JP2006023428A - Electrostatic charge image developing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developer which has improved cleaning properties, and with which, even if many recording papers are repeatedly used over a long period, proper image density can be obtained and the stain of surface is extremely little, further, to provide a developer which has a sharp distribution in an electrostatic charge amount, does not contaminate a charging device, a developing device, a photoreceptor and an intermediate transferring body and can form images of high quality, and to provide a toner which copes with a low temperature fixing system, has satisfactory offset resistance and does not stain a fixing device and images. <P>SOLUTION: The electrostatic charge image developing toner is obtained by dissolving or dispersing at least a resin or a resin precursor comprising a monomer, a coloring agent and a metal oxide and solvent-dispersed body comprising one or more kinds of metal oxides into an organic phase, dispersing the solution or dispersed liquid into a water base medium, thereafter, removing the organic solvent and the water base medium and performing cleaning and drying. The metal oxide and solvent-dispersed body is either a sol body or a wetting gel, and its pH reaches 2 to 6 by equal amount dilution with water. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrostatic charge image developing toner for developing an electrostatic charge image formed on the surface of a photoreceptor in electrophotography and electrostatic recording, and a developer using the toner.

  In an electrophotographic apparatus, an electrostatic recording apparatus, or the like, an electrical or magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a transfer material such as paper and then fixed by a method such as heating. Toner used for electrostatic image development is generally colored particles in which a binder, a colorant, a charge control agent, and other additives are contained in a binder resin. There is a suspension polymerization method. In the pulverization method, a colorant, a charge control agent, an offset preventive agent, and the like are melt-mixed and uniformly dispersed in a thermoplastic resin, and the resulting composition is pulverized and classified to produce a toner.

  According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment. From this requirement, the melt-mixed composition must be made sufficiently brittle. For this reason, when the above composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, the particle size There is a disadvantage that the fine powder of 5 μm or less and the coarse powder of 20 μm or more must be removed by classification and the yield becomes very low.

  Further, considering the average particle size in the toner particle size distribution from the viewpoint of yield, productivity and cost, it is a very big problem for the pulverized toner to make the particle size small, particularly 6 μm or less. In addition, the chargeability of the irregular shaped toner prepared by pulverization is different for each toner particle because the adhesion area to the developing roll in a one-component developer and the adhesion area to a carrier in a two-component developer are different for each toner particle. The adhesion to the carrier is different and the ease of development is also different. Since toners having different particle diameters have different charge amounts, the ease of development is also different. Due to these differences, easily developable toner is selectively developed, and difficultly developed toner remains in the developing device, and developability changes with time.

  Similarly, when transferring to recording paper, there are toners that are easily transferred and toners that are difficult to transfer, and therefore image quality deterioration such as toner scattering is likely to occur. Further, when a toner is produced by internally adding a release agent such as wax, the release agent may be exposed on the toner surface by combination with a thermoplastic resin. In particular, in a combination of a resin imparted with elasticity by a high molecular weight component and slightly pulverized resin and a brittle wax such as polypropylene, the exposure of the wax is often observed on the toner surface. The exposure of the release agent is advantageous for releasability at the time of fixing and cleaning of the toner remaining on the photoconductor after transfer, but since the fluidizing agent on the toner surface is easily moved by mechanical force, This easily causes wax contamination of the photoreceptor and carrier, leading to a decrease in reliability of the image forming apparatus.

  In recent years, in order to overcome these problems in the pulverization method, toner particles are obtained by a polymerization method. However, the toner particles obtained by the polymerization method have a higher sphericity than the kneading and pulverization method, and are advantageous in terms of charging stability and transferability. On the other hand, in the cleaning process, the toner remaining on the image carrier is removed. It becomes difficult to scrape with a blade, causing problems such as poor cleaning and system problems in which the development density cannot be controlled due to the influence of toner remaining on the photosensitive member after the transfer process (Japanese Patent Laid-Open No. 11-149177). Publication: It is described that when the shape factor SF-1 is 110 or less, it is difficult to clean the transfer residual toner remaining on the latent image carrier, and defective cleaning is likely to occur).

For this reason, a method of obtaining irregular toner particles by associating resin fine particles obtained by an emulsion polymerization method has been disclosed (Japanese Patent No. 2537503). However, in the toner particles obtained by the emulsion polymerization method, a large amount of the surfactant remains not only on the surface but also inside the particles even after the water washing step, and the environmental stability of the toner charging is impaired. The amount distribution is widened, and the background stain of the obtained image becomes poor. In addition, the remaining surfactant contaminates the photoreceptor, the charging roller, the developing roller, and the like, and the original charging ability cannot be exhibited.

  In addition, the following problems occur in the method of obtaining irregularly shaped toner particles by associating resin fine particles obtained by an emulsion polymerization method. That is, when the release agent fine particles are associated with each other in order to improve the offset resistance, the release agent fine particles are taken into the toner particles, and as a result, the offset resistance can be sufficiently improved. Can not. Resin fine particles, release agent fine particles, colorant fine particles, etc. are randomly fused to constitute toner particles, so there is a variation in composition (content ratio of constituent components) and molecular weight of constituent resins among the obtained toner particles. As a result, the toner particles have different surface characteristics, and a stable image cannot be formed over a long period of time.

  In addition, suspension polymerization methods (Patent Document 3, Japanese Patent Laid-Open No. 8-44111, Patent Document 4, Japanese Patent Laid-Open No. 8-286416) have been proposed. In the case of suspension polymerization, it is necessary to adjust the particles to an appropriate size in the suspended state. For this purpose, the desired quality cannot be produced unless the dispersion liquid is stirred at a high speed and the toner material is finely dispersed. However, since the viscosity difference between the release agent and the monomer is large and incompatible, it is extremely difficult to finely disperse at this stage. As a result, a large number of particles in which the wax is not present in the resin are generated, causing uneven distribution between the toner particles and causing a problem of unstable toner charging.

  In addition, in a two-component developing device equipped with development, transfer, and cleaning, toner particles that are manifested by a developer via a development carrier and transferred to a transfer material to obtain an image are used for the toner particles Is characterized by using a developer containing an irregular shape (Japanese Patent Laid-Open No. 5-34979). The toner having a concavo-convex shape described in this publication is a toner having a convex portion on a projected image, and in a two-component developer using a carrier, the shape of the toner convex portion changes due to stress due to stirring. It may also lead to deterioration of the cleaning performance. Further, since the polymerization method is suspension polymerization, residual components of styrene monomer and acrylic monomer are included, which remains as an environmental problem.

  In addition, although WAX is encapsulated, fluidity and adhesion to the photoreceptor are reduced, but the fixing property is the same as that of the pulverization method in which wax as a release agent is present at the particle interface. Therefore, it becomes a toner that is disadvantageous in terms of power consumption. Furthermore, the amount of WAX is increased in order to improve the fixing property, and the transparency of the color toner is increasingly deteriorated in order to increase the dispersed particle size of WAX, so that it becomes difficult to use for presentation by OHP.

  In addition to suspension polymerization, there are emulsion polymerization methods and dissolution suspension methods in which the shape of the toner particles can be made relatively different in the polymerized toner method, but also in the emulsion polymerization method, complete removal of styrene monomer, emulsifier and dispersant Removal is difficult, and in recent years, environmental issues have become particularly important. In addition, the photosensitive member is caused by the fact that the adhesion of the silica added as a fluidizing agent to the concave portion is weak by making the shape uneven, and the silica is detached in the long-term use of the developer by moving the silica to the concave portion during use. Contamination problems and adhesion problems to the fixing roller are likely to occur.

  In addition, the dissolution suspension method has the advantage that a low-temperature fixing polyester resin can be used. However, in order to achieve oil-less fixing, polymer control and production in order to widen the release range, resin and colorant Since the high molecular weight component is added in the step of dissolving or dispersing the solvent in the solvent, the liquid viscosity increases and productivity problems are likely to occur. They have not been solved yet. In particular, in the dissolution suspension method, the toner surface shape is made spherical and concavo-convex to improve the cleaning (Patent Document 6, Japanese Patent Laid-Open No. 9-15903), but is an irregularly shaped toner having no regularity. For this reason, high molecular weight design for charging stability and further ensuring basic durability and releasability has not been achieved, and satisfactory quality has not been obtained.

In addition, by controlling the temperature of the intermediate composition and the composition liquid in which polyaddition reaction and desolvation are performed under granulation, the desolvation conditions, etc., toner particles are caused by the partial internal pressure imbalance phenomenon that occurs in the toner particles. Although a method for gently forming a dent on the surface has been disclosed (Patent Document 7, Japanese Patent Application Laid-Open No. 2002-287400), it is necessary to finely set the temperature, the evaporation speed of the solvent, the liquid stirring speed, and the like when removing the solvent. As the production scale increases, uniform and stable shape changes are less likely to occur.
JP-A-11-149177 Japanese Patent No. 2537503 JP-A-8-44111 JP-A-8-286416 JP-A-5-34979 JP 9-15903 A JP 2002-287400 A

  SUMMARY OF THE INVENTION An object of the present invention is to provide a developer that improves cleaning properties, has an appropriate image density and has very little background stain even when repeatedly used for a long period of time, and provides an electrophotographic developing apparatus using the developer. is there. Also provided is a developer having a sharp charge distribution and capable of forming a high-quality image without the charging device, developing device, photoconductor, and intermediate transfer member being contaminated by the developer, and electrophotographic development using the developer. To provide an apparatus. Another object of the present invention is to provide a toner that is compatible with a low-temperature fixing system, has good offset resistance, and does not contaminate the fixing device and the image.

  As a result of intensive studies by the present inventors to solve such problems, at least a resin precursor containing a resin or a monomer in the organic phase, a colorant, and one or more metal oxide solvent dispersions Is dissolved or dispersed, and the solution or dispersion is dispersed in an aqueous medium, and then the organic solvent or aqueous medium is removed, washed, and dried, and the metal oxide solvent dispersion is a sol or A wet gel that has a pH of 2 to 6 when diluted with water at the same magnification to improve cleaning performance. Even if it is used repeatedly for a long period of time, it is a toner with an appropriate image density and low background contamination. I found out that I could get a mother.

When the metal oxide solvent dispersion satisfies the above conditions, when an appropriate amount of the metal oxide solvent dispersion is added, the toner particles when dispersed and dissolved in the aqueous solvent to remove the organic solvent are generally spherical. It was found that the surface was shaped like an umeboshi with large irregularities. The following can be considered as the reason.
The metal oxide is often used as a dry powder in the toner field. However, when the metal oxide is dispersed in an organic solvent, the metal oxide often aggregates. Therefore, by using a metal oxide solvent dispersion in which a solvent and a metal oxide are dispersed in advance to obtain a uniform dispersion, such as a sol or wet gel, agglomeration in an organic solvent is suppressed, and metal oxidation is performed. This results in a uniform distribution of objects. Further, by using a metal oxide having a pH within a predetermined range, the metal oxide particles are attracted to the interface of the aqueous medium, so that the metal oxide particles cover the vicinity of the surface of the toner particles during dispersion / dissolution. become. When the organic solvent is removed in this state, the organic solvent inside is removed while trying to maintain the shape in the vicinity of the surface. As a result, the surface is generally spherical but has large irregularities on the surface, such as plum blossoms. Become a shape.

If the metal oxide is simply not in the state of a sol or wet gel with a pH within a predetermined range, the metal oxide aggregates when trying to disperse in an organic solvent as described above, and the metal oxide is A large amount of metal oxide is required to cover the vicinity of the toner particle surface, which adversely affects low-temperature fixability. Further, when a metal oxide having a pH of more than 6 is used by diluting with water, it is difficult to form a state in which the metal oxide particles cover the vicinity of the surface of the toner particles because the orientation to the interface of the aqueous medium is small. When a metal oxide having a pH of less than 2 is used when diluted with water at the same magnification, the affinity with the aqueous medium is too strong, so that the metal oxide particles come out of the toner particles into the aqueous medium and remain in the vicinity of the surface. I can't do anything. In addition, it is necessary to make the process equipment acid-resistant, and the capital investment is expensive. Therefore, the metal oxide solvent dispersion must satisfy both of a) either a sol body or a wet gel, and b) a pH of 2 to 6 when diluted with water at the same magnification. .
In addition, the measuring method of 1 time dilution here means diluting the dispersion liquid containing a metal oxide with the same weight of water.

ここで
: 蒸発エネルギーcal/mol
: 密度g/cc
: モル容積cc/mol
: グラム分子量g/mol
: 蒸発潜熱cal/mol
: 絶対温度K
: ガス定数 1.987 cal/(mol*K)
Further, the SP value of the solvent that is used in the metal oxide solvent dispersion [delta] _MS, the metal oxide when the SP value of the solvent used, excluding the solvent dispersion was [delta] _PS, [delta] relationship _MS and [delta] _PS Preferably satisfies −2.0 <δ _MS −δ _PS <4.0. The reason is that even if the metal oxide is uniformly dispersed in the solvent, if the SP value of the dispersed solvent and the solvent in which the binder resin or the like is dispersed are too far apart, the solvents are mixed well. It will not fit. For this reason, the presence state of the metal oxide becomes non-uniform, or the metal oxide dispersed in the solvent causes aggregation / precipitation.
The solvent used in the metal oxide solvent dispersion, and the solvent when the solvent dispersion is removed are, for example, when a metal oxide methyl ethyl ketone dispersion is mixed in an ethyl acetate dispersion. , The solvent used in the metal oxide dispersion is methyl ethyl ketone, and the solvent when the solvent dispersion is removed is ethyl acetate.
In addition, the SP value is determined by Yujiro Sakurauchi “Polymer Chemistry Class 2nd Edition” (published by Mitsui Publishing Co., Ltd.), more specifically, cohesive energy density (CED), that is, per unit volume of one molecule. Is a numerical value indicating the magnitude of the polarity per unit volume, and can be obtained experimentally from the following equation.

here
: Evaporation energy cal / mol
: Density g / cc
: Molar volume cc / mol
: Gram molecular weight g / mol
: Evaporation latent heat cal / mol
: Absolute temperature K
: Gas constant 1.987 cal / (mol * K)

Examples of the metal oxide dispersion include (organo) silica sol, titanium oxide sol, alumina oxide sol, tin oxide sol, tin oxide-antimony sol, zinc antimonate sol, ceria sol, antimony pentoxide sol, cerium oxide sol, niobium oxide sol, yttrium oxide sol. In addition, (organo) silica wet gel, titanium oxide wet gel, alumina oxide wet gel, tin oxide wet gel, tin oxide-antimony wet gel, zinc antimonate wet gel, which can be obtained by polycondensation of the metal oxide gel, Ceria wet gel, antimony pentoxide wet gel, cerium oxide wet gel, niobium oxide wet gel, yttrium oxide wet gel, and the like. Among these, organosilica sol is particularly preferable.
Moreover, since it is preferable that the metal oxide particles are uniformly and finely dispersed, it is desirable that the metal oxide be present as primary particles.
The present invention has been found and the present invention has been completed.

That is, according to the present invention, the following (1) to (18) are provided.
(1) At least, in the organic phase, a resin precursor containing a resin or monomer, a colorant, and one or more metal oxide solvent dispersions are dissolved or dispersed, and the solution or dispersion is dispersed in an aqueous medium. Then, the organic solvent and the aqueous medium are removed, and the toner is washed and dried. The metal oxide solvent dispersion is either a sol body or a wet gel and is diluted with water at an equal volume to pH 2. A toner for developing electrostatic charge, characterized in that the toner becomes .about.6.
(2) The SP value δ _{MS of the} solvent used in the metal oxide solvent dispersion and the SP value δ _PS of the solvent when the metal oxide solvent dispersion is removed are -2.0 <δ _MS − The electrostatic image developing toner according to (1), wherein δ _PS <4.0 is satisfied.
(3) The toner for developing an electrostatic charge image according to (1) or (2), wherein the metal oxide solvent dispersion has a metal oxide as primary particles in a solvent.
(4) The electrostatic image developing toner according to any one of (1) to (3), wherein the metal oxide solvent dispersion is an organosilica sol.
(5) In the organic phase, a resin or resin precursor having a site capable of reacting with a compound having an active hydrogen group, a colorant, and one or more metal oxide solvent dispersions are dissolved or dispersed, and the solution or The dispersion is dispersed in an aqueous medium, and the organic solvent and the aqueous medium are removed after or while reacting the compound having an active hydrogen group and the polymer having a site capable of reacting with the compound, The toner for developing an electrostatic charge image according to any one of (1) to (4), wherein the toner is a washed and dried toner.
(6) The toner for developing an electrostatic charge image according to any one of (1) to (5), wherein the toner particles have a volume average particle diameter of 3 to 7 μm.
(7) The ratio Dv / Dn between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner particles is 1.25 or less, and any one of (1) to (6) The toner for developing an electrostatic image according to the description.
(8) A resin or a resin precursor having a site capable of reacting with the compound having an active hydrogen group contains an unmodified polyester resin (ii) together with the modified polyester resin (i), ) And (ii) have a weight ratio of 5/95 to 25/75. The electrostatic image developing toner according to any one of (5) to (7),
(9) The electrostatic charge developing toner according to any one of (1) to (8), wherein the toner has a glass transition point (Tg) of 40 to 70 ° C.
(10) The toner for developing an electrostatic charge image according to any one of (1) to (9), wherein an outflow start temperature (Tfb) of the toner is 80 to 170 ° C.
(11) In the molecular weight distribution of the THF-soluble component of the polyester resin contained in the toner, a molecular weight peak exists at 1000 to 30000, the component of 30000 or more is 1 wt% or more, and the number average molecular weight is 2000. The toner for developing an electrostatic charge image according to any one of (1) to (10), which is ˜15000.
(12) In the molecular weight distribution of the THF-soluble component of the polyester resin contained in the toner, the component having a molecular weight of 1000 or less is 0.1 to 5.0 wt% (1) to (11) The toner for developing an electrostatic image according to any one of the above.
(13) The toner for developing an electrostatic charge image according to any one of (1) to (12), wherein the polyester resin contained in the toner has a THF-insoluble content of 1 to 15 wt%.
(14) The electrostatic image developing toner according to any one of (1) to (13), wherein the step of removing the solvent of the dispersion is performed at least under reduced pressure and / or heating conditions. .
(15) The electrostatic image developing toner according to any one of (1) to (14), wherein resin fine particles are added to the aqueous medium.
(16) The electrostatic image developing toner according to any one of (1) to (15), wherein the resin fine particles have an average particle size of 5 to 500 nm.
(17) The residual ratio of the resin fine particles to the toner particles is 0.5 to 5.0 wt% with respect to the toner particles as measured by a pyrolysis gas chromatograph mass spectrometer (1) to (1) 16) The electrostatic image developing toner according to any one of 16).
(18) The toner for developing an electrostatic charge image according to any one of (1) to (17), wherein the toner contains a wax as a release agent.

  The toner of the present invention is excellent in cleaning properties, and can form a high-quality image even if it is repeatedly used for a long time. Moreover, it can respond to a low-temperature fixing system and has good offset resistance.

The present invention is described in detail below.
(Metal oxide and metal oxide solvent dispersion)
As the metal oxide (solvent dispersion) of the present invention, for example, a hydrogel dispersion of a linear / ring-shaped metal oxide synthesized by a wet method (hydrothermal synthesis method, sol-gel method, etc.) is subjected to a hydrophobic treatment. There is a method of replacing the dispersion solvent with an arbitrary solvent.
Examples of metal oxides synthesized by a wet method include, for example, silicon dioxide (silica), titanium dioxide (titania), aluminum oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide Zinc oxide, tin oxide, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, and the like. Among these, silicon dioxide (silica), titanium dioxide (titania), aluminum oxide, particularly silica are preferable.

Further, as a method of hydrophobizing treatment, a surface treating agent is often used, and it is necessary to optimize the hydrophilicity / hydrophobicity balance on the surface of the metal oxide. For example, a coupling agent (Q) x-Si (P) y- (A) z as shown on the right (wherein Q represents a hydrolyzable group such as a halogen atom, an amino group or an alkoxy group, and A is an alkyl group) An organic functional group P represents —BOOC (R ′) C═CH ₂ , —BNHR ″ or —BNH ₂ (R ′ represents an alkyl group, R ″ represents an alkyl group or an aryl group) And B represents an alkylene group or an alkylene group containing —O—, —NH—, and —CO—).

  X and y are integers of 1 or more, z is an integer of 0 or more, and x + y + z = 4 is satisfied. Specifically, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, Vinyl triacetoxysilane, 2- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane [γ-glycidoxypropyltrimethoxysilane], 3-glycidoxypropylmethyldiethoxysilane [γ-glycidoxypropylmethyldimethoxysilane], 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane [γ-methacrylic] Roxypropyltrimethoxysilane], 3-methacryloxypropylmethyldiethoxysilane, 3- Tacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane [γ- (2-aminoethyl) aminopropylmethyldimethoxysilane], N-2 ( Aminoethyl) 3-aminopropyltrimethoxysilane [γ- (2-aminoethyl) aminopropyltrimethoxysilane], N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane [γ-anilinopropyltrimethoxysilane], N -(Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride [N-β- (N-vinylbenzylamino Noethyl) -γ-aminopropyltrimethoxysilane hydrochloride], octadecyldimethyl (3- (trimethoxysilyl) propyl) ammonium chloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyl Examples include dimethoxysilane, 3-mercaptopropyltrimethoxysilane (γ-mercaptopropyltrimethoxysilane), bis (triethoxysilylpropyl) tetrasulfide, and 3-isocyanatopropyltriethoxysilane.

  The effect can also be obtained by using a silylating agent, a silane coupling agent having an alkyl fluoride group, an organic titanate coupling agent, an aluminum coupling agent, or a silicone oil as a hydrophobizing agent.

  As a solvent for dispersing the metal oxide, for example, methanol, ethanol, 1-pentanol, n-butanol, isopropanol, 2-methoxyethanol, isobutanol, methyl ethyl ketone, methyl isobutyl ketone, 2-methyl tetrahydrofuran, cyclohexanone, formaldehyde, dioxane Dimethylformamide, ethyl acetate, n-butyl acetate, methyl methacrylate, diisopropyl ether, dibutyl ether, benzene, toluene and the like, and a solvent in which two or more of these are mixed can also be used.

It is desirable that the SP value δ _{MS of the} solvent used in the metal oxide solvent dispersion and the SP value δ _PS of the solvent when the metal oxide solvent dispersion is removed are as close as possible, δ _MS and δ _PS needs to satisfy at least −2.0 <δ _MS −δ _PS <4.0, and preferably −0.5 <δ _MS −δ _PS <1.0. Most preferably, it is in the range of −0.1 <δ _MS −δ _PS <0.3. For example, ethyl acetate and methyl ethyl ketone are most preferable as a solvent in which a resin or resin precursor and a colorant are dissolved or dispersed in ethyl acetate and the metal oxide added to the ethyl acetate solution [dispersion] is dispersed.
The metal oxide solvent dispersion itself used in the present invention is known and commercially available products such as MEK-ST and MEK-ST-UP (manufactured by Nissan Chemical Industries), which are organosilica sols, can be used.

  The primary particles in the solvent are desirable because the dispersibility of the metal oxide is good until the formation of toner particles and the effect of changing the toner shape is greater, which is desirable in terms of dispersibility, stability over time, and productivity. Therefore, it is more desirable to use organosilica sol as the metal oxide solvent dispersion. The organosilica sol refers to a state in which colloidal silica in which a part of silanol groups on the particle surface is silylated is dispersed in an organic solvent in a stable state or a dispersion thereof. JP-A-11-43319 can be referred to for a detailed description and production method of the organosilica sol.

The pH measurement of dilution with water is performed as follows. First, the metal oxide solvent dispersion is uniformly dispersed. If it is already a sol, it is easy to disperse, but if it is a wet gel, it is crushed with a disper as required. The mixture is diluted with an equal amount of ion-exchanged water and stirred for 3 minutes at a homomixer rotation of 2000, and the pH is measured.
By using a metal oxide solvent dispersion in which a metal oxide is dispersed in advance, such as a sol or wet gel, and a uniform dispersion is obtained by containing a solvent and an organic solvent or a polymerizable monomer A uniform dispersion of the metal oxide in the body results. When the liquid in which the metal oxide is uniformly dispersed comes into contact with the aqueous medium, the metal oxide particles are attracted to the interface of the aqueous medium. It becomes a state of covering. In this state, when the droplet viscosity increases due to organic solvent removal or polymerization reaction, and when the droplet volume decreases due to organic solvent removal, the internal organic solvent is removed while trying to maintain the shape near the surface. As a result, it has a generally sphere-like shape with a large unevenness on the surface, and is shaped like an umeboshi. In addition, since the metal oxide can be selectively brought out in the vicinity of the particle surface, the chargeability and fluidity are also improved.
The metal oxide solvent dispersion is preferably a resin or monomer-containing solution or dispersion in which a resin precursor or monomer-containing resin precursor / colorant is dissolved or dispersed before the metal oxide solvent dispersion is added. Alternatively, it is desirable that the resin precursor containing the monomer and the colorant are dispersed in advance. In addition, when the monomer is contained, it becomes difficult to obtain a liquid viscosity sufficient for the shape change only with the monomer. Therefore, when a monomer is used, it is desirable that the monomer is polymerized using a polymerization initiator or the like before the solvent removal step to form a polymer inside the droplet. The polymer (including the polymer obtained by polymerizing the monomer) contained in the droplets during the solvent removal step preferably has a weight average molecular weight of 1000 or more, more preferably 2000 or more.

The amount of metal oxide added may be 0.05 to 50 wt%, preferably 0.25 to 10 wt%, based on the toner. If it is smaller than this range, the absolute amount of metal oxide on the toner particle surface is insufficient, and it is difficult to obtain a sufficient improvement effect on the toner particle shape change. If it is larger than this range, the amount of metal oxide present on the toner particle surface is small. Since the amount becomes excessive and the metal oxide acts as a fixing inhibiting factor, the minimum fixing temperature increases, and the low-temperature fixing property is impaired.
Moreover, the average particle diameter of the primary particle of a metal oxide is 3-150 nm, More preferably, it is 5-100 nm, Most preferably, it is 8-25 nm. If it is smaller than this range, separation from the organic solvent to the aqueous medium tends to occur, and it is difficult to obtain a sufficient improvement effect on the toner particle shape change, and if it is larger than this range, an interval occurs between the metal oxides, The effect on the toner particle shape change is reduced. As the shape of the inorganic fine particles, spherical particles, irregular particles, linear types, network types, and the like can be used, and they are properly used depending on the dispersion state in the organic solvent.

These inorganic fine particles may be used alone or in combination of two or more.
The average particle diameter here is a number average particle diameter. The particle size of the inorganic fine particles used in the present invention can be measured by a particle size distribution measuring device using dynamic light scattering, for example, DLS-700 manufactured by Otsuka Electronics Co., Ltd. or Coulter N4 manufactured by Coulter Electronics. However, since it is difficult to dissociate the secondary agglomeration of the particles after the silicone oil treatment, it is preferable to directly determine the particle diameter from a photograph obtained by a scanning electron microscope or a transmission electron microscope. In this case, at least 100 or more inorganic fine particles are observed, and the average value of the major axis is obtained.

(Toner shape)
In the present invention, at least the circularity of the toner is 0.92 to 0.99, and it is necessary to be spherical particles having a plurality of depressions on the surface. If it is less than 0.92, the transferability and image quality are adversely affected, and if it exceeds 0.99, the cleaning property is deteriorated. Preferably, the toner has a circularity of 0.94 to 0.97 that sufficiently satisfies transferability, image quality, and cleaning properties. In addition, when measuring a plurality of indentations on the toner surface with a scanning electron microscope (SEM image), the major axis of the indentation is 1/2 or less of the toner particle diameter, and the major axis of the indentations on the particle surface is 1.0 to 5. It is desirable that the depth is 0.0 μm, and the depth of the indentation is at least 1/10 or more of the major axis, preferably 1/8 or more. Such a toner has a plurality of indentations on the surface to compensate for the difficulty of cleaning a spherical shape, and improves the transferability compared to the irregular toner, thereby achieving charging stability. In general, crushed toner and particles on irregularities produced by emulsion polymerization tend to accumulate silica in the recesses to improve fluidity, and when the additive is stirred and mixed with a high-speed mixer, it can be used to fix silica. However, it is difficult to fix and the silica fine particles are liberated, causing photocontamination contamination and adhesion to the carrier. However, this time, the dent on the toner surface is a dent with a gentle recess and the major axis is 1 μm or more. It is presumed that the accumulation and movement of the additive silica, which was easy to become, and the liberation in the immobilization of the silica do not occur.

(Urea-modified polyester)
In the present invention, a resin or resin precursor having a site capable of reacting with a compound having an active hydrogen group reacts with a compound having an active hydrogen group to become a toner binder resin. An example of such a resin or resin precursor is a modified polyester resin having a site capable of reacting with active hydrogen. As the toner binder resin, there is a resin obtained by reacting the modified polyester with a crosslinking agent and / or an extending agent having an active hydrogen group. As such a polyester, a polyester modified with a urea bond is preferable.

Examples of the polyester (i) modified with a urea bond include a reaction product of a polyester prepolymer (A) having an isocyanate group and an amine (B). Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group, which is further reacted with a polyisocyanate (3). Can be mentioned.
Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes 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 phenol compound (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 polyol (1-2) 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 polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (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 polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactams And a combination of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal 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 prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. 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.

  As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (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 the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines 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. Moreover, amines (B) can be used as a crosslinking agent and an extender.

  Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio 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] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low, and the hot offset resistance deteriorates. In the present invention, the polyester (i) modified with a urea bond 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 urea-modified polyester (i) of the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the urea-modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester 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 apparatus are deteriorated.

(Unmodified polyester)
In the present invention, not only the polyester (i) modified with a urea bond but also the polyester (ii) not modified may be contained as a toner binder 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 the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (i) above, 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. When (ii) is contained, the weight ratio of (i) to (ii) is usually 5/95 to 25/75, preferably 8/92 to 25/75, particularly preferably 8/92 to 22/78. is there. When 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.
Moreover, the peak molecular weight of (ii) is 1000-30000 normally, Preferably it is 1500-10000, More preferably, it is 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate.

  In the present invention, the glass transition point (Tg) of the toner is usually 40 to 70 ° C., preferably 50 to 65 ° C. If it is less than 40 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the urea-modified polyester resin, the dry toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester-based toners. As the storage elastic modulus of the toner, the temperature (TG ′) at which 10000 dyne / cm 2 is obtained at a measurement frequency of 20 Hz is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the toner, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or less, preferably 80 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or higher. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC. In addition, it is important that the outflow start temperature (Tfb) of the toner after the reaction is 80 to 170 ° C. as a condition for the toner to obtain both low-temperature fixability and offset resistance.

(Dv / Dn (ratio of volume average particle diameter / number average particle diameter))
In the present invention, the volume average particle size (Dv) of the toner is preferably 3 to 7 μm, and the ratio (Dv / Dn) to the number average particle size (Dn) is preferably 1.25 or less, more preferably 1.05 to 5. 1.20 dry toner is excellent in all of heat-resistant storage stability, low-temperature fixability, and hot-offset resistance, and particularly excellent in image gloss when used in a full-color copying machine, and in a two-component developer. Even if the balance of toner for a long period of time is performed, fluctuations in the toner particle diameter in the developer are reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. Even when used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner is filmed on the developing roller and the toner is made thin. The toner was not fused to a member such as a blade, and good and stable developability and images were obtained even when the developing device was used (stirred) for a long time.

  In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced, or the one-component development is performed. When used as an agent, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.

Further, these phenomena are the same for the toner having a fine powder content higher than the above range of the present invention.
On the contrary, when the toner particle diameter is larger than the above range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and the toner in the developer is balanced. In many cases, the fluctuation of the particle size of the particles becomes large. It was also clarified that the same is true when the volume average particle diameter / number average particle diameter (Dv / Dn) is larger than 1.25.
Further, when the volume average particle diameter / number average particle diameter (Dv / Dn) is smaller than 1.05, there are preferable aspects from the standpoint of stabilizing the behavior of the toner and uniformizing the charge amount, but the toner is sufficient. May not be able to be charged or the cleaning property may be deteriorated.

(Both fixing and transparency / gloss)
In addition to heat-resistant storage stability, low-temperature fixability, and offset resistance, toners are required to have characteristics such as color reproducibility, transparency, and glossiness, particularly in full-color toners. As a general method for achieving both low-temperature fixability and offset resistance, for example, a method using a binder resin having a wide molecular weight distribution, a high molecular weight component having a molecular weight of hundreds of thousands to several million, and a molecular weight of There is a method in which a resin having at least two molecular weight peaks of thousands to tens of thousands of low molecular weight components is mixed and used, and the mechanism of each component is separated. When the high molecular weight component has a cross-linked structure or is in a gel state, it is more effective for hot offset.

On the other hand, in order to achieve transparency, glossiness, etc., it is preferable that the molecular weight is as small as possible and the molecular weight distribution is sharp, and it is difficult to achieve both of these contradictory characteristics only by the above method. .
The toner of the present invention has a molecular weight peak at 1000 to 30000 in the molecular weight distribution of the THF-soluble polyester-based resin contained in the toner, a component of 30000 or more is 1 wt% or more, and a number average molecular weight Of 2000 to 15000, both low-temperature fixability and offset resistance are achieved. The reason why the content of the high molecular weight component is relatively small is that the modified group in the modified polyester (part of the bonded group other than the ester bond) has a strong cohesive force such as a hydrogen bond. Resin properties that cannot be controlled by molecular weight or degree of crosslinking can be controlled by the cohesive force of the modifying group.

Further, in the molecular weight distribution of the THF-soluble component of the polyester resin contained in the toner, it is preferable that the component having a molecular weight of 1000 or less is 0.1 to 5.0 wt%. When the component having a molecular weight of 1,000 or less is 5.0 wt% or more, it is not preferable for the offset property. When the component having a molecular weight of 1000 or less is 0.1 wt% or less, the cost increases due to problems in the production of raw materials and the manufacturing process.
Furthermore, when the high molecular weight component effective for hot offset, that is, the THF-insoluble content of the polyester-based resin contained in the toner is 1 to 15 wt%, sufficient transparency and glossiness are not hindered. Offset resistance can be imparted.

(Fine particles)
In the present invention, in order to obtain a toner particle size in which the chargeability and particle size distribution of toner particles are uniform, fine particles may be dispersed in an aqueous medium in which the toner composition is dispersed. The fine particles are present in an aqueous medium as a solid hardly soluble in water, and those having an average particle size of 0.01 to 1 μm are preferable.
Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. More preferably, tricalcium phosphate, calcium carbonate, colloidal titanium oxide, colloidal silica, hydroxyapatite and the like can also be used. In particular, hydroxyapatite synthesized by reacting sodium phosphate and calcium chloride in water under a basic condition is preferable. In addition, organic fine particles include microcrystals of low molecular weight organic compounds.

  The relationship between the size of the toner particles and the fine particles fixed on the surface thereof is such that when the particle size of the toner particles is R and the particle size of the fine particles is Rs, at least the relationship satisfies 5 ≦ R / Rs ≦ 2000. Preferably, it is desirable to satisfy 20 ≦ R / Rs ≦ 200. It has been found that when the relationship between the two is out of this range, the effect of controlling the particle size by the fine particles is remarkably reduced. Further, the amount of fine particles to be fixed on the surface of the resin particles should be selected according to the purpose in the range of 0.1 to 20 wt%, preferably 1 to 10 wt% with respect to the resin particles.

  From the viewpoint of particle size control, at least resin fine particles satisfying 5 ≦ Dv ≦ 500, desirably resin fine particles satisfying 50 ≦ Dv ≦ 200 (volume average particle size: Dv [nm]) are desirable. In order to control the particle size, it is required that the particle size distribution of the fine particles to be added be narrow (Dv / Dn of resin fine particles: less than 1.25). It is easy to be done.

  The resin fine particles are obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization or the like, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin, silicone resin, benzoguanamine resin, nylon resin Etc. As the resin fine particles, 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.

Examples of the vinyl resin include polystyrene copolymerized with a monomer having a carboxyl group such as methacrylic acid, a methacrylic acid ester and an acrylic acid ester copolymer. From the viewpoint of emulsifiability, it is preferable to use a surfactant having radical polymerizability as a reaction initiator.
The resin fine particles have a glass transition point (Tg) of 40 to 100 ° C. and a weight average molecular weight of 9000 to 200,000. As described above, the glass transition point (Tg) is less than 40 ° C. If the weight average molecular weight is less than 9,000, the storage stability of the toner deteriorates, and blocking occurs during storage and in the developing machine. When the glass transition point (Tg) is 100 ° C. or higher and / or the weight average molecular weight is 200,000 or higher, the resin fine particles inhibit the adhesiveness to the fixing paper, and the minimum fixing temperature increases.

It is necessary that the residual ratio of the resin fine particles with respect to the toner particles is 0.5 to 5.0 wt%. When the residual ratio is less than 0.5 wt%, the storage stability of the toner is deteriorated, and blocking occurs during storage and in the developing machine. When the residual amount is 5.0 wt% or more, the resin fine particles are not present. The exudation of the wax is obstructed, the effect of releasing the wax is not obtained, and the occurrence of offset is observed.
The residual rate of the resin fine particles can be measured by analyzing a substance caused by the resin fine particles, not by the toner particles, using a pyrolysis gas chromatograph mass spectrometer, and calculating from the peak area. The detector is preferably a mass spectrometer, but is not particularly limited.

(Release agent)
Further, a wax may be contained together with the toner binder and the colorant. Known waxes can be used as the wax of the present invention, such as polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. It is done. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18 -Octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability.
The content of wax in the toner is usually less than 40 wt%, preferably 3 to 30 wt%.

(Coloring agent)
As the colorant of the present invention, 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 , Fais red, parachlorol Nitroaniline 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, Tolujing 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 , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen 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, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithobon 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 used in the present invention can also be used as a resin colorant complex combined with a resin.
There are methods for producing resin colorant composites, such as dissolution in a solvent, dissolution / dispersion in a small amount of solvent or liquid polymer, high viscosity solution, stirring and shearing, etc., but the strongest method is available. Mixing and kneading in which force can be applied is more desirable. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

  A resin colorant composite (hereinafter referred to as a master batch) obtained by mixing and kneading can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shearing force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used.

The binder resin kneaded with the master batch includes styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and substituted polymers thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene. -Vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl Methyl ketone copolymer Styrene copolymers such as styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; 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, aliphatic fork Can be used alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. Further, by adding the modified polyester resin, or the modified polyester resin and the unmodified polyester resin, the dispersion of the colorant can be further strengthened.
The content of the colorant in the resin colorant complex is usually 80% by weight or less, preferably 30 to 60% by weight.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. All 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). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, 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 Co., Ltd.), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined uniquely by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. 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 main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they can be added directly when dissolved and dispersed in an organic solvent, or fixed on the toner surface after preparation of toner particles. May be.

(External additive)
As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m <2> / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5 wt% of the toner, and particularly preferably 0.01 to 2.0 wt%. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

Other polymer fine particles, for example, polycondensation systems such as polystyrene, methacrylic acid ester, acrylic acid ester copolymer, silicone resin, benzoguanamine resin, nylon obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, thermosetting Polymer particles made of a functional resin.
Such a fluidizing agent 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, silylating agents, silane coupling agents having a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
Further, it is more preferable that the inorganic fine particles used as the external additive are the same type as the inorganic fine particles added in the organic solvent.

  A cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium may be added. Examples of the cleaning property improver include fatty acids such as zinc stearate, calcium stearate, stearic acid, and the like. Mention may be made, for example, of polymer salts produced by soap-free emulsion polymerization of metal salts such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

(Production method)
The weight body added to the organic solvent can be produced by the following method. The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (3) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group. Further, (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester modified with a urea bond. When (3) is reacted and (A) and (B) are reacted, a solvent can be used as necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to the isocyanate (3), such as tetrahydrofuran (such as tetrahydrofuran). When polyester (ii) not modified with urea bond is used in combination, (ii) is produced in the same manner as polyester having a hydroxyl group, and this is dissolved in the solution after completion of the reaction of (i) and mixed. To do.
The dry toner of the present invention can be produced by the following method, but is not limited thereto.

(Toner production method in aqueous medium)
The aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.
Toner particles dissolve or disperse a resin precursor containing a resin or monomer, a colorant, and one or more metal oxide solvent dispersions in an organic phase, and the solution or dispersion is dissolved in an aqueous medium. After the dispersion, the organic solvent and the aqueous medium are removed, washed and dried.
Preferably, a resin or resin precursor having a site capable of reacting with a compound having an active hydrogen group, a colorant, and one or more metal oxide solvent dispersions are dissolved or dispersed in the organic phase, and the solution or After dispersing or dispersing the dispersion in an aqueous medium and reacting the compound having an active hydrogen group with a resin or resin precursor having a site capable of reacting with the compound, or while reacting, the organic solvent and the aqueous medium Remove, wash and dry to make. For example, a dispersion composed of a prepolymer (A) having an isocyanate group in an aqueous medium may be formed by reacting with (B), or a urea-modified polyester (i) produced in advance may be used. .

  As a method for stably forming a dispersion comprising urea-modified polyester (i) or prepolymer (A) in an aqueous medium, urea-modified polyester (i), prepolymer (A), or resin colorant is used in an aqueous medium. Examples thereof include a method of adding a toner raw material composition comprising a composite and dispersing the composition by shearing force. The prepolymer (A) and other toner compositions (hereinafter referred to as toner raw materials), a release agent, a charge control agent, an unmodified polyester resin, etc. may be mixed when forming a dispersion in an aqueous medium. However, it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner raw materials such as a release agent and a charge control agent are not necessarily mixed when particles are formed in an aqueous medium, and are added after particles are formed. May be. For example, after forming particles containing no charge control agent, the charge control agent can be immobilized on the toner surface by a known method.

  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. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. 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. Higher temperatures are preferred in that the dispersion composed of the urea-modified polyester (i), the prepolymer (A), and the resin colorant composite has a low viscosity and is easy to disperse.

  The amount of the aqueous medium used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts by weight of the toner composition containing the urea-modified polyester (i) and the prepolymer (A). If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  In the step of synthesizing the urea-modified polyester (i) and the prepolymer (A), the amine (B) may be added and reacted before the toner composition is dispersed in the aqueous medium, or may be dispersed in the aqueous medium. An amine (B) may be added later to cause a reaction from the particle interface. In this case, urea-modified polyester is preferentially produced on the surface of the manufactured toner, and a concentration gradient can be provided inside the particles.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and alkylamines as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in a liquid containing water Amine salts such as salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl N, amphoteric surfactants such as N- dimethyl ammonium betaine and the like.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6- C11) sodium oxy] -1-alkyl (C3-C4) sulfonate, sodium 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) Carboxylic acid and metal salt, perfluoroalkylcarboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl- N- (2hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned,

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-ll0, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF- 102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C 6 -C 10) sulfonamidopropyltrimethylammonium salt which right the fluoroalkyl group, Benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) ), Megafuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.) and the like.
Moreover, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite, etc. can be used as an inorganic compound dispersant which is hardly soluble in water.

  Further, 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 β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, 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, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, 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 imidazole, ethylene imine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

  Furthermore, in order to lower the viscosity of the toner composition, a solvent in which the urea-modified polyester (i) or the prepolymer (A) is soluble can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include 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 the solvent with respect to 100 weight part of prepolymers (A) is 0-300 weight part normally, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after elongation and / or crosslinking reaction.

  The elongation and / or cross-linking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. The reaction temperature is usually 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.

In order to remove the organic solvent from the obtained emulsified dispersion, a method can be employed in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely evaporated and removed. Alternatively, it is also possible to spray the emulsified dispersion in a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and to evaporate and remove the aqueous dispersant together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air streams heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used are generally used. Sufficient quality can be obtained with a short processing time such as spray dryer, belt dryer, rotary kiln.
When the particle size distribution at the time of emulsification dispersion is wide, and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.

In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying, but it is preferably performed in a liquid in terms of efficiency. The obtained unnecessary fine particles or coarse particles can be returned to the kneading step and used for forming particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

By mixing the resulting dried toner powder with dissimilar particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by giving mechanical impact force to the mixed powder By immobilizing and fusing on the surface, it is possible to prevent detachment of the foreign particles from the surface of the resulting composite particle.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier and the toner in the developer is 1 to 10 weights of toner with respect to 100 parts by weight of the carrier. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resin such as vinyl, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to this. Hereinafter, a part shows a weight part.
~ Creation of master batch ~

Production Example 1-1
1200 parts of water, 800 parts of carbon black and 1200 parts of styrene-butyl methacrylate copolymer were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, and then cooled by rolling. And then pulverized with a pulperizer to obtain [Masterbatch 1].
Production Example 1-2
1200 parts of water, 800 parts of Cu-phthalocyanine 15: 3, and 1200 parts of styrene-butyl methacrylate copolymer were mixed with a Henschel mixer (Mitsui Mining Co., Ltd.), and the mixture was kneaded at 150 ° C. for 30 minutes using two rolls. Thereafter, the product was rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 2].

-Creation of polymer particles-
Example 1
First, an aqueous medium is manufactured. After adding 360 parts by weight of a 0.1M Na3 PO4 aqueous solution to 600 parts by weight of ion-exchanged water and heating to 50 ° C., the mixture was stirred at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). While maintaining the stirring, 55 parts by weight of 1.0 M CaCl2 aqueous solution was gradually added thereto and cooled to 25 ° C., and then 180 parts of methyl ethyl ketone was added and stirred to prepare an aqueous medium.
Next, a dispersion containing a polymerizable monomer is prepared. 80 parts by weight of methyl ethyl ketone, 170 parts by weight of styrene, 30 parts by weight of n-butyl acrylate, 20 parts of [Masterbatch 1], 0.5 parts by weight of divinylbenzene, 2 parts by weight of metal salicylate, 20% MEK-ST (Nissan Chemical Industries) Manufactured: 20 parts of pH 4.6) was added at an equal dilution with water, and dissolved and dispersed uniformly at 8000 rpm using a TK homomixer. In this, 5 parts by weight of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a dispersion containing a polymerizable monomer.
The aqueous medium and the dispersion were charged into a 5 L three-necked flask equipped with a stirrer, a Dimroth condenser and a thermometer, and heated and stirred at 60 ° C. in an N 2 atmosphere to obtain a suspension. When the suspension was obtained, the temperature was raised to 60 ° C. in 2 hours, and after 4 hours, the temperature raising rate was 40 ° C./Hr. The temperature was raised to 70 ° C. The conversion rate of the monomer into the obtained polymer was confirmed by gas chromatography, and it was considered that the polymerization was completed when the monomer residual ratio became 1% or less. Methyl ethyl ketone was distilled off to obtain [Polymer particle dispersion 1].

~ Washing⇒Drying ~
[Polymer Particle Dispersion 1] 100 parts are cooled, hydrochloric acid is added to dissolve calcium phosphate, a) treatment is performed at 2000 rpm, b) the supernatant is removed, c) 120 parts of ion-exchanged water is added, and d) TK. The mixture was mixed with a homomixer (rotation speed: 12,000 rpm for 10 minutes), stirred and redispersed, and then centrifuged again. Filtration was performed after repeating a) to d) several times. The obtained cake was loosened, air-dried for one day and night, and then dried at 45 ° C. for 48 hours with a circulating drier, and sieved with a mesh of 75 μm to obtain [Toner 1].

(Example 2)
[Toner 2] was obtained in the same manner as in Example 1 except that [Masterbatch 1] in Example 1 was changed to [Masterbatch 2].

~ Synthesis of low molecular weight polyester ~
Production Example 3
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 319 parts bisphenol A propylene oxide 2-mole adduct, 449 parts bisphenol A ethylene oxide 2-mole adduct, 243 parts terephthalic acid, 53 parts adipic acid and dibutyl Add 2 parts of tin oxide, react for 8 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 7 parts of trimellitic anhydride to the reaction vessel at 180 ° C. under normal pressure. The mixture was reacted for 2 hours to obtain [Low molecular weight polyester]. [Low molecular weight polyester] had a number average molecular weight of 2000, a weight average molecular weight of 6600, Tg of 46 ° C., and an acid value of 1.3.

~ Creation of master batch ~
Production Example 1-3
1200 parts of water, 800 parts of carbon black and 1200 parts of [low molecular weight polyester] were mixed with a Henschel mixer (Mitsui Mining Co., Ltd.), the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled with a pulverizer. Grinding to obtain [Masterbatch 3].

Production Example 1-4
1200 parts of water, 800 parts of Cu-phthalocyanine 15: 3, and 1200 parts of [low molecular weight polyester] were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, and then rolled. The mixture was cooled and pulverized with a pulverizer to obtain [Masterbatch 4].

Production Example 1-5
1200 parts of water, C.I. I. 800 parts of Pigment yellow 155 and 1200 parts of [low molecular weight polyester] were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer. A master batch 5] was obtained.

Production Example 1-6
1200 parts of water, C.I. I. 800 parts of Pigment red 184 and 1200 parts of [low molecular weight polyester] were mixed with a Henschel mixer (manufactured by Mitsui Mining), the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer. A master batch 6] was obtained.

~ Synthesis of organic fine particle emulsion ~
Production Example 4
In a reaction vessel equipped with a stir bar and a thermometer, 680 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 69 parts of styrene, 110 parts of methacrylic acid, When 69 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the temperature in the system 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 dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate sodium salt) [fine particles Dispersion] was obtained. The volume average particle size of the [fine particle dispersion] measured by LA-920 [Laser diffraction / scattering flow rate distribution measuring device, manufactured by Horiba, Ltd.] was 0.11 μm. A part of the [fine particle dispersion] was dried to isolate the resin component. The resin content Tg was 150 ° C.

-Adjustment of aqueous phase-
Production Example 5
240 parts of water, 13 parts of [fine particle dispersion], 40 parts of 50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7): manufactured by Sanyo Chemical Industries, Ltd. and 25 parts of ethyl acetate were mixed and stirred. A liquid was obtained. This is referred to as [aqueous phase].

~ Creation of oil phase ~
Production Example 6-1
A container equipped with a stir bar and a thermometer was charged with 25 parts of synthetic ester wax WAX, 15 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industries), and 165 parts of ethyl acetate, and the temperature was raised to 80 ° C. with stirring. After maintaining at 80 ° C. for 5 hours, it was cooled to 30 ° C. over 1 hour. Next, 125 parts of [Masterbatch 3] were mixed in the container for 1 hour to obtain [Raw material solution 1].
[Raw Material Solution 1] 66 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. The pigment and WAX were dispersed under conditions of filling and 6 to 24 passes. Next, 130 parts of a 65 wt% ethyl acetate solution of [low molecular weight polyester], 10 parts of 20 wt% MEK-ST (manufactured by Nissan Chemical Industries, Ltd.) and 34 parts of ethyl acetate were added, and the mixture was passed through a bead mill under the above conditions for 3 passes. -WAX dispersion 1] was obtained. The solid content concentration of [Pigment / WAX Dispersion 1] (calculated from the weight after standing at 150 ° C. for 45 minutes) was 50%.

Example 3
~ Toner granulation ⇒ Toner conversion ~
In a container equipped with a TK homomixer, 150 parts of [Aqueous Phase] are added and stirred at 13,000 rpm, and 100 parts of [Pigment / WAX Dispersion 1] is placed in the container and mixed for 20 minutes. An emulsified slurry 1] was obtained.
[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 60 ° C. for 10 hours to obtain [Dispersion slurry 1].
[Dispersion Slurry 1] After 100 parts under reduced pressure,
a): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
b): 20 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of a), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
c): 20 parts of 10% hydrochloric acid was added to the filter cake of b), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
d): 300 parts of ion-exchanged water was added to the filter cake of c), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. The obtained cake was blown off and dried at 45 ° C. for 48 hours in a circulating air dryer, and sieved with a mesh of 75 μm to obtain [Toner 3].

Production Example 6-2
[Pigment / WAX dispersion 2] was prepared in the same manner as in Production Example 6-1 except that [Masterbatch 3] in Production Example 6-1 was changed to [Masterbatch 4].

Production Example 6-3
[Pigment / WAX dispersion 3] was prepared in the same manner as in Production Example 6-1 except that [Master batch 3] in Production example 6-1 was changed to [Master batch 5].

Production Example 6-4
[Pigment / WAX dispersion 4] was prepared in the same manner as in Production Example 6-1, except that [Master batch 3] in Production example 6-1 was changed to [Master batch 6].

Example 4
[Toner 4] was obtained in the same manner as in Example 3, except that [Pigment / WAX Dispersion 1] in Example 3 was changed to [Pigment / WAX Dispersion 2].

(Example 5)
[Toner 5] was obtained in the same manner as in Example 3, except that [Pigment / WAX Dispersion 1] in Example 3 was changed to [Pigment / WAX Dispersion 3].

(Example 6)
[Toner 6] was obtained in the same manner as in Example 3, except that [Pigment / WAX Dispersion 1] in Example 3 was changed to [Pigment / WAX Dispersion 4].

~ Synthesis of intermediate polyester and prepolymer ~
Production Example 7
In a reaction vessel equipped with a condenser, 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, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain an [intermediate polyester]. The [intermediate polyester] had a number average molecular weight of 2100, a weight average molecular weight of 9600, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer] was obtained. [Prepolymer] had a free isocyanate weight% of 1.60%. The solid content concentration of [Prepolymer] (calculated from the weight after standing at 150 ° C. for 45 minutes) was 50%.

~ Synthesis of ketimine ~
Production Example 8
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]. The amine value of [ketimine compound] was 423.

~ Creation of oil phase ~
Production Example 6-5
A container equipped with a stir bar and a thermometer was charged with 50 parts of synthetic ester wax WAX, 30 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industries), 330 parts of ethyl acetate, and heated to 80 ° C. with stirring. After maintaining at 80 ° C. for 5 hours, it was cooled to 30 ° C. over 1 hour. Next, 250 parts of [Masterbatch 3] were mixed in the container for 1 hour to obtain [Raw material solution 2].
[Raw material solution 2] 132 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80% by volume. The pigment and WAX were dispersed under conditions of filling and 6 to 24 passes. Next, 200 parts of a 70 wt% ethyl acetate solution of [low molecular weight polyester] and 80 parts of ethyl acetate were added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 5]. The solid content concentration of [Pigment / WAX Dispersion 5] (calculated from the weight after standing at 150 ° C. for 45 minutes) was 50%.

(Example 7)
~ Toner granulation ⇒ Toner conversion ~
[Pigment / WAX dispersion 5] 206 parts, [Prepolymer] 30 parts, 20 wt% MEK-ST 10 parts, [Ketimine compound] 2.8 parts are put in a container, and TK homomixer (manufactured by Tokushu Kika) 5 After mixing at 000 rpm for 1 minute, 360 parts of [aqueous phase] was added to the container and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsion slurry 2]. [Emulsion slurry 2] 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 performed at 50 ° C. for 8 hours to obtain [Dispersion slurry 2].
[Dispersion slurry 2] After filtering 100 parts under reduced pressure,
a): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
b): 20 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of a), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
c): 20 parts of 10% hydrochloric acid was added to the filter cake of b), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
d): 300 parts of ion-exchanged water was added to the filter cake of c), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. The obtained cake was blown off and dried at 45 ° C. for 48 hours with a circulating drier, and sieved with a mesh of 75 μm mesh [Toner 7].

Production Example 6-6
[Pigment / WAX dispersion 6] was prepared in the same manner as in Production Example 6-5, except that [Masterbatch 3] in Production Example 6-5 was changed to [Masterbatch 4].

Production Example 6-7
[Pigment / WAX dispersion 7] was prepared in the same manner as in Production Example 6-7, except that [Masterbatch 3] in Production Example 6-7 was changed to [Masterbatch 5].

Production Example 6-8
[Pigment / WAX dispersion 8] was prepared in the same manner as in Production Example 6-8, except that [Masterbatch 3] in Production Example 6-8 was changed to [Masterbatch 6].

(Example 8)
[Toner 8] was obtained in the same manner as in Example 7, except that [Pigment / WAX Dispersion 5] in Example 7 was changed to [Pigment / WAX Dispersion 6].

Example 9
[Toner 9] was obtained in the same manner as in Example 7, except that [Pigment / WAX Dispersion 5] in Example 7 was changed to [Pigment / WAX Dispersion 7].

(Example 10)
[Toner 10] was obtained in the same manner as in Example 7, except that [Pigment / WAX Dispersion 5] in Example 7 was changed to [Pigment / WAX Dispersion 8].

(Example 11)
Except for changing 10 parts of 20 wt% MEK-ST of Example 7 to 10 parts of 20 wt% MEK-ST-UP (manufactured by Nissan Chemical Industries, Ltd .: pH 4.9 by equal dilution with water), the same as Example 7 [Toner 11] was obtained.

(Example 12)
[Toner 12] was obtained in the same manner as in Example 8, except that 10 parts of 20 wt% MEK-ST in Example 8 was changed to 10 parts of 20 wt% MEK-ST-UP.

(Example 13)
[Toner 13] was obtained in the same manner as in Example 9, except that 10 parts of 20 wt% MEK-ST in Example 9 was changed to 10 parts of 20 wt% MEK-ST-UP.

(Example 14)
[Toner 14] was obtained in the same manner as in Example 10, except that 10 parts of 20 wt% MEK-ST in Example 10 were changed to 10 parts in 20 wt% MEK-ST-UP.

(Comparative Example 1)
[Toner 15] was obtained in the same manner as in Example 1 except that 10 parts of 20 wt% MEK-ST in Example 1 was changed to 6 parts of ethyl acetate.

(Comparative Example 2)
100 parts of 20 wt% MEK-ST was heated to evaporate MEK to obtain a white powdered solid. This was again diluted with 80 parts of MEK and dispersed with a bead mill for 24 hours to obtain white [MEK-ST redispersed liquid]. It was confirmed that the [MEK-ST redispersion] was allowed to settle to leave a white solid.
[Toner 16] was obtained in the same manner as in Example 1 except that 10 parts of 20 wt% MEK-ST (manufactured by Nissan Chemical Industries, Ltd.) in Example 1 was changed to 10 parts of [MEK-ST redispersed liquid].

(Evaluation item)
(1) Particle Size The particle size of the toner was measured with a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. The volume average particle size and the number average particle size were determined by the particle size measuring instrument.
(2) Circularity The average circularity was measured by a flow type particle image analyzer FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.). A surfactant, preferably alkylbenzene sulfonate, is added in an amount of 0.1 to 0.5 ml as a dispersant in 100 to 150 ml of water from which impure solids have been removed in advance. Add about 5g. The suspension in which the sample was dispersed was subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the shape and distribution of the toner were measured with the above apparatus with the dispersion concentration being 3000 to 10,000 / μl.

(3) Particles whose particle diameter and indentation can be measured from 20 screens obtained by observing the surface of the shaped toner particles with a scanning electron microscope S-2700 SEM (Hitachi SEM image) at a magnification of 5000 times the SEM image Was selected, and the major axis of the indentation and the depth of the indentation / the major axis of the indentation (hereinafter referred to as the indentation depth ratio) were measured. The major axis of the dent represents the average of the observed dents in μm, and the dent depth ratio was evaluated in the following three steps for the deepest dent in one toner particle.
○: When averaged between particles, the depth of the depression is 1/8 or more of the major axis. Δ ... When averaged between the particles, the depth of the depression is 1/10 to 1/8 of the major axis.
X: When averaged between particles, the depth of the indentation is less than 1/10 of the major axis

(4) Fixability Using Ricoh's imgio Neo 450, it is 1.0 ± 0.1 mg as a solid image on plain paper and cardboard transfer paper (Ricoh type 6200 and NBS Ricoh copy printing paper <135>). The toner was adjusted so that the toner of / cm 2 was developed, and the temperature of the fixing belt was adjusted to be variable, and the temperature at which no offset occurred on plain paper and the fixing lower limit temperature on thick paper were measured. The minimum fixing temperature was determined as the fixing minimum temperature at which the remaining ratio of the image density after rubbing the obtained fixed image with a pad was 75% or more.

(5) Charge amount 6 g of the developer was weighed, charged into a metal cylinder that could be sealed, and blown to obtain the charge amount. The toner concentration was adjusted to 4.5 to 5.5 wt%.
(6) Cleanability Transfer residual toner on the photosensitive member that has passed through the cleaning process is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Co., Ltd.), and measured with a Macbeth reflection densitometer RD514. Those with 0.01 or less were evaluated as ◯ (good), and those exceeding it were evaluated as x (bad).

(Evaluation results)

Claims (18)

At least a resin precursor containing a resin or monomer, a colorant, and one or more metal oxide solvent dispersions are dissolved or dispersed in an organic phase, and the solution or dispersion is dispersed in an aqueous medium. Thereafter, the organic solvent and the aqueous medium are removed, and the toner is washed and dried. The metal oxide solvent dispersion is either a sol body or a wet gel, and is diluted to 1 to 2 with water to a pH of 2 to 6. An electrostatic charge developing toner characterized by comprising: The SP value δ _{MS of the} solvent used in the metal oxide solvent dispersion and the SP value δ _PS of the solvent when the metal oxide solvent dispersion is removed are −2.0 <δ _MS −δ _PS < The electrostatic image developing toner according to claim 1, wherein the toner satisfies 4.0. 3. The electrostatic image developing toner according to claim 1, wherein the metal oxide solvent dispersion contains metal oxide as primary particles in a solvent. 4. The electrostatic image developing toner according to claim 1, wherein the metal oxide solvent dispersion is an organosilica sol. In an organic phase, a resin or resin precursor having a site capable of reacting with a compound having an active hydrogen group, a colorant, and one or more metal oxide solvent dispersions are dissolved or dispersed, and the solution or dispersion is After dispersing in an aqueous medium and reacting the compound having the active hydrogen group with a resin or resin precursor having a site capable of reacting with the compound, or while reacting, the organic solvent and the aqueous medium are removed. The electrostatic image developing toner according to claim 1, wherein the toner is a washed, dried toner. 6. The electrostatic image developing toner according to claim 1, wherein the toner particles have a volume average particle diameter of 3 to 7 [mu] m. The electrostatic charge image according to claim 1, wherein a ratio Dv / Dn of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner particles is 1.25 or less. Development toner. The resin or resin precursor having a site capable of reacting with the compound having an active hydrogen group contains, together with the modified polyester resin (i), an unmodified polyester resin (ii), and (i) and (ii) 8) The toner for developing an electrostatic charge image according to any one of claims 5 to 7, wherein the weight ratio is 5/95 to 25/75. The toner for electrostatic charge development according to any one of claims 1 to 8, wherein the toner has a glass transition point (Tg) of 40 to 70 ° C. The toner for developing an electrostatic charge image according to any one of claims 1 to 9, wherein an outflow start temperature (Tfb) of the toner is 80 to 170 ° C. In the molecular weight distribution of the THF-soluble component of the polyester resin contained in the toner, a molecular weight peak exists at 1000 to 30000, a component of 30000 or more is 1 wt% or more, and a number average molecular weight is 2000 to 15000. The toner for developing an electrostatic charge image according to claim 1, wherein the toner is for developing an electrostatic image. 12. The component according to claim 1, wherein a component having a molecular weight of 1,000 or less is 0.1 to 5.0 wt% in a molecular weight distribution of a THF-soluble component of the polyester resin contained in the toner. The toner for developing an electrostatic image according to the description. The toner for developing an electrostatic charge image according to any one of claims 1 to 12, wherein the polyester resin contained in the toner has a THF insoluble content of 1 to 15 wt%. The toner for developing an electrostatic charge image according to any one of claims 1 to 13, wherein the step of removing the solvent of the dispersion is performed at least under reduced pressure and / or heating conditions. The electrostatic image developing toner according to claim 1, wherein resin fine particles are added to the aqueous medium. 16. The electrostatic image developing toner according to claim 1, wherein the resin fine particles have an average particle size of 5 to 500 nm. The residual ratio of the resin fine particles to toner particles is 0.5 to 5.0 wt% with respect to the toner particles as measured by a pyrolysis gas chromatograph mass spectrometer. The toner for developing an electrostatic charge image according to 1. 18. The electrostatic image developing toner according to claim 1, wherein the toner contains a wax as a release agent.