JP2017134164A - Method for manufacturing toner particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing toner particles with which toner particles can be obtained having a surface covered by fine particles and a silicon compound and exhibiting a good charging property even in a high-temperature and high-humidity environment at a high productivity.SOLUTION: There is provided a method for manufacturing toner particles including the steps of: preparing a liquid composition having a specific silicon compound, fine particles with a number average particle diameter of 10 nm or more and 500 nm or less, and a toner particle precursor coexisting in an aqueous medium; condensing the silicon compound at a temperature of 60°C or more and 105°C or less to fix the fine particles to the surface of the toner particle precursor; and filtering the toner particle precursor out from the aqueous medium to obtain toner particles, where the fine particles are present on the surface of the toner particle in an amount of 0.10 mass% or more and 5.00 mass% or less.SELECTED DRAWING: None

Description

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

  Many techniques for improving toner production performance have been proposed, but the present inventors have focused on a manufacturing method in which the surface of toner particles is covered with a silicon compound mainly using a method of obtaining toner particles in an aqueous medium. doing. Conventionally, many techniques have been used to fix various toner performances by fixing fine particles on the surface of toner particles in an aqueous medium. On the other hand, there are few examples focusing on improving productivity in the production method in which particles are fixed to the toner particle surface in an aqueous medium.

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

JP 08-292599 A US Pat. No. 8,872,692

  INDUSTRIAL APPLICABILITY According to the present invention, in a method for producing toner particles in an aqueous medium, toner particles that are covered with fine particles and a silicon compound and exhibit good charging characteristics even in a high temperature and high humidity environment can be obtained with high productivity. Another object 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 compounds represented by the following formulas (1) to (3);
ii) fine particles having a number average particle diameter of 10 nm to 500 nm, and iii) a toner particle precursor,
Preparing a liquid composition that coexists in an aqueous medium,
Step 2: condensing the silicon compound in the liquid composition at a temperature of 60 ° C. to 105 ° C. to fix the fine particles on the surface of the toner particle precursor, and Step 3: fixing the fine particles. A step of filtering the toner particle precursor thus obtained from the aqueous medium and then drying to obtain toner particles;
A method for producing toner particles comprising:
The method for producing toner particles, wherein the fine particles are present on the surface of the toner particles on the basis of the mass of the toner particles based on 0.10 mass% or more and 5.00 mass% or less.

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 represent a halogen atom, a hydroxy group or an alkoxy group.

  According to the present invention, in a method for producing toner particles in an aqueous medium, it is possible to provide a production method for 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 a container wall surface used when toner particles are produced in an aqueous medium. Indicates. Further, it is shown that the toner particles are effectively prevented from adhering to the inside of the drying apparatus and the pipe for conveying the toner particles after the drying step of powdering the toner particles. The toner particles obtained by the present invention exhibit 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 having the following steps.
Step 1:
i) at least one silicon compound selected from the group consisting of compounds represented by the following formulas (1) to (3);
ii) fine particles having a number average particle diameter of 10 nm to 500 nm, and iii) a toner particle precursor,
Preparing a liquid composition that coexists in an aqueous medium,
Step 2: condensing the silicon compound in the liquid composition at a temperature of 60 ° C. to 105 ° C. to fix the fine particles on the surface of the toner particle precursor, and Step 3: fixing the fine particles. A step of filtering the toner particle precursor thus prepared from the aqueous medium and then drying to obtain toner particles.
Further, the surface of the toner particles is characterized in that the fine particles are present in an amount of 0.10% by mass to 5.00% by mass based on the mass of the toner particles.

  Hereinafter, each step will be described in detail. In the following detailed description, a container used when performing various reactions and particle formation in an aqueous medium in a means for producing toner particles in an aqueous medium is defined as a “reaction vessel”. In the present invention, in the reaction vessel, reaction vessel contamination, which is a problem in production, that is, adhesion due to a substance constituting the toner particle precursor on the reaction vessel surface is effectively prevented. Alternatively, even when the toner particles are produced in an aqueous medium, even in the drying step required as the final step, the toner particles are contaminated due to toner particle adhesion inside the drying device, or the toner particles are placed in a pipe for conveying the toner particles. Effectively prevent adhering contamination. Further, the toner particles of the present invention exhibit good charging characteristics even in a high temperature and high humidity environment. Hereinafter, the presumed mechanism which expresses such an effect is also explained.

<Step 1>
Step 1 is a step of preparing a liquid composition in which i) to iii) coexist in an aqueous medium. Hereinafter, i), ii), and iii) are also referred to as components i), ii), and iii), respectively. Here, the components i), ii) and iii) “coexist” in the aqueous medium means that the silicon compound or a hydrolyzate thereof, fine particles and toner particle precursor exist individually in the aqueous medium. Means that As described above, the coexistence of the components i), ii) and iii) in the aqueous medium is one of the necessary conditions of the present invention. The conditions will be considered.

As a result of investigations 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 required.
A: When a silicon compound is used but fine particles having a number average particle diameter of 10 nm to 500 nm are not used.
B: When the silicon compound is introduced into the aqueous medium after the fine particles have been fixed to the toner particle precursor (the fine particles are not present alone in the aqueous medium).
The above A suggests that a 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 suggests that the adhesion force of the toner particle precursor to the reaction kettle surface is reduced by reducing the contact area when the toner particle precursor is brought into contact with the reaction kettle surface. On the other hand, it is presumed that the above B suggests an appropriate uneven condition for maintaining the adhesion preventing function throughout the manufacturing process. That is, it is presumed that when the condensation compound 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 adhesion area to the reaction vessel is impaired. The

[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 formula (2) and the formula (3). This is because the viscosity of the toner particle precursor surface in each step is lower in the condensation polymer derived from the trifunctional or tetrafunctional silicon compound than in the condensation polymer derived from the bifunctional silicon compound. Presumed. Moreover, it is more preferable to use the compound represented by the formula (2) from the viewpoint that the effect of the present invention for improving productivity is most easily obtained. The toner particles covered with the condensation polymer derived from the silicon compound represented by the formula (2) are more excellent in charging performance of the toner particles in a high temperature and high humidity environment. Furthermore, R ^f in formula (2) is particularly preferably a methyl group or an ethyl group. This is because the anti-contamination effect in each production process of the present invention is most remarkable and the charging characteristics are 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 represent 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 are functional groups involved in the condensation polymerization. In addition, 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. Is.

  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. As said alkenyl group, C2-C6 alkenyl groups, such as a vinyl group, an allyl group, a butenyl group, a hexenyl group, can be mentioned, for example. As said acyl group, C2-C6 acyl groups, such as an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, can be mentioned, for example. As said aryl group, a phenyl group can be mentioned, for example. As said halogen atom, a fluorine atom, a chlorine atom, and a bromine atom can be mentioned, for example. As said alkoxy group, C1-C6 alkoxy groups, such as a methoxy group, an ethoxy group, a propyloxy group, a butyloxy group, can be mentioned, for example. 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, and propyltrimethoxysilane. , Propyltriethoxysilane, propyltrichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butylmethoxydichlorosilane, butylethoxydichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrimethoxysilane, phenyl Examples include triethoxysilane, vinyltriethoxysilane, methacryloxypropyltriethoxysilane, and the like. A tetraethoxysilane is mentioned as a silicon compound represented by Formula (3). Moreover, these hydrolysates may be sufficient. These silicon compounds may be used individually by 1 type, and may use 2 or more types together.

[Component ii): Fine particles]
In the present invention, fine particles having a number average particle diameter of 10 nm to 500 nm are used. The number average particle diameter of the fine particles is preferably 20 nm to 400 nm, more preferably 30 nm to 300 nm, and particularly preferably 50 nm to 200 nm. This condition suggests that it 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 include inorganic fine particles such as silica, titania, alumina and hydrotalcite, and polymer resin fine particles such as polymethyl methacrylate resin, urethane resin, phenol resin and polystyrene resin. Among these, inorganic fine particles are preferable. Not only the convex shape present on the toner particle surface, but also the hardness of the fine particles contributes to both the reaction vessel adhesion prevention effect and the effect of peeling off the initial thin deposits. It is estimated to work effectively.

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

[Aqueous medium]
Examples of the aqueous medium in the present invention include alcohols such as water, 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 and the fine particles are dispersed, that is, after preparing the fine particle dispersion, the fine particle dispersion is put into an aqueous medium containing the toner particle precursor. A method of preparing the liquid composition is preferred. This is considered to be a suitable condition in which the fine particles are fixed to the surface of the toner particle precursor and are not buried too much by the condensation of the silicon compound. Hereinafter, the reason why this condition is suitable will be considered.

  The silicon compound used in the present invention dissolves in water, or even if it is initially hydrophobic, it becomes a hydrolyzate by hydrolysis, so it can be finally dissolved in an aqueous medium and condensed. Changes to a new material. 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, from which the condensation further proceeds. 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, the silicon compound is hydrolyzed, dissolved in the aqueous medium, and absorbed into the toner particle precursor first. Here, it is assumed that condensation of the silicon compound hardly occurs on the outermost surface of the fine particles existing alone in the aqueous medium under the above-mentioned preferable conditions. For this reason, it is presumed that the fine particles are more firmly fixed in the vicinity of the outermost surface by maintaining a suitable balance between the condensation progress rate of the silicon compound on the surface of the toner particle precursor and the fine particles. From the above, it is considered that the shape of the fine particles is easily reflected in the convex shape on the surface of the toner particles, and consequently affects the adhesion preventing effect of the toner particle precursor and the toner particles during the manufacturing process.

<Process 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. to 105 ° C. As long as the silicon compound used in the present invention is used in an aqueous medium, the silicon compound is dissolved in the aqueous medium as it is, or is hydrolyzed through an intermediate (hydrolyzate) containing a silanol group (Si-OH). Dissolve in the medium. And when silanol groups condense, it changes to the condensation polymer of a solid 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 a temperature lower than 60 ° C., the effect of improving the reaction kettle adhesion was not observed. This is presumed to be because the silicon compound in the middle of condensation tends to adhere to the reaction kettle, the condensation rate is slow when the temperature is low, and the state during the condensation lasts longer. On the other hand, even when the condensation was carried out at a temperature higher than 105 ° C., the effect of improving the reaction vessel adhesion was not observed. This is thought to be because molecular motion becomes too active. Therefore, in this step, it is necessary to perform the condensation of the silicon compound at a temperature of 60 ° C. or higher and 105 ° C. or lower.

  In addition, when the condensation proceeds at a temperature lower 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 In the steps after the step, toner particles may adhere. This is presumed to be caused by the fact that the condensation of the silicon compound is insufficient and the drying process is reached. That is, when condensation is insufficient, it is considered that silanol groups remaining on the surface induce adhesion of toner particles. As one means for solving this, for example, it is conceivable to extend the condensation time. However, this method leads to a decrease in the production amount per hour, and even if it takes a long time for condensation, there is a limit to the condensation rate, and thus the adhesion of toner particles may not be completely prevented. is there. Furthermore, the toner particles of the present invention show 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., 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 performed at a temperature of 85 ° C. or higher and 100 ° C. or lower. Moreover, it is preferable to implement the process 2 in the range of 3 hours or more and 10 hours or less in the temperature range of 60 degreeC or more and 105 degrees C or less. As the condensation temperature is higher, the condensation proceeds in a shorter time, 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. The condensation can be carried out under normal pressure, reduced pressure, or pressurized conditions.

<Step 3>
Step 3 is a step in which the toner particle precursor having fine particles fixed thereon is filtered from an aqueous medium and then dried to obtain toner particles. In the present invention, the toner particle precursor can be obtained by filtering (separating) by a known method. Moreover, drying can be performed at 30-80 degreeC using a well-known dryer, for example.

  On the surface of the toner particles of the present invention obtained through the above steps, the fine particles are present at a ratio 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 toner particles from adhering to the reaction vessel and pipes in each step is manifested by the convex shape being in an appropriate state. One is that the fine particles are present in an amount of 0.10% by mass to 5.00% by mass. The fine particles are preferably present in an amount of 0.12% by mass or more and 2.0% by mass or less, more preferably 0.15% by mass or more and 1.0% by mass or less, based on the mass of the toner particles.

  If the amount of fine particles on the surface of the toner particles is less than 0.1% by mass, the convex shape is not sufficiently formed, and it is difficult to obtain the reaction vessel adhesion preventing effect. On the other hand, if the amount of fine particles present on the toner particle surface is more than 5.0% by mass, the distance between the convex shapes becomes narrow, and the particle surface becomes finally smooth. It becomes difficult to obtain the effect.

<Method for producing toner particles>
Hereinafter, although the specific manufacturing method of the toner particle of this invention is demonstrated, this invention is not limited to these.

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

  The second production method includes a method of adding a silicon compound and fine particles in an aqueous medium after obtaining a solid toner particle precursor. The toner particle precursor may be obtained by melt-kneading and pulverizing a binder resin and, if necessary, a colorant and other additives. Alternatively, the binder resin particles and, if necessary, the colorant particles and other particles may be aggregated and associated in an aqueous medium. Alternatively, an organic phase dispersion prepared by dissolving a binder resin, a silicon compound and, if necessary, other additives such as a colorant in an organic solvent is suspended in an aqueous medium, granulated, and optionally polymerized. Thereafter, the organic solvent may be removed to obtain a toner particle precursor.

  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 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, diethylphos Fate ethyl methacrylate, dibutyl phosphate ethyl methacrylate Methacrylic polymerizable monomers such as rate; vinyl esters 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 Vinyl vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone;

  Moreover, the following are mentioned as a polymerization initiator used in the case of superposition | polymerization. 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, diisopropyloxycarbonate, cumene hydroperoxide, 2,4-dichloro Peroxide 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.

  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. The chain transfer agent is preferably added in a proportion of 0.001% by mass to 15.000% by mass with respect to the polymerizable monomer.

In order to control the molecular weight of the binder resin constituting the toner particles, a crosslinking agent may be added during the polymerization. The following are mentioned as a crosslinkable monomer. 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 (Neopentyl glycol diacrylate hydroxypivalate, 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 methacrylate thereof, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylphthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate.
The crosslinking 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. Styrenes such as polystyrene and polyvinyltoluene, and substituted homopolymers 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-butadiene Styrene 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 particles of the polymerizable monomer composition can be used. The dispersion stabilizer can stabilize the toner particle precursor in the aqueous medium with little influence on the formation of the convex shape on the surface. Moreover, 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 . 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.

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 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 the form of a solid solution.

  In addition, it is preferable that content of a coloring agent is 3.0 to 15.0 mass parts with respect to 100 mass parts of binder resin or a polymerizable monomer.

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

  A release agent may be added to the toner particles of the present invention, and known ones can be used. The addition amount of the release agent 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 polymerizable monomer.

  FIG. 1 is an example of an image forming apparatus capable of forming an image using 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 photoreceptor 1. The toner 4 on the developing roller 2 is used to develop the electrostatic latent image formed on the photoreceptor to form a toner image. The toner image is transferred to the transfer conveyance belt 16. The toner image transferred onto the transfer conveyance belt 16 is transferred to a recording medium 18 such as paper by the action of a transfer bias applied to the transfer means. Then, the toner image transferred onto the recording medium 18 is fixed by the fixing device 21.

  Below, the measuring method of each physical-property value which concerns on this invention is described.

<Method for Measuring Weight Average Particle Size (D4) of Toner Particles>
The measurement of the weight average particle diameter (D4) of the toner particles is performed using a precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube. To do. 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. Measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, a solution prepared by dissolving special grade sodium chloride in ion exchange water to 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 By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush 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 250 ml round bottom beaker made exclusively for Multisizer 3 and set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic solution is placed in a glass 100 ml flat bottom beaker. In this, as a dispersant, “Contaminone (registered trademark) N” (non-ionic surfactant, anionic surfactant, 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments having a pH of 7 comprising an organic builder, About 0.3 ml of a diluted solution obtained by diluting 3 times by mass with ion-exchanged 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 particles are added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in 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 (1) installed in the sample stand, the electrolytic solution (5) in which the toner particles are dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. To do. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “arithmetic diameter” on the “analysis / volume statistic (arithmetic average)” screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Measurement of number average particle diameter of fine particles>
Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and a predetermined amount is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora150” (manufactured by Nikki Bios) with an electrical output of 120 W Ion-exchanged water is added, and about 2 ml of the above-mentioned Contaminone N is prepared in this water tank.
Next, 30 ml of methanol is put into a glass 100 ml flat bottom beaker. This flat bottom beaker 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 methanol liquid level in a beaker may become the maximum.
Next, in a state where the methanol in the beaker is irradiated with ultrasonic waves, about 30 mg of fine particles used in the present invention are added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
One drop of the obtained methanol fine particle dispersion is dropped onto a collodion membrane affixed mesh, air-dried for 3 hours or more, and then attached to 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 diameter of the fine particles, and the image is sharpened at the magnification. As a measure of magnification, when a transmission image is output on A4 paper, particles having the same number average particle diameter as measured using a caliper described later (approximately within ± 10% of the number average particle diameter) are 1.0 cm to The magnification is such that the output is in the 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, when the fine particle is not a true sphere, 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 size of the fine particles used in the present invention. When particles having a number equivalent to the number average particle diameter of 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 toner charge amount>
The charge amount of the toner of the present invention can be determined by the following method. First, a toner and a standard carrier for negatively charged polarity toner (trade name: N-01, manufactured by the Japan Imaging Society) are left in an environment of 30 ° C./80% RH for 24 hours. After being allowed to stand, the toner is mixed with the 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 “initial agent”. Next, 0.40 g of the initial agent is put into a metal container equipped with a conductive screen having an opening of 20 μm at the bottom, and sucked with a suction machine, and the mass difference before and after suction and the capacitor connected to the container 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 capacity of the capacitor, the toner charge amount Q is calculated using the following equation. The charge amount obtained here is the high temperature and high humidity initial charge amount (mC / kg). Further, the initial agent left as it is for 24 hours is referred to as a “leaving agent”, and the charge amount obtained by measuring the leaving agent in the same manner is referred to as a high temperature and high humidity leaving charge amount (mC / kg). The standard carrier for negatively charged polarity toner used for the measurement is one that has passed 250 mesh.
| Q | = | C × V / (W1-W2) |
Q: Charge amount of toner C (μF): Capacitance of capacitor V (volt): Potential accumulated in capacitor W1-W2 (kg): Mass difference 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, 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 surface of the toner particles is observed at a magnification of 10,000 to 100,000. 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 confirmation may be performed based on the fact that when the atomic weight is large, the contrast becomes brighter by utilizing the difference in atomic weight between silicon atoms and other atoms in the toner.

  Hereinafter, the present invention will be described in more detail with specific production methods, examples, and comparative examples, but these do not limit the present invention in any way. In addition, all the parts in the following mixing | blending are a mass part.

<Manufacture of polyester resin 1>
-110 mol of terephthalic acid-109 mol of bisphenol A-propylene oxide 2 mol adduct (PO-BPA) The above monomers are charged into an autoclave together with an esterification catalyst, and a pressure reducing device, a water separator, a nitrogen gas introducing device, and a temperature measuring device. The polyester resin 1 was obtained by attaching a stirrer to the autoclave and performing a reaction at 210 ° C. while reducing the pressure in a nitrogen atmosphere until the Tg (glass transition temperature) reached 68 ° C. according to a conventional method. The weight average molecular weight (Mw) was 7,400, and the number average molecular weight (Mn) was 3,020.

<Manufacture 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 grade) 70 parts by mass In a three-neck pressure vessel (made of stainless steel) equipped with a thermometer and a thermometer introduction tube, the temperature was raised to 60 ° C. while stirring. Then, it hold | maintained at 60 degreeC for 12 hours and cooled to room temperature. As a result, a slurry in which silica fine particles were dispersed and became cloudy was obtained. After cooling, the slurry was put into a pressure filter and filtered. Further, 100 parts by mass of primary ethanol was put into a 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.

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

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

<Alumina fine particles>
Alumina (product name: AO-502) manufactured by Admatech Co., Ltd. was used, and the particle size was adjusted 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 size was adjusted by several times of air classification to obtain hydrotalcite fine particles having a number average particle size of 252 nm.

<Manufacture of polystyrene resin fine particles>
-100 parts by weight of styrene-400 parts by weight of ion-exchanged water-2 parts by weight of divinylbenzene-10 parts by weight of ammonium persulfate

  The above raw materials were put into a three-neck pressure vessel (made of stainless steel) equipped with a reflux pipe, a stirrer, and a thermometer introduction pipe having heating devices 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 in which polystyrene resin fine particles were dispersed and became cloudy was obtained. After cooling, the slurry was put into a pressure filter and filtered. Furthermore, 100 mass parts of primary methanol was thrown into the filter, and it filtered again. Subsequently, 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, polystyrene resin fine particles were obtained. Furthermore, the obtained polystyrene resin fine particle powder was adjusted in particle size by air classification to obtain polystyrene resin fine particles having a number average particle diameter of 201 nm.

<Acrylic resin fine 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]
In a five-neck pressure vessel (made of stainless steel) equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 200 parts by mass of ion-exchanged water, 300 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, Then, 6.5 parts by mass of a 1.0 mol / liter HCl aqueous solution was added, and the mixture was kept at 63 ° C. while stirring at a peripheral speed of 29 m / s using a high-speed stirring device CLEARMIX (manufactured by M Technique). 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 hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

(Dissolution process)
Thereafter, 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 1 part by mass, polyester resin 1 6.0 parts by mass, 0.5 parts by mass of charge control agent (aluminum compound of 3,5-di-tert-butylsalicylic acid)
Release agent (behenyl behenate) 10.0 parts by mass The above raw materials were dispersed with a handy mill (manufactured by Nihon Coke Kogyo Co., Ltd.) for 3 hours to obtain a polymerizable monomer composition. Next, this polymerizable monomer composition was transferred to another container and kept at 63 ° C. for 5 minutes with stirring. Thereafter, 20.0 parts by mass of t-butyl peroxypivalate as a polymerization initiator (toluene solution 50%) was added and held for 5 minutes while stirring. This 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 at a peripheral speed of 29 m / s using a high-speed stirring device. The process up to here is defined as a granulation process.

(Reaction 1 step)
Thereafter, the composition obtained in the granulation step was transferred into a five-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 then with a propeller type stirrer. The internal temperature was raised to 70 ° C. with slow stirring. The time required for raising the temperature was 10 minutes. Furthermore, it was made to react for 5 hours, stirring slowly. The process up to this point is defined as one reaction step. At the end of one reaction step, it was confirmed that the hydrolyzate of methyltriethoxysilane was dissolved in water.
A fine particle dispersion in which 1.0 part by mass of silica fine particles 1 was dispersed in 3.0 parts by mass of methyltriethoxysilane was prepared before the end of one reaction step. In this example, in order to disperse more uniformly, dispersion by a homogenizer was performed.

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

(Distillation process)
After completion of the reaction step 2, the composition obtained at the end of the reaction step 2 was added to the pressure-resistant reaction kettle 2 (made of stainless steel) equipped with a stirrer, a thermometer, a steam introduction tube, and a distillation apparatus capable of cooling and collecting the fraction. , And steam was blown in to raise the temperature in the kettle to 100 ° C. The time required for the temperature increase was 80 minutes. Thereafter, distillation was performed at a temperature in the kettle 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 the 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 distillation was performed was defined as the distillation temperature, and the time during which the distillation temperature was maintained was defined as the distillation time. In this step, residual monomers and ethanol and other solvents generated by hydrolysis were also removed.

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

  Furthermore, the dispersion stabilizer was removed by performing filtration. After filtration, the obtained cake was not taken out, and ion-exchanged water was further added and filtered again to perform washing. Subsequently, the cake after filtration was taken out, dried with a flash dryer with an airflow dryer (manufactured by Seishin Enterprise Co., Ltd.), and the powder was collected with a cyclone. Thereafter, air classification was performed while feeding this powder with compressed air to cut the fine coarse powder. After passing through a pipe of 10 m, the powder was collected by the cyclone 2. The powder thus obtained is toner particles 1. At the end of the cooling step, the content of methyltriethoxysilane-derived material present in the water was less than 10 ppm, and the fine particles were less than 100 ppm. In consideration of the stoichiometry, the calculation was made assuming that all toner particles were formed. Table 2 shows the conditions of the above steps. The obtained toner particles 1 were measured for weight average particle diameter (D4). Table 4 shows the physical properties of Toner Particles 1. Moreover, the evaluation shown below was performed.

<Evaluation of charge amount>
The initial charge amount and the left charge amount at high temperature and high humidity measured according to the above measurement method were ranked as follows. In addition, the following evaluation is excellent in the order of ranks A, B, C, and D, and ranks A to C were determined to be a range in which the effects of the present invention can be obtained. The evaluation results are shown in Table 4.
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 Canon laser beam printer LBP9510C having the configuration shown in FIG. 1 has been modified to enable printing only with the cyan station. In addition, it was modified so that the back contrast can be set arbitrarily. Using this LBP9510C toner cartridge, 200 g of toner particles 1 were filled. The toner cartridge was allowed to stand for 24 hours in an environment of high temperature and high humidity (30.0 ° C./80.0% RH). After being left in the environment for 24 hours, the toner cartridge was attached to the LBP9510C, and an image having a printing ratio of 1.0% was printed out to 15,000 sheets in the A4 paper lateral direction.
At this time, an initial image density (initial density) and an image density at the time of outputting 15,000 sheets (endurance density) 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. The image density was measured by using “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to an image of a white background portion having a document density of 0.00. In the image evaluation, the image density was ranked as follows. In addition, the following evaluation is excellent in the order of ranks A, B, C, D, and E, and ranks A to D were determined to be a range in 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 higher Rank B: Image density 1.39 to 1.30
Rank C: Image density of 1.29 to 1.25
Rank D: Image density of 1.24 to 1.20
Rank E: Image density 1.19 or less

<Evaluation of reaction kettle contamination>
The reaction kettle 1 and the reaction kettle 2 on which the toner particles 1 were once prepared were washed only by jetting of high-pressure water, and the same toner particles 1 as described above were further produced using these reaction kettles. Further, the same operation was repeated, and the same toner particles 1 were produced three times in total. Finally, these reaction kettles were washed by high-pressure water jet and visually evaluated for reaction kettle contamination according to the following criteria. In addition, the following evaluation is excellent in the order of ranks A, B, C, D, and E, and ranks A to C were determined to be a range in which the effects of the present invention can be obtained. The evaluation results are shown in Table 4.
Rank A: Adhering of the toner composition is observed at the gas-liquid interface, but no adhering is observed on the wall surface of the pot where the slurry is always immersed. Rank B: Adhering of the toner composition is observed at the gas-liquid interface. A thin adhesion of the toner composition is partially observed on the wall of the pot where the slurry is always immersed. Rank C: A thick adhesion of the toner composition is observed at the gas-liquid interface, and the wall of the pot where the slurry is always immersed. Rank D: The toner composition is thickly adhered at the gas-liquid interface, and the entire surface of the toner composition is seen on the wall surface where the slurry is always immersed. Rank E: Thick adhesion of the toner composition is observed at the gas-liquid interface, and thick adhesion of the toner composition is generally observed on the wall of the pot where the slurry is constantly immersed.

<Evaluation of cyclone contamination and piping contamination>
About the cyclone and piping, preparation of the same toner particle 1 was performed 3 times in succession, and cleaning by air blow was performed. Then, it evaluated visually according to the following judgment criteria. In addition, the following evaluation is excellent in the order of ranks A, B, C, D, and E, and ranks A to C were determined to be a range in which the effects of the present invention can be obtained. The evaluation results are shown in Table 4.
Rank A: 99% or more of the toner particles on the wall surface are removed by air blowing Rank B: 80% or more of the toner particles on the wall surface of less than 99% are removed by air blowing Rank C: 50% or more of the wall surface of less than 80 by air blowing Rank D: Air blow removes 10% or more and less than 50% wall toner particles Rank E: Air blow removes less than 10% wall toner particles

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

[Examples 2 to 15, Examples 19 to 27]
Toner particles 2 to 15 and 19 to 27 were produced in accordance with Example 1 except that the production conditions and formulations shown in Tables 2 and 3 were changed. For the obtained toner particles, the weight average particle diameter was measured in the same manner as in Example 1, and each evaluation was performed. Table 4 shows the physical properties of the toner particles, and Table 5 shows the evaluation results. In addition, the method of vacuum distillation and pressure distillation is as follows.
In vacuum distillation, the steam introduction tube is removed and the reaction kettle itself is heated to change the specification to adjust the temperature. A decompressor is attached to the open port, so that it is not drawn into the distillation unit that collects fractions. By depressurizing to
At the time of pressure distillation, a pressurizer is attached to the vacant port, and a valve is attached to the distillation device side so as not to be affected by pressure. During distillation, the valve on the distillation apparatus side was opened once every 3 minutes to return to normal pressure, and the volatile matter was recovered.

[Example 16]
In a five-neck pressure vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 700 parts by mass of ion-exchanged water, 1000 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, and 1.0 mol 24.0 parts by mass of a 1 / liter HCl aqueous solution was added, and the mixture was kept at 63 ° C. while stirring at a peripheral speed of 29 m / s using a high-speed stirring device CLEARMIX (manufactured by M Technique). To this was added 25 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

(Dissolution process)
Thereafter, 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 weight Toluene 40.0 parts by weight The above raw materials are dispersed with a handy mill (manufactured by Nippon Coke Kogyo Co., Ltd.) for 3 hours and then heated to 63 ° C. A particle precursor composition was obtained.

(Granulation process)
Next, the 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 Technique).

(Reaction 1 step)
Thereafter, the composition obtained in the granulation step was transferred into a five-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 then with a propeller type stirrer. 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 one reaction step.
A fine particle dispersion in which 1.0 part by mass of silica fine particles 1 was dispersed in 10.0 parts by mass of methyltriethoxysilane was prepared before the completion of one reaction step. In this example, in order to disperse more uniformly, dispersion by a homogenizer was performed.

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

(Distillation process)
After completion of the reaction step 2, the composition obtained at the end of the reaction step 2 is 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 apparatus that can cool and collect the fraction. Then, steam was blown in and the temperature in the kettle was raised to 100 ° C. The time required for the temperature increase was 80 minutes. Thereafter, distillation was performed at a temperature in the kettle 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 the 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 poorly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ as a dispersion stabilizer was dissolved. This is defined as the cooling process. At the end of the cooling step, the hydrolyzate of methyltriethoxysilane present in the water was less than 10 ppm. Also, at the end of the cooling step, it was confirmed that the fine particles present in the water were less than 100 ppm at most.

Furthermore, the dispersion stabilizer was removed by performing filtration. After filtration, the obtained cake was not taken out, and ion-exchanged water was further added and filtered again to perform washing.
Subsequently, the cake after filtration was taken out, dried with a flash dryer with an airflow dryer (manufactured by Seishin Enterprise Co., Ltd.), and the powder was collected with a cyclone. Thereafter, air classification was performed while feeding this powder with compressed air to cut the fine coarse powder. After passing through a pipe of 10 m, the powder was collected by the cyclone 2. The powder thus obtained is toner particles 16. In addition, since the substance derived from methyltriethoxysilane present in the water was less than 10 ppm at the end of the cooling step, and the fine particles were less than 100 ppm, the fine particle content in the toner particles 16 is a chemical reaction. In consideration of the stoichiometry, the calculation was made assuming that all toner particles were formed. The obtained toner particles 16 were measured for weight average particle diameter and evaluated in the same manner as in Example 1. The physical properties of the toner particles 16 are shown in Table 4, and the evaluation results are shown in Table 5.

[Example 17]
(Manufacture of styrene acrylic resin)
In a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer and a nitrogen introduction tube, 300 parts by mass of ion-exchanged water and 100 parts by mass of an aqueous solution of 0.1 mol / liter Na ₃ PO ₄ and 1.0 mol / liter Then, 5.0 parts by mass of an aqueous HCl solution was added, and the mixture was kept at 60 ° C. while stirring at 5,000 rpm using a high-speed stirring device TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Here slowly added CaCl ₂ aqueous solution 20 parts by mass of 1.0 mol / liter, to prepare an aqueous dispersion medium containing fine sparingly water-soluble dispersion stabilizer _Ca 3 _{(PO 4) 2.} Then, the monomer mixture was produced 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. while stirring, and then 16.0 parts by mass of a polymerization initiator t-butyl peroxypivalate (toluene solution 50%) was added, Hold for 5 minutes with stirring. Next, the monomer mixture was put into an aqueous dispersion medium and granulated for 10 minutes while stirring with a high-speed stirring device. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 5 hours with slow 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 a distillation apparatus was attached. Distillation was performed for 5 hours at a temperature of 100 ° C. in the container to remove the residual monomer, 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. Further, 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 part 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 the above materials were mixed with an FM mixer (manufactured by Nippon Coke Kogyo Co., Ltd.), a twin-screw kneading extruder was used. Then, melt kneading was performed at 135 ° C. After the kneaded product was cooled, coarse pulverization with a cutter mill, pulverization with a fine pulverizer using a jet stream, and classification using an air classifier were performed to obtain a toner particle precursor.

(Preparation of aqueous dispersion medium)
In a five-neck pressure vessel (made of stainless steel) equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 200 parts by mass of ion-exchanged water, 300 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, Then, 6.5 parts by mass of a 1.0 mol / liter HCl aqueous solution was added, and the mixture was kept at 63 ° C. while stirring at a peripheral speed of 29 m / s using a high-speed stirring device CLEARMIX (manufactured by M Technique). To this was added 25 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution to prepare an aqueous dispersion medium containing a fine hardly 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 in which 1.0 part by mass of silica fine particles 1 was dispersed in 10.0 parts by mass of methyltriethoxysilane was prepared. In this example, in order to disperse more uniformly, dispersion by a homogenizer was performed.

(Injection of toner particle precursor into aqueous dispersion medium)
Into the reaction vessel 1 containing the aqueous dispersion medium, 165 parts by mass of the toner particle precursor was charged, and the temperature was raised to 85 ° C. while gently stirring.

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

(Distillation process)
Next, 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 apparatus capable of cooling and collecting the fraction, and steam was blown into the kettle. The temperature was raised until the temperature reached 100 ° C. The time required for the temperature increase was 80 minutes. Further, distillation was performed at a temperature in the kettle 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 the 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 poorly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ as a dispersion stabilizer was dissolved. This is defined as the cooling process. At the end of the cooling step, the hydrolyzate of methyltriethoxysilane present in the water was less than 10 ppm. Also, at the end of the cooling step, it was confirmed that the fine particles present in the water were less than 100 ppm at most.

Furthermore, the dispersion stabilizer was removed by performing filtration. After filtration, without removing the obtained cake, ion-exchanged water was further added, followed by filtration and washing.
Subsequently, the cake after filtration was taken out, dried with a flash dryer with an airflow dryer (manufactured by Seishin Enterprise Co., Ltd.), and the powder was collected with a cyclone. Thereafter, air classification was performed while feeding this powder with compressed air to cut the fine coarse powder. After passing through a pipe of 10 m, the powder was collected by the cyclone 2. The powder thus obtained is toner particles 17. At the end of the cooling step, the content of methyltriethoxysilane-derived material present in the water was less than 10 ppm, and the fine particles were less than 100 ppm. In consideration of the theory, the calculation was made assuming that all toner particles were formed. The obtained toner particles 17 were measured for weight average particle diameter and evaluated in the same manner as in Example 1. The physical properties of the toner particles 17 are shown in Table 4, and the 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 charged into a container. Thereafter, the above resin was gradually added, stirred, and completely dissolved to obtain a crystalline polyester resin 1 solution. A container containing the polyester resin 1 solution is set at 65 ° C., and a 10% aqueous ammonia solution is gradually added dropwise to a total of 5 parts by mass with stirring, and 230 parts by mass of ion-exchanged water is further added at 10 ml / The mixture was gradually added dropwise at a rate of min for phase inversion emulsification. Further, the solvent was removed by reducing the pressure with an evaporator to obtain a resin particle dispersion. The volume average particle size of the resin particles in the obtained resin particle dispersion was 140 nm. The resin particle solid content was adjusted to 20% with ion-exchanged water.

(Preparation of colorant particle dispersion)
Copper phthalocyanine (Pigment Blue 15: 3) 45 parts by mass Charge control agent 0.7 parts by mass (aluminum compound of 3,5-di-tert-butylsalicylic acid)
-Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by mass-Ion-exchanged water 190 parts by mass Machine, manufactured by Sugino Machine Co., Ltd.) for 20 minutes at a pressure of 250 MPa to obtain a colorant particle dispersion having a volume average particle diameter 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 Daiichi Kogyo Seiyaku Co., Ltd.) 2.0 parts by mass-240 parts by mass of ion-exchanged water After sufficiently dispersing with Thalax T50, it is heated to 115 ° C. with a pressure discharge type gorin homogenizer and dispersed for 1 hour to obtain a release agent particle dispersion having a volume average particle size of 160 nm and a solid content of 20%. It was.

(Preparation of toner particle precursor)
-Resin particle dispersion 600 parts by weight-Colorant particle dispersion 39 parts by weight-Release agent particle dispersion 60 parts by weight After adding 2.2 parts by weight of the ionic surfactant Neogen RK to the reaction vessel 1, 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 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 and held for 40 minutes. As a result, a toner particle precursor was obtained.

(Preparation of fine particle dispersion)
Prior to the end of the steps so far, a fine particle dispersion in which 1.0 part by mass of silica fine particles 1 was dispersed in 10.0 parts by mass of methyltriethoxysilane was prepared. In this example, in order to disperse more uniformly, dispersion by a homogenizer was performed.

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

(Distillation process)
Next, 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 apparatus capable of cooling and collecting the fraction, and steam was blown into the kettle. The temperature was raised until the temperature reached 100 ° C. The time required for the temperature increase was 80 minutes. Thereafter, distillation was performed at a temperature in the kettle 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 the 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 completion of the distillation step, the mixture was cooled to 30 ° C., diluted hydrochloric acid was added to the vessel to lower the pH to 1.5, and the poorly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ as a dispersion stabilizer was dissolved. . This is defined as the cooling process. At the end of this cooling step, the hydrolyzate of methyltriethoxysilane present in the water was less than 10 ppm. Also, at the end of the cooling step, it was confirmed that the fine particles present in the water were less than 100 ppm at most.

  Furthermore, the dispersion stabilizer was removed by performing filtration. After filtration, without removing the obtained cake, ion-exchanged water was further added, followed by filtration and washing. Subsequently, the cake after filtration was taken out, dried with a flash dryer with an airflow dryer (manufactured by Seishin Enterprise Co., Ltd.), and the powder was collected with a cyclone. Thereafter, air classification was performed while feeding this powder with compressed air to cut the fine coarse powder. After passing through a pipe of 10 m, the powder was collected by the cyclone 2. The powder thus obtained is toner particles 18. At the end of the cooling step, the content of methyltriethoxysilane-derived material present in the water was less than 10 ppm, and the fine particles were less than 100 ppm. In consideration of the stoichiometry, the calculation was made assuming that all toner particles were formed. The obtained toner particles 18 were measured for weight average particle diameter and evaluated 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]
In accordance with the production conditions and formulation shown in Table 3, the stirring of the two reaction steps was carried out except that the stirring method was changed to a method of stirring at a peripheral speed of 29 m / s using a high-speed stirring device CLEARMIX (M Technique Co., Ltd.). Toner particles were prepared according to Example 1. Table 4 shows the physical properties of the obtained toner particles, and Table 6 shows the evaluation results.

[Comparative Examples 2 and 3, Comparative Examples 5-8]
According to the manufacturing conditions and formulation shown in Table 3, the same operations as in Example 1 were performed except that, and toner particles were produced. Table 4 shows the physical properties of the obtained toner particles, and Table 6 shows the evaluation results.

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

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: Charging for cleaning Device: 11: stirring blade, 12: driving roller, 13: transfer roller, 14: bias power source, 15: tension roller, 16: transfer conveying belt, 17: driven roller, 18: paper, 19: paper feeding roller, 20: Adsorption roller, 21: fixing device

Claims (7)

Step 1:
i) at least one silicon compound selected from the group consisting of compounds represented by the following formulas (1) to (3);
ii) fine particles having a number average particle diameter of 10 nm to 500 nm, and iii) a toner particle precursor,
Preparing a liquid composition that coexists in an aqueous medium,
Step 2: condensing the silicon compound in the liquid composition at a temperature of 60 ° C. to 105 ° C. to fix the fine particles on the surface of the toner particle precursor, and Step 3: fixing the fine particles. A step of filtering the toner particle precursor thus obtained from the aqueous medium and then drying to obtain toner particles;
A method for producing toner particles comprising:
The method for producing toner particles, wherein the fine particles are present on the surface of the toner particles on the basis of the mass of the toner particles based on 0.10 mass% or more and 5.00 mass% or less.

(In the formulas (1), (2) and (3), R ^d , R ^e and R ^f each independently represents an alkyl group, an alkenyl group, an acetoxy group, an acyl group or an aryl group, R ² , 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.)   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. The manufacturing method of the toner particle of description.   In the step 1, after the silicon compound and the fine particles are mixed to prepare a fine particle dispersion, the fine particle dispersion is introduced into the aqueous medium in which the toner particle precursor is present, and the liquid composition The method for producing toner particles according to claim 1, wherein the product is prepared.   The said silicon compound is at least 1 sort (s) of silicon compound selected from the group which consists of a compound represented by the said Formula (2) and the said Formula (3). A method for producing toner particles.   The method for producing toner particles according to claim 1, wherein the fine particles are inorganic fine particles.   The method for producing toner particles according to claim 1, wherein the silicon compound is a compound represented by the formula (2). The method for producing toner particles according to claim 6, wherein, in the formula (2), R ^f is a methyl group or an ethyl group.

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