JP6679323B2 - Method for producing toner particles - Google Patents

Description

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

  Although various techniques for improving toner production performance have been proposed, the present inventors have mainly focused on a production method in which toner particles are covered with a silicon compound by a method of obtaining toner particles in an aqueous medium. are doing. Heretofore, many methods have been used in which fine particles are fixed on the surface of toner particles in an aqueous medium to improve various toner performances. On the other hand, in the manufacturing method in which the particles are fixed to the surface of the toner particles in the aqueous medium, there are few examples focused on improving the productivity.

  Patent Documents 1 and 2 disclose a technique of fixing silica particles to the surface of a toner particle composition by using a silane compound in an aqueous medium. These techniques present some common challenges. One is that there is a problem in productivity, and some improvement is necessary for mass production. Further, the performance as a toner may be impaired by simplifying each step or shortening the time required for each step in order to improve the productivity. Alternatively, in order to carry out mass production using an aqueous medium, there is a problem of toner composition contamination in a production apparatus in repeated production.

Japanese Patent Laid-Open No. 08-292599 U.S. Pat. No. 8,728,692

  INDUSTRIAL APPLICABILITY According to the present invention, in a method for producing toner particles in an aqueous medium, it is possible to obtain, with high productivity, toner particles whose surfaces are covered with fine particles and a silicon compound and which show good charging characteristics even in a high temperature and high humidity environment. An object of the present invention is to provide a method for producing toner particles.

The above problems can be solved by a method for producing toner particles having the following steps.
Step 1:
(I) at least one silicon compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3),
(Ii) fine particles having a number average particle diameter of 10 nm or more and 500 nm or less, and (iii) a toner particle precursor,
A step of preparing a liquid composition in which the coexisting in an aqueous medium,
Step 2: a step of condensing the silicon compound in the liquid composition at a temperature of 60 ° C. or higher and 105 ° C. or lower to fix the fine particles on the surface of the toner particle precursor, and step 3: fix the fine particles Filtering the obtained toner particle precursor from the aqueous medium, and then drying to obtain toner particles;
A method for producing toner particles having:
The fine particles are present on the surface of the toner particles in an amount of 0.10% by mass or more and 5.00% by mass or less, based on the mass of the toner particles .
In the step 1, after the silicon compound and the fine particles are mixed to prepare a fine particle dispersion liquid, the fine particle dispersion liquid is put into the aqueous medium in which the toner particle precursor is present, and the liquid composition is obtained. Prepare things,
A method for producing toner particles, comprising:

In formulas (1), (2) and (3), R ^d , R ^e and R ^f each independently represent an alkyl group, an alkenyl group, an acetoxy group, an acyl group or an aryl group, and R ² and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a halogen atom, a hydroxy group or an alkoxy group.

  According to the present invention, it is possible to provide a method for producing toner particles in an aqueous medium, which is capable of obtaining toner particles whose surfaces are covered with fine particles and a silicon compound with high productivity. In the present specification, “high productivity” means effectively preventing adhesion of a toner composition such as a toner particle precursor to the wall surface of a container used when manufacturing toner particles in an aqueous medium. Indicates. Further, it is shown that the adhesion of the toner particles to the inside of the drying device and the pipe for conveying the toner particles is effectively prevented after the drying step of pulverizing the toner particles. The toner particles obtained by the present invention show good charging characteristics even in a high temperature and high humidity environment.

1 is an example of an image forming apparatus using toner particles according to the present invention.

Hereinafter, the present invention will be described in detail. The present invention is a method for producing toner particles, which has the following steps.
Step 1:
( I) at least one silicon compound selected from the group consisting of a compound represented by the following formula (1) , a compound represented by the following formula (2), and a compound represented by the following formula (3),
( Ii) Fine particles having a number average particle diameter of 10 nm or more and 500 nm or less, and
( Iii) Toner particle precursor,
A step of preparing a liquid composition in which the coexisting in an aqueous medium,
Step 2: a step of condensing the silicon compound in the liquid composition at a temperature of 60 ° C. or higher and 105 ° C. or lower to fix the fine particles on the surface of the toner particle precursor, and step 3: fix the fine particles A step of filtering the obtained toner particle precursor from the aqueous medium and then drying to obtain toner particles.
Further, the fine particles are present on the surface of the toner particles in an amount of 0.10% by mass or more and 5.00% by mass or less based on the mass of the toner particles.

  Hereinafter, each step will be described in detail. In the detailed description below, the container used when various reactions and particle formation in the means for producing toner particles in an aqueous medium are performed is defined as a “reaction vessel”. In the present invention, in the reaction kettle, the reaction kettle contamination, which is a problem in production, that is, the adhesion due to the substance constituting the toner particle precursor to the reaction kettle surface is effectively prevented. Alternatively, even when the toner particles are manufactured in an aqueous medium, even in the drying step that is required as the final step, the contamination due to the adhesion of the toner particles inside the drying device or the toner particles in the piping for conveying the toner particles may be generated. Effectively prevent adhered pollution. Further, the toner particles of the present invention exhibit good charging characteristics even in a high temperature and high humidity environment. Hereinafter, the estimation mechanism by which such effects are exhibited will also be described.

<Step 1>
Step 1 is a step of preparing a liquid composition in which ( i) to ( iii) coexist in an aqueous medium. Hereinafter, the (i), (ii), a (iii), respectively, the component (i), component (ii), also referred to as (iii). Here, “the component ( i), the component ( ii) and the component ( iii)“ coexist ”in the aqueous medium means that the silicon compound or the hydrolyzate thereof, the fine particles and the toner particle precursor are individually water-based. Means existing in the medium. Thus, coexistence of the component ( i), the component ( ii), and the component ( iii) in the aqueous medium is one of the necessary conditions of the present invention, and the conditions will be discussed.

As a result of examination by the inventors, it has been found that in the following cases where the above conditions are not satisfied, the toner composition tends to adhere to the reaction kettle, and some measures are necessary.
A: A silicon compound is used, but fine particles having a number average particle size of 10 nm or more and 500 nm or less are not used.
B: When the silicon compound was added to the aqueous medium after the fixing of the fine particles to the toner particle precursor was completed (the fine particles do not exist alone in the aqueous medium).
The above A suggests that the presence of the convex shape on the surface of the toner particles is one of the conditions for preventing the toner composition from adhering to the reaction kettle. That is, it is suggested that the contact area between the toner particle precursor and the surface of the reaction kettle becomes small, so that the adhesion of the toner particle precursor to the surface of the reaction kettle is reduced. On the other hand, it is presumed that the above B suggests an appropriate uneven condition for maintaining the anti-adhesion function throughout the manufacturing process. That is, it is presumed that when the condensation polymer of the silicon compound is added after the fine particles are fixed to the toner particle precursor, the toner particle surface becomes smooth and the effect of reducing the area of adhesion to the reaction vessel is impaired. It

[Component ( i): Silicon compound]
In the present invention, as the silicon compound, at least one silicon compound selected from the group consisting of the compounds represented by the formulas (1) to (3) is used. The silicon compound in the present invention is preferably at least one silicon compound selected from the group consisting of the compounds represented by the formulas (2) and (3). This is because the condensation polymer derived from the trifunctional or tetrafunctional silicon compound has a lower viscosity on the surface of the toner particle precursor during each step than the condensation polymer derived from the bifunctional silicon compound. Presumed. In addition, it is more preferable to use the compound represented by the formula (2) from the viewpoint that the effect of the present invention of improving productivity is most easily obtained. The toner particles covered with the condensation polymer derived from the silicon compound represented by the formula (2) have more excellent charging performance of the toner particles in a high temperature and high humidity environment. Further, Rf in formula (2) is particularly preferably a methyl group or an ethyl group. This is because the anti-contamination effect in each production step of the present invention is most remarkable and the charging property is the best.

In the formulas (1), (2) and (3), R ^d , R ^e and R ^f each independently represent an alkyl group, an alkenyl group, an acetoxy group, an acyl group or an aryl group, and R ² , ^{R 3, R 4, R 5} , R 6, R 7, R 8, R 9 and ^{R 10} each independently represents a halogen atom, a hydroxy group or an alkoxy group. ^{R 2, R 3, R 4} , R 5, R 6, R 7, R 8, R 9 and ^{R 10} is a functional group involved in condensation polymerization. Further, the hydroxy group in R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is obtained as a hydrolyzate of a compound in which these are halogen atoms or alkoxy groups. It is a thing.

  The alkyl group may be linear or branched, and examples thereof include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. it can. Examples of the alkenyl group include alkenyl groups having 2 to 6 carbon atoms such as vinyl group, allyl group, butenyl group, and hexenyl group. Examples of the acyl group include an acyl group having 2 to 6 carbon atoms such as an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, and a valeryl group. Examples of the aryl group include a phenyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the alkoxy group include alkoxy groups having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propyloxy group and a butyloxy group. In addition, these groups may further have a substituent.

  Specific examples of the silicon compound according to the present invention represented by the formulas (1) to (3) include the following compounds. For example, examples of the silicon compound represented by the formula (1) include dimethyldimethoxysilane and dimethyldiethoxysilane. Examples of the silicon compound represented by the formula (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, propyltrimethoxysilane. , Propyltriethoxysilane, propyltrichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butylmethoxydichlorosilane, butylethoxydichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrimethoxysilane, phenyl Examples thereof include triethoxysilane, vinyltriethoxysilane and methacryloxypropyltriethoxysilane. Examples of the silicon compound represented by the formula (3) include tetraethoxysilane. Moreover, these hydrolyzates may be sufficient. These silicon compounds may be used alone or in combination of two or more.

[Component ( ii): Fine particles]
In the present invention, fine particles having a number average particle diameter of 10 nm or more and 500 nm or less are used. The number average particle diameter of the fine particles is preferably 20 nm or more and 400 nm or less, more preferably 30 nm or more and 300 nm or less, and particularly preferably 50 nm or more and 200 nm or less. It is suggested that this condition is in the range of a suitable convex shape that exhibits the effect of preventing adhesion to the reaction kettle.

  The fine particles in the present invention are not particularly limited, but examples thereof include inorganic fine particles such as silica, titania, alumina and hydrotalcite, and polymer resin fine particles such as polymethylmethacrylate resin, urethane resin, phenol resin and polystyrene resin. Among these, inorganic fine particles are preferable. Not only the convex shape present on the surface of the toner particles, but also the hardness of the fine particles contributes to both the effect of preventing the reaction vessel from adhering and the effect of stripping off the initial thin deposits, so that the effect of preventing contamination from adhering to the reaction vessel and piping is more Estimated to work effectively.

[Component ( iii): Toner Particle Precursor]
In the present specification, the “toner particle precursor” means a particulate material including a constituent material itself included in final toner particles and a raw material that reacts to become a constituent material of final toner particles. . The constituent materials of the toner particles and the like will be described in the method of manufacturing toner particles described later.

[Aqueous medium]
Examples of the aqueous medium in the present invention include water, alcohols such as methanol, ethanol and propanol. These may be used alone or in combination of two or more.

  In this step, the silicon compound and the fine particles are mixed to disperse the fine particles, that is, after the fine particle dispersion is prepared, the fine particle dispersion is added to an aqueous medium in which the toner particle precursor is present. The method of preparing the liquid composition is preferred. It is considered that this is a preferable condition in which the fine particles adhere to the surface of the toner particle precursor and are not buried too much due to the condensation of the silicon compound. The reason why this condition is suitable will be considered below.

  The silicon compound used in the present invention is soluble in water, or even if it is initially hydrophobic, it becomes a hydrophilic hydrolyzate by hydrolysis, so it can be finally dissolved in an aqueous medium and condensed. Change to a different substance. When the condensation starts, a hydrophobic siloxane bond is formed, so that it moves to the surface of the toner particle precursor, which is a stable field, and the condensation further proceeds from there. In this way, it is considered that the condensation polymer of the silicon compound is formed on the surface of the toner particle precursor and the fine particles are fixed. Therefore, when the silicon compound and the fine particles are mixed and dispersed and then the dispersion is added to the aqueous medium, hydrolysis of the silicon compound, dissolution in the aqueous medium, and absorption into the toner particle precursor occur first. Here, under the above-mentioned preferable conditions, it is presumed that the condensation of the silicon compound on the outermost surface of the fine particles existing solely in the aqueous medium is unlikely to occur. Therefore, it is presumed that the fine particles will be fixed closer to the outermost surface by maintaining a proper balance between the rate of condensation of the silicon compound on the surface of the toner particle precursor surface and the fixation of the fine particles. From the above, it is considered that the shape of the fine particles is likely to be reflected in the convex shape of the surface of the toner particles, which in turn affects the effect of preventing the adhesion of the toner particle precursor and the toner particles during the manufacturing process.

<Step 2>
Step 2 is a step of fixing the fine particles on the surface of the toner particle precursor by condensing the silicon compound in the liquid composition prepared in Step 1 at a temperature of 60 ° C. or higher and 105 ° C. or lower. As long as the silicon compound used in the present invention is used in an aqueous medium, it is dissolved in the aqueous medium as it is, or is hydrolyzed to form an aqueous system via an intermediate (hydrolyzate) containing a silanol group (Si—OH). It dissolves in the medium. Then, the silanol groups are condensed with each other to be converted into a solid condensation polymer of a silicon compound. Since this condensation proceeds on the surface of the toner particle precursor, how to control the condensation is important.

  When the condensation proceeded at less than 60 ° C., the effect of improving the reaction vessel adhesion was not observed. It is presumed that this is because the silicon compound during the condensation tends to adhere to the reaction kettle, the condensation rate is low when the temperature is low, and the state during the condensation continues longer. On the other hand, when the condensation proceeded at a temperature higher than 105 ° C., the effect of improving the reaction vessel adhesion was not observed. It is considered that this is because the molecular motion becomes too active. Therefore, in this step, it is necessary to condense the silicon compound at a temperature of 60 ° C. or higher and 105 ° C. or lower.

  Further, when the condensation is carried out at less than 60 ° C., the toner particle precursor in the aqueous medium obtained through each step is filtered from the aqueous medium and then dried to obtain toner particles, and the drying step. Adhesion of toner particles may occur in the steps after the step. It is speculated that this is because the condensation process of the silicon compound is insufficient and reaches the drying step. That is, when the condensation is insufficient, it is considered that the silanol groups remaining on the surface induce the adhesion of the toner particles. As one of means for solving this, for example, prolonging the condensation time can be considered. However, this method leads to a reduction in the amount of production per hour, and even when the condensation is carried out for a long time, the condensation rate is limited, so that the adhesion of toner particles may not be completely prevented. is there. Further, the toner particles of the present invention exhibit good charging characteristics even in a high temperature and high humidity environment, but in the toner particles produced at a condensation temperature of less than 60 ° C., the condensation is insufficient and silanol groups remain. , The charging characteristics tend to deteriorate.

  In step 2, the condensation of the silicon compound is preferably performed at a temperature of 70 ° C. or higher and 105 ° C. or lower, and more preferably at a temperature of 85 ° C. or higher and 100 ° C. or lower. In addition, it is preferable that the step 2 is performed in a temperature range of 60 ° C. or higher and 105 ° C. or lower for 3 hours or more and 10 hours or less. Since the higher the condensation temperature is, the shorter the condensation progresses, the higher the condensation temperature is, which is preferable in terms of production efficiency. However, the time required for this step may be appropriately adjusted according to various situations and circumstances. Further, the condensation can be carried out under any conditions of normal pressure, reduced pressure, or increased pressure.

<Step 3>
Step 3 is a step of obtaining the toner particles by filtering the toner particle precursor to which the fine particles are fixed from the aqueous medium and then drying. In the present invention, a toner particle precursor can be obtained by filtering (separating) by a known method. In addition, the drying can be performed using a known dryer, for example, at 30 to 80 ° C.

  On the surface of the toner particles of the present invention obtained through the above steps, the fine particles are present in a proportion of 0.1% by mass or more and 5.0% by mass or less based on the mass of the toner particles. Through the steps of the present invention, these fine particles are finally fixed on the surface of the toner particles. As described above, it was considered that the effect of preventing the toner particle precursor or the toner particles from adhering to the reaction kettle or adhering to the pipe in each step is exhibited when the convex shape is in an appropriate state. One is that the fine particles are present in an amount of 0.10 mass% or more and 5.00 mass% or less. The fine particles are preferably present in an amount of 0.12% by mass or more and 2.0% by mass or less, and more preferably 0.15% by mass or more and 1.0% by mass or less, based on the mass of the toner particles.

  When the amount of the fine particles present on the surface of the toner particles is less than 0.1% by mass, the convex shape is insufficiently formed, and it is difficult to obtain the effect of preventing reaction vessel adhesion. On the other hand, if the amount of fine particles present on the surface of the toner particles is more than 5.0% by mass, the distance between the convex shapes becomes narrower and the particle surface finally becomes smooth. It is difficult to obtain the effect.

<Method of manufacturing toner particles>
Hereinafter, a specific method for producing the toner particles of the present invention will be described, but the present invention is not limited thereto.

  A suspension polymerization method is mentioned as a 1st manufacturing method. First, a polymerizable monomer composition containing a binder resin polymerizable monomer, a silicon compound, and, if necessary, a colorant and other additives, suspended and granulated in an aqueous medium. Forming a toner particle precursor in an aqueous medium. After that, a silicon compound in which fine particles are dispersed is added to the aqueous medium, and polymerization of the polymerizable monomer composition and condensation polymerization of the silicon compound are performed to obtain toner particles having fine particles fixed on the surface. The toner particles thus obtained are subjected to condensation polymerization in the vicinity of the surface of the toner particles in such a manner that the fine particles are surrounded by the silicon compound, so that a layer containing the condensation polymer of the silicon compound and the fine particles is formed on the surface of the toner particles. be able to. Such a suspension polymerization method is the most preferable method from the viewpoint of the uniformity of the layer containing the condensation polymer of the silicon compound and the fine particles on the surface of the toner particles.

  As the second production method, a method of adding a silicon compound and fine particles in an aqueous medium after obtaining a solid toner particle precursor can be mentioned. The toner particle precursor may be obtained by melt-kneading a binder resin, and optionally a colorant and other additives, and pulverizing. Alternatively, the binder resin particles, and optionally the colorant particles and other particles, may be obtained by aggregating and associating in an aqueous medium. Alternatively, a binder resin, a silicon compound, and other additives such as a coloring agent, if necessary, are dissolved in an organic solvent to produce an organic phase dispersion, which is suspended in an aqueous medium, granulated, or polymerized in some cases. After that, the organic solvent may be removed to obtain a toner particle precursor.

  Suitable examples of the polymerizable monomer in the suspension polymerization method include the vinyl-based polymerizable monomers shown below. 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-hexylstyrene, pn-octyl, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene and p-phenylstyrene; methyl acrylate, ethyl Acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate 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, diethyl phos Fate ethyl methacrylate, dibutyl phosphate ethylmethac Methacrylic polymerizable monomers such as rate; vinyl acetates such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc. Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

  Further, the following may be mentioned as the polymerization initiator used in the polymerization. 2,2'-azobis- (2,4-divaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis Azo-based or diazo-based 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 type polymerization initiators such as benzoyl peroxide and lauroyl peroxide. These polymerization initiators may be used alone or in combination of two or more. The polymerization initiator is preferably added in a proportion of 0.5% by mass or more and 30.0% by mass or less with respect to the polymerizable monomer.

  A chain transfer agent may be added during the polymerization in order to control the molecular weight of the binder resin constituting the toner particles. The chain transfer agent is preferably added in a proportion of 0.001% by mass or more and 15.000% by mass or less with respect to the polymerizable monomer.

Further, in order to control the molecular weight of the binder resin constituting the toner particles, a crosslinking agent may be added during the polymerization. Examples of the crosslinkable monomer include the following. 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 diacrylates, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester type diacrylate (hydroxypivalic acid neopentyl glycol diacrylate, trade name: Kaya Head MANDA, manufactured by Nippon Kayaku Co., Ltd.), and more acrylate what was changed to methacrylate.
The following are mentioned as a polyfunctional crosslinking monomer. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy polyethoxyphenyl) propane, diacryl phthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate.
The cross-linking agent is preferably added in a proportion of 0.001% by mass or more and 15.000% by mass or less with respect to the polymerizable monomer.

  When the toner particles are produced using the binder resin, the following resins are preferable as the binder resin. Polystyrene, homopolymers of styrene such as polyvinyltoluene and its substitution products; styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-methyl acrylate copolymers, 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-butadier Styrene-based copolymers such as copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene , Polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. These may be used alone or in combination of two or more.

When the medium used in the suspension polymerization method is an aqueous medium, a dispersion stabilizer for the particles of the polymerizable monomer composition can be used. The dispersion stabilizer can stabilize the toner particle precursor in the aqueous medium with almost no influence on the formation of the convex shape on the surface. Further, it can be easily dissolved by adjusting the pH. Examples of the dispersion stabilizer include the following. 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 . Further, examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch.
In addition, commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such a surfactant include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate.

The colorant used in the toner particles of the present invention is not particularly limited, and the following known ones can be used.
Examples of yellow pigments include condensed azo compounds such as yellow iron oxide, Navels 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. Specifically, the following are mentioned. 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.
The following are mentioned as an orange pigment. Permanent Orange GTR, Pyrazolone Orange, Vulcan Orange, Benzidine Orange G, Induslen Brilliant Orange RK, Induslen Brilliant Orange GK.
Examples of red pigments include condensation of red iron oxide, permanent red 4R, resole red, pyrazolone red, watching red calcium salt, lake red C, lake D, brilliant carmine 6B, brillant carmine 3B, eosin lake, rhodamine lake B, and alizarin lake. Examples thereof include azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, the following are mentioned. 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.
Examples of blue pigments include copper phthalocyanine compounds and their derivatives such as alkali blue lake, Victoria blue lake, phthalocyanine blue, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, fast sky blue, and indanthrene blue BG, anthraquinone compounds, and basic dyes. Examples include lake compounds. Specifically, the following are mentioned. 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 green pigments 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-mentioned yellow colorant, red colorant and blue colorant which are toned in black. These colorants can be used alone or in a mixture, and can be used in the state of a solid solution.

  The content of the colorant is preferably 3.0 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the binder resin or the polymerizable monomer.

  A charge control agent may be added to the toner particles of the present invention, and known particles can be used. The addition amount of the charge control agent is preferably 0.01 part by mass or more and 10.00 parts by mass or less with respect to 100 parts by mass of the binder resin or the polymerizable monomer.

  A release agent may be added to the toner particles of the present invention, and known ones can be used. The amount of the release agent added is preferably 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the binder resin or the polymerizable monomer.

  FIG. 1 is an example of an image forming apparatus capable of forming an image using the toner particles according to the present invention. The outline of the image forming process is as follows. An electrostatic latent image is formed on the photoconductor 1. The toner 4 on the developing roller 2 is used to develop the electrostatic latent image formed on the photoconductor to form a toner image. The toner image is transferred to the transfer / transport belt 16. By the action of the transfer bias applied to the transfer unit, the toner image transferred on the transfer / transport belt 16 is transferred to the recording medium 18 such as paper. Then, the toner image transferred onto the recording medium 18 is fixed by the fixing device 21.

  The methods for measuring each physical property value according to the present invention will be described below.

<Method of measuring weight average particle diameter (D4) of toner particles>
The weight average particle diameter (D4) of the toner particles is measured by a precision particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with an aperture tube of 100 μm by a pore electrical resistance method. Perform using. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, one prepared by dissolving special grade sodium chloride in ion-exchanged water to have a concentration of about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used. .

Before the measurement and analysis, the dedicated software is set as follows.
On the "Change standard measurement method (SOM) screen" of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). Set the value obtained by using the product. The threshold and noise level are automatically set by pressing the “Threshold / noise level measurement button”. In addition, the current is set to 1600 μA, the gain is set to 2, and the electrolytic solution is set to ISOTON II, and a check is put in “Flash of aperture tube after measurement”.
On 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 measuring method is as follows.
(1) In a 250 ml round-bottom beaker made of glass exclusively for Multisizer 3, about 200 ml of the electrolytic aqueous solution was put, set on a sample stand, and stirring of the stirrer rod was performed counterclockwise at 24 revolutions / second. Then, the dirt and air 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 placed in a glass 100 ml flat-bottom beaker. In this, as a dispersant, "Contaminone (registered trademark) N" (a nonionic surfactant, an anionic surfactant, a 10 mass% aqueous solution of a neutral detergent for washing precision measuring instruments of pH 7 consisting of an organic builder, Approximately 0.3 ml of a diluted solution prepared by diluting (Kou Pure Chemical Industries, Ltd.) 3 times by mass with ion-exchanged water is added.
(3) Two oscillators with an oscillating frequency of 50 kHz are built in with the phases shifted by 180 degrees, and are placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electric output of 120 W. A predetermined amount of ion-exchanged water is put, and about 2 ml of the 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. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker becomes maximum.
(5) About 10 mg of toner particles are added little by little to the electrolytic aqueous solution in a state where the electrolytic aqueous solution in the beaker of the above (4) is irradiated with ultrasonic waves and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to 10 ° C or higher and 40 ° C or lower.
(6) Using a pipette, drop the electrolytic aqueous solution of (5) into which the toner particles are dispersed into the round-bottom beaker of (1) installed in the sample stand, and adjust so that the measured concentration is about 5%. To do. Then, the measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the apparatus to calculate the weight average particle diameter (D4). The "arithmetic diameter" of the "analysis / volume statistical value (arithmetic mean)" screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

<Measurement of number average particle size of fine particles>
Two oscillators with an oscillating frequency of 50 kHz are built in with the phases shifted by 180 degrees, and a predetermined amount is stored in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetra 150" (manufactured by Nikkaki Bios) with an electric output of 120 W. Ion-exchanged water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
Next, 30 ml of methanol is placed in a glass 100 ml flat-bottom beaker. The flat bottom beaker is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of methanol in the beaker becomes maximum.
Next, while irradiating ultrasonic waves to the methanol in the beaker, about 30 mg of the fine particles used in the present invention are added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to 10 ° C or higher and 40 ° C or lower.
One drop of the obtained fine particle dispersion of methanol was dropped on a collodion film-attached mesh, air-dried for 3 hours or more, and then mounted on a transmission electron microscope (JEM-2800, manufactured by JEOL Ltd.) to adjust the focus. To do. The magnification is appropriately changed depending on the particle size of the fine particles, and the image is made clear at that magnification. As a guideline for the magnification, when a transmitted image is output on A4 paper, particles having a number average particle diameter (approximately within ± 10% of the number average particle diameter) measured using a caliper described below are 1.0 cm to The magnification is such that the output is within a range of 2.0 cm.
The obtained transmission image is output to A4 paper and the number average particle diameter is measured using a caliper. At this time, if the fine particles are not true spheres, the longest diameter is visually selected and measured. Thus, 100 randomly selected particles are measured, and the average value of the 100 particles is taken as the number average particle diameter of the fine particles used in the present invention. When particles having the same number average particle diameter as the fine particles are output outside the range of 1.0 cm to 2.0 cm, the magnification is adjusted again and the measurement is performed again.

<Measurement of charge amount of toner>
The charge amount of the toner of the present invention can be determined by the method described below. First, a toner and a standard carrier for negatively charged polar toner (trade name: N-01, manufactured by Japan Imaging Society) are left for 24 hours in an environment of 30 ° C./80% RH. After standing, the toner is mixed with the above carrier so that the mass of the toner becomes 5% by mass, and mixed for 120 seconds using a turbula mixer. This is defined as the "initial agent". Next, 0.40 g of the initial agent was placed in a metal container equipped with a conductive screen having an opening of 20 μm on the bottom and sucked with a suction machine, and the mass difference before and after suction and the condenser connected to the container were measured. Measure the accumulated potential. At this time, the suction pressure is set to 2.5 kPa. From the mass difference, the stored potential, and the capacitance of the capacitor, the toner charge amount Q is calculated using the following formula. The charge amount obtained here is defined as the high temperature and high humidity initial charge amount (mC / kg). In addition, the initial agent left as it is for 24 hours is referred to as a "leaving agent", and the charge amount obtained by similarly measuring the leaving agent is set as a high temperature and high humidity leaving charge amount (mC / kg). The standard carrier for negatively charged polar toner used for the measurement is one that has passed through 250 mesh.
| Q | = | C × V / (W1-W2) |
Q: Toner charge amount C (μF): Capacitance of capacitor V (volt): Potential accumulated in capacitor W1-W2 (kg): Difference in mass before and after suction

<Confirmation of condensation polymer of silicon compound on toner particle surface>
In the present invention, it was confirmed as follows that a condensation polymer of a silicon compound was formed on the surface of the toner particles. First, the toner particles are sufficiently dispersed in a room temperature curable epoxy resin, and then cured in an atmosphere of 40 ° C. for 2 days. A flaky sample is cut out from the obtained cured product using a microtome equipped with diamond teeth. Using a transmission electron microscope (TEM), the tomographic plane of the toner particles is observed at a magnification of 10,000 to 100,000 times. Here, when silicon atom mapping is performed using EDX (energy dispersive X-ray spectroscopy), it can be confirmed that a condensation polymer of a silicon compound is formed on the surface of the toner particles of the present invention. In the examples shown below, it was confirmed that a condensation polymer of a silicon compound was formed on the surface of the toner particles. In the present invention, the above confirmation may be made based on the difference in atomic weight between silicon atoms and other atoms in the toner and the fact that the contrast becomes brighter when the atomic weight is large.

  Hereinafter, the present invention will be described in more detail with reference to specific production methods, examples, and comparative examples, but these do not limit the present invention in any way. All parts in the following formulations are parts by mass.

<Manufacture of polyester resin 1>
-Terephthalic acid 110 mol-Bisphenol A-propylene oxide 2 mol adduct (PO-BPA) 109 mol The above monomer was charged into an autoclave together with an esterification catalyst, and a decompression device, a water separation device, a nitrogen gas introduction device, and a temperature measurement device were used. Then, the stirrer was attached to an autoclave, and the reaction was carried out at 210 ° C. according to a conventional method under a reduced pressure in a nitrogen atmosphere until Tg (glass transition temperature) reached 68 ° C. to obtain a polyester resin 1. The weight average molecular weight (Mw) was 7,400 and the number average molecular weight (Mn) was 3,020.

<Production of silica fine particles 1>
・ Tetraethoxysilane 100 parts by mass ・ Ammonia water (28%) 6 parts by mass ・ Ion-exchanged water 300 parts by mass ・ Ethanol (first-class) 70 parts by mass The above raw materials are reflux tubes with a heating device inside and outside the container, stirring. It was placed in a three-neck pressure resistant container (made of stainless steel) equipped with a machine and a thermometer introduction tube, and the temperature was raised to 60 ° C. with stirring. Then, it hold | maintained at 60 degreeC for 12 hours, and cooled to room temperature. As a result, a slurry was obtained in which fine silica particles were dispersed and became cloudy. After cooling, the slurry was put in a pressure filter and filtered. Furthermore, 100 parts by mass of primary ethanol was charged into the filter and filtered again. Next, the cake obtained by filtration was taken out into a stainless steel vat, put into a dryer set at 40 ° C., and left for 24 hours. By these operations, silica fine particles 1 were obtained. The number average particle diameter of the obtained silica fine particles 1 was 103 nm.

<Production of silica fine particles 2 to 6>
Silica fine particles 2 to 6 were obtained in the same manner as the silica fine particles 1 except that the raw materials and prescription amounts shown in Table 1 were changed. Regarding the silica fine particles 5, the particle size was further adjusted by a wet sieve. Table 1 shows the number average particle diameter of each of the obtained silica fine particles.

<Titanium oxide fine particles>
Titanium oxide (product name: JR) manufactured by Teika Co., Ltd. was used to adjust the particle size by air classification to obtain titanium oxide fine particles having a number average particle size of 201 nm.

<Alumina fine particles>
Alumina manufactured by Admatech Co., Ltd. (product name: AO-502) was used to adjust the particle size by several times of air classification to obtain alumina fine particles having a number average particle size of 205 nm.

<Hydrotalcite fine particles>
Using hydrotalcite (product name: DHT-4A) manufactured by Kyowa Chemical Industry Co., Ltd., the particle diameter was adjusted by several times of air classification to obtain hydrotalcite fine particles having a number average particle diameter of 252 nm.

<Production of polystyrene resin fine particles>
・ Styrene 100 parts by mass ・ Ion-exchanged water 400 parts by mass ・ Divinylbenzene 2 parts by mass ・ Ammonium persulfate 10 parts by mass

  The above raw materials were placed in a three-neck pressure resistant container (made of stainless steel) equipped with a reflux pipe, a stirrer, and a thermometer introduction pipe having a heating device inside and outside the container, and the temperature was raised to 65 ° C. while stirring. . Then, it hold | maintained at 65 degreeC for 12 hours, and cooled to room temperature. As a result, a slurry was obtained in which the polystyrene resin fine particles were dispersed and became cloudy. After cooling, the slurry was put in a pressure filter and filtered. Furthermore, 100 parts by mass of primary methanol was charged into the filter and filtration was performed again. Next, the cake obtained by filtration was taken out into a stainless steel vat, put into a dryer set at 30 ° C., and left for 24 hours. By these operations, powder of polystyrene resin fine particles was obtained. Further, the particle size of the obtained polystyrene resin fine particles was adjusted by air classification to obtain polystyrene resin fine particles having a number average particle diameter of 201 nm.

<Acrylic resin particles>
Acrylic resin particles (product name: FS-101) manufactured by Nippon Paint Co., Ltd. were used as they were. The number average particle diameter was 105 nm.

[Example 1]
200 parts by mass of ion-exchanged water and 300 parts by mass of 0.1 mol / liter aqueous solution of Na ₃ PO _{4 in} a 5-neck pressure resistant container (made of stainless steel) equipped with a reflux pipe, a stirrer, a thermometer and a nitrogen introduction pipe. 6.5 parts by mass of 1.0 mol / liter HCl aqueous solution were added, and the mixture was maintained at 63 ° C. while stirring at a peripheral speed of 29 m / s using a high speed stirring device CLEARMIX (manufactured by M Technic Co., Ltd.). To this, 25 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution was added to prepare an aqueous dispersion medium containing a fine sparingly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

(Dissolution process)
Then, a polymerizable monomer composition was prepared using the following raw materials. This process is defined as a dissolution process.
-Styrene monomer 75.0 parts by mass-n-butyl acrylate 25.0 parts by mass-Divinylbenzene 0.1 part by mass-Methyltriethoxysilane 7.0 parts by mass-Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.5 Parts by mass Polyester resin 1 6.0 parts by mass Charge control agent 0.5 parts by mass (aluminum compound of 3,5-di-tert-butylsalicylic acid)
-Release agent (behenyl behenate) 10.0 parts by mass The above raw materials were dispersed for 3 hours with a handy mill (manufactured by Nippon Coke Industry Co., Ltd.) to obtain a polymerizable monomer composition. Next, this polymerizable monomer composition was transferred to another container and kept at 63 ° C. for 5 minutes while stirring. After that, 20.0 parts by mass of a polymerization initiator, t-butylperoxypivalate (50% toluene solution), was added, and the mixture was kept for 5 minutes while stirring. The process up to this point is the dissolution process.

(Granulation process)
Next, the polymerizable monomer composition was put into the aqueous dispersion medium, and granulated for 10 minutes while stirring with a high speed stirring device at a peripheral speed of 29 m / s. The process up to this point is defined as the granulation process.

(1 step of reaction)
After that, the composition obtained in the granulation step was transferred into a 5-neck pressure resistant reaction kettle 1 (made of stainless steel) equipped with a reflux pipe, a stirrer, a thermometer, and a nitrogen introduction pipe, and a propeller-type stirrer was used. The internal temperature was raised to 70 ° C. with slow stirring. The time required for raising the temperature was 10 minutes. Furthermore, the reaction was carried out for 5 hours with slow stirring. The process up to this point is defined as the reaction 1 step. It was confirmed that the hydrolyzate of methyltriethoxysilane was dissolved in water at the end of the first reaction step.
A fine particle dispersion liquid was prepared in which 1.0 part by mass of silica fine particles 1 was dispersed in 3.0 parts by mass of methyltriethoxysilane before the completion of the reaction 1 step. In this example, a homogenizer was used to disperse more uniformly.

(2 steps of reaction)
After the completion of the reaction 1 step, the fine particle dispersion was charged into the reaction kettle 1 while slowly stirring with a propeller stirrer, and the temperature in the container was raised to 85 ° C. The time required for raising the temperature was 20 minutes. Then, the inside of the container was maintained at 85 ° C. for 3.0 hours. The process up to this point is defined as the reaction 2 step.

(Distillation process)
After the completion of the reaction step 2, the composition obtained at the end of the reaction step 2 was placed in a pressure resistant reaction kettle 2 (made of stainless steel) equipped with a stirrer, a thermometer, a steam introduction pipe, and a distillation device capable of cooling and collecting the fraction. Was transferred, steam was blown in, and the temperature inside the kettle was raised to 100 ° C. The time required for raising the temperature was 80 minutes. Then, distillation was carried out at a pot temperature of 100 ° C. for 5.0 hours. The process up to this point is defined as a distillation process. In this example, it was confirmed that about 15% of the total amount of added methyltriethoxysilane was condensed at the start of this distillation step, and the remaining about 85% was condensed at the end of the distillation step. Therefore, the condensation temperature can be defined as 100 ° C. Further, the temperature at which the distillation was carried out was the distillation temperature, and the time during which the distillation temperature was maintained was the distillation time. In this step, residual monomers and ethanol and other solvents generated by hydrolysis were also removed.

(Cooling process)
Immediately after the end of the distillation step, the mixture was cooled to 30 ° C., diluted hydrochloric acid was added to the container to lower the pH to 1.5, and the sparingly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ as a dispersion stabilizer was dissolved. . The process up to this point is defined as a cooling process. At the end of the cooling step, the hydrolyzate of methyltriethoxysilane present in the water was less than 10 ppm. In addition, it was confirmed that the amount of fine particles present in water at the end of the cooling step was less than 100 ppm at most.

  Furthermore, the dispersion stabilizer was removed by performing filtration. After filtration, the obtained cake was not taken out, ion-exchanged water was further added, and filtration was performed again to wash. Then, the cake after filtration was taken out, dried by a flash jet dryer flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.), and powder was collected by a cyclone. Then, this powder was subjected to air classification while being sent with compressed air to cut fine coarse powder, which was passed through a 10 m pipe and then collected by a cyclone 2. The powder thus obtained is toner particle 1. At the end of the cooling process, the content of the substance derived from methyltriethoxysilane in water was less than 10 ppm, and the amount of fine particles was less than 100 ppm. In consideration of the stoichiometry by the above, it was calculated as toner particles. Table 2 shows the conditions of the above steps. The weight average particle diameter (D4) of the obtained toner particles 1 was measured. Table 4 shows the physical properties of Toner Particles 1. Moreover, the following evaluation was performed.

<Evaluation of charge amount>
The initial charge amount and the charge amount after standing at high temperature and high humidity, which were measured according to the above measuring method, were ranked as follows. The following evaluations were excellent in the order of ranks A, B, C and D, and ranks A to C were judged to be ranges in which the effects of the present invention can be obtained. Table 4 shows the evaluation results.
Rank A: 35.0 mC / kg or more Rank B: 34.9 mC / kg to 30.0 mC / kg
Rank C: 29.9 mC / kg to 25.0 mC / kg
Rank D: 24.9 mC / kg or less

<Image evaluation>
The tandem type Canon laser beam printer LBP9510C having the configuration shown in FIG. 1 was modified to enable printing only at the cyan station. In addition, it was modified so that the back contrast could be set arbitrarily. Using this LBP9510C toner cartridge, 200 g of toner particles 1 were filled. Then, the toner cartridge was left standing for 24 hours in an environment of high temperature and high humidity (30.0 ° C./80.0% RH). After being left in this environment for 24 hours, the toner cartridge was attached to the LBP9510C, and an image with a print ratio of 1.0% was printed out to 15,000 sheets in the lateral direction of A4 paper.
At this time, the initial image density (initial density) and the image density when outputting 15,000 sheets (density after endurance) were evaluated. The paper was evaluated by outputting a solid image using XEROX BUSINESS 4200 (manufactured by XEROX, 75 g / m ² ) and measuring the density thereof. The image density was measured by using "Macbeth reflection densitometer RD918" (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to the image of the white background portion where the document density was 0.00. In image evaluation, the image densities were ranked as follows. The following evaluations were excellent in the order of ranks A, B, C, D, and E, and ranks A to D were judged to be ranges within which the effects of the present invention can be obtained. The evaluation results are shown in Table 5.
Rank A: Image density 1.40 or more Rank B: Image density 1.39 to 1.30
Rank C: Image density 1.29 to 1.25
Rank D: Image density 1.24 to 1.20
Rank E: Image density 1.19 or less

<Evaluation of reactor contamination>
With respect to the reaction kettle 1 and the reaction kettle 2 where the toner particles 1 were once produced, only washing with high-pressure water was stopped, and the same toner particles 1 as described above were produced using the reaction kettles. The same operation was repeated, and the same toner particles 1 were produced three times in total. Finally, the reaction kettles were washed with high-pressure water and visually evaluated for contamination of the reaction kettles according to the following criteria. The following evaluations were excellent in the order of ranks A, B, C, D, and E, and ranks A to C were judged to be ranges in which the effects of the present invention can be obtained. Table 4 shows the evaluation results.
Rank A: Adhesion of the toner composition is seen at the gas-liquid interface, but no adhesion is seen on the wall surface of the pot where the slurry is constantly immersed. Rank B: Adhesion of the toner composition is seen at the gas-liquid interface, A thin adhesion of the toner composition is partially seen on the wall surface of the kettle where the slurry is constantly immersed. Rank C: A thick adhesion of the toner composition is seen at the gas-liquid interface, and the wall surface of the kettle where the slurry is constantly immersed. Partly, a thin adhesion of the toner composition is seen. Rank D: A thick adhesion of the toner composition is found at the gas-liquid interface, and the toner composition Thin adhesion is seen Rank E: Thick adhesion of the toner composition is seen at the gas-liquid interface, and thick adhesion of the toner composition is generally seen on the pot wall surface where the slurry is constantly immersed.

<Evaluation of cyclone pollution and piping pollution>
With respect to the cyclone and the pipe, the same toner particles 1 were continuously prepared three times and cleaned by air blow. Then, the evaluation was visually performed according to the following criteria. The following evaluations were excellent in the order of ranks A, B, C, D, and E, and ranks A to C were judged to be ranges in which the effects of the present invention can be obtained. Table 4 shows the evaluation results.
Rank A: 99% or more of the toner particles on the wall surface are removed by air blow Rank B: 80% or more and less than 99% of the toner particles on the wall surface are removed by air blow Rank C: 50% or more but less than 80 wall surface of the air blow Rank D: Toner particles on the wall surface of 10% or more and less than 50% are removed by air blow Rank E: Toner particles on the wall surface of less than 10% are removed by air blow

  Although not shown in Table 5, the contamination status of the cyclone 2 was also confirmed, and the result was the same as the piping contamination result. The same applies to the following examples.

[Examples 2 to 15, Examples 19 to 27]
Toner particles 2 to 15 and 19 to 27 were produced according to the above-described Example 1 except that the manufacturing conditions and the formulations shown in Tables 2 and 3 were changed. With respect to the obtained toner particles, the weight average particle diameter was measured in the same manner as in Example 1 and each evaluation was performed. Physical properties of the toner particles are shown in Table 4, and evaluation results are shown in Table 5. The methods of vacuum distillation and pressure distillation are as follows.
For vacuum distillation, remove the steam introduction tube and change the specification to adjust the temperature by heating the reaction kettle itself, and attach a pressure reducer to the open port so that it is not drawn into the distillation equipment side that collects the distillate. It was carried out by reducing the pressure.
During pressure distillation, attach a pressurizer to the open port and a valve on the side of the distillation device so that it is not affected by pressure. During distillation, the valve on the side of the distillation apparatus was opened once every three minutes to return to normal pressure, and volatile matter was collected.

[Example 16]
In a 5-neck pressure vessel equipped with a reflux tube, a stirrer, a thermometer and a nitrogen introducing tube, 700 parts by mass of ion-exchanged water and 1000 parts by mass and 1.0 part by mass of 0.1 mol / liter Na ₃ PO ₄ aqueous solution. Per liter of HCl aqueous solution (24.0 parts by mass) was added, and the mixture was maintained at 63 ° C. with stirring at a peripheral speed of 29 m / s using a high speed stirrer CLEARMIX (manufactured by M Technique Co., Ltd.). To this, 25 parts by mass of 1.0 mol / liter CaCl ₂ aqueous solution was added to prepare an aqueous dispersion medium containing a fine sparingly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

(Dissolution process)
Then, a toner particle precursor composition was prepared using the following raw materials. This process is defined as a dissolution process.
Polyester resin 1 100.0 parts by mass Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.5 parts by mass Charge control agent 0.5 parts by mass (aluminum compound of 3,5-di-tert-butylsalicylic acid)
-Release agent (behenyl behenate) 10.0 parts by mass-Toluene 400.0 parts by mass The above raw materials are dispersed in a handy mill (manufactured by Nippon Coke Industry Co., Ltd.) for 3 hours, and then heated to 63 ° C to obtain a toner. A particle precursor composition was obtained.

(Granulation process)
Next, the above toner particle precursor composition was put into an aqueous dispersion medium, and granulated for 10 minutes while stirring at a peripheral speed of 29 m / s using a high speed stirring device CLEARMIX (manufactured by M Technic Co., Ltd.).

(1 step of reaction)
After that, the composition obtained in the granulation step was transferred into a 5-neck pressure resistant reaction kettle 1 (made of stainless steel) equipped with a reflux pipe, a stirrer, a thermometer, and a nitrogen introduction pipe, and a propeller-type stirrer was used. The internal temperature was raised to 70 ° C. with slow stirring. The time required for raising the temperature was 10 minutes. Furthermore, it was maintained for 1 hour with slow stirring. The process up to this point is defined as the reaction 1 step.
A fine particle dispersion liquid was prepared in which 1.0 part by mass of silica fine particles 1 was dispersed in 10.0 parts by mass of methyltriethoxysilane before the completion of the reaction 1 step. In this example, a homogenizer was used to disperse more uniformly.

(2 steps of reaction)
After the completion of the reaction 1 step, the fine particle dispersion was charged into the reaction kettle 1 and the temperature in the container was raised to 85 ° C. The time required for raising the temperature was 20 minutes. Then, the inside of the container was maintained at 85 ° C. for 3.0 hours. The process up to this point is defined as the reaction 2 step.

(Distillation process)
After the completion of the reaction step 2, the composition obtained at the end of the reaction step 2 was placed in a pressure resistant reaction kettle 2 (made of stainless steel) equipped with a stirrer, a thermometer, a steam introduction tube, and a distillation device capable of cooling and collecting the fraction. After transferring, steam was blown in and the temperature inside the kettle was raised to 100 ° C. The time required for raising the temperature was 80 minutes. Then, distillation was carried out at a pot temperature of 100 ° C. for 5.0 hours. The process up to this point is defined as a distillation process. In this example, it was confirmed that about 5% of the total amount of methyltriethoxysilane added was condensed at the start of this distillation step, and the remaining about 95% was condensed at the end of the distillation step. Therefore, the condensation temperature can be defined as 100 ° C. In this step, the solvent used and other solvents such as ethanol generated by hydrolysis were also removed.

(Cooling process)
Immediately after the completion of distillation, the mixture was cooled to 30 ° C., diluted hydrochloric acid was added to the container to lower the pH to 1.5, and the sparingly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ as a dispersion stabilizer was dissolved. The process up to this point is defined as a cooling process. At the end of the cooling step, the hydrolyzate of methyltriethoxysilane present in the water was less than 10 ppm. In addition, it was confirmed that the amount of fine particles present in water at the end of the cooling step was less than 100 ppm at most.

Furthermore, the dispersion stabilizer was removed by performing filtration. After filtration, the obtained cake was not taken out, ion-exchanged water was further added, and filtration was performed again to wash.
Then, the cake after filtration was taken out, dried by a flash jet dryer flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.), and powder was collected by a cyclone. Then, this powder was subjected to air classification while being sent with compressed air to cut fine coarse powder, which was passed through a 10 m pipe and then collected by a cyclone 2. The powder thus obtained is the toner particle 16. At the end of the cooling step, the substance derived from methyltriethoxysilane present in water was less than 10 ppm, and the fine particles were less than 100 ppm. In consideration of the stoichiometry by the above, it was calculated as toner particles. With respect to the obtained toner particles 16, the weight average particle diameter was measured and each evaluation was performed in the same manner as in Example 1. Table 4 shows the physical properties of the toner particles 16, and Table 5 shows the evaluation results.

[Example 17]
(Manufacture of styrene acrylic resin)
300 parts by mass of ion-exchanged water and 100 parts by mass of 1.0 mol / l Na ₃ PO ₄ aqueous solution and 1.0 mol / l in a 4-necked container equipped with a reflux tube, a stirrer, a thermometer and a nitrogen introduction tube. 5.0 parts by mass of HCl aqueous solution was added, and the mixture was maintained at 60 ° C. while stirring at 5,000 rpm using a high-speed stirring device TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 20 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine sparingly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ . Then, a monomer mixture was prepared using the following materials.
-Styrene 70.0 parts by mass-n-butyl acrylate 30.0 parts by mass-Divinylbenzene 0.10 parts by mass

  Next, the obtained monomer mixture was heated to 60 ° C. with stirring, and then 16.0 parts by mass of t-butylperoxypivalate (toluene solution 50%) as a polymerization initiator was added, Hold for 5 minutes with stirring. Next, the above monomer mixture was put into an aqueous dispersion medium, and granulated for 10 minutes while stirring with a high-speed stirring device. Then, the high-speed stirring device was changed to a propeller-type stirrer, the internal temperature was raised to 70 ° C., and the reaction was carried out for 5 hours while slowly stirring. Next, the temperature inside the container was raised to 90 ° C. and maintained for 7.5 hours. Next, 300 parts by mass of ion-exchanged water was added, the reflux tube was removed, and the distillation apparatus was attached. Distillation was carried out at a temperature of 100 ° C. in the container for 5 hours to remove residual monomers, and a polymer slurry was obtained. Dilute hydrochloric acid was added to the container containing the polymer slurry after cooling to 30 ° C. to remove the dispersion stabilizer. Furthermore, filtration, washing, and drying were performed to obtain a styrene acrylic resin.

(Preparation of toner particle precursor)
Styrene acrylic resin 100.0 parts by mass Copper phthalocyanine pigment (pigment blue 15: 3) 6.5 parts by mass Charge control agent 0.1 parts by mass (aluminum compound of 3,5-di-tert-butylsalicylic acid)
-Polyester resin 1 4.0 parts by mass-Release agent (behenyl behenate) 10.0 parts by mass After mixing the above materials with an FM mixer (manufactured by Nippon Coke Industry Co., Ltd.), a twin-screw kneading extruder is used. Melt kneading was performed at 135 ° C. After cooling the kneaded product, coarse pulverization was performed using a cutter mill, pulverization was performed using a fine pulverizer using a jet stream, and classification was performed using an air classifier to obtain a toner particle precursor.

(Preparation of aqueous dispersion medium)
200 parts by mass of ion-exchanged water and 300 parts by mass of 0.1 mol / liter aqueous solution of Na ₃ PO _{4 in} a 5-neck pressure resistant container (made of stainless steel) equipped with a reflux pipe, a stirrer, a thermometer and a nitrogen introduction pipe. 6.5 parts by mass of 1.0 mol / liter HCl aqueous solution were added, and the mixture was maintained at 63 ° C. while stirring at a peripheral speed of 29 m / s using a high speed stirring device CLEARMIX (manufactured by M Technic Co., Ltd.). To this, 25 parts by mass of 1.0 mol / liter CaCl ₂ aqueous solution was added to prepare an aqueous dispersion medium containing a fine sparingly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ . Further, the aqueous dispersion medium was transferred to the same reaction kettle 1 as in Example 1.

(Preparation of fine particle dispersion)
A fine particle dispersion was prepared by dispersing 1.0 part by weight of silica fine particles 1 in 10.0 parts by weight of methyltriethoxysilane. In this example, a homogenizer was used to disperse more uniformly.

(Adding the toner particle precursor to the aqueous dispersion medium)
165 parts by mass of the toner particle precursor was charged into a reaction kettle 1 containing the aqueous dispersion medium, and the temperature was raised to 85 ° C. with gentle stirring.

  Then, the fine particle dispersion liquid was charged into the reaction kettle 1 in which the toner particle precursor was dispersed in the aqueous medium. Then, the inside of the container was maintained at 85 ° C. for 3.0 hours.

(Distillation process)
Then, the obtained composition was transferred to a pressure-resistant reaction kettle 2 (made of stainless steel) equipped with a stirrer, a thermometer, a steam introduction tube, and a distillation device capable of cooling and recovering a distillate, and steam was blown into the kettle to cool the inside of the kettle. The temperature was raised to 100 ° C. The time required for raising the temperature was 80 minutes. Further, distillation was carried out at a pot temperature of 100 ° C. for 5.0 hours. In this example, it was confirmed that about 5% of the total amount of methyltriethoxysilane added was condensed at the start of this distillation step, and the remaining about 95% was condensed at the end of the distillation step. Therefore, the condensation temperature can be defined as 100 ° C. In this step, ethanol and the like generated by hydrolysis were also removed.

(Cooling process)
Immediately after the completion of distillation, the mixture was cooled to 30 ° C., diluted hydrochloric acid was added to the container to lower the pH to 1.5, and the sparingly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ as a dispersion stabilizer was dissolved. The process up to this point is defined as a cooling process. At the end of the cooling step, the hydrolyzate of methyltriethoxysilane present in the water was less than 10 ppm. In addition, it was confirmed that the amount of fine particles present in water at the end of the cooling step was less than 100 ppm at most.

Furthermore, the dispersion stabilizer was removed by performing filtration. After filtration, the cake obtained was not taken out, ion-exchanged water was further added, and filtration was performed again to wash.
Then, the cake after filtration was taken out, dried by a flash jet dryer flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.), and powder was collected by a cyclone. Then, this powder was subjected to air classification while being sent with compressed air to cut fine coarse powder, which was passed through a 10 m pipe and then collected by a cyclone 2. The powder thus obtained is the toner particles 17. At the end of the cooling step, the substance derived from methyltriethoxysilane present in water was less than 10 ppm, and the fine particles were less than 100 ppm. After taking account of the theory, it was calculated as toner particles. With respect to the obtained toner particles 17, the weight average particle diameter was measured and each evaluation was performed in the same manner as in Example 1. Physical properties of the toner particles 17 are shown in Table 4, and evaluation results are shown in Table 5.

[Example 18]
(Preparation of resin particle dispersion)
-Polyester resin 1 100 parts by mass-Methyl ethyl ketone 50 parts by mass-Isopropyl alcohol 20 parts by mass Methyl ethyl ketone and isopropyl alcohol were placed in a container. Then, the above resin was gradually added and stirred to completely dissolve it to obtain a crystalline polyester resin 1 solution. The container containing the polyester resin 1 solution was set to 65 ° C., 10% aqueous ammonia solution was gradually added dropwise with stirring to a total amount of 5 parts by mass, and further 230 parts by mass of ion-exchanged water was added at 10 ml / It was gradually added dropwise at a rate of min to carry out phase inversion emulsification. Further, the solvent was removed under reduced pressure by an evaporator to obtain a resin particle dispersion liquid. The volume average particle diameter of the resin particles in the obtained resin particle dispersion was 140 nm. The solid content of resin particles was adjusted to 20% with ion-exchanged water.

(Preparation of colorant particle dispersion)
45 parts by mass of copper phthalocyanine (Pigment Blue 15: 3) 0.7 parts by mass of charge control agent (aluminum compound of 3,5-di-tert-butylsalicylic acid)
・ Ionic surfactant Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 5 parts by mass ・ Ion-exchanged water 190 parts by mass The above components were mixed and dispersed by a homogenizer for 10 minutes, and then an ultimizer (counter-collision type wet pulverization). Machine, manufactured by Sugino Machine Ltd., for 20 minutes at a pressure of 250 MPa to obtain a colorant particle dispersion liquid having a volume average particle diameter of the colorant particles of 130 nm and a solid content of 20%.

(Preparation of release agent particle dispersion)
-Behenyl behenate 60 parts by mass-Ionic surfactant Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 2.0 parts by mass-Ion-exchanged water 240 parts by mass The above components are heated to 100 ° C to produce IKA Ultra After being sufficiently dispersed by Turrax T50, the dispersion liquid is heated to 115 ° C. with a pressure discharge type Gohlin homogenizer for 1 hour to obtain a release agent particle dispersion liquid having a volume average particle diameter of 160 nm and a solid content of 20%. It was

(Preparation of toner particle precursor)
Resin particle dispersion liquid 600 parts by mass Colorant particle dispersion liquid 39 parts by mass Release agent particle dispersion liquid 60 parts by mass After adding 2.2 parts by mass of the ionic surfactant Neogen RK to the reaction kettle 1, the above The dispersion was added with stirring. Next, 1M nitric acid was added dropwise to adjust the pH to 3.7, 0.35 parts by mass of polyaluminum sulfate was added thereto, and dispersion was performed with Ultra Turrax. The flask was heated to 50 ° C. with stirring in a heating oil bath and held for 40 minutes. As a result, a toner particle precursor was obtained.

(Preparation of fine particle dispersion)
Before the above steps were completed, a fine particle dispersion liquid was prepared in which 1.0 part by mass of silica fine particles 1 was dispersed in 10.0 parts by mass of methyltriethoxysilane. In this example, a homogenizer was used to disperse more uniformly.

  Then, the fine particle dispersion liquid was charged into the same reaction kettle 1 as in Example 1. Next, the temperature in the container was raised to 85 ° C. The time required for raising the temperature was 20 minutes. Furthermore, the inside of the container was maintained at 85 ° C. for 3.0 hours.

(Distillation process)
Then, the obtained composition was transferred to a pressure-resistant reaction kettle 2 (made of stainless steel) equipped with a stirrer, a thermometer, a steam introduction tube, and a distillation device capable of cooling and recovering a distillate, and steam was blown into the kettle to cool the inside of the kettle. The temperature was raised to 100 ° C. The time required for raising the temperature was 80 minutes. Then, distillation was carried out at a pot temperature of 100 ° C. for 5.0 hours. In this example, it was confirmed that about 5% of the total amount of methyltriethoxysilane added was condensed at the start of this distillation step, and the remaining about 95% was condensed at the end of the distillation step. Therefore, the condensation temperature can be defined as 100 ° C. In this step, the solvent used and other solvents such as ethanol generated by hydrolysis were also removed.

(Cooling process)
Immediately after the end of the distillation step, the mixture was cooled to 30 ° C., diluted hydrochloric acid was added to the container to lower the pH to 1.5, and the sparingly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ as a dispersion stabilizer was dissolved. . The process up to this point is defined as a cooling process. At the end of this cooling step, the hydrolyzate of methyltriethoxysilane present in water was less than 10 ppm. In addition, it was confirmed that the amount of fine particles present in water at the end of the cooling step was less than 100 ppm at most.

  Furthermore, the dispersion stabilizer was removed by performing filtration. After filtration, the cake obtained was not taken out, ion-exchanged water was further added, and filtration was performed again to wash. Then, the cake after filtration was taken out, dried by a flash jet dryer flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.), and powder was collected by a cyclone. Then, this powder was subjected to air classification while being sent with compressed air to cut fine coarse powder, which was passed through a 10 m pipe and then collected by a cyclone 2. The powder thus obtained is the toner particles 18. At the end of the cooling step, the substance derived from methyltriethoxysilane present in water was less than 10 ppm, and the fine particles were less than 100 ppm. In consideration of the stoichiometry by the above, it was calculated as toner particles. With respect to the obtained toner particles 18, the weight average particle diameter was measured and each evaluation was performed in the same manner as in Example 1. The physical properties of the obtained toner particles 18 are shown in Table 4, and the evaluation results are shown in Table 5.

[Comparative Example 1]
According to the production conditions and prescriptions shown in Table 3, and except that the stirring in the two reaction steps was changed to a method of stirring at a peripheral speed of 29 m / s using a high speed stirrer CLEARMIX (manufactured by M Technique Co., Ltd.). Toner particles were prepared according to Example 1. The physical properties of the obtained toner particles are shown in Table 4, and the evaluation results are shown in Table 6.

[Comparative Examples 2 and 3, Comparative Examples 5-8]
According to the manufacturing conditions and prescriptions shown in Table 3, the same operations as in Example 1 were carried out except the above, to prepare toner particles. The physical properties of the obtained toner particles are shown in Table 4, and the evaluation results are shown in Table 6.

[Comparative Example 4]
After completion of the reaction 2 step, toner particles were prepared in the same manner as in Comparative Example 1 except that 10.0 parts by mass of methyltriethoxysilane was added. The physical properties of the obtained toner particles are shown in Table 4, and the evaluation results are shown in Table 6.

1: photoconductor, 2: developing roller, 3: toner supply roller, 4: toner, 5: regulating blade, 6: developing device, 7: laser light, 8: charging device, 9: cleaning device, 10: charging for cleaning Device: 11: stirring blade, 12: drive roller, 13: transfer roller, 14: bias power supply, 15: tension roller, 16: transfer / convey belt, 17: driven roller, 18: paper, 19: paper feed roller, 20: Adsorption roller, 21: fixing device

Claims (6)

Step 1:
(I) at least one silicon compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3),
(Ii) fine particles having a number average particle diameter of 10 nm or more and 500 nm or less, and (iii) a toner particle precursor,
A step of preparing a liquid composition in which the coexisting in an aqueous medium,
Step 2: a step of condensing the silicon compound in the liquid composition at a temperature of 60 ° C. or higher and 105 ° C. or lower to fix the fine particles on the surface of the toner particle precursor, and step 3: fix the fine particles Filtering the obtained toner particle precursor from the aqueous medium, and then drying to obtain toner particles;
A method for producing toner particles having:
The fine particles are present on the surface of the toner particles in an amount of 0.10% by mass or more and 5.00% by mass or less, based on the mass of the toner particles .
In the step 1, after the silicon compound and the fine particles are mixed to prepare a fine particle dispersion liquid, the fine particle dispersion liquid is put into the aqueous medium in which the toner particle precursor is present, and the liquid composition is obtained. Prepare things,
A method for producing toner particles, comprising:

(In the formulas (1), (2) and (3), R ^d , R ^e and R ^f each independently represent an alkyl group, an alkenyl group, an acetoxy group, an acyl group or an aryl group, and R ² , ^{R 3, R 4, R 5} , R 6, R 7, R 8, R 9 and ^{R 10} each independently represents a halogen atom, a hydroxy group or an alkoxy group.)   The step 2 is a step of condensing the silicon compound in the liquid composition at a temperature of 85 ° C. or higher and 100 ° C. or lower to fix the fine particles on the surface of the toner particle precursor. A method for producing the toner particles described above. Wherein the silicon compound is the formula (2) compound and the formula (3) at least one silicon compound selected from the group consisting of compounds represented by the represented by the according to claim 1 or 2 Method of manufacturing toner particles. The fine particles are inorganic fine particles, method for producing toner particles according to any one of claims 1-3. The silicon compound is a compound represented by formula (2), method for producing the toner particles according to any one of claims 1-4. The method for producing toner particles according to claim 5 , wherein R ^f in the formula (2) is a methyl group or an ethyl group.

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