JP2017203890A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner including a surface layer containing a specific organic silicon polymer, the toner capable of suppressing charge-up to suppress ghost when continuous printing is performed at a low printing ratio in a low-temperature and low-humidity environment.SOLUTION: There is provided a toner including toner particles each of which include a core part containing a binder resin and a surface layer containing an organic silicon polymer, wherein the toner particle contains a polyvalent metal element having a resistivity at 20°C of 2.5×10Ω m or more and 10.0×10Ω m or less, and the net intensity based on the polyvalent metal element of the toner in fluorescent X-ray analysis is 0.10 kcps or more and 30.00 kcps or less.SELECTED DRAWING: None

Description

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

A method of visualizing image information through an electrostatic latent image such as electrophotography is currently used in various fields, and improvement in performance such as high image quality and high speed is demanded. In addition, environmental stability and storage stability are also required because it may be used under various temperatures and humidity and may be stored for a long time. Under high temperature environment, the colorant, release agent, etc. contained in the toner used for visualization of the electrostatic image ooze out to the toner surface and change in charge amount, contamination of members such as developing roller, regulating blade, and photoreceptor It is easy to invite such a problem.
In response to this problem, Patent Document 1 discloses a toner technology that contains a specific organosilicon polymer in the surface layer of toner particles. With this technology, it is possible to suppress the material seepage on the toner surface under a high temperature environment, and it is possible to provide a toner having excellent development durability, storage stability, environmental stability and low temperature fixability. .
On the other hand, it has been found that ghosts are likely to occur when continuous printing is performed at a low printing rate in a low temperature and low humidity environment. This is considered to be because the developer carrying member is repeatedly rotated at a low printing rate, and the toner is repeatedly rubbed against the regulating blade, so that the toner is overcharged, so-called charge-up.
As a technique for suppressing the charge-up, Patent Document 2 discloses a technique in which three kinds of silica fine particles having a specific particle diameter and one kind of alumina fine particles are contained as external additives. Patent Document 3 discloses a technique in which composite inorganic fine particles made of an inorganic compound containing magnesium and aluminum are externally added so that the content ratio and static resistance are within a certain range.

JP 2014-130238 A JP, 2014-130202, A JP, 2014-010224, A

In a toner that is easily charged up, in a non-image portion where the toner is not consumed, the toner carried on the developer carrying member is repeatedly rubbed and the charge amount increases. On the other hand, since the toner is consumed in the image portion, repeated friction does not occur. Therefore, the charged state differs between the image portion and the non-image portion. When printing is performed in such a state, a ghost phenomenon is likely to occur in which the history before printing appears in the next image.
As a technique for suppressing charge-up, the text of Patent Document 2 describes that charge-up can be suppressed as the amount of externally added alumina increases. Furthermore, Patent Document 3 describes that a substance having a specific static resistance value is externally added. In either case, the idea is to leak excessive charges, which is an excellent technique for suppressing charge-up. On the other hand, when this technique was applied to a toner having a surface layer containing a specific organosilicon polymer as in Patent Document 1, the effect was limited. That is, although the effect is seen with the developer which has begun to be used, the effect is reduced when the developer is used for developing a large number of sheets. This is because the surface of the toner particles whose surface layer is an organosilicon polymer is harder than the conventional toner, and the external additive cannot be completely fixed, so that the external additive is detached from the toner during use. I guess.
As described above, it is difficult for the conventional technology to suppress charge-up in a toner containing an organosilicon polymer in the surface layer of toner particles.
It is an object of the present invention to suppress ghosts when continuous printing is performed at a low printing rate in a low temperature and low humidity environment by suppressing charge-up in a toner having a surface layer containing a specific organosilicon polymer. To provide toner.

The present invention is a toner having toner particles having a core portion containing a binder resin and a surface layer containing an organosilicon polymer,
The organosilicon polymer has a partial structure represented by the following formula (1) or (2):

（式（２）中のＬは、メチレン基、エチレン基またはフェニレン基を表わす。）
前記トナー粒子の表面のＸ線光電子分光分析において、トナー粒子表面の、炭素原子の濃度ｄＣ、酸素原子の濃度ｄＯ、及びケイ素原子の濃度ｄＳｉの合計を１００．０ａｔｏｍｉｃ％としたときに、ケイ素原子の濃度ｄＳｉが２．５ａｔｏｍｉｃ％以上２２．２ａｔｏｍｉｃ％以下であり、
前記トナー粒子のテトラヒドロフラン不溶分の²⁹Ｓｉ−ＮＭＲの測定で得られるチャートにおいて、有機ケイ素重合体の全ピーク面積に対する式（１）または式（２）の構造に帰属されるピーク面積の割合が２０％以上であり、
前記トナー粒子は２０℃における抵抗率２．５×１０^-8Ω・ｍ以上１０．０×１０^-8Ω・ｍ以下の多価金属元素を含有し、
前記トナー粒子の蛍光Ｘ線分析における、前記多価金属元素に基づくＮｅｔ強度が０．１０ｋｃｐｓ以上３０．００ｋｃｐｓ以下であることを特徴とするトナーである。

(L in the formula (2) represents a methylene group, an ethylene group or a phenylene group.)
In the X-ray photoelectron spectroscopic analysis of the toner particle surface, when the total of the carbon atom concentration dC, oxygen atom concentration dO, and silicon atom concentration dSi on the toner particle surface is 100.0 atomic%, silicon atoms The concentration dSi is 2.5 atomic% or more and 22.2 atomic% or less,
In the chart obtained by ²⁹ Si-NMR measurement of the tetrahydrofuran-insoluble part of the toner particles, the ratio of the peak area attributed to the structure of formula (1) or formula (2) to the total peak area of the organosilicon polymer is 20 % Or more,
The toner particles contain a polyvalent metal element having a resistivity at 20 ° C. of 2.5 × 10 ⁻⁸ Ω · m to 10.0 × 10 ⁻⁸ Ω · m,
In the fluorescent X-ray analysis of the toner particles, the toner has a Net intensity based on the polyvalent metal element of 0.10 kcps to 30.00 kcps.

  According to the present invention, by containing a specific organosilicon polymer in the surface layer of the toner particles, it is possible to suppress the material exudation on the toner surface in a high temperature and high humidity environment. Charge up in a low temperature and low humidity environment, which is a problem at that time, can be suppressed by containing an appropriate amount of a polyvalent metal element having an appropriate resistivity. As a result, according to the present invention, it is possible to provide a toner that is excellent in development durability, storage stability, and environmental stability, and that hardly causes ghost even if continuous printing is performed at a low printing rate in a low temperature and low humidity environment. . Furthermore, even when a strong share is added to the toner, it is possible to provide a toner in which small particles are not easily detached or broken, and problems such as development streaks due to these are unlikely to occur.

It is an example of a ²⁹ Si-NMR measurement chart of the toner particles of the present invention. It is a conceptual diagram which defines surface layer thickness about the surface layer containing the organosilicon compound in this invention.

The toner of the present invention is a toner having toner particles having a core portion containing a binder resin and a surface layer containing a specific organosilicon polymer. Furthermore, it contains a polyvalent metal element having a resistivity of 2.5 × 10 ⁻⁸ Ω · m or more and 10.0 × 10 ⁻⁸ Ω · m or less at 20 ° C., and in the fluorescent X-ray analysis of toner particles, The Net intensity based on the metal element is 0.10 kcps or more and 30.00 kcps or less. In fluorescent X-ray analysis, a sample is irradiated with continuous X-rays to generate characteristic X-rays (fluorescent X-rays) unique to the elements constituting the sample. Then, the generated fluorescent X-ray is spectrally separated (spectral dispersion type) by a spectral crystal to generate a spectrum, the obtained spectrum is measured, and the constituent elements are quantitatively analyzed from the intensity. Net intensity refers to the X-ray intensity obtained by subtracting the background intensity from the X-ray intensity at the peak angle indicating the presence of a metal element. The “polyvalent metal element” in the present invention is a metal element that generates a polyvalent metal ion.

  It has been considered that the charge-up, which is a problem to be solved by the present invention, can be solved by the idea of leaking excessive charges as disclosed in the prior art. Accordingly, it is considered that a component capable of appropriately leaking charge may be contained. In order to appropriately leak the electric charge, it is conceivable that the toner contains a substance having a specific resistivity. The inventors have found that selecting a polyvalent metal element among substances having a specific resistivity has a particular effect on suppressing charge-up. This is because not only the action of leaking excessive charges by a substance having a specific resistivity was obtained, but also it can be coordinated to a silanol group by being a polyvalent metal, and has a high negative chargeability as a charging site. It is speculated that this is due to the effect of reducing silanol groups.

  Further, it has been found that even when a strong share is added to the toner as a heterogeneous effect, separation and cracking of small particles are unlikely to occur, and problems such as development streaks due to these are unlikely to occur. This is presumed to be due to the fact that the organosilicon polymer was metal-crosslinked and the strength was increased due to the polyvalent metal contained.

The resistivity of various substances at 20 ° C. is, for example, “Chemical Dictionary” (1st edition, Tokyo Kagaku Dojin, 1989) and “Chemical Handbook Basics II” (5th revised edition, The Chemical Society of Japan, Maruzen, Heisei) 16, page 611). In the present invention, it is necessary to use a polyvalent metal element of 2.5 × 10 ⁻⁸ Ω · m to 10.0 × 10 ⁻⁸ Ω · m. For example, aluminum 2.7 × 10 ⁻⁸ Ω · m, calcium 3.5 × 10 ⁻⁸ Ω · m, magnesium 4.5 × 10 ⁻⁸ Ω · m, tungsten 5.5 × 10 ⁻⁸ Ω · m, molybdenum 5.6 × 10 ⁻⁸ Ω · m, cobalt 5.8 × 10 ⁻⁸ Ω · m, zinc 5.9 × 10 ⁻⁸ Ω · m, nickel 7.0 × 10 ⁻⁸ Ω · m, iron 9. 7 × 10 ⁻⁸ Ω · m. When the resistivity at 20 ° C. is smaller than 2.5 × 10 ⁻⁸ Ω · m, charge leakage occurs in a high-temperature and high-humidity environment, and when it exceeds 10.0 × 10 ⁻⁸ Ω · m, charging occurs. The suppression effect of up is not enough.

  Further, when the Net intensity based on the polyvalent metal element in the fluorescent X-ray analysis is 0.10 kcps or more, the charge-up suppressing effect can be obtained satisfactorily. On the other hand, if the amount is too large, fogging due to charge leakage may occur in a high-temperature and high-humidity environment, so it is necessary that the amount be 30.00 kcps or less. More preferable is 20.00 kcps or less. When two or more kinds of polyvalent metal elements in the resistivity range are contained, the range of the Net intensity is a total value of the respective polyvalent metal elements.

  The means for containing the polyvalent metal element in the toner particles is not particularly limited. However, it is difficult after the surface layer is formed with the organosilicon polymer, and therefore it is preferable to include it before or while forming the surface layer. . For example, when the toner particles are produced by a pulverization method, the polyvalent metal element may be previously contained in the raw material resin, or may be added to the toner particles when the raw material is melt kneaded. When the toner particles are produced by a wet production method such as a polymerization method, the toner particles can be contained in the raw material or added via an aqueous medium in the production process. In the wet production method, it is preferable that the toner particles are contained in the toner particles after being ionized in an aqueous medium. It is particularly preferable that the polyvalent metal element is aluminum, iron, magnesium, or calcium because it has a relatively large ionization tendency and is easily ionized.

  The aspect of the polyvalent metal element when mixing at the time of production is not particularly limited, but simple substance, halide, hydroxide, oxide, sulfide, carbonate, sulfate, hexafluorosilylated product, acetate salt, thiosulfuric acid Examples thereof include salts, phosphates, chlorates, and nitrates. As described above, it is preferable that these are contained in the toner particles after being ionized once in an aqueous medium. An aqueous medium refers to a medium comprising 50% by mass or more of water and 50% by mass or less of a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran.

When the aqueous medium contains hydroxyapatite and the polyvalent metal element is calcium, attention should be paid to the amount of calcium added. The chemical formula of hydroxyapatite is Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ , and the ratio of the number of moles of calcium and phosphorus is 1.67. Therefore, when the number of moles of calcium is M (Ca) and the number of moles of phosphorus is M (P), calcium is easily incorporated into hydroxyapatite crystals under the condition of M (Ca) ≦ 1.67M (P). Therefore, it is necessary to make an amount of calcium exceeding this amount exist.

[Surface layer containing organosilicon polymer]
The surface layer in the present invention is a layer that covers the core and exists on the outermost surface of the toner particles. The surface layer preferably covers the entire surface of the core, but a portion where the surface layer is not formed may be present on a part of the core surface. Although a detailed method will be described later, in the present invention, the ratio of the number of split axes where the surface layer thickness of the toner particles containing the organosilicon polymer is 2.5 nm or less (hereinafter, the ratio of the surface layer thickness of 2.5 nm or less) Is preferably 20.0% or less. This condition approximates that at least 80.0% or more of the surface layer of toner particles is composed of a surface layer containing the organosilicon polymer of 2.5 nm or more. That is, when this condition is satisfied, the surface layer containing the organosilicon polymer sufficiently covers the core surface. More preferably, it is 10.0% or less. Although the measurement can be defined by cross-sectional observation using a transmission electron microscope (TEM), details will be described later.

  The organosilicon polymer of the toner in the present invention has a partial structure represented by formula (1) or formula (2). Further, in the X-ray photoelectron spectroscopy (ESCA) of the surface of the toner particles, when the total of the carbon atom concentration dC, the oxygen atom concentration dO, and the silicon atom concentration dSi is 100.0 atomic%, silicon atoms The concentration dSi is 2.5 atomic% or more and 22.2 atomic% or less.

（式（２）中のＬは、メチレン基、エチレン基またはフェニレン基を表わす。）

(L in the formula (2) represents a methylene group, an ethylene group or a phenylene group.)

In the organosilicon polymer, one of the four valences of Si atoms is bonded to R, and the remaining three are bonded to O atoms. O atoms constitute a state in which two valences are both bonded to Si, that is, a siloxane bond (Si—O—Si). Considering Si atoms and O atoms as the organosilicon polymer, two Si atoms have three O atoms, and therefore it is expressed as -SiO _3/2 . The —SiO _3/2 structure of this organosilicon polymer is considered to have properties similar to silica (SiO ₂ ) composed of a large number of siloxane bonds. Therefore, the toner of the present invention is considered to create a situation similar to the case where silica is added to the surface. Thereby, it is considered that the hydrophobicity of the toner particle surface can be improved and the environmental stability of the toner can be improved.

  ESCA performs elemental analysis of the surface layer existing at a thickness of several nanometers from the surface of the toner particle to the center of the toner particle (midpoint of the long axis). When the concentration dSi of silicon atoms in the surface layer of the toner particles is 2.5 atomic% or more, the surface free energy of the surface layer can be reduced, the fluidity is improved, and the occurrence of contamination and fogging of members can be suppressed. it can. On the other hand, the silicon atom concentration dSi in the present invention needs to be 22.2 atomic% or less from the viewpoint of chargeability. If it exceeds this, even if the polyvalent metal compound is contained, the effect of suppressing charge-up cannot be sufficiently obtained.

  The concentration of silicon atoms in the surface layer of the toner particles can be controlled by the type and amount of the organosilicon compound used for forming the organosilicon polymer. It can also be controlled by the ratio between the hydrophilic group and the hydrophobic group of the organosilicon polymer, the method for producing the toner particles when forming the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent and the pH.

Furthermore, the toner according to the present invention has a structure represented by the formula (1) or the formula (2) with respect to the total peak area of the organosilicon polymer in a chart obtained by measurement of ²⁹ Si-NMR of the tetrahydrofuran (THF) insoluble content of the toner particles. The ratio of the peak area attributed to is 20% or more. Although a detailed measurement method will be described later, this approximates that the organosilicon polymer contained in the toner particles has a partial structure represented by —SiO _3/2 of 20% or more. As described above, among the four valences of Si atoms, three are bonded to oxygen atoms, and these oxygen atoms are bonded to other Si atoms, which is the meaning of the partial structure of —SiO _3/2 . If one of the oxygens is a silanol group, the partial structure of the organosilicon polymer is represented by —SiO _2/2 —OH. Furthermore, if two oxygens are silanol groups, the partial structure is —SiO _1/2 (—OH) ₂ . When these structures are compared, it is closer to the silica structure represented by SiO ₂ when more oxygen atoms form a crosslinked structure with Si atoms. Therefore, the more the —SiO _3/2 skeleton, the lower the surface free energy on the surface of the toner particles, and the more excellent the environmental stability and anti-member contamination. On the other hand, the smaller the —SiO _3/2 skeleton, the more negatively charged silanol groups will increase, and the charge-up may not be suppressed, so the partial structure represented by —SiO _3/2 is 20% or more. It is necessary to have. From the viewpoint of chargeability and durability, it is preferably 100% or less, and more preferably 40% or more and 80% or less.

  In addition, due to the durability, hydrophobicity and chargeability of the partial structure, a low molecular weight (Mw 1000 or less) resin, a low Tg (40 ° C. or less) resin, and a TBT (40 ° C. or less) resin that are more easily oozed than the surface layer, and in some cases Release agent bleeding can be suppressed. As a result, it is possible to obtain a toner with improved toner agitation, storage stability, and excellent environmental stability and development durability during image output durability with a high printing rate of 30% or more.

  The ratio of the peak area of the partial structure is the type and amount of the organosilicon compound used for forming the organosilicon polymer, and the reaction temperature, reaction time, reaction time of hydrolysis, addition polymerization, and condensation polymerization during the organosilicon polymer formation. It can be controlled by solvent and pH.

  A typical production example of the organosilicon polymer used in the present invention is a method called a sol-gel method. The sol-gel method is a method in which a liquid raw material is used as a starting material, and is hydrolyzed and condensed and polymerized through a sol state, and is used for a method of synthesizing glass, ceramics, organic-inorganic hybrid, and nanocomposite. By using this production method, functional materials having 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 present in the surface layer of the toner particles is preferably produced by hydrolysis and condensation polymerization of a silicon compound represented by alkoxysilane.

  By providing a surface layer containing this organosilicon polymer uniformly on the toner particles, environmental stability is improved without external addition, and the toner performance is less likely to deteriorate during long-term use. A toner having excellent properties can be obtained.

  Further, since the sol-gel method starts with a liquid and forms the material by gelling the liquid, various microstructures and shapes can be created. In particular, when the toner particles are produced in an aqueous medium, the toner particles are easily deposited on the surface of the toner particles due to the hydrophilicity of a hydrophilic group such as a silanol group of the organosilicon compound. The fine structure and shape can be adjusted by the reaction temperature, reaction time, reaction solvent, pH, type and amount of the organometallic compound, and the like.

  The organosilicon polymer in the present invention is preferably a product obtained by condensation polymerization of an organosilicon compound having a structure represented by the following formula (Z). Furthermore, when the organosilicon polymer is subjected to polycondensation, it is preferably performed in the presence of the ionized polyvalent metal element from the viewpoint of improving the strength of the organosilicon polymer.

（式（Ｚ）中、Ｒ１は、下記式（ｉ）または（ｉｉ）であり、Ｒ２、Ｒ３、Ｒ４は、それぞれ独立して、ハロゲン原子、ヒドロキシ基、アセトキシ基、又は、アルコキシ基を表す。）

(In formula (Z), R1 is the following formula (i) or (ii), and R2, R3, and R4 each independently represent a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group. )

（式（ｉ）、式（ｉｉ）中の＊は、ケイ素原子との結合部、式（ｉｉ）中のＬはメチレン基、エチレン基またはフェニレン基を表わす。）

(In formula (i) and formula (ii), * represents a bond to a silicon atom, and L in formula (ii) represents a methylene group, an ethylene group, or a phenylene group.)

  R2, R3, and R4 are each independently a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group (hereinafter also referred to as a reactive group). These reactive groups are hydrolyzed, addition-polymerized and condensation-polymerized to form a crosslinked structure, and a toner having excellent resistance to member contamination and development durability can be obtained. From the viewpoints of moderate hydrolyzability at room temperature, precipitation on the surface of the toner particles and coverage, an alkoxy group is preferable, and a methoxy group or an ethoxy group is more preferable. Further, hydrolysis, addition polymerization and condensation polymerization of R2, R3 and R4 can be controlled by reaction temperature, reaction time, reaction solvent and pH.

  In order to obtain the organosilicon polymer used in the present invention, one or more organosilicon compounds having three reactive groups (R2, R3, R4) in one molecule excluding R1 in the formula (Z) shown above are used. A combination of a plurality of species may be used.

  Examples of the organosilicon compound having a structure represented by the formula (Z) include the following.

  Vinyltrimethoxysilane, vinyltrimethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinyltrichlorosilane, vinylmethoxydichlorosilane, vinylethoxydichlorosilane, vinyldimethoxychlorosilane, vinylmethoxyethoxychlorosilane, vinyldiethoxychlorosilane, vinyl Triacetoxysilane, vinyldiacetoxymethoxysilane, vinyldiacetoxyethoxysilane, vinylacetoxydimethoxysilane, vinylacetoxymethoxyethoxysilane, vinylacetoxydiethoxysilane, vinyltrihydroxysilane, vinylmethoxydihydroxysilane, vinylethoxydihydroxysilane, vinyldimethoxy Hydroxysilane, vinylethoxymethoxyhydroxysila , Trifunctional vinyl silanes such as vinyldiethoxyhydroxysilane; allyltrimethoxysilane, allyltriethoxysilane, allyldiethoxymethoxysilane, allylethoxydimethoxysilane, allyltrichlorosilane, allylmethoxydichlorosilane, allylethoxydichlorosilane, allyl Dimethoxychlorosilane, allylmethoxyethoxychlorosilane, allyldiethoxychlorosilane, allyltriacetoxysilane, allyldiacetoxymethoxysilane, allyldiacetoxyethoxysilane, allylacetoxydimethoxysilane, allylacetoxymethoxyethoxysilane, allylacetoxydiethoxysilane, allyltrihydroxy Silane, allylmethoxydihydroxysilane, allylethoxydihydroxysilane, Dimethoxy hydroxy silane, allyl ethoxymethoxy hydroxy silane, such as such as allyl diethoxy hydroxy silane trifunctional allylsilanes.

  The organosilicon compounds may be used alone or in combination of two or more.

  The content of the organosilicon compound satisfying the formula (Z) is preferably 50 mol% or more, more preferably 60 mol% or more in the organosilicon polymer. By setting the content of the organosilicon compound satisfying the formula (Z) to 50 mol% or more, the environmental stability of the toner can be further improved.

  In addition to the organosilicon compound having the structure of the formula (Z), another organosilicon compound having three reactive groups in one molecule (trifunctional silane), and organosilicon having two reactive groups in one molecule. You may use the organosilicon polymer obtained by using together the compound (bifunctional silane) or the organosilicon compound (monofunctional silane) which has one reactive group. Examples of the organosilicon compound that may be used in combination include the following.

  Dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxy Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3-phenylaminopropyltrimethoxysilane 3-anilinopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Methyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, hexamethyldisilane, tetraisocyanatesilane, methyltriisocyanatesilane, vinyltriisocyanatesilane.

  Further, the content of the organosilicon polymer in the toner is 0.5% by mass or more and 10.5% by mass or less, and the average thickness Dav. Is particularly preferably from 5.0 nm to 100.0 nm.

  When the content of the organosilicon polymer is 0.5% by mass or more, the surface free energy of the surface layer can be further reduced, the fluidity is improved, and the occurrence of member contamination and fogging is further suppressed. Can do. By being 10.5 mass% or less, the charge-up suppression effect by the said polyvalent metal compound can be acquired more fully. The content of the organosilicon polymer is controlled by the type and amount of the organosilicon compound used for forming the organosilicon polymer, the method of producing the toner particles during the formation of the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent and the pH. Can do.

  The method for determining the average thickness of the surface layer in the present invention is determined by the method described later. In the present invention, the surface layer containing the organosilicon polymer and the core portion are preferably in contact with each other without any gap. In other words, it is preferably not a granular lump coating layer as disclosed in JP-A-2001-75304. As a result, the occurrence of bleeding due to the resin component and the release agent inside the surface layer of the toner particles is suppressed, and a toner having excellent storage stability, environmental stability, and development durability can be obtained. The average thickness Dav. If it is less than 5.0 nm, bleeding due to a resin component or a release agent in the toner particles tends to occur. For this reason, the surface properties of the toner particles change and the environmental stability and the development durability tend to deteriorate. The average thickness Dav. When the thickness exceeds 100.0 nm, the low-temperature fixability tends to deteriorate. The average thickness Dav. Can be controlled by the content of the organosilicon polymer and the method for producing the toner particles during the formation of the organosilicon polymer. It can also be controlled by the reaction temperature, reaction time, reaction solvent, and pH of addition polymerization and condensation polymerization when forming the organosilicon polymer.

  In addition to the specific organosilicon polymer, the surface layer may contain a resin such as styrene-acrylic copolymer resin, polyester resin, urethane resin, various additives, and the like.

[About core part containing binder resin]
The core part constituting the toner particles in the present invention contains a binder resin. The binder resin is not particularly limited, and conventionally known resins can be used. In the present invention, the binder resin contains a carboxyl group, and the polyvalent metal element is any one of aluminum, iron, magnesium, and calcium. Combinations of more than one type are particularly preferred. At that time, when the polyvalent metal element contained is aluminum, the Net intensity based on aluminum in the fluorescent X-ray analysis of the toner particles is particularly preferably 0.10 kcps or more and 0.50 kcps or less. When the polyvalent metal element contained is iron, the Net intensity based on iron in the X-ray fluorescence analysis of the toner particles is particularly preferably 1.00 kcps or more and 5.00 kcps or less. When the polyvalent metal element contained is magnesium and / or calcium, the Net intensity based on magnesium and / or calcium is particularly preferably 3.00 kcps or more and 20.00 kcps or less. It has been found that the combination described above makes it easier for small particles to detach and crack when a strong share is added to the toner. This is presumed that the bond strength between the core and the surface layer increased due to the presence of the carboxyl group of the binder resin, the silanol group of the organosilicon polymer, and the relatively ionizable polyvalent metal. ing. Moreover, it is thought that it is related to the valence of a metal that the range of preferable Net intensity | strength changes with substances. That is, when the valence is high, it can coordinate with many silanol groups and carboxyl groups with a small amount of metal, so trivalent aluminum is small, divalent magnesium and calcium are large, and the mixed valence is taken. The iron gained is considered to be the amount in between.

[Binder resin]
Preferred examples of the binder resin include vinyl resins and polyester resins. Examples of vinyl resins, polyester resins, and other binder resins include the following resins or polymers.

  Styrene such as polystyrene and polyvinyltoluene, and homopolymers of substituted styrene; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene -Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-methacrylic acid Ethyl copolymer, styrene-butyl methacrylate copolymer, styrene-dimethyl methacrylate ethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Coalescence, styrene-pig Styrene copolymers such as ene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene , Polypropylene, polyvinyl butyral, silicone resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. These binder resins can be used alone or in combination.

  In the present invention, the binder resin preferably contains a carboxyl group, and is preferably a resin produced using a polymerizable monomer containing a carboxyl group. For example, (meth) acrylic acid such as α-ethylacrylic acid and crotonic acid, and α-alkyl derivatives or β-alkyl derivatives; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid; monoacryloyl succinate Unsaturated dicarboxylic acid monoester derivatives such as oxyethyl ester, succinic acid monoacryloyloxyethylene ester, phthalic acid monoacryloyloxyethyl ester, and phthalic acid monomethacryloyloxyethyl ester.

  As the polyester resin, those obtained by condensation polymerization of the following carboxylic acid component and alcohol component can be used. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. Examples of the alcohol component include bisphenol A, hydrogenated bisphenol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, glycerin, trimethylolpropane, and pentaerythritol.

  Further, the polyester resin may be a polyester resin containing a urea group. As a polyester resin, it is preferable not to cap carboxyl groups such as terminals.

  In the toner of the present invention, the resin may have a polymerizable functional group for the purpose of improving the viscosity change of the toner at high temperature. Examples of the polymerizable functional group include a vinyl group, an isocyanate group, an epoxy group, an amino group, a carboxy group, and a hydroxy group.

[Crosslinking agent]
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.

  For example, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, 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 type diacrylate (MANDA Nippon Kayaku), and above acrylates Is changed to methacrylate.

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

[About mold release agent]
In the present invention, it is preferable that a release agent is contained as one of the materials constituting the toner particles. As the release agent usable for the toner particles, paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof by Fischer-Tropsch method, polyethylene, Polyolefin wax such as polypropylene and derivatives thereof, natural wax such as carnauba wax and candelilla wax and derivatives thereof, fatty acids such as higher aliphatic alcohol, stearic acid and palmitic acid, or compounds thereof, acid amide wax, ester wax , Ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes, and silicone resins. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. In addition, it is preferable that content of a mold release agent is 5.0 to 20.0 mass parts with respect to binder resin or 100.0 mass parts of polymerizable monomers.

[About colorants]
In the present invention, when a colorant is contained in the toner particles, the toner particles are not particularly limited, and the following known materials can be used.

  Examples of yellow pigments include yellow iron oxide, navel yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake. Isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specific examples include the following.

  C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180.

  Examples of the orange pigment include the following.

  Permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK.

  Red pigments include Bengala, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eoxin Lake, Rhodamine Lake B, Alizarin Lake, etc. Examples thereof include azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following.

  C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254.

  Blue pigments include alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, indanthrene blue BG and other copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dyes Examples include lake compounds. Specific examples include the following.

  C. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

  Examples of purple pigments include fast violet B and methyl violet lake.

  Examples of the green pigment include Pigment Green B, Malachite Green Lake, and Final Yellow Green G. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

  Examples of the black pigment include carbon black, aniline black, non-magnetic ferrite, magnetite, the above-described yellow colorant, red colorant, and blue colorant, and those that are toned in black. These colorants can be used alone or in combination and further in the form of a solid solution.

  Further, depending on the toner production method, it is necessary to pay attention to the polymerization inhibiting property and the dispersion medium transferability of the colorant. If necessary, the surface of the colorant may be subjected to surface modification with a substance that does not inhibit polymerization. In particular, since dyes and carbon black often have polymerization inhibiting properties, care must be taken when using them.

  In addition, it is preferable that content of a coloring agent is 3.0 to 15.0 mass parts with respect to 100.0 mass parts of binder resins or polymerizable monomers.

[Charge control agent]
In the present invention, the toner particles may contain a charge control agent. A well-known thing can be used as a charge control agent. In particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous medium is particularly preferable.

  Examples of the charge control agent that control toner particles to be negatively charged include the following.

  As an organic metal compound and a chelate compound, a monoazo metal compound, an acetylacetone metal compound, an aromatic oxycarboxylic acid, an aromatic dicarboxylic acid, an oxycarboxylic acid, and a dicarboxylic acid-based metal compound. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides or esters, and phenol derivatives such as bisphenol. Furthermore, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, and calixarene can be mentioned.

  On the other hand, examples of the charge control agent for controlling the toner particles to be positively charged include the following.

  Nigrosine modified products such as nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and these Onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and their lake pigments (including phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; resin charge control agents.

  These charge control agents can be contained alone or in combination of two or more. In addition, when a charge control agent containing a metal is used in the toner of the present invention, care must be taken so that the resistivity and content of the metal do not depart from the scope of the present invention. The addition amount of these charge control agents is preferably 0.01 parts by mass or more and 10.00 parts by mass or less with respect to 100.00 parts by mass of the binder resin.

(External additive)
The toner particles of the present invention can constitute the toner of the present invention without external addition, but in order to improve fluidity, chargeability, cleaning properties, etc., so-called external additives such as fluidizing agents, cleaning An auxiliary agent or the like may be added to constitute the toner of the present invention.

Examples of the external additive include inorganic oxide fine particles composed of silica fine particles, alumina fine particles, titanium oxide fine particles, inorganic stearate compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, strontium titanate, titanium, and the like. Inorganic titanic acid compound fine particles such as zinc acid are listed. These can be used individually by 1 type or in combination of 2 or more types. These inorganic fine particles are preferably subjected to a gloss treatment with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil or the like in order to improve heat-resistant storage stability and environmental stability. The BET specific surface area of the external additive is preferably 10 m ² / g or more and 450 m ² / g or less.

The BET specific surface area can be determined by a low temperature gas adsorption method by a dynamic constant pressure method according to a BET method (preferably a BET multipoint method). For example, by using a specific surface area measuring apparatus (trade name: Gemini 2375 Ver. 5.0, manufactured by Shimadzu Corporation), nitrogen gas is adsorbed on the sample surface, and measurement is performed using the BET multipoint method. The BET specific surface area (m ² / g) can be calculated.

  The total amount of these various external additives added is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the toner. is there. In addition, various external additives may be used in combination.

(Developer)
The toner of the present invention can be used as a magnetic or non-magnetic one-component developer, but may be mixed with a carrier and used as a two-component developer.

  As the carrier, for example, magnetic particles made of conventionally known materials such as metals such as iron, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead can be used. Among these, ferrite particles Is preferably used. As the carrier, a coated carrier in which the surface of magnetic particles is coated with a coating agent such as a resin, a resin-dispersed carrier in which a magnetic fine powder is dispersed in a binder resin, or the like may be used.

  The carrier preferably has a volume average particle size of 15 μm to 100 μm, more preferably 25 μm to 80 μm.

[Toner particle manufacturing method]
As a method for producing the toner particles of the present invention, known means can be used, and a kneading and pulverizing method or a wet production method can be used. From the viewpoint of uniform particle size and shape controllability, a wet production method can be preferably used. Furthermore, examples of the wet production method include a suspension polymerization method, a dissolution suspension method, an emulsion polymerization aggregation method, and an emulsion aggregation method. In the present invention, the emulsion aggregation method can be preferably used. This is because the polyvalent metal element is easily ionized in an aqueous medium, the polyvalent metal element is easily contained in the toner particles when the binder resin is agglomerated, and the binder is bonded to the organosilicon polymer. This is because the resin is easily metal-crosslinked.

  In the emulsion aggregation method, materials such as binder resin fine particles and a colorant are first dispersed and mixed with a dispersion stabilizer. Thereafter, aggregation is performed by adding an aggregating agent to a desired toner particle size, and thereafter or simultaneously with aggregation, fusion between the resin fine particles is performed. Further, it is a method of forming toner particles by performing shape control by heat as necessary. Here, the fine particles of the binder resin may be composite particles formed of a plurality of layers having two or more layers made of resins having different compositions. For example, it can be produced by an emulsion polymerization method, a miniemulsion polymerization method, a phase inversion emulsification method or the like, or can be produced by combining several production methods.

  When an internal additive is contained in the toner particles, the resin fine particles may contain an internal additive, or a dispersion of internal additive fine particles consisting of only the internal additive is separately prepared and the internal additive is added. The agent fine particles may be aggregated together when the resin fine particles are aggregated. In addition, toner particles having different layer compositions can be produced by adding resin particles having different compositions at a time difference during aggregation and aggregating them.

  The following can be used as the dispersion stabilizer.

  As the surfactant, a known cationic surfactant, anionic surfactant, or nonionic surfactant can be used. Specific examples of the cationic surfactant include dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl anonium bromide and the like. Specific examples of nonionic surfactants include dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, norylphenyl polyoxyethylene ether, lauryl polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, styrylphenyl poly Examples thereof include oxyethylene ether and monodecanoyl sucrose. Specific examples of the anionic surfactant include aliphatic soaps such as sodium stearate and sodium laurate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene (2) sodium lauryl ether sulfate and the like. it can.

  As an inorganic dispersion stabilizer, tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate , Bentonite, silica, and alumina.

  Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, and starch.

  In the invention, the toner preferably has a weight average particle size of 3.0 μm or more and 10.0 μm or less from the viewpoint of high definition and high resolution of the image. The particle size of the toner can be measured by the pore electrical resistance method. For example, measurement and calculation can be performed using “Coulter Counter Multisizer 3” and attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.).

  The toner of the present invention preferably has an average circularity of 0.930 to 1.000, more preferably 0.950 to 0.995, from the viewpoint of improving transfer efficiency. In the present invention, the average circularity of the toner can be measured and calculated using “FPIA-3000” (manufactured by Sysmex).

[Measurement method of toner properties]
<Method for preparing THF-insoluble matter in toner particles for NMR measurement>
The tetrahydrofuran (THF) insoluble matter in the toner particles was prepared as follows.

  10.0 g of toner particles are weighed, put into a cylindrical filter paper (No. 86R, manufactured by Toyo Filter Paper), and passed through a Soxhlet extractor. Extraction was carried out for 20 hours using 200 mL of THF as a solvent, and the residue obtained by vacuum drying the filtrate in the cylindrical filter paper at 40 ° C. for several hours was defined as the THF-insoluble content of the toner particles for NMR measurement.

  If the surface of the toner particles is treated with an external additive or the like, the external additive is removed by the following method to obtain toner particles.

  160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water, and dissolved with a water bath to prepare a sucrose concentrate. 31 g of the above sucrose concentrate in a centrifuge tube, and 10% by weight aqueous solution of neutral detergent for cleaning a precision measuring instrument having a pH of 7, comprising non-ionic surfactant, anionic surfactant and organic builder, 6 mL of Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion. To this dispersion, 1.0 g of toner is added, and the mass of toner is loosened with a spatula or the like.

  The centrifuge tube is shaken with a shaker at 350 spm (strokes per min) for 20 min. After shaking, the solution is replaced with a glass tube for swing rotor (50 mL) and separated by a centrifuge at 3500 rpm for 30 min. By this operation, the toner particles are separated from the detached external additive. It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the toner separated in the uppermost layer is collected with a spatula or the like. The collected toner is filtered with a vacuum filter and then dried with a dryer for 1 hour or longer to obtain toner particles. Perform this operation multiple times to ensure the required amount.

<The confirmation method of the partial structure represented by Formula (1) or Formula (2)>
Presence or absence of a methine group (> CH—Si) bonded to the silicon atom of formula (1), or a methylene group (Si—CH ₂ —), ethylene group (Si— The presence or absence of C ₂ H ₄ —) or a phenylene group (Si—C ₆ H ₄ —) was confirmed by ¹³ C-NMR.

"Measurement conditions for ¹³ C-NMR (solid)"
Device: AVANCE III 500 manufactured by BRUKER
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

  In the case of the unit represented by the formula (1), the presence of the unit represented by the formula (1) is determined by the presence or absence of a signal due to the methine group (> CH—Si) bonded to the silicon atom of the formula (1). confirmed.

In the case of a unit represented by the formula (2), a methylene group (Si—CH ₂ —), an ethylene group (Si—C ₂ H ₄ —), or a phenylene group (Si) bonded to the silicon atom of the formula (2) -C ₆ H ₄ - the presence or absence of the signal due to), confirmed the presence of units of the formula (2).

<Calculation Method of Ratio of Partial Structure Represented by Formula (1) in Organosilicon Polymer Contained in Toner Particle>
²⁹ Si-NMR (solid) measurement of the toner insoluble matter in the toner particles is performed under the following measurement conditions.

" ²⁹ Si-NMR (solid) measurement conditions"
Device: AVANCE III 500 manufactured by BRUKER
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
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

After the above measurement, a plurality of silane components having different substituents and bonding groups of toner particles are peak-separated into the following X1 structure, X2 structure, X3 structure, and X4 structure by curve fitting. Calculate mol% of ingredients.
X1 structure: (Ri) (Rj) (Rk) SiO _1/2 formula (2)
X2 structure: (Rg) (Rh) Si (O _1/2 ) ₂ formula (3)
X3 structure: RmSi (O _1/2 ) ₃ formula (4)
X4 structure: Si (O _1/2 ) ₄ formula (5)

（式（２）、（３）及び（４）中のＲｉ、Ｒｊ、Ｒｋ、Ｒｇ、Ｒｈ、Ｒｍはケイ素に結合している有機基、ハロゲン原子、水酸基またはアルコキシ基を示す。）

(Ri, Rj, Rk, Rg, Rh, and Rm in the formulas (2), (3), and (4) represent an organic group, a halogen atom, a hydroxyl group, or an alkoxy group bonded to silicon.)

  For curve fitting, JOEL Delta version 5.0.4 (trade name), software for JNM-ECX500II manufactured by JEOL RESONANCE is used. Each peak was peaked up. Waveform separation was performed using a Gaussian peak. An example is shown in FIG. Peak division is performed so that the peak of the synthetic peak difference (a), which is the difference between the synthetic peak (b) and the measurement result (d), becomes the smallest.

In the present invention, the silane monomer is specified by the chemical shift value, and the unreacted 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, and the area of the X3 structure. And the total area of the X4 structure was defined as the total peak area of the 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)}

In the present invention, the ratio of the peak area attributed to the structure of the formula (1) to the total peak area of the organosilicon polymer is 20 in the chart obtained by measurement of ²⁹ Si-NMR of the THF insoluble content of the toner particles. % Or more. In this measurement method, the value indicating the —SiO _3/2 structure is SX3. It is a condition of the present invention that this value is 0.20 or more.

<Average thickness Dav. Of the surface layer of the toner particles measured by cross-sectional observation of the toner particles using a transmission electron microscope (TEM). And measuring method in which the thickness of the surface layer is 2.5 nm or less>
In the present invention, cross-sectional observation of toner particles is performed by the following method.

  As a specific method for observing the cross section of the toner particles, the toner particles are sufficiently dispersed in a room temperature curable epoxy resin and then cured in an atmosphere of 40 ° C. for 2 days. A flaky sample is cut out from the obtained cured product using a microtome equipped with diamond teeth. This sample is magnified by a magnification of 10,000 to 100,000 times with a transmission electron microscope (Electron microscope Tecnai TF20XT manufactured by FEI) (TEM), and the cross section of the toner particles is observed.

  In the present invention, the difference between the atomic weights of the resin used and the organosilicon compound is utilized, and the confirmation is performed utilizing the fact that the contrast becomes brighter when the atomic weight is large. Further, a ruthenium tetroxide staining method and an osmium tetroxide staining method may be used in order to provide contrast between materials.

  For the particles used for the measurement, the equivalent circle diameter Dtem was determined from the cross-section of the toner particles obtained from the TEM micrograph, and the value was ± 10% of the weight average particle diameter D4 of the toner particles determined by the method described later. It was included in the width.

  As described above, a bright field image of the cross section of the toner particles is obtained with an acceleration voltage of 200 kV using the FEI electron microscope Tecnai TF20XT. Next, using an EELS detector GIF Tridiem manufactured by Gatan, an EF mapping image at the Si-K end (99 eV) is obtained by the Three Window method, and it is confirmed that the organosilicon polymer is present in the surface layer.

  Next, for one toner particle in which the equivalent circle diameter Dtem falls within the width of ± 10% of the weight average particle diameter D4 of the toner particles, the long axis L of the cross section of the toner particles and the axis that passes through the center of the long axis L and is perpendicular The toner particle cross section is equally divided into 16 with the intersection of L90 as the center (see FIG. 2). Next, the dividing axis from the center toward the surface layer of the toner particles is An (n = 1 to 32), the length of the dividing axis is RAn, and the thickness of the surface layer of the toner particles containing the organosilicon polymer is FRAn. To do.

  The average thickness Dav. Of the surface layer of the toner particles containing the organosilicon polymer at 32 locations on the split axis is obtained. Ask for. Further, the ratio of the number of divided axes in which the thickness of the surface layer of the toner particles containing the organosilicon polymer on each of the 32 existing divided axes is 2.5 nm or less is determined.

  In the present invention, in order to average, 10 toner particles were measured, and an average value per toner particle was calculated.

[Equivalent circle diameter (Dtem) obtained from cross section of toner particle obtained from transmission electron microscope (TEM) photograph]
The equivalent circle diameter (Dtem) obtained from the cross section of the toner particles obtained from the TEM photograph is obtained by the following method. First, for one toner particle, a circle equivalent diameter Dtem obtained from a cross section of the toner particle obtained from the TEM photograph is obtained according to the following formula.
[Equivalent circle diameter (Dtem) obtained from cross section of toner particles obtained from TEM photograph] = (RA1 + RA2 + RA3 + RA4 + RA5 + RA6 + RA7 + RA8 + RA9 + RA10 + RA11 + RA12 + RA13 + RA14 + RA15 + RA16 + RA17 + RA18 + RA21 + RA22 + RA23 + RA24 + RA22 + RA24 + RA24 + RA24 + RA24 + RA24 + RA24 + RA24 +

  The equivalent circle diameter of 10 toner particles is obtained, and the average value per one particle is calculated to obtain the equivalent circle diameter (Dtem) obtained from the cross section of the toner particles.

[Average thickness of surface layer of toner particles (Dav.)]
The average thickness (Dav.) Of the surface layer of the toner particles is determined by the following method.

First, the average thickness D _(n) of the surface layer of one toner particle is determined by the following method.
D _(n) = (total of 32 thicknesses of the surface layer on the dividing axis) / 32
In order to average, the average thickness D _(n) (n = 1 to 10) of the surface layer of 10 toner particles is calculated, the average value per toner particle is calculated, and the average of the surface layer of the toner particles is calculated. Thickness (Dav.).
Dav. = {D ₍₁₎ + D ₍₂₎ + D ₍₃₎ + D ₍₄₎ + D ₍₅₎ + D ₍₆₎ + D ₍₇₎ + D ₍₈₎ + D ₍₉₎ + D ₍₁₀₎ } / 10

[Ratio of surface layer thickness of 2.5 nm or less]
[Ratio in which surface layer thickness (FRAn) is 2.5 nm or less] = [{number of split axes in which surface layer thickness (FRAn) is 2.5 nm or less} / 32] × 100
This calculation is performed on 10 toner particles, and the average value of the ratio of the obtained 10 surface layer thicknesses (FRAn) is 2.5 nm or less is obtained, and the surface layer thickness (FRAn) of the toner particles is determined. The ratio was 2.5 nm or less.

<Concentration (atomic%) of silicon element present on surface layer of toner particles>
X-ray photoelectron spectroscopy (ESCA) is used for the concentration dSi (atomic%) of silicon atoms, the concentration dO (atomic%) of carbon atoms, and the concentration dO (atomic%) of oxygen atoms present on the surface layer of the toner particles. The surface composition analysis was performed and calculated. 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
Sweep number: Si 15 times, C 10 times, O 5 times In the present invention, silicon present in the surface layer of toner particles is measured from the measured peak intensity of each element using a relative sensitivity factor provided by ULVAC-PHI. The concentration dSi of atoms, the concentration dC of carbon atoms, and the concentration dO of oxygen atoms (all are atomic%) were calculated.

<Measurement of toner particle size>
A precision particle size distribution measuring apparatus (trade name: Coulter Counter Multisizer 3) by a pore electrical resistance method and dedicated software (trade name: Beckman Coulter Multisizer 3 Version 3.51, manufactured by Beckman Coulter, Inc.) are used. The aperture diameter is 100 μm, the number of effective measurement channels is 25,000, the 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 (trade name) 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 measurement count is 1 time, and the Kd value is (standard particle 10.0 μm, Beckman Coulter, Inc. 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 (trade name), 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.
(1) About 200 mL of the electrolytic solution is placed in a glass 250 mL round-bottom beaker dedicated to 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.
(2) About 30 mL of the electrolytic solution is placed in a glass 100 mL flat bottom beaker. Here, a diluted solution obtained by diluting Contaminone N (trade name) (10% by weight aqueous solution of a neutral detergent for precision measuring instrument washing, manufactured by Wako Pure Chemical Industries, Ltd.) 3 times by weight with ion-exchanged water was about 0.00. Add 3 mL.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and an ultrasonic disperser having an electric output of 120 W (trade name: Ultrasonic Dispersion System Tetora 150, manufactured by Nikka Bios Co., Ltd.)
A predetermined amount of ion-exchanged water and about 2 mL of Contaminone N (trade name) are added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. 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.
(5) About 10 mg of toner (particles) is added to the electrolytic aqueous solution little by little in a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In 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) The electrolytic solution (5) in which the toner (particles) is dispersed with a pipette is dropped into the round bottom beaker (1) installed in the sample stand so that the measured concentration becomes about 5%. Adjust to. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4). When the graph / number% is set in the dedicated software, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Measuring method of average circularity of toner (particle)>
The average circularity of the toner (particles) is measured using “FPIA-3000 type” (manufactured by Sysmex Corporation), which is a flow type particle image analyzer, under the measurement / analysis conditions during calibration.

  A suitable amount of a surfactant and alkylbenzene sulfonate as a dispersant is added to 20 mL of ion-exchanged water, and then 0.02 g of a measurement sample is added. Dispersion treatment for 2 minutes using a tabletop ultrasonic cleaner disperser (trade name: VS-150, manufactured by VervoCrea Co., Ltd.) with an oscillation frequency of 50 kHz and an electric output of 150 Watts, and a measurement dispersion liquid And In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC.

  The flow type particle image analyzer equipped with a standard objective lens (10 ×) is used for measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion liquid prepared according to the above procedure is measured for 3000 toners (particles) in the HPF measurement mode and in the total count mode. The binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the circle equivalent diameter of 1.98 μm or more and 19.92 μm or less, and the average circularity of the toner (particles) is obtained.

  In measurement, automatic focus adjustment is performed using standard latex particles (for example, 5100A (trade name) manufactured by Duke Scientific is diluted with ion-exchanged water) before the measurement is started. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  Further, when the mode circularity is 0.98 or more and 1.00 or less in the circularity distribution of the toner (particles), it means that most of the toner (particles) have a shape close to a true sphere. The decrease in the adhesion force of the toner (particles) to the photoreceptor due to the mirror image force, van der Waals force, etc. becomes more remarkable, and the transfer efficiency becomes high, which is preferable.

  Here, the mode circularity is a circularity from 0.40 to 1.00, 0.40 or more and less than 0.41, 0.41 or more and less than 0.42,... Or more and less than 1.00 and Divide 61 units every 0.01, such as 1.00. The measured circularity of each particle is assigned to each divided range, and the circularity of the divided range in which the frequency value is maximum in the circularity frequency distribution.

<X-ray fluorescence>
The measurement of the fluorescent X-ray of each element is in accordance with JIS K 0119-1969, and is specifically as follows.

  As a measuring device, a wavelength dispersion type fluorescent X-ray analyzer “Axios” (manufactured by PANalytical) and attached dedicated software “SuperQ ver. 4.0F” (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data ) Is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).

  As a measurement sample, 4 g of toner particles were put in a dedicated aluminum ring for press and leveled, and a tablet molding compressor “BRE-32” (manufactured by Maekawa Test Instruments Co., Ltd.) was used. Pellets that have been pressed for 2 seconds and formed into a thickness of 2 mm and a diameter of 39 mm are used.

  The measurement is performed under the above conditions, the element is identified based on the obtained X-ray peak position, and the count rate (unit: kcps) which is the number of X-ray photons per unit time is measured.

<Measurement of content of organosilicon polymer in toner particles>
The content of the organosilicon polymer is measured using a wavelength dispersive X-ray fluorescence analyzer “Axios” (manufactured by PANalytical) and attached dedicated software “SuperQ ver.4. 0F "(manufactured by PANalytical) is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).

  As a measurement sample, 4 g of toner particles were put in a dedicated aluminum ring for press and leveled, and a tablet molding compressor “BRE-32” (manufactured by Maekawa Test Instruments Co., Ltd.) was used. Pellets that have been pressed for 2 seconds and formed into a thickness of 2 mm and a diameter of 39 mm are used.

Silica (SiO ₂ ) fine powder is added to 0.5 parts by mass with respect to 100 parts by mass of toner particles not containing an organosilicon polymer, and sufficiently mixed using a coffee mill. Similarly, the silica fine powder is mixed with the toner particles so as to be 5.0 parts by mass and 10.0 parts by mass, respectively, and these are used as samples for the calibration curve.

For each sample, a pellet for a calibration curve was prepared as described above using a tablet molding compressor, and the diffraction angle (2θ) was observed at 109.08 ° when PET was used as a spectroscopic crystal. The counting rate (unit: cps) of Si-Kα rays is measured. At this time, the acceleration voltage and current value of the X-ray generator are 24 kV and 100 mA, respectively. A calibration curve of a linear function is obtained with the X-ray count rate obtained on the vertical axis and the added amount of SiO ₂ in each calibration curve sample on the horizontal axis.

  Next, the toner to be analyzed is pelletized as described above using a tablet molding compressor, and the counting rate of the Si-Kα rays is measured. Then, the organosilicon polymer content in the toner is determined from the above calibration curve.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these. In addition, the number of parts in the following compounding shows a mass part.

  First, a method for evaluation performed in Examples will be described below.

<Evaluation of toner developability with LBP>
A toner cartridge of a tandem Canon laser beam printer LBP9600C was charged with 220 g of toner. Then, the toner cartridge has various environments of high temperature and high humidity HH (30.0 ° C./80% RH), normal temperature and normal humidity NN (25 ° C./50% RH), and low temperature and low humidity LL (temperature 10 ° C./humidity 15% RH). Left under for 24 hours. The toner cartridge after being left for 24 hours in each environment is attached to the LBP 9600C. A print rate of 35.0% in the HH and NN environments, and a print rate of 1.0% in the LL environment are printed up to 1,000 sheets in the A4 paper horizontal direction. The images were compared. The evaluations performed in each environment are shown below.

<Evaluation of HH environmental fog>
The white background of the output image measured by “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.) in the initial 0% print ratio image and the 0% print ratio image after 1,000 sheets durability output in HH environment The fog density (%) was calculated from the difference between the whiteness of the portion and the whiteness of the transfer paper. The fog density was evaluated as image fog according to the following criteria. The transfer paper was A4 size of 70 g / m ² and printed in the A4 horizontal direction. The level up to the standard D has no practical problem.
A: Less than 1.0% B: 1.0% or more and less than 1.5% C: 1.5% or more and less than 2.0% D: 2.0% or more and less than 2.5% E: 2.5% or more

<Evaluation of NN environmental development durability>
The development durability was evaluated by the degree of member contamination (filming, development streaks, drum fusion) in the NN environment. After the durability of 1,000 sheets is output, the first half portion is output as a halftone image (toner applied amount 0.25 mg / cm ² ) and the second half portion is a solid image (toner applied amount 0.40 mg / cm ² ). A mixed image was output and evaluated according to the following criteria. The transfer paper was A4 size of 70 g / m ² and printed in the A4 horizontal direction. The standard C is at a level that is not problematic in practice.
A: Vertical streaks in the paper discharge direction and spots with different densities are not seen on the developing roller or on the halftone and solid images.
B: Although there are 1 to 2 circumferential thin stripes on both ends of the developing roller or 1 to 3 fusions on the photosensitive drum, the discharge direction is on the halftone and solid images. There are no vertical streaks or spots with different concentrations.
C: There are 3 or more and 5 or less narrow streaks in the circumferential direction at both ends of the developing roller, or 3 or more and 5 or less fused material on the photosensitive drum, but in the discharge direction on the image of the halftone portion or the solid portion. There are only a few vertical streaks and spots with different concentrations. However, it can be erased by image processing.
D: There are 6 to 20 circumferential thin stripes on both ends of the developing roller or 6 to 20 fusions on the photosensitive drum, and fine stripes on the halftone and solid images. Several lines and pots with different concentrations can be seen. It cannot be erased even with image processing.
E: 21 or more streaks and spots with different densities are seen on the developing roller and the halftone image, and cannot be erased even by image processing.

<Evaluation of LL environmental ghost>
A ghost when continuous printing is performed at a low printing rate in the LL environment is evaluated. An image having a printing ratio of 1.0% was continuously printed on 1000 sheets of A4 paper in the horizontal direction. Then, after printing 10 consecutive images composed of a solid black vertical line and a solid white vertical line with a width of 3 cm, print a halftone image and visually check the history of the previous image remaining on the image. It was judged. The image density of the halftone image was adjusted so that the reflection density was 0.4 by measuring the reflection density using an SPI filter with a Macbeth densitometer (manufactured by Macbeth). The standard C is at a level that is not problematic in practice.
A: No ghost occurs.
B: A slight history of the previous image can be visually confirmed.
C: The history of the previous image can be partially confirmed visually.
D: The history of the previous image can be visually confirmed as a whole.

<Evaluation of storage stability>
10 g of toner was placed in a 100 mL glass bottle and left to stand for 15 days at a temperature of 50 ° C. and a humidity of 20%, and then judged visually. The standard C is at a level that is not problematic in practice.
A: No change.
B: Although there is an aggregate, it is loosened immediately.
C: Aggregates that are difficult to loosen are generated.
D: No fluidity.
E: Obvious caking occurred.

<Measurement of triboelectric charge amount of toner>
276 g of a negatively charged polarity toner standard carrier (trade name: N-01, manufactured by Japan Imaging Society) and 24 g of evaluation toner were put into a 500 cc plastic bottle with a lid. A two-component developer was obtained by shaking for 1 minute at a speed of 4 reciprocations per second with a shaker (YS-LD: manufactured by Yayoi Co., Ltd.). 30 g of this two-component developer was dispensed into an insulating 50 cc plastic container and conditioned for 5 days and nights in each of an HH environment and an LL environment. The humidity-adjusted two-component developer is shaken at a speed of 200 times / minute for 30 seconds in order to evaluate the charge start-up and leakage in the HH environment, and is shaken for 600 seconds in the LL environment to evaluate excessive charge. From the above, the charge amount was measured by the following method.

The sample was placed in a metal container equipped with a conductive screen having an opening of 20 μm at the bottom, and sucked with a suction machine, and the difference in mass before and after suction and the potential accumulated in a capacitor connected to the container were measured. At this time, the suction pressure was set to 2.0 kPa. From the mass difference before and after the suction, the stored potential, and the capacity of the capacitor, the triboelectric charge amount of the toner particles or toner was calculated using the following formula.
Q = (A × B) / (W1-W2)
Q (mC / kg): Toner particle or toner triboelectric charge amount A (μF): Capacitor capacity B (V): Potential difference accumulated in the capacitor W1-W2 (kg): Mass difference before and after suction

<Surface strength>
When the surface layer strength is weak, the surface layer peels off due to the share of an ultrasonic disperser or the toner is chipped, and particles having a small particle size increase.

  As a measuring apparatus, a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) and “autosampler with automatic sample dispersion function for FPIA-3000” (manufactured by Sysmex Corporation) are used. Use the attached dedicated software to set the measurement conditions and analyze the measurement data.

  For the measurement, a high-magnification imaging unit (objective lens “LUCPLFLN” (magnification 20 ×, numerical aperture 0.40)) is used, and focus adjustment is performed using 1.0 μm polystyrene latex particle # 5100A (manufactured by DUKE SCIENTIFIC CORP.). Then measure. As the sheath liquid, a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used. The conditions of the autosampler were as follows: Dispersant dispensing volume 0.5 ml, particle sheath dispensing volume 10 ml, rocking stirring intensity 80%, rocking stirring time 30 seconds, ultrasonic irradiation intensity 100%, ultrasonic irradiation time 600 seconds, propeller The stirring speed is 500 rpm and the propeller stirring time is 600 seconds. For the sample, about 40 mg of dried toner is weighed in an autosampler beaker and set in the autosampler. Measurement conditions are set in the measurement mode HPF and the total count number 2000. In the measurement of the present invention, the number frequency of particles having a particle circumference of 6.3 μm or less was analyzed with attached software. Toner particles with low surface layer strength have a large number of particles with a particle circumference of 6.3 μm or less.

[Example 1]
<Preparation of binder resin particle dispersion>
89.5 parts of styrene, 9.2 parts of butyl acrylate, 1.3 parts of acrylic acid as a carboxyl group-providing monomer, and 3.2 parts of n-lauryl mercaptan were mixed and dissolved. To this solution, an aqueous solution of 150 parts of ion-exchanged water of 1.5 parts of Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) was added and dispersed. Further, with stirring slowly for 10 minutes, an aqueous solution of 10 parts of ion-exchanged water of 0.3 part of potassium persulfate was added. After nitrogen substitution, emulsion polymerization was performed at 70 ° C. for 6 hours. After completion of the polymerization, the reaction solution was cooled to room temperature, and ion exchange water was added to obtain a resin particle dispersion having a solid content concentration of 12.5% by mass and a volume-based median diameter of 0.2 μm.

<Preparation of release agent dispersion>
100 parts of a release agent (behenyl behenate, melting point: 72.1 ° C.) and 15 parts of neogen RK are mixed with 385 parts of ion-exchanged water, and dispersed for about 1 hour using a wet jet mill JN100 (manufactured by Toko). Thus, a release agent dispersion was obtained. The concentration of the release agent dispersion was 20% by mass.

<Preparation of colorant dispersion>
As a colorant, 100 parts of carbon black “Nipex 35 (manufactured by Orion Engineered Carbons)” and 15 parts of Neogen RK are mixed with 885 parts of ion-exchanged water, and dispersed for about 1 hour using a wet jet mill JN100. Got.

<Preparation Example of Toner 1>
265 parts of the resin particle dispersion, 10 parts of the wax dispersion, and 10 parts of the colorant dispersion are dispersed using a homogenizer (manufactured by IKA: Ultra Turrax T50). The temperature in the container was adjusted to 30 ° C. while stirring, and 1N aqueous sodium hydroxide solution was added to adjust the pH to 8.0 (pH adjustment 1). As a flocculant, an aqueous solution in which 0.3 part of magnesium sulfate was dissolved in 10 parts of ion-exchanged water was added over 10 minutes with stirring at 30 ° C. After standing for 3 minutes, the temperature was raised and the temperature was raised to 50 ° C. to produce associated particles. In this state, the particle size of the associated particles is measured with “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter). When the weight average particle diameter reached 6.5 μm, 0.9 part of sodium chloride and 5.0 part of Neogen RK were added to stop the particle growth.

  To this, 0.5 part of magnesium sulfate was added as an additional metal compound, and then 14.0 parts of vinyltriethoxysilane, which is an organosilicon compound, was added, and 1N aqueous sodium hydroxide solution was added to adjust pH = 9. After adjusting to 0 (pH adjustment 2), the temperature was raised to 95 ° C. The aggregated particles were fused and spheroidized while hydrolyzing and condensing vinyltriethoxysilane by stirring and holding at 95 ° C. When the average circularity reaches 0.980, temperature lowering is started, the temperature is lowered to 85 ° C., 1N aqueous sodium hydroxide solution is added to adjust pH = 9.5 (pH adjustment 3), and the mixture is stirred for 180 minutes. Then, after further condensation, cooling was performed to obtain a toner particle dispersion 1.

  Hydrochloric acid was added to the obtained toner particle dispersion 1 to adjust to pH = 1.5 or less, and the mixture was left stirring for 1 hour, followed by solid-liquid separation with a pressure filter to obtain a toner cake. This was reslurried with ion-exchanged water to obtain a dispersion again, followed by solid-liquid separation with the above-mentioned filter. Reslurry and solid-liquid separation were repeated until the electric conductivity of the filtrate was 5.0 μS / cm or less, and finally solid-liquid separation was performed to obtain a toner cake. The obtained toner cake was dried with an air-flow dryer, a flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.), and fine particles were cut using a multi-division classifier utilizing the Coanda effect to obtain toner particles 1. The drying conditions were adjusted such that the blowing temperature was 90 ° C., the dryer outlet temperature was 40 ° C., and the supply speed of the toner cake was adjusted so that the outlet temperature did not deviate from 40 ° C. according to the moisture content of the toner cake. Silicon mapping is performed in cross-sectional TEM observation of the toner particle 1, the ratio of the number of split axes that the surface layer of the toner particle containing the organosilicon polymer has a thickness of 2.5 nm or less is uniform silicon atoms Was confirmed to be 20.0% or less. Also in the following examples and comparative examples, the surface layer containing the organosilicon polymer has a uniform silicon atom in the surface layer by the same silicon mapping, and the ratio of the number of split axes having a surface layer thickness of 2.5 nm or less. Was 20.0% or less. In this example, the obtained toner particles 1 were used as toner 1 as they were without external addition.

  The analysis results of the obtained toner 1 by ESCA, NMR, X-ray fluorescence, and TEM are shown in Table 2, and the evaluation results of development evaluation, storage stability, charge amount, and surface layer strength are shown in Table 3.

[Example 2]
The organosilicon compound to be added was changed to allyltriethoxysilane. In addition, Toner 2 was prepared in the same manner as in Toner 1 except that the addition amount of the organosilicon compound was changed as shown in Table 1. Table 2 shows the results of ESCA, NMR, X-ray fluorescence, and TEM analysis of the toner 2, and Table 3 shows the evaluation results of development evaluation, storage stability, charge amount, and surface layer strength.

[Example 3]
Toner 3 was prepared in the same manner as in Toner 1 except that the amount of the organosilicon compound to be added and the pH adjusted during pH adjustment were changed as shown in Table 1. The analysis results of the toner 3 by ESCA, NMR, fluorescent X-ray, and TEM are shown in Table 2, and the evaluation results of development evaluation, storage stability, charge amount, and surface layer strength are shown in Table 3.

[Examples 4 to 8]
Toners 4 to 8 were produced in the same manner as in Toner 1 except that the pH adjusted during pH adjustment was changed as shown in Table 1. Table 2 shows the results of ESCA, NMR, X-ray fluorescence, and TEM analysis of toners 4 to 8, and Table 3 shows the evaluation results of development evaluation, storage stability, charge amount, and surface layer strength.

[Examples 9 to 14]
Toners 9 to 14 were produced in the same manner as in Toner 1 except that the type and amount of flocculant to be added and the type and amount of added metal compound were changed as shown in Table 1. The analysis results of the toners 9 to 14 by ESCA, NMR, X-ray fluorescence, and TEM are shown in Table 2, and the evaluation results of development evaluation, storage stability, charge amount, and surface layer strength are shown in Table 3.

[Example 15]
The blending ratio in <Preparation of resin particle dispersion> in Example 1 was 89.5 parts of styrene, 10.5 parts of butyl acrylate, and 3.2 parts of n-lauryl mercaptan. Acrylic acid which is a carboxyl group-providing monomer was not blended. Other than that, Toner 15 was prepared in the same manner as in Toner 1 Preparation Example. The analysis results of the toner 15 by ESCA, NMR, fluorescent X-ray and TEM are shown in Table 2, and the evaluation results of development evaluation, storage stability, charge amount and surface layer strength are shown in Table 3.

[Examples 16 to 30]
Toners 16 to 30 were produced in the same manner as in Toner 1 except that the type and amount of the flocculant and the type and amount of the added metal compound were changed as shown in Table 1. The analysis results of the toners 16 to 30 by ESCA, NMR, X-ray fluorescence, and TEM are shown in Table 2, and the evaluation results of development evaluation, storage stability, charge amount, and surface layer strength are shown in Table 3.

[Examples 31 to 34]
Toners 31 to 34 were produced in the same manner as in Toner 1 except that the amount of the organosilicon compound to be added was changed as shown in Table 1. The analysis results of the toners 31 to 34 by ESCA, NMR, fluorescent X-ray, and TEM are shown in Table 2, and the evaluation results of development evaluation, storage stability, charge amount, and surface layer strength are shown in Table 3.

[Example 35]
Toner 35 was produced in the same manner as in Toner 1 except that the organosilicon compound to be added was changed to p-styryltrimethoxysilane. The analysis results of the toner 35 by ESCA, NMR, fluorescent X-ray, and TEM are shown in Table 2, and the evaluation results of development evaluation, storage stability, charge amount, and surface layer strength are shown in Table 3.

[Comparative Example 1]
A comparative toner 1 was produced in the same manner as in the toner 1 production example, except that no organosilicon compound was added. When silicon mapping was performed in the cross-sectional TEM observation of the comparative toner particles 1, no silicon atoms were present in the surface layer. Further, in the comparative toner particles 1, the ratio of the number of split axes in which the thickness of the surface layer of the toner particles containing the organosilicon polymer is 2.5 nm or less was 20.0% or more.

  Table 2 shows the analysis results of the comparative toners 1 to 3 by ESCA, NMR, X-ray fluorescence, and TEM, and Table 3 shows the evaluation results of development evaluation, storage stability, charge amount, and surface layer strength.

[Comparative Example 2]
A comparative toner 2 was produced in the same manner as in the toner 1 production example, except that the organosilicon compound to be added was changed to 3-methacryloxypropyltrimethoxysilane. In the comparative toner particles 2, the ratio of the number of split axes in which the thickness of the surface layer of the toner particles containing the organosilicon polymer is 2.5 nm or less was 20.0% or more. Table 2 shows the analysis results of the comparative toner 2 by ESCA, NMR, X-ray fluorescence, and TEM, and Table 3 shows the evaluation results of development evaluation, storage stability, charge amount, and surface layer strength.

[Comparative Example 3]
The organosilicon compound to be added was changed to allyltriethoxysilane. A comparative toner 3 was prepared in the same manner as in the toner 1 preparation example except that the amount of the organosilicon compound and the pH adjusted during pH adjustment were changed as shown in Table 1.

  Table 2 shows the analysis results of the comparative toner 3 by ESCA, NMR, fluorescent X-ray, and TEM, and Table 3 shows the evaluation results of development evaluation, storage stability, charge amount, and surface layer strength.

[Comparative Examples 4 and 5]
Comparative toners 4 and 5 were prepared in the same manner as in the toner 1 preparation example except that the amount of the organosilicon compound to be added and the pH adjusted during pH adjustment were changed as shown in Table 1.

  Table 2 shows the analysis results of the comparative toners 4 and 5 by ESCA, NMR, X-ray fluorescence, and TEM, and Table 3 shows the evaluation results of development evaluation, storage stability, charge amount, and surface layer strength.

[Comparative Examples 6-12]
Comparative toners 6 to 12 were prepared in the same manner as in the toner 1 preparation example except that the type and amount of the flocculant to be added and the type and amount of the added metal compound were changed as shown in Table 1. Table 2 shows the analysis results of the comparative toners 6 to 12 by ESCA, NMR, fluorescent X-ray, and TEM, and Table 3 shows the evaluation results of development evaluation, storage stability, charge amount, and surface layer strength. In addition, since the X-ray fluorescence analysis result of Comparative Examples 6-8 did not detect the polyvalent metal element, it shows the value of potassium used in the flocculant and the additional metal compound.

  As is apparent from Tables 2 and 3, “Examples 1 to 35” which are the toner particle production methods of the present invention are compared with “Comparative Examples 1 to 12” in terms of development durability, storage stability, and environment. Excellent stability and ghosting is unlikely to occur even when continuous printing is performed at a low printing rate in a low temperature and low humidity environment.

Claims (3)

A toner having toner particles having a core portion containing a binder resin and a surface layer containing an organosilicon polymer,
The organosilicon polymer has a partial structure represented by the following formula (1) or (2):

(L in the formula (2) represents a methylene group, an ethylene group or a phenylene group.)
In the X-ray photoelectron spectroscopic analysis of the toner particle surface, when the total of the carbon atom concentration dC, oxygen atom concentration dO, and silicon atom concentration dSi on the toner particle surface is 100.0 atomic%, silicon atoms The concentration dSi is 2.5 atomic% or more and 22.2 atomic% or less,
In the chart obtained by ²⁹ Si-NMR measurement of the tetrahydrofuran-insoluble part of the toner particles, the ratio of the peak area attributed to the structure of formula (1) or formula (2) to the total peak area of the organosilicon polymer is 20 % Or more,
The toner particles contain a polyvalent metal element having a resistivity at 20 ° C. of 2.5 × 10 ⁻⁸ Ω · m to 10.0 × 10 ⁻⁸ Ω · m,
A toner having a Net intensity based on the polyvalent metal element of 0.10 kcps to 30.00 kcps in a fluorescent X-ray analysis of the toner particles. The binder resin contains a carboxyl group, and the polyvalent metal is one or more of aluminum, iron, magnesium, and calcium,
When the polyvalent metal element contained is aluminum, the Net intensity based on aluminum in the fluorescent X-ray analysis of the toner particles is 0.10 kcps or more and 0.50 kcps or less,
When the contained polyvalent metal element is iron, the Net intensity based on iron in the fluorescent X-ray analysis of the toner particles is 1.00 kcps to 5.00 kcps, and the contained polyvalent metal element is magnesium and / or calcium. 2. The toner according to claim 1, wherein the Net intensity based on magnesium and / or calcium is 3.00 kcps or more and 20.00 kcps or less. The content of the organosilicon polymer in the toner particles is 0.5% by mass or more and 10.5% by mass or less,
Average thickness Dav. Of the surface layer containing the organosilicon polymer measured by observation of a cross section of the toner particles using a transmission electron microscope (TEM). The toner according to claim 1, wherein the toner is 5.0 nm or more and 100.0 nm or less.

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