JP6316117B2 - toner - Google Patents

Description

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

  In recent years, with the development of computers and multimedia, there is a demand for means for outputting high-definition full-color images in a wide range of fields from offices to homes. Further, when used in offices where many copies or prints are made, high durability without deterioration in image quality is required even with a large number of copies or prints. On the other hand, for use in small offices and homes, there is a demand for downsizing of the apparatus from the viewpoints of obtaining high-quality images and saving space, energy, and weight. In order to meet the above requirements, it is necessary to further improve the toner performance such as environmental stability, member contamination, low-temperature fixability, development durability and storage stability.

  In the case of full color in particular, color toners are superimposed to form an image. However, if the color toners of the respective colors are not developed in the same manner, color reproduction is inferior and color unevenness occurs. When pigments or dyes used as toner colorants are deposited on the surface of toner particles, the developability is affected and color unevenness may occur.

  Further, in a full-color image, fixability and color mixing at the time of fixing are important. For example, in order to achieve the desired high speed, a binder resin suitable for low-temperature fixability is selected, but the influence on the developability and durability of the binder resin is also great.

  Furthermore, there is a demand for means for outputting a high-definition full-color image that can be used for a long period of time in various environments having different temperatures and humidity. In order to meet such demands, changes in toner charge amount and toner surface properties caused by differences in the usage environment of temperature and humidity, and members such as developing rollers, charging rollers, regulating blades, and photosensitive drums It is necessary to solve problems such as pollution. Therefore, there is a demand for development of a toner having stable development durability that does not cause stable charging and member contamination even when stored for a long time in a wide range of environments.

  One of the causes of fluctuations in storage stability and charge amount of toner due to temperature and humidity is a phenomenon in which the toner release agent and resin component ooze out from the inside of the toner (hereinafter this phenomenon is called bleed). And the surface property of the toner is changed.

  As one means for solving such a problem, there is a method of covering the surface of toner particles with a resin.

  Patent Document 1 discloses a toner in which inorganic fine particles are strongly fixed to the surface as a toner excellent in high temperature storage stability and printing durability in a normal temperature and normal humidity environment during printing or in a high temperature and high humidity environment. However, even if the inorganic fine particles are strongly fixed to the toner particles, the occurrence of bleeding due to the release agent or the resin component from the gaps between the inorganic fine particles and the liberation of the inorganic fine particles due to the deterioration of durability may cause durability and member contamination in harsh environments. On the other hand, further improvements are needed.

  In Patent Document 2, a silane coupling is used in the reaction system in order to obtain a toner having a narrow charge amount distribution and a very small humidity dependency of the charge amount without exposing the colorant or polar substance to the toner surface. A method for producing a polymerized toner comprising adding an agent is disclosed. However, in such a method, the amount of silane compound deposited on the toner surface and hydrolysis polycondensation are insufficient, and further improvements are required for environmental stability and development durability.

  Further, Patent Document 3 includes a silicon compound applied in the form of a continuous thin film on the surface as a means for controlling the charge amount of toner and forming a high-quality printed image regardless of the environment of temperature and humidity. A polymerized toner is disclosed. However, the polarity of the organic functional group is large, the amount of silane compound deposited on the toner surface and hydrolysis polycondensation are insufficient, the degree of crosslinking is weak, and the image density change and durability due to the change in chargeability under high temperature and high humidity. Further improvement is necessary for component contamination due to deterioration.

  Furthermore, in Patent Document 4, as a toner for improving fluidity, release of fluidizing agent, low-temperature fixability, and anti-blocking property, polymerization having a coating layer formed by adhering granular lumps containing a silicon compound. Toner is disclosed. However, there is a need for further improvement against the occurrence of bleeding in which the release agent and the resin component ooze out from the gaps between the particle blocks containing the silicon compound. In addition, the amount of silane compound deposited on the toner surface and the change in image density due to the change in chargeability under high temperature and high humidity caused by insufficient hydrolysis polycondensation, toner fusing and granular lump containing silicon compound There is a need for further improvements in the occurrence of component contamination and storage stability due to separation.

JP 2006-146056 A Japanese Patent Laid-Open No. 03-089361 JP 09-179341 A JP 2001-75304 A

  The present invention provides a toner that solves the above problems. More specifically, the object is to provide a toner having excellent development durability, storage stability, environmental stability, member contamination, and low-temperature fixability.

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

That is, the present invention is a toner having toner particles having a surface layer containing an organosilicon polymer and a charge control agent,
The organosilicon polymer has the following formula (T3R)

（式中のＲは炭素数が１以上６以下の炭化水素基である。）
で表わされるユニットを有し、
前記トナー粒子の表面のＥＳＣＡ（Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ ｆｏｒ Ｃｈｅｍｉｃａｌ Ａｎａｌｙｓｉｓ）を用いた測定において、トナー粒子表面の炭素元素濃度ｄＣ、酸素元素濃度ｄＯ、ケイ素元素濃度ｄＳｉの合計濃度（ｄＣ＋ｄＯ＋ｄＳｉ）に対するケイ素濃度ｄＳｉが０．５０ａｔｏｍｉｃ％以上であり、
前記荷電制御剤が式（ａ１）で示される構造ａを有する重合体Ａであることを特徴とするトナーに関する。

(R in the formula is a hydrocarbon group having 1 to 6 carbon atoms.)
Having a unit represented by
In the measurement using ESCA (Electron Spectroscopy for Chemical Analysis) on the surface of the toner particles, the silicon concentration dSi with respect to the total concentration (dC + dO + dSi) of the carbon element concentration dC, the oxygen element concentration dO, and the silicon element concentration dSi on the toner particle surface is 0. .50 atomic% or more,
The toner is characterized in that the charge control agent is a polymer A having a structure a represented by the formula (a1).

（式中、Ｒ¹は、ヒドロキシル基、カルボキシル基、炭素数１以上１８以下のアルキル基、または、炭素数１以上１８以下のアルコキシル基を表し、Ｒ²は、水素原子、ヒドロキシル基、炭素数１以上１８以下のアルキル基、または、炭素数１以上１８以下のアルコキシル基を表し、ｇは１以上３以下の整数を表し、ｈは０以上３以下の整数を表し、ｈが２または３の場合、Ｒ¹はそれぞれ独立して選択でき、＊＊は重合体Ａにおける結合部位である。）

(Wherein R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms, and R ² represents a hydrogen atom, a hydroxyl group, or a carbon number. Represents an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms, g represents an integer of 1 to 3, h represents an integer of 0 to 3, and h is 2 or 3. In this case, each R ¹ can be independently selected, and ** is a binding site in the polymer A.)

  According to the present invention, a toner excellent in development durability, storage stability, environmental stability, member contamination, and low-temperature fixability can be provided.

It is a figure which shows an example of the cross-sectional image of the toner of this invention observed by TEM. 3 is a chart measured by ²⁹ Si-NMR of the toner particles of the present invention. a. D. From the measurement result b. It is a synthetic peak difference obtained by subtracting a synthetic peak. b. Is a synthetic peak obtained by synthesizing split peaks. c. Is a divided peak obtained by dividing the synthetic peak. d. Is the peak of the measurement result. It is a figure which shows the reversing heat flow curve measured by the differential scanning calorimeter (DSC) of the toner of this invention. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus used in the present invention.

  Hereinafter, the present invention will be described in detail.

The toner of the present invention is a toner having toner particles having a surface layer containing an organosilicon polymer and a charge control agent,
The organosilicon polymer has the following formula (T3R)

（式中のＲは炭素数が１以上６以下の炭化水素基である。）
で表わされるユニットを有し、
前記トナー粒子の表面のＥＳＣＡ（Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ ｆｏｒ Ｃｈｅｍｉｃａｌ Ａｎａｌｙｓｉｓ）を用いた測定において、トナー粒子表面の炭素元素濃度ｄＣ、酸素元素濃度ｄＯ、ケイ素元素濃度ｄＳｉの合計濃度（ｄＣ＋ｄＯ＋ｄＳｉ）に対するケイ素濃度ｄＳｉが０．５０ａｔｏｍｉｃ％以上であり、
前記荷電制御剤が式（ａ１）で示される構造ａを有する重合体Ａを満たすことを特徴とする。

(R in the formula is a hydrocarbon group having 1 to 6 carbon atoms.)
Having a unit represented by
In the measurement using ESCA (Electron Spectroscopy for Chemical Analysis) on the surface of the toner particles, the silicon concentration dSi with respect to the total concentration (dC + dO + dSi) of the carbon element concentration dC, the oxygen element concentration dO, and the silicon element concentration dSi on the toner particle surface is 0. .50 atomic% or more,
The charge control agent satisfies the polymer A having the structure a represented by the formula (a1).

（式中、Ｒ¹は、ヒドロキシル基、カルボキシル基、炭素数１以上１８以下のアルキル基、または、炭素数１以上１８以下のアルコキシル基を表し、Ｒ²は、水素原子、ヒドロキシル基、炭素数１以上１８以下のアルキル基、または、炭素数１以上１８以下のアルコキシル基を表し、ｇは１以上３以下の整数を表し、ｈは０以上３以下の整数を表し、ｈが２または３の場合、Ｒ¹はそれぞれ独立して選択でき、＊＊は重合体Ａにおける結合部位である。）

(Wherein R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms, and R ² represents a hydrogen atom, a hydroxyl group, or a carbon number. Represents an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms, g represents an integer of 1 to 3, h represents an integer of 0 to 3, and h is 2 or 3. In this case, each R ¹ can be independently selected, and ** is a binding site in the polymer A.)

  By having a surface layer containing an organosilicon polymer having a partial structure represented by the formula (T3R), hydrophobicity due to the organic structure can be improved, and a toner excellent in environmental stability can be obtained.

  The toner particles of the present invention have a silicon element concentration dSi, an oxygen element concentration dO, and a carbon element concentration dC in the measurement using X-ray photoelectron for chemical analysis (ESCA) of the toner particle surface. The silicon element concentration DSi with respect to the total is preferably 0.50 atomic% or more, more preferably 2.5 atomic% or more, and further preferably 5.0 atomic%. ESCA performs elemental analysis of the outermost surface of several nm. When the concentration of silicon element is 0.50 atomic% or more in the outermost layer of toner particles, the surface free energy of the outermost layer can be reduced. By adjusting the concentration of silicon element to 0.50 atomic% or more, the fluidity is improved, and the occurrence of member contamination and fogging can be further suppressed.

  The silicon concentration of the outermost layer of the toner particles can be controlled by the hydrocarbon group, reaction temperature, reaction time, reaction solvent and pH in the formula (T3R). Moreover, it can control by the quantity of an organosilicon polymer. In the present invention, the outermost layer is 0.0 to 10.0 nm from the toner surface to the center of the toner (midpoint of the long axis).

  Examples of the hydrocarbon group in R include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, etc. Examples of the alkoxyl group include methoxy group. Group, ethoxy group, propoxy group and the like.

  The polymer A is a polymer having the structure a and the structure a connected at the ** part. The toner using the polymer A as a charge control agent suppresses a decrease in fluidity of the toner even when stored under high temperature and high humidity, as compared to the case where a conventional resin having a salicylic acid structure is used. Can do. The structure a is characterized in that a benzyloxy moiety is interposed between the connecting portion with the main chain and the salicylic acid structural moiety, and is structurally flexible. This has the effect of facilitating the molecular arrangement that makes charge transfer more advantageous, and is considered to lead to an increase in the amount of saturated charge as compared with a conventional resin having a salicylic acid structure. As a result, a necessary amount for obtaining a desired saturation charge amount can be reduced, and therefore, it is possible to suppress a decrease in toner fluidity when stored under high temperature and high humidity.

  The main chain structure of the polymer A is not particularly limited as long as the structure a can be linked at the ** part. Examples thereof include vinyl polymers, polyester polymers, polyamide polymers, polyurethane polymers, polyether polymers, and the like. Moreover, the hybrid type polymer which combined these 2 or more types is also mentioned. Among these, a polyester polymer or a vinyl polymer is preferable in consideration of manufacturability, cost merit, and affinity with a binder resin. More preferably, it is a vinyl polymer having the structure a as a partial structure represented by the following formula (a2).

（式中、Ｒ³は、ヒドロキシル基、カルボキシル基、炭素数１以上１８以下のアルキル基、または、炭素数１以上１８以下のアルコキシル基を表し、Ｒ⁴は、水素原子、ヒドロキシル基、炭素数１以上１８以下のアルキル基、または、炭素数１以上１８以下のアルコキシル基を表し、Ｒ⁵は、水素原子またはメチル基を表し、ｉは１以上３以下の整数を表し、ｊは０以上３以下の整数を表し、ｊが２または３の場合、Ｒ³はそれぞれ独立して選択できる。）

(In the formula, R ³ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms, and R ⁴ represents a hydrogen atom, a hydroxyl group, or a carbon number. Represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms, R ⁵ represents a hydrogen atom or a methyl group, i represents an integer of 1 to 3 and j is 0 to 3; Represents the following integer, and when j is 2 or 3, each R ³ can be independently selected.)

Examples of the alkyl group in R ³ and R ⁴ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, etc., and alkoxyl group Examples of these include methoxy group, ethoxy group, propoxy group and the like. Thus, since the polymer A is a vinyl polymer, it is easily compatible in the toner particles containing the vinyl resin as a main component. Compatibilization makes it possible to take a more optimal molecular arrangement, and the charging ability of the polymer A is more effectively exhibited. When the toner is produced in an aqueous medium, the effect is further enhanced, and the arrangement of the highly polar polymer A component on the toner particle surface layer proceeds smoothly, so that the particle size distribution is improved.

  As for the molecular weight of the polymer A, the weight average molecular weight calculated by gel permeation chromatography (GPC) is preferably 1,000 or more and 100,000 or less. By setting the weight average molecular weight of the polymer A to 1000 or more, exudation under high temperature and high humidity is suppressed, and good fluidity can be secured. In addition, by setting the weight average molecular weight to 100000 or less, the toner has good fixability and can suppress uneven distribution among toner particles, resulting in a sharp charge amount distribution. In order to make a weight average molecular weight into said range, it can control by changing conditions, such as the amount of reagents at the time of manufacturing superposition | polymerization A, reaction temperature, and solvent concentration. Moreover, the polymer A of desired molecular weight can be obtained by fractionating by GPC.

  Further, the content of the structure a in the polymer A is preferably 10 μmol / g or more and 1500 μmol / g or less. When the content of the structure a in the polymer A is 10 μmol / g or more, the triboelectric chargeability is improved. Moreover, since it is 1500 micromol / g or less, since the influence of the hygroscopic property which the structure a has can be suppressed smaller, fluidity | liquidity becomes favorable. The content of the structure “a” in the polymer A can be adjusted by a charging ratio at the time of synthesizing the polymer A and reaction conditions such as a reaction temperature.

  It does not specifically limit as a manufacturing method of the polymer A of this invention, It can manufacture by a well-known method. In the case of a vinyl polymer, for example, a polymerizable monomer (formula (a3)) containing a structure a having a structure represented by the formula (a1) is polymerized with a vinyl monomer. This is a method of copolymerization using an initiator.

（式中、Ｒ⁶は、ヒドロキシル基、カルボキシル基、炭素数１以上１８以下のアルキル基、または、炭素数１以上１８以下のアルコキシル基を表し、Ｒ⁷は、水素原子、ヒドロキシル基、炭素数１以上１８以下のアルキル基、または、炭素数１以上１８以下のアルコキシル基を表し、Ｒ⁸は、水素原子またはメチル基を表し、ｍは１以上３以下の整数を表し、ｎは０以上３以下の整数を表し、ｎが２または３の場合、Ｒ⁶はそれぞれ独立して選択できる。）

(In the formula, R ⁶ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms, and R ⁷ represents a hydrogen atom, a hydroxyl group, or a carbon number. Represents an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms, R ⁸ represents a hydrogen atom or a methyl group, m represents an integer of 1 to 3 and n is 0 to 3; The following integers are represented, and when n is 2 or 3, each R ⁶ can be independently selected.)

  Specific examples of polymerizable monomers containing structure a are shown in Table 1.

  Moreover, it does not restrict | limit especially as a vinyl-type monomer copolymerized with the polymerizable monomer A containing the structure a. Specifically, styrene and its derivatives such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; Vinyl halides such as vinyl, vinylidene chloride, vinyl bromide, vinyl fluoride; vinyl ester acids such as vinyl acetate, vinyl propionate, vinyl benzoate; acrylic acid-n-butyl, acrylic acid-2-ethylhexyl, etc. Acrylic acid esters; Methacrylic acid esters obtained by changing the acrylic acid of the acrylic acid esters to methacrylic acid; Methacrylic acid amino esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; Vinyl methyl ether, vinyl ethyl ether Vinyl ethers; vinyl ketones such as vinyl methyl ketone; N-vinyl compounds such as N-vinyl pyrrole; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, acrylic acid, methacrylic acid, etc. Can be mentioned. In addition, you may use a vinyl monomer in combination of 2 or more type as needed.

  As a polymerization initiator that can be used when copolymerizing the polymerizable monomer component described above, various substances such as a peroxide polymerization initiator and an azo polymerization initiator can be used. Examples of the peroxide polymerization initiator that can be used include peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, and diacyl peroxides. Examples of the inorganic system include persulfate and hydrogen peroxide. Specifically, t-butyl peroxyacetate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-hexyl peroxyacetate, t-hexyl peroxypivalate, t-hexyl peroxyiso Peroxyesters such as butyrate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate; diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate; 1 , 1-di-t-hexylperoxycyclohexane and other peroxyketals; di-t-butyl peroxide and other dialkyl peroxides; and other examples include t-butyl peroxyallyl monocarbonate and the like. It is. Examples of the azo polymerization initiator that can be used include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane- 1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, dimethyl-2,2′-azobis (2-methylpropionate), etc. Illustrated.

  If necessary, two or more of these polymerization initiators can be used simultaneously. It is preferable that the usage-amount of the polymerization initiator used in this case is 0.100 mass part or more and 20.0 mass parts or less with respect to 100 mass parts of polymerizable monomers. As the polymerization method, any method such as solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization and bulk polymerization can be used, and it is not particularly limited.

  On the other hand, when the polymer A containing the structure a of the present invention is a polyester resin, various known production methods can be used. For example, i) a method of converting to a structure a represented by the formula (a1) by an organic reaction using a reaction residue of a carboxyl group or a hydroxyl group contained in the polyester structure, ii) represented by the formula (a1) A method for producing a polyester using a polyhydric alcohol or polyvalent carboxylic acid having the structure a as a substituent, iii) introduction of the structure a represented by the formula (a1) into the polyhydric alcohol or polycarboxylic acid as a substituent For example, a method in which a functional group that can be easily introduced is introduced in advance.

  When the polymer A is a hybrid resin, iv) a method of hybridizing a polyester resin containing the structure a represented by the formula (a1) as a substituent with a vinyl monomer, v) a vinyl monomer And a method of converting the carboxyl group into a structure represented by the formula (a1) by an organic reaction after polymerization using a compound having a carboxyl group such as acrylic acid or methacrylic acid, and vi) represented by the formula (a1) Examples include a method of hybridizing a polyester resin using a vinyl monomer having the structure a.

  As a method for hybridizing the polyester resin with a vinyl monomer, a known method can be used, and it is effective as the method iv). Specific examples include a method of vinyl-modifying polyester with a peroxide-based initiator and a method of preparing a hybrid resin by graft-modifying a polyester resin having an unsaturated group.

  Alternatively, as a specific method of v), when the structure a represented by the formula (a1) is introduced, a compound in which an amino group is introduced into the ** part of the formula (a1) is used as the carboxyl group present in the resin. A method of amidation can be mentioned.

  Moreover, as a specific method of vi), the polymerizable monomer shown by the above-mentioned formula (a3) can be used as a usable vinyl monomer.

  In the present invention, a known method can be used as a method for adjusting the weight average molecular weight of the polymer. Specifically, in the case of a polyester resin, it can be arbitrarily adjusted by adjusting the charging ratio of the acid component and the alcohol component and the polymerization time. In addition, in the hybrid resin, in addition to the adjustment of the molecular weight of the polyester component, the weight average molecular weight of the polymer can be adjusted by adjusting the molecular weight of the vinyl-modified unit. Specifically, it can be arbitrarily adjusted by adjusting the amount of radical initiator, polymerization temperature and the like in the vinyl modification reaction step. As the vinyl monomer that can be used for hybridization of the polyester resin in the present invention, the above-described vinyl monomers can be used.

  Content of the structure a in the polymer A can be calculated | required by the below-mentioned method. First, the polymer A is titrated by the method described later to obtain the hydroxyl value of the polymer A, and the amount of hydroxyl groups derived from the structure a possessed by the polymer A is calculated. And based on this, content (mmol / g) of the structure a in the polymer A is calculated. In the case where the polymer A has a hydroxyl group at a site other than the structure a, the hydroxyl value of the compound (for example, polyester resin) immediately before the structure a is subjected to addition reaction when the polymer A is prepared is measured in advance. Keep it. The addition amount of structure a can be calculated by the difference from the hydroxyl value of polymer A after the addition reaction.

  In the toner of the present invention, the content x of the structure a in the toner is preferably from 0.10 μmol / g to 200 μmol / g. When the content x of the structure a in the toner is within the above range, a sufficient charge amount can be obtained, and moisture absorption can be suppressed, so that good fluidity can be secured. The content x of the structure a in the toner can be controlled by adjusting the charged amount of the polymer A at the time of toner preparation, the content of the structure a in the polymer A, and the like. The content x of the structure a in the toner, which will be described later, is calculated from the charged amount of the compound containing the structure a at the time of toner preparation.

  In the present invention, the toner particle surface contains the formula (T3R) and the charge control agent of the formula (a1) improves the fluidity before and after durability at a high printing rate (35%). This has an excellent effect on a phenomenon in which a toner-developed region is generated in a circular shape having a size of about 10 mm.

In addition, the charging stability in a humid environment is improved by the charging effect of the salicylic acid structure of structure a and the formula (T3R) structure. Furthermore, since the dielectric constant is appropriate due to the hydrophobic effect by the R group of the formula (T3R) and the siloxane (SiO ₂ ) structure, it has a stable charge holding effect. In addition, the organosilicon polymer having the formula (T3R) structure and the salicylic acid structure reduce the surface energy and improve the fluidity of the toner, so that a high printing rate (35%) after severe storage is used when using a large number of sheets. Followability (image density stability during continuous solid image output) and black spots improve.

In the ²⁹ Si-NMR measurement of the THF-insoluble matter in the toner particles, the formula (T3R) with respect to the area SS obtained by removing the silane monomer component from the total peak area of the organosilicon polymer having the partial structure represented by the formula (T3R) It is preferable that the ratio RS (T3R) of the peak area of the structure (hereinafter also referred to as T3R structure) satisfies RS (T3R) ≧ 0.20. Since the surface free energy of the toner surface can be lowered, there are excellent effects in environmental stability and member contamination.

  In addition, due to the durability of the polymer by the T3R structure and the hydrophobicity and chargeability of R in the formula (T3R), the resin has a low molecular weight (Mw 1000 or less) and a low Tg (40 ° C. or less) that is more easily oozed out than the surface layer. ) Resin and release agent bleed, toner stirrability is improved, and a toner with excellent storage stability, environmental stability and development durability when the printing rate is 30% or more, especially when the printing rate is high. Can be obtained.

  The ratio of RS (T3R) can be controlled by the monomer species, reaction temperature, reaction time, reaction solvent and pH.

In the present invention, the structure of (SX3) in which the number of O _1/2 bonded to silicon with respect to the total peak area of the organosilicon polymer is 3.0 in the ²⁹ Si-NMR measurement of the THF-insoluble matter of the toner particles The relationship between the ratio S (SX3) / S (SX2) of the peak area S (SX3) and the ratio of the peak area S (SX2) of the (SX2) structure in which the number of O _1/2 bonded to silicon is 2.0. ) ≧ 1.00 (2)
It is preferable to satisfy.

（式（ＳＸ３）中のＲｆはケイ素に結合している有機基、ハロゲン原子、ヒドロキシ基またはアルコキシ基）

(Rf in Formula (SX3) is an organic group, halogen atom, hydroxy group or alkoxy group bonded to silicon)

（式（ＳＸ２）中のＲｇ、Ｒｈはケイ素に結合している有機基、ハロゲン原子、ヒドロキシ基またはアルコキシ基）

(Rg and Rh in the formula (SX2) are organic groups, halogen atoms, hydroxy groups or alkoxy groups bonded to silicon)

  When S (SX3) is equal to or higher than S (SX2), the balance between durability and chargeability due to the crosslinked structure of the siloxane structure is improved. Therefore, it is excellent in environmental stability, storage stability and development durability, and is excellent in fog and image density stability even in a wide range of environments. More preferably, S (SX3) / S (SX2) ≧ 1.50, and still more preferably S (SX3) / S (SX2) ≧ 2.00. The peak area ratio of S (SX3) / S (SX2) can be controlled by the monomer species, reaction temperature, reaction time, reaction solvent and pH.

  The organosilicon polymer having a partial structure represented by the formula (T3R) of the present invention is preferably a hydrocarbon group having 1 to 6 carbon atoms in R. When the hydrophobicity of R is large, there is a tendency that the charge amount fluctuation becomes large in a wide range of environments. In particular, a hydrocarbon or aryl group having 5 or less carbon atoms, which is excellent in environmental stability, is preferable.

  In the present invention, a methyl group, an ethyl group, a propyl group, and a vinyl group are particularly preferable as the organosilicon compound having 3 or less carbon atoms in the hydrocarbon group R in the formula (T3R). Chargeability is good and fog is good.

  Particularly preferably, R is a methyl group from the viewpoints of environmental stability and storage stability. When the charging property is good, the transfer property is good and the residual toner is small, so that the contamination of the drum, the charging member and the transfer member is improved.

  In the organosilicon polymer used in the present invention, the T unit structure represented by the formula (T3R) is preferably 50 mol% or more, more preferably 60 mol% or more in the organosilicon polymer. By setting the content of the T unit structure represented by the formula (T3R) to 50 mol% or more, the environmental stability of the toner can be further improved.

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

  Specifically, the surface layer of the toner particles is generated by hydrolysis polycondensation of a silicon compound typified by alkoxysilane. By providing this surface layer uniformly on the surface of the toner particles, the environmental stability can be improved and the toner can be used for a long period of time without fixing or adhering the inorganic fine particles as is done with conventional toners. Thus, it is possible to obtain a toner having excellent storage stability.

  Furthermore, since the sol-gel method forms a material by starting from a solution and gelling the solution, various microstructures and shapes can be created. In particular, when the toner particles are produced in an aqueous medium, the toner particles are likely to be 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. However, when the hydrophobicity of the organosilicon compound is large (for example, when the hydrocarbon group of the organosilicon compound is a hydrocarbon group having 6 or more carbon atoms), the weight average particle size (μm) of the toner particles on the surface of the toner particles. ) Tends to form an aggregate that is 1/10 or less of the above. When the number of carbon atoms of the hydrocarbon group of the organosilicon compound is 0, the hydrophobicity is weakened, so that the charging stability tends to be poor. The microstructure and shape can be adjusted by the reaction temperature, reaction time, reaction solvent, pH, type and amount of organometallic compound, and the like.

  Average thickness Dav. Of the surface layer of the toner particles containing the organosilicon polymer, measured by observation of a cross section of the toner particles using a transmission electron microscope (TEM). Is preferably 2.5 nm or more and 150.0 nm or less. As a result, the occurrence of bleeding due to the release agent or resin component 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. From the viewpoint of storage stability, the average thickness Dav. Is 3.0 nm or more and 125.0 nm or less, and a more preferable range is 5.0 nm or more and 100.0 nm or less. In the present invention, the surface layer containing the organosilicon polymer and the portion other than the toner particle surface layer (so-called core portion) are preferably in contact with each other without a gap. In other words, it is preferable that the coating layer is not agglomerated as disclosed in Patent Document 4. The average thickness Dav. If it is less than 2.5 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 150.0 nm, the low-temperature fixability tends to deteriorate.

  The average thickness Dav. Of the surface layer of the toner particles containing the organosilicon polymer. Can be controlled by the number of carbon atoms of the hydrocarbon group in the formula (T3R), the number of hydrophilic groups, the reaction temperature of addition polymerization and condensation polymerization, the reaction time, the reaction solvent and the pH. Moreover, it can control by the quantity of an organosilicon polymer.

  In the cross-sectional observation of the toner particle using a transmission electron microscope (TEM) in the cross-sectional observation of the toner particle, the toner particle crosses the long axis L of the cross section of the toner particle and the axis L90 perpendicular to the center of the long axis L. The average thickness Dav of the surface layer containing the organosilicon polymer of the toner particles at 32 locations on the axis where the axes from the center when equally divided into 16 with respect to the center are Arn (n = 1 to 32), respectively. . Is 2.5 nm or more, and the number having an average thickness of 2.5 nm or less is preferably 20.0% by number or less (see FIG. 1).

  Average thickness Dav. Of surface layer containing organosilicon polymer of toner particles at 32 locations on the shaft. Is preferably 2.5 nm or more, and S (SX3) is preferably 0.20 or more. Since the generation of bleeding due to the release agent or resin of the toner particles can be reduced, environmental stability, storage stability and development durability are improved. Toner having an average layer thickness of 2.5 nm or less containing an organosilicon polymer of toner particles is 20.0% by number or less, thereby obtaining a toner having excellent fog and image density stability even in a wide range of environments. Can do.

  The average thickness of the surface layer containing the organosilicon polymer of 32 toner particles on the shaft and the average thickness of the toner surface layer containing the organosilicon polymer of 2.5 nm or less are hydrocarbon groups of the formula (T3R) structure The number of carbon atoms, the number of hydrophilic groups, temperature, reaction time, reaction solvent, and pH can be controlled. Moreover, it can control by the quantity of an organosilicon polymer.

  It is preferable to have a surface layer containing an organosilicon polymer obtained by polymerizing a compound having a structure represented by the following formula (Z).

（式中のＲ１は炭素数１〜６の炭化水素基であり、Ｒ２、Ｒ３及びＲ４は、それぞれ独立してハロゲン原子、水酸基またはアルコキシ基である。）

(R1 in the formula is a hydrocarbon group having 1 to 6 carbon atoms, and R2, R3 and R4 are each independently a halogen atom, a hydroxyl group or an alkoxy group.)

  The hydrophobicity due to the hydrocarbon group of R1 can be improved, and a toner excellent in environmental stability can be obtained. R1 is preferably a hydrocarbon or aryl group having 6 or less carbon atoms. When the hydrophobicity of R1 is large, the charge amount variation tends to increase in a wide range of environments. In particular, a carbon number of 3 or less, which is excellent in environmental stability, is preferable.

  In the present invention, a methyl group, an ethyl group, or a propyl group is particularly preferable as the organosilicon compound having 3 or less carbon atoms in the hydrocarbon group R1 of the formula (Z). Chargeability is good and fog is good.

  Particularly preferably, R1 is a methyl group from the viewpoints of environmental stability and storage stability.

  R2 to R4 are independent halogen atoms, hydroxyl groups and alkoxy groups (hereinafter also referred to as reactive groups), and these reactive groups undergo hydrolysis, addition polymerization and condensation polymerization to form a cross-linked structure, resulting in member contamination and development durability. A toner having excellent properties can be obtained. A methoxy group or an ethoxy group is most preferable from the viewpoints of moderate hydrolyzability and toner surface precipitation and coverage. The hydrolysis, addition polymerization and condensation polymerization of R2 to R4 can be controlled by the reaction temperature, reaction time, reaction solvent and pH.

  In order to obtain the organosilicon polymer, an organosilicon compound having three reactive groups (R2, R3 and R4) in one molecule excluding the hydrocarbon group R1 in the formula (Z) (hereinafter also referred to as trifunctional silane). It is preferable to use one or more types.

  Examples of the formula (Z) include the following.

For example, methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane , Methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, Methyldimethoxyhydroxysilane, methylethoxymethoxyhydro Shishiran, methylsilane methyl diethoxy hydroxy silane, such as trifunctional;
Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltri Trifunctional such as methoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane Hexylsilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyl Triacetoxy silane, such as trifunctional phenylsilane phenyl trihydroxy silane;
Vinyl triisocyanate silane, p-styryltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinyltrichlorosilane, vinylmethoxydichlorosilane, vinylethoxydichlorosilane, vinyldimethoxychlorosilane , Vinylmethoxyethoxychlorosilane, vinyldiethoxychlorosilane, vinyltriacetoxysilane, vinyldiacetoxymethoxysilane, vinyldiacetoxyethoxysilane, vinylacetoxydimethoxysilane, vinylacetoxymethoxyethoxysilane, vinylacetoxydiethoxysilane, vinyltrihydroxysilane, Vinylmethoxydihydroxysilane, vinylethoxydihydroxysilane, vinyl Trifunctional vinyl silanes such as methoxyhydroxysilane, vinylethoxymethoxyhydroxysilane, vinyldiethoxyhydroxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriacetoxysilane, allyltrihydroxysilane, etc. And 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), an organosilicon compound having three reactive groups in one molecule (trifunctional silane), and an organosilicon compound having two reactive groups in one molecule ( An organosilicon polymer obtained by using a bifunctional silane) or an organosilicon compound having one reactive group (monofunctional silane) may be used. 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 Examples include methyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, hexamethyldisilane, tetraisocyanate silane, and methyltriisocyanate silane.

In general, it is known that in the sol-gel reaction, the bonding state of siloxane bonds generated varies depending on the acidity of the reaction medium. Specifically, when the reaction medium is acidic, hydrogen ions are electrophilically added to oxygen of one reactive group (for example, an alkoxy group (—OR group)). Next, the oxygen atom in the water molecule is coordinated to the silicon atom and becomes a hydrosilyl group by a substitution reaction. When water is present sufficiently, one H ⁺ attacks one oxygen of a reactive group (for example, an alkoxy group-OR group), so when the content of H ^{+ in} the reaction medium is low, the reaction proceeds to a hydroxy group. The substitution reaction becomes slow. Therefore, a polycondensation reaction occurs before all of the reactive groups attached to the silane are hydrolyzed, and a one-dimensional linear polymer or a two-dimensional polymer is easily generated relatively easily.

  On the other hand, when the reaction medium is alkaline, hydroxide ions are added to silicon and go through a pentacoordinate intermediate. For this reason, all reactive groups (for example, alkoxy groups (—OR groups)) are easily removed and easily substituted with silanol groups. In particular, when a silicon compound having three or more reactive groups on the same silane is used, hydrolysis and polycondensation occur three-dimensionally to form an organosilicon polymer having a large number of three-dimensional crosslinks. . The reaction is also completed in a short time.

  Therefore, in order to form the organosilicon polymer, it is preferable to proceed the sol-gel reaction with the reaction medium being in an alkaline state. Specifically, when producing in an aqueous medium, the pH should be 8.0 or more. preferable. As a result, an organosilicon polymer having higher strength and superior durability can be formed. The sol-gel reaction is preferably performed at a reaction temperature of 90 ° C. or more and a reaction time of 5 hours or more.

  By performing this sol-gel reaction at the above reaction temperature and reaction time, formation of coalesced particles in which silane compounds in a sol or gel state on the surface of the toner particles are bonded to each other can be suppressed.

  Further, examples of the titanium coupling agent include the following. Titanium methoxide, titanium ethoxide, titanium n-propoxide, tetra-i-propoxy titanium, tetra-n-butoxy titanium, titanium isobutoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxide, titanium diiso Propoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide), titanium diisopropoxybis (ethylacetoacetate), tetrakis (2 -Ethylhexyloxy) titanium, di-i-propoxy bis (acetylacetonato) titanium, titanium lactate, titanium methacrylate isopropoxide, triisopropoxy titanate, titanium methoxypropoxide, titanium steari Oxide.

  The following are mentioned as an aluminum type coupling agent. Aluminum (III) n-butoxide, Aluminum (III) s-butoxide, Aluminum (III) s-butoxide bis (ethyl acetoacetate), Aluminum (III) t-butoxide, Aluminum (III) di-s-butoxide ethyl aceto Acetate, aluminum (III) diisopropoxide ethyl acetoacetate, aluminum (III) ethoxide, aluminum (III) ethoxyethoxy ethoxide, aluminum hexafluoropentandionate, aluminum (III) 3-hydroxy-2-methyl-4- Pyronate, aluminum (III) isopropoxide, aluminum-9-octadecenyl acetoacetate diisopropoxide, aluminum (III) 2,4-pe Tanjioneto, aluminum phenoxide, aluminum (III) 2,2,6,6-tetramethyl-3,5-heptanedionate.

  These coupling agents may be used alone or in combination. The charge amount can be adjusted by appropriately combining these or changing the addition amount.

  Next, a method for producing toner particles in the present invention will be described.

  Hereinafter, specific embodiments in which the organosilicon polymer of the present invention is contained on the surface of the toner particles will be described, but the present invention is not limited thereto.

  In the first production method, a polymerizable monomer composition containing a polymerizable monomer, a colorant, and an organosilicon compound is granulated in an aqueous medium, and the polymerizable monomer is polymerized to form a toner. This is an embodiment for obtaining particles (hereinafter also referred to as suspension polymerization method).

  The second production method is an embodiment in which after obtaining a toner base first, the toner base is put into an aqueous medium and a surface layer of an organosilicon polymer is formed on the toner base in the aqueous medium. The toner base may be obtained by melt-kneading the binder resin and the colorant and pulverizing them, and the binder resin particles and the colorant particles are aggregated and associated in an aqueous medium. The organic phase dispersion prepared by dissolving a binder resin and a colorant in an organic solvent may be suspended, granulated, and polymerized in an aqueous medium, and then the organic solvent. The toner base material obtained by removing the toner may be used.

  As a third production method, an organic phase dispersion prepared by dissolving a binder resin, a silane compound and a colorant in an organic solvent is suspended, granulated and polymerized in an aqueous medium, and then the organic solvent is removed. In this embodiment, toner particles are obtained.

  The fourth production method is an embodiment in which binder resin particles, colorant particles, and organic silicon compound-containing particles in a sol or gel state are aggregated in an aqueous medium and associated to form toner particles.

  As the fifth production method, an organosilicon compound-containing compound is sprayed onto the surface of the toner base by a spray-drying method, and the surface is polymerized or dried by hot air and cooling to form an organosilicon compound-containing surface layer It is. The toner base may be obtained by melt-kneading and pulverizing the binder resin and the colorant, and may be obtained by aggregating and associating the binder resin particles and the colorant particles in an aqueous medium. An organic phase dispersion prepared by dissolving a binder resin, a silane compound, and a colorant in an organic solvent may be obtained by suspending, granulating, and polymerizing in an aqueous medium and then removing the organic solvent.

  The toner particles produced by these production methods are formed in a state where the organosilicon polymer is deposited on the toner particle surface in the vicinity of the toner particle surface, so that environmental stability (chargeability under harsh environment) is good. It becomes. Further, even in a harsh environment, changes in the surface state of the toner particles due to the release agent inside the toner and the bleeding of the resin are suppressed.

  In the present invention, surface treatment of toner particles or toner may be performed using hot air. By performing the surface treatment of the toner particles or toner using hot air, it is possible to promote the polycondensation of the organosilicon polymer in the vicinity of the surface of the toner particles and improve the environmental stability and the development durability.

  As the surface treatment using hot air, any means that can treat toner particles or toner surface with hot air and that can cool the toner particles or toner treated with hot air with cold air can be used. It may be something like this. As a device for performing surface treatment using hot air, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a mechano-fusion system (manufactured by Hosokawa Micron Corporation), a faculty (manufactured by Hosokawa Micron Corporation), Meteor Inbo MR Type (manufactured by Nippon Pneumatic Co., Ltd.) Is mentioned.

  Examples of the preferable aqueous medium in the present invention include the following. Water, alcohols such as methanol, ethanol and propanol, and mixed solvents thereof.

  As the method for producing the toner of the present invention, among the above-described production methods, the suspension polymerization method which is the first production method is preferable. In the suspension polymerization method, the organosilicon polymer is likely to be uniformly deposited on the surface, the adhesion between the surface layer and the inside is excellent, and the storage stability, environmental stability and development durability are improved. Hereinafter, the suspension polymerization method will be further described.

(Low molecular weight resin)
As the low molecular weight resin, the following resins can be used as long as the effects of the present invention are not affected.

  As the toner additive, the following resins can be used as long as the effects of the present invention are not affected. Homopolymers of styrene such as polystyrene and polyvinyltoluene and substituted products thereof; 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-ethyl methacrylate Copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer , Styrene-butadi Copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene copolymer such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, Polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. It can be used alone or in combination.

  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 a high temperature. Examples of the polymerizable functional group include a vinyl group, an isocyanate group, an epoxy group, an amino group, a carboxylic acid group, and a hydroxyl group.

  In addition, it is preferable that the weight average molecular weight (Mw) of the THF soluble part of low molecular weight resin calculated | required by GPC is 2000-6000.

  The purpose of the resin is to improve toner particle shape, material dispersibility, fixability, or image characteristics. Monomers containing hydrophilic functional groups such as amino groups, carboxylic acid groups, hydroxyl groups, sulfonic acid groups, glycidyl groups, and nitrile groups cannot be used because they are soluble in water and dissolve in aqueous suspension to cause emulsion polymerization. In order to introduce the monomer components in the toner particles, random copolymers of these with vinyl compounds such as styrene or ethylene, block copolymers, copolymers such as graft copolymers, polyesters and polyamides. Such polycondensates or addition polymers such as polyethers and polyimines can be used.

  The above resins can be used alone or in combination.

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

  In addition, it is preferable that the weight average molecular weight (Mw) of the THF soluble part of low molecular weight resin calculated | required by GPC is 2000-6000.

(Polar resin)
As the polar resin, a saturated or unsaturated polyester resin is preferable.

  As the polyester-based resin, those obtained by condensation polymerization of the following acid component monomers and alcohol component monomers can be used. Examples of the acid component monomer include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid.

  Examples of the alcohol component monomer include bisphenol A, hydrogenated bisphenol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, glycerin, trimethylolpropane, and pentaerythritol.

(Release agent)
As one of the materials constituting the toner of the present invention, a release agent is preferably contained. Examples of the release agent component usable in the toner according to the present invention include 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, Polyolefin wax such as polyethylene and polypropylene and derivatives thereof, natural wax such as carnauba wax and candelilla wax and derivatives thereof Fatty acids such as higher fatty alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones , Hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, and silicone resins.

  Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products.

(Polymerizable monomer)
Preferred examples of the polymerizable monomer in the suspension polymerization method include the following vinyl polymerizable monomers. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, ethyl Acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl Acrylic polymerizable monomers such as acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n- Propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethylphos Fate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic polymerizable monomers such as acrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl Vinyl ethers such as ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  Further, a polymerization initiator may be added during the polymerization of the polymerizable monomer. The following are mentioned as a polymerization initiator. 2,2′-azobis- (2,4-divaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyloxy carbonate, cumene hydroperoxide, 2,4-dichloro Peroxide polymerization initiators such as benzoyl peroxide and lauroyl peroxide. These polymerization initiators are preferably added in an amount of 0.5 to 30.0% by mass relative to the polymerizable monomer, and may be used alone or in combination.

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

  On the other hand, in order to control the molecular weight of the binder resin constituting the toner particles, a crosslinking agent may be added during the polymerization of the polymerizable monomer. The following are mentioned as a crosslinking agent. 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 the above acrylates were changed to methacrylate The.

  The following are mentioned as a polyfunctional crosslinking agent. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate thereof, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylphthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate. As an addition amount of a crosslinking agent, it is preferable that it is 0.001-15,000 mass% with respect to a polymerizable monomer.

  The binder resin constituting the toner particles is preferably a vinyl resin. The vinyl resin is produced by polymerization of the vinyl polymerizable monomer described above. Vinyl resin is excellent in environmental stability. In addition, the vinyl-based resin is excellent in the precipitation property on the toner particle surface, surface uniformity, and long-term storage stability of the organosilicon polymer obtained by polymerizing the compound having the structure represented by the formula (Z). Therefore, it is preferable.

(Dispersion stabilizer)
When the medium used in the polymerization of the polymerizable monomer is an aqueous medium, the following can be used as a dispersion stabilizer for the particles of the polymerizable monomer composition. 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, alumina . Examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, starch.

  Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate.

  In the present invention, when an aqueous medium is prepared using a hardly water-soluble inorganic dispersion stabilizer, the amount of these dispersion stabilizers added is 0.2 with respect to 100.0 parts by mass of the polymerizable monomer. It is preferable that it is -2.0 mass parts. Moreover, it is preferable to prepare an aqueous medium using 300-3,000 mass parts water with respect to 100 mass parts of polymerizable monomer compositions.

  In the present invention, when preparing an aqueous medium in which the above poorly water-soluble inorganic dispersant is dispersed, a commercially available dispersion stabilizer may be used as it is. In order to obtain a dispersion stabilizer having a fine and uniform particle size, a poorly water-soluble inorganic dispersant may be produced in a liquid medium such as water under high-speed stirring. Specifically, when tricalcium phosphate is used as a dispersion stabilizer, a preferred dispersion stabilizer is formed by mixing a sodium phosphate aqueous solution and a calcium chloride aqueous solution under high-speed stirring to form fine particles of tricalcium phosphate. Can be obtained.

(Coloring agent)
The colorant used in the toner of the present invention is not particularly limited, and known ones shown below 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, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment Yellow 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 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, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 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, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment Blue 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 a solid solution state.

  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 may be modified by subjecting the colorant to a surface treatment 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.

  A preferable method for treating the dye includes a method in which a polymerizable monomer is previously polymerized in the presence of the dye and the obtained colored polymer is added to the polymerizable monomer composition. Moreover, about carbon black, you may process with the substance (for example, organosiloxane etc.) which reacts with the surface functional group of carbon black besides the process similar to the said dye.

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

(Charge control agent)
The toner of the present invention may have a charge control agent. A well-known thing can be used as said 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 the toner to be negatively charged include the following. As organometallic compounds and chelate compounds, monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acid metal compounds. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, 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. Examples of the charge control agent that controls the toner 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 the like Onium salts such as phosphonium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (phosphorungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, Gallic acid, ferricyanide, ferrocyanide, etc.); metal salt of higher fatty acid; resin charge control agent. These charge control agents can be contained alone or in combination of two or more. Among these charge control agents, metal-containing salicylic acid compounds are preferable, and the metal is particularly preferably aluminum or zirconium. The most preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound.

  The charge control agent that can be used in the present invention is preferably a polymer having a sulfonic acid functional group. The polymer having a sulfonic acid functional group is a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group.

  Examples of the polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group include a polymer compound having a sulfonic acid group in the side chain. In particular, styrene and / or styrene (meta) containing a sulfonic acid group-containing (meth) acrylamide monomer in a copolymerization ratio of 2% by mass or more, preferably 5% by mass or more and having a glass transition temperature (Tg) of 40 to 90 ° C. ) A polymer compound which is an acrylate copolymer is preferred. Charge stability under high humidity is improved.

  As said sulfonic-acid-group-containing (meth) acrylamide type monomer, what can be represented by the following general formula (X) is preferable, and 2-acrylamido-2-methylpropanoic acid and 2-methacrylamido-2-methyl are specifically mentioned. And propanoic acid.

［上記一般式（Ｘ）中、Ｒ₁は水素原子、又はメチル基を示し、Ｒ₁とＲ₃は、それぞれ水素原子、Ｃ₁〜Ｃ₁₀のアルキル基、アルケニル基、アリール基又はアルコキシ基を示し、ｎは１〜１０の整数を示す。］

[In the general formula (X), R ₁ represents a hydrogen atom or a methyl group, and R ₁ and R ₃ represent a hydrogen atom, a C _{1 to} C ₁₀ alkyl group, an alkenyl group, an aryl group, or an alkoxy group, respectively. N represents an integer of 1 to 10. ]

  The polymer having a sulfonic acid group according to the present invention contains 0.1 to 10.0 parts by mass of the binder resin in 100 parts by mass of the binder resin, so that the toner can be used in combination with a water-soluble initiator. The charged state can be further improved.

  The addition amount of these charge control agents is preferably 0.01 to 10.00 parts by mass with respect to 100.00 parts by mass of the binder resin or polymerizable monomer.

  The toner of the present invention can be obtained by externally adding various organic or inorganic fine powders to toner particles for the purpose of imparting various properties. The organic or inorganic fine powder preferably has a particle size of 1/10 or less of the weight average particle size of the toner particles in view of durability when added to the toner particles.

(Organic or inorganic fine powder)
The following organic or inorganic fine powders are used.
(1) Fluidity imparting agent: silica, alumina, titanium oxide, carbon black, and carbon fluoride.
(2) Abrasive: metal oxide such as strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide, nitride such as silicon nitride, carbide such as silicon carbide, metal such as calcium sulfate, barium sulfate, calcium carbonate salt.
(3) Lubricant: Fluorine resin powders such as vinylidene fluoride and polytetrafluoroethylene, and fatty acid metal salts such as zinc stearate and calcium stearate.
(4) Charge controllable particles: metal oxides such as tin oxide, titanium oxide, zinc oxide, silica and alumina, carbon black.

  The organic fine powder or the inorganic fine powder treats the surface of the toner particles in order to improve the fluidity of the toner and to make the charge of the toner uniform. By adjusting the hydrophobicity of the organic or inorganic fine powder, it is possible to adjust the chargeability of the toner and improve the charging characteristics in a high humidity environment. Therefore, the organic or inorganic fine powder subjected to the hydrophobic treatment is used. It is preferable. When the organic or inorganic fine powder added to the toner absorbs moisture, the chargeability as the toner is lowered, and the developability and transferability are easily lowered.

  As treatment agents for the hydrophobic treatment of organic fine powder or inorganic fine powder, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, and other organic silicon Examples of the compound include organic titanium compounds. These treatment agents may be used alone or in combination.

  Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, the inorganic fine powder is treated with silicone oil at the same time or after the hydrophobic treatment with the coupling agent. Hydrophobized inorganic fine powder treated with silicone oil is preferable for maintaining a high toner charge amount even under a high humidity environment and reducing selective developability.

  The addition amount of these organic fine powder or inorganic fine powder is preferably 0.01 to 10.00 parts by weight, more preferably 0.02 to 1.00 parts by weight with respect to 100.00 parts by weight of the toner particles. It is preferable that it is 0.03-1.00 mass part. Component contamination due to embedding and release of organic fine powder or inorganic fine powder in toner particles is improved. These organic fine powders or inorganic fine powders may be used alone or in combination.

Here, the BET specific surface area of the organic fine powder or the inorganic fine powder is preferably 10 m ² / g or more and 450 m ² / g or less.

The specific surface area BET of the organic fine powder or inorganic fine powder can be determined by a low temperature gas adsorption method by a dynamic constant pressure method according to the BET method (preferably the BET multipoint method). For example, by using a specific surface area measuring device “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. m ² / g) can be calculated.

  The organic fine powder or inorganic fine powder may be firmly fixed or adhered to the toner particle surface. For firmly fixing or adhering to the surface of the toner particles of the present invention, a Henschel mixer, mechanofusion, cyclomix, turbulizer, flexomix, hybridization, mechanohybrid, and nobilta can be used.

  Further, the organic fine powder or the inorganic fine powder can be strongly fixed or adhered by increasing the rotational peripheral speed or extending the processing time.

(Viscosity by capillary rheometer)
The 80 ° C. viscosity of the toner of the present invention measured by a constant load extrusion type capillary rheometer is preferably 1,000 Pa · s or more and 40,000 Pa · s or less. When the 80 ° C. viscosity is 1,000 to 40,000 Pa · s, the toner has excellent low-temperature fixability. The viscosity at 80 ° C. is more preferably 2,000 Pa · s to 20,000 Pa · s. In the present invention, the 80 ° C. viscosity can be adjusted by the addition amount of the low molecular weight resin, the monomer species at the time of producing the binder resin, the initiator amount, the reaction temperature, and the reaction time.

  The value of 80 ° C. viscosity measured by a constant-load extrusion type capillary rheometer of toner can be obtained by the following method.

As an apparatus, for example, a flow tester CFT-500D (manufactured by Shimadzu Corporation) is used, and measurement is performed under the following conditions.
Sample: About 1.0 g of toner is weighed and molded using a pressure molding machine at a load of 100 kg / cm ² for 1 minute to obtain a sample.
-Die hole diameter: 1.0 mm
-Die length: 1.0 mm
・ Cylinder pressure: 9.807 × 10 ⁵ (Pa)
・ Measurement mode: Temperature rising method ・ Temperature rising speed: 4.0 ° C./min

  By the above method, the viscosity (Pa · s) of the toner at 30 to 200 ° C. is measured to obtain the viscosity (Pa · s) at 80 ° C. This value is the 80 ° C. viscosity measured by a capillary rheometer of the toner constant load extrusion method.

(Weight average particle diameter of toner (D4))
The weight average particle diameter (D4) of the toner of the present invention is preferably 4.0 to 9.0 μm, more preferably 5.0 to 8.0 μm, and still more preferably 5.0 to 7.0 μm. It is.

(Glass transition temperature (Tg) of toner)
The glass transition temperature (Tg) of the toner of the present invention is preferably 35 to 100 ° C, more preferably 40 to 80 ° C, and still more preferably 45 to 70 ° C. When the glass transition temperature is in the above range, the blocking resistance, the low temperature offset resistance, and the transparency of the transmission image of the overhead projector film can be further improved.

(THF insoluble in toner)
The content of insoluble content of tetrahydrofuran (THF) in the toner of the present invention is preferably less than 50.0% by mass, more preferably 0.0% by mass with respect to toner components other than the toner colorant and inorganic fine powder. % Or more and less than 45.0% by mass, and more preferably 5.0% by mass or more and less than 40.0% by mass. By setting the content of the THF-insoluble matter to less than 50.0% by mass, the low-temperature fixability can be improved.

  The content of the THF-insoluble matter in the toner means the mass ratio of the ultra-high polymer component (substantially crosslinked polymer) that has become insoluble in the THF solvent. In the present invention, the content of the THF-insoluble matter in the toner is a value measured as follows.

1.0 g of toner is weighed (W1 g), placed in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Filter Paper), subjected to a Soxhlet extractor, extracted for 20 hours using 200 ml of THF as a solvent, and soluble components extracted by the solvent are extracted. After concentration, vacuum drying is performed at 40 ° C. for several hours, and the amount of THF-soluble resin component is weighed (W2 g). The mass of components other than the resin component such as a pigment in the toner is (W3 g). The THF-insoluble content is obtained from the following formula.
Content (mass%) of THF-insoluble matter = {(W1- (W3 + W2)) / (W1-W3)} × 100

  The content of the toner insoluble matter in the toner can be adjusted by the degree of polymerization and the degree of crosslinking of the binder resin.

(Weight average molecular weight of toner)
In the present invention, the weight average molecular weight (Mw) (hereinafter also referred to as the weight average molecular weight of the toner) measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble part of the toner is 5,000 to 50. , 000 is preferable. When the weight average molecular weight (Mw) of the toner is within the above range, blocking resistance and development durability, low-temperature fixability, and high gloss of an image can be established. In the present invention, the weight average molecular weight (Mw) of the toner includes the addition amount and the weight average molecular weight (Mw) of the low molecular resin, the reaction temperature, the reaction time, the initiator amount, the chain transfer agent amount, and the crosslinking amount at the time of toner production. It can be adjusted by the amount of the agent.

  In the present invention, the ratio [Mw / Mn] of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble part of the toner is: It is preferably 5.0 to 100.0, and more preferably 5 to 30. When [Mw / Mn] is within the above range, the fixable temperature range can be widened.

<Method for adjusting THF-insoluble content of toner particles>
The tetrahydrofuran (THF) insoluble content of the toner particles of the present invention was adjusted as follows. 10.0 g of toner is weighed, put into a cylindrical filter paper (for example, Toyo Filter Paper No. 86R), passed through a Soxhlet extractor, extracted with 200 ml of THF as a solvent for 20 hours, and the filtrate in the cylindrical filter paper at 40 ° C. for several hours. The product obtained by vacuum drying was used as the THF-insoluble content of the toner particles for NMR measurement.

<Method for measuring acid value of resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

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

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

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

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

The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.611] / S
(In the formula, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide ethyl alcohol solution in blank test (ml), C: addition amount (ml) of potassium hydroxide ethyl alcohol solution in this test, f: Factor of potassium hydroxide solution, S: Sample (g))

<Measurement method of hydroxyl value of resin>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

  Add 25.0 g of special grade acetic anhydride to a 100 ml volumetric flask, add pyridine to a total volume of 100 ml and shake well to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.

  Titration is performed using a 1.0 mol / l potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potentiometric titrator AT-510 manufactured by Kyoto Electronics Co., Ltd.).

  100 ml of 1.00 mol / l hydrochloric acid is placed in a 250 ml tall beaker, titrated with the potassium hydroxide solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 1.00 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

The measurement conditions for the hydroxyl value measurement are shown below.
Titration device: potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters at the time of titration are as follows.
Titration parameters Titration mode: Blank titration Titration style: Total titration Maximum titration: 80 ml
Waiting time before titration: 30 seconds Titration direction: Automatic control parameter end point determination potential: 30 dE
End point determination potential value: 50 dE / dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.5 ml

  2.00 g of the pulverized measurement sample is precisely weighed into a 200 ml round bottom flask, and 5.00 ml of the acetylating reagent is accurately added to this using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.

  Place a small funnel in the mouth of the flask and immerse 1 cm of the bottom of the flask in a 97 ° C. glycerin bath and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole.

  After 1 hour, the flask is removed from the glycerin bath and allowed to cool. After standing to cool, 1.00 ml of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further complete hydrolysis. After cooling, wash the funnel and flask walls with 5.00 ml of ethyl alcohol.

  The obtained sample is transferred to a 250 ml tall beaker, and 100 ml of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 1 hour. Titrate with the potassium hydroxide ethyl alcohol solution using the potentiometric titrator.

(B) Blank test Titration similar to the above operation is performed except that no sample is used.

(3) Substituting the obtained results into the following formula to calculate the hydroxyl value.
A = [{(BC) × 28.05 × f} / S] + D

  Here, A: hydroxyl value (mgKOH / g), B: addition amount (ml) of potassium hydroxide ethyl alcohol solution in blank test, C: addition amount (ml) of potassium hydroxide ethyl alcohol solution in this test, f : Factor of potassium hydroxide solution, S: Sample (g), D: Acid value of resin (mgKOH / g).

<Partial structure confirmation method of T3R, SX1, SX2, SX3 and SX4>
The partial structure confirmation method of T3R, SX1, SX2, SX3 and SX4 can be confirmed by ¹ H-NMR, ¹³ C-NMR and ²⁹ Si-NMR.

The presence or absence of a hydrocarbon group of the formula (T3R) was confirmed by ¹³ C-NMR and ²⁹ Si-NMR. A structure in which the number of O _1/2 bonded to silicon is 1.0 was defined as a structure (SX1). Further, the peak area of the (SX1) structure was defined as S (SX1). A structure in which the number of O _1/2 bonded to silicon is 4.0 was defined as a structure of (SX4). Further, the peak area of the (SX4) structure was defined as S (SX4).

（式（ＳＸ１）中のＲｉ、Ｒｊ、Ｒｋはケイ素に結合している有機基、ハロゲン原子、ヒドロキシ基またはアルコキシ基）

(In the formula (SX1), Ri, Rj and Rk are organic groups, halogen atoms, hydroxy groups or alkoxy groups bonded to silicon)

装置：ＢＲＵＫＥＲ製 ＡＶＡＮＣＥＩＩＩ ５００
プローブ：４ｍｍ ＭＡＳ ＢＢ／１Ｈ
測定温度：室温
試料回転数：６ｋＨｚ
試料：測定試料（ＮＭＲ測定用のトナー粒子のＴＨＦ不溶分）１５０ｍｇを直径４ｍｍのサンプルチューブに入れる。

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.

  The presence or absence of the R hydrocarbon group of the formula (T3R) was confirmed. If the signal was confirmed, the structure of the formula (T3R) was determined to be “Yes”.

"Measurement conditions for ¹³ C-NMR (solid)"
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

<Confirmation and quantification method of SX1, SX2, SX3 and SX4 structure>
The SX1, SX2, SX3 and SX4 structures were confirmed by ²⁹ Si-NMR.

"Measurement method of ²⁹ Si-NMR (solid)"
"Measurement condition"
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
²⁹ Si 90 ° Pulse width: 4.00 μs @ -1 dB
Contact time: 1.75 ms to 10 ms
Repeat time: 30 s (DD / MASS), 10 s (CP / MAS)
Integration count: 2048 times LB value: 50 Hz

  After the measurement, a plurality of silane components having different substituents and bonding groups of the toner particles are peak-separated into SX1 structure, SX2 structure, SX3 structure, and SX4 structure by curve fitting. Calculate mol% of ingredients. Curve fitting was performed using EXcalibur for Windows (registered trademark) version 4.2 (EX series), software for JNM-EX400 manufactured by JEOL. Click “1D Pro” from the menu icon to read the measurement data. Next, “Curve fitting functonon” was selected from “Command” on the menu bar, and curve fitting was performed. An example is shown in FIG. Peak splitting was 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), was the smallest.

  The area of the SX1 structure, the area of the SX2 structure, the area of the SX3 structure, and the area of the SX4 structure were obtained, and S (SX1), S (SX2), S (SX3), and S (SX4) were obtained by the following equations.

In the present invention, the silane monomer is specified by the chemical shift value, and the ²⁹ Si-NMR measurement of the toner particles is used to determine the silane monomer component from the total peak area of the organosilicon polymer having a partial structure represented by the formula (T3R). The removed area was designated as SS.
SX1 structure area + SX2 structure area + SX3 structure area + SX4 structure area = SS
S (SX1) + S (SX2) + S (SX3) + S (SX4) = 1.0
S (SX1) = area of SX1 structure / SS)
S (SX2) = area of SX2 structure / SS
S (SX3) = area of SX3 structure / SS
S (SX4) = area of SX4 structure / SS

For example, chemical shift values of silicon in the partial structures represented by formula (SX1), formula (SX2), formula (SX3), and formula (SX4) are shown below.
Example of SX1 structure (Y = —OC ₂ H ₅ , —OC ₂ H ₅ , —CH ₃ ): −47 ppm
Example of SX2 structure (Y = —OC ₂ H ₅ , —CH ₃ ): −56 ppm
Example of T3R structure (R = —CH ₃ ): −65 ppm

Further, the chemical shift value of silicon in the case of having the SX4 structure is shown below.
SX4 structure: -108 ppm

<Dav. Of average thickness of surface layer containing organosilicon polymer of toner particles measured by observation of cross section of toner particles using transmission electron microscope (TEM). And measurement of ratio of surface layer containing organosilicon polymer having average thickness of 2.5 nm or less>
The cross section of the toner particles of the present invention can be observed by the following method.

  As a specific method for observing the cross section, 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. Using a transmission electron microscope (TEM), the cross section of the toner is observed at a magnification of 10,000 to 100,000. In the present invention, the difference between the atomic weights of the binder resin and the organosilicon compound to be used is utilized, and the confirmation is made by 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.

  Furthermore, a TEM bright field image was acquired at an acceleration voltage of 200 kV using an electron microscope Tecnai TF20XT manufactured by FEI. Next, using an EELS detector GIF Tridiem manufactured by Gatan, an EF mapping image of the Si-K end (99 eV) was obtained by the Three Window method, and it was confirmed that the organosilicon polymer was present on the surface layer.

  The average thickness Dav. Of the surface layer containing the organosilicon polymer of toner particles by TEM. In addition, the particles for determining the ratio of the surface layer containing the organosilicon polymer having an average thickness of 2.5 nm or less are obtained by calculating the equivalent circle diameter Dtem from the cross-sectional area of the toner obtained from the TEM micrograph, and the value is the Coulter The particles included in a width of ± 10% of the weight average particle diameter determined by the method described later using a counter are defined as the corresponding particles.

  One toner particle corresponding to the above is divided into 16 equal parts around the intersection of the long axis L90 and the vertical axis L90 passing through the center of the long axis L (see FIG. 1). Next, the axis from the center is An (n = 1 to 32), the axis length is RAn, and the thickness of the toner surface layer containing the organosilicon polymer is FRAn. The average thickness D of the surface layer containing the organosilicon polymer of the 32 toner particles on the shaft is determined. A ratio (%) in which the thickness of the surface layer containing the organosilicon polymer in 32 locations on the shaft is 2.5 nm or less is obtained.

  In the present invention, 10 particles were measured for averaging, and the average value per particle was calculated.

[Equivalent circle diameter Dtem obtained from cross-sectional area of toner obtained from TEM micrograph]
The equivalent circle diameter Dtem obtained from the cross-sectional area of the toner obtained from a TEM micrograph was obtained by the method described later.
Equivalent circle diameter Dtem determined from the cross-sectional area of the toner obtained from the TEM micrographs = (RA1 + RA2 + RA3 + RA4 + RA5 + RA6 + RA7 + RA8 + RA9 + RA10 + RA11 + RA12 + RA13 + RA14 + RA15 + RA16 + RA17 + RA18 + RA19 + RA22 + RA21 + RA22 + RA23 + RA26 + RA22 + RA24 + RA22 + RA24 + RA24 + RA22 + RA24 + RA24 + RA24 + RA24 + RA24 + RA24 + RA24 + RA24 + RA24 + RA24 + RA26 +

  The equivalent circle diameter of 10 particles was obtained, the value per particle was calculated, and the equivalent circle diameter obtained from the cross-sectional area of the toner was calculated as Dtemav. And

[Average thickness Dav. Of surface layer of toner particles containing organosilicon polymer] ]
The average thickness Dav. Of the surface layer of the toner particles containing the organosilicon polymer. Was determined by the following method.

First, the average thickness D ⁽ⁿ⁾ of the surface layer containing the organosilicon polymer of one toner particle was determined by the following method.
D ⁽ⁿ⁾ = (total of 32 locations of the thickness of the surface layer containing the organosilicon polymer on the shaft) / 32

This calculation was performed for 10 toner particles. The average value per toner particle is calculated from the thickness D ⁽ⁿ⁾ (n is an integer of 1 to 10 ⁾ of the surface layer of the obtained toner particles according to the following formula, and the surface layer containing the organosilicon polymer of the toner particles Average thickness Dav. Asked.
Dav. = {D ⁽¹⁾ + D ⁽²⁾ + D ⁽³⁾ + D ⁽⁴⁾ + D ⁽⁵⁾ + D ⁽⁶⁾ + D ⁽⁷⁾ + D ⁽⁸⁾ + D ⁽⁹⁾ + D ⁽¹⁰⁾ } / 10

[Ratio of the surface layer containing the organosilicon polymer in which the thickness FRAn of the surface layer containing the organosilicon polymer is 2.5 nm or less]
The ratio of the surface layer containing the organosilicon polymer in which the thickness FRAn of the surface layer containing the organosilicon polymer is 2.5 nm or less was determined by the following method.

First, the ratio of the surface layer containing an organosilicon polymer having a thickness FRAN of 2.5 nm or less with respect to one toner particle was determined based on the following formula.
(Ratio of the surface layer containing the organosilicon polymer in which the thickness FRAn of the surface layer containing the organosilicon polymer is 2.5 nm or less) = ((the thickness FRAN of the surface layer containing the organosilicon polymer is 2.5 nm or less) Number) / 32) × 100

  This calculation was performed for 10 toner particles. Thickness of the surface layer containing the organosilicon polymer of the toner particles The average value is obtained from the ratio of the surface layer containing the organosilicon polymer having a thickness FRAN of 2.5 nm or less containing the organosilicon polymer. It was set as the ratio of the surface layer containing the organosilicon polymer whose FRAn is 2.5 nm or less.

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

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

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

<Method of measuring weight average molecular weight (Mw), number average molecular weight (Mn) and main peak molecular weight (Mp) of toner and various resins>
The weight average molecular weight (Mw), number average molecular weight (Mn), and main peak molecular weight (Mp) of the toner and various resins are measured under the following conditions using gel permeation chromatography (GPC).

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

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

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

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

<Method for Measuring Glass Transition Temperature (Tg) of Toner and Various Resins>
The glass transition temperature (Tg) of the toner and various resins is measured according to the following procedure using a differential scanning calorimeter (DSC) M-DSC (trade name: Q2000, manufactured by TA Instruments). Weigh precisely 3 mg of the sample (toner, various resins) to be measured. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 1 ° C./min and normal temperature and humidity in a measurement temperature range of 20 to 200 ° C. Measurement is performed at a modulation amplitude of ± 0.5 ° C. and a frequency of 1 / min. The glass transition temperature (Tg: ° C.) is calculated from the obtained reversing heat flow curve. Tg is obtained as Tg (° C.) as the center value of the intersection of the baseline before and after endotherm and the tangent of the curve due to endotherm.

  In the endothermic chart at the time of temperature rise measured by DSC, the integrated value of heat per gram of toner (J / g) represented by the peak area of the endothermic main peak was measured. An example of a reversing flow curve obtained by DSC measurement of the toner is shown in FIG.

  The calorie integral value (J / g) is obtained using the reversing flow curve obtained from the above measurement. For the calculation, analysis software Universal Analysis 2000 for Windows (registered trademark) 2000 / XP Version 4.3A (manufactured by TA Instruments) was used, and a straight line connecting the measurement points at 35 ° C. and 135 ° C. using the function of Integral Peak Linear. And an integral value of heat (J / g) are determined from the region surrounded by the endothermic curve.

<Method for Measuring Weight Average Particle Size (D4) and Number Average Particle Size (D1) of Toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are measured with a fine particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, Beckman 2) Effective measurement channel number 25,000 using “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) and attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” for measurement condition setting and measurement data analysis Measure in the channel, analyze the measurement data, and calculate.

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

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

  In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.

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

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion exchange water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is put, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. 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) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . 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. When the graph / volume% is set with the dedicated software, the “average diameter” on the analysis / volume statistics (arithmetic average) screen is the weight average particle size (D4), and the graph / number% is set with the dedicated software. The “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

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

  A suitable amount of a surfactant, preferably an alkylbenzene sulfonate, is added to 20 ml of ion-exchanged water, and then 0.02 g of a measurement sample is added. A desktop ultrasonic cleaner with an oscillation frequency of 50 kHz and an electric output of 150 watts. Dispersion treatment is performed for 2 minutes using a disperser (for example, “VS-150” (manufactured by Vervo Creer, etc.) to obtain a dispersion for measurement, and the temperature of the dispersion is 10 ° C. or more and 40 ° C. or less. Cool as appropriate.

  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 prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, 3000 toner particles are measured in the total count mode in the HPF measurement mode, and the binarization threshold at the time of particle analysis is 85%. The analysis particle diameter is limited to the equivalent circle 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, Duke Scientific 5100A diluted with ion-exchanged water) before the start of measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  Further, in the circularity distribution of the toner, when the mode circularity is 0.98 to 1.00, 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 to the photoreceptor due to the mirror image force, van der Waals force, etc. becomes more remarkable, and the transfer efficiency becomes very 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 It is divided into 61 every 0.01 as 1.00, and the measured circularity of each particle is assigned to each divided range, and the circularity of the divided range where the frequency value is maximum in the circularity frequency distribution is said.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In addition, the part in the following mixing | blending shows a mass part unless there is particular description.

  A production example of the charge control agent used in the present invention will be described.

<Synthesis example of vinyl monomer a>
(Process 1)
100 g of 2,5-dihydroxybenzoic acid and 1441 g of 80% sulfuric acid were heated and mixed at 50 ° C. To this dispersion, 144 g of tert-butyl alcohol was added and stirred at 50 ° C. for 30 minutes. Thereafter, 144 g of tert-butyl alcohol was added to this dispersion and stirring was performed for 30 minutes three times. The reaction solution was cooled to room temperature and poured slowly into 1 kg of ice water. The precipitate was filtered, washed with water, and then washed with hexane. This precipitate was dissolved in 200 mL of methanol and reprecipitated in 3.6 L of water. After filtration, it was dried at 80 ° C. to obtain 74.9 g of a salicylic acid intermediate represented by the following formula (4).

式（４）

Formula (4)

(Process 2)
25.0 g of the obtained salicylic acid intermediate was dissolved in 150 mL of methanol, 37.0 g of potassium carbonate was added, and the mixture was heated to 65 ° C. To this reaction solution, a mixture of 19.0 g of 4- (chloromethyl) styrene and 100 mL of methanol was added dropwise and reacted at 65 ° C. for 3 hours. The reaction solution was cooled and then filtered, and the filtrate was concentrated to obtain a crude product. The crude product was dispersed in 1.5 L of water at pH = 2 and extracted by adding ethyl acetate. Thereafter, it was washed with water and dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and purified by recrystallization from toluene and ethyl acetate to obtain 22.4 g of vinyl monomer a represented by the following formula (5).

式（５）

Formula (5)

<Synthesis of vinyl monomer b>
Except for changing the salicylic acid intermediate of the formula (4) to 20 g of 2,4-dihydroxybenzoic acid, the vinyl monomer b of the following formula (6) is synthesized in the same manner as the synthesis of the vinyl monomer a (step 2). Got.

式（６）

Formula (6)

<Synthesis of vinyl monomer c>
Synthesis of vinyl monomer a (step 2), except that the formula (4) salicylic acid intermediate is changed to 2,5-dihydroxybenzoic acid and 4- (chloromethyl) styrene is changed to p-aminobenzyl chloride. By the same method, the vinyl monomer c of the following formula (7) was obtained.

式（７）

Formula (7)

<Synthesis Example of Charge Control Agent (1)>
9.90 g of vinyl monomer a represented by formula (5) and 60.0 g of styrene were dissolved in 40.0 ml of toluene, stirred for 1 hour, and then heated to 110 ° C. To this reaction solution, a mixed solution of 4.60 g of tert-butyl peroxyisopropyl monocarbonate (trade name Perbutyl I, manufactured by NOF Corporation) and 40.0 ml of toluene was added dropwise. Furthermore, it reacted at 110 degreeC for 4 hours. Then, it cooled and it was dripped at methanol 1L, and the deposit was obtained. The obtained precipitate was dissolved in 120 ml of THF and then added dropwise to 1.80 L of methanol to precipitate a white precipitate, which was filtered and dried at 90 ° C. under reduced pressure, whereby 58. 0 g was obtained.

<Synthesis Example of Charge Control Agent (2)>
In the synthesis example of the charge control agent 1, the same procedure as in the synthesis example of the charge control agent (1) was performed except that 9.90 g of vinyl monomer a shown in formula (5) was changed to 9.90 g of vinyl monomer b. Thus, a charge control agent (2) was obtained.

<Synthesis Example of Charge Control Agent (3)>
-Bisphenol A-Propylene oxide 2.2 mol adduct 68.0 parts-Terephthalic acid 22.0 parts-Trimellitic anhydride 10.0 parts-Dibutyltin oxide 0.00500 parts in a four-necked flask, thermometer Then, a stir bar, a condenser, and a nitrogen introducing tube were attached, and the reaction was carried out at 215 ° C. for 5 hours in a nitrogen atmosphere to obtain polyester resin P.

  In a reaction vessel, 85.0 parts of the obtained polyester resin P and 16.0 parts of a compound represented by the following formula (7) were placed, and a condenser, a stirrer, and a thermometer were immersed therein. After adding 270 parts of pyridine and stirring, 95.0 parts of triphenyl phosphite is added and stirred at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 360 parts of ethanol. The obtained polymer was washed twice with 140 parts of 1N hydrochloric acid, then washed twice with 140 parts of water, and dried under reduced pressure to obtain a charge control agent (3). The hydroxyl value was measured and the content of the component derived from the formula (7) was confirmed.

<Production Example of Charge Control Agent A1>
In a reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 250 parts of methanol as a solvent, 150 parts of 2-butanone and 100 parts of 2-propanol, and 88 parts of styrene as a monomer Then, 6.0 parts of 2-ethylhexyl acrylate and 6.0 parts of 2-acrylamido-2-methylpropanesulfonic acid were added and heated under reflux at normal pressure with stirring. A solution prepared by diluting 1.1 parts of 2,2′-azobisisobutyronitrile as a polymerization initiator with 20 parts of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 5 hours. Further, a solution obtained by diluting 1.0 part of 2,2′-azobisisobutyronitrile with 20 parts of 2-butanone was added dropwise over 30 minutes, and further stirred for 5 hours under reflux at normal pressure to complete the polymerization. did.

  Next, the polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less by a cutter mill equipped with a 150 mesh screen, and further finely pulverized by a jet mill. The fine powder was classified with a 250 mesh sieve to obtain particles of 60 μm or less. Next, methyl ethyl ketone was added to dissolve the particles so as to have a concentration of 10%, and the resulting solution was gradually poured into 20 times the amount of methyl ethyl ketone in methanol for reprecipitation. The resulting precipitate was washed with one-half the amount of methanol used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours.

  Furthermore, methyl ethyl ketone was added and redissolved so that the particles after the vacuum drying had a concentration of 10%, and the obtained solution was gradually poured into n-hexane 20 times the amount of methyl ethyl ketone and reprecipitated. The obtained precipitate was washed with half the amount of n-hexane used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours. The charge control agent thus obtained has a Tg of about 82 ° C., a main peak molecular weight (Mp) of 18,200, a number average molecular weight (Mn) of 11,500, and a weight average molecular weight (Mw) of 19,800. The acid value was 16.2 mg KOH / g. Let the obtained resin be charge control agent A1.

<Example of production of polyester resin (1)>
・ Terephthalic acid: 11.2 mol
Bisphenol A-propylene oxide 2 mol adduct (PO-BPA): 11.1 mol
The above monomer is charged into an autoclave together with an esterification catalyst, and a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirring device are attached to the autoclave, and the pressure is reduced to 210 ° C. according to a conventional method while reducing the pressure in a nitrogen atmosphere. The polyester resin 1 was obtained by reacting until Tg reached 70 ° C. The weight average molecular weight (Mw) was 6,400, and the number average molecular weight (Mn) was 3,400.

<Example of production of polyester resin (2)>
(Synthesis of isocyanate group-containing prepolymer)
Bisphenol A ethylene oxide 2 mol adduct 725 parts phthalic acid 290 parts dibutyltin oxide 3.0 parts Stirred at 215 ° C for 8 hours, further reacted under reduced pressure for 5 hours, then cooled to 80 ° C, Reaction with 190 parts of isophorone diisocyanate in ethyl acetate for 2 hours gave an isocyanate group-containing polyester resin. 25 parts of the isocyanate group-containing polyester resin and 1 part of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain a polyester resin (2) mainly composed of a polyester containing a urea group. The resulting polyester resin (2) had a weight average molecular weight (Mw) of 23100, a number average molecular weight (Mn) of 3100, and a peak molecular weight of 7200.

<Production Example of Toner Particle 1>
In a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 700 parts of ion exchange water, 1000 parts of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, and 1.0 mol of an aqueous HCl solution 22.0 parts was added and kept at 60 ° C. while stirring at 12,000 rpm using a high-speed stirring device TK-homomixer. To this, 85 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene 70.0 parts n-Butyl acrylate 30.0 parts Methyltriethoxysilane 1.0 part Copper phthalocyanine pigment (Pigment Blue 15: 3) (P.B.15: 3) 6.5 parts Polyester resin (1) 4.0 parts charge control agent (1) 0.4 parts charge control agent (A1) 0.5 parts release agent [behenyl behenate, endothermic main peak temperature 72.1 ° C.] 10.0 parts The polymerizable monomer composition 1 obtained by dispersing for 3 hours with a lighter was held at 60 ° C. for 20 minutes. Thereafter, the polymerizable monomer composition 1 in which 15.0 parts of t-butyl peroxypivalate as a polymerization initiator (toluene solution 50%) was added to the polymerizable monomer composition 1 was added to the aqueous dispersion medium. And granulated for 10 minutes while maintaining the rotation speed of the high-speed agitator at 12,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 72 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring. At this time, the pH of the aqueous medium was 5.1. Next, 10.0 parts of 1.0N NaOH was added to adjust the pH to 8.0, and the temperature inside the container was raised to 90 ° C. and maintained for 7.5 hours. Thereafter, 4.0 parts of 10% hydrochloric acid was added to 50 parts of ion-exchanged water to adjust the pH to 5.1. Next, 300 parts of ion exchange water was added, the reflux tube was removed, and a distillation apparatus was attached. Distillation at a temperature in the vessel of 100 ° C. was performed for 5 hours to obtain a polymer slurry 1. The distillation fraction was 300 parts. Dilute hydrochloric acid was added to the container containing the polymer slurry 1 after cooling to 30 ° C. to remove the dispersion stabilizer. Further, the toner particles having a weight average particle diameter of 5.7 μm were obtained by filtration, washing and drying. This toner particle was designated as toner particle 1. The formulation and conditions of toner particles 1 are shown in Table 2, and the physical properties are shown in Table 7.

<Production Example of Toner Particle 2>
Toner particles 2 were obtained in the same manner as in the production example of toner particles 1 except that 1.00 parts of methyltriethoxysilane used in the production example of toner particles 1 was changed to 1.00 parts of phenyltrimethoxysilane. The formulation and conditions of toner particles 2 are shown in Table 2, and the physical properties are shown in Table 7.

<Production Example of Toner Particle 3>
Toner particles 3 were obtained in the same manner as in the production example of toner particles 1, except that 1.00 parts of ethyltrimethoxysilane was used instead of 1.00 parts of methyltriethoxysilane used in the production example of toner particles 1. The formulation and conditions of the toner particles 3 are shown in Table 2, and the physical properties are shown in Table 7.

<Production Example of Toner Particle 4>
Toner particles 4 are obtained in the same manner as in the production example of toner particles 1 except that 1.00 part of methyltriethoxysilane used in the production example of toner particle 1 is changed to 1.00 part of n-propyltriethoxysilane. It was. The formulation and conditions of the toner particles 4 are shown in Table 2, and the physical properties are shown in Table 7.

<Production Example of Toner Particle 5>
Toner particles 5 are obtained in the same manner as in the production example of toner particles 1 except that 1.00 parts of n-butyltriethoxysilane is used instead of 1.00 parts of methyltriethoxysilane used in the production example of toner particles 1. It was. The formulation and conditions of toner particles 5 are shown in Table 2, and the physical properties are shown in Table 7.

<Production Example of Toner Particle 6>
Instead of 1.00 part of methyltriethoxysilane used in the production example of toner particle 1, 0.70 part of methyltriethoxysilane and 0.30 part of methyltrichlorosilane were used. The toner particles 6 were obtained in the same manner as in the production example of the toner particles 1 except that the pH was adjusted to 5.1 in part. The formulation and conditions of toner particles 6 are shown in Table 2, and the physical properties are shown in Table 7.

<Production Example of Toner Particle 7>
Toner particles 7 were obtained in the same manner as in the production example of toner particles 1 except that 1.00 parts of methyltrimethoxysilane was used instead of 1.00 parts of methyltriethoxysilane used in the production example of toner particles 1. The formulation and conditions of the toner particles 7 are shown in Table 2, and the physical properties are shown in Table 7.

<Production Example of Toner Particle 8>
Toner particles 8 were obtained in the same manner as in the production example of toner particles 1 except that 1.00 parts of methyltriethoxypropoxysilane used in the production example of toner particles 1 was changed to 1.00 parts of methyltriisopropoxysilane. . The formulation and conditions of the toner particles 8 are shown in Table 2, and the physical properties are shown in Table 7.

<Production Example of Toner Particle 9>
Toner particles 9 were obtained in the same manner as in the production example of toner particles 1 except that 1.00 part of methyldiethoxychlorosilane was used instead of 1.00 parts of methyltriethoxysilane used in the production example of toner particles 1. The formulation and conditions of toner particles 9 are shown in Table 2, and the physical properties are shown in Table 7.

<Production Example of Toner Particle 10>
Toner particles 10 were obtained in the same manner as in the production example of toner particles 1 except that instead of 1.00 parts of methyltriethoxysilane used in the production example of toner particles 1, methyltriethoxysilane was changed to 0.50 parts. . The formulation and conditions of the toner particles 10 are shown in Table 2, and the physical properties are shown in Table 7.

<Production Example of Toner Particle 11>
Toner particles 11 were obtained in the same manner as in the production example of toner particles 1 except that 1.00 part of methyltriethoxysilane used in the production example of toner particle 1 was changed to 2.00 parts of methyltriethoxysilane. . The formulation and conditions of the toner particles 11 are shown in Table 3, and the physical properties are shown in Table 8.

<Production Example of Toner Particle 12>
Toner particles 12 were obtained in the same manner as in the production example of toner particles 1 except that methyltriethoxysilane used in the production example of toner particles 1 was changed to 3.00 parts instead of 1.00 parts of methyltriethoxysilane. . The formulation and conditions of the toner particles 12 are shown in Table 3, and the physical properties are shown in Table 8.

<Production Example of Toner Particle 13>
Toner particles 13 were obtained in the same manner as in the production example of toner particles 1 except that 1.00 parts of methyltriethoxysilane used in the production example of toner particles 1 were changed to 5.00 parts of methyltriethoxysilane. . The formulation and conditions of the toner particles 13 are shown in Table 3, and the physical properties are shown in Table 8.

<Production Example of Toner Particle 14>
Toner particles 14 were obtained in the same manner as in the toner particle 1 production example, except that instead of 1.00 parts of methyltriethoxysilane used in the toner particle 1 production example, 7.00 parts of methyltriethoxysilane was used. . The formulation and conditions of the toner particles 14 are shown in Table 3, and the physical properties are shown in Table 8.

<Production Example of Toner Particle 15>
In the production example of the toner particle 1, a solution of 1.2 parts of 10% hydrochloric acid and 50 parts of ion-exchanged water was added to change the pH to 4.0, and hydrochloric acid was not added after completion of the reaction 2. Toner particles 15 were obtained in the same manner as in the production example. The formulation and conditions of the toner particles 15 are shown in Table 3, and the physical properties are shown in Table 8.

<Production Example of Toner Particle 16>
In the production example of toner particles 1, 10.0 parts of 1.0N-NaOH was added to pH 8.0, and 10.0 parts of 1.0N-NaOH was changed to 20.0 parts of 1.0N-NaOH, pH 8.0. Was changed to pH 10.1, and after completion of the reaction 2, toner particles 16 were obtained in the same manner as in the production example of the toner particles 1 except that hydrochloric acid was added to adjust the pH to 5.2. The formulation and conditions of the toner particles 16 are shown in Table 3, and the physical properties are shown in Table 8.

<Production Example of Toner Particles 17>
In the production example of toner particles 1, 10.0 parts of 1.0N NaOH and 10.0 parts of 1.0N NaOH obtained by adjusting the pH to 8.0 are obtained. Was changed to pH 9.0, and after completion of the reaction 2, toner particles 17 were obtained in the same manner as in the production example of toner particles 1 except that hydrochloric acid was added to adjust the pH to 5.1. The formulation and conditions of toner particles 17 are shown in Table 3, and the physical properties are shown in Table 8.

<Production Example of Toner Particle 18>
A toner particle 1 production example except that methyltriethoxysilane 0.50 parts and ethyltriethoxysilane 0.50 parts were used instead of 1.00 parts methyltriethoxysilane used in the toner particle 1 production example. Similarly, toner particles 18 were obtained. The formulation and conditions of the toner particles 18 are shown in Table 3, and the physical properties are shown in Table 8.

<Production Example of Toner Particles 19>
Similar to the production example of the toner particle 1 except that instead of 1.00 part of the methyltriethoxysilane used in the production example of the toner particle 1, 0.76 part of methyltriethoxysilane and 0.24 part of tetraethoxysilane were used. Thus, toner particles 19 were obtained. The formulation and conditions of the toner particles 19 are shown in Table 3, and the physical properties are shown in Table 8.

<Production Example of Toner Particle 20>
Toner particle 1 production example, except that instead of 1.00 part of methyltriethoxysilane used in the production example of toner particle 1, 0.50 part of methyltriethoxysilane and 0.50 part of methyltrimethoxysilane were used. Similarly, toner particles 20 were obtained. The formulation and conditions of the toner particles 20 are shown in Table 3, and the physical properties are shown in Table 8.

<Production Example of Toner Particles 21>
In the production example of the toner particle 1, the temperature was raised to 90 ° C. and maintained for 7.5 hours, but the temperature was raised to 95 ° C. and maintained for 12 hours. Thus, toner particles 21 were obtained. The formulation and conditions of the toner particles 21 are shown in Table 4, and the physical properties are shown in Table 9.

<Production Example of Toner Particles 22>
In the production example of the toner particle 1, the temperature was raised to 90 ° C. and maintained for 7.5 hours, but the temperature was raised to 100 ° C. and maintained for 10 hours. Thus, toner particles 22 were obtained. The formulation and conditions of the toner particles 22 are shown in Table 4, and the physical properties are shown in Table 9.

<Production Example of Toner Particles 23>
[Production of Toner Base 23]
Polyester resin (1) 65.0 parts Polyester resin (2) 35.0 parts Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.5 parts Charge control agent (A2) 0.5 part Charge control agent (1 0.4 parts Release agent [behenyl behenate] 10.0 parts After mixing the above materials with a Henschel mixer, melt kneading with a twin-screw kneading extruder at 135 ° C, cooling the kneaded material, cutter mill The toner base material 23 having a weight average particle diameter of 5.6 μm was obtained by coarsely pulverizing with a fine pulverizer using a jet stream and further pulverizing with an air classifier.

[Production of Toner Particles 23]
In a four-necked vessel equipped with a Liebig reflux tube, 700 parts of ion-exchanged water, 1000 parts of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution and 24.0 parts of a 1.0 mol aqueous HCl solution were added, and high speed While stirring at 12,000 rpm using a stirrer TK-homomixer, the temperature was maintained at 60 ° C. To this, 85 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium 23 containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

  Next, a toner material prepared by mixing 125.9 parts of toner base 23 and 1.00 parts of methyltriethoxysilane with a Henschel mixer is added to the aqueous dispersion medium 23 stirred at 5,000 rpm with a TK-homomixer for 5 minutes. Stir.

  Subsequently, this mixed liquid was kept at 70 ° C. for 5 hours. The pH was 5.1. Next, 10.0 parts of 1.0N NaOH was added to adjust the pH to 8.0, and then the temperature was raised to 90 ° C. and maintained for 7.5 hours. Thereafter, 4.0 parts of 10% hydrochloric acid and 50 parts of ion-exchanged water were added to adjust the pH to 5.1. 300 parts of ion exchange water was added, the reflux tube was removed, and a distillation apparatus was attached. Next, distillation at a temperature in the container of 100 ° C. was performed for 5 hours to obtain a polymer slurry 23. The distillation fraction was 320 parts. Dilute hydrochloric acid was added to the container containing the polymer slurry 23 to remove the dispersion stabilizer. Silicon mapping was performed in the TEM observation of the toner particles 23, and it was confirmed that uniform silicon atoms were present on the surface layer. After filtering, washing and drying, toner particles having a weight average particle diameter of 5.6 μm were obtained. The toner particles were designated as toner particles 23. The formulation and conditions of the toner particles 23 are shown in Table 4, and the physical properties are shown in Table 9.

<Production Example of Toner Particles 24>
Polyester resin (1) 60.0 parts Polyester resin (2) 40.0 parts Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.5 parts Charge control agent (1) 0.4 part Charge control agent ( A1) 0.5 part Methyltriethoxysilane 1.00 part Release agent [behenyl behenate] 10 parts The above materials were dissolved in 400 parts of toluene to obtain a solution.

In a four-necked vessel equipped with a Liebig reflux tube, 700 parts of ion-exchanged water, 1000 parts of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution and 22.0 parts of a 1.0 mol aqueous HCl solution are added, and high speed While stirring at 12,000 rpm using a stirrer TK-homomixer, the temperature was maintained at 60 ° C. To this, 85 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium 24 containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

  Next, 100 parts of the solution was added to the aqueous dispersion medium 24 stirred at 12,000 rpm with a TK-homomixer and stirred for 5 minutes. Subsequently, this mixed liquid was kept at 70 ° C. for 5 hours. The pH was 5.1. 10.0 parts of 1.0 N NaOH was added to bring the pH to 8.0. Next, it heated up to 90 degreeC and hold | maintained for 7.5 hours. Thereafter, 4.0 parts of 10% hydrochloric acid and 50 parts of ion-exchanged water were added to adjust the pH to 5.1. 300 parts of ion exchange water was added, the reflux tube was removed, and a distillation apparatus was attached. Next, distillation at a temperature in the container of 100 ° C. was performed for 5 hours to obtain a polymer slurry 20. The distillation fraction was 300 parts. Dilute hydrochloric acid was added to the container containing the polymer slurry 24 to remove the dispersion stabilizer. Furthermore, the toner particles having a weight average particle diameter of 5.6 μm were obtained by filtration, washing and drying. The formulation and conditions of the toner particles 24 are shown in Table 4, and the physical properties are shown in Table 9.

<Production Example of Toner Particles 25>
“Synthesis of Amorphous Polyester Resin (1)”
-Bisphenol A ethylene oxide 2-mol adduct: 9 mol%
-Bisphenol A propylene oxide 2 mol adduct: 95 mol%
・ Terephthalic acid: 50 mol%
・ Fumaric acid: 30 mol%
-Dodecenyl succinic acid: 25 mol%
The above monomer was charged into a flask equipped with a stirrer, a nitrogen introduction tube, a temperature sensor, and a rectifying tower, and the temperature was raised to 200 ° C. over 1 hour, and it was confirmed that the reaction system was uniformly stirred.

  1.2% by mass of tin distearate was added relative to the total mass of these monomers. Furthermore, the temperature was raised from 20 ° C. to 250 ° C. over 3 hours while distilling off the generated water, and a dehydration condensation reaction was carried out at 250 ° C. for another 2 hours. As a result, the glass transition temperature was 58.1 ° C., the acid value was 15.8 mgKOH / g, the hydroxyl value was 27.4 mgKOH / g, the weight average molecular weight was 12,000, the number average molecular weight was 3,900, and the softening point was 109 ° C. Amorphous polyester resin (1) was obtained.

“Synthesis of Amorphous Polyester Resin (2)”
-Bisphenol A ethylene oxide 2-mol adduct: 48 mol%
(2-mole adduct in terms of both ends)
-Bisphenol A propylene oxide 2 mol adduct: 48 mol%
(2-mole adduct in terms of both ends)
・ Terephthalic acid: 65 mol%
-Dodecenyl succinic acid: 30 mol%
The above monomer was put into a flask equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, and a rectifying tower, and the temperature was raised to 200 ° C. over 1 hour, and it was confirmed that the inside of the reaction system was uniformly stirred.

  0.9 mass% of tin distearate was added with respect to the total mass of these monomers. Furthermore, the temperature was raised from 200 ° C. to 240 ° C. over 3 hours while distilling off generated water, and a dehydration condensation reaction was performed at 240 ° C. for another 2 hours. Next, the temperature was lowered to 190 ° C., 3 mol% of trimellitic anhydride was gradually added, and the reaction was continued at 190 ° C. for 1 hour. As a result, the glass transition temperature was 54.7 ° C., the acid value was 12.4 mgKOH / g, the hydroxyl value was 24.8 mgKOH / g, the weight average molecular weight was 43,400, the number average molecular weight was 5,400, and the softening point was 106 ° C. Amorphous polyester resin (2) was obtained.

"Preparation of resin particle dispersion (1)"
Amorphous polyester resin (1): 100 parts Methyl ethyl ketone: 50 parts Isopropyl alcohol: 20 parts Methyl ethyl ketone and isopropyl alcohol were charged into a container. Thereafter, the resin was gradually added, stirred, and completely dissolved to obtain an amorphous polyester resin (1) solution. The container containing the amorphous polyester solution was set at 65 ° C., and a 10% aqueous ammonia solution was gradually added dropwise to a total of 5 parts while stirring, and 200 parts of ion-exchanged water was further added at 10 ml / min. The solution was gradually added dropwise at a speed to effect phase inversion emulsification. Further, the solvent was removed by reducing the pressure with an evaporator to obtain a resin particle dispersion (1) of an amorphous polyester resin (1). The resin particles had a volume average particle size of 130 nm. The solid content of the resin particles was adjusted to 20% with ion exchange water.

"Preparation of resin particle dispersion (2)"
Amorphous polyester resin (2): 100 parts Methyl ethyl ketone: 50 parts Isopropyl alcohol: 20 parts Methyl ethyl ketone and isopropyl alcohol were charged into a container. Thereafter, the above materials were gradually added, stirred and completely dissolved to obtain an amorphous polyester resin (2) solution. The container containing the amorphous polyester resin (2) solution is set at 40 ° C., and a 10% aqueous ammonia solution is gradually added dropwise to a total of 4.0 parts with stirring. The portion was gradually added dropwise at a rate of 10 ml / min for phase inversion emulsification. Further, the solvent was removed under reduced pressure to obtain a resin particle dispersion (2) of an amorphous polyester resin (2). The volume average particle diameter of the resin particles was 135 nm. The solid content of the resin particles was adjusted to 20% with ion exchange water.

"Preparation of sol-gel solution of resin particle dispersion (1)"
Resin Particle Dispersion (1) 100 parts (20.0 parts solids) of methyltriethoxysilane was added to 20.0 parts of methyltriethoxysilane and held at 70 ° C. for 1 hour with stirring. Held for 3 hours. Thereafter, the mixture was cooled to obtain a sol-gel solution of resin particle dispersion (1) in which resin fine particles were coated with sol-gel. The resin particles had a volume average particle size of 210 nm. The solid content of the resin particles was adjusted to 20% with ion exchange water. The sol-gel solution of the resin particle dispersion (1) was stored at 10 ° C. or lower with stirring, and used within 48 hours after preparation. It is preferable that the particle surface is in a viscous sol or gel state because the adhesion between the particles is improved.

“Preparation of Colorant Particle Dispersion 1”
・ Copper phthalocyanine (Pigment Blue 15: 3): 45 parts ・ Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts ・ Ion-exchanged water: 190 parts The above ingredients were mixed and homogenizer (IKA) After dispersing for 10 minutes by ultra turrax), dispersion treatment is performed for 20 minutes at a pressure of 250 MPa using an optimizer (counter-impact type wet pulverizer: manufactured by Sugino Machine Co., Ltd.), and the volume average particle diameter of the colorant particles is 125 nm. Thus, a colorant particle dispersion 1 having a solid content of 20% was obtained.

"Preparation of release agent particle dispersion"
・ Olefin wax (melting point: 84 ° C.): 60 parts ・ Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 2.0 parts ・ Ion-exchanged water: 240 parts , Fully dispersed with IKA Ultra Turrax T50, then heated to 110 ° C. with a pressure discharge type gorin homogenizer and dispersed for 1 hour to disperse the release agent particles having a volume average particle size of 155 nm and a solid content of 20% A liquid was obtained.

“Preparation of Toner Particles 25”
-Resin particle dispersion (1): 19.5 parts-Resin particle dispersion (2): 80.0 parts-Sol-gel solution of resin particle dispersion (1): 2.0 parts-Colorant particle dispersion 1: 7.0 parts Release agent particle dispersion: 10.0 parts After adding 2.0 parts by weight of the ionic surfactant Neogen RK to the flask, the above materials were stirred. Subsequently, 1N nitric acid aqueous solution was dropped to adjust the pH to 3.6, 0.35 parts of aluminum polysulfate was added thereto, and the mixture was dispersed with an ultra turrax. The flask was heated to 50 ° C. with stirring in an oil bath for heating. After holding at 50 ° C. for 40 minutes, a mixed solution of 1.0 part of the sol-gel solution of the resin particle dispersion (1) was gradually added thereto.

  Then, after adding 1N aqueous sodium hydroxide solution to bring the pH of the system to 7.0, the stainless steel flask was sealed, gradually heated to 90 ° C. while continuing stirring, and maintained at 90 ° C. for 5 hours. did. Furthermore, it hold | maintained at 95 degreeC for 7.5 hours. Thereafter, 2.0 parts of the ionic surfactant Neogen RK was added and reacted at 100 ° C. for 5 hours. After completion of the reaction, 320 parts of a fraction was collected at 85 ° C. by distillation under reduced pressure. Then, cooling, filtration, and drying were performed. It re-dispersed in 5 L of ion-exchanged water at 40 ° C., stirred with a stirring blade (300 rpm) for 15 minutes, and filtered.

  This redispersion and filtration washing were repeated, and when the electric conductivity was 6.0 μS / cm or less, the washing was terminated and toner particles 25 were obtained. The formulation and conditions of the toner particles 25 are shown in Table 4, and the physical properties are shown in Table 9.

<Production Example of Toner Particles 26>
While stirring 100.0 parts of toner base 19 in a high-speed stirrer using a Henschel mixer, 10.0 parts of toluene, 5.0 parts of ethanol, 5.0 parts of water, and 20.0 parts of methyltriethoxysilane were mixed at 90 ° C. 3.5 parts of the organosilicon polymer solution reacted for 5 hours was sprayed and mixed uniformly.

  The particles were circulated in the fluidized bed dryer for 30 minutes under conditions of an inlet temperature of 90 ° C. and an outlet temperature of 45 ° C. to perform drying and polymerization. Similarly, the obtained treated toner was sprayed with 3.5 parts of the organosilicon polymer solution in a Henschel mixer on 100 parts of the treated toner, and fluidized bed under the conditions of an inlet temperature of 90 ° C. and an outlet temperature of 45 ° C. The inside of the dryer was circulated for 30 minutes. Similarly, spraying and drying of the organosilicon polymer solution was repeated a total of 10 times to obtain toner particles 26.

<Production Example of Toner Particles 27>
Production of toner particle 1 except that 6.5 parts of copper phthalocyanine was changed to 10.0 parts of carbon black and 0.4 part of charge control agent (1) was changed to 1.5 parts in the production example of toner particles 1. In the same manner as in Example, toner particles 27 were obtained. The formulation and conditions of toner particles 27 are shown in Table 4, and the physical properties are shown in Table 9.

<Production Example of Toner Particles 28>
Except that 70.0 parts of styrene and 30.0 parts of n-butyl acrylate used in the production example of toner particles 1 were changed to 40.0 parts, and 0.10 parts of aluminum trisecpropoxide was added. In the same manner as in the production example of toner particles 1, toner particles 28 were obtained. The formulation and conditions of the toner particles 28 are shown in Table 4, and the physical properties are shown in Table 9.

<Production Example of Toner Particles 29>
Except for changing 6.5 parts of copper phthalocyanine (Pigment Blue 15: 3) used in Production Example of Toner Particle 1 to 8.0 parts of Pigment Red 122 (P.R. 122), Similarly, toner particles 29 were obtained. The formulation and conditions of the toner particles 29 are shown in Table 4, and the physical properties are shown in Table 9.

<Production Example of Toner Particle 30>
Except for changing 6.5 parts of copper phthalocyanine (Pigment Blue 15: 3) used in Preparation Example of Toner Particle 1 to 6.0 parts of Pigment Yellow 155 (P.Y.155), Similarly, toner particles 30 were obtained. The formulation and conditions of the toner particles 30 are shown in Table 4, and the physical properties are shown in Table 9.

<Example of production of toner particles 31>
The toner particles 31 were prepared in the same manner as in the production example of the toner particles 1 except that 0.40 part of the charge control agent (1) used in the production example of the toner particle 1 was changed to 0.40 part of the charge control agent (2). Obtained. The formulation and conditions of the toner particles 31 are shown in Table 5, and the physical properties are shown in Table 10.

<Production Example of Toner Particles 32>
The toner particles 32 were prepared in the same manner as in the production example of the toner particle 1 except that 0.40 part of the charge control agent (1) used in the production example of the toner particle 1 was changed to 0.40 part of the charge control agent (3). Obtained. The formulation and conditions of the toner particles 33 are shown in Table 5, and the physical properties are shown in Table 10.

<Production Example of Comparative Toner Particle 1>
Comparative toner particles 1 were obtained in the same manner as in the toner particle 1 production example, except that 1.00 parts of methyltriethoxysilane used in the production example of toner particles 1 was changed to 0.10 parts of methyltriethoxysilane. . The formulation and conditions of Comparative Toner Particles 1 are shown in Table 6, and the physical properties are shown in Table 11.

<Production Example of Comparative Toner Particle 2>
Comparative toner particles 2 were obtained in the same manner as in Comparative toner particle 1 except that 0.10 parts of tetramethylsilane were used instead of 1.00 parts of methyltriethoxysilane used in the production example of comparative toner particles 1. It was. The formulation and conditions of the comparative toner particles 2 are shown in Table 6, and the physical properties are shown in Table 11.

<Production Example of Comparative Toner Particle 3>
A comparison was made in the same manner as in the production example of the comparative toner particle 1 except that 1.00 part of 3-methylacryloxypropyltriethoxysilane was used instead of 1.00 part of the methyltriethoxysilane used in the production example of the comparative toner particle 1. Toner particles 3 were obtained. The formulation and conditions of Comparative Toner Particles 3 are shown in Table 6, and the physical properties are shown in Table 11.

<Production Example of Comparative Toner Particle 4>
6. Instead of 1.00 part of methyltriethoxysilane used in the production example of comparative toner particles 1, the content is changed to 0.50 part of 3-methacryloxypropyltriethoxysilane, and the temperature inside the container is raised to 90 ° C. The comparative toner was prepared in the same manner as in the production example of the comparative toner particle 1 except that the temperature 90 ° C. maintained for 5 hours was changed to 70 ° C. and the internal temperature was changed to 70 ° C. Particles 4 were obtained. The formulation and conditions of the comparative toner particles 4 are shown in Table 6, and the physical properties are shown in Table 11.

<Production Example of Comparative Toner Particle 5>
Instead of 1.00 part of methyltriethoxysilane used in the production example of comparative toner particles 1, the internal temperature was changed to 0.50 part of 3-methacryloxypropyltriethoxysilane and the internal temperature was raised to 70 ° C. Was changed to 80 ° C., the temperature inside the container was raised to 90 ° C. and maintained for 7.5 hours, the temperature was changed to 80 ° C., and the internal temperature was raised to 100 ° C. Comparative toner particles 5 were obtained in the same manner as in Production Example of Comparative Toner Particles 1 except that The formulation and conditions of the comparative toner particles 5 are shown in Table 6, and the physical properties are shown in Table 11.

<Production Example of Comparative Toner Particle 6>
In place of 1.00 part of methyltriethoxysilane used in the production example of comparative toner particle 1, 0.50 part of methyltriethoxysilane was added, and 0.40 part of charge control agent (1) was added. The temperature was raised to 90 ° C. and maintained for 7.5 hours, the temperature 90 ° C. was changed to 70 ° C., and the internal temperature was raised to 100 ° C., except that the internal temperature was changed to 70 ° C. Comparative toner particles 6 were obtained in the same manner as in the production example of toner particles 1. The formulation and conditions of the comparative toner particles 6 are shown in Table 6, and the physical properties are shown in Table 11.

<Production Example of Comparative Toner Particle 7>
Instead of 1.00 part of methyltriethoxysilane used in the production example of comparative toner particles 1, the internal temperature was changed to 3.00 parts of methyltriethoxysilane and the internal temperature was raised to 90 ° C to 70 ° C. Comparative toner particles 7 were obtained in the same manner as in the production example of comparative toner particles 1 except that the temperature in the container was raised to 100 ° C. and the temperature was changed to 70 ° C. The formulation and conditions of the comparative toner particles 6 are shown in Table 6, and the physical properties are shown in Table 11.

<Production Example of Comparative Toner Particle 8>
Comparative toner particles were prepared in the same manner as in the production example of comparative toner particles 1 except that 12.00 parts of aminopropyltrimethoxysilane was used instead of 1.00 parts of methyltriethoxysilane used in the production example of comparative toner particles 1. 8 was obtained. The formulation and conditions of the comparative toner particles 8 are shown in Table 6, and the physical properties are shown in Table 11.

<Production Example of Comparative Toner Particle 9>
Comparative toner particles 9 were obtained in the same manner as in the toner particle 1 production example, except that 1.00 part of methyltriethoxysilane used in the production example of comparative toner particle 1 was changed to 0.0 part. The formulation and conditions of the comparative toner particles 9 are shown in Table 6, and the physical properties are shown in Table 11.

<Production Example of Comparative Toner Particle 10>
In a four-necked flask equipped with a high-speed stirrer TK-homomixer, 900 parts of ion-exchanged water and 95 parts of polyvinyl alcohol are added and heated to 55 ° C. while stirring at a rotational speed of 1300 rpm. did.

(Composition of monomer dispersion)
Styrene 70.0 parts n-Butyl acrylate 30.0 parts Carbon black 10.0 parts Salicylic acid silane compound 1.0 parts Release agent (behenyl behenate) 10.0 parts The above materials were dispersed with an attritor for 3 hours. Thereafter, 14.0 parts of t-butyl peroxypivalate as a polymerization initiator was added to prepare a monomer dispersion.

  Next, the obtained monomer dispersion was put into the dispersion medium in the above four-necked flask and granulated for 10 minutes while maintaining the above rotation speed. Subsequently, under stirring at 50 rpm, polymerization was carried out at 55 ° C. for 1 hour, then at 65 ° C. for 4 hours, and further at 80 ° C. for 5 hours. After completion of the above polymerization, the slurry was cooled, and the dispersant was removed by repeating washing with purified water. Further, washing and drying were performed to obtain black toner particles as a base material. The weight average particle size was 5.70 μm.

  3 parts of 0.3 part% sodium dodecylbenzenesulfonate solution is added to a solution obtained by mixing 2 parts of isoamyl acetate, 4.0 parts of tetraethoxysilane as a silicon compound and 0.5 part of methyltriethoxysilane, and an ultrasonic homogenizer is used. The mixed solution A of isoamyl acetate, tetraethoxysilane, and methyltriethoxysilane was prepared by using and stirring.

The above mixed solution A was added to 30 parts of 0.3% sodium dodecylbenzenesulfonate aqueous solution, 1.0 part of the base black toner particles, and 4.2 parts of 30% NH ₄ OH aqueous solution was mixed. ) For 12 hours. After washing with ethanol, it was washed with purified water, and the particles were filtered and dried to obtain comparative toner particles 10. The weight average particle diameter of the obtained toner was 5.6 μm. Comparative toner particle 10 had a coating layer formed by adhering the granular masses together.

<Production Example of Toner 1>
To 100 parts of toner particles 1, 0.4 part of hydrophobic silica whose surface was hydrophobized with 2% of silicone oil with a specific surface area of 220 m ² / g according to the BET method, hexamethyldisilazane 2.0%, and 100 cps; Toner 1 is obtained by mixing 0.15 part of aluminum oxide having a specific surface area of 50 m ² / g by BET method with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.).

<Production Example of Toners 2 to 34>
Toners 2 to 33 were obtained in the same manner as in Toner 1 except that Toner 1 was changed to Toner Particles 2 to 34 in Toner 1 Production Example. The toner 34 is toner particles 1.

<Production example of comparative toners 1 to 10>
Comparative toners 1 to 10 were obtained in the same manner as in the production example of the comparative toner particles 1 except that the toner particles 1 in the production example of the toner 1 were changed to the comparative toner particles 1 to 10.

"Evaluation of properties after cleaning toner 1"
A mixture of 1.0 part of toner 1, 100 parts of ion-exchanged water, and 0.01 part of sodium dodecylbenzenesulfonate was ultrasonically dispersed for 5 minutes and centrifuged. The upper 20% of the filtrate was collected. The obtained filtrate was dried and the physical properties were measured. As a result, the toner 1 after washing was almost the same as the result of the toner physical properties of the toner particles 1 (Tables 7 and 12).

"Evaluation of physical properties of Toner 2-34 and Comparative Toner 2-10"
In the physical property evaluation of the toner 1, when the toner 1 is changed to the toner N (N = 2 to 34) and the comparative toner M (M = 2 to 10), the toner N, the toner particle N, the comparative toner M, and the comparative toner particle M are changed. Was almost the same as the results of physical properties of the toner (Tables 6 to 15).

<Example 1>
A toner cartridge of a tandem Canon laser beam printer LBP9600C having the configuration as shown in FIG. 4 was used and 230 g of toner 1 was loaded. And low temperature low humidity L / L (temperature 10 ° C / humidity 15% RH), normal temperature normal humidity N / N (25 ° C / 50% RH), high temperature high humidity H / H (32.5 ° C / 85% RH) It was left for 24 hours in each environment. After leaving for 24 hours under each environment, an image with a printing ratio of 35.0% is printed out to 1,200 sheets in the A4 paper lateral direction, and the solid image density and fog at the initial time and 1,200 sheets are output. Evaluation of member contamination (filming, development streaks, drum fusion) at the time of outputting 200 sheets was performed.

  Further, a toner cartridge of a tandem Canon laser beam printer LBP9600C having a configuration as shown in FIG. 4 was used, and 230 g of toner 1 was loaded and left in a harsh environment (40 ° C./90%) for 168 hours. Then, after leaving it in ultra high temperature and high humidity SHH (35.0 ° C./85% RH) for 24 hours, printing out an image with a printing ratio of 35.0% up to 1,200 sheets, the initial solid image Density and fog, and evaluation of member contamination (filming, development streaks, drum fusion) at the time of outputting 1,200 sheets were performed.

<Measurement of triboelectric charge amount of toner particles and toner>
The toner particles of the present invention and the triboelectric charge amount of the toner can be determined by the following method. First, toner particles or toner and a standard carrier for negatively charged polarity toner (trade name: N-01, manufactured by the Japan Imaging Society) are left for a predetermined time in the following environment. 24 hours at low temperature and low humidity (10 ° C./15% RH), 24 hours at normal temperature and normal humidity (25 ° C./50% RH), 24 hours at high temperature and high humidity (32.5 ° C./85% RH), (C / 90%), after 168 hours, it is left for 24 hours at ultra-high temperature and high humidity (35.0 ° C./85% RH). The mixture is left for 120 seconds using a turbula mixer in each environment so that the toner particles or the toner content is 5% after standing. Next, within 1 minute after mixing, the mixed developer is placed in a metal container equipped with a conductive screen having an opening of 20 μm at room temperature and humidity (25 ° C./50% RH) and sucked with a suction machine. The difference between before and after the suction and the potential accumulated in the capacitor connected to the container are measured. At this time, the suction pressure is set to 4.0 kPa. From the difference, the stored potential, and the capacity of the capacitor, the frictional charge amount of the toner is used to calculate the following formula.

A standard carrier for negatively charged polarity toner (trade name: N-01, manufactured by the Japan Imaging Society) used for measurement is one that has passed 250 mesh.
Q = (A × B) / (W1-W2)
Q (C / kg): triboelectric charge amount of charge control agent and toner A (μF): capacitance of capacitor B (V): potential difference accumulated in capacitor W1-W2 (g): difference before and after suction

<Image density measurement>
Regarding the image density, a Macbeth densitometer (RD-914; manufactured by Macbeth) was used, an SPI auxiliary filter was used, and low temperature and low humidity (L / L) (10 ° C./15% RH), normal temperature and normal humidity (N / N) ) (25 ° C./50% RH), high temperature and high humidity (H / H) (32.5 ° C./85% RH) and harsh environment (40 ° C./90% RH) after 168 hours, ultra high temperature and high humidity (35. (0 ° C./85% RH) The image density of the fixed image portion of the image output in an environment after standing for 24 hours was measured.

<Image density measurement before and after durability>
An example in which the toner of the present invention is applied to a laser beam printer will be described below.

  A toner cartridge of a tandem Canon laser beam printer LBP9600C having the configuration as shown in FIG. 4 was used and 230 g of toner 1 was loaded.

  It was allowed to stand for 24 hours in each environment of low temperature and low humidity (10 ° C./15% RH), normal temperature and normal humidity (25 ° C./50% RH), and high temperature and high humidity (32.5 ° C./85% RH). After leaving for 24 hours under each environment, up to 1,200 images with a printing ratio of 35.0% were printed, and solid images were evaluated at the initial time and when 1,200 sheets were output.

  Further, a toner cartridge of a tandem Canon laser beam printer LBP9600C having a configuration as shown in FIG. 4 was used, and 230 g of toner 1 was loaded and left in a harsh environment (40 ° C./90%) for 168 hours. Then, after leaving it in ultra high temperature and high humidity (35.0 ° C / 85% RH) for 24 hours, printing out an image with a printing ratio of 35.0% under ultra high temperature and high humidity up to 1,200 sheets, The solid images were evaluated at the initial time and when 1,200 sheets were output.

<Evaluation of image density>
Regarding the image density, the image density of the fixed image portion of the output image was measured using a Macbeth densitometer (RD-914; manufactured by Macbeth Co.) equipped with an SPI auxiliary filter, and evaluated according to the following criteria.
A: 1.45 or more B: 1.40 or more and less than 1.45 C: 1.30 or more and less than 1.40 D: 1.25 or more and less than 1.30 E: 1.20 or more and less than 1.25 F: 1. 20 or less

<Parts contamination assessment>
After 1,200 sheets were printed, the first half was a mixed image with a halftone image (toner applied amount 0.25 mg / cm ² ) and the latter half a solid image (toner applied amount 0.40 mg / cm ² ). The evaluation was made according to the following criteria.
A: Vertical stripes in the paper discharge direction and spots with different densities are not seen on the halftone and solid images.
B: Although there are 1 to 2 thin streaks in the circumferential direction of the developing roller or 1 to 3 fusion products on the drum, vertical streaks and densities in the paper discharge direction are different on the halftone and solid images. There is no spot.
C: Although there are 3 to 5 thin streaks in the circumferential direction of the developing roller or 3 to 5 fusion products on the drum, vertical streaks in the paper discharge direction and spots with different densities are printed on the halftone and solid images. Can be seen just a little. However, it can be erased by image processing.
D: There are 6 to 20 thin streaks in the circumferential direction of the developing roller or 6 to 20 melts on the drum, and there are several fine streaks on the image of the halftone part and the solid part and spots with different densities. It can be seen. It cannot be erased even with image processing.
E: 20 or more streaks or spots with different densities are seen on the developing roller and the halftone image, and cannot be erased even by image processing.

<Evaluation of low temperature fixability (low temperature offset end temperature)>
An unfixed toner image with a process load of 245 mm / sec and a toner loading of 0.4 mg / cm ² is received by a modified fixing device modified so that the fixing temperature of the laser beam printer LBP9600C manufactured by Canon can be adjusted. Then, heat and pressure were applied without oil to form a fixed image on the image receiving paper.

The fixing property is Kimwipe [S-200 (Crecia)], and the fixed image is rubbed 10 times with a load of 75 g / cm ² , and the temperature at which the density reduction rate before and after the rub is less than 5% is finished at the low temperature offset. It was temperature. Evaluation was carried out at room temperature and normal humidity (25 ° C./50% RH).

<Evaluation of fog>
The fog density (%) is calculated from the difference between the whiteness of the white portion of the printed image and the whiteness of the transfer paper measured by “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.), and the image fog is evaluated according to the following criteria. did. A, B, and C are practical levels.
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 Less than 3.0% F: 3.0% or more

<Preservation test>
About 10 g of toner was put in a 100 ml glass bottle and left to stand for 15 days at a temperature of 55 ° C. and a humidity of 20%, and then judged visually.
A: No change B: There is an aggregate, but loosens immediately C: Hard to loosen D: No fluidity E: Obvious caking

<Storage stability test>
About 10 g of toner was placed in a 100 ml glass bottle and left for 3 months at a temperature of 45 ° C. and a humidity of 95%.
A: No change B: There is an aggregate, but loosens immediately C: Hard to loosen D: No fluidity E: Obvious caking

<Evaluation of solid followability>
Regarding the evaluation of the solid followability, after printing 1,200 sheets, three solid images (toner applied amount 0.40 mg / cm ² ) were continuously drawn, and the first sheet (density A) and three sheets were printed. A difference (density A−density B) in the density of the eyes (density B) is obtained. The smaller the difference between the density A and the density B, the better the solid followability. Solid followability (concentration A-concentration B) was evaluated according to the following criteria.

Regarding the image density, the image density of the fixed image portion of the output image was measured using a Macbeth densitometer (RD-914; manufactured by Macbeth) equipped with an SPI auxiliary filter.
A: 0.00 or more and 0.04 or more B: 0.05 or more and less than 0.09 C: 0.10 or more and less than 0.14 D: 0.15 or more and less than 0.19 E: 0.20 or more

<Examples 2-34>
The same evaluation as in Example 1 was performed except that the toner 1 of Example 1 was changed to toners 2-34. The results are shown in Tables 16-19.

<Comparative Examples 1-10>
The same evaluation as in Example 1 was performed except that the comparative toner 1 of Example 1 was changed to Comparative toners 1 to 10. The results are shown in Table 20.

<Example 35>
A toner cartridge of a tandem Canon laser beam printer LBP9600C having the configuration as shown in FIG. 4 was used, and 230 g of toner 1 (cyan) was loaded. Similarly, 230 g of toner 27 (black), toner 29 (magenta), and toner 30 (yellow) were filled in each LBP9600C toner cartridge. Each of the four color cartridge sets has a low temperature and low humidity L / L (10 ° C./15% RH), a normal temperature and normal humidity N / N (25 ° C./50% RH), and a high temperature and high humidity H / H (32.5 ° C./85). % RH) for 24 hours. After 24 hours in each environment, set cyan, black, magenta, and yellow cartridges to LBP9600C, print out an image with a print ratio of 35.0% up to 1,200 sheets in the A4 paper horizontal direction, The solid image density and fog at the time of outputting 1,200 sheets, and the member contamination (filming, development streaks, drum fusion) at the time of outputting 1,200 sheets were evaluated. As a result, there were no practical problems and good results were obtained.

  Further, a toner cartridge of a tandem-type Canon laser beam printer LBP9600C having a configuration as shown in FIG. 4 was used and 240 g of toner 1 (cyan) was loaded. Similarly, 230 g of toner 27 (black), toner 29 (magenta), and toner 30 (yellow) were filled in each LBP9600C toner cartridge. The four-color cartridge set was left in a harsh environment (40 ° C./90%) for 168 hours. Then, after being left in ultra-high temperature and high humidity SHH (35.0 ° C./85% RH) for 24 hours, a cyan, black, magenta and yellow cartridge was set in LBP9600C and an image with a printing ratio of 35.0% 1,200 sheets were printed out, and the initial solid image density and fog, and member contamination (filming, development streaks, drum fusion) at the time of outputting 1,200 sheets were evaluated. As a result, there were no practical problems and good results were obtained.

  DESCRIPTION OF SYMBOLS 1 Photoconductor, 2 Developing roller, 3 Toner supply roller, 4 Toner, 5 Regulating blade, 6 Developing device, 7 Laser beam, 8 Charging device, 9 Cleaning device, 10 Cleaning charging device, 11 Stirring blade, 12 Driving roller, 13 Transfer roller, 14 Bias power supply, 15 Tension roller, 16 Transfer conveyance belt, 17 Driven roller, 18 Paper, 19 Paper feed roller, 20 Adsorption roller, 21 Fixing device

Claims (9)

A toner having toner particles having a surface layer containing an organosilicon polymer and a charge control agent;
The organosilicon polymer has the following formula (T3R)

(R in the formula is a hydrocarbon group having 1 to 6 carbon atoms.)
Having a unit represented by
In measurement using ESCA (Electron Spectroscopy for Chemical Analysis) of the surface of the toner particles, the carbon element concentration dC surface of the toner particles, an oxygen element concentration dO, silicon element concentration dSi for the total concentration of the silicon element concentration dSi (dC + dO + dSi) 0.50 atomic% or more,
A toner, wherein the charge control agent is a polymer A having a structure a represented by the formula (a1).

(Wherein R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms, and R ² represents a hydrogen atom, a hydroxyl group, or a carbon number. Represents an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms, g represents an integer of 1 to 3, h represents an integer of 0 to 3, and h is 2 or 3. In this case, R ¹ can be independently selected, and ** is a binding site in the polymer A.) In the measurement of ²⁹ Si-NMR of the THF-insoluble matter of the toner particles, the ratio RS (T3R) of the peak area of the structure of the formula (T3R) to the total peak area of the organosilicon polymer is
RS (T3R) ≧ 0.20 (1)
The toner according to claim 1, wherein: In the ²⁹ Si-NMR measurement of the THF-insoluble matter of the toner particles, the peak area of the structure (SX3) in which the number of siloxy groups bonded to silicon is 3.0 with respect to the total peak area of the organosilicon polymer. The relationship between the ratio S (SX3) and the ratio of the peak area S (SX2) of the (SX2) structure in which the number of O _1/2 bonded to silicon is 2.0 is S (SX3) / S (SX2) ≧ 1 .00 (2)
The toner according to claim 1, wherein the toner satisfies the following condition.   The average thickness D of the surface layer containing the organosilicon polymer, measured by observing the cross section of the toner particles using a transmission electron microscope (TEM), is 2.5 nm or more and 150.0 nm or less. The toner according to claim 1. The organosilicon polymer has the following formula (Z)

(R1 in the formula is a hydrocarbon group having 1 to 6 carbon atoms, and R2, R3 and R4 are each independently a halogen atom, a hydroxyl group or an alkoxy group.)
The toner according to claim 1, wherein the toner is a polymer of a compound having a structure represented by:   The toner according to claim 5, wherein R 1 in the formula (Z) is a methyl group, an ethyl group, a propyl group, or an aryl group.   7. The toner according to claim 5, wherein R 2, R 3, and R 4 in the formula (Z) are each independently an alkoxy group. The toner according to claim 1, wherein the structure a is a partial structure represented by the formula (a2) and is contained in the polymer A.

(In the formula, R ³ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms,
R ⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms,
R ⁵ represents a hydrogen atom or a methyl group,
i represents an integer of 1 to 3, j represents an integer of 0 to 3, and when j is 2 or 3, R ³ can be independently selected. )   The toner according to claim 1, wherein the content of the structure a in the polymer A is 10 μmol / g or more and 1500 μmol / g or less.

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