JP4681997B2 - Method for producing toner - Google Patents

Description

One aspect of the present invention relates to a method for producing a toner .

As a main method for transferring conventional toner, (A) a sending source and a sending destination are connected by a pipe, and toner is transferred by a coil screw provided inside the pipe, and (B) the sending source and the sending destination are close to each other. Known to be placed in a vertical position and transported mainly by gravity, and (C) using a powder pump to transport the pipe from the source to the destination placed in a free positional relationship. (For example, refer to Japanese Unexamined Patent Application Publication No. 2002-139906 ( Patent Document 1 ) and Japanese Unexamined Patent Application Publication No. 2002-139902 ( Patent Document 2 ) .)

  The above (A) and (B) have many problems such as being greatly limited in the arrangement of the source and destination, and not suitable for long distance transfer, and currently there are few such problems. The toner transfer technique (C) is drawing attention. In particular, in the electrophotographic image forming apparatus, the volume of the toner container is large, and by using the toner transfer device (C), it is possible to increase the degree of freedom in layout and to make a space-saving device. Become. In particular, in a full-color electrophotographic image forming apparatus using four color toners, the method (C) is advantageous in terms of layout and space saving.

  However, the toner transfer technique (C) is not completely free of problems. Since the source and destination are connected by a pipe, etc., toner clogging may occur in the pipe due to the characteristics of the toner. When such toner clogging occurs, toner transfer will not be performed and the entire system will be fatal. Problem. In order to prevent the occurrence of toner clogging, it is necessary to shorten the length of the tube, which restricts the freedom of layout. Further, even if toner clogging does not occur, the toner transfer speed is not stable, and there is a problem that the control during the transfer becomes complicated.

In addition to the transfer from the toner supply unit to the developing unit, these toner transfer techniques include a latent image formed on the photosensitive member by toner as disclosed in Japanese Patent Application Laid-Open No. 60-41079 ( Patent Document 3 ). In some cases, the image forming apparatus is also used as a developing image apparatus having a cleaner for removing toner remaining on the photosensitive drum after transfer and a recycling apparatus for returning the toner removed by the cleaner to the developing apparatus.

However, in order to form an image of good image quality in such a system, it is necessary that the toner has high fluidity and is extremely resistant to stress. From this point, a fluidizing agent composed of silica fine particles or the like is used. Mixing with toner powder is performed. For example, it is disclosed in Japanese Patent Laid-Open No. 51-120631 ( Patent Document 4 ) , Japanese Patent Laid-Open No. 48-47346 ( Patent Document 5 ) , Japanese Patent Laid-Open No. 51-101535 ( Patent Document 6 ), and the like. In addition, there is a method in which an oxide such as silicon, titanium, or aluminum is added to the developer composition. Recently, a resin or wax having a low softening point has been used, such as a toner used for low-temperature fixing and high-speed copying. In the toner, due to the adhesiveness of the resin, the fluidity is not sufficient, and an additive that further improves the fluidity is desired. Furthermore, as a method for solving this problem, a method in which two types of additives having different characteristics are mixed and used has been proposed. For example, Japanese Patent Application Laid-Open No. 60-136755 ( Patent Document 7 ) discloses a mixture of silica and titanium. Japanese Patent Application Laid-Open No. 61-188546 ( Patent Document 8 ) and Japanese Patent Application Laid-Open No. 2-151872 ( Patent Document 9 ) disclose mixing additives having different particle diameters. Further, Japanese Patent Laid-Open No. 61-249059 ( Patent Document 10 ) discloses a mixture of hydrophobic silica and hydrophilic silica, and Japanese Patent Laid-Open No. 61-20053 ( Patent Document 11 ) has a positive polarity. A mixture of the additive and the negative additive is disclosed. The use of these additives has led to a comparative improvement in the disadvantages of the prior art.

  However, when obtaining the predetermined fluidity using the above additive, any of the above additives may be buried in the toner resin due to the stress caused by transportation or due to liberation of the additive, etc. There is a problem that a predetermined fluidity is gradually lost over time after a certain amount of use is started. In addition, even when the above additives are fixed to the outside of the particles by mechanical energy, since other than the additives come out due to the embedding, the fluidity is lowered, which causes a problem in toner supply due to poor conveyance during conveyance. Or an image defect occurs, which is not sufficient.

  In recent years, market demands for energy saving and high speed have been increasing for image forming apparatuses such as printers, copiers and facsimiles. In order to achieve these required performances, it is important to improve the thermal efficiency of the fixing device used in the image forming apparatus. In an image forming apparatus, an unfixed toner image is transferred to a recording material sheet, printing paper, photosensitive paper, electrostatic recording paper, etc. by an image transfer method or a direct method by an image forming process such as electrophotographic recording, electrostatic recording, and magnetic recording. Formed on recording material. As a fixing device for fixing an unfixed toner image, a contact heating method fixing device such as a heat roller method, a film heating method, and an electromagnetic induction heating method is widely used.

  The heat roller type fixing device has a basic configuration of a rotating roller pair including a fixing roller having a heat source such as a halogen lamp inside and adjusted to a predetermined temperature, and a pressure roller pressed against the fixing roller. A recording material is introduced into a contact portion of the pair of rotating rollers, a so-called fixing nip portion, and conveyed, and an unfixed toner image is melted and fixed by heat and pressure from the fixing roller and the pressure roller.

A film heating type fixing device has been proposed in, for example, Japanese Patent Laid-Open No. 63-313182 ( Patent Document 12 ) and Japanese Patent Laid-Open No. 1-263679 ( Patent Document 13 ) .

  In this apparatus, a recording material is brought into close contact with a heating body fixedly supported by a support member through a thin fixing film having heat resistance, and the heat of the heating body is transferred while the fixing film is slid relative to the heating body. The recording material is supplied to the recording material. In this fixing device, for example, a ceramic heater including a resistance layer on a ceramic substrate such as alumina or aluminum nitride having characteristics such as heat resistance, insulation, and good thermal conductivity is used as a heating body. Since this fixing device can use a thin film with a low heat capacity as the fixing film, it has higher heat transfer efficiency than the heat roller type fixing device, can shorten the warm-up time, and can achieve quick start and energy saving. It becomes possible.

However, among image forming apparatuses, in particular, a fixing device in a full-color image forming apparatus is required to have a capability of sufficiently heating and melting a toner particle layer having a thickness of four or more layers. In order to achieve this requirement, the electromagnetic induction heating type fixing device needs a rubber elastic layer of a certain thickness on the surface of the film in order to sufficiently enclose the toner image and uniformly heat and melt it. Become. In order to solve these problems, when an elastic layer such as silicon rubber is coated on the surface of the film to some extent, the thermal responsiveness deteriorates due to the low thermal conductivity of the elastic layer, and the inner surface of the film and the toner heated from the heating body When the amount of toner is very large due to a very large temperature difference with the outer surface in contact with the belt, the belt surface temperature decreases rapidly, so that sufficient fixing performance cannot be secured, and so-called cold offset occurs. I was doing it. For this reason, the toner for electrophotography has been improved so that it can be fixed at a low temperature and has a high thermal efficiency. However, such a direction is severe to the toner transportability and stress described above. Thus far, no one satisfying the fixability and fluidity has been obtained.
JP 2002-139906 A JP 2002-139902 A JP 60-41079 A JP-A-51-120631 JP-A-48-47346 JP 51-101535 A JP 60-136755 A JP-A 61-188546 Japanese Patent Laid-Open No. 2-151872 JP-A 61-249059 JP-A-61-20053 JP-A-63-313182 Japanese Patent Laid-Open No. 1-263679 Japanese Patent No. 2537503 JP-A-7-152202 Japanese Patent Laid-Open No. 62-209541 JP-A-63-198070 Japanese Patent Laid-Open No. 5-281787

One object of the present invention is to provide a method for producing toner .

One aspect of the present invention is:
A step of dispersing a toner material liquid containing at least unmodified polyester, a polyester prepolymer having an isocyanate group, a colorant, and a release agent in an aqueous medium in the presence of resin fine particles ;
Adding amines to the aqueous medium and reacting the amines with the polyester prepolymer having an isocyanate group;
A step of treating the surface with a fluorine-containing compound in the aqueous medium to obtain matrix-colored fine particles, and
In a method for producing a toner, comprising a step of mixing at least one kind of inorganic fine particles with the matrix coloring fine particles to obtain a toner,
% By weight of the base resin fine particles remaining on the sieve having a sieve size of 355 μm +
Weight% of the mother-colored fine particles remaining on the sieve having a sieve size of 250 μm × 0.6 +
Weight% of matrix coloring fine particles remaining on sieve having a sieve size of 150 μm × 0.2
The degree of aggregation of the toner defined by is from 8% to 30%,
The acid value of the unmodified polyester is 3 or more and 24 or less,
The aqueous medium includes 90 parts of ethyl acetate with respect to 1055 parts of water,
The fluorine-containing compound is a fluorine-containing quaternary ammonium salt;
The fluorine-containing quaternary ammonium salt is N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide ;
In the step of obtaining the mother-colored fine particles by treating the surface, the addition amount of the fluorine-containing quaternary ammonium salt is 0.01 parts by weight or more and 3 parts by weight or less with respect to 100 parts by weight of the mother-colored fine particles,
In the step of dispersing the toner material liquid in the aqueous medium in the presence of resin fine particles, the amount of the aqueous medium used with respect to 100 parts by weight of the toner material liquid is 50 parts by weight or more and 2000 parts by weight or less,
In the step of obtaining the matrix-colored fine particles by treating the surface, the temperature of the aqueous medium is in the range of 10 ° C. or higher and 30 ° C. or lower,
In the step of obtaining matrix-colored fine particles by treating the surface, the time for treating the surface of the toner is from 0.1 hours to 24 hours, and is a method for producing a toner.

According to one aspect of the present invention , a method for producing toner can be provided.

Next, an embodiment (embodiment) of the present invention will be described with reference to the drawings.

The toner according to the exemplary embodiment of the present invention is a toner obtained by mixing at least one kind of inorganic fine particles with colored fine particles including at least a binder resin, a colorant, a release agent, and a fluorine compound, and the fluorine compound is a fluorine-containing compound. It is preferably a quaternary ammonium salt compound, and further obtained by dispersing colored fine particles comprising a binder resin, a colorant and a release agent in an aqueous medium and treating the toner surface with a fluorinated quaternary ammonium salt compound. Colored fine particles, which are toners obtained by mixing one or more kinds of inorganic fine particles.

The inventors of the present invention have intensively studied and found that by adding a fluorine compound having excellent releasability into the toner composition, the fluidity of the toner base particles is improved, and the inorganic fine particles added externally due to stress over time are obtained. Even when embedded or released, the fluidity of the base colored particles themselves does not cause a dramatic deterioration in fluidity, so that stable fluidity can be maintained and high-quality image formation can be provided. In order to stabilize the fluidity, the fluidity can be maintained if there is a fluorine compound on the surface of the base colored particles. Therefore, the toner is dispersed in an aqueous medium, and the toner surface is treated with a fluorine-containing quaternary ammonium salt compound. The obtained toner is preferable.

  The fluorine-containing quaternary ammonium salt compound has the formula (1)

で表される化合物であることが好ましく、式（１）において、Ｘは、−ＳＯ_２−又は−ＣＯ−であり、Ｙは、Ｉ又はＢｒであり、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は、それぞれ独立に、水素原子、炭素数１以上１０以下の低級アルキル基、又はアリール基であり、ｒ及びｓは、それぞれ独立に、１以上２０以下の整数である。

In formula (1), X is —SO ₂ — or —CO—, Y is I or Br, and R ¹ , R ² , R ³ , and R ⁴ is each independently a hydrogen atom, a lower alkyl group having 1 to 10 carbon atoms or an aryl group, and r and s are each independently an integer of 1 to 20;

  The acid value of the toner composition is preferably 5-30. More preferably, the toner is 10 to 25.

The inventors of the present invention have made extensive studies and found that a toner having a stable chargeability and excellent fixability can be obtained by performing a surface treatment step on the toner having an acid value in the above range. Found that you can get.

  Specifically, if the acid value of the toner composition is less than 5, the fluorine compound cannot be satisfactorily applied to the surface, and the obtained toner is difficult to impart sufficient fluidity, and scumming is observed. It became to be. On the other hand, if the acid value of the toner composition exceeds 30, it is not desirable because it adversely affects environmental stability.

Generally, a toner has an acidic group in its constituent material. Examples of the acidic group include carboxylic acid, and this acidic group undergoes an exchange reaction shown in the following (a) with the fluorine-containing quaternary ammonium salt compound represented by the structural formula (1). It is thought that.
(A)

本発明の実施形態のトナーは、トナー組成物中に一定量の酸性基を有するため、上記塩交換反応により、構造式（１）で表される含フッ素４級アンモニウム塩化合物が、トナー粒子表面に吸着する。

Since the toner of the embodiment of the present invention has a certain amount of acidic groups in the toner composition, the fluorine-containing quaternary ammonium salt compound represented by the structural formula (1) is converted into the toner particle surface by the salt exchange reaction. Adsorb to.

  That is, since the fluorine-containing quaternary ammonium salt compound is stably present on the surface of the toner particles, the effect of fluidity control by the fluorine-containing quaternary ammonium salt compound can be surely obtained, and even in the stress caused by timely toner conveyance. By adsorbing, separation from the toner surface does not occur, and a stable fluidity effect can be obtained.

As one aspect of the toner of the embodiment of the present invention , a dispersant such as resin fine particles is added to an aqueous medium used for polymerizing a toner composition dissolved or dispersed in an organic solvent at the time of preparation. What was added as appropriate is included. This is added in order to improve the dispersibility in the aqueous medium, but after the toner particles are formed, the resin fine particles are mainly present on the surface of the toner particles. Since this toner is produced by using the resin fine particles having an acidic group, the acidic group is also involved in the reaction formula, and the fluorine-containing quaternary ammonium salt compound represented by the structural formula (1) is obtained. This contributes to stable existence on the surface of the toner particles.

Further, as another aspect of the toner of the embodiment of the present invention , a toner of a kneading and pulverizing method is also included. In this toner, for example, a polyester resin having a carboxylic acid group as an acidic group is used in the binder resin. The fluorine-containing quaternary ammonium salt compound represented by (1) is adsorbed on the toner particle surfaces.

  In addition, the fluorine-containing quaternary ammonium salt compound specifically corresponds to, for example, compounds represented by structural formulas 1) to 54).

（温度規定）
また、上述の逆極性の含フッ素４級アンモニウム塩化合物は、トナー粒子表面に作用させる時の温度が高いと、その一部がトナー内部に浸透してしまう。この浸透の量が多くなると、流動性に寄与できる表面存在量が低減してしまうため、含フッ素４級アンモニウム塩化合物の量が増えてしまい定着性などへの悪影響が懸念されてしまう。

(Temperature regulation)
In addition, the above-mentioned fluorine-containing quaternary ammonium salt compound having the opposite polarity is partially penetrated into the toner if the temperature at the time of acting on the toner particle surface is high. If the amount of penetration increases, the amount of the surface existing that can contribute to fluidity decreases, so the amount of the fluorine-containing quaternary ammonium salt compound increases, and there is a concern about adverse effects on fixing properties and the like.

In the embodiment of the present invention , when the temperature of the aqueous medium in the surface treatment step is set to a temperature range of 10 to 30 ° C., the fluorine-containing quaternary ammonium salt compound is prevented from penetrating into the toner particles. .

  Thus, the fluorine-containing quaternary ammonium salt compound can be reliably present on the surface of the toner particles, so that a toner capable of obtaining stable fluidity in a small amount can be obtained.

  When surface treatment is performed at a temperature lower than 10 ° C., adsorption itself is difficult to occur, and therefore, a fluorine-containing quaternary ammonium salt compound in an amount necessary for controlling fluidity cannot be adsorbed.

(Toner glass transition point)
Generally, the glass transition point of the binder resin of the toner is usually 40 to 70 ° C. However, if the temperature (Trt) of the aqueous medium used in the surface treatment process is higher than this, the specific volume of the toner particles changes suddenly. Thus, the fluorine-containing quaternary ammonium salt compound present in the water is likely to penetrate into the toner particles.

  Therefore, the relationship between the temperature (Tg) of the glass transition point of the toner and the temperature (Trt) of the aqueous medium at the time of the surface treatment is such that Tg> Trt, so that the fluorine-containing quaternary ammonium salt The penetration of the compound into the toner can be suppressed.

This confirms the validity of the temperature range of the aqueous medium in the surface treatment process defined in the embodiment of the present invention.

The toner used in the embodiment of the present invention is preferably as low as possible from the viewpoint of low-temperature fixability, and it is preferable to use a toner having a glass transition point in the range of 40 to 60 ° C. (If it is lower than this, a problem of storability appears, so 40 degrees or more is preferable)
(Amount of fluorine compound / fluorine-containing quaternary ammonium salt compound)
In order to add fluidity as a toner, it is preferable that the fluorine compound is added from the viewpoint of fluidity in order to add the fluorine compound. However, it is possible to increase the amount of the fluorine compound to be added. However, in this case, the exudation of the wax added to the toner as a release agent is inhibited, and the effect is reduced. That is, from the adverse effect on the hot offset property, and from the trouble due to the release / release from the toner, in the case of normal addition, it is 0.1 part by weight with respect to 100 parts by weight of the toner base particles, and the addition amount is the toner. The amount is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the base particles. If it is 3 parts by weight or more, the fluidity is effective, but the fixability, particularly the low-temperature fixing, is greatly affected, causing problems.

The toner according to the exemplary embodiment of the present invention is effective for this problem since the effect can be obtained efficiently without increasing the amount of the fluorinated quaternary ammonium salt compound added in an aqueous medium. When the surface treatment is carried out with a fluorine-containing quaternary ammonium salt compound, the surface layer can be uniformly and efficiently applied, so that fluidity can be efficiently imparted even in a small amount.

As a result of intensive studies by the inventors of the present invention, the amount of the fluorine-containing quaternary ammonium salt compound added is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the toner base particles. The amount is preferably 0.03 to 0.5 parts by weight with respect to 100 parts by weight of the toner base particles. The reaction time is preferably relatively short from the viewpoint of penetration into the interior, and is preferably 0.1 to 24 hours. Moreover, there exists a possibility that favorable fluidity | liquidity may not be acquired as it is 0.01 or less.

The toner according to the exemplary embodiment of the present invention exhibits stable fluidity and excellent fixing characteristics by adding the above-described fluorine-containing quaternary ammonium salt compound at the processing temperature, processing time, and addition amount within the above-described ranges. Can be.

  In a conventional toner obtained by treating the surface with a charge treating agent, the charge treating agent is easily detached, and the developing sleeve and the photosensitive member are easily contaminated.

However, in the toner according to the embodiment of the present invention, the fluorine-containing quaternary ammonium salt compound is subjected to a salt exchange reaction represented by the formula (a) by subjecting the toner composition having an acid value in the above range to surface treatment. Since it is adsorbed on the surface, desorption by the charging agent alone is suppressed. Thereby, the occurrence of filming is suppressed and the durability of the image forming apparatus main body can be improved.

  Furthermore, the influence of the surfactant used when forming the base particles on the chargeability can be more reliably suppressed, and a toner having good chargeability can be provided.

The toner for image formation according to the embodiment of the present invention is preferably a toner having a small particle size and a nearly spherical shape, in order to output a high-quality and high-definition image. As a method for producing such a toner, there are a suspension polymerization method, an emulsion polymerization method, a polymer suspension method and the like in which an oil phase is emulsified, suspended or aggregated in an aqueous medium to form toner base particles. Hereinafter, these toner production methods and materials, additives, and the like used in the production methods will be described.

(Suspension polymerization method)
A colorant, a release agent and the like are dispersed in an oil-soluble polymerization initiator and a polymerizable monomer, and then emulsified and dispersed by an emulsification method described later in an aqueous medium containing a surfactant and other solid dispersants. Thereafter, after the polymerization reaction to form particles, a wet process for attaching the inorganic fine particles A to the toner particle surfaces in the embodiment of the present invention may be performed. At that time, it is preferable to treat the toner particles from which excess surfactant and the like are removed by washing.

  Polymerizable monomers such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, acrylamide, methacrylamide, diacetone Functional groups can be introduced on the surface of toner particles by using a part of acrylate or methacrylate such as acrylamide or these methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate and other amino groups. .

  Further, by selecting a dispersant having an acid group or a basic group as a dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

(Emulsion polymerization aggregation method)
A water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by an ordinary emulsion polymerization technique. Separately, a dispersion in which a colorant, a release agent and the like are dispersed in an aqueous medium is prepared, and after mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. Thereafter, a wet treatment of inorganic fine particles A described later may be performed. A functional group can be introduced on the surface of the toner particles by using a latex similar to the monomer that can be used in the suspension polymerization method.

(Polymer suspension method)
As an aqueous medium used in the embodiment of the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  In the oil phase of the toner composition, a colorant such as resin, prepolymer and pigment, a release agent, a charge control agent and the like are dissolved or dispersed in a volatile solvent.

  An oil phase composed of a toner composition is dispersed in an aqueous medium in the presence of a surfactant, a solid dispersant and the like, and a prepolymer is reacted to form particles. Thereafter, a wet treatment of inorganic fine particles A described later may be performed.

  In order to introduce a functional group into the toner particles, a copolymer with a monomer having a functional group used in the suspension polymerization method, or a functional group of an acid group as an acid monomer in the case of a polyester resin is used. It can be obtained by using one having three or more or esterifying the terminal hydroxyl group of the obtained polyester resin with a compound having a plurality of acid groups. Further, as a dispersion stabilizer in an aqueous medium, which will be described later, an acid group-containing surfactant, polar polymer, organic or inorganic resin fine particles can be used, and an acid group can be introduced by remaining on the toner particle surface. Examples of the acid group include a carboxyl group, a sulfone group, a sulfonic acid group, and a phosphoric acid group.

  In any of these toner production methods, the toner particles can be subjected to a surface treatment.

  This step is preferably performed after the toner particles are formed and the used surfactant and the like are removed by washing. Excess surfactant present in water is removed by solid-liquid separation operations such as filtration and centrifugation, and the resulting slurry is redispersed in an aqueous medium. Here, a fluorine-containing quaternary ammonium salt compound aqueous solution having a polarity opposite to that of the previously used surfactant is gradually added with stirring. The reverse polarity fluorine-containing quaternary ammonium salt compound is preferably used in an amount of 0.03 to 2 parts by weight based on the solid content of the toner particles. Moreover, it is preferable to perform the time of this surface treatment process in the range of 0.1 to 24 hours.

The toner of the embodiment of the present invention more preferably dissolves or dissolves at least a polymer having a site capable of reacting with a compound having an active hydrogen group, a polyester, a colorant, and a release agent in an organic solvent. It is a toner obtained by subjecting a dispersed toner material liquid to crosslinking and / or elongation reaction in an aqueous medium. Hereinafter, the constituent material and the manufacturing method of the toner will be described.

(Modified polyester)
The toner according to the embodiment of the present invention contains the modified polyester (i) as a binder resin. The modified polyester (i) refers to a state in which a bonding group other than an ester bond is present in the polyester resin, or resin components having different configurations are bonded to the polyester resin through a covalent bond or an ionic bond. Specifically, the polyester terminal is modified by introducing a functional group such as a carboxylic acid group or an isocyanate group that reacts with a hydroxyl group into the polyester terminal and further reacting with an active hydrogen-containing compound.

  Examples of the modified polyester (i) include urea-modified polyester obtained by a reaction between a polyester prepolymer (A) having an isocyanate group and amines (B). As the polyester prepolymer (A) having an isocyanate group, a polyester having a polycondensate of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC) and having an active hydrogen group is further added to a polyvalent isocyanate compound (PIC). And those reacted with. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

  The urea-modified polyester is produced as follows.

  Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO) and trihydric or higher polyhydric alcohol (TO). (DIO) alone or a mixture of (DIO) and a small amount of (TO) preferable. Examples of the dihydric alcohol (DIO) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide bisphenol (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyhydric alcohol (TO) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC). (DIC) alone and (DIC) with a small amount of (TC) Mixtures are preferred. Divalent carboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polyhydric carboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

  The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) ); Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanates; Those blocked with caprolactam or the like; and combinations of two or more of these.

  The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.

  The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. . If it is less than 0.5 wt%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40 wt%, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  Next, as amines (B) to be reacted with the polyester prepolymer (A), a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), an amino mercaptan (B4) ), Amino acid (B5), and amino acid block of B1 to B5 (B6).

  Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diamine cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like. Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of B1 to B5 blocked amino groups (B6) include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). Is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.

  The urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

The modified polyester (i) used in the embodiment of the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. The peak molecular weight at this time is preferably 1000 to 10000. When the molecular weight is less than 1000, the elongation reaction hardly occurs, the elasticity of the toner is small, and as a result, the resistance to hot offset deteriorates. On the other hand, when it exceeds 10,000, the problem in production becomes high in the deterioration of fixability, particle formation and pulverization. The number average molecular weight of the modified polyester (i) is not particularly limited when the unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. (I) When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.

  In the crosslinking and / or extension reaction between the polyester prepolymer (A) and the amines (B) to obtain the modified polyester (i), a reaction terminator is used as necessary to adjust the molecular weight of the resulting urea-modified polyester. be able to. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

(Unmodified polyester)
In the embodiment of the present invention, not only the modified polyester (i) is used alone but also the unmodified polyester (ii) can be contained as a binder resin component together with the (i). By using (ii) in combination, the low-temperature fixability and the gloss when used in a full-color device are improved, which is preferable to the single use. Examples of (ii) include polycondensates of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC), which are the same as the polyester component (i), and preferred ones are also the same as (i). . Further, (ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, for example, may be modified with a urethane bond. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, the polyester component (i) and (ii) preferably have similar compositions. In the case of containing (ii), the weight ratio of (i) to (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. If the weight ratio of (i) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (ii) is 1000-10000 normally, Preferably it is 2000-8000, More preferably, it is 2000-5000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. As for the acid value of (ii), 1-5 are preferable, More preferably, it is 2-4. Since a high acid value wax is used as the wax, the low acid value binder leads to electrification and high volume resistance, so that it is easy to match the toner used for the two-component developer.

The glass transition point (Tg) of the binder resin is usually 35 to 70 ° C, preferably 55 to 65 ° C. If it is less than 35 ° C., the heat resistant storage stability of the toner is deteriorated, and if it exceeds 70 ° C., the low-temperature fixability is insufficient. Since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the toner according to the embodiment of the present invention has excellent heat-resistant storage stability even when the glass transition point is low as compared with the known polyester-based toner. Show a trend.

(Coloring agent)
As the colorant, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher , Yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sayred, Parachlor Ortonito Aniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thio Indigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Lid Russian nin green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant can also be used as a master batch combined with a resin. As a binder resin to be kneaded with the production of the master batch or the master batch, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene or the like, or a copolymer of these and a vinyl compound, Polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

(Charge control agent)
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.

(Release agent)
As a release agent, a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface. The effect on high temperature offset is exhibited without applying a release agent such as oil. Examples of such a wax component include the following. Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, and paraffin, microcrystalline, And petroleum waxes such as petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones, and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. .

  The charge control agent and the release agent can be melt-kneaded together with the master batch and the binder resin, and of course, they may be added when dissolved and dispersed in the organic solvent.

(External additive)
As the external additive, inorganic fine particles such as a metal oxide, a metal carbide, a metal nitride, and a metal carbonate can be used. Specifically, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide Cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like.

  Furthermore, organic fine particles can be used as the external additive. Specifically, polymer fine particles, for example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, methacrylic acid ester or acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine, nylon, You may use the polymer particle by a thermosetting resin.

Further, the external additive used in the toner according to the exemplary embodiment of the present invention can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents that may contain alkyl groups, fluorinated alkyl groups, titanate coupling agents, coupling agents such as aluminum coupling agents, silicone oils, higher fatty acids, fluorine compounds and the like are preferable surface treatment agents. Can be mentioned.

  In particular, a silane coupling agent, which is an example of a coupling agent, is used for improving the degree of hydrophobicity and fluidity. Specifically, as the silane coupling agent, chlorosilane, alkoxysilane, silazane, special silylating agent and the like can be used, and alkoxysilane is more preferable. Examples of the alkoxysilane include vinyltrimethoxysilane, propyltrimethoxysilane, i-butyltrimethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, and n-dodecyltrimethoxy. A silane etc. can be mentioned.

  As the silicone oil, polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane or the like can be used, and fluorine-containing siloxane or the like may be used.

  The fluorine compound is preferably an organosilicon compound having a fluorine atom, such as 3,3,4,4,5,5,6,6,6-nonafluorohexyltrichlorosilane, 3,3,3-trifluoropropyl. Trimethoxysilane, methyl-3,3,3-trifluoropropyldichlorosilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,4,4,5,5,6,6,6- Nonafluorohexylmethyldichlorosilane and the like can be mentioned.

  Further, examples of higher fatty acids include stearic acid, oleic acid, palmitic acid, and linoleic acid, and metal salts of these higher fatty acids may be used. Specific examples include zinc stearate, aluminum stearate, copper stearate, magnesium stearate, calcium stearate, zinc oleate, manganese oleate, zinc palmitate, zinc linoleate, and calcium linoleate.

In the toner of the embodiment of the present invention, the external additive uses dry mixing in which inorganic / organic fine particles such as hydrophobic silica fine powder are externally added in a mixer together with a mixing medium such as glass beads. For mixing external additives, a general mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. The external additive is appropriately added at the beginning or in the middle. Examples of the mixer include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, and a Henschel mixer.

  Further, wet mixing is used in which the toner is externally added in a water-based and / or alcohol-based solvent. In this wet mixing, an external additive is added to the toner dispersed in an aqueous solvent and adhered to the toner surface. Further, when this external additive has been subjected to a hydrophobic treatment, it may be dispersed after a small amount of alcohol or the like is used in combination to lower the interfacial tension to facilitate wetting. Thereafter, the solvent can be removed by heating and fixed to prevent desorption. As a result, the external additive can be uniformly dispersed on the toner surface. Further, when the toner and the external additive are dispersed in the aqueous solvent, the external additive can be uniformly dispersed on the toner surface by adding the surfactant. Further, it is preferable to use an external additive or a surfactant having a polarity opposite to that of the toner.

  Next, a toner manufacturing method will be described. Here, although a preferable manufacturing method is shown, it is not limited to this.

(Toner production method)
1) A toner material solution is prepared by dispersing a colorant, unmodified polyester, a polyester prepolymer having an isocyanate group, and a release agent in an organic solvent.

  The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of an organic solvent is 0-300 weight part normally with respect to 100 weight part of polyester prepolymers, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part.

  2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.

  The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.

  The amount of the aqueous medium used relative to 100 parts by weight of the toner material liquid is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner material liquid is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical.

  Further, in order to improve the dispersion in the aqueous medium, a dispersant such as a surfactant and resin fine particles is appropriately added.

  As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, fatty acid amide derivatives, polyhydric alcohols Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like. Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount.

  As the resin fine particles, any resin can be used as long as it can form an aqueous dispersion, and it may be a thermoplastic resin or a thermosetting resin. Examples thereof include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin, two or more of the above resins may be used in combination.

  Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained. For example, vinyl resins are polymers obtained by homopolymerization or copolymerization of vinyl monomers, such as styrene- (meth) acrylic acid ester copolymers, styrene-butadiene copolymers, (meth) acrylic acid-acrylic acid esters. Examples thereof include resins such as a polymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, and a styrene- (meth) acrylic acid copolymer. The average particle size of the resin fine particles is 5 to 200 nm, preferably 20 to 300 nm. In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.

  As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxy Propyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl Nitrogen compounds such as imidazole and ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, poly Xoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

  3) At the same time as the preparation of the emulsion, the amines (B) are added to cause a reaction with the polyester prepolymer (A) having an isocyanate group.

  This reaction involves molecular chain crosslinking and / or elongation. The reaction time is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

  4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.

  In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent base is removed to produce spindle-shaped toner base particles. . Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.

  5) The obtained base particles are redispersed in an aqueous medium in the range of 10 to 30 ° C. Thereto, a charge control agent is gradually added under stirring, and then a fluorine-containing quaternary ammonium salt compound having a polarity opposite to that of the previously used surfactant is gradually added. The reaction time is preferably 0.1 to 24 hours.

  The amount of the reverse polarity surfactant added here is determined by the toner production method, and is not uniquely limited, but is preferably 0.1 to 100 parts by weight of the binder resin. It is used in the range of 10 parts by weight. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is lowered, and the image density is lowered. Invite.

  6) Toner is obtained by externally adding inorganic fine particles such as silica fine particles and titanium oxide fine particles to the toner base particles obtained above.

  The external addition of the inorganic fine particles is performed by a known method using a mixer or the like.

  Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained. Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between the spherical shape and the rugby ball shape can be controlled, and the surface morphology is also controlled between the smooth shape and the umeboshi shape. be able to.

Furthermore, the toner according to the embodiment of the present invention has a volume average particle size in the range of 3.0 to 8.0 μm. By using this toner, the toner can be developed densely with respect to the latent image, and a high-quality image can be obtained. If the volume average particle size is less than 3.0 μm, an appropriate image density cannot be obtained unless a large amount of toner is developed, and thus the burden on the development process increases, making it practically difficult to use in an image forming apparatus. . On the other hand, if the volume average particle diameter exceeds 8.0 μm, the reproducibility of fine lines is lowered, so that a high-quality image cannot be obtained. In particular, in a full-color image, the graininess becomes remarkable, the color halftone part becomes rough visually, and it is difficult to obtain a high-quality color image.

In the toner according to the exemplary embodiment of the present invention, the degree of dispersion, which is the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn), is in the range of 1.00 to 1.40. . By reducing the degree of dispersion and narrowing the particle size distribution, the toner charge amount distribution becomes uniform, a high-quality image with little background fogging can be obtained, and during electrostatic transfer from a photoreceptor. The transfer rate can be increased by allowing the toner on the photoreceptor to receive a uniform electric field.

Furthermore, the toner according to the embodiment of the present invention has an average circularity of 0.94 or more. Average circularity SR = (peripheral length of circle having the same area as the projected particle area / perimeter length of projected particle image) × 100%. The closer the toner is to a true sphere, the closer to 100%. Toner having a high degree of circularity is easily affected by the developing electric field, and is developed faithfully along the electric field of the electrostatic latent image. When reproducing minute latent image dots, fine line reproducibility is enhanced by dense and uniform development. In addition, toner with a high degree of circularity has a smooth surface and appropriate fluidity, so it is easily affected by the electric field, and is easily transferred faithfully along the electric field, resulting in a high transfer rate and a high-quality image. Can be obtained. However, if the average circularity of the toner is less than 0.94, faithful development and transfer with a high transfer rate cannot be performed. Therefore, the average circularity is preferably 0.94 or more.

  This degree of circularity is thermally or mechanically spheroidized with toner produced by dry grinding. Thermally, for example, the spheronization treatment can be performed by spraying toner base particles together with a hot air stream on an atomizer or the like. In addition, a spheroidizing treatment can be performed by mechanically charging the mixture into a mixer such as a ball mill together with a mixed medium such as glass having a low specific gravity and stirring. However, in the thermal spheronization process, toner base particles that are aggregated and have a large particle size or fine particles are generated in the mechanical spheronization process, and thus a second classification step is required. In addition, in a toner manufactured in an aqueous solvent, the shape can be controlled by applying strong stirring in the process of removing the solvent.

In addition, the toner according to the exemplary embodiment of the present invention has a substantially spherical appearance, and the ratio of the major axis to the minor axis (r2 / r1) is in the range of 0.5 to 1.0. (R3 / r2) is in the range of 0.7 to 1.0, and the relationship of major axis r1 ≧ minor axis r2 ≧ thickness r3 is satisfied. The toner has a substantially spherical shape and can be represented by the following shape rule. When a substantially spherical toner is defined by a major axis r1, a minor axis r2, and a thickness r3 (where r1 ≧ r2 ≧ r3), the toner of the embodiment of the present invention has a major axis and a minor axis. The ratio (r2 / r1) (see (b)) is 0.5 to 1.0, and the ratio of thickness to minor axis (r3 / r2) (see (c)) is in the range of 0.7 to 1.0. It is preferable that it exists in. If the ratio of the major axis to the minor axis (r2 / r1) is less than 0.5, the separation from the true spherical shape results in poor fine line reproducibility and transfer rate, and high-quality image quality cannot be obtained. On the other hand, if the ratio of thickness to minor axis (r3 / r2) is less than 0.7, the shape is close to a flat shape, and a high transfer rate like a spherical toner cannot be obtained. In particular, when the ratio of the thickness to the minor axis (r3 / r2) is 1.0, the rotating body has a major axis as a rotation axis, and the fluidity of the toner can be improved.

  Note that r1, r2, and r3 were measured with a scanning electron microscope (SEM) while changing the angle of field of view and taking pictures.

The toner produced as described above may be mixed with a magnetic carrier when used in a two-component developer. As the magnetic carrier, a divalent metal such as iron, magnetite, Mn, Zn, or Cu is used. a ferrite containing, weight average particle diameter _D 4 20 to 100 [mu] m is preferred. If the average particle size is less than 20 μm, carrier adhesion is likely to occur on the photoreceptor 1 during development, and if it exceeds 100 μm, the miscibility with the toner is low and the charge amount of the toner is insufficient, resulting in poor charging during continuous use. Cheap. In addition, Cu ferrite containing Zn is preferable because of high saturation magnetization, but can be appropriately selected according to the process of the image forming apparatus. The resin for coating the magnetic carrier is not particularly limited, and examples thereof include silicone resin, styrene-acrylic resin, fluorine-containing resin, and olefin resin. In the manufacturing method, the coating resin may be dissolved in a solvent, sprayed into a fluidized bed and coated on the core, or the resin particles are electrostatically attached to the core particles and then thermally melted for coating. It may be a thing. The resin to be coated has a thickness of 0.05 to 10 μm, preferably 0.3 to 4 μm.

It can also be used as a one-component magnetic toner that does not use a magnetic carrier or as a non-magnetic toner.
1 and 2 are schematic views of a toner transfer device provided in an electrophotographic image forming apparatus according to an embodiment of the present invention.

In FIG. 1 and FIG. 2, the toner container 71 and the toner transport destination 74 are connected by a toner transport pipe 72, and the toner is transported from the toner container 71 to the toner transport destination 74 by pressure using a powder pump 73. In the case of FIG. 1, the discharge type powder pump 73 is used, the powder pump 73 is attached near the toner containing portion 71, and the toner is transferred by applying pressure to the toner transport pipe 72. In FIG. 2, a suction type powder pump 73 ′ is used, the powder pump 73 ′ is installed near the toner transfer destination 74, and the toner is transferred by applying suction pressure to the toner transport pipe 72. In the embodiment of the present invention , toner transfer is possible using either a discharge type or suction type powder pump.

The toner container 71 may be detachable by devising a joint portion with the toner transport pipe 72 for toner transport. In the electrophotographic image forming apparatus, the toner container 71 is used as a toner cartridge so that the toner cartridge 71 can be removed, so that new toner can be replenished easily and conveniently. Of course, the toner container 71 may be fixed and replenished with new toner. In the embodiment of the present invention , it is possible to use not only new toner but also cleaning toner generated on the photoreceptor of the electrophotographic image forming apparatus in the toner container 71.
The position where the toner transport pipe 72 is attached to the toner storage section 71 is effective at the bottom surface portion of the toner storage section 71 from the viewpoint that the toner easily enters the toner transport pipe 72 by gravity. In addition, the lower portion 75 of the toner containing portion 71 is tapered toward the attachment position of the toner transport pipe 72, or has a conical shape or a polygonal pyramid shape, and is tapered toward the attachment position of the toner transport pipe 72. By doing so, the toner is less likely to remain in the toner container 71.
Further, when air is introduced into the toner container 71 or the toner is stirred by adding a stirring blade to the toner container 71, the toner is fluidized and easily enters the toner transport pipe 72. In particular, when air is introduced, if the air is introduced from the toner transport pipe 72 near the toner accommodating portion 71 as in the air insertion port 76 of FIGS. 1 and 2, the toner becomes stable and easily enters the toner transport pipe 72.
The toner transport pipe 72 for transferring the toner can be made of an elastic material or an inelastic material. If a material such as elastic rubber is used for the toner transport tube 72, the electrophotographic image forming apparatus can be freely circulated like a rubber tube, and can be easily assembled in the electrophotographic image forming apparatus. Become.

  The toner transport pipe 72 preferably has an internal cross-sectional area of 0.05 to 1.00 cm2. More preferably, the internal cross-sectional area is 0.1 to 0.5 cm2. When the toner transport pipe 72 is too thick, the volume in the toner transport pipe 72 is large with respect to the air or toner amount flowing by the powder pump, and the pressure in the toner transport pipe 72 is lowered, so that the toner transport is performed well. I can't. If the tube is too thin, the friction between the toner and the inner wall of the toner transport tube 72 becomes large with respect to the toner amount, which also prevents the toner from being transferred successfully.

  In order to reduce the friction between the inner wall of the toner transport pipe 72 and the toner, it is preferable that the inner wall of the toner transport pipe 72 has a high smoothness and a low frictional resistance. The cross section of the toner transport pipe 72 may naturally have any shape, but a circular shape is preferable in which the area of the inner wall surface is small and the toner transfer resistance is small with respect to the toner amount. The length of the toner transport pipe 72 is preferably 2 m or less. More preferably, it is 1 m or less. In the figure, reference numeral 77 denotes an air filter.

  Next, the powder pumps 73 and 73 ′ shown in FIGS. 1 and 2 will be described.

  The powder pump 73 is a discharge pump, and the powder pump 73 ′ is a suction pump. The compression pressure can be used as long as it is a pump that generates a suction pressure, and it can be used in a piston type pump with a valve although it is not used in powder.

In an embodiment of the present invention , a female screw type stator having a double-pitch spiral groove therein, a powder pump using a screw pump having a male screw type rotor rotatably inserted in the stator, commonly called If a so-called Monopump is used, the structure is simple and small, and no load is applied to the toner to be transported, so there is no need for toner deterioration.

A specific example of a pump used in an embodiment of the present invention will be described with reference to the accompanying drawings. FIG. 3 is a perspective view showing an internal configuration of the discharge-type screw pump, and FIG. 4 is an overall configuration diagram of a toner transfer device using the discharge-type screw pump.

  3 and 4, a screw pump 1 includes a female screw type stator 2 having a double-pitch spiral groove made of an elastic member such as rubber, and is inserted into the stator 2 so as to be freely rotatable. And an externally threaded rotor 3 made of the like. The periphery of the stator 2 is covered with a holder 4 fixedly supported by a side plate 11 shown in FIG. 4, and a gap 5 is provided between the inner peripheral surface of the holder 4 and the outer peripheral surface of the stator 2. Yes.

  This gap communicates with a toner discharge port 6 provided on the downstream side of the rotor 3, and the holder 4 is provided with an air supply port 7 that leads to the gap 5. An air supply tube 33 from the air pump 30 is fitted into the air supply port 7, and air from the air pump 30 is supplied from the air supply port 7 through the gap 5 to the toner discharge port 6.

  The rotor 3 is connected to the shaft of the transfer screw 10 on the upstream side by a spring pin 12 or the like, and is driven to rotate when the transfer screw 10 is rotated by a driving device (not shown). As the rotor 3 rotates, a discharge pressure is generated at the discharge port, and the toner sent by the transfer screw 10 is transferred by the discharge pressure. At this time, the air is supplied from the air pump 30 through the air supply port 7 through the gap 5 to the toner discharge port 6, thereby fluidizing the toner and smoothly and reliably supplying the toner with the discharge pressure of the screw pump 1. Exhale in the direction.

  One end of the transfer tube 13, which is a toner transport pipe fitted to the toner receiving portion 81 of the developing device 80, is connected to the toner discharge port 6 by fitting. As the transfer tube 13, for example, a flexible tube having an inner diameter of 3 to 7 mm and made of a rubber material having excellent toner resistance (for example, polyurethane, nitrile, EPDM, silicon, etc.) is extremely effective. Yes, flexible tubes can be easily routed in any direction, up, down, left, or right.

  The toner storage container 20 is configured as a back-in-box type having an outer box 21 as a protective case and a toner bag 22 as a flexible and deformable bag-like body detachably accommodated in the outer box 21. ing. The outer box 21 is made of a material such as rigid paper, cardboard, or resin, and has an internal space in which the toner bag 22 can be accommodated with almost no gap. Even if the toner bag 22 containing the toner is flexible, the toner storage container 20 is not only protected by being stored in the outer box 21, but also handling is improved and the container can be easily handled and stored. The advantage is that it is easy to organize time.

  In addition, the bag portion of the toner bag 22 is made of origami by making a flexible sheet material (thickness of about 80 to 125 μm) such as a polyester film or a polyethylene film into a single layer or a multi-layer structure. It is made in the shape of a sealed bag-like container. The toner bag 22 is provided with a toner discharge hole 24 in the lower center thereof, and a cap member 23 made of a resin such as polyethylene or nylon is fixed.

  The toner discharge hole 24 of the base member 23 is provided with a single-layer or multi-layer seal 25 having a role of a self-closing valve, and the seal 25 is made of an elastic body made of a non-breathing foam sponge or the like. The toner bag 22 is formed in a shape that tapers toward the toner discharge hole 24 so that the toner hardly remains.

  The set unit 50 in which the toner storage container 20 is mounted is provided with a container holder 51 and a nozzle 52 that is inserted into the seal 25. The nozzle 52 is linear and is formed in a cylindrical shape, and a receiving port 54 for receiving toner is provided following a pointed portion 53 provided at the top. The inside of the nozzle 52 has a single tube structure in which a toner passage 55 following the receiving port 54 is provided, and a case 14 for temporarily storing toner to be replenished is provided at the lower end of the toner passage 55. The side plate 11 constitutes a part of the case 14. A filter 15 for preventing an increase in pressure in the case is provided at the upper part of the case 14, and the transfer screw 10 is disposed in the case 14.

  Air is supplied to the toner storage container 20 from the air pump 30 through the air tube 31 and the nozzle 52. The air supplied into the toner container 20 agitates and fluidizes the toner in the container, prevents the toner cross-linking phenomenon, and realizes a reduction in the final toner remaining amount in the container. At this time, as shown in FIG. 5, a breathable filter 26 can be provided on the upper part of the toner storage container 20, and the toner storage container 20 is reversed by the air supplied from the air pump 30 by the breathable filter 26. It serves to depressurize the rise of the inside to a positive pressure.

  In addition, a switching valve 32 is provided in front of the supply destination so that one air pump 30 can supply air to both the toner container 20 and the screw pump 1, and the supply destination is controlled by switching the valve. is doing.

  The toner transfer device configured as described above is used as a toner replenishing device that replenishes the developing device 80 with toner.

  FIG. 6 is a perspective view showing the internal configuration of the suction-type screw pump.

  The suction type screw pump 1 ′ shown in FIG. 6 is provided with a shaft 10 ′ instead of the transfer screw 10 shown in FIGS. 3 and 4, and the discharge of FIG. 3 except that the holder 4 does not have an air supply port 7. Same as type. If the same rotor 3 and stator 2 as the discharge type screw pump 1 are used, a suction pressure is generated at the toner suction port 6 by rotating the shaft 10 'in the opposite direction, and the suction is performed from here. The toner is discharged in the direction of the shaft 10 '.

  In addition, when the rotation direction is the same direction, the one in which the winding direction of the rotor 3 and the stator 2 is reversed is used.

  In the uniaxial eccentric screw pump described above, the stator 2 is made of a rubber material, and the rotor 2 made of metal or resin rotates while sliding in the stator 2, so that the inner diameter of the stator 2 is worn over time. Gradually expands, and the discharge pressure or suction pressure decreases.

FIG. 7 is a cross-sectional view of the rotor 3 fitted in the stator 2. The biting amounts of the rotor 3 and the stator 2 are three types of D1, D2, and D3 for convenience, and D1 is the biting amount of the cross section of the rotor 3 and the minimum inner diameter of the stator 2. D3 is the amount of biting of the cross section of the rotor 3 and the end portion R of the stator 2. D2 is the amount of biting between the outer diameter of the spiral of the rotor 3 and the inner diameter of the stator 2. From the experimental results of the inventors of the present invention , it has been found that the above three biting amounts D1, D2, D3 are important in the discharge pressure and suction pressure of the screw pump 1 and screw pump 1 ′.

  FIG. 8 shows an overall configuration diagram of a toner transfer device using the suction-type screw pump of FIG. When a suction-type screw pump is used, the pump is disposed on the toner receiving portion 81 side of the developing device 80, and the toner transfer device shown in FIG. Since the general configuration is the same, detailed description is omitted.

Further illustrate the embodiments of the present invention by the following examples, but the present invention is not limited thereto. In the following, “part” means part by weight, and “%” means weight%.

Hereinafter, a specific method for producing the toner according to the exemplary embodiment of the present invention will be described.

<Synthesis of resin fine particle emulsion>
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 80 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate, 12 parts of butyl thioglycolate and 1 part of ammonium persulfate were added and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion was obtained. This is designated as [fine particle dispersion 1]. The volume average particle size of the [fine particle dispersion 1] measured by a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corp.) was 120 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 42 ° C., and the weight average molecular weight was 30,000.

<Preparation of aqueous phase>
990 parts of water, 65 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (ELEMINOL MON-7 manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred to give a milky white color Obtained liquid. This is designated as [Aqueous Phase 1].

<Synthesis of non-reactive resin>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 8 hours at normal pressure, and further react for 5 hours at 10-15 mmHg reduced pressure, then add 44 parts of trimellitic anhydride to the reaction vessel at 180 ° C at normal pressure. It reacted for 2 hours and obtained polyester of non-reactive resin [A]. The non-reactive resin [A] had a number average molecular weight of 2500, a weight average molecular weight of 6700, Tg of 43 ° C., and an acid value of 24.

  In the method for producing the non-reactive resin [A], the amount of trimellitic anhydride added is changed, and the acid value is adjusted to the following value to adjust the non-reactive resins [B] to [D]. Got.

＜中間体ポリエステルの合成＞
冷却管、撹拌機および窒索導入管の付いた反応容器中に、ビスフェノールＡエチレンオキサイド２モル付加物６８２部、ビスフェノールＡプロピレンオキサイド２モル付加物８１部、テレフタル酸２８３部、無水トリメリット酸２２部およびジブチルチンオキサイド２部を入れ、常圧で２３０℃で８時間反応し、さらに１０〜１５ｍｍＨｇの減圧で５時間反応し［中間体ポリエステル１］を得た。［中間体ポリエステル１］は、数平均分子量２１００、重量平均分子量９５００、Ｔｇ５５℃、酸価０．５、水酸基価５１であった。

<Synthesis of intermediate polyester>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.

-Synthesis of a modified polyester resin (hereinafter referred to as "prepolymer 1") capable of reacting with a compound having at least an active hydrogen group-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 410 parts of the above [intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate were added and reacted at 100 ° C. for 5 hours. ] Was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

<Synthesis of ketimine>
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

<Synthesis of master batch>
1200 parts of water, 40 parts of carbon black (manufactured by Cabot, Regal 400R), 60 parts of the non-reactive resin [A] and 30 parts of water are further added and mixed with a Henschel mixer (manufactured by Mitsui Mining). Was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

(Toner preparation example 1)
<Creation of oil phase>
In a container equipped with a stir bar and a thermometer, 400 parts of the non-reactive resin [A], 110 parts of carnauba wax, and 947 parts of ethyl acetate are charged, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. After that, it was cooled to 30 ° C. at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].

  [Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed is 1 kg / hr, a disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. The wax was dispersed under the conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of the non-reactive resin [A] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1]. The solid content concentration of [Pigment / Wax Dispersion 1] (130 ° C., 30 minutes) was 50%.

<Emulsification>
[Pigment / Wax Dispersion 1] 648 parts, [Prepolymer 1] 154 parts, [Ketimine Compound 1] 8.5 parts in a container, TK homomixer (manufactured by Tokushu Kika) 1 After mixing for 1 minute, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at a rotation speed of 10,000 rpm for 20 minutes to obtain [Emulsion Slurry 1].

  That is, it is dispersed in an aqueous medium containing resin fine particles and an elongation reaction is performed.

<Desolvent>
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

<Washing and drying>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.

  (2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.

  (3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.

  (4): 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered twice to obtain a cake. . This is referred to as [mother fine particles A]. The acid value of [base fine particles A] was 22.5.

<Surface treatment>
(1): Add 100 parts of ion-exchanged water to the filter cake of [mother fine particles A], and mix with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes).

  (2): N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium, iodide (product name Aftergent 310 (manufactured by Neos)) is used as a 1% aqueous methanol solution. .

  (3): The temperature of the slurry of (1) was adjusted to 2 ° C. while maintaining the temperature, and while stirring, (2) was added to N, N, N-trimethyl- [3- (4- Perfluorononenyloxybenzamido) propyl] ammonium and iodide are added so that the methanol solution is 0.1 wt%, and the mixture is stirred at 25 ° C. for 60 minutes.

  (4): The product was separated by filtration, and the resulting cake was dried under reduced pressure at 40 ° C. for 24 hours to obtain toner base particles.

<External additive treatment>
To 100 parts of the toner base particles obtained above, 1.0 part of hydrophobic silica R-972 (manufactured by Nippon Aerosil Co., Ltd.) was mixed in a Henschel mixer to obtain toner [A].

(Toner preparation example 2)
Toner B was obtained in the same manner as in Toner Preparation Example 1 except that nonreactive resin [A] was changed to nonreactive resin [B].

(Toner preparation example 3)
Toner C was obtained in the same manner as in Toner Preparation Example 1 except that nonreactive resin [A] was changed to nonreactive resin [C].

(Toner preparation example 4)
Toner D was obtained in the same manner as in Toner Preparation Example 1 except that nonreactive resin [A] was changed to nonreactive resin [D].

(Toner preparation example 5)
In the surface treatment of Toner Preparation Example 1, N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium and iodide were adjusted to 2.0 wt% with respect to 100 parts by weight of the mother fine particles. A toner F was obtained in the same manner except that.

(Toner preparation example 6)
In the surface treatment of Toner Preparation Example 1, N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium, iodide was 0.01 wt% with respect to 100 parts by weight of the mother fine particles. A toner F was obtained in the same manner except that.

(Toner preparation example 15)
This was carried out in the same manner as in Toner Preparation Example 6, but an aqueous methanol solution was added so that N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium and iodide were 0.1 wt%. The stirring was carried out for 48 hours while charging and stirring for 60 minutes.

(Toner Preparation Example 16)
This was carried out in the same manner as in Toner Preparation Example 6, but an aqueous methanol solution was added so that N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium and iodide were 0.1 wt%. The mixture was charged and stirred at 25 ° C. for 60 minutes at 40 ° C.

(Toner Preparation Example 17)
This was carried out in the same manner as in Toner Preparation Example 6, but an aqueous methanol solution was added so that N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium and iodide were 0.1 wt%. The mixture was charged and stirred at 25 ° C. for 60 minutes at 2 ° C.

(Toner preparation example 7)
<Creation of oil phase>
In a container equipped with a stir bar and a thermometer, 400 parts of the non-reactive resin [A], 110 parts of carnauba wax, and 947 parts of ethyl acetate are charged, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. After that, it was cooled to 30 ° C. at 1 hour. Next, 500 parts of [Masterbatch 1], 500 parts of ethyl acetate, N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium and 37 parts of iodide are charged in a container. After mixing for a time, [Raw material solution 2] was obtained.

  [Raw material solution 2] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed is 1 kg / hr, disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. The wax was dispersed under the conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of the non-reactive resin [A] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1]. The solid content concentration of [Pigment / Wax Dispersion 1] (130 ° C., 30 minutes) was 50%.

  Toner G was obtained in the same manner as in Toner Preparation Example 1 except that the above and <Surface Treatment> steps were not performed.

(Toner preparation example 8)
Similar to Toner Preparation Example 7 except that N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium and iodide in Toner Preparation Example 7 were changed from 37 parts to 2 parts. The toner H was obtained.

(Toner preparation example 9)
Toner J was obtained in the same manner as in Toner Preparation Example 1 except that <Surface Treatment> in Toner Preparation Example 1 was not performed.

(Toner preparation example 10)
Except for the toner preparation example 9 and the external additive processing step,
<External additive treatment>
Toner K was obtained by mixing 100 parts of the toner base particles obtained above with 1.0 part of hydrophobic silica R-972 (manufactured by Nippon Aerosil Co., Ltd.) and 1.0 part of PTFE in a Henschel mixer.

(Toner Preparation Example 11)
<Kneading and grinding toner>
(Synthesis of linear polyester resin)
In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 320 parts of bisphenol A / EO2 mole adduct, 480 parts of bisphenol A · EO2 mole adduct, 200 parts of terephthalic acid, 65 parts of phthalic acid and a polycondensation catalyst 2 parts of potassium titanyl oxalate was added and reacted at 225 ° C. for 10 hours while distilling off the water generated under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg, and after cooling to room temperature, it grind | pulverized and the linear polyester resin M-1 was obtained. Resin M-1 did not contain THF-insoluble matter, and had an acid value of 14, a hydroxyl value of 40, a Tg of 59 ° C., a number average molecular weight of 5100, a weight average molecular weight of 22000, and a peak top molecular weight of 4400. It was.

(Create master batch)
Using the linear polyester resin M-1, a pigment, a polyester resin, and pure water were mixed at a ratio of 1: 1: 0.5 and kneaded by two rolls. Kneading was performed at 70 ° C., and then the roll temperature was raised to 120 ° C. to evaporate water and prepare a master batch in advance.

Binder resin M-1 100 parts Black pigment (carbon black) 100 parts Pure water 50 parts (synthesis of non-linear polyester resin)
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introducing tank, 400 parts of bisphenol A · EO 2 mol adduct, 269 parts of bisphenol A · P03 mol adduct, 50 parts trimellitic acid, 278 parts terephthalic acid, 40 phthalic anhydride 2 parts of potassium titanyl oxalate was added as a polycondensation catalyst and reacted for 10 hours at 230 ° C. while distilling off the water generated under a nitrogen stream. Next, the reaction is carried out under a reduced pressure of 5 to 20 mmHg. When the acid value becomes 10 or less, the mixture is cooled to 180 ° C., 6 parts of trimellitic anhydride is added, taken out after reaction for 2 hours under normal pressure sealing, and cooled to room temperature. To obtain a non-linear polyester resin H-1.

  Resin H-1 contains 5% of THF-insoluble matter, its acid value is 13, hydroxyl value is 67, Tg is 70 ° C., number average molecular weight is 9600, weight average molecular weight is 45000, peak top molecular weight is 11000. there were.

Polyester resin M-1 10 parts Polyester resin H-1 90 parts Masterbatch 20 parts Ester wax 3 parts (Acid value: 8 mg KOH / g, Mw: 1600, particle size: 120 μm)
The material was premixed using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.] so as to be the same as the above recipe, and then the kneaded material temperature was adjusted in a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. It knead | mixed at 120 degreeC. Then, after finely pulverizing using a supersonic jet crusher, Labojet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I made by Nippon Pneumatic Industry Co., Ltd.], and the volume average particle size is reduced. 6.8 μm toner base particles were obtained.

<Surface treatment>
(1): 100 parts of ion-exchanged water is added to the base microparticles and sufficiently moistened, followed by mixing with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes).

  (2): N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium, iodide (product name Aftergent 310 (manufactured by Neos)) is used as a 1% aqueous methanol solution. .

  (3): The temperature of the slurry of (1) was adjusted to 2 ° C. while maintaining the temperature, and while stirring, (2) was added to N, N, N-trimethyl- [3- (4- Perfluorononenyloxybenzamido) propyl] ammonium and iodide are added so that the methanol solution is 0.1 wt%, and the mixture is stirred for 60 minutes.

  (4): The product was separated by filtration, and the resulting cake was dried under reduced pressure at 40 ° C. for 24 hours to obtain toner base particles.

<External additive treatment>
To 100 parts of the toner base particles obtained above, 1.0 part of hydrophobic silica R-972 (manufactured by Nippon Aerosil Co., Ltd.) was mixed in a Henschel mixer to obtain toner [L].

(Toner preparation example 12)
(Create master batch)
Using the linear polyester resin M-1, a pigment, a polyester resin, and pure water were mixed at a ratio of 1: 1: 0.5 and kneaded by two rolls. Kneading was performed at 70 ° C., and then the roll temperature was raised to 120 ° C. to evaporate water and prepare a master batch in advance.

Binder resin M-1 100 parts Black pigment (carbon black) 100 parts Pure water 50 parts (Synthesis of non-linear polyester resin)
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introducing tank, 400 parts of bisphenol A · EO 2 mol adduct, 269 parts of bisphenol A · P03 mol adduct, 50 parts trimellitic acid, 278 parts terephthalic acid, 40 phthalic anhydride 2 parts of potassium titanyl oxalate was added as a polycondensation catalyst and reacted for 10 hours at 230 ° C. while distilling off the water generated under a nitrogen stream. Next, the reaction is carried out under a reduced pressure of 5 to 20 mmHg. When the acid value becomes 10 or less, the mixture is cooled to 180 ° C., 6 parts of trimellitic anhydride is added, taken out after reaction for 2 hours under normal pressure sealing, and cooled to room temperature. To obtain a non-linear polyester resin H-1.

  Resin H-1 contains 5% of THF-insoluble matter, its acid value is 13, hydroxyl value is 67, Tg is 70 ° C., number average molecular weight is 9600, weight average molecular weight is 45000, peak top molecular weight is 11000. there were.

Polyester resin M-1 10 parts Polyester resin H-1 90 parts N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium, iodide 2 parts Masterbatch 20 parts Ester wax 3 Parts (acid value: 8 mg KOH / g, Mw: 1600, particle size: 120 μm)
The material was premixed using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.] so as to be the same as the above recipe, and then the kneaded material temperature was adjusted in a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. It knead | mixed at 120 degreeC. Then, after finely pulverizing using a supersonic jet crusher, Labojet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I made by Nippon Pneumatic Industry Co., Ltd.], and the volume average particle size is reduced. 6.8 μm toner base particles were obtained.

<External additive treatment>
To 100 parts of the toner base particles obtained above, 1.0 part of hydrophobic silica R-972 (manufactured by Nippon Aerosil Co., Ltd.) was mixed in a Henschel mixer to obtain toner [M].

(Toner Preparation Example 13)
Same as Preparation Example 12 except that N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium and iodide in Toner Preparation Example 12 were changed to PTFE (polytetrafluoroethylene). And toner N was obtained.

(Toner Preparation Example 14)
Toner O was obtained in the same manner as in Toner Preparation Example 11 except that <Surface Treatment> in Toner Preparation Example 11 was not performed.

  Aggregation degree of the mother fine particles. In addition, these aggregation degrees and circularity are obtained by measuring by the following method.

(Degree of aggregation)
Using a powder tester PN-T (manufactured by Hosokawa Micron Corporation), openings 355 μm (Sieving S1), 250 μm (Sieving S2) and 150 μm (Sieving S3) are arranged in this order from above, and 2 g of toner is placed on the sieve S1 with 150 μm opening. Then, vibration is applied for 10 seconds with an amplitude of 1 mm. After the vibration, the weights W1, W2, and W3 of the toner remaining on the sieves S1, S2, and S3 are measured. A value obtained by multiplying W1, W2, and W3 by weights of 1.0, 0.6, and 0.2, respectively, and adding them together to calculate a percentage by the following formula was defined as an aggregation degree AG (%).

AG = [(1.0 × (W1) + 0.6 × (W2) + 0.2 × (W3)) / 2] × 100
The degree of aggregation of the mixture. These cohesion and circularity can be obtained by the following method (coagulation degree)
Using a powder tester PN-T (manufactured by Hosokawa Micron Corporation), openings 75 μm (sieving m1), 45 μm (sieving M2), and 22 μm (sieving M3) are arranged in this order from above, and 2 g of toner is placed on the sieve S1 with 150 μm opening. Then, vibration is applied for 10 seconds with an amplitude of 1 mm, and after the vibration, the weights WM1, WM2, and WM3 of the toner remaining on the sieves S1, S2, and S3 are measured. A value obtained by multiplying W1, W2, and W3 by weights of 1.0, 0.6, and 0.2, and adding them together to calculate a percentage by the following formula was defined as the degree of aggregation BG (%).

BG = [(1.0 × (WM1) + 0.6 × (WM2) + 0.2 × (WM3)) / 2] × 100
<Fixability>
Using a fixing device, fixing was evaluated with a solid image and a toner adhesion amount of 0.85 ± 0.1 mg / cm 2 on a copying paper <135> made of thick transfer paper NBS Ricoh. A fixing test was performed by changing the temperature of the fixing belt, and the minimum fixing temperature was measured. The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more. The fixing lower limit temperature is ◎ for 135 ° C. or less, ◯ for 135 to 145 ° C., Δ for 145 to 155 ° C., and × for 155 ° C. or more.

<Toner transportability>
Using the transfer device shown in FIGS. 3 and 8, an experiment was conducted in which 100 g of toner was actually transferred.
The length of the pipe was set to 1 m, and the toner after being repeatedly transferred 20 times was evaluated for the degree of aggregation and the transportability of the mixture.

Toner transportability evaluation results XX: The toner could not be transferred at all.

  X: Toner clogging occurred in the tube, and the toner was not transferred halfway.

  Δ: All the toner in the bottle was transported, but there was a problem that sometimes the toner transfer stopped.

○: The toner was stably transferred (transported).
A: The toner was stably transferred, and the powder pump output time (between 0.1 seconds and 1 second) and the amount of powder transport were almost proportional.

以上、本発明の実施の形態及び実施例を具体的に説明してきたが、本発明は、これらの実施の形態及び実施例に限定されるものではなく、これら本発明の実施の形態及び実施例を、本発明の主旨及び範囲を逸脱することなく、変更又は変形することができる。
［付記］
本発明の実施形態は、トナー、画像形成方法、及びトナーの定着方法に関する。
本発明の実施形態の目的は、定着性に大幅に影響を与えることなく流動性を維持することが可能なトナー、画像形成方法、及びトナーの定着方法を提供することである。
付記（１）に記載の発明は、少なくとも結着樹脂、ワックス、着色剤及びフッ素化合物を含む母体着色微粒子に少なくとも一種類以上の無機微粒子を混合して得られるトナーにおいて、ふるい目３５５μｍのふるいに残った母体着色微粒子の重量％＋ふるい目２５０μｍのふるいに残った母体着色微粒子の重量％×０．６＋ふるい目１５０μｍのふるいに残った母体着色微粒子の重量％×０．２で定義されるトナーの凝集度が、５％以上３０％以下であることを特徴とする、トナーである。
付記（２）に記載の発明は、付記（１）に記載のトナーにおいて、前記含フッ素化合物の添加量は、前記母体着色微粒子１００重量部に対して、０．０１重量部〜３重量部であることを特徴とする、トナーである。
付記（３）に記載の発明は、少なくとも結着樹脂、着色剤、離型剤を含有し、且つ、水系媒体中に分散させ、該水系媒体中において含フッ素化合物で表面を処理して得られる母体着色微粒子に、少なくとも一種類以上の無機微粒子を混合して得られるトナーにおいて、ふるい目３５５μｍのふるいに残った母体樹脂微粒子の重量％＋ふるい目２５０μｍのふるいに残った母体着色微粒子の重量％×０．６＋ふるい目１５０μｍのふるいに残った母体着色微粒子の重量％×０．２で定義されるトナーの凝集度が、５％以上３０％以下であることを特徴とする、トナーである。
付記（４）に記載の発明は、付記（１）乃至（３）のいずれか一つに記載のトナーにおいて、前記フッ素含有化合物が、含フッ素４級アンモニウム塩であることを特徴とする、トナーである。
付記（５）に記載の発明は、付記（１）乃至（３）のいずれか一つに記載のトナーにおいて、前記含フッ素４級アンモニウム塩が、式（１）

で示される化合物であり、Ｘは、−ＳＯ _２ −又は−ＣＯ−であり、Ｙは、Ｉ又はＢｒであり、Ｒ ^１ 、Ｒ ^２ 、Ｒ ^３ 、及びＲ ^４ は、それぞれ独立に、水素原子、炭素数１以上１０以下の低級アルキル基、又はアリール基であり、ｒ及びｓは、それぞれ独立に、１以上２０以下の整数であることを特徴とする、トナーである。
付記（６）に記載の発明は、付記（１）乃至（５）のいずれか一つに記載のトナーにおいて、当該トナーの酸価は、５〜３０であることを特徴とする、トナーである。
付記（７）に記載の発明は、付記（１）乃至（６）のいずれか一つに記載のトナーにおいて、当該トナーの平均円形度は、０．９４〜０．９７であることを特徴とする、トナーである。
付記（８）に記載の発明は、付記（１）乃至（７）のいずれか一つに記載のトナーにおいて、当該トナーのガラス転移点は、４５℃〜６０℃の範囲にあることを特徴とする、トナーである。
付記（９）に記載の発明は、付記（４）又は（５）に記載のトナーにおいて、前記含フッ素４級アンモニウム塩の添加量は、前記母体着色微粒子１００重量部に対して、０．０１重量部〜１重量部であることを特徴とする、トナーである。
付記（１０）に記載の発明は、付記（３）乃至（９）のいずれか一つに記載のトナーにおいて、前記含フッ素化合物の添加量は、前記母体着色微粒子１００重量部に対して、０．０３重量部〜０．５重量部であることを特徴とする、トナーである。
付記（１１）に記載の発明は、付記（３）乃至（１０）のいずれか一つに記載のトナーにおいて、前記表面処理工程において、前記水系媒体の温度は、１０℃〜３０℃の範囲にあることを特徴とする、トナーである。
付記（１２）に記載の発明は、付記（３）乃至（１１）のいずれか一つに記載のトナーにおいて、前記表面処理工程において、当該トナーの表面を処理する時間は、０．１時間〜２４時間であることを特徴とする、トナーである。
付記（１３）に記載の発明は、画像形成方法において、付記（１）乃至（１２）のいずれか一つに記載のトナーを用いて画像を形成することを特徴とする、画像形成方法である。
付記（１４）に記載の発明は、付記（１３）に記載の画像形成方法において、トナーを収容するトナー収容部と、該トナーを移送するトナー輸送管と、該トナーを移送するための粉体ポンプとを備えたトナー移送装置を配備した画像形成装置を用いて、前記画像を形成することを特徴とする、画像形成方法である。
付記（１５）に記載の発明は、付記（１４）に記載の画像形成方法において、前記トナーの移送先が、二成分式現像部であり、該二成分式現像部における二成分現像剤のトナー濃度が、前記粉体ポンプの出力により制御されることを特徴とする、画像形成方法である。
付記（１６）に記載の発明は、付記（１４）又は（１５）に記載の画像形成方法において、前記粉体ポンプは、内部にダブルピッチの螺旋溝を設けた雌ネジ形ステータ、該ステータ内に回動自在に嵌挿された雄ネジ形ロータを有するスクリューポンプであることを特徴とする、画像形成方法である。
付記（１７）に記載の発明は、付記（１４）乃至（１５）のいずれか一つに記載の画像形成方法において、前記画像形成装置は、リサイクル機能を備えることを特徴とする、画像形成方法である。
付記（１８）に記載の発明は、トナーの定着方法において、付記（１）乃至（１２）のいずれか一つに記載のトナーを媒体に定着させることを特徴とする、トナーの定着方法である。
付記（１９）に記載の発明は、付記（１８）に記載のトナーの定着方法において、磁性金属から構成されて電磁誘導により加熱される加熱ローラと、該加熱ローラと平行に配置された定着ローラと、該加熱ローラと該定着ローラとに張り渡され、該加熱ローラにより加熱されるとともに該加熱ローラ及び該定着ローラによって回転される無端帯状のトナー加熱媒体と、該トナー加熱媒体を介して該定着ローラに圧接されるとともに、該トナー加熱媒体に対して順方向に回転して定着ニップ部を形成する加圧ローラとを有する定着装置を用いて、前記トナーを前記媒体に定着させることを特徴とする、トナーの定着方法である。
本発明の実施形態によれば、定着性に大幅に影響を与えることなく流動性を維持することが可能なトナー、画像形成方法、及びトナーの定着方法を提供することができる。

Although the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to these embodiments and examples, and these embodiments and examples of the present invention are not limited thereto. Can be changed or modified without departing from the spirit and scope of the present invention.
[Appendix]
Embodiments described herein relate generally to a toner, an image forming method, and a toner fixing method.
An object of an embodiment of the present invention is to provide a toner, an image forming method, and a toner fixing method capable of maintaining fluidity without significantly affecting the fixing property.
The invention described in appendix (1) is a toner obtained by mixing at least one kind of inorganic fine particles with matrix-colored fine particles containing at least a binder resin, a wax, a colorant and a fluorine compound. Toner defined by weight% of remaining mother colored fine particles + weight% of mother colored fine particles remaining on sieve with 250 μm sieve × 0.6 +% by weight of mother colored fine particles remaining on sieve with 150 μm sieve × 0.2 The toner has a cohesion degree of 5% or more and 30% or less.
The invention described in appendix (2) is the toner described in appendix (1), wherein the amount of the fluorine-containing compound added is 0.01 to 3 parts by weight with respect to 100 parts by weight of the base colored fine particles. A toner characterized by being.
The invention described in appendix (3) is obtained by containing at least a binder resin, a colorant, and a release agent, and dispersing in an aqueous medium and treating the surface with a fluorine-containing compound in the aqueous medium. In the toner obtained by mixing at least one kind of inorganic fine particles with the matrix coloring fine particles, the weight percentage of the matrix resin fine particles remaining on the sieve having a sieve size of 355 μm + the weight percentage of the matrix coloring fine particles remaining on the sieve having a sieve diameter of 250 μm. A toner having a degree of aggregation of the toner defined by weight% × 0.2 of the base coloring fine particles remaining on the sieve of × 0.6 + sieve 150 μm is 5% or more and 30% or less.
The invention according to appendix (4) is characterized in that in the toner according to any one of appendices (1) to (3), the fluorine-containing compound is a fluorine-containing quaternary ammonium salt. It is.
The invention described in appendix (5) is the toner according to any one of appendices (1) to (3), wherein the fluorine-containing quaternary ammonium salt is represented by formula (1).

Wherein X is —SO ₂ — or —CO—, Y is I or Br, and R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom The toner is a lower alkyl group having 1 to 10 carbon atoms or an aryl group, and r and s are each independently an integer of 1 to 20;
The invention described in appendix (6) is a toner according to any one of appendices (1) to (5), wherein the toner has an acid value of 5 to 30. .
The invention according to appendix (7) is characterized in that, in the toner according to any one of appendices (1) to (6), the average circularity of the toner is 0.94 to 0.97. Toner.
The invention according to appendix (8) is characterized in that in the toner according to any one of appendices (1) to (7), the glass transition point of the toner is in the range of 45 ° C to 60 ° C. Toner.
In the invention described in appendix (9), in the toner described in appendix (4) or (5), the addition amount of the fluorine-containing quaternary ammonium salt is 0.01% with respect to 100 parts by weight of the base colored fine particles. It is a toner characterized by being 1 part by weight to 1 part by weight.
The invention according to appendix (10) is the toner according to any one of appendices (3) to (9), wherein the addition amount of the fluorine-containing compound is 0 with respect to 100 parts by weight of the base colored fine particles. 0.03 part by weight to 0.5 part by weight of the toner.
The invention according to appendix (11) is the toner according to any one of appendices (3) to (10), wherein in the surface treatment step, the temperature of the aqueous medium is in the range of 10 ° C to 30 ° C. A toner characterized by being.
In the invention according to appendix (12), in the toner according to any one of appendices (3) to (11), the time for treating the surface of the toner in the surface treatment step is 0.1 hour to The toner is characterized in that it is 24 hours.
The invention described in appendix (13) is an image forming method, wherein an image is formed using the toner described in any one of appendices (1) to (12). .
The invention according to appendix (14) is the image forming method according to appendix (13), wherein a toner accommodating portion that accommodates toner, a toner transport pipe that conveys the toner, and a powder that conveys the toner An image forming method comprising: forming an image using an image forming apparatus provided with a toner transfer device including a pump.
The invention according to appendix (15) is the image forming method according to appendix (14), wherein the toner is transferred to a two-component developing unit, and the toner of the two-component developer in the two-component developing unit The density is controlled by the output of the powder pump.
The invention according to appendix (16) is the image forming method according to appendix (14) or (15), wherein the powder pump includes a female screw type stator having a double pitch spiral groove therein, An image forming method characterized in that the screw pump has a male screw type rotor that is rotatably inserted into the screw pump.
The invention according to appendix (17) is the image forming method according to any one of appendices (14) to (15), wherein the image forming apparatus has a recycling function. It is.
The invention according to appendix (18) is a toner fixing method, wherein the toner according to any one of appendices (1) to (12) is fixed on a medium. .
The invention according to appendix (19) is the toner fixing method according to appendix (18), wherein the heating roller is made of magnetic metal and is heated by electromagnetic induction, and the fixing roller arranged in parallel with the heating roller And an endless belt-shaped toner heating medium that is stretched between the heating roller and the fixing roller, heated by the heating roller and rotated by the heating roller and the fixing roller, and the toner heating medium through the toner heating medium The toner is fixed to the medium by using a fixing device having a pressure roller that is pressed against the fixing roller and rotates forward with respect to the toner heating medium to form a fixing nip portion. And a toner fixing method.
According to the embodiments of the present invention, it is possible to provide a toner, an image forming method, and a toner fixing method capable of maintaining fluidity without significantly affecting the fixability.

  (1) In an electrophotographic toner obtained by mixing at least one kind of inorganic fine particles with matrix colored fine particles containing at least a binder resin, a wax, a colorant and a fluorine compound, the matrix colored fine particles remain on a sieve having a sieve size of 355 μm. (A) Weight% of toner remaining on sieve with 250 μm sieve × 0.6 (b) Weight% of toner remaining on sieve with 150 μm sieve × 0.2 · An electrophotographic toner characterized in that the degree of aggregation of the toner, defined as the sum of the calculated values obtained by the formulas (a) to (c) of (c), is 5% or more and 30% or less.

  (2) The toner, wherein the fluorine-containing amount is 0.01 to 3 parts by weight.

  (3) Maternally colored fine particles obtained through a surface treatment step containing at least a binder resin, a colorant, and a release agent, dispersed in an aqueous medium, and treating the toner surface with a fluorine-containing compound in the aqueous medium. In the electrophotographic toner obtained by mixing at least one kind of inorganic fine particles with the toner, the weight percentage of the toner in which the matrix resin fine particles remain on the sieve having a sieve size of 355 μm (a) The toner remaining on the sieve having a sieve size of 250 μm (%) Of the toner remaining on the sieve having a sieve mesh of 150 μm × 0.2 (2) of the calculated value obtained by the equations (a) to (c) of (c). An electrophotographic toner having a toner aggregation degree defined as the sum of 5% or more and 30% or less.

  (4) An electrophotographic toner, wherein the fluorine-containing compounds (1) to (3) are fluorine-containing quaternary ammonium salt compounds.

  (5) The fluorine-containing quaternary ammonium salt compound is represented by the following formula (1)

で示される化合物であることを特徴とする（１）〜（３）記載のトナー。

The toner according to any one of (1) to (3), wherein

  (6) The toner, wherein the toner composition has an acid value of 5 to 30.

  (7) The toner according to (1) to (6), wherein the toner has an average circularity of 0.94 to 0.97.

  (8) The toner according to any one of (1) to (7), wherein the toner has a glass transition point in the range of 45 to 60 ° C.

  (9) The toner according to (4) or (5), wherein the fluorine-containing quaternary ammonium salt is added in an amount of 0.01 to 1 part by weight.

  (10) The toner according to (1) to (9), wherein the addition amount of the fluorine-containing compound is 0.03 to 0.5 parts by weight.

  (11) The toner according to (3) to (10), wherein the surface treatment step is obtained by treating an aqueous medium in a temperature range of 10 to 30 ° C.

  (12) The toner according to any one of (3) to (11), wherein the surface treatment time in the surface treatment step is 0.1 to 24 hours.

  (13) Used in an electrophotographic image forming apparatus provided with a toner transfer device including a toner storage unit for storing toner, a toner transport pipe for transferring the toner, and a powder pump for transferring the toner. An electrophotographic toner using the electrophotographic toner according to any one of (1) to (11).

  (14) The electrophotographic image forming method, wherein the toner is transferred to a two-component developing unit, and the toner concentration of the two-component developer in the two-component developing unit is controlled by the output of the powder pump. An electrophotographic toner comprising the electrophotographic toner (1) to (11) used in the apparatus.

  (15) The powder pump is a screw pump having an internal thread type stator provided with a double pitch spiral groove therein, and an external thread type rotor that is rotatably inserted in the stator. An electrophotographic toner comprising the electrophotographic toners (1) to (11) used in a toner transfer device.

  (16) An electrophotographic toner using the electrophotographic toner (1) to (11) used in an image forming apparatus having a recycling function.

  (17) A heating roller made of a magnetic metal and heated by electromagnetic induction, a fixing roller arranged in parallel with the heating roller, and stretched between the heating roller and the fixing roller, and heated by the heating roller And an endless belt-shaped toner heating medium rotated by these rollers, and pressed against the fixing roller via the toner heating medium, and rotated in the forward direction with respect to the toner heating medium, and a fixing nip portion An electrophotographic toner and an image forming apparatus, wherein the toner is used in a fixing device having a pressure roller for forming the toner.

According to the embodiment of the present invention, the fixing property is not affected, the occurrence of abnormal images due to toner aggregation due to transfer is prevented, the toner fluidity is maintained even during long-term operation, and the toner conveying force is maintained. An electrophotographic toner that can be provided can be provided.

  In addition, the use of a toner with an optimized degree of aggregation of the matrix coloring particles in the toner allows the toner to maintain fluidity even if the additive is embedded or released due to a strong stress, and a long toner transport tube. Even if the inside is transferred, the toner can be stably transferred without causing clogging.

  Further, even if the toner is transferred through a long toner transfer tube, it is possible to stably transfer the toner without causing clogging, and it is possible to realize high-quality image formation without ground fogging.

  In addition, even in an electrophotographic image forming apparatus in which the stress on the toner including a mechanism such as recycling is greater, it is possible to realize a high-quality image formation that is resistant to stress and maintains fluidity.

FIG. 1 is a schematic configuration diagram of a toner transfer device using a discharge type powder pump according to an embodiment of the present invention. FIG. 2 is a schematic configuration diagram of a toner transfer device using the suction type powder pump according to the embodiment of the present invention. FIG. 3 is a cutaway perspective view showing an internal configuration of a discharge-type screw pump provided in the toner transfer device according to the embodiment of the present invention. FIG. 4 is an overall configuration diagram of a toner transfer device provided with a discharge-type screw pump according to an embodiment of the present invention. FIG. 5 is a perspective view for explaining a breathable filter provided in the toner storage container in FIG. FIG. 6 is a cutaway perspective view showing the internal configuration of a suction-type screw pump provided in the toner transfer device according to the embodiment of the present invention. FIG. 7 is a cross-sectional view for explaining a state where the rotor and the stator of the screw pump are fitted in the embodiment of the present invention. FIG. 8 is an overall configuration diagram of a toner transfer device provided with a suction-type screw pump according to an embodiment of the present invention.

DESCRIPTION OF SYMBOLS 1 Screw pump 1 'Screw pump 2 Stator 3 Male threaded rotor 4 Holder 5 Crevice 6 Toner discharge port 7 Air supply port 10 Transfer screw 10' Shaft 11 Side plate 12 Spring pin 13 Transfer tube 14 Case 15 Filter 20 Toner storage container 21 Outer box 22 Toner bag 23 Cap member 24 Toner discharge hole 25 Seal 26 Air permeable filter 30 Air pump 31 Air tube 32 Switching valve 33 Air supply tube 50 Set part 51 Container holder 52 Nozzle 53 Pointed part 54 Receptor 55 Toner passage 71 Toner accommodating part 72 Toner transport pipe 73 Powder pump 73 'Powder pump 74 Toner transfer destination 75 Lower part 76 Air insertion port 77 Air filter 80 Pump is developing device 81 Toner receiving part

Claims (4)

A step of dispersing a toner material liquid containing at least unmodified polyester, a polyester prepolymer having an isocyanate group, a colorant, and a release agent in an aqueous medium in the presence of resin fine particles ;
Adding amines to the aqueous medium and reacting the amines with the polyester prepolymer having an isocyanate group;
A step of treating the surface with a fluorine-containing compound in the aqueous medium to obtain matrix-colored fine particles, and
In a method for producing a toner, comprising a step of mixing at least one kind of inorganic fine particles with the matrix coloring fine particles to obtain a toner,
% By weight of the base resin fine particles remaining on the sieve having a sieve size of 355 μm +
Weight% of the mother-colored fine particles remaining on the sieve having a sieve size of 250 μm × 0.6 +
Weight% of matrix coloring fine particles remaining on sieve having a sieve size of 150 μm × 0.2
The degree of aggregation of the toner defined by is from 8% to 30%,
The acid value of the unmodified polyester is 3 or more and 24 or less,
The aqueous medium includes 90 parts of ethyl acetate with respect to 1055 parts of water,
The fluorine-containing compound is a fluorine-containing quaternary ammonium salt;
The fluorine-containing quaternary ammonium salt is N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide ;
In the step of obtaining the mother-colored fine particles by treating the surface, the addition amount of the fluorine-containing quaternary ammonium salt is 0.01 parts by weight or more and 3 parts by weight or less with respect to 100 parts by weight of the mother-colored fine particles,
In the step of dispersing the toner material liquid in the aqueous medium in the presence of resin fine particles, the amount of the aqueous medium used with respect to 100 parts by weight of the toner material liquid is 50 parts by weight or more and 2000 parts by weight or less,
In the step of obtaining the matrix-colored fine particles by treating the surface, the temperature of the aqueous medium is in the range of 10 ° C. or higher and 30 ° C. or lower,
A method for producing a toner, characterized in that, in the step of treating the surface to obtain matrix-colored fine particles, the time for treating the surface of the toner is from 0.1 hours to 24 hours. The method for producing a toner according to claim 1.
A method for producing a toner, wherein the acid value of the toner is 5 or more and 30 or less. The method for producing the toner according to claim 1 or 2,
The method for producing a toner, wherein the toner has an average circularity of 0.94 to 0.97. In the method for producing the toner according to any one of claims 1 to 3,
A method for producing a toner, wherein the glass transition point of the toner is in a range of 45 ° C. or more and 60 ° C. or less .

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