JP4191627B2 - Toner and developer for developing electrostatic image - Google Patents

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 image (latent image) is formed on a latent image carrier (also referred to as a photoconductor), and then the latent image is developed with toner to visualize the toner image. Is forming. The toner image on the photoreceptor thus formed 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 the selection of the toner material is limited. For example, since the composition obtained by melt mixing must be capable of being pulverized and classified by an economically usable device, the composition obtained by melt mixing must be sufficiently brittle. Absent. Therefore, when the composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed. However, in order to obtain a copy image with good resolution and gradation, the particle size may be Since a limited range is required, for example, fine powder having a particle size of 5 μm or less and coarse powder having a particle size of 20 μm or more must be removed by classification, resulting in a disadvantage that 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 irregularly shaped toner produced 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. Since the adhesion force to the carrier is different, the ease of development is also different, and furthermore, the toner having different particle diameters is also different in the ease of development because the charge amount of one toner particle is different. Due to these differences, easily developable toner is selectively developed, and toner that is difficult to develop remains in the developing device, and developability changes with time.
Similarly, in transfer to a transfer material such as 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, when a resin imparted with elasticity by a high molecular weight component and slightly pulverized resin is combined with a brittle wax such as polypropylene, the toner surface is exposed to a large amount of release agent.
The exposure of the release agent is advantageous for releasability at the time of fixing and cleaning of the toner remaining on the latent image carrier after transfer. However, since the fluidizing agent on the toner surface moves easily by mechanical force, This easily causes wax contamination of the roll, the photoconductor, and the carrier, leading to a decrease in the reliability of the image forming apparatus.

In recent years, in order to overcome the problems in these pulverization methods, 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 particles remain on the image carrier. It becomes difficult to scrape off the toner with a blade, and there is a problem that a systematic problem that the developing density cannot be controlled due to the occurrence of defective cleaning or the influence of the toner remaining on the photoconductor after the transfer process occurs.

In an image forming method in which a toner image formed on a latent image carrier is primarily transferred onto an intermediate transfer member and then secondarily transferred onto a transfer material, the shape factor SF-1 is 110 <SF-1 There has been proposed a technique for improving the cleaning of transfer residual toner on a latent image carrier using toner of ≦ 180 or less (see, for example, Patent Document 1).
Further, a technique has been proposed in which resin fine particles obtained by an emulsion polymerization method are associated to obtain irregular toner particles (see, for example, Patent Document 2).
However, the toner particles obtained by the emulsion polymerization method have a large amount of surfactant remaining not only on the surface but also inside the particles even after the water washing step, impairing the environmental stability of toner charging, and the charge amount distribution. The background of the obtained image becomes poor. Further, the remaining surfactant contaminates the photosensitive member, the charging roller, the developing roller, and the like, and the original charging ability cannot be exhibited.
In addition, the following problems arise 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 is sufficiently improved. In addition, since resin particles, release agent particles, colorant particles and the like are randomly fused to constitute toner particles, the composition (content ratio of constituent components) and configuration among the obtained toner particles Variations in the molecular weight and the like of the resin occur, and as a result, the surface characteristics differ between the toner particles, and a stable image cannot be formed over a long period of time.

In addition, a method for producing a toner by a suspension polymerization method has been proposed (see, for example, Patent Documents 3 and 4).
In the case of the suspension polymerization method, it is necessary to adjust the particles to an appropriate size in the suspended state. I can't make it. 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. There is a problem of causing uneven distribution and causing the problem of toner charging instability.

Further, in an image forming method in which a two-component developing device having at least development, transfer, and cleaning means is used to make an image appear with a developer via a developing carrier and is transferred to a transfer material to obtain an image. There has been proposed a technique characterized by using a developer containing toner particles that are uneven in toner particles (see, for example, Patent Document 5).
The toner having a concavo-convex shape obtained by this technique is a toner having a convex portion on a projected image. In a two-component developer using a carrier, the toner convex portion causes a change in shape due to stress due to stirring. As a result, the cleaning performance is also lowered.
In addition, when the suspension polymerization method is used, residual components of styrene monomer and acrylic monomer are included and left as an environmental problem. In addition, since WAX is included, fluidity and adhesion to the photoreceptor are reduced. However, in the toner using the pulverization method, the wax that is a release agent is present in the particle interface state. In some cases, the toner is encapsulated, so that the toner surface is less likely to bleed out, resulting in a layer structure with poor fixing efficiency, and toner that is disadvantageous to power consumption.
In this case, if the amount of WAX is increased in order to improve the fixing property or the dispersed particle size of WAX is increased, the transparency of the color toner is further deteriorated, so that it becomes difficult to use it 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, as well as suspension polymerization. In the emulsion polymerization method, styrene monomer is completely removed. It is difficult to remove water, emulsifiers, and dispersants, and the issues are becoming increasingly serious as environmental problems have been highlighted in recent years.
In addition, when the shape is made uneven, the silica adhering to the concave portion added as a fluidizing agent weakens, and the silica moves to the concave portion during use. When the developer is used for a long time, the silica is detached and photosensitive. Problems of body contamination and adhesion to the fixing roller are likely to occur.
In addition, in the dissolution suspension method, there is an advantage that a polyester resin that enables low-temperature fixing can be used. However, in order to achieve oil-less fixing, it is necessary to control the polymer to widen the mold release width. Since a high molecular weight component is added in the process of dissolving or dispersing the colorant in the solvent, there is a problem that the viscosity of the liquid is increased and a problem in productivity is likely to occur, but it is not yet solved. is there.
In addition, a technique has been proposed in which the toner surface shape is made spherical and uneven by using the dissolution suspension method to improve the cleaning property. However, the charging stability is improved because the toner becomes irregularly shaped with no regularity. In addition, a high molecular weight design for ensuring basic durability and releasability has not been achieved, and satisfactory quality has not been obtained (for example, see Patent Document 6).

  In addition, in the process where polyaddition reaction and solvent removal are performed under granulation, the temperature of the composition and the composition liquid, the solvent removal conditions, etc. are controlled to cause a partial internal pressure imbalance phenomenon in the toner particles. Although a technique to gently form dents on the toner particle surface has been proposed, it is necessary to finely set the temperature, solvent evaporation speed, liquid stirring speed, etc. during solvent removal, which is uniform and stable as the production scale increases. The shape change is less likely to occur (see, for example, Patent Document 7).

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

In view of the above circumstances, an object of the present invention is to provide an electrostatic charge image developing toner (simply a toner) that can improve the cleaning property and can form an image with an appropriate image density and extremely low background stain even when used repeatedly for a long time. Also providing a developer.
Another object of the present invention is to provide an electrostatic charge image developing toner having a sharp charge amount distribution and capable of forming a high-quality image without contamination of the charging device, developing device, photoconductor, and intermediate transfer member with the developer. And providing a developer.
Another object of the present invention is to provide a toner and a developer for developing an electrostatic charge image that are compatible with a low-temperature fixing system, have good offset resistance, and do not contaminate the fixing device and the image.
It is another object of the present invention to provide an electrophotographic developing apparatus using these electrostatic charge image developing toner and developer.

  As a result of intensive studies to solve such problems, the present inventors have dissolved or dispersed a polymer, a colorant, a release agent and an inorganic additive in at least an organic solvent, and the solution or dispersion liquid. After the organic solvent is dispersed in the aqueous medium, the organic solvent is removed, washed, and dried, and the inorganic additive includes two or more rigid parts and a connecting part that connects the rigid parts. It has been found that by using such a toner, it is possible to improve the cleaning property, and to obtain a toner base with an appropriate image density and little background stain even when repeatedly used for a long period of time.

The inorganic additive used in the present invention is composed of two or more rigid parts and a connecting part that connects the rigid parts.
The inorganic additive means an inorganic compound mainly composed of an inorganic compound, for example, a metal or a metal oxide, a surface or the like modified or coated with an organic compound or an organic polymer, and a chemical treatment. The thing etc. which etc. were given are included.
The rigid part means a particulate part composed of an inorganic compound, and the connecting part means a part that firmly connects the rigid parts by physical bonds or chemical bonds.
For example, when the rigid body portions are directly connected to each other to form a constricted state in which the diameter is smaller than the diameter of the rigid body portions, as shown in FIG. The case where it is connected in a rosary shape by chain-like molecules as shown in FIG. 5 and the case where the rigid body part is maintained by the graft-like chain are included. The chain molecule may be an organic polymer or an inorganic compound.
As a suitable example, as shown in FIG. 1, an inorganic compound in which a rigid body part and a connecting part are formed in a gourd shape can be mentioned.
However, a weakly bonded state, such as agglomeration due to aggregation or contact by van der Waals force, which is dissociated by, for example, ultrasonic waves is not included in the connecting portion in the present invention.

When an appropriate amount of an inorganic additive having a rigid part is added to an organic solvent, the toner particles when the organic solvent is removed after being dispersed and dissolved in an aqueous solvent are generally spherical but have large irregularities on the surface. It was confirmed that it became a shape like this.
The reason can be considered as follows.
Since the entire inorganic additive is attracted to the interface of the aqueous medium by the rigid body portion containing the inorganic metal atom, the inorganic additive covers the vicinity of the surface of the toner particles during dispersion / dissolution. However, since the rigid parts are connected to each other, it is difficult to detach from the aqueous medium, and the inorganic additive is sterically entangled between molecules, so that the detachment to the aqueous medium is less likely to occur. For this reason, the state in which the inorganic additive covers the vicinity of the surface of the toner particles is maintained. 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. It is inferred that it will be in shape.

Even when a simple inorganic fine particle having two or more rigid portions not connected to each other is added to an organic solvent, the manufactured toner particles are spherical without forming irregularities on the surface.
When inorganic fine particles are added to an organic solvent to be dispersed in an aqueous medium, the inorganic fine particles added at the time of dispersion are attracted to the interface of the aqueous medium and cover the vicinity of the surface of the toner particles, like the inorganic additive. .
However, since the inorganic fine particles exist as single particles, they are easily detached from the aqueous medium. Assuming that most of the inorganic fine particles dispersed / dissolved in the organic solvent are desorbed to the aqueous medium, but assuming that some of the inorganic fine particles remain in the organic solvent, the inorganic fine particles are used excessively. However, some of the remaining inorganic fine particles cause secondary aggregation in an approximately spherical shape in the organic solvent, making it difficult to obtain an effect commensurate with the amount added.

Examples of the inorganic metal contained in the inorganic additive include silicon, titanium, aluminum, zinc, magnesium, cerium, iron, copper, tin, and the like.
Examples of the inorganic fine particles include silicon dioxide (silica), titanium dioxide (titania), aluminum oxide, zinc oxide, magnesium oxide, cerium oxide, iron oxide, copper oxide, and tin oxide.
In view of hydrophilicity and dispersibility in an organic solvent by mixing an organic solvent to which inorganic fine particles are added and an aqueous medium, the inorganic additive preferably contains silica, more preferably inorganic fine particles, particularly silica. An organosilica sol having a rigid body resembling particles and more preferably bonded to each other is desired.

When a tertiary or quaternary amine is used for such an inorganic additive, a hydroxyl group derived from an inorganic metal (silanol group in silica) reacts with the amine to form a silanolamine salt, and the rigid body becomes more hydrophobic. .
However, since primary and secondary amines may cause undesirable chemical reactions other than hydrophobization, it is preferable to use tertiary or higher amines. In particular, a compound that does not become a volatile component near the fixing temperature is preferable in consideration of addition to the toner.
The present invention has been found and the present invention has been completed.

That is, the above-mentioned problem is (1) of the present invention “at least, a polymer, a colorant, a release agent and one or more inorganic additives are dissolved and / or dispersed in an organic solvent, Or a toner prepared by dispersing the dispersion in an aqueous medium and then removing the organic solvent, washing and drying, wherein the inorganic additive is between two or more rigid parts and the rigid parts. An electrostatic charge developing toner characterized by comprising a connecting portion for connecting
(2) “The toner for developing an electrostatic charge image according to (1) above, wherein the inorganic additive contains a silica composition”,
(3) “Toner for developing electrostatic image according to item (1) or (2), wherein the inorganic additive is an organosilica sol”,
( 4 ) "A polymer or a colorant, a release agent, and hydrophobic treated inorganic fine particles having a site capable of reacting with an active hydrogen group-containing compound are dissolved or dispersed in an organic solvent. Prepared by dispersing the organic solvent in an aqueous medium and reacting the polymer having a site capable of reacting with the compound having an active hydrogen group, or by reacting the polymer, washing and drying. The electrostatic image developing toner according to any one of (1) to ( 3 ) above,
( 5 ) "The toner for developing an electrostatic charge image according to any one of (1) to ( 4 ) above, wherein the toner particles have a volume average particle diameter of 3 to 7 µm",
(6) "the said first (1) and a ratio Dv / Dn of the volume average particle diameter of the toner particles (Dv) to the number average particle size (Dn) of is 1.25 or less claim to the (5 The toner for developing an electrostatic image according to any one of items 1),
( 7 ) "The polymer having a site capable of reacting with the compound having an active hydrogen group contains the polyester resin (ii) not modified together with the modified polyester resin (i), and (i) and ( The toner for developing an electrostatic charge image according to any one of ( 4 ) to ( 6 ), wherein the weight ratio of ii) is 5/95 to 25/75 ”,
( 8 ) “The electrostatic charge developing toner according to any one of (1) to ( 7 ) above, wherein the toner has a glass transition point (Tg) of 40 to 70 ° C.”,
( 9 ) "The electrostatic charge image developing toner according to any one of (1) to ( 8 ) above, wherein the toner flow start temperature (Tfb) is 80 to 170 ° C") ,
( 10 ) "In the molecular weight distribution of the THF soluble content of the polyester resin contained in the toner, the molecular weight peak is 1000 to 30000, the component of 30000 or more is 1 wt% or more, and the number average molecular weight is 2000 to 15000. The electrostatic image developing toner according to any one of (1) to ( 9 ), wherein:
( 11 ) "Item (1) above, wherein the component having a molecular weight of 1000 or less is 0.1 to 5.0 wt% in the molecular weight distribution of the THF-soluble component of the polyester resin contained in the toner. Thru | or the toner for electrostatic image development in any one of ( 10 ) term | claims,
( 12 ) The electrostatic charge according to any one of (1) to ( 11 ), wherein the polyester resin contained in the toner has a THF-insoluble content of 1 to 15 wt%. Image developing toner ",
( 13 ) The method according to any one of (1) to ( 12 ), wherein the step of removing the solvent of the dispersion is performed at least under reduced pressure and / or heating conditions. Toner for developing electrostatic image ",
( 14 ) "The electrostatic image developing toner according to any one of items (1) to ( 13 ), wherein resin fine particles are added to the aqueous medium",
(15) "the said first (15) toner according to claim, wherein the average particle diameter of the resin fine particles are 5~500nm"
(16) "residual ratio to the toner particles of the resin particles, as measured by pyrolysis gas chromatograph mass spectrometer, the first (14, which is a 0.5 to 5.0% with respect to the toner particles Or the electrostatic charge image developing toner according to item ( 15 ),
( 17 ) “Toner for electrostatic image development according to any one of items (1) to ( 16 ), wherein the toner contains a wax as a release agent”.
Further, the above-mentioned object is achieved by ( 18 ) “Developer comprising toner for developing electrostatic image and carrier according to any one of (1) to ( 17 )” of the present invention.
Further, the above-described problem is that the electrostatic charge image developing toner according to any one of (19) and (1) to ( 17 ) of the present invention, or the developer according to the above ( 18 ). This is achieved by a toner container characterized by being housed.
In addition, the above-mentioned problems include ( 20 ) “developing means for developing at least a latent image carrier and a latent image formed on the latent image carrier with a toner for developing an electrostatic image. The toner storage unit according to any one of Items (1) to ( 17 ) stores the electrostatic image developing toner according to any one of Items (1) to ( 17 ) or the developer according to Item (19). Achieved by a "process cartridge".
Further, the above-mentioned problems are solved by ( 21 ) “Latent image carrier, developing means for developing a latent image formed on the latent image carrier with toner for developing an electrostatic image, and recording the developed toner image. An electrophotographic image forming comprising at least a transfer means for transferring to a medium and a fixing means for fixing a toner image transferred onto a recording medium, wherein the toner container described in the item ( 19 ) is mounted. apparatus",
( 22 ) “At least a transfer means for transferring the developed toner image to the recording medium and a fixing means for fixing the toner image transferred onto the recording medium, and the process cartridge according to the item ( 20 ) is mounted. This is achieved by an electrophotographic image forming apparatus characterized by the above.
Further, the above-mentioned problems are solved by ( 23 ) “Latent image carrier of the present invention, developing means for developing a latent image formed on the latent image carrier with electrophotographic toner, and developing the toner image on a recording medium. The latent image formed on the latent image carrier is transferred to a transfer unit for transferring and an image forming apparatus having at least a fixing unit for fixing the toner image transferred onto the recording medium. ( 17 ) An electrophotographic image forming method comprising developing with the electrophotographic toner according to any one of ( 17 ) or the developer according to ( 18 ).

  According to the present invention, it is possible to improve the cleaning property, provide a developer with an appropriate image density and extremely low background stain even when repeatedly used for a long period of time, and provide an electrophotographic developing apparatus using the developer. 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. The present invention can provide an image forming apparatus, and further exhibits a very excellent effect of being able to provide a toner that is compatible with a low-temperature fixing system, has good offset resistance, and does not contaminate the fixing apparatus and the image. It is.

The present invention is described in detail below.
(Inorganic additive)
As described above, the inorganic additive used in the present invention means an inorganic compound mainly composed of an inorganic compound, for example, a metal or a metal oxide, and the surface is modified or coated with an organic compound or an organic polymer. And those subjected to chemical treatment and the like are included.
The inorganic additive needs to form a state in which at least the rigid body parts are strongly bonded to each other, and even if it is in an agglomerated state, it is so strong that it cannot be easily dissociated. What is connected is included in this state.
In addition, it is desirable that the inorganic additive has a strong physical or chemical bond between the rigid parts even in the primary aggregation state, and more preferably exists stably in an organic solvent.
As described above, for example, in the case where the constriction shape having a diameter smaller than the diameter of the rigid body portion is formed, the connecting portions between the rigid body portions are connected in a rosary shape by chain molecules. And the case where the rigid part is maintained by the graft-like chain, that is, the form in which the particles are connected in a bead shape, the rigid part is bound to the side chain of the linear molecule. And the like, such as a form in which daisy-chained molecules are branched in a graft, a ring-like form, and a form in which the whole is constructed three-dimensionally, such as a network or a spiral. The
As an index for measuring the presence or absence of a rigid part, for example, when there is a “neck (a part that narrows in the middle)” between an arbitrary part of an inorganic additive and another arbitrary part, both the optional part and the other optional part It can be regarded as a rigid part.
The example of the inorganic additive used for this invention is shown to schematic FIGS.
1-3, it is shown that the rigid body parts (A) are connected to each other at the connecting part (B) or the connecting point (C).
As a representative inorganic additive in the present invention, as shown in FIG. 1, the rigid body portions (A) are directly connected to each other at a point (connection point (C)), and the connection point (C) is connected to the connection portion. In the case of (B), and as shown in FIGS. 2 and 3, the two adjacent rigid body parts (A) are not directly connected but chained molecules or grafted chains or the like as a connecting part (B). In the former case, the desired effect can be brought about, but the latter case is preferred because the unevenness of the toner particle surface tends to be larger.

  Examples of the inorganic additive satisfying the above conditions include WACKER HDK (registered trademark) (manufactured by Clariant Japan Co., Ltd.), which can exist in a branched form as an aggregate of primary particles. Among them, residual silanol group ratio, surface treatment HDK H20 is preferable from the viewpoint of the surface area of the agent and particles.

  In addition, as the inorganic fine particles used in 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. Thereafter, a dispersion solvent prepared by substituting the dispersion solvent with a solvent such as alcohol, ethyl acetate, or methyl ethyl ketone (MEK) from water can be used.

Examples of the metal oxide synthesized by the wet method include silicon dioxide (silica), titanium dioxide (titania), aluminum oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, and 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) and aluminum oxide are preferable, and silica is particularly preferable.

  In addition, as a method of hydrophobizing treatment, a surface treating agent is often used, and it is necessary to optimize the balance between hydrophilicity / hydrophobicity of the surface of the metal oxide. For example, a cup represented by the following formula (1) A ring agent is preferably used.

（式中Ｑはハロゲン原子、アミノ基又はアルコキシ基等の加水分解可能な基を表し、Ａはアルキル基又はアリール基を表し、有機官能基Ｐは−ＢＯＯＣ（Ｒ'）Ｃ＝ＣＨ_２、−ＢＮＨＲ''又は−ＢＮＨ_２を表す（Ｒ'はアルキル基、Ｒ''はアルキル基またはアリール基）。なお、Ｂはアルキレン基または−Ｏ−、−ＮＨ−、−ＣＯ−を含むアルキレン基を表す。また、ｘ及びｙは１以上の整数、ｚは０以上の整数を表し、ｘ＋ｙ＋ｚ＝４を満たす）。

(In the formula, Q represents a hydrolyzable group such as a halogen atom, an amino group, or an alkoxy group, A represents an alkyl group or an aryl group, and the 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). B represents an alkylene group or an alkylene group including —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).

Examples of the coupling agent represented by the above formula (1) include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3 -Glycidoxypropyltrimethoxysilane [γ-glycidoxypropyltrimethoxysilane], 3-glycidoxypropylmethyldiethoxysilane [γ-glycidoxypropylmethyldimethoxysilane], 3-glycidoxypropyltriethoxy Silane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane [γ-methacryloxypropyltrimethoxysilane], 3-methacryloxypropylmethyldiet Sisilane, 3-methacryloxypropyltriethoxysilane, 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 Methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane [γ-anilinopropyltrimethoxy Silane], N- (vinyl vinyl Gil) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride [N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride], octadecyldimethyl (3- (trimethoxy Silyl) propyl) ammonium chloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane (γ-mercaptopropyltrimethoxysilane), bis ( (Triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane and the like.
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.

Furthermore, as the inorganic additive, it is desirable that the rigid bodies are bonded in the form of primary particles, and the sol body is stably dispersed in the solvent from the viewpoint of dispersibility in the organic solvent. It is desirable that organosilica sol can be given as a typical example that satisfies this condition. Commercially available organosilica sol includes MEK-ST-UP (manufactured by Nissan Chemical Industries). The organosol can be produced, for example, using the method described in JP-A-11-43319.
The addition amount of the organosilica sol can be 0.1 to 40 wt%, preferably 0.75 to 20 wt% with respect to the toner. If the amount added is too small, it is not sufficient to change the shape of the toner particles. If the amount added is too large, the toner particles may be deformed more than necessary or the fixability may be hindered.
Further, as a result of studies by the present inventors, the lowering of the lower limit of fixing is observed by using two or more types of water-repellent treatment agents for the hydrophobic treatment of inorganic fine particles. For example, there is a method in which two or more of the above-described hydrophobizing agents are used for the hydrophobizing treatment.

More preferably, there is a method in which the above hydrophobizing agent and an amine are used in combination.
The term amine in the present invention is expressed as R ₁ R ₂ NR ₃ as used in a broad sense (R ₁ , R ₂ and R ₃ are each an alkyl group, an aryl group, an alkoxy group, a phenyl group, a phenoxy group, etc. entering. you can _also modify the polymer to the end of _{R 1, R 2, R 3} , R 1, R 2, R 3 also includes the case where combined with end the amine cyclic or heterocyclic ring), Suitable amine species and amounts vary greatly from system to system.
Examples of the tertiary amine compound include triethylamine, N, N′-dimethylaminodiethyl ether, tetramethylhexamethylenediamine, tetramethylethylenediamine, dimethylethanolamine, and N-methyl-N ′-(2-dimethylamino) ethylpiperazine. 1,2-dimethylimidazole, triethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine , Tetramethylguanidine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), bis (2-monomorpholinoethyl) ether, and the like, which may be used in combination of two or more. Preferably, bis (2-monophorinoethyl) ether is used.
As this hydrophobizing treatment method, a method in which a hydrophobizing agent and an amine are allowed to act on untreated inorganic fine particles simultaneously or stepwise, or a powder obtained by treating inorganic fine particles with a hydrophobizing agent in advance or There is a method in which the dispersion [dissolution] liquid is dissolved in an organic solvent to form a solution containing inorganic fine particles, and then an amine is added to further hydrophobize.

In addition, after adding the above-mentioned “inorganic additive in which two or more rigid body parts are continuous”, one or more general-purpose inorganic fine particles can be used together. Can be improved. As this general-purpose inorganic fine particle, there may be one portion that is regarded as a rigid body including a sphere.
Examples of the inorganic fine particles used in the present invention include silicon dioxide (silica), titanium dioxide (titania), aluminum oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, and oxidation. Zinc, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, nitride Silicon etc. can be mentioned.
Among these, silicon dioxide (silica), titanium dioxide (titania) or aluminum oxide is preferable, and silica is particularly preferable.
These inorganic fine particles may be used alone or in admixture of two or more when used as an electrostatic charge image developing toner.
Further, it is effective to use those inorganic fine particles that have been surface-treated with a hydrophobizing agent. In addition, as the hydrophobizing agent, the hydrophobizing agent for treating the inorganic additive can be used.

The addition amount of the inorganic fine particles is preferably 0.05 to 50 wt%, particularly preferably 0.25 to 10 wt% with respect to the toner.
Within this range, not only is the colorant uniformly dispersed in the organic solvent, the offset resistance is improved, and it is effective in producing a toner having improved flow characteristics and charging characteristics. The external additive is less likely to be buried or liberated during strong agitation deterioration, suppressing a decrease in charging ability, and the inorganic fine particles exposed on the toner surface exert an effect as a lubricant, further improving fluidity. Can be improved.
When the amount of inorganic fine particles added is smaller than this range, it is difficult to obtain a sufficient improvement effect. On the other hand, when the amount is larger than this range, the amount of inorganic fine particles present inside and on the toner particles becomes excessive, Since the inorganic fine particles act as a fixing inhibitor, the minimum fixing temperature increases, and the low-temperature fixability tends to be impaired.

Moreover, as an average particle diameter of the primary particle of an inorganic fine particle, 5-200 nm is preferable and especially 10-180 nm is preferable.
When inorganic fine particles having an average particle size within this range are used, a spacer effect that prevents aggregation between the toners is sufficiently exhibited. Further, when the toner is stored at a high temperature or when the toner is strongly stirred and deteriorated, an external additive is contained in the toner. It has excellent effects such as preventing burial.
If it is smaller than this range, toner aggregation and external additives are liable to occur, and if it is larger than this range, the minimum fixing temperature tends to increase and the low-temperature fixability is impaired.

The average particle size is a number average particle size, and the particle size of the inorganic fine particles used in the present invention is a particle size distribution measuring device using dynamic light scattering, for example, manufactured by Otsuka Electronics Co., Ltd. It can be measured by DLS-700 or Coulter Electronics N4 manufactured by Coulter Electronics. However, since it may be difficult to dissociate the secondary aggregation 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.
In addition, as the inorganic fine particles, those having various shapes such as spherical particles, irregular particles, linear shapes, and mesh shapes can be properly used depending on the dispersion state in the organic solvent.

(Toner shape)
It is important that the toner of the present invention is a spherical particle having a circularity of 0.92 to 0.99 and 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 tends to be deteriorated. 94 to 0.97 is desired.
Further, as for the dent on the toner surface, as measured with a scanning electron microscope (SEM image), the major axis is preferably ½ or less of the toner particle diameter and 1.0 to 5.0 μm, and the depth is the major axis. It is desired that it is at least 1/10 or more, preferably 1/8 or more.
In the present invention, if there are a plurality of indentations on the surface of the toner, the plurality of indentations not only compensate for the difficulty of cleaning the spherical shape, but also improve the transferability and bring about the stability of charging compared with the irregular toner. It works effectively.
In general, uneven particles produced by pulverized toner or emulsion polymerization have a problem that silica or the like added to improve fluidity tends to accumulate in the recesses, and the additive is a high-speed mixer. In the case of stirring and mixing, the silica is difficult to fix to the toner, and the silica fine particles may be liberated to cause photoconductor contamination or adhesion to the carrier.
However, since the toner of the present invention has a dent in the surface and has a long diameter of 1 μm or more, it is presumed that the toner does not cause problems due to pulverized toner or particles produced by emulsion polymerization.

(Urea-modified polyester)
As the binder resin used in the toner of the present invention, a resin obtained by reacting a modified polyester resin capable of reacting with active hydrogen with a crosslinking agent and / or an extender is preferably used, and in particular, a polyester modified with a urea bond is preferably used. It is done.

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).
As the polyester prepolymer (A) having an isocyanate group, a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group further reacted with a polyisocyanate (3), etc. 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.
Further, as the trivalent or higher polyol (1-2), a trihydric or higher polyhydric aliphatic alcohol (such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol); Phenols (trisphenol PA, phenol novolac, cresol novolac, etc.); alkylene oxide adducts of the above trivalent or higher polyphenols and the like.

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.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactam 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, the low-temperature fixability tends to deteriorate. When the molar ratio of [NCO] is less than 1, the urea content in the modified polyester becomes low, and hot offset resistance Tend to get worse.
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%. is there.
If it is less than 0.5 wt%, the hot offset resistance deteriorates, and tends to be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability, and if it exceeds 40 wt%, the low-temperature fixability tends to deteriorate. come.

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 tends to be low, and the hot offset resistance tends to deteriorate.

As amines (B), diamine (B1), triamine or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and amino groups of (B1) to (B5) (B6) etc. that are blocked. 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.
As (B6) which blocked the amino group of (B1) to (B5), ketimine compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of (B1) to (B5), Examples include oxazoline compounds.
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) tends to be low, and the hot offset resistance tends to deteriorate.
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 tends to deteriorate.

The urea-modified polyester (i) in 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 tends to deteriorate.
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, more preferably 2000 to 8000.
If it exceeds 20000, the low-temperature fixability and the gloss when used in a full-color device tend to deteriorate.

(Unmodified polyester)
In the present invention, not only the polyester (i) modified with a urea bond but also the polyester (ii) not modified can be included as a toner binder component together with the (i).
The combined use of the unmodified polyester (ii) improves the low-temperature fixability and the gloss when used in a full-color device, and is therefore preferable to the case where the polyester (ii) is used alone. Examples of the unmodified polyester (ii) include the polycondensates of the polyol (1) and the polycarboxylic acid (2) described above for the polyester component modified with a urea bond, and the unmodified polyester. Preferable as (ii) is the same as polyester (i) modified with a urea bond.
(Ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example.

It is preferable in terms of low-temperature fixability and hot offset resistance that at least a part of the polyester (i) modified with a urea bond and the unmodified polyester (ii) are compatible.
Accordingly, 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%, 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.
When the temperature is lower than 40 ° C., the heat-resistant storage stability of the toner is deteriorated.
By allowing the urea-modified polyester resin to coexist, 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 the measurement frequency is 20 Hz is 10000 dyne / cm ² is usually 100 ° C. or higher, preferably 110 to 200 ° C.
If it is less than 100 ° C., the hot offset resistance tends to deteriorate.

As the viscosity of the toner, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or lower, preferably 80 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability tends to deteriorate.
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.
Further, 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 diameter (Dv) of the toner is preferably 3 to 7 μm, and the ratio (Dv / Dn) to the number average particle diameter (Dn) is preferably 1.25 or less, particularly 1.05-1. 20 is preferable.
A toner having this condition 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 further, the toner is mixed with a carrier. In the two-component developer, the toner particle diameter fluctuation in the developer is reduced even if the toner balance is maintained over a long period of time, and a good and stable developability can be achieved even with long-term stirring in the developing device. can get.
Further, 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 filming on the developing roller and the toner layer are made thin. The toner is not fused to a member such as a blade, and both the developability and the image are stable and stable even when the developing device is 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. Tend to be.
In the toner of the present invention, when the volume average particle diameter is smaller than the above range, in the case of a two-component developer, if the developer is stirred for a long time with a developing device, the toner is fused to the surface of the carrier, and the charging ability of the carrier is lowered. When used as a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.
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 volume average particle diameter of the toner of the present invention is larger than the above range, it becomes difficult to obtain a high-resolution and high-quality image, and the balance of the toner in the developer is performed. In many cases, the fluctuation of the particle diameter of the toner 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)
Toners are required to have heat-resistant storage stability, low-temperature fixability, and offset resistance. In addition to these, full-color toners are required to have characteristics such as color reproducibility, transparency, and glossiness.
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 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.
However, in order to improve properties such as transparency and glossiness, 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 properties only by the above method. ing.

The toner of the present invention contains a polyester resin having a molecular weight peak of 1000 to 30000, a component of 30000 or more of 1 wt% or more, and a number average molecular weight of 2000 to 15000 in the molecular weight distribution of THF-soluble matter. As a result, 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 modifying group in the modified polyester (the portion of the linking group other than the ester bond) has a strong cohesion such as a hydrogen bond. Can control resin properties that cannot be controlled by molecular weight or degree of crosslinking.
In particular, 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 1000 or less is 5.0 wt% or more, it is not preferable for offset resistance. 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, a high molecular weight component that is effective for hot offset, that is, if the THF-insoluble content of the polyester-based resin contained in the toner is 1 to 15 wt%, it is sufficient without inhibiting transparency and glossiness. Offset resistance can be imparted.

(Fine particles)
In the present invention, fine particles can be dispersed in an aqueous medium in which the toner composition is dispersed in order to obtain a toner particle size having uniform chargeability and particle size distribution of the toner particles.
The fine particles are present in a solid state hardly soluble in water in an aqueous medium, and preferably have an average particle size of 0.01 to 1 μm.

As the fine particles, inorganic particles and organic particles can be used.
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.

  Examples of the organic fine particles include fine crystals of low molecular weight organic compounds and resin fine particles. The resin fine particles are obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, etc., and the material thereof can be either a thermoplastic resin or a thermosetting resin. For example, vinyl resin, polyurethane resin, epoxy Examples thereof include resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins, silicone resins, benzoguanamine resins, and nylon resins.

The relationship between the size of the toner particles and the fine particles fixed on the surface thereof is as follows. 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 that 20 ≦ R / Rs ≦ 200 is satisfied.
When it is out of this range, the particle size control effect by the fine particles tends to be remarkably reduced.
The amount of fine particles to be fixed on the surface of the resin particles should be selected in accordance with the purpose within 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 added fine particles be narrow (resin fine particle Dv / Dn: less than 1.25). Is easy to obtain.

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.

Further, it is necessary that the residual ratio 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 cannot be 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 (ethylenediamine 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 coloring agent of the present invention, known dyes and pigments can be used, such as 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, Fayce Red, Parachlor Ortoni Roaniline 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, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Fu Talocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used.
The content of the colorant is usually 1 to 15 wt%, preferably 3 to 10 wt%, 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 shearing 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 high shearing force to obtain a master batch. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin.
In addition, a so-called flushing method, which is a wet cake of a colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing 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; 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 wt% or less, preferably 30 to 60 wt%.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary.
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, 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), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, a carboxyl group include compounds of polymers having a functional group such as quaternary ammonium salts.

The amount of charge control agent used in the present invention is uniquely determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method. However, 0.1 to 10 parts by weight is preferably used with respect to 100 parts by weight of the binder resin, and more preferably 0.2 to 5 parts by weight.
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, or the image The concentration tends to decrease.
These charge control agents can be melt-kneaded together with a masterbatch and resin, and then dissolved and dispersed. Of course, they can be added when dissolved and dispersed directly in an organic solvent, or fixed on the toner surface after toner particles are prepared. You may make it.

(External additive)
As the external additive for assisting the fluidity, developability and chargeability of the toner 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.
Further, 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.
In addition, polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylate copolymer, silicone resin, benzoguanamine resin, nylon and other polycondensation systems, heat Examples thereof include polymer particles made of a curable 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 an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. It is done.
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 improving agent 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 polymer fine particles produced by soap-free emulsion polymerization such as fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, for example, polymethyl methacrylate fine particles and polystyrene fine particles. it can.
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 the polyester (ii) not modified with urea bond is used in combination, (ii) is produced in the same manner as the polyester having a hydroxyl group, and this is dissolved in the solution after completion of the reaction of (i), Mix.

The toner for developing an electrostatic charge image of the present invention can be produced by each method described below, 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 the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.
Toner particles are obtained by dissolving or dispersing a polymer, a colorant, a release agent, and one or more types of hydrophobic particles in an organic solvent, and dispersing the solution or dispersion in an aqueous medium. Thereafter, the organic solvent is removed, washed and dried.
Further, 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 composition (hereinafter referred to as toner raw material) release agent, charge control agent, unmodified polyester resin, etc. may be mixed when forming the 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 that do not contain a 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 type, a high-speed shear type, a friction type, a high-pressure jet type, 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 method is preferable.
When a high-speed shearing disperser is used, the number of rotations 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 comprising the urea-modified polyester (i), the prepolymer (A), and the resin colorant composite has a low viscosity and is easily dispersed.

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 generated on the surface of the toner to be produced, and a concentration gradient can be provided inside the particles.

  Examples of the dispersant for emulsifying and dispersing the oily phase in which the toner composition is dispersed in a liquid containing water include anionic surfactants such as alkylbenzene sulfonate, α-olefin sulfonate, and phosphate ester, Alkylamine salt, amino alcohol fatty acid derivative, polyamine fatty acid derivative, amine salt type such as imidazoline, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, etc. Quaternary ammonium salt type cationic surfactants, nonionic surfactants such as 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.

Moreover, the effect can be raised in a very small amount by using a surfactant having a fluoroalkyl group.
Preferred anionic surfactants having a fluoroalkyl group 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 metal salt thereof, perfluoroalkyl (C4 to C12) sulfonic acid and metal salt thereof, 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. Is 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 salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries, Ltd.) ), 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.

  In addition, as the inorganic compound dispersant that is hardly soluble in water, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite, and the like can also be used.

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, or other (meth) acrylic simple substances containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, acrylic acid 3 -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, or esters of compounds containing vinyl alcohol and a carboxyl group, For example, vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine Homopolymers or copolymers such as those having a nitrogen atom, or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Reoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl Polyoxyethylenes such as phenyl esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In addition, when a dispersion stabilizer that is soluble in an acid or alkali such as calcium phosphate salt is used, the calcium phosphate salt is removed from the fine particles by, for example, washing with water after dissolving the calcium phosphate salt with an acid such as hydrochloric acid. 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, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation 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, particularly 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 by short-time treatment 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 classifying 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 after drying, but it is preferably performed in a liquid from the viewpoint 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 in a wet state.
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 Examples include a system (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic mortar.

(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 resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins, and epoxy resins. Furthermore, polyvinyl and polyvinylidene resins such as acrylic resins, Methyl methacrylate resin, polyacrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, polyvinyl butyral resin, polystyrene resins such as polystyrene resin and styrene acrylic copolymer resin, halogenated olefin resins such as polyvinyl chloride, polyethylene terephthalate resin and poly Polyester resins such as butylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene Ren resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomer Fluoroterpolymers such as terpolymer and silicone resin can be used.
Moreover, you may make conductive powder etc. contain 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.

The toner for developing an electrostatic charge image of the present invention is generally used in a conventional manner such as a container having an agitator therein, a plastic container having a spiral wall structure, a flexible bag-like container, or a cartridge type container. In many cases, the container itself containing the toner separately from the main body of the image forming apparatus is supplied to the user, and more recently, the shortage of toner in the container at the user's hand is reduced. The sales system to supply is also considered.
Such an electrostatic charge image developing toner of the present invention comprises a latent image carrier, developing means for developing a latent image formed on the latent image carrier with an electrophotographic toner, and the developed toner image as a recording medium. In addition to a mono-color type and a full-color type electrophotographic image forming apparatus including a tandem method, including at least a transfer unit for transferring to a recording medium and a fixing unit for fixing a toner image transferred onto a recording medium. Generally, what is housed in the container is mounted on the image forming apparatus and used as a part of the developing means.
In recent years, a process cartridge having at least a latent image carrier and a developing unit that is detachable from the main body of the image forming apparatus has been separately prepared and used. Needless to say, the present invention is also applicable to such a process cartridge.
The latent image formed on the latent image carrier is developed with the electrostatic charge image developing toner by a normal electrophotographic method using the image forming apparatus configured as described above, and the developed toner image is transferred to a recording medium. Then, the toner image transferred last is fixed, and a copy image is formed on the recording medium.

FIG. 4 is a schematic diagram illustrating an example of an image forming apparatus.
A charging charger (3) is used as a means for charging the photoconductor on average. As the charging means, a corotron device, a scorotron device, a solid discharge element, a needle electrode device, a roller charging device, a conductive brush device, or the like is used, and a known system can be used.
Next, the image exposure unit (5) is used to form an electrostatic latent image on the uniformly charged photoreceptor (1). As the light source, all luminescent materials such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL) can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
Next, the developing unit (6) is used for visualizing the electrostatic latent image formed on the photoreceptor (1). As a developing method using the toner for developing an electrostatic image of the present invention, one component is used. There are development methods and two-component development methods. When the photosensitive member is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.
Next, a transfer charger (10) is used to transfer the toner image visualized on the photoconductor onto the transfer body (9). In addition, a pre-transfer charger (7) may be used for better transfer. As these transfer means, a transfer charger, an electrostatic transfer method using a bias roller, a mechanical transfer method such as an adhesive transfer method and a pressure transfer method, and a magnetic transfer method can be used. As the electrostatic transfer method, the charging means can be used.
Next, a separation charger (11) and a separation claw (12) are used as means for separating the transfer body (9) from the photoreceptor (1). As other separation means, electrostatic adsorption induction separation, side end belt separation, tip grip conveyance, curvature separation, and the like are used. As the separation charger (11), the charging means can be used.
Next, a fur brush (14) and a cleaning blade (15) are used to clean the toner remaining on the photoreceptor after transfer. Further, a pre-cleaning charger (13) may be used in order to perform cleaning more efficiently. As other cleaning means, there are a web system, a magnet brush system, and the like, but a single system or a plurality of systems may be used together.
Next, a neutralizing unit is used for the purpose of removing the latent image on the photoreceptor as required. As the charge removal means, a charge removal lamp (2) and a charge removal charger are used, and the exposure light source and the charging means can be used respectively.
In addition, known processes can be used for reading, feeding, fixing, paper discharge and the like that are not close to the photoconductor.

The present invention includes an image forming method and an image forming apparatus in which the toner for developing an electrostatic charge image of the present invention is used for such image forming means.
The image forming means may be fixedly incorporated in a copying apparatus, facsimile, or printer, but may be incorporated in these apparatuses in the form of a process cartridge and detachable. An example of the process cartridge is shown in FIG.
The process cartridge for the image forming apparatus includes a photoreceptor (101), and in addition, a charging unit (102), a developing unit (104), a transfer unit (106), a cleaning unit (107), and a discharging unit (not shown). ), And an apparatus (part) that can be attached to and detached from the image forming apparatus main body.

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.
~ Manufacture 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. Then, the mixture was pulverized with a pulverizer to obtain [Masterbatch 1].

Production Example 1-2
1200 parts of water, 800 parts of Cu-phthalocyanine 15: 3, 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].

-Production of polymer particles-
(Example 1)
Into a 5 L three-necked flask equipped with a stirrer and a thermometer, 225 parts of ethyl acetate and 100 parts of ethanol were added, and 12 parts of vinyl ether-maleic acid copolymer (average molecular weight 40,000) with respect to the total amount of the solvent [Masterbatch 1] Twenty parts was added in small portions with stirring, and dissolved completely.
Furthermore, 54 parts of styrene, 36 parts of n-butyl methacrylate, 6 parts of HDK-H20 (manufactured by Clariant Japan Co., Ltd.) as an inorganic additive, and 2 parts of 2,2′-azobisisobutyronitrile are sufficiently added. Dispersed. While stirring, the inside of the flask was replaced with nitrogen gas, and the internal oxygen concentration was reduced to 0.1% or less.
Polymerization was started while stirring at a stirring speed of 100 rpm in a constant temperature water bath controlled at 60 ± 0.1 ° C., and the reaction was continued as it was for 20 hours.
The conversion rate of the monomer into the obtained polymer was confirmed by gas chromatography, and when the residual monomer ratio became 1% or less, it was considered that the polymerization was completed, and [Polymer particle dispersion 1] was obtained. .

~ Washing⇒Drying ~
[Polymer particle dispersion 1] 100 parts are cooled, (1) processed at 2000 rpm, (2) removed the supernatant, (3) added 60 parts of methanol, and (4) mixed with TK homomixer (rotation speed 12) The mixture was stirred and redispersed at 10 000 rpm for 10 minutes, and then centrifuged again. Repeat (1) to (3) several times.
Thereafter, the polymer particle cake of (2) was taken out, 180 parts of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), stirred and redispersed, and then filtered. . The obtained cake was loosened, air-dried for one day and night, and then dried at 45 ° C. for 48 hours in a circulating dryer, 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 2
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 at 230 ° C for 8 hours at 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 at normal pressure. Reaction was performed 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.

~ Manufacture 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 (made by 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 Cooled and pulverized with a pulverizer to obtain [Masterbatch 4].

-Adjustment of aqueous phase-
Production Example 3-1
Ion-exchanged water 54 parts, 10 wt% hydroxyapatite suspension (Nippon Chemical Industry Co., Ltd. Superite 10) 206 parts, sodium dodecyl diphenyl ether disulfonate 50% aqueous solution (Eleminol MON-7): Sanyo Chemical Industries 16 parts Then, 24 parts of ethyl acetate was mixed and stirred. This is designated as [Aqueous Phase 1].

~ Creation of oil phase ~
Production Example 4-1
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, 10 parts HDK-H20 (manufactured by Clariant Japan Co., Ltd.) as an inorganic additive and 50 parts ethyl acetate are added, and a bead mill (Ultra Visco Mill, produced by Imex Corporation) is added. The pigment and WAX were dispersed under the conditions of a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / second, 80% by volume of 0.5 mm zirconia beads, and 6 to 24 passes.
Next, 130 parts of a 65 wt% ethyl acetate solution of [low molecular weight polyester] was added, and three passes were performed with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. 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⇒Tonerization ~
Add 150 parts of [Aqueous Phase 1] to a container equipped with a TK homomixer and stir at 13,000 rpm. Place 118 parts of [Pigment / WAX Dispersion 1] in the container and mix for 20 minutes. [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 filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 20 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 20 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (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 dryer, and sieved with a mesh of 75 μm to obtain [Toner 3].

Production Example 4-2
[Pigment / WAX dispersion 2] was obtained in the same manner as in Production Example 4-1, except that [Master batch 3] in Production example 4-1 was changed to [Master batch 4]. The solid content concentration of [Pigment / WAX Dispersion 2] (calculated from the weight after standing at 150 ° C. for 45 minutes) was 50%.

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].

~ Creation of master batch ~
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. 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 (made 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. Master batch 6] was obtained.

~ Creation of oil phase ~
Production Example 4-3
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 65 wt% ethyl acetate solution of [low molecular weight polyester], 10 parts of 20 wt% MEK-ST-UP (Nissan Chemical Industries) and 34 parts of ethyl acetate were added, and 3 passes were performed with the bead mill under the above conditions. [Pigment / WAX dispersion 3] was obtained.
The solid content concentration of [Pigment / WAX Dispersion 3] (calculated from the weight after standing at 150 ° C. for 45 minutes) was 50%.

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

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

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

(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].

(Example 7)
[Toner 7] 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 5].

(Example 8)
[Toner 8] 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 6].

~ Creation of oil phase ~
Production Example 4-7
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% organosilica sol: MEK-ST-UP (manufactured by Nissan Chemical Industries), 0.4 parts of bis (2-monophorinoethyl) ether, ethyl acetate 34 parts were added, and 3 passes were performed with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 7]. The solid content concentration of [Pigment / WAX Dispersion 7] (calculated from the weight after standing at 150 ° C. for 45 minutes) was 50%.

Production Example 4-8
[Pigment / WAX dispersion 8] was prepared in the same manner as in Production Example 4-7, except that [Masterbatch 3] in Production Example 4-7 was changed to [Masterbatch 4].

Production Example 4-9
[Pigment / WAX dispersion 9] was prepared in the same manner as in Production Example 4-7, except that [Masterbatch 3] in Production Example 4-7 was changed to [Masterbatch 5].

Production Example 4-10
[Pigment / WAX dispersion 10] was prepared in the same manner as in Production Example 4-7, except that [Masterbatch 3] in Production Example 4-7 was changed to [Masterbatch 6].

Example 9
[Toner 9] 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 7].

(Example 10)
[Toner 10] 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 8].

(Example 11)
[Toner 11] 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 9].

(Example 12)
[Toner 12] 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 10].

~ Synthesis of intermediate polyester and prepolymer ~
Production Example 5
In a reaction vessel equipped with a cooling tube, 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].
[Intermediate polyester] had a number average molecular weight of 2,100, a weight average molecular weight of 9,600, 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 6
170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stirrer and a thermometer, and reacted at 50 ° C. for 5 hours to obtain a [ketimine compound].
The amine value of [ketimine compound] was 423.

~ Synthesis of organic fine particle emulsion ~
Production Example 7
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 system temperature to 75 ° C. and reacted for 5 hours.
Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous 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 diameter of the [fine particle dispersion] measured by LA-920 was 0.12 μm. A part of the [fine particle dispersion] was dried to isolate the resin component. The resin content Tg was 152 ° C.

-Adjustment of aqueous phase-
Production Example 3-2
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 designated as [Aqueous Phase 2].

~ Creation of oil phase ~
Production Example 4-11
In a container in which a stir bar and a thermometer are set, 50 parts of synthetic ester wax WAX, 30 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industry), 330 parts of ethyl acetate are charged 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 1].
[Raw material solution 1] 132 parts were 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 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 11].
The solid content concentration of [Pigment / WAX Dispersion 11] (calculated from the weight after standing at 150 ° C. for 45 minutes) was 50%.

(Example 13)
~ Toner granulation⇒Tonerization ~
[Pigment / WAX Dispersion 11] 206 parts, [Prepolymer] 30 parts, 20 wt% MEK-ST-UP 10 parts, bis (2-monophorinoethyl) ether 0.1 part, [ketimine compound] 2.8 parts in a container After mixing at 5,000 rpm for 1 minute with a TK homomixer (made by Tokushu Kika), add 375 parts of [Aqueous Phase 1] to the container, and mix with a TK homomixer at 13,000 rpm for 20 minutes. An emulsified slurry 2] was obtained.
[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 carried out at 50 ° C. for 8 hours to obtain [Dispersion slurry 2].
[Dispersion slurry 2] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 20 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 20 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (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 mesh [Toner 13].
6A is a TEM photograph of [Toner 13], and FIG. 6B is an enlarged photograph thereof. Very small particles in the vicinity of the surface are organosilica, and large particles in the interior are carbon black. It is.
Further, FIG. 6C is an SEM photograph of [Toner 13], and it can be seen that a concave portion is formed on the surface.

Production Example 4-12
[Pigment / WAX dispersion 12] was produced in the same manner as in Production Example 4-11 except that [Masterbatch 3] in Production Example 4-11 was changed to [Masterbatch 4].

Production Example 4-13
[Pigment / WAX dispersion 13] was prepared in the same manner as in Production Example 4-11 except that [Masterbatch 3] in Production Example 4-11 was changed to [Masterbatch 5].

Production Example 4-14
[Pigment / WAX dispersion 14] was produced in the same manner as in Production Example 4-11 except that [Masterbatch 3] in Production Example 4-11 was changed to [Masterbatch 6].

(Example 14)
[Toner 14] was obtained in the same manner as in Example 13, except that [Pigment / WAX Dispersion 11] in Example 13 was changed to [Pigment / WAX Dispersion 12].

(Example 15)
[Toner 15] was obtained in the same manner as in Example 13, except that [Pigment / WAX Dispersion 11] in Example 13 was changed to [Pigment / WAX Dispersion 13].

(Example 16)
[Toner 16] was obtained in the same manner as in Example 13, except that [Pigment / WAX Dispersion 11] in Example 13 was changed to [Pigment / WAX Dispersion 14].

(Comparative Example 1)
[Toner 17] was obtained in the same manner as in Example 1 except that 6 parts of HDK-H20 as an inorganic additive was changed to 6 parts of ethyl acetate.

(Comparative Example 2)
[Toner 18] was obtained in the same manner as in Example 1 except that 6 parts of HDK-H20 as an inorganic additive in Example 1 was changed to 6 parts of SA-SB-300 (manufactured by Miyoshi Kasei Co., Ltd.). .

(Evaluation item)
(1) Particle Size The particle size of the toner was measured using 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 diameter and the number average particle diameter were determined by the particle size measuring instrument.

(2) Circularity It measured as an average circularity with the flow type particle image analyzer FPIA-1000 (made 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) Shape Particles whose particle diameter and indentation can be measured from 20 screens obtained by observing the toner particle surface with a scanning electron microscope S-2700 type SEM (Hitachi SEM image) and 5,000 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 for the deepest dent among the toner particles in the following three stages.
○: 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 A solid image and 1.0 ± 0.1 mg / solid image on plain paper and thick paper transfer paper (Ricoh type 6200 and NBS Ricoh copy printing paper <135>) using Ricoh's imgio Neo 450. Adjustment was performed so that toner of cm ² was developed, and adjustment was performed so that the temperature of the fixing belt was variable, and the temperature at which no offset occurred on plain paper and the minimum fixing temperature on thick paper were measured.
The lower limit fixing temperature was defined as the fixing lower limit 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 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) Cleaning property The transfer residual toner on the photosensitive member that has passed 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).

It is the schematic diagram which showed the example of the inorganic additive in this invention. It is another schematic diagram which showed the example of the inorganic additive in this invention. It is another schematic diagram which showed the example of the inorganic additive in this invention. 1 is a schematic diagram illustrating an example of an image forming apparatus to which an electrostatic charge image developing toner of the present invention can be applied. FIG. 3 is a schematic diagram illustrating an example of a process cartridge to which the electrostatic charge image developing toner of the present invention can be applied. 2 is a TEM photograph and an SEM photograph of the toner of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Static elimination lamp 3 Charger 4 Eraser 5 Image exposure part 6 Developing unit 7 Pre-transfer charger 8 Registration roller 9 Transfer paper 10 Transfer charger 11 Separation charger 12 Separation claw 13 Pre-cleaning charger 14 Fur brush 15 Cleaning blade 101 Photosensitive drum 102 Charging device 103 Exposure 104 Developing device 105 Transfer body 106 Transfer device 107 Cleaning blade

Claims (23)

At least after dissolving and / or dispersing each of a polymer, a colorant, a release agent and one or more inorganic additives in an organic solvent, and dispersing the solution or dispersion in an aqueous medium, A toner prepared by removing the organic solvent, washing, and drying, wherein the inorganic additive is composed of two or more rigid body portions and a connecting portion that connects the rigid body portions. Toner for developing electrostatic charge. The electrostatic image developing toner according to claim 1, wherein the inorganic additive contains a silica composition. The electrostatic image developing toner according to claim 1, wherein the inorganic additive is an organosilica sol. In an organic solvent, a polymer having a site capable of reacting with a compound having an active hydrogen group, a colorant, a release agent, and hydrophobic treated inorganic fine particles are dissolved or dispersed, and the solution or dispersion is dispersed in an aqueous medium. The organic solvent is removed, washed and dried after reacting with or reacting a polymer having a site capable of reacting with the active hydrogen group-containing compound. The toner for developing an electrostatic image according to any one of claims 1 to 3 . The toner according to any one of claims 1 to 4 volume-average particle size of the toner particles is characterized by a 3 to 7 [mu] m. Electrostatic image according to any one of claims 1 to 5 ratio Dv / Dn of the volume average particle diameter of the toner particles (Dv) to the number average particle size (Dn) of is characterized in that 1.25 or less Development toner. The polymer having a site capable of reacting with the compound having an active hydrogen group contains the unmodified polyester resin (ii) together with the modified polyester resin (i), and the weight of (i) and (ii) ratio 5 / 95-25 / 75 a toner according to any one of claims 4 to 6, characterized in that. The toner for electrostatic charge development according to any one of claims 1 to 7 , wherein the toner has a glass transition point (Tg) of 40 to 70 ° C. The toner according to any one of claims 1 to 8, wherein the toner outflow start temperature (Tfb) is 80 to 170 ° C.. In the molecular weight distribution of the THF-soluble component of the polyester resin contained in the toner, the molecular weight peak is 1000 to 30000, 30000 or more components are 1 wt% or more, and the number average molecular weight is 2000 to 15000. the toner according to any one of claims 1 to 9, wherein. In the molecular weight distribution of THF-soluble matter of the polyester resin contained in the toner, according to any one of claims 1 to 10 molecular weight of 1,000 or less components are characterized by a 0.1 to 5.0% Toner for developing electrostatic images. The toner according to any one of claims 1 to 11, wherein the THF-insoluble matter of polyester resin contained in the toner is 1 to 15 wt%. Wherein the step of removing the solvent of the dispersion, at least reduced pressure and / or toner according to any one of claims 1 to 12, characterized in that is carried out under conditions of heating. Wherein in an aqueous medium, an electrostatic image developing toner according to any one of claims 1 to 13, characterized in that the addition of the resin particles. The electrostatic charge image developing toner according to claim 14 , wherein the resin fine particles have an average particle diameter of 5 to 500 nm. Residual rate for the toner particles of the resin particles, as measured by pyrolysis gas chromatograph mass spectrometer of claim 14 or 15, characterized in that a 0.5 to 5.0% with respect to the toner particles Toner for developing electrostatic images. The toner according to any one of claims 1 to 16, wherein the toner contains a wax as a release agent. A developer comprising the electrostatic image developing toner according to any one of claims 1 to 17 and a carrier. A toner container containing the electrostatic image developing toner according to any one of claims 1 to 17 or the developer according to claim 18 . 18. A developing device for developing at least a latent image carrier and a latent image formed on the latent image carrier with an electrostatic charge image developing toner, and a toner storage portion of the developing device in any one of claims 1 to 17 . A process cartridge comprising the electrostatic charge image developing toner according to claim 1 or the developer according to claim 19. A latent image carrier, a developing unit for developing the latent image formed on the latent image carrier with a toner for developing an electrostatic image, a transfer unit for transferring the developed toner image to a recording medium, and a transfer unit on the recording medium An electrophotographic image forming apparatus comprising at least fixing means for fixing a toner image, wherein the toner container according to claim 19 is mounted. 21. A process cartridge according to claim 20 , further comprising: a transfer unit that transfers the developed toner image onto a recording medium; and a fixing unit that fixes the toner image transferred onto the recording medium. Electrophotographic image forming apparatus. A latent image carrier, developing means for developing a latent image formed on the latent image carrier with electrophotographic toner, transfer means for transferring the developed toner image to a recording medium, and toner transferred onto the recording medium using the image forming apparatus characterized by at least a fixing unit for fixing the image, according to the electrophotographic toner or claim 18, wherein the latent image formed on the latent image bearing member to any one of claims 1 to 17 An electrophotographic image forming method, wherein the development is performed with a developer.

Images