JP2019128515A - toner - Google Patents

Abstract

To provide a toner that has an excellent charging start-up property and prevents a reduction in charging start-up property and the occurrence of contamination of a charging member even after a long-term use.SOLUTION: A toner has toner particles containing a binder resin; the toner particles each have a surface layer containing a condensate of an organic silicon compound and have fine particles containing a composite compound in the surface layer; the composite compound is a composite compound of an organic silicon compound and a metallic compound containing at least one metallic element selected from all the metallic elements belonging to the group 3 elements to the group 13 elements.SELECTED DRAWING: None

Description

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

In recent years, in printers and copiers, FPOT (First Printout Time) or FCOT (First Copyout Time), which is the time until the first printed product is output, has come to be emphasized. Therefore, various studies have been conducted to shorten FPOT and FCOT. Further, in order to reduce the frequency of replacement of the toner cartridge and improve the maintainability, it is required to increase the printable number of toner cartridges.
In order to shorten the FPOT and the FCOT, there is a need for a toner having an excellent charge rising property that is quickly charged by friction with a charging member such as a developing roller or a carrier. The toner is charged by the movement of the charge from the charge imparting member when it comes in contact with the charge imparting member such as the developing roller or the carrier. Therefore, in order to impart an excellent charge rising property to the toner, it is effective to move the charges smoothly at the time of contact with the charge imparting member. For this reason, studies have been made to improve the charge rising property of the toner by including fine particles containing a metal element having low resistance on the surface of the toner particle.

Further, in order to increase the number of printable sheets of the toner cartridge, it is necessary to use a toner in which fine particles are not easily detached from the surface of the toner particles even during long-term use, and the charge rising property is reduced and the developing roller is less contaminated. Therefore, studies have been conducted to suppress migration of the particles to the developing roller during long-term use by fixing the particles to the surface of the toner particles.
In Patent Document 1, as a toner having excellent charge rising property and charge holding property and capable of suppressing fluctuation of image density and fogging, it is selected from titanium atoms, aluminum atoms, zirconium atoms, and calcium atoms on the surface of toner particles 1 Disclosed is a method of containing composite oxide fine particles containing atoms of a kind or more and silicon atoms.
Patent Document 2 discloses a silane coupling agent as a toner capable of preventing direct contact between the inorganic fine particles and the developing member and suppressing the transfer of the inorganic fine particles to the developing roller. A method of coating with a membrane is disclosed.

JP 2010-72285 A JP-A-8-292599

The toner described in Patent Document 1 has excellent charge rising property and charge retention property by having the complex oxide fine particles on the toner particle surface. However, in an environment where a high load is applied to the toner, such as a high speed charging process, the complex oxide fine particles may be detached from the toner particles. As a result, the charging performance of the toner may be reduced, and the released composite oxide fine particles may be transferred to the developing roller to contaminate the developing roller. In this case, it was found that due to the deterioration of the toner charging performance and the contamination of the developing roller material, the same charge rising property as the initial one can not be obtained.
Further, the toner described in Patent Document 2 can make the inorganic fine particles less likely to be detached by coating with a silane coupling agent than before. However, as in Patent Document 1, when a high load is applied to the toner, the charge rising property similar to the initial stage may not be obtained due to the separation of the inorganic fine particles from the toner particles. This is because the inorganic fine particle and the film of the silane coupling agent are different materials, and the adhesion at the interface is low, so the ability to fix the inorganic fine particle is weak even if the toner particle surface is covered with the film of the silane coupling agent. It is thought that.
The present invention aims to solve these problems. That is, an object of the present invention is to obtain a toner which has excellent charge rising properties, and at the same time, does not deteriorate in charge rising properties even in long-term use and does not cause development roller contamination.

The present invention is a toner having toner particles containing a binder resin,
The toner particles have a surface layer containing a condensation product of an organosilicon compound, and have fine particles containing a composite compound on the surface layer,
The composite compound is characterized in that it is a composite compound of a metal compound containing at least one metal element selected from all metal elements belonging to Groups 3 to 13 and an organosilicon compound. It is a toner.
Further, the present invention is a toner having toner particles containing a binder resin,
The toner particles have, on their surfaces, a condensate of an organosilicon compound and fine particles containing a composite compound,
The fine particles containing the composite compound are fixed to the condensate of the organosilicon compound,
The composite compound is characterized in that it is a composite compound of a metal compound containing at least one metal element selected from all metal elements belonging to Groups 3 to 13 and an organosilicon compound. It is a toner.

  According to the present invention, it is possible to provide a toner which has excellent charge rising properties, and at the same time, does not decrease in charge rising properties even in long-term use and does not cause development roller contamination.

In the present invention, the description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit as endpoints unless otherwise specified.
The toner of the present invention is a toner having toner particles containing a binder resin, wherein the toner particles have a surface layer containing a condensation product of an organosilicon compound, and particles having a composite compound on the surface layer And the composite compound is a composite compound of a metal compound containing at least one metal element selected from all metal elements belonging to Group 3 to Group 13, and an organosilicon compound. I assume.
With the above configuration, the present inventors presume the mechanism that can provide a toner that has excellent charge rising property and at the same time does not deteriorate charge rising property even during long-term use and does not cause development roller contamination. doing.

The conventional toner has improved the charge rising property by adding fine particles containing a metal compound having low resistance (hereinafter also referred to as metal compound fine particles). However, the transfer of the metal compound fine particles to the developing roller sometimes causes a decrease in the charge rising property of the toner during long-term use. Further, while the metal compound fine particles have an effect of improving the charge rising property of the toner, when attached to the developing roller, the charge imparting ability of the developing roller may be lowered. This is because, usually, the developing roller and the toner are made of a material that is easily charged to the opposite polarity.
As described above, the toner to which the metal compound fine particles have been added tends to cause deterioration in charge rising property and contamination of the developing roller during long-term use. Therefore, in order to suppress the migration of the metal compound fine particles to the developing roller, it is necessary to firmly fix the metal compound fine particles to the toner particle surface.

Therefore, in the present invention, instead of the metal compound fine particles, fine particles containing a composite compound of a metal compound and an organosilicon compound (hereinafter also referred to as composite compound fine particles) are used. Compared to the metal compound fine particles, the composite compound fine particles are more likely to adhere to the condensate of the organosilicon compound on the surface of the toner particles, so that the migration of the composite compound fine particles to the developing roller can be suppressed. The adhesion between the fine particles of the composite compound and the condensation product of the organosilicon compound on the surface of the toner particle is secured by the formation of a bond by silanol condensation of the silanol group of the organosilicon compound contained in the composite compound and the silanol group of the condensation product of the organosilicon compound. It can.
In the present invention, the toner particles have a surface layer containing a condensate of an organosilicon compound, and the composite layer is contained in the surface layer. Alternatively, the surface of the toner particles has an organosilicon compound condensate and fine particles containing a composite compound fixed to the organosilicon compound condensate.

The fixing of the composite compound fine particles and the condensate of the organosilicon compound on the surface of the toner particles will be described by taking as an example a production method for producing the composite compound fine particles in an aqueous medium in which the toner base particles are dispersed. Other manufacturing methods will be described later.
In this manufacturing method, an organic silicon compound and a metal source, which are raw materials for composite compound fine particles, are reacted with an acid or water in an aqueous medium in which toner base particles are dispersed to precipitate the composite compound fine particles, and then the composite compound fine particles are Onto the toner particles containing the condensate of the organosilicon compound.

The process in which the fine particles of the composite compound adhere to the condensate of the organosilicon compound on the surface of the toner particle will be described in detail. First, the condensation product of the hydrophobic organosilicon compound migrates to the surface of the toner particle which is also hydrophobic. Next, since the condensate of the organosilicon compound is viscous, the composite compound fine particles adhere to the condensate of the organosilicon compound transferred to the surface of the toner particles. Subsequently, when the silanol group of the organosilicon compound contained in the composite compound and the silanol group of the condensate of the organosilicon compound are bonded by silanol condensation, the composite compound fine particles and the condensate of the organosilicon compound are fixed.
Further, when the organosilicon compound is transferred to the toner particle surface, the complex compound fine particles already attached to the toner particle surface, or the organosilicon compound condensate on the toner particle surface in a state where the condensation product of the organosilicon compound is partially attached. There are also complex compound particles which adhere to the Therefore, the composite compound fine particles can exist in various modes from those fixed on the condensate on the surface layer to those partially or entirely encased in the condensate on the surface layer.
As a result, the adhesion of the fine particles of the composite compound to the toner particles can be greatly improved, and the transfer of the fine particles of the compound compound to the developing roller can be suppressed. According to the present invention, it is possible to provide a toner that has an excellent charge rising property and at the same time does not deteriorate the charge rising property even during long-term use and does not cause development roller contamination.

Here, the condensation product of the organosilicon compound used in the present invention will be described in detail.
<Condensed product of organosilicon compound>
The toner particles have a surface layer containing a condensate of an organosilicon compound on the surface.
Since the condensation product of the organosilicon compound has a low surface free energy, the flowability of the toner is improved, and the charge rising property is further improved.
The organosilicon compound is preferably an organosilicon compound represented by the following formula (1). The condensation product of the organosilicon compound represented by the following formula (1) has high hydrophobicity, so that the chargeability in a high humidity environment is good.
Ra _(n) -Si-Rb _(4-n) (1)
(In formula (1), each Ra independently represents a halogen atom, or an alkoxy group (preferably having 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms), and each Rb independently represents , (Preferably 1 to 8 carbon atoms, more preferably 3 to 6 carbon atoms) alkyl groups, (preferably 1 to 6 carbon atoms, more preferably 3 to 6 carbon atoms) alkenyl groups, (preferably carbon atoms number 6 to 14, more preferably 6 to 10 carbon atoms) aryl group (preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms) acyl group or 1 to 3 carbon methacryloxy of the alkyl moiety Alkyl group (preferably methacryloxypropyl group) is shown, n is an integer of 1 to 4 (preferably 1 to 3, more preferably 3).

As an organosilicon compound represented by Formula (1), a monofunctional, bifunctional, trifunctional, tetrafunctional various organosilicon compound is mentioned.
Specifically, as monofunctional organosilicon compounds, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triisobutylmethoxysilane, triisopropylmethoxysilane, tri2-ethylhexylmethoxysilane and the like can be mentioned.
Examples of difunctional organosilicon compounds include dimethyldimethoxysilane and dimethyldiethoxysilane.
As a trifunctional organosilicon compound,
A trifunctional methylsilane compound of methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane;
Trifunctional silane compounds such as ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane and hexyltriethoxysilane (in addition, propyl) Is n-propyl or isopropyl, butyl is n-butyl, sec-butyl, isobutyl or tert-butyl, and so on);
Trifunctional phenylsilane compounds such as phenyltrimethoxysilane and phenyltriethoxysilane;
Trifunctional vinylsilane compounds such as vinyltrimethoxysilane and vinyltriethoxysilane;
Trifunctional allylsilane compounds such as allyltrimethoxysilane, allyltriethoxysilane, allyldiethoxymethoxysilane, allylethoxydimethoxysilane;
Trifunctional γ-methacryloxypropylsilane compounds such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldiethoxymethoxysilane, and γ-methacryloxypropylethoxydimethoxysilane; Can be mentioned.
Examples of tetrafunctional organosilicon compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane.

The content of the element Si on the surface of the toner particles, which is determined by X-ray photoelectron spectroscopy, is preferably 2.0 atomic% or more. More preferably, it is 3.0 atomic% or more. On the other hand, the upper limit is not particularly limited, but it is preferably 15.0 atomic% or less, more preferably 10.0 atomic% or less.
Here, as represented by said Formula (1), an organosilicon compound is a compound containing Si element. Therefore, the fact that the content of elemental Si on the toner particle surface is high means that the area occupied by the organosilicon compound on the toner particle surface is wide, that is, the condensate of the organosilicon compound sufficiently covers the toner particle surface. Indicates
When the content is 2.0 atomic% or more, the condensation product of the organosilicon compound sufficiently covers the surface of the toner particles, so that the transfer of the fine particles of the composite compound to the developing roller can be suppressed.
The mechanism is presumed as follows. First, the condensation product of the organosilicon compound sufficiently covers the toner particle surface, and the condensation product of the organosilicon compound forms a network on the toner particle surface. Then, the composite compound fine particles are easily fixed firmly to the toner particle surface via the condensation product of the organosilicon compound. Thereby, the transfer of the composite compound fine particles to the developing roller can be suppressed.

Further, when the content is 2.0 atomic% or more, in addition to suppressing the transfer of the fine particles of the compound compound to the developing roller, the transfer efficiency becomes high.
The mechanism is presumed as follows. The condensation product of the organosilicon compound forms a network on the surface of the toner particles, whereby the charge generated by the rubbing between the fine particles of the composite compound and the developing roller moves to the entire toner particle through the network of the condensate of the organosilicon compound. it can. As a result, the charge in the toner particles can be made uniform, and it becomes easy to follow the potential in the transfer step, so that the transfer efficiency becomes high.
The toner having high transfer efficiency can increase the printable number of toner cartridges by suppressing the toner consumption amount during long-term use.
The content of the element Si on the surface of the toner particles can be controlled by the reaction conditions such as pH, reaction temperature, reaction time, and the addition amount of the organosilicon compound used as a raw material.

Subsequently, the composite compound fine particles used in the present invention will be described in detail.
<Compound Compound Fine Particles>
The composite compound fine particle is a fine particle containing a composite compound of an organic silicon compound and a metal compound containing at least one metal element selected from all the metal elements belonging to Group 3 to Group 13.
The composite compound is a compound having a structure in which an organosilicon compound and a metal compound are finely and uniformly dispersed. Here, “finely and uniformly dispersed” is a state in which the respective compounds are distributed in the nano order without large deviation.

The composite compound fine particle is a composite compound of an organic silicon compound and a metal compound containing at least one metal element selected from all metal elements belonging to Group 3 to Group 13; As well as suppressing the transition of the toner to the developing roller, the charge rising property of the toner can be further improved.
The mechanism is presumed as follows. When the complex compound contains the organosilicon compound, the silanol group of the condensation product of the organosilicon compound covering the toner particle surface and the silanol group of the organosilicon compound contained in the complex compound are bonded by silanol condensation. As a result, the composite compound fine particles are firmly fixed to the surface of the toner particles, whereby the transfer of the composite compound fine particles to the developing roller can be suppressed.
Furthermore, the metal element belonging to Groups 3 to 13 has a valence of 2 or more, and can form a crosslinked structure with the organosilicon compound. Thereby, the metal compound having a metal element belonging to Group 3 to Group 13 easily forms a crosslinked structure with the condensate of the organosilicon compound in the composite compound fine particles and on the surface of the toner particles. By suppressing the transfer of the fine particles of the compound compound to the developing roller and promoting the movement of electrons by the crosslinked structure of the metal compound, the charge rising property of the toner can be further improved.
The organosilicon compound forming the surface layer containing the condensate of the organosilicon compound and the organosilicon compound forming the composite compound fine particles may be the same or different. These organosilicon compounds are each preferably an organosilicon compound represented by the formula (1), and more preferably the same compound.

The preferred states of the organosilicon compound and the metal compound can be quantified as follows.
When the maximum value of the respective abundance ratios of Si elements on the toner particle surface and metal elements belonging to Group 3 to Group 13 obtained by energy dispersive X-ray spectroscopy (hereinafter referred to as EDX) is set to 100 Preferably, the overlap between the abundance ratio of the Si element and the abundance ratio of the metal elements belonging to the groups 3 to 13 is 40% or more.
Here, the abundance ratio of the Si element on the toner particle surface and the metal element belonging to Group 3 to Group 13 is the surface of the toner particle (the surface of a flaky sample cut out from the top of the toner to a thickness of 50 nm). Are observed with a transmission electron microscope (hereinafter referred to as TEM), and each element in a TEM-EDX image obtained by mapping Si elements of the toner particle surface and metal elements belonging to Groups 3 to 13 using EDX. It shows the ratio of peak intensity when line analysis of the peak intensity of the element is performed. In line analysis, peak intensities at 256 points are measured at equal intervals with respect to a straight line of 200 nm on the toner particle surface, and distribution analysis of elemental Si and metallic elements in nano order is possible.

Further, the overlap of the abundance ratio of the Si element and the metal element means that when the maximum value of the abundance ratio of the Si element and the metal element is normalized to 100, the abundance ratio is the sum of the maximum abundance ratio of each element. Represents the value obtained by dividing the sum of minimum values. A large overlap of the abundance ratio of the Si element and the metal element indicates that each element is uniformly present in the same region. On the other hand, when the overlap of the abundance ratio of the Si element and the metal element is small, it indicates that each element exists separately.
When the overlap of the abundance ratio of the Si element and the abundance ratio of the metal element is 40% or more, overcharging of the toner can be suppressed.

The large overlap between the abundance ratio of the Si element and the abundance ratio of the metal element indicates that the metal compound and the organosilicon compound contained in the composite compound fine particles are finely mixed. The metal compound contained in the composite compound fine particles functions as a conductor, and the organosilicon compound functions as a dielectric. Therefore, when the toner is charged, the organosilicon compound contained in the composite compound fine particles causes dielectric polarization, and the composite compound fine particles serve as a capacitor that suppresses excessive charging. Thereby, overcharging of the toner can be suppressed.
By suppressing the overcharging of the toner, the electrostatic adhesion between the toner and the developing roller is stabilized, which enables stable regulation by the regulating blade. Therefore, the toner layer on the developing roller does not become thick, and the occurrence of uneven density on the image can be suppressed. Therefore, in the case of a toner excellent in suppression of overcharge, unevenness in density does not occur on an image, and a good image can be obtained.
More preferably, the overlap of the abundance ratio of the Si element and the abundance ratio of the metal element is 50% or more. On the other hand, the upper limit is not particularly limited, but preferably 90% or less, more preferably 80% or less. The overlap between the abundance ratio of the Si element and the abundance ratio of the metal element can be controlled by the type and the addition amount of the organosilicon compound and the metal source.

The number average particle diameter of the composite compound fine particles is preferably 1 nm or more and 200 nm or less. By setting the amount in this range, the composite compound fine particles are less likely to be detached, and the change of the toner particle surface and the contamination of the developing roller can be suppressed. More preferably, it is 5 nm or more and 150 nm or less.
The number average particle diameter of the composite compound fine particles can be controlled by the reaction temperature or the like at the time of formation. Specifically, the higher the reaction temperature, the smaller the number average particle diameter of the composite compound fine particles tends to be.

Subsequently, the metal compound used in the present invention will be described in detail.
<Metal compound>
The metal compound contains at least one metal element selected from all the metal elements belonging to Groups 3 to 13. By disposing such a metal compound on the surface of the toner particles, the resistance of the toner is reduced, and the chargeability of the toner is improved.
Specific examples of the metal element include titanium, zirconium, hafnium, copper, iron, silver, zinc, indium, aluminum and the like. More preferably, titanium, zirconium, copper and aluminum are used.

Further, the Pauling electronegativity of the metal element is preferably 1.25 or more and 1.85 or less, and more preferably 1.30 or more and 1.75 or less. A metal compound containing a metal element having an electronegativity in the above-described range can increase the polarization in the metal compound in addition to the suppression of the hygroscopicity, and thus can further improve the effect on the charge rising property.
The value of Pauling's electronegativity is described in “The Chemical Society of Japan (2004)“ Chemical Handbook Basics ”, revised edition, front and back, Maruzen Publishing”.

On the other hand, metal compounds having only Group 1 and Group 2 metal elements are unstable, and their characteristics are easily changed by reacting with water in the air or absorbing water in the air. Performance tends to change during long-term use.
The metal compound is preferably a reaction product of a compound containing at least one metal element selected from all metal elements belonging to Group 3 to Group 13 and a polyvalent acid or a salt thereof. Any polyvalent acid may be used as long as it is a divalent or higher acid. A metal salt with a divalent or higher acid can form a cross-linked structure between the metal compound and the polyvalent acid, promote the movement of electrons by the cross-linked structure, and improve the charge rising property. Although metal sources and acids that can be used to obtain metal compounds are described later, for example, polyvalent acids such as phosphoric acid, carbonic acid and sulfuric acid, or salts thereof such as alkali metal salts thereof are preferable.

Specific examples of the metal compound include the following: reaction product of phosphoric acid and a compound containing titanium, reaction product of phosphoric acid and a compound containing zirconium, reaction product of a compound containing phosphoric acid and aluminum, phosphoric acid and copper Metal salts represented by the reaction product with a compound containing iron, the reaction product with a compound containing phosphoric acid and the like; the reaction product with a compound containing sulfuric acid and titanium, the reaction product with a compound containing sulfuric acid and zirconium A metal salt of sulfuric acid represented by a reaction product of sulfuric acid and a compound containing silver; a reaction product of carbonic acid and a compound containing titanium, a reaction product of a carbonic acid and a compound containing zirconium, a compound containing carbonic acid and iron metal carbonates typified reaction product; alumina (aluminum _oxide: Al _{2 O} 3), alumina hydrate, titania (titanium oxide: _TiO 2), strontium titanate (TiSrO _3), titanium Barium (TiBaO _3), zinc oxide (ZnO), iron oxide _{(Fe 2 O 3, Fe 3} O 4), indium oxide _{(In 2 O} 3), metal oxides typified by indium tin oxide or the like; and the like can be mentioned Be
For example, a metal phosphate is preferable because it has high strength because phosphate ions cross-link between metals, and has excellent ionic bond properties due to having an ionic bond in the molecule. Specifically, a reaction product of phosphoric acid and a compound containing titanium, a reaction product of phosphoric acid and a compound containing zirconium, a reaction product of phosphoric acid and a compound containing aluminum, or the like is preferable.

Subsequently, other materials used in the present invention will be described in detail below.
<Binder resin>
The toner of the present invention contains a binder resin.
Examples of the binder resin include vinyl resins, polyester resins, polyurethane resins, and polyamide resins. The binder resin preferably contains a vinyl resin or a polyester resin. A polymer obtained by graft polymerization of a vinyl monomer to polyolefin may be added to the binder resin.
Examples of vinyl monomers that can be used for the synthesis of vinyl resins include styrene monomers such as styrene and α-methylstyrene;
Acrylic acid esters such as methyl acrylate and butyl acrylate;
Methacrylic acid esters such as methyl methacrylate, 2-hydroxyethyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate;
Unsaturated carboxylic acids such as acrylic acid and methacrylic acid;
Unsaturated dicarboxylic acids such as maleic acid;
Unsaturated dicarboxylic acid anhydrides such as maleic acid anhydride;
Nitrile vinyl monomers such as acrylonitrile; Halogen-containing vinyl monomers such as vinyl chloride;
Nitro-based vinyl monomers such as nitrostyrene;

The polyester resin is preferably a condensation polymer of an alcohol component and an acid component. The following compounds are mentioned as a monomer which produces | generates a polyester resin.
Examples of the alcohol component include the following dihydric alcohols.
Ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol And 2-ethyl-1,3-hexanediol, hydrogenated Bisphenol A, and bisphenol represented by the following formula (I) and derivatives thereof.
As the alcohol component, 1,2,3-propanetriol, trimethylolpropane, hexanetriol, pentaerythritol, or the like may be used as a trihydric or higher polyhydric alcohol.

(In the formula, R represents an ethylene group or a propylene group, X and Y each represent an integer of 0 or more, and the average value of X + Y is 0 or more and 10 or less.)

Examples of the acid component include the following divalent carboxylic acids.
Phthalic acid, terephthalic acid, isophthalic acid, benzenedicarboxylic acids such as phthalic anhydride, or anhydrides thereof; succinic acids, adipic acid, sebacic acid, alkyl dicarboxylic acids such as azelaic acid or anhydrides thereof; Succinic acid or anhydride thereof substituted with the following alkyl group or alkenyl group having 6 to 18 carbon atoms; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid or anhydride thereof.

  It is also preferable to use a trivalent or higher polyvalent carboxylic acid as the acid component. For example, 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid and acid anhydrides or lower alkyl esters thereof Is mentioned.

<Polymerization initiator>
A polymerization initiator may be used to form the binder resin. As a polymerization initiator, a well-known polymerization initiator can be used without a special restriction | limiting.
Specifically, the following may be mentioned.
Hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide, ammonium persulfate, Sodium persulfate, potassium persulfate, diisopropyl percarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid-tert-hydroperoxide, tert-butyl formate, peracetic acid- tert-Butyl, tert-Butyl Perbenzoate, tert-Butyl Perphenylacetate, tert-Butyl Permethoxyacetate, Per-N- (3-Toluyl) palmitate-tert-Butylbenzoyl Peroxide, t-Butylpa Oxy 2-ethylhexanoate, t-butyl peroxypiperate, t-butyl peroxyisobutyrate, t-butyl peroxy neodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxy carbonate, cumene hydro Peroxide type polymerization initiators represented by peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide and the like;
2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis Azo or diazo polymerization initiators represented by -4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile etc.

<Colorant>
The toner particles may contain a colorant.
As the colorant, conventionally known pigments and dyes of black, yellow, magenta, and cyan, and other colors, dyes, magnetic materials, and the like can be used without particular limitation.
Specific examples of the black colorant include black pigments represented by carbon black and the like.
Specific examples of yellow colorants include monoazo compounds; disazo compounds; condensed azo compounds; isoindolinone compounds; benzimidazolone compounds; anthraquinone compounds; azo metal complexes; methine compounds; And pigments and yellow dyes.
Specifically, C.I. I. Pigment yellow 74, 93, 95, 109, 111, 128, 155, 174, 180, 185, C.I. I. Solvent Yellow 162 and the like.

Specific examples of magenta colorants include monoazo compounds; condensed azo compounds; diketopyrrolopyrrole compounds; anthraquinone compounds; quinacridone compounds; base dye lake compounds; naphthol compounds: Representative examples include magenta pigments and magenta dyes.
Specifically, C.I. I. Pigment red 2,3,5,6,7,23,48: 2,48: 3,48: 4,57: 1,81: 1,122,144,146,150,166,169,177,184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment bio red 19 and the like.
Specific examples of the cyan colorant include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds; cyan pigments and cyan dyes represented by basic dye lake compounds and the like. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like.

It is preferable that content of a coloring agent is 1.0-20.0 mass parts with respect to 100.0 mass parts of polymerizable monomers which can produce | generate a binder resin or a binder resin.
The toner may be a magnetic toner containing a magnetic material. In this case, the magnetic material can also serve as a colorant. As magnetic substances, iron oxides represented by magnetite, hematite, ferrite etc .; metals represented by iron, cobalt, nickel etc., or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony , Alloys with metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

<Wax>
The toner particles may contain a wax.
Specifically, esters of monohydric alcohols such as behenyl behenate, stearyl stearate, palmityl palmitate and the like;
Esters of dihydric carboxylic acids and monoalcohols such as dibehenyl sebacate;
Esters of a dihydric alcohol such as ethylene glycol distearate, hexanediol dibehenate and a monocarboxylic acid;
Esters of trihydric alcohols such as glycerin tribehenate and monocarboxylic acids;
Esters of a tetrahydric alcohol such as pentaerythritol tetrastearate, pentaerythritol tetrapalmitate, and a monocarboxylic acid;
Esters of a hexahydric alcohol and a monocarboxylic acid such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate;
Esters of polyfunctional alcohols such as polyglycerin behenate and monocarboxylic acids; natural ester waxes such as carnauba wax and rice wax;
Petroleum-based hydrocarbon waxes such as paraffin wax, microcrystalline wax, petrolatum and derivatives thereof;
Fischer-Tropsch hydrocarbon wax and its derivatives;
Polyolefin hydrocarbon waxes such as polyethylene wax and polypropylene wax and derivatives thereof; Higher aliphatic alcohols;
Examples include fatty acids such as stearic acid and palmitic acid; acid amide waxes and the like.
The content of the wax is preferably 1.0 to 30.0 parts by mass with respect to 100.0 parts by mass of the binder resin or the polymerizable monomer capable of forming the binder resin from the viewpoint of releasability. . It is more preferable that it is 5.0-20.0 mass parts.

<Charge control agent>
The toner particles may contain a charge control agent.
As the charge control agent, conventionally known charge control agents can be used without particular limitation. Specifically, as a negative charge control agent, a metal compound of an aromatic carboxylic acid such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid or a polymer or copolymer having a metal compound of the aromatic carboxylic acid United;
A polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group; a metal salt or metal complex of an azo dye or an azo pigment;
Boron compounds, silicon compounds, calixarenes and the like can be mentioned.

On the other hand, examples of the positive charge control agent include quaternary ammonium salts, polymer compounds having a quaternary ammonium salt in the side chain; guanidine compounds; nigrosine compounds; imidazole compounds.
Examples of the polymer or copolymer having a sulfonate group or a sulfonate group include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamide-2-methylpropane sulfonic acid, vinyl sulfone. A homopolymer of a sulfonic acid group-containing vinyl monomer such as acid or methacrylsulfonic acid or a copolymer of the vinyl monomer shown in the section of the binder resin and the sulfonic acid group-containing vinyl monomer may be used. it can.
The content of the charge control agent is preferably 0.01 to 5.0 parts by mass with respect to 100.0 parts by mass of the binder resin or the polymerizable monomer capable of producing the binder resin.

<External additive>
Since the toner particles have composite compound fine particles, they exhibit excellent characteristics such as fluidity even when there is no external additive. However, external additives may be contained for the purpose of further improvement.
As the external additive, a conventionally known external additive can be used without any particular limitation. Specifically, fine silica particles such as wet process silica and dry process silica or silica fine particles of the bulk silica are surface-treated with a treating agent such as silane coupling agent, titanium coupling agent and silicone oil, Examples thereof include resin fine particles such as vinylidene fluoride fine particles and polytetrafluoroethylene fine particles.
The content of the external additive is preferably 0.1 to 5.0 parts by mass with respect to 100.0 parts by mass of the toner particles.

The method of producing the toner will be described in detail.
<Formation of Surface Layer Containing Condensate of Organosilicon Compound>
The method for producing toner particles is not particularly limited, but in order to form the surface layer containing the condensation product of the organosilicon compound, the following production method may be specifically mentioned.
1. A production method of condensing an organosilicon compound in an aqueous medium in which toner mother particles are dispersed.
2. A method in which a solvent having an organosilicon compound is jetted onto the surface of a toner base particle by a spray dry method, condensed on the surface by hot air, and then dried to form a condensation product of an organosilicon compound on the surface of the toner base particle.
Among these, the method of condensing the organosilicon compound in the aqueous medium in which the toner base particles are dispersed is preferable from the viewpoint of film uniformity.
The organosilicon compound can be added to and mixed with the aqueous medium by any method. For example, the organosilicon compound may be added as it is. Alternatively, it may be added after being mixed with an aqueous medium and hydrolyzed.

<Method for Fixing to the Surface of Composite Compound Fine Particle Toner Particles>
In order to fix the composite compound fine particles to the surface of the toner particles, the following production method can be specifically mentioned.
I. In an aqueous medium in which toner base particles are dispersed, an organic silicon compound and a metal source as raw materials of composite compound fine particles are reacted with acid or water to precipitate a composite compound as fine particles and fix on the toner base particles. Manufacturing method to obtain particles. In the production method, it is preferable to react an organosilicon compound and a metal source with an acid, whereby a composite compound of a metal compound containing a metal element and an organosilicon compound can be obtained.
II. A method of producing toner particles by adding composite compound fine particles prepared in advance to an aqueous medium in which an organosilicon compound and toner base particles are dispersed, and fixing them on the toner base particles.
The aforementioned materials can be used for the organosilicon compound.
In the present invention, the above 1. And I. It is preferable to adopt the method of That is, the organosilicon compound is condensed in an aqueous medium in which toner mother particles are dispersed to form a surface layer containing a condensate of the organosilicon compound, and the organosilicon compound and the metal source are reacted with an acid to form fine particles of composite compound. A method of precipitating (fine particles of a complex compound of a metal compound and an organic silicon compound) and adhering the complex compound fine particles to the surface layer is preferable.

It is known that the condensation reaction of the organosilicon compound is pH dependent, and the pH of the aqueous medium is preferably 6.0 or more and 12.0 or less for the progress of the condensation. What is necessary is just to control pH adjustment of an aqueous medium or a liquid mixture with the existing acid or base. Examples of the acid for adjusting the pH include the following.
Hydrochloric acid, bromic acid, iodic acid, perbromic acid, perbromic acid, metaperiodic acid, metamanganic acid, permanganic acid, thiocyanic acid, sulfuric acid, nitric acid, phosphonic acid, phosphoric acid, phosphoric acid, diphosphoric acid, hexafluorophosphoric acid, tetrafluoroboronic acid Acid, tripolyphosphate, aspartic acid, o-aminobenzoic acid, p-aminobenzoic acid, isonicotinic acid, oxaloacetic acid, oxaloacetic acid, citric acid, 2-glyceryl phosphate, glutamic acid, cyanoacetic acid, oxalic acid, trichloroacetic acid, o-nitro Benzoic acid, nitroacetic acid, picric acid, picolinic acid, pyruvic acid, fumaric acid, fluoroacetic acid, bromoacetic acid, o-bromobenzoic acid, maleic acid, malonic acid.

As the base for adjusting pH, the following may be mentioned.
Alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide and aqueous solutions thereof, alkali metal carbonates such as potassium carbonate, sodium carbonate and lithium carbonate and aqueous solutions thereof, potassium sulfate, sodium sulfate, Alkali metal sulfates such as lithium sulfate and aqueous solutions thereof, alkaline metal phosphates such as potassium phosphate, sodium phosphate and lithium phosphate and aqueous solutions thereof, alkaline earths such as calcium hydroxide and magnesium hydroxide Metal hydroxides and their aqueous solutions, basic amino acids such as ammonia, histidine, arginine, lysine and their aqueous solutions, trishydroxymethylaminomethane.

The above I. When the toner is obtained by this manufacturing method, a conventionally known material can be used as the metal source without any particular limitation. The metal element contained in the metal compound is derived from the metal source. Specifically, the following may be mentioned.
Titanium diisopropoxybisacetylacetonate, titanium tetraacetylacetonate, titanium diisopropoxybisethylacetoacetate, titanium di-2-ethylhexoxybis 2-ethyl-3-hydroxyhexoxide, titanium diisopropoxybisethyl Acetoacetate, titanium lactate, titanium lactate ammonium salt, titanium diisopropoxy bis triethanolaminate, titanium isostearate, titanium aminoethyl aminoethanolate, titanium triethanol aminate;
Zirconium tetraacetylacetonate, zirconium tributoxy monoacetylacetonate, zirconium dibutoxy bis (ethylacetoacetate), zirconium lactate, zirconium lactate ammonium salt;
Aluminum lactate, aluminum lactate ammonium salt, aluminum trisacetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum trisethylacetoacetate;
Iron (II) lactate; copper (II) lactate; silver (I) lactate;
Metal chelate compounds represented by
Metal alkoxide compounds represented by tetraisopropyl titanate, tetrabutyl titanate, tetraoctyl titanate, zirconium tetrapropoxide, zirconium tetrabutoxide, aluminum secondary butoxide, aluminum isopropoxide, trisisopropoxy iron, tetraisopropoxy hafnium and the like.
Metal halides represented by titanium chloride, zirconium chloride, aluminum chloride and the like.

Among these, a metal chelate compound is preferably used because a toner satisfying the provisions of the present invention can be easily obtained by suppressing the aggregation of the composite compound fine particles by suppressing the reaction rate.
Furthermore, titanium lactate, titanium lactate ammonium salt, zirconium lactate, zirconium lactate ammonium salt, aluminum lactate, aluminum lactate ammonium salt are more preferable.

On the other hand, as the acid to be reacted with the metal source, a conventionally known acid can be used without any particular limitation. Specifically, the following may be mentioned.
Inorganic polyvalent acids represented by phosphoric acid, carbonic acid, sulfuric acid and the like;
Inorganic monobasic acid represented by nitric acid etc .;
Organic polyvalent organic compounds represented by oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. acid;
Examples thereof include organic monovalent acids such as formic acid, acetic acid, benzoic acid, and trifluoroacetic acid.
Among them, use of an inorganic polyvalent acid is preferable because the composite compound fine particles having high strength can be obtained by crosslinking between metal atoms, and thus the durability is excellent.
Furthermore, it is more preferable to use ions of polyvalent acids such as phosphate ions, carbonate ions, and sulfate ions. The acid may be used as it is, or as an alkali metal salt such as sodium, potassium or lithium, or an alkaline earth metal salt such as magnesium, calcium, strontium or barium, or as an ammonium salt. Good.

Subsequently, the toner measurement method of the present invention will be described below.
<Method for Measuring the Abundance Ratio of Si Element and Metal Element on Toner Surface and Calculation Method for Overlap of Each Abundance Ratio>
Cross-sectional observation of the toner is performed by the following method using a TEM.
The specific method of observing the cross section of the toner is as follows. After sufficiently dispersing the toner in a room temperature curable epoxy resin, it is cured for 2 days under an atmosphere of 40 ° C. From the resulting cured product, a thin sample of 50 nm in thickness is cut out from the top of the toner using a microtome equipped with a diamond blade. This sample is magnified by a TEM (trade name: electron microscope Tecnai TF20XT, manufactured by FEI) to a magnification of 500,000 times, and the surface on the top side of the flaky sample is observed. A toner cross section having a major axis (μm) of the number average particle diameter of the toner ± 10% is selected.
Elemental analysis is performed by line analysis of peak intensities of each element in a TEM-EDX image in which each element on the toner surface is mapped.
For each toner, the surface of 20 toners (the surface of a flaky sample having a thickness of 50 nm from the top of the toner) is observed by the above-described method, and line analysis of the straight line 200 nm using EDX (256 points) is performed. Then, the peak intensities of Si element and all metal elements belonging to Groups 3 to 13 are measured. The ratio of the peak intensity of each element at each of the 256 points is taken as the abundance ratio.
Further, when the maximum value of the abundance ratio of each element at the 256 points was normalized to 100, “the most important of all the metal elements belonging to the Si element and the Group 3 to Group 13 at the 256 points. The sum of the abundance ratio values of elements having a high abundance ratio, “the abundance ratio of the element having the lowest abundance ratio among the above-mentioned 256 elements, among Si elements and all metal elements belonging to Group 3 to Group 13. A value obtained by dividing “sum of the values of” × 100 is calculated as an overlap of the respective abundance ratios. The overlap of the abundance ratios of each of the 20 toners is obtained, and the arithmetic mean value thereof is adopted.
In the examples, Si is detected as the element having the highest abundance ratio, and the metal element derived from the used metal compound material is detected as the element having the lowest abundance ratio. The complex compound can be evaluated by

<Confirmation of presence of surface layer containing condensate of organosilicon compound>
The presence of the surface layer containing the condensation product of the organosilicon compound can be confirmed as follows.
In the same manner as described above, the toner is cured in a room temperature curable epoxy resin. From the obtained cured product, using a microtome equipped with a diamond blade, a thin sample of 50 nm thickness is cut out near the center of the toner. This sample is magnified by a TEM (trade name: electron microscope Tecnai TF20XT, manufactured by FEI) to a magnification of 500,000 times, and the toner cross section is observed. A toner cross section having a major axis (μm) of the number average particle diameter of the toner ± 10% is selected. At this time, if Si element is detected on the toner surface layer and no metal element is detected by element mapping, it is determined that a surface layer containing a condensate of an organosilicon compound exists.

<Method of measuring number average particle diameter of composite compound fine particles>
The number average particle diameter of the composite compound fine particles is calculated from the observation of the toner particle surface.
The toner particles are observed using an ultra-high resolution field emission scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation). The observation conditions of S-4800 are as follows.
Inject the liquid nitrogen into the anticontamination trap attached to the S-4800 housing until it overflows, and place for 30 minutes. The "PC-SEM" of S-4800 is activated to perform flushing (cleaning of the FE chip as an electron source). Click the acceleration voltage display part of the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Check that the flushing intensity is 2 and execute. Confirm that the emission current by flushing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 chassis. Press [Origin] on the control panel to move the sample holder to the observation position.
Click the acceleration voltage display to open the HV setting dialog, and set the acceleration voltage to [2.0 kV] and the emission current to [10 μA].
Similarly, in the [Basic] tab of the operation panel, set the probe current of the electron optical system condition block to [Normal], the focus mode to [UHR], and WD to [3.0 mm]. Press the [ON] button in the acceleration voltage display section of the control panel to apply the acceleration voltage.
After adjusting the aperture alignment, set the magnification to 100,000 (100 k) and adjust the focus. Adjust the brightness in the mode and take a picture with a size of 640 x 480 pixels.
The toner particles are observed to calculate the particle diameter of the composite compound fine particles present on the surface of the toner particles. The maximum diameter of 100 composite compound fine particles was calculated for a plurality of toners, and the average value was taken as the number average particle diameter.

<Content of elemental Si on toner particle surface>
The content (atomic%) of the Si element on the surface of the toner particle is calculated by performing surface composition analysis by X-ray photoelectron spectroscopy (ESCA).
When an external additive is present in the toner, the following processing is performed, and surface composition analysis is performed on the toner particles from which the external additive has been removed.
The toner is put in isopropanol, and vibration is applied for 10 minutes with an ultrasonic cleaner. Thereafter, the toner particles and the solution are separated by a centrifuge (5 minutes at 1000 rpm). The supernatant liquid is separated, and the precipitated toner particles are dried under vacuum to be dried to obtain toner particles from which the external additive has been removed.
The equipment and measurement conditions of ESCA are as follows.
Device used: ULVAC-PHI Quantum 2000
Measurement condition of X-ray photoelectron spectrometer: X-ray source Al Kα
X-ray: 100 μm 25 W 15 kV
Raster: 300 μm × 200 μm
PassEnergy: 58.70 eV StepSize: 0.125 eV
Neutralizing electron gun: 20μA, 1V Ar ion gun: 7mA, 10V
Number of sweeps: Si 15 times, C 10 times, O 10 times The Si element content (atomic%) is calculated from the peak intensity of each element measured using a relative sensitivity factor provided by PHI.

<Measurement of Weight Average Particle Size (D4) and Number Average Particle Size (D1) of Toner>
The weight average particle size (D4) and the number average particle size (D1) of the toner etc. (toner, toner particles or toner base particles) are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method provided with a 100 μm aperture tube is used. For setting of measurement conditions and analysis of measurement data, attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 channels of effective measurement channels.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of 1.0%, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used. .
In addition, before performing measurement and analysis, set dedicated software as follows.
On the “Change Standard Measurement Method (SOMME)” 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 Set the value obtained using Coulter Co., Ltd.). The threshold and noise level are automatically set by pressing the "Threshold / noise level measurement button". Also, set the current to 1,600 μA, the gain to 2, and the electrolyte to ISOTON II, and check “Aperture tube flush after measurement”.
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 to 60 μm.

The specific measurement method is as follows.
(1) Place 200.0 mL of the electrolytic solution in a glass 250 mL round bottom beaker exclusively for Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) Put 30.0 mL of electrolytic aqueous solution into a glass 100 mL flat bottom beaker. As a dispersant, “Contaminone N” (nonionic surfactant, anionic surfactant, 10% aqueous solution of neutral detergent for cleaning precision measuring instruments with pH 7 consisting of organic builder, Wako Pure Chemical Industries, Ltd. (3) in deionized water, and 0.3 mL of the diluted solution is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetra 150” (manufactured by Nikki Bios Co., Ltd.) with an electrical output of 120 W is prepared. To do. 3.3 L of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and 2.0 mL of Contaminone N is added to the water tank.
(4) The beaker of said (2) is set to the beaker fixing hole of the said ultrasonic dispersion device, and an ultrasonic dispersion device 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, 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 of the water tank is appropriately adjusted so as to be 10 ° C. or more and 40 ° C. or less.
(6) To the round bottom beaker (1) installed in a sample stand, the electrolytic solution (5) in which toner particles are dispersed is dropped using a pipette, and the measurement concentration is adjusted to 5%. . Then, measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by dedicated software attached to the apparatus to calculate the weight average particle size (D4) and the number average particle size (D1). When the graph / volume% is set in the dedicated software, the “average diameter” on the “Analysis / volume statistics (arithmetic average)” screen is the weight average particle diameter (D4). The “average diameter” on the “Analysis / number statistics (arithmetic mean)” screen when set is the number average particle diameter (D1).

  The present invention will be specifically described by the following examples. However, this does not limit the present invention at all. In the examples and comparative examples, “part” and “%” are all based on mass unless otherwise specified.

<Preparation Method of Organosilicon Compound Liquid 1>
Ion-exchanged water 90.0 parts Hexyltrimethoxysilane 10.0 parts The above materials were weighed in a 200 mL beaker, and the pH was adjusted to 3.5 with 10% hydrochloric acid. Then, it stirred for 1 hour, heating at 60 degreeC with a water bath, and the organosilicon compound liquid 1 was prepared.

<Method of preparing organosilicon compound liquids 2 to 6>
Except having changed the kind of organosilicon compound as shown in Table 1, it carried out similarly to the preparation method of the organosilicon compound liquid 1, and prepared the organosilicon compound liquids 2-6.

<Preparation Method of Toner Base Particle Dispersion 1>
(Preparation of aqueous medium)
Into a reaction vessel containing 390.0 parts of ion-exchanged water, 14.0 parts of sodium phosphate (12 hydrate manufactured by Lhasa Kogyo Co., Ltd.) was added and purged with nitrogen, and then kept at 65 ° C. for 1 hour.
T. K. Calcium chloride aqueous solution in which 9.2 parts of calcium chloride (dihydrate) is dissolved in 10.0 parts of ion-exchanged water while stirring at 12,000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Were all put into a reaction vessel to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, 1.0 mol / L hydrochloric acid was added to the aqueous medium in the reaction vessel to adjust the pH to 6.0 to prepare an aqueous medium.

(Preparation of Polymerizable Monomer Composition)
Styrene 60.0 parts C.I. I. Pigment Blue 15: 3 6.5 parts The above-mentioned material is put into atorita (made by Nippon Coke Industry Co., Ltd.), and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 1.7 mm to prepare a pigment dispersion. did. The following materials were then added to the pigment dispersion.
Styrene 10.0 parts n-butyl acrylate 30.0 parts polyester resin (terephthalic acid-propylene oxide modified (2 mol addition) bisphenol A copolymer) 5.0 parts Fischer-Tropsch wax (melting point 70 ° C.) 7.0 parts Keep this at 65 ° C. K. Using a homomixer, the solution was uniformly dissolved and dispersed at 500 rpm to prepare a polymerizable monomer composition.

(Granulation process)
The polymerizable monomer composition is introduced into the aqueous medium while maintaining the temperature of the aqueous medium at 70 ° C. and the number of revolutions of the stirring device at 12,000 rpm, and t-butylperoxypivalate 9, which is a polymerization initiator, .0 part was added. It granulated for 10 minutes, maintaining 12,000 rpm with a stirring apparatus as it was.
(Polymerization process)
T. K. The stirring apparatus was changed from a homomixer to a propeller stirring blade, polymerization was performed for 5 hours while maintaining the temperature at 70 ° C. while stirring at 150 rpm, and the temperature was raised to 85 ° C. and heating was performed for 2 hours. Ion exchange water was added to adjust the toner base particle concentration in the dispersion to 20.0% to obtain toner base particle dispersion 1 in which toner base particles 1 were dispersed.
The number average particle diameter (D1) of the toner base particles 1 was 5.9 μm, and the weight average particle diameter (D4) was 6.5 μm.

<Preparation Method of Toner Base Particle Dispersion 2>
The following materials were mixed in a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe.
Terephthalic acid 29.0 parts Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
80.0 parts Titanium dihydroxy bis (triethanolaminate) 0.1 parts After nitrogen substitution, the mixture was heated to 200 ° C. and reacted for 9 hours while removing generated water. Further, 5.8 parts of trimellitic anhydride was added, and the mixture was heated to 170 ° C. and reacted for 3 hours to synthesize polyester resin A.

Then, the following materials were charged into an autoclave and purged with nitrogen, and then kept at 180 ° C. while heating and stirring.
Low density polyethylene (melting point 100 ° C.) 20.0 parts Styrene 64.0 parts n-Butyl acrylate 13.5 parts Acrylonitrile 2.5 parts Subsequently, 2.0% of t-butyl hydroperoxide was added to the system. 50.0 parts of a xylene solution was continuously added dropwise for 5 hours, and after cooling, the solvent was separated and removed to obtain graft polymer A in which a styrene acrylic copolymer was grafted onto polyethylene.

The following materials were thoroughly mixed with an FM mixer (Nihon Coke Kogyo Co., Ltd.) and then melt kneaded with a twin-screw kneader (Ikegai Iron Works Co., Ltd.) set at a temperature of 100 ° C.
Polyester resin A 100.0 parts Fischer-Tropsch wax (melting point 70 ° C) 5.0 parts Graft polymer A 5.0 parts C.I. I. Pigment Blue 15: 3 5.0 parts The obtained kneaded product was cooled, and roughly crushed to 1 mm or less with a hammer mill to obtain a roughly crushed product. Next, after obtaining a finely pulverized material of about 5 μm using the turbo mill manufactured by Turbo Kogyo Co., Ltd., the coarse particles obtained are further pulverized using fine coarse particles using a multi-division classifier utilizing the Coanda effect. The toner mother particles 2 were obtained by cutting. The number average particle diameter (D1) of the toner base particles 2 was 5.6 μm, and the weight average particle diameter (D4) was 6.5 μm.
In a reaction vessel containing 390.0 parts of ion-exchanged water, 14.0 parts of sodium phosphate (12 hydrate manufactured by Lhasa Kogyo Co., Ltd.) was added and kept at 65 ° C. for 1.0 hour while purging with nitrogen. .
T. K. Using a homomixer, while stirring at 12,000 rpm, calcium chloride aqueous solution in which 9.2 parts of calcium chloride (dihydrate) is dissolved in 10.0 parts of ion-exchanged water is collectively charged to the reaction vessel, and dispersed. An aqueous medium was prepared containing the stabilizer. Furthermore, 1.0 mol / L hydrochloric acid was added to the aqueous medium in the reaction vessel to adjust the pH to 6.0, thereby preparing an aqueous medium.
200.0 parts of toner base particles 2 were put in an aqueous medium, and T.I. K. The mixture was dispersed for 15 minutes while rotating at 5,000 rpm using a homomixer. Ion exchange water was added to adjust the toner base particle concentration in the dispersion to 20.0% to obtain toner base particle dispersion 2.

<Preparation Method of Toner Base Particle Dispersion 3>
The following materials were weighed, mixed and dissolved.
Styrene 82.6 parts n-butyl acrylate 9.2 parts acrylic acid 1.3 parts hexanediol diacrylate 0.4 parts n-lauryl mercaptan 3.2 parts this solution Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 10% aqueous solution was added and dispersed. An aqueous solution of 0.15 parts of potassium persulfate dissolved in 10.0 parts of ion-exchanged water was added while slowly stirring for 10 minutes. After nitrogen substitution, emulsion polymerization was performed at a temperature of 70 ° C. for 6.0 hours. After completion of the polymerization, the reaction solution was cooled to room temperature, and ion-exchanged water was added to obtain a resin particle dispersion having a solid content concentration of 12.5% and a number average particle diameter of 0.2 μm.

The following materials were weighed and mixed.
Ester wax (melting point: 70 ° C.) 100.0 parts Neogen RK 15.0 parts Ion-exchanged water 385.0 parts Dispersed for 1 hour using a wet jet mill JN100 (manufactured by Joko Corporation) to obtain a wax dispersion. The solid content concentration of the wax particle dispersion was 20.0%.

The following materials were weighed and mixed.
C. I. Pigment Blue 15: 3 100.0 parts Neogen RK 15.0 parts Ion-exchanged water 885.0 parts Wet jet mill Using a JN 100, dispersion was performed for 1 hour to obtain a colorant dispersion. The solid concentration of the colorant dispersion was 10.0%.

Resin particle dispersion 160.0 parts Wax dispersion 10.0 parts Colorant dispersion 10.0 parts Magnesium sulfate 0.2 parts Dispersed using a homogenizer (manufactured by IKA Co., Ltd.) and then, while stirring, to 65 ° C. It warmed up. After stirring at 65 ° C. for 1 hour, observation with an optical microscope confirmed that aggregate particles having a number average particle diameter of 6.0 μm were formed. After 2.2 parts of Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was added, the temperature was raised to 80 ° C. and stirring was carried out for 2 hours to obtain a fused toner particle precursor.
After cooling, it was filtered and the filtered solid was stirred and washed with 720.0 parts of ion exchange water for 1 hour. The dispersion containing the toner particle precursor was filtered and then dried to obtain toner mother particles 3. The number average particle diameter (D1) of the toner base particles 3 was 6.2 μm, and the weight average particle diameter (D4) was 7.1 μm.
Into a reaction vessel containing 390.0 parts of ion-exchanged water, 14.0 parts of sodium phosphate (12 hydrate manufactured by Lhasa Kogyo Co., Ltd.) was added and kept at 65 ° C. for 1 hour while purging with nitrogen.
T. K. While stirring at 12,000 rpm using a homomixer, a calcium chloride aqueous solution in which 9.2 parts of calcium chloride (dihydrate) was dissolved in 10.0 parts of ion-exchanged water was added all at once. Further, 1.0 mol / L hydrochloric acid was added, and then the pH was adjusted to 6.0 to prepare an aqueous medium.
Into an aqueous medium, 100.0 parts of toner base particles 3 are charged, and T.I. K. The mixture was dispersed for 15 minutes while rotating at 5000 rpm using a homomixer. Ion exchange water was added to adjust the solid content concentration of the toner base particles 3 in the dispersion to be 20.0%, whereby a toner base particle dispersion liquid 3 was obtained.

<Preparation Method of Toner Base Particle Dispersion 4>
Mix 660.0 parts of ion-exchanged water and 25.0 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate, K. The aqueous medium was prepared by stirring at 10,000 rpm using a homomixer.
The following materials were put into 500.0 parts of ethyl acetate, and dissolved with a propeller stirring blade at 100 rpm to prepare a solution.
Styrene / butyl acrylate copolymer (copolymerization ratio: 80/20) 100.0 parts polyester resin 3.0 parts (terephthalic acid-propylene oxide modified (2 mol addition) bisphenol A copolymer) C.I. I. Pigment blue 15: 3 6.5 parts Fischer Tropsch wax (melting point 70 ° C.) 9.0 parts Next, 150.0 parts of an aqueous medium is placed in a container, and T.I. K. Using a homomixer, the mixture was stirred at a rotational speed of 12,000 rpm, 100.0 parts of the solution was added thereto, and mixed for 10 minutes to prepare an emulsified slurry.
Then, 100.0 parts of the emulsified slurry is charged into a flask set with a degassing pipe, a stirrer and a thermometer, and the solvent is removed under reduced pressure at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min. It was made to age for 4 hours at ° C, and it was set as a solvent removal slurry. After filtering the solvent-free slurry under reduced pressure, 300.0 parts of deionized water is added to the obtained filter cake, and T. K. After mixing with a homomixer, redispersion (rotation speed 12000 rpm for 10 minutes), it filtered.
The obtained filter cake was dried in a drier at 45 ° C. for 48 hours to obtain toner mother particles 4 sieved with a mesh of 75 μm mesh. The number average particle diameter (D1) of the toner base particles 4 was 5.7 μm, and the weight average particle diameter (D4) was 6.9 μm.
In a reaction vessel containing 390.0 parts of ion-exchanged water, 14.0 parts of sodium phosphate (12 hydrate manufactured by Lhasa Kogyo Co., Ltd.) was added and kept at 65 ° C. for 1.0 hour while purging with nitrogen. .
T. K. Using a homomixer, while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 9.2 parts of calcium chloride (dihydrate) was dissolved in 10.0 parts of ion-exchanged water was added all at once. Furthermore, 1.0 mol / L hydrochloric acid was added to adjust the pH to 6.0 to prepare an aqueous medium.
Into an aqueous medium, 100.0 parts of toner base particles 4 are charged, and T.I. K. The mixture was dispersed for 15 minutes while rotating at 5000 rpm using a homomixer. Ion exchange water was added to adjust the solid content concentration of the toner base particles 4 in the dispersion to be 20.0%, to obtain a toner base particle dispersion liquid 4.

Method of Producing Toner 1
The following materials were weighed and mixed in a reaction vessel.
Titanium lactate 44% aqueous solution (TC-310: manufactured by Matsumoto Fine Chemical Co.):
1.5 parts (equivalent to 0.66 parts as titanium lactate)
Toner mother particle dispersion 1: 500.0 parts Next, 1.0 mol / L hydrochloric acid was added to adjust the pH of the mixture to 5.5, and then 10.0 parts of organosilicon compound liquid 1 was added. The pH was adjusted to 7.0 using a 1.0 mol / L aqueous NaOH solution. After the temperature of the mixture was 60 ° C., the mixture was held for 1 hour while mixing using a propeller stirring blade.
Thereafter, the pH was adjusted to 9.5 using a 1.0 mol / L aqueous NaOH solution, and the temperature was kept at 60 ° C. for 2 hours while stirring.
After the temperature was lowered to 25 ° C., the pH was adjusted to 1.5 with 1.0 mol / L hydrochloric acid and stirred for 1 hour, followed by filtration while washing with ion-exchanged water to obtain toner particles 1. This is called toner 1.
As a result of the element mapping of the toner particles, it was confirmed that the surface layer containing the condensation product of the organosilicon compound and the presence of the composite compound fine particle on the surface layer. The overlap between the abundance ratio of the Si element and the abundance ratio of the metal element was 66.8%, the number average particle diameter of the composite compound fine particles was 15 nm, and the Si element content on the toner particle surface was 4.5 atomic%.
In the toner 1, a metal compound is formed by using titanium lactate as a metal source (containing a metal element) and sodium phosphate contained in an aqueous medium as an acid (salt of a polyvalent acid), and further, the metal compound and an organic compound. The silicon compound forms composite compound fine particles.

<Production Method of Toner 2 to 21>
Toners 2 to 21 are obtained in the same manner as in the method of preparing toner 1 except that the type of toner mother particle dispersion, the type and amount of organosilicon compound liquid and metal compound material, and the reaction temperature are changed as shown in Table 2. The Physical properties of the obtained toner are shown in Table 3.

<Method of Producing Toner 22>
Hydrophobic silica (NY 50: Nippon Aerosil Co., Ltd.) 2.2 having a volume average particle size of 30 nm and hydrophobic silica treated with decylsilane-treated hydrophobic titania having a volume average particle size of 15 nm relative to 100.0 parts of the toner base particle 1 Mixed for 10 minutes at a peripheral speed of 32 m / s with an FM mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) so as to be 2.0 parts of hydrophobic silica (X-24: manufactured by Shin-Etsu Chemical Co., Ltd.) having a volume average particle diameter of 100 nm. The toner was obtained by removing coarse particles with a mesh having an opening of 45 μm.
As a result of the element mapping of the toner particles, it was confirmed that the surface layer containing the condensation product of the organosilicon compound and the composite compound fine particle on the surface layer were not present. The overlap between the abundance ratio of the Si element and the abundance ratio of the metal element was 8.6%, and the Si element on the toner particle surface could not be detected.

<Method of Producing Toner 23>
The following samples were weighed into a reaction vessel, K. The mixture was mixed at 10,000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).
Titanium oxide (volume average particle size 15 nm) 1.6 parts Toner mother particle dispersion 1 500.0 parts Next, 1.0 mol / L hydrochloric acid is added to adjust the pH of the mixed solution to 5.5, and then organic 10.0 parts of silicon compound solution 1 was added, and the pH was adjusted to 7.0 using a 1.0 mol / L aqueous NaOH solution.
After the temperature of the mixture was 60 ° C., the mixture was held for 1 hour while mixing using a propeller stirring blade. Thereafter, the pH was adjusted to 9.5 using a 1.0 mol / L aqueous NaOH solution, and the temperature was kept at 60 ° C. for 2 hours while stirring.
After lowering the temperature to 25 ° C., adjusting the pH to 1.5 with 1.0 mol / L hydrochloric acid, stirring for 1 hour, and filtering while washing with ion-exchanged water, the titanium oxide is present on the surface Toner particles 23 were obtained. This is called toner 23.
As a result of the element mapping of the toner particles, it was confirmed that the surface layer containing the condensation product of the organosilicon compound was present, and the composite compound fine particles were not present on the surface layer. The overlap of the content ratio of the Si element and the content ratio of the metal element was 23.8%, and the content ratio of the Si component on the surface of the toner particle was 4.3 atomic%.

<Method of Producing Composite Compound Fine Particles 22>
Ion-exchanged water 100.0 parts Sodium phosphate (12-hydrate) (manufactured by Lasa Kogyo Co., Ltd.) 8.5 parts K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), 10.0 parts of titanium lactate (TC-310, Matsumoto Fine Chemical Co., Ltd.) was added while stirring at 10,000 rpm. Next, after adding 1.0 mol / L hydrochloric acid to adjust the pH of the mixed solution to 5.5, 5.0 parts of organosilicon compound solution 1 is added, and 1.0 mol / L NaOH aqueous solution is used. The pH was adjusted to 7.0. After the temperature of the mixture was 60 ° C., the mixture was held for 1 hour while mixing using a propeller stirring blade. Thereafter, the pH was adjusted to 9.5 using a 1.0 mol / L aqueous NaOH solution, and the temperature was kept at 60 ° C. for 2 hours while stirring.
Thereafter, solids were removed by centrifugation. Thereafter, the steps of redispersion in ion exchange water and removing the solid content by centrifugation were repeated three times to remove ions such as sodium. Again, it was dispersed in ion exchange water and dried by spray drying to obtain composite compound fine particles 22 having a number average particle diameter of 15 nm.

<Method of Producing Toner 24>
Based on 100.0 parts of toner base particles 1, 1.6 parts of composite compound fine particles 22, hydrophobic silica (NY 50: manufactured by Nippon Aerosil Co., Ltd.) of 2.2 parts in volume average particle diameter of 30 nm, volume average particle diameter of 100 nm Is mixed with an FM mixer (Nihon Coke Kogyo Co., Ltd.) for 10 minutes at a peripheral speed of 32 m / s so as to be 2.0 parts of hydrophobic silica (X-24: manufactured by Shin-Etsu Chemical Co., Ltd.), and a mesh with an opening of 45 μm. The coarse particles were removed to obtain a toner 24.
The overlap between the abundance ratio of the Si element and the abundance ratio of the metal element was 53.1%, the number average particle diameter of the composite compound fine particles was 15 nm, and the surface layer containing the condensate of the organosilicon compound on the toner particle surface could not be detected.

（表２中、金属化合物材料の量は、材料そのものの投入量を示す。）

(In Table 2, the amount of metal compound material indicates the amount of input of the material itself.)

[Examples 1 to 21, Comparative Examples 1 to 3]
The following evaluation was performed using the toners 1 to 24. The evaluation results are shown in Table 4.

Below, the evaluation method and evaluation criteria of this invention are demonstrated.
As an image forming apparatus, a modified laser printer LBP-7700C (manufactured by Canon), which is a commercially available laser printer, is modified to have a process speed of 240 mm / sec, and a commercially available process cartridge Toner Cartridge 323 (black) (manufactured by Canon) Using. Product toner was extracted from the inside of the cartridge, cleaned by air blow, and then filled with 150 g of toner to be evaluated.
In addition, the product toner was extracted from each of the yellow, magenta, and cyan stations, and evaluation was performed by inserting yellow, magenta, and cyan cartridges with the remaining toner amount detection mechanism disabled.
(Preparation before evaluation)
Convert the process cartridge, the modified laser printer, and the evaluation paper (GF-C081 (Canon) A4: 81.4 g / m ² ) into a low-temperature, low-humidity environment (15 ° C / 10% RH, hereinafter L / L environment) Let stand for 48 hours. After that, the loading amount of all black image area on paper is 0.4.
It adjusted so that it might become 0 mg / cm < ² >.

<1. Evaluation of charge buildup properties>
In the L / L environment, the all black image is output on the evaluation sheet, and the image density of the portion corresponding to one rotation of the developing roller from the top of the all black image and the image density of the portion corresponding to the second rotation Measurement was performed with a color reflection densitometer (X-Rite 404A), and evaluation was performed as follows from the difference in image density at that time.
(Evaluation criteria for charge buildup)
A: The image density difference is less than 0.05.
B: The image density difference is 0.05 or more and less than 0.10.
C: The image density difference is 0.10 or more and less than 0.15.
D: The image density difference is 0.15 or more.

<2. Durability evaluation>
After the evaluation of charge buildup, 25,000 sheets of an image having a printing ratio of 0.5% were continuously output on an evaluation sheet in an L / L environment. After standing for 24 hours in the same environment, the same evaluation as the evaluation of the charge rising property was performed.
Evaluation was performed according to the evaluation criteria for the charge rising property, and the durability was evaluated. Further, the developing roller was visually observed to confirm the presence or absence of contamination by fine particles.

<3. Evaluation of overcharge suppression>
In the L / L environment, 10,000 sheets of an image having a printing rate of 0.5% were continuously output on the evaluation sheet. Thereafter, one halftone image with a loading amount of 0.20 mg / cm ² was output, and the image was confirmed. At the same time, the surface of the developing roller was visually observed to confirm the state of the toner layer on the developing roller. Overcharge suppression performance was evaluated based on the following evaluation criteria.
(Evaluation criteria for overcharge suppression)
A: The toner layer on the developing roller is uniform and there is no density unevenness in the image.
B: The toner layer on the developing roller has a somewhat thick edge, but there is no unevenness in the image density. C: The toner layer on the developing roller is slightly uneven as a whole, but the image has no density unevenness.
D: The toner layer on the developing roller is slightly uneven as a whole, and minute density unevenness occurs at the edge of the image.

<4. Evaluation of transfer efficiency>
In an L / L environment, an all black image is output on an evaluation sheet, the apparatus is stopped during transfer from the photosensitive member to the intermediate transfer member, and the toner amount M1 (mg / cm ² ) on the photosensitive member before the transfer process. The amount of applied toner M2 (mg / cm ² ) on the photosensitive member after the transfer step was measured.
For measurement of the amount of applied toner, first, the toner on the photosensitive member is set in a range of 20.0 cm ² with a suction device (VF-50 (manufactured by Amano Corporation)) attached with a filter (THIMBLE FILTER (manufactured by ADVANTEC)) The toner was absorbed, and the amount of toner captured by the filter was weighed. Next, a value obtained by dividing the toner amount captured by the filter by the suctioned area (20.0 cm ² ) was calculated as the applied toner amount. From the amount of applied toner, (M1-M2) × 100 / M1 was defined as the transfer efficiency (%).
(Evaluation criteria for transfer efficiency)
A: Transfer efficiency is 95% or more.
B: Transfer efficiency is 90% or more and less than 95%.
C: Transfer efficiency is 85% or more and less than 90%.
D: Transfer efficiency is less than 85%.

Claims (11)

A toner having toner particles containing a binder resin,
The toner particles have a surface layer containing a condensation product of an organosilicon compound, and have fine particles containing a composite compound on the surface layer,
The composite compound is characterized in that it is a composite compound of a metal compound containing at least one metal element selected from all metal elements belonging to Groups 3 to 13 and an organosilicon compound. toner.   When the maximum value of the respective abundance ratios of the Si element and the metal element on the toner particle surface obtained by energy dispersive X-ray spectroscopy is set to 100, the abundance ratio of the Si element and the abundance ratio of the metal element The toner according to claim 1, wherein the overlap of 40% or more.   The toner according to claim 1, wherein the electronegativity of poling of the metal element is 1.25 or more and 1.85 or less. The organosilicon compound forming the surface layer containing the condensate of the organosilicon compound and the organosilicon compound forming the fine particles containing the composite compound are each represented by the following formula (1) The toner according to any one of claims 1 to 3, which is at least one selected from the group consisting of
Ra _(n) -Si-Rb _(4-n) (1)
(In formula (1), each Ra independently represents a halogen atom or an alkoxy group, and each Rb independently represents an alkyl group, an alkenyl group, an acyl group, an aryl group or an alkyl moiety having 1 carbon atom -3 represents a methacryloxyalkyl group, and n represents an integer of 1 to 4.)   The toner according to any one of claims 1 to 4, wherein the metal compound is a reaction product of a compound containing the metal element and a polyvalent acid or a salt thereof.   The toner according to any one of claims 1 to 5, wherein a number average particle diameter of fine particles containing the composite compound is 1 nm or more and 200 nm or less.   The toner according to any one of claims 1 to 6, wherein the content of the Si element on the surface of the toner particle determined by X-ray photoelectron spectroscopy is 2.0 atomic% or more.   The toner according to claim 1, wherein the metal element is at least one selected from the group consisting of titanium, zirconium, hafnium, copper, iron, silver, zinc, indium, and aluminum.   The said organosilicon compound which forms the surface layer containing the condensate of the said organosilicon compound and the said organosilicon compound which forms the microparticles | fine-particles containing the said complex compound are the same compounds. The toner described in 1.   The toner according to claim 1, wherein the binder resin includes a vinyl resin or a polyester resin. A toner having toner particles containing a binder resin,
The toner particles have on their surface a condensate of an organosilicon compound and fine particles containing a composite compound,
The fine particles containing the complex compound are fixed to the condensation product of the organosilicon compound,
The composite compound is characterized in that it is a composite compound of a metal compound containing at least one metal element selected from all metal elements belonging to Groups 3 to 13 and an organosilicon compound. toner.