight (M _n ) and main peak molecular weight (M _p ) of toner and various resins Weight average molecular weight (M _w ) and number average molecular weight of toner and various resins (M _n ) and main peak molecular weight (M _p ) are measured under the following conditions using gel permeation chromatography (GPC).

[Measurement condition]
Column (made by Showa Denko KK): Shodex GPC KF-801, KF-802, KF-803, KF-804, KF-805, KF-806, KF-807 (diameter 8.0 mm, length 30 cm) 7 stations, eluent: tetrahydrofuran (THF)
・ Temperature: 40 ℃
・ Flow rate: 0.6ml / min
・ Detector: RI
Sample concentration and amount: 10 μl of 0.1% by mass sample

[Sample preparation]
0.04 g of a measurement target (toner, various resins) was dispersed and dissolved in 20 ml of tetrahydrofuran, allowed to stand for 24 hours, and filtered with a 0.2 μm filter [Mysholy disk H-25-2 (manufactured by Tosoh Corporation)]. The filtrate is used as a sample.

  The calibration curve uses a molecular weight calibration curve created with a monodisperse polystyrene standard sample. As standard polystyrene samples for preparing calibration curves, TSK standard polystyrenes F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F- manufactured by Tosoh Corporation 4, F-2, F-1, A-5000, A-2500, A-1000, and A-500 are used. At this time, at least about 10 standard polystyrene samples are used.

  In preparation of GPC molecular weight distribution, the chromatogram rises from the baseline on the high molecular weight side and starts measurement from the starting point, and the molecular weight is measured up to about 400 on the low molecular weight side.

(5) The toner and the glass transition temperature (T _g) of the various resins, the measurement method the glass transition temperature of the toner and various resins of a polyester having a melting point (T _m) (Tg), the differential scanning calorimeter (DSC) M-DSC ( (Product name: Q2000, manufactured by TA-Instruments Co., Ltd.) Weigh precisely 3 mg of the sample (toner, various resins) to be measured. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 1 ° C./min and normal temperature and humidity in a measurement temperature range of 20 to 200 ° C. Measurement is performed at a modulation amplitude of ± 0.5 ° C. and a frequency of 1 / min. The glass transition temperature (Tg: ° C.) is calculated from the obtained reversing heat flow curve. Tg is obtained as Tg (° C.) as the center value of the intersection of the baseline before and after endotherm and the tangent of the curve due to endotherm. The melting point (Tm) and endothermic amount of the crystalline polyester are the maximum endothermic peak temperature in the specific heat change curve and the endothermic amount at the endothermic peak.

(6) Measuring method of weight average particle diameter (D4) and number average particle diameter (D1) of toner The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are fine particles having an aperture tube of 100 μm. Precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) by pore electrical resistance method and attached dedicated software “Beckman Coulter Multisizer 3” for setting measurement conditions and analyzing measurement data Using “Version 3.51” (manufactured by Beckman Coulter, Inc.), measurement is performed with 25,000 effective measurement channels, and measurement data is analyzed and calculated.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software is set as follows.

  In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using The threshold and 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, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.

  In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.

  The specific measurement method is as follows.

  (6-1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.

  (6-2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and “Contaminone N” (nonionic surfactant, anionic surfactant, organic builder having a pH of 7 is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for precision measuring instrument, manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water three times as much, is added.

  (6-3) A water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkatsu Bios Co., Ltd.) having an electric output of 120 W, which includes two oscillators with an oscillation frequency of 50 kHz and a phase shifted by 180 degrees. A predetermined amount of ion-exchanged water is put into the tank, and about 2 ml of the contamination N is added to the water tank.

  (6-4) The beaker of (6-2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

  (6-5) In a state where the electrolytic aqueous solution in the beaker of (6-4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.

  (6-6) The electrolyte solution of (6-5) in which toner is dispersed with a pipette is dropped into the round bottom beaker of (6-1) installed in a sample stand, and the measured concentration is about 5%. Adjust so that Measurement is performed until the number of measured particles reaches 50,000.

  (6-7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. When the graph / volume% is set with the dedicated software, the “average diameter” on the analysis / volume statistics (arithmetic average) screen is the weight average particle size (D4), and the graph / number% is set with the dedicated software. The “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

(7) Measuring method of ratio of polyester part and vinyl polymer part of block polymer Ratio of polyester part and vinyl polymer part of block polymer was determined by nuclear magnetic resonance spectroscopy ( ¹ H-NMR) [400 MHz, CDCl ₃ , room temperature (25 ° C. )] Can be used. Specific examples of measurement conditions are shown below.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 64 times

  The mass ratio (C / A ratio) between the polyester moiety and the vinyl polymer moiety is calculated from the integral value of the obtained spectrum.

(8) Acid value of resin fine particles 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 in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

  Titration is performed using a 0.1 mol / l potassium hydroxide ethyl alcohol solution (Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potential difference titrator AT-510 manufactured by Kyoto Electronics Industry Co., Ltd.). 100 ml of 0.100 mol / l hydrochloric acid is placed in a 250 ml tall beaker, titrated with the potassium hydroxide ethyl alcohol solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 0.100 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

The measurement conditions for the acid value measurement are shown below.
Titration device: potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters during titration are as follows.
Titration parameters Titration mode: Blank titration Titration style: Total titration Maximum titration: 20 ml
Waiting time before titration: 30 seconds Titration direction: Automatic control parameter end point judgment potential: 30 dE
End point determination potential value: 50 dE / dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.1 ml

(8-1) Main test 0.100 g of the measurement sample is precisely weighed in a 250 ml tall beaker, 150 ml of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 1 hour. Titrate with the potassium hydroxide ethyl alcohol solution using the potentiometric titrator.

(8-2) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (3: 1) is used).

  The acid value is calculated by substituting the obtained result into the following formula.

A = [(C−B) × f × 5.611] / S
(In the formula, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide ethyl alcohol solution in blank test (ml), C: addition amount (ml) of potassium hydroxide ethyl alcohol solution in this test, f: Factor of potassium hydroxide solution, S: Sample (g))

(9) Volume-based D50 of resin fine particles
The volume-based median diameter (D50) of the resin fine particles was measured using a laser diffraction / scattering particle size distribution measuring apparatus. Specifically, it is measured according to JIS Z8825-1 (2001). As a measuring device, a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.) is used. The dedicated software “HORIBA LA-920 for Windows (registered trademark) WET (LA-920) Ver. 2.02” attached to LA-920 is used for setting measurement conditions and analyzing measurement data. As the measurement solvent, ion-exchanged water from which impure solids are removed in advance is used. The measurement procedure is as follows.
(9-1) A batch type cell holder is attached to LA-920.
(9-2) A predetermined amount of ion-exchanged water is put into a batch type cell, and the batch type cell is set in a batch type cell holder.
(9-3) The inside of the batch type cell is stirred using a dedicated stirrer chip.
(9-4) Press the “refractive index” button on the “display condition setting” screen to set the relative refractive index to a value corresponding to the resin fine particles.
(9-5) In the “display condition setting” screen, the particle size standard is set as the volume standard.
(9-6) After performing warm-up operation for 1 hour or longer, the optical axis is adjusted, the optical axis is finely adjusted, and blank measurement is performed.
(9-7) 3 ml of the resin fine particle dispersion is placed in a glass 100 ml flat bottom beaker. Further, 57 ml of ion exchange water is added to dilute the resin fine particle dispersion. Among them, as a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. 0.3 ml of a diluted solution obtained by diluting the product 3) with ion-exchanged water.
(9-8) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W is prepared. To do. Into the water tank of the ultrasonic disperser, 3.3 l of ion-exchanged water is added, and 2 ml of Contaminone N is added to the water tank.
(9-9) The beaker of (9-7) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the aqueous solution in a beaker may become the maximum.
(9-10) The ultrasonic dispersion process is continued for 60 seconds. Moreover, in ultrasonic dispersion, it adjusts suitably so that the water temperature of a water tank may become 10 to 40 degreeC.
(9-11) The resin fine particle dispersion prepared in (9-10) above is immediately added little by little to a batch-type cell while taking care to prevent bubbles from entering, and the transmittance of the tungsten lamp is 90% to 95%. Adjust to be%. Then, the particle size distribution is measured. Based on the obtained volume-based particle size distribution data, D50 is calculated.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. The “parts” described in the following examples are all parts by mass.

[Synthesis Example 1] Synthesis of Resin Fine Particles A (1) Step 1: Synthesis of Resin a After charging the following monomers into a reaction vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen introduction tube, tetrabutoxy titanate. (Esterification catalyst) 0.03 part by mass was added, the temperature was raised to 220 ° C. in a nitrogen atmosphere, and the reaction was carried out for 5 hours while stirring.
Bisphenol A-propylene oxide 2 mol adduct: 53.0 parts by mass Ethylene glycol: 6.0 parts by mass Terephthalic acid: 23.0 parts by mass Isophthalic acid: 14.0 parts by mass Trimellitic anhydride: 4.0 parts by mass While the pressure inside the reaction vessel was reduced to 5 mmHg to 20 mmHg, the reaction was further performed for 5 hours to obtain Resin a.

(2) Step 2: Production of resin fine particles A Reagents and solvents listed below were charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube.
Resin a: 100.0 parts by mass Methyl ethyl ketone: 45.0 parts by mass Tetrahydrofuran: 45.0 parts by mass Dimethylaminoethanol (DMAE): 2.0 parts by mass Sodium dodecylbenzenesulfonate (DBS): 0.5 parts by mass The contents contained in the container were heated to 80 ° C. and dissolved.

  Next, while stirring the contents, 300.0 parts by mass of ion-exchanged water at 80 ° C. was added and dispersed in water, and then the resulting aqueous dispersion was transferred to a distillation apparatus and the fraction temperature reached 100 ° C. Distilled until.

  After cooling, ion-exchanged water was added to the obtained aqueous dispersion to adjust the resin concentration in the dispersion to 20%. Thereby, resin fine particles A dispersed in the dispersion were obtained. In the following description, the resin fine particles A dispersed in the dispersion are referred to as a resin fine particle dispersion A. The physical properties of the obtained resin fine particles A are shown in Table 1.

[Synthesis Examples 2 to 8] Synthesis of Resin Fine Particles B to H The same as Synthesis Example 1 (Synthesis of Resin Fine Particles A) except that the types and amounts of raw materials used in Synthesis Example 1 were changed as shown in Table 1. According to the method, resin fine particles B to H were produced in a manner dispersed in a dispersion. Table 1 shows the physical properties of the obtained resin fine particles.

[Production Method of Crystalline Polyester Resin 1]
While adding 100.0 parts by mass of sebacic acid and 83.0 parts by mass of 1,9-nonanediol to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dehydration tube, and a decompression device, the mixture is stirred. The reaction solution was heated to 130 ° C. Next, after adding 0.7 parts by mass of titanium (IV) isopropoxide (esterification catalyst), the reaction solution was heated to 160 ° C. and subjected to condensation polymerization for 5 hours. Thereafter, the temperature of the reaction solution was raised to 180 ° C., and the reaction was carried out until the desired molecular weight was reached while reducing the pressure inside the container, thereby obtaining crystalline polyester 1. The obtained crystalline polyester 1 had a weight average molecular weight (M _w ) of 20000 and a melting point (T _m ) of 73 ° C.

[Method for producing block polymer 1]
While adding 100.0 parts by mass of sebacic acid and 93.5 parts by mass of 1,10-decanediol to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dehydration tube, and a decompression device, while stirring The reaction solution was heated to 130 ° C. Next, after adding 0.7 parts by mass of titanium (IV) isopropoxide (esterification catalyst), the reaction solution was heated to 160 ° C. and subjected to condensation polymerization for 5 hours. Thereafter, the reaction solution was heated to 180 ° C. and reacted until the desired molecular weight was reached while reducing the pressure, thereby obtaining a crystalline polyester (1). The crystalline polyester (1) had a weight average molecular weight (M _w ) of 19000 and a melting point (T _m ) of 83 ° C.

  Subsequently, 100.0 parts by mass of the crystalline polyester (1) obtained above and 440.0 parts by mass of dehydrated chloroform were completely added to a reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube. Dissolved. Next, 5.0 parts by mass of triethylamine was added, and 15.0 parts by mass of 2-bromoisobutyryl bromide was gradually added while cooling with ice. Thereafter, the reaction solution was stirred overnight at room temperature (25 ° C.).

  Next, the resin solution is gradually dropped into a container containing 550.0 parts by mass of methanol to reprecipitate the resin component, followed by filtration, purification, and drying to obtain a crystalline polyester (2). It was.

  Next, 100.0 parts by mass of the crystalline polyester (2) obtained above, 300.0 parts by mass of styrene, and copper (I) bromide were added to a reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube. 5 parts by mass and 8.5 parts by mass of pentamethyldiethylenetriamine were added and stirred. Next, while stirring the reaction solution, the temperature was raised to 110 ° C. to conduct a polymerization reaction. When the desired molecular weight was reached, the reaction was stopped, and reprecipitation, filtration and purification were performed with 250.0 parts by mass of methanol to remove unreacted styrene and catalyst. Thereafter, the purified product was dried with a vacuum dryer set at 50 ° C. to obtain a block polymer 1 having a polyester portion and a vinyl polymer portion.

The block resin 1 had a weight average molecular weight (M _w ) of 33,000, a melting point (T _m ) of 76 ° C., and C / A of 55/45.

[Production method of block polymers 2 and 3]
In the production method of block polymer 1, block polymers 2 and 3 were obtained by the same method as the production method of block polymer 1 except that the raw materials and production conditions were changed as shown in Table 2 below. Table 3 shows the physical properties of the obtained block polymers 2 and 3, respectively.

[Example 1] Production of toner 1 (1) Production of core particles In a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer and a nitrogen introduction tube, 700 parts by mass of ion-exchanged water and 0.125 mol 1000 parts by weight of a 1 / liter Na ₃ PO ₄ aqueous solution and 24.0 parts by weight of a 1.0 mol-liter aqueous HCl solution were added. Next, the reaction solution was stirred at 12,000 rpm using a high-speed stirring device TK-homomixer and kept at 60 ° C. To this, 85 parts by mass of a 1.25 mol / liter CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Next, the polymerizable monomer composition 1 obtained by dispersing the materials listed below with an attritor for 3 hours was held at 60 ° C. for 20 minutes.
-Styrene: 72.0 parts-n-butyl acrylate: 28.0 parts-Methyltriethoxysilane: 5.0 parts-Block polymer 1: 15.0 parts-Pigment blue (15: 3): 6.0 parts- Aluminum salicylate compound (Bontron E-88: manufactured by Orient Chemical Co., Ltd.): 1.2 parts, divinylbenzene: 0.04 parts, mold release agent (Fischer-Tropsch wax, endothermic main peak temperature 77.1 ° C.): 9.0 Thereafter, the polymerizable monomer composition 1 obtained by adding 16.0 parts by mass (a 50% toluene solution) of t-butyl peroxypivalate (polymerization initiator) to the polymerizable monomer composition 1 is used as an aqueous medium. Then, the mixture was granulated for 10 minutes while maintaining the rotation speed of the high-speed stirrer at 12,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was carried out for 4 hours while slowly stirring. At this time, the pH of the aqueous medium was 5.1. Next, 10.0 parts by mass of 1.0 N NaOH was added to adjust the pH to 8.0, and the temperature inside the container was raised to 95 ° C. and maintained for 6.5 hours. Thereafter, 4.0 parts by mass of 10% hydrochloric acid was added to 50 parts by mass of ion-exchanged water to adjust the pH to 5.1. Next, after adding 300 mass parts of ion-exchange water, the reflux tube was removed and the distillation apparatus was attached. Next, after the temperature in the container was set to 100 ° C., distillation was performed for 5 hours. At this time, the distillation fraction was 300 parts by mass. Then, the polymer slurry was obtained by cooling to 30 degreeC. Next, ion exchange water was added to this polymer slurry to adjust the concentration of polymer particles in the dispersion to 20%, thereby obtaining a core particle dispersion.

  Next, a small amount of the core particle dispersion was taken out, adjusted to pH = 1.5 by adding dilute hydrochloric acid and stirred for 2 hours, and then filtered, washed with water, and dried to obtain core particles. . The obtained core particles were observed with TEM. As a result of performing silicon mapping at the time of observation, it was confirmed that silicon atoms exist uniformly in the surface layer of the core particle. In the following examples and comparative examples, the surface layer containing the organosilicon polymer was also confirmed by silicon mapping.

(2) Adhesion of resin fine particles In a reaction vessel equipped with a reflux condenser, a stirrer, and a thermometer, 500.0 parts (solid content 100.0 parts) of the core particle dispersion obtained in the step (1) above was added. While stirring, the resin fine particle dispersion A (25.0 parts, solid content 5.0 parts) was slowly added. Next, the contents in the reaction vessel were stirred at 200 rpm for 15 minutes. Next, using a heating oil bath, the temperature of the core particle dispersion with the resin fine particles adhered is maintained at 55 ° C. (temperature 1), and 0.3 mol / liter hydrochloric acid is added at a dropping rate of 1.0 part / min. The solution was added dropwise to adjust the pH of the dispersion to 1.5, and stirring was further continued for 2 hours. Thereafter, a 1.0 mol / liter aqueous sodium hydroxide solution was added dropwise with stirring until the pH of the dispersion reached 7.5. Next, this dispersion was kept at 70 ° C. (temperature 2) and further stirred for 1 hour. Next, after cooling the dispersion to 20 ° C. at a rate of 1.0 ° C./min, 10% hydrochloric acid was added until the pH reached 1.5. Further, the toner particles 1 were obtained by thoroughly washing with ion exchange water, filtering, drying and classifying. The obtained toner particles were subjected to NMR measurement to calculate ST3. In the following examples and comparative examples, the NMR measurement was similarly performed and ST3 was calculated.

(3) External addition By treating 100 parts of silica fine powder with 10 parts of hexamethyldisilazane and further with 10 parts of silicone oil, the primary particle size is 12 nm and the BET specific surface area is 120 m ² / g. Hydrophobic silica fine powder was prepared. Next, weigh out the toner particles 1 (100.0 parts) obtained in (2) above, add 1.0 part of the hydrophobic silica fine powder, and mix using a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.). Thus, Toner 1 was obtained. Table 5 shows the physical properties of Toner 1 thus obtained.

[Examples 2 to 20] Preparation of Toners 2 to 20 Toner (Toner 2) was prepared in the same manner as in Example 1 except that the raw materials and production conditions shown in Table 4 were changed. To 20) were obtained respectively. Table 5 shows the physical properties of the obtained toner.

  Further, in the obtained toner (toners 2 to 20), a small amount of the core particle dispersion was extracted, diluted hydrochloric acid was added to adjust to pH = 1.5, and the mixture was stirred for 2 hours, followed by filtration, washing with water and drying. Particles were obtained. The obtained core particles were observed with a TEM, and silicon mapping was performed based on the results of the observation. As a result, it was confirmed that uniform silicon atoms were present on the surface layer of each core particle.

[Comparative Examples 1 and 4] Preparation of toners 21 and 24 In Example 1, toners 21 and 24 were prepared in the same manner as in Example 1 except that the raw materials and production conditions shown in Table 4 were changed. I got each. Table 5 shows the physical properties of the toners (Toners 21 and 24) obtained.

  Further, in the obtained toner (toners 21 and 24), a small amount of the core particle dispersion was extracted, diluted hydrochloric acid was added to adjust pH = 1.5, and the mixture was stirred for 2 hours, followed by filtration, washing with water and drying. Particles were obtained. The obtained core particles were observed with a TEM, and silicon mapping was performed based on the results of this observation. As a result, it was confirmed that a few silicon atoms were present in the surface layer.

[Comparative Example 2] Preparation of toner 22 (1) Preparation of aqueous dispersion medium In a four-necked flask equipped with a high-speed stirrer TK-homomixer, 900 parts by mass of ion-exchanged water and 95 parts by mass of polyvinyl alcohol were added. While stirring at a rotational speed of 1300 rpm, the mixture was heated to 55 ° C. to prepare an aqueous dispersion medium.

(2) Preparation of monomer dispersion The following materials were dispersed with an attritor for 3 hours.
Styrene: 70.0 parts by mass n-butyl acrylate: 30.0 parts by mass Carbon black: 10.0 parts by mass Salicylic acid silane compound: 1.0 parts by mass Release agent [Fischer-Tropsch wax, endothermic main peak temperature 77.1 ° C.]: 9.0 parts by mass Next, 14.0 parts by mass of t-butyl peroxypivalate (polymerization initiator) was added to prepare a monomer dispersion.

(3) Preparation of toner particles Next, the obtained monomer dispersion was put into the dispersion medium in the four-necked flask, and granulated for 10 minutes while maintaining the rotation speed. Subsequently, polymerization was carried out under stirring at 50 rpm at 55 ° C. for 1 hour, then at 65 ° C. for 4 hours, and further at 80 ° C. for 5 hours. After the completion of the polymerization, the slurry was cooled, and the dispersant was removed by repeating washing with purified water. Further, washing and drying were performed to obtain black toner particles as a base material.

  Next, 0.3 parts by mass of dodecylbenzenesulfonic acid was added to a solution obtained by mixing 2 parts by mass of isoamyl acetate, 3.5 parts by mass of tetraethoxysilane (silicon compound), and 0.5 parts by mass of methyltriethoxysilane. 3 parts by mass of sodium solution was added. Next, a mixed solution A containing isoamyl acetate, tetraethoxysilane, and methyltriethoxysilane was prepared by stirring using an ultrasonic homogenizer.

Next, 1.0 part by weight of the base black toner particles and 30 parts by weight of a 0.3% by weight aqueous sodium dodecylbenzenesulfonate solution were added, and then the mixed solution A was added, and then 29% by weight NH _4. 5 mass parts of OH aqueous solution was mixed, and it stirred at room temperature (25 degreeC) for 12 hours. Next, after washing with ethanol, washing with purified water, the particles were filtered and dried to obtain toner particles. The obtained toner particles were observed with a TEM. When silicon mapping was performed based on the results of this observation, it was confirmed that a few silicon atoms were present on the surface layer.

(4) External addition (preparation of toner)
100 parts of silica fine powder is treated with 10 parts of hexamethyldisilazane and further with 10 parts of silicone oil to prepare a hydrophobic silica fine powder having a primary particle size of 12 nm and a BET specific surface area of 120 m ² / g. did. Next, after classifying the toner particles obtained in the above (3), 100.0 parts thereof are weighed out, 1.0 part of the hydrophobic silica fine powder is added, and a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) is used. Then, toner 22 was obtained. Table 5 shows the physical properties of Toner 22 thus obtained.

[Comparative Example 3] Production of Toner 23 (1) Production Example of Polyester Resin (1) The following monomer (terephthalic acid) was charged into an autoclave together with an esterification catalyst, and a decompression device, a water separation device, a nitrogen gas introduction device, A temperature measuring device and a stirring device were attached to the autoclave.
・ Terephthalic acid: 11.1 mol
Bisphenol A-propylene oxide 2 mol adduct (PO-BPA): 11.0 mol
Next, under reduced pressure in a nitrogen atmosphere, the reaction was carried out at 210 ° C. until T _g reached 66 ° C. according to a conventional method to obtain a polyester resin (1). The weight average molecular weight (M _w ) was 7,100, and the number average molecular weight (M _n ) was 3,030.

(2) Production Example of Polyester Resin (2) (2-1) Synthesis of Isocyanate Group-Containing Prepolymer The following reagents were charged into a reaction vessel.
Bisphenol A ethylene oxide 2 mol adduct 730 parts by mass phthalic acid 295 parts by mass dibutyltin oxide 3.0 parts by mass Next, the temperature of the contents of the reaction vessel was raised to 220 ° C., and then reacted for 7 hours while stirring. The reaction was allowed to proceed for 5 hours under reduced pressure. Thereafter, the contents of the reaction vessel were cooled to 80 ° C. and reacted with 190 parts by mass of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate group-containing polyester resin.

(2-2) Synthesis of polyester-based resin (2) By reacting 25 parts by mass of the isocyanate group-containing polyester resin obtained in (2-1) above with 1 part by mass of isophoronediamine at 50 ° C. for 2 hours, A polyester resin (2) containing a urea group and containing polyester as a main component was obtained. The weight average molecular weight (M _w ) of the obtained polyester resin (2) was 23300, the number average molecular weight (M _n ) was 3010, and the peak molecular weight was 7300.

(3) Preparation of oil phase [Oil phase] was obtained by dissolving the following materials in 200 parts by mass of ethyl acetate.
Polyester resin (1): 57.0 parts by weight Polyester resin (2): 43.0 parts by weight Pigment Blue (15: 3): 6.0 parts Release agent [Fischer-Tropsch wax, endothermic main peak temperature 77 .1 ° C.]: 9.0 parts by mass

(4) Preparation of aqueous phase 150 parts of ion-exchanged water, 20 parts of a 1% aqueous solution (thickener) of carboxymethylcellulose, 25 parts of a 50% aqueous solution of sodium dodecyldiphenyl ether disulfonate, and 18 parts of ethyl acetate are mixed and stirred. As a result, an [aqueous phase] was obtained.

(5) Preparation of core particle [Oil phase] which had been stirred in advance was added to the obtained [aqueous phase]. Next, in order to suppress the temperature rise due to the shear heat of the mixer, the temperature in the liquid is adjusted to be in the range of 20 ° C. to 23 ° C. by cooling with a water bath. The mixture was adjusted at 000 rpm to 12,000 rpm and mixed for 3 minutes. Next, stirring is performed for 10 minutes while adjusting the rotational speed between 200 rpm to 600 rpm with a three-one motor with an anchor blade attached thereto, thereby obtaining [core particle slurry] in which oil phase droplets that become core particles are dispersed in an aqueous phase. It was. Next, a small amount of the core particle slurry was extracted, filtered, washed with water, and dried to obtain core particles. The obtained core particles were observed with a TEM, and silicon mapping was performed based on the observation results. It was confirmed that no silicon atoms were present on the surface layer.

(6) Resin fine particle adhering step [Core particle slurry] is adjusted at a rotational speed of 200 rpm to 600 rpm using a three-one motor with an anchor blade, and stirred while the liquid temperature is 22 ° C. The fine particle dispersion A was dropped so that the core particle weight ratio was 7%. After the dropping, the composite number slurry was obtained by maintaining the rotation speed between 200 rpm and 600 rpm and continuing stirring for 30 minutes.

(7) Solvent removal / washing / drying [Composite particle slurry] is put into a container equipped with a stirrer and a thermometer, and the solvent is removed at 30 ° C. for 8 hours while stirring to obtain [dispersed slurry]. Obtained. Further, after sufficiently washing with ion exchange water, the resultant was filtered, dried and classified to obtain toner particles.

(8) External addition By treating 100 parts of silica fine powder with 10 parts of hexamethyldisilazane and further with 10 parts of silicone oil, hydrophobicity having a primary particle size of 12 nm and a BET specific surface area of 120 m ² / g Silica fine powder was prepared. Next, 100.0 parts of the toner particles obtained in (7) above are weighed out, 1.0 part of the hydrophobic silica fine powder is added, and the mixture is mixed using a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.). 23 was obtained. Table 5 shows the physical properties of Toner 23 thus obtained.

[Evaluation of toner]
The performance of each toner obtained in Examples (Examples 1 to 20) and Comparative Examples (Comparative Examples 1 to 4) was evaluated according to the following method. The results are summarized in Table 6.

(1) Fixing property Using a commercially available color laser printer (LBP-7700C, manufactured by Canon), the toner in the cyan cartridge was taken out, filled in the toner, and the cartridge was mounted on the cyan station. Next, on the image receiving paper (Canon office planner, 64 g / m ² ), an unfixed toner image (0.5 mg / cm ² ) having a length of 2.0 cm and a width of 15.0 cm is placed at the upper end with respect to the sheet passing direction. To 2.0 cm. Next, the fixing unit removed from the commercially available color laser printer (LBP-7700C, manufactured by Canon) was remodeled so that the fixing temperature and the process speed could be adjusted respectively, and a fixing test of unfixed images was performed using this remodeled printer. It was.

  First, under normal temperature and humidity, the process speed was set to 230 mm / s, and the initial temperature was set to 120 ° C. Next, the unfixed image was fixed at each temperature while the set temperature was raised by 5 ° C. sequentially.

In the present invention, the low temperature fixability is such that when the obtained fixed image is rubbed five times with sylbon paper applied with a load of 4.9 kPa (50 g / cm ² ), the density reduction rate before and after rubbing is 10%. The following temperature was set as the low temperature side fixing start point. Moreover, the high temperature offset performance was evaluated according to the following criteria.

(Evaluation criteria for high-temperature offset performance)
A: No high temperature offset occurs in the temperature range of the low temperature side fixing start point + 80 ° C. or higher B: No high temperature offset occurs in the temperature range of the low temperature side fixing start point + 70 ° C. or higher C: Temperature of the low temperature side fixing start point + 60 ° C. or higher High temperature offset does not occur in the region D: High temperature offset does not occur in the temperature region of the low temperature side fixing start point + 50 ° C. or higher

(2) Durability A color laser printer (LBP-7700C, manufactured by Canon) was used to take out the toner from the cyan cartridge, and 90 g of the toner was filled in the cartridge. Next, the cartridge filled with the toner was allowed to stand for 10 days in an environment of a temperature of 30 ° C. and a humidity of 80% RH. Next, this cartridge is mounted on a cyan station of a printer, and a printing rate 2% chart is 8000 using an image receiving paper (Canon office planner 64 g / m ² ) under normal temperature and humidity (23 ° C., 60% RH). Images were printed continuously and halftone images were printed. The printed halftone image was evaluated according to the following criteria.

(Evaluation criteria for halftone images (durability evaluation criteria))
A: No streak on the developing roller or halftone part B: There are 1 to 3 streaks on the developing roller, but no halftone part streak C: 4 to 6 streaks on the developing roller Yes, some streaks are seen in the halftone part D: There are 7 or more streaks on the developing roller, and streaks are clearly seen in the halftone part

(3) Heat-resistant storage stability 5 g of toner was collected from the cyan cartridge subjected to the durability evaluation in (2) above, and weighed into a 100 ml capacity polycup, and the weighed toner was put in a thermostatic chamber having an internal temperature of 50 ° C. Left for days. Thereafter, the polycup was taken out and the state change of the toner inside was visually evaluated. The criteria for determining the heat resistant storage stability are as follows.

(Evaluation criteria for heat-resistant storage stability)
A: No change before standing B: There is an aggregate, but loosens immediately C: A little aggregate, but loosens when shocked D: Many aggregates, not easily loosened E: Little loosened

(4) Chargeability 4.0 g of the produced toner and 46.0 g of ferrite carrier F813-300 (manufactured by Powdertech Co., Ltd.) were separated, and the low temperature and low humidity environment (15 ° C./10%) and the high temperature and high humidity environment ( (30 ° C / 80%) for 3 days and nights. Thereafter, it was put in a 50 cc plastic container and shaken 200 times over 1 minute to obtain a two-component developer. Next, the charge amount of the toner was measured using the measuring apparatus of FIG. The method for measuring the charge amount is shown in (5) below. In the evaluation, the charge amount at low temperature and low humidity and the charge amount at high temperature and high humidity were measured, the stability of the charge was evaluated by the following formula (i), and judged according to the following criteria.
Environmental dependency of toner charge (%)
= {(Absolute value of charge amount at low temperature and low humidity)-(Absolute value of charge amount at high temperature and humidity)} / (Absolute value of charge amount at low temperature and low humidity) × 100% (i)

(Evaluation criteria for chargeability (environment dependence of toner charge))
A: 0% or more and less than 15% B: 15% or more and less than 30% C: 30% or more and less than 45% D: 45% or more

(5) Method for measuring charge amount In a metal measuring container 2 having a screen 3 having a mesh of 500 mesh (aperture 25 μm) at the bottom, 0.5 g of a two-component developer whose friction charge amount is to be measured is put in metal. The lid 4 was attached. The mass of the entire measurement container 2 at this time was weighed, and the weighed amount was defined as W ₁ (g). Next, in the suction device 1 (the portion in contact with the measurement container 2 is an insulator), the pressure of the vacuum gauge 5 is set to 250 mmAq by suction from the suction port 7 and adjusting the air volume control valve 6. In this state, suction was performed preferably for 2 minutes to remove the toner by suction.

The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor, and the capacity is C (μF). The mass of the entire measurement container after suction is weighed and is defined as W ₂ (g). The toner triboelectric charge amount (mC / kg) is calculated based on the following equation (ii).
Triboelectric charge (mC / kg) = (C × V) / (W ₁ −W ₂ ) (ii)

Claims (5)

Core particles,
An outer shell covering the core particles;
A toner having toner particles comprising:
The core particles are
A binder resin,
An organosilicon polymer having a partial structure represented by the following formula (T3);
_{R f -Si-O 3/2 (T3} )
(In the formula (T3), R _f represents a hydrocarbon group.)
Containing
The organosilicon polymer is unevenly distributed on the surface of the core particles;
It said shell is state, and are not formed by a glass transition temperature on the outer surface of the surface portion of the core particles to stick to 50.0 ° C. to 95.0 ° C. of the fine resin particles,
In the NMR chart obtained by ²⁹ Si-NMR measurement of the THF-insoluble matter of the toner particles, it belongs to the structure of the formula (T3) with respect to the total area of all the peaks of the organosilicon polymer shown in the NMR chart. the ratio of the peak area ST3 is, the toner which is characterized in der Rukoto 0.40 or more. The toner according to claim 1, wherein the organosilicon polymer is a polymer produced from an organosilicon compound represented by the following formula (Z).

(In Formula (Z), R ₁ represents an alkyl group having 1 to 5 carbon atoms or an aryl group, and R ₂ , R _3, and R ₄ each represent a halogen atom, a hydroxyl group, or an alkoxy group.) The toner according to claim 1 or 2, characterized in that the volume-based median diameter of the resin fine particles (D50) is 30nm or more 200nm or less. The toner according to the core particles, any one of claims 1 to 3 having a melting point, characterized in that it contains 55 to 90 ° C. of the polyester resin. The toner according to claim 4 , wherein the polyester resin is a block polymer having a vinyl polymer portion and a polyester portion.

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