JP4846630B2 - Toner, manufacturing method thereof, image forming method, and image forming apparatus - Google Patents

Description

  The present invention relates to a toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like, and an electrophotographic developing apparatus using the toner. More specifically, the present invention relates to an electrophotographic toner used in a copying machine, a laser printer, a plain paper fax machine, and the like using a direct or indirect electrophotographic developing system, and an image forming method.

In order to control the charging of the toner, a large amount of charge adjusting agent is added. After melt-kneading a thermoplastic resin as a binder resin with a colorant and additives used as required. In the method of producing toner by pulverization and classification, so-called pulverization method, (1) There is a limit to reducing the particle diameter, and the improvement in image quality becomes severe.
(2) Kneading => Although it can be uniformly dispersed in each particle due to pulverization, it is impossible to control the arrangement of materials in the particle.
(3) When the amount of the charge control agent is increased in order to impart chargeability, a side effect on filming / fixing property occurs.
A malfunction occurred.
In recent years, as shown in Patent Documents 1 to 4, modified layered inorganic minerals obtained by modifying some of the ions present between layers in layered inorganic minerals with organic ions have been proposed as charge control agents. This also has the above problems.
JP-T-2003-515795 Special table 2006-500605 gazette JP-T-2006-503313 Special table 2003-202708 gazette

The subject of this invention is as follows.
(1) To provide a dry toner having a small amount and excellent chargeability.
(2) To provide a dry toner that does not cause filming, has excellent low-temperature fixability, and has excellent chargeability stability.
(3) To provide a toner and an image forming apparatus capable of obtaining a high quality image with excellent fine dot reproducibility.
(4) A toner and an image forming apparatus capable of achieving the same problems (1) to (3) are provided.

The present inventors have completed the present invention to solve the above-described problems. The present invention is as follows.
(1) Granulation by dispersing and / or emulsifying in an aqueous medium an oil phase containing at least a binder resin and / or a binder resin precursor, and a layered inorganic mineral obtained by modifying at least some of the ions between layers with organic ions. In the toner, the atomic concentration% of the specific element constituting the layered inorganic mineral when the toner is measured by XPS is A, and the atomic concentration% of the specific element is B when the toner is measured by XPS after melt-kneading the toner. A toner having a relationship of A> B.

(2) The toner according to (1), wherein A> B × 1.4.
(3) The toner according to (1) or (2), wherein the specific element is Al and A> 0.5 atomic%.
(4) The toner according to any one of (1) to (3), wherein the modified layered inorganic mineral is a layered inorganic mineral obtained by modifying at least a part of cations between layers with an organic cation. .
( 5 ) The amount of the layered inorganic mineral obtained by modifying at least a part of ions between layers contained in the toner with organic ions is 0.05 to 5.0% by weight. 4 ) The toner according to any one of the above.
( 6 ) The amount of the layered inorganic mineral obtained by modifying at least a part of ions between layers contained in the toner with organic ions is 0.05 to 2.0% by weight. The toner according to any one of 5 ).

( 7 ) The toner according to any one of (1) to ( 6 ), wherein the toner contains at least two kinds of binder resins.
( 8 ) The toner according to any one of ( 3 ) to ( 7 ), wherein the first binder resin contained in the binder resin is a resin having a polyester skeleton.
( 9 ) The toner according to ( 8 ), wherein the first binder resin is a polyester resin.
( 10 ) The toner according to ( 9 ), wherein the polyester resin is an unmodified polyester resin.
( 11 ) The toner according to any one of ( 3 ) to ( 10 ), wherein the content of the polyester resin component contained in the binder resin is 50 to 100% by weight.
( 12 ) The polyester resin component contained in the binder resin has a weight-average molecular weight of THF-soluble matter of 1,000 to 30,000, and is described in any one of ( 3 ) to ( 11 ). Toner.

( 13 ) The toner according to any one of ( 8 ) to ( 12 ), wherein the acid value of the first binder resin is 1.0 to 50.0 (KOHmg / g).
( 14 ) The toner according to any one of ( 8 ) to ( 13 ), wherein the glass transition point of the first binder resin is 30 to 70 ° C.
( 15 ) The toner according to any one of ( 3 ) to ( 14 ), wherein the binder resin precursor is a modified polyester resin.

( 16 ) Dissolve the first binder resin, the binder resin precursor, a compound that extends or crosslinks with the binder resin precursor, a colorant, a release agent, and the modified layered inorganic mineral in at least an organic solvent. Alternatively, it is obtained by dispersing, dissolving or dispersing the solution or dispersion in an aqueous medium, and removing the solvent from the obtained solution or dispersion. The toner according to any one of ( 8 ) to ( 15 ).
( 17 ) The binder resin precursor has a site capable of reacting with a compound having an active hydrogen group, and the binder resin precursor has a weight average molecular weight of 3,000 to 30,000. The toner according to ( 16 ) above.

( 18 ) A ratio Dv / Dn between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner is 1.00 to 1.30, and particles having a circularity of 0.950 or less are all toners. The toner according to any one of (1) to ( 17 ), wherein 20 to 80% of the particles are contained.
( 19 ) The toner according to any one of (1) to ( 18 ), wherein the toner has a volume particle size Dv / number average particle size Dn of 1.20 or less.
( 20 ) The toner according to any one of (1) to ( 19 ), wherein 1 to 20% by number of particles having a particle diameter of 2 μm or less is formed.
( 21 ) The toner according to any one of (1) to ( 20 ), wherein the toner has an acid value of 0.5 to 40.0 (KOHmg / g).
( 22 ) The toner according to any one of (1) to ( 21 ), wherein the toner has a glass transition point of 40 to 70 ° C.
( 23 ) The toner according to any one of (1) to ( 22 ) above, which is a toner used for a two-component developer.

( 24 ) A toner-containing container comprising the toner according to any one of (1) to ( 23 ).
( 25 ) A developer containing the toner according to any one of (1) to ( 23 ).
( 26 ) An image forming apparatus, wherein an image is formed using the developer according to ( 25 ).
( 27 ) An image forming method, wherein an image is formed using the developer according to ( 25 ).
( 28 ) A process cartridge comprising a developing unit having the developer according to ( 25 ) and an image carrier.

( 29 ) Granulation by dispersing and / or emulsifying in an aqueous medium an oil phase containing at least a binder resin and / or a binder resin precursor and a layered inorganic mineral in which at least some of the ions between layers are modified with organic ions. In the toner manufacturing method,
When the atomic concentration% of the specific element constituting the layered inorganic mineral when the toner is measured by XPS is A, and the atomic concentration% of the specific element when the toner is measured by XPS after melt-kneading is B, A method for producing a toner, comprising granulating so that A> B.

( 30 ) At least part of the binder resin, the binder resin precursor, the compound that extends or crosslinks with the binder resin precursor, the colorant, the release agent, and the ions between the layers in at least an organic solvent are organic ions. A toner production method in which a modified layered inorganic mineral is dissolved or dispersed, the solution or dispersion is subjected to a crosslinking reaction and / or elongation reaction in an aqueous medium, and the solvent is removed from the obtained solution or dispersion. The atomic concentration% of the specific element constituting the layered inorganic mineral when the toner is measured by XPS is A, and the atomic concentration% of the specific element when the toner is measured by XPS after melt-kneading is B. Then, the toner is granulated so that A> B.
( 31 ) The toner production method as described in ( 29 ) or ( 30 ) above, wherein the toner contains at least two kinds of binder resins.
( 32 ) The method for producing a toner according to ( 30 ), wherein the first binder resin among the binder resins is a resin having a polyester skeleton.
( 33 ) The toner production method as described in ( 32 ) above, wherein the first binder resin is a polyester resin.

  To provide a toner excellent in charging stability, low-temperature fixability, durability, fine dot reproducibility, and cleaning properties, and to provide an excellent image forming method and image forming apparatus using the toner. Can do.

  The present invention relates to a toner in which an oil phase containing at least a toner composition and / or a toner composition precursor is dispersed and / or emulsified in an aqueous medium and granulated. The toner contains at least part of ions between layers as an organic substance. When the toner has a layered inorganic mineral modified with ions and the toner is measured by XPS, the atomic concentration% of the specific element constituting the layered inorganic mineral is A, and the toner is melt-kneaded and then measured by XPS. The toner is characterized in that when the atomic concentration% of the specific element is B, A> B. When the toner is melt-kneaded, it is considered that the layered inorganic mineral is uniformly dispersed in the toner. Therefore, A> B indicates that the layered inorganic mineral is unevenly distributed near the surface in the toner.

Although the layered inorganic mineral is hydrophobic during granulation, depending on the type of interlayer ions, the amount of exchange of interlayer ions, etc., the water phase and the oil phase (the oil phase also varies depending on the polarity of the oil phase itself) The affinity is thought to change.
The present invention uses a layered inorganic mineral (hereinafter also referred to as a modified layered inorganic mineral) in which at least part of ions between layers is granulated with an organic ion in granulating toner as an oil phase in an aqueous medium, and toner particles The layered inorganic mineral is unevenly distributed in the vicinity of the surface of the toner, and is modified with organic ions between the layers at a level suitable for the presence of the layered inorganic mineral.
That is, the modified layered inorganic mineral has a characteristic that it moves to the surface side in the oil droplets and tends to be unevenly distributed on the toner surface. When the amount of modification with organic ions between layers is small, the hydrophobicity of the layered inorganic mineral is insufficient, making it difficult to separate the layered inorganic mineral between the layers, making it difficult to disperse in the toner, and the layered inorganic mineral on the surface Not enough minerals are observed.
When the amount of modification of the layered inorganic mineral with organic ions is increased, the ionic species are changed, or surface treatment is performed to increase the hydrophobicity, the inorganic mineral is uniformly dispersed in the toner or unevenly distributed in the center of the toner. Have a tendency to
The present invention can be achieved by appropriately selecting the water phase, the oil phase, and the layered inorganic mineral so that the uneven distribution state is as defined in the claims.

Generally, it is considered that the chargeability is greatly affected by the charge control agent on the surface of the toner. In fact, sufficient chargeability can be obtained by allowing a large amount of the modified layered inorganic mineral to exist on the surface.
From another viewpoint, in a so-called pulverized toner in which the kneading ⇒ pulverization step is performed, the additive is present in the toner without being unevenly distributed in the kneading step. For this reason, surface uneven distribution does not occur. For this reason, it is disadvantageous in chargeability than the above-mentioned toner capable of uneven surface distribution.
In order to solve this problem, if the amount added is increased and the effect is obtained in the same manner, as a side effect, the low-temperature fixability deteriorates and sufficient quality cannot be obtained. Further, in kneading, the layered inorganic mineral is not sufficiently crushed / dispersed and the dispersion diameter becomes large, so that the toner is detached from the toner, and the spent is deteriorated. When kneading is strengthened and pulverization / dispersion is performed, spent is generated from cutting of the resin and the like.

The surface uneven distribution can be verified as follows by using XPS.
XPS is a photoelectron X-ray that can usually detect an atomic concentration of about several tens of nanometers from the particle surface.
Therefore, for the specific elements used in the layered inorganic mineral, the atomic concentration% A obtained when the normal toner is measured by XPS, and the product obtained by once melting and kneading the toner are measured by XPS in the same manner as the normal toner. When the atomic concentration% obtained at this time is B, it is proved from the fact that A> B for the toner in which the layered inorganic mineral is unevenly distributed.
The melt-kneading temperature may be a temperature at which the toner resin can be melt-kneaded so long as other compositions can be uniformly dispersed in the binder resin. Specifically, the dispersion state can be generally made uniform by kneading at a temperature of about 120 to 150 ° C.
At this time, it is preferable that A> B × 1.4 because the effect of surface uneven distribution is high and the charging property can be stably provided even with a small addition amount.

In addition, when it can be verified with Al contained in the layered inorganic mineral, it is preferable that the atomic concentration% A of Al measured by XPS is A> 0.5 atomic% because environmental characteristics are excellent.
Specific elements of layered inorganic minerals include Al, Si, Mg, Fe, etc., but Si cannot be distinguished from external additives because it is a known technique to separately add additives to the toner surface. . On the other hand, Al is an element that is easily detected because it is often contained only in the layered inorganic mineral in the toner although it cannot be said that there is no case of external addition.

  Further, since the surface of the modified layered inorganic mineral can be unevenly distributed in the aqueous medium, the charging function can be sufficiently exerted with a small amount of the modified layered inorganic mineral, and this can minimize the influence on the fixing property. In addition, since it can be granulated in an aqueous system, the particle size can be reduced. Further, since the toner is granulated by dispersion / or emulsification in an oil / water phase, it can be dispersed in a liquid and the modified layered inorganic mineral can be sufficiently dispersed.

In the present invention, the oil phase containing the toner composition and / or the toner composition precursor (hereinafter also referred to as toner material) is preferably such that the toner material is dissolved or dispersed in a solvent. The toner composition includes a binder resin, a colorant, a release agent, a modified layered inorganic mineral, and the like, and the toner composition precursor is dispersed in an aqueous medium like the binder resin precursor shown below. And the like that react to form a toner composition. The solvent preferably contains an organic solvent. The organic solvent is preferably removed when forming the toner base particles or after forming the toner base particles.
On the other hand, for the toner obtained by melt kneading ⇒ pulverization, A = B for the normal toner measured by XPS and the atomic concentrations A and B of the layered inorganic mineral of the toner after melt kneading are the same. . This is because the layered inorganic mineral is uniformly present in the toner. In such a case, in order to stabilize the chargeability, the addition amount must be increased as described above, and the fixing property deteriorates / spent. Causes side effects such as sex.

The organic solvent can be appropriately selected according to the purpose, but since the removal is easy, the boiling point is preferably less than 150 ° C. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, And methyl isobutyl ketone. Of these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used alone or in combination of two or more.
The amount of the organic solvent used can be appropriately selected according to the purpose, but is preferably 40 to 300 parts by weight, more preferably 60 to 140 parts by weight, and more preferably 80 to 140 parts by weight with respect to 100 parts by weight of the toner material. More preferably, 120 parts by weight.

  Toner materials other than the layered inorganic mineral obtained by modifying at least part of the metal cations of the binder resin, colorant, and modified layered inorganic mineral with an organic cation can be appropriately selected according to the purpose. As a binder resin, any one of a monomer, a polymer, a compound having an active hydrogen group and a polymer having reactivity to the active hydrogen group is contained, and if necessary, a release agent and other components are further added. You may contain.

Next, the modified layered inorganic mineral used in the present invention will be described.
A layered inorganic mineral refers to an inorganic mineral made up of layers with a thickness of several nanometers, and to modify means to introduce organic ions into ions existing between the layers. Specifically, it is described in the cited documents 2, 3, and 4. This is called intercalation in a broad sense. As the layered inorganic mineral, smectite group (montmorillonite, saponite, etc.), kaolin group (kaolinite, etc.), magadiite, and kanemite are known. The modified layered inorganic mineral is highly hydrophilic due to its modified layered structure. Therefore, when used in toners that are dispersed in an aqueous medium and granulated without modifying the layered inorganic mineral, the layered inorganic mineral migrates into the aqueous medium and the toner cannot be deformed. By modifying with ions, moderate hydrophobicity is obtained, and the modified layered inorganic mineral increases in the vicinity of the surface of the toner particles, easily deformed during granulation, dispersed and refined, and fully exhibits the charge adjusting function. Further, since the modified layered inorganic mineral hardly contributes to the low-temperature fixing of the toner, if it is present in a large amount on the surface of the toner, it is considered that the low-temperature fixing is inhibited. However, since the modified layered inorganic mineral exhibits a toner deforming and charge adjustment function in a very small amount, it is possible to achieve both shape control, charge adjustment function and low-temperature fixing.

  The layered inorganic mineral modified in the present invention is preferably a layered inorganic mineral having a smectite basic crystal structure modified with an organic cation. Smectite clay minerals are negatively charged in the layer, and cations exist between the layers to compensate for this. Intercalation compounds can be formed by ion exchange of these cations and adsorption of polar molecules. Moreover, a metal ion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since a hydrophilic property is high when a metal ion is introduced, a layered inorganic compound in which at least a part of the metal ion is modified with an organic anion is desirable. Thereby, moderate hydrophobicity can be given.

Examples of the organic ion modifier of the layered inorganic mineral obtained by modifying at least part of the ions of the layered inorganic mineral with organic ions include quaternary alkyl ammonium salts, phosphonium salts and imidazolium salts. A quaternary alkyl ammonium salt is desirable. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.
As the layered inorganic mineral, kaolinite, layered phosphate, layered double hydroxide and the like can be used. In this case, an organic ion modifier can be appropriately selected as the modifier depending on the charge of the layer. When the layer has a negative charge, the organic ion modifier can be used. When the layer has a positive charge, the modifier is branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene Sulfates, sulfonates, carboxylates or phosphates with oxides, propylene oxides and the like are raised. A carboxylic acid having an ethylene oxide skeleton is desirable.

By modifying at least part of the layered inorganic mineral with organic ions, it has moderate hydrophobicity, the oil phase containing the toner composition and / or toner composition precursor has non-Nutnian viscosity, and the toner is deformed Can be At this time, the content of the layered inorganic mineral obtained by modifying a part of the toner with organic ions is preferably 0.05 to 5% by weight, and more preferably 0.05 to 2% by weight.
The layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.

Commercially available layered inorganic minerals partially modified with an organic cation include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. As the layered inorganic mineral partially modified with an organic anion, a hydrotalcite compound DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) modified with an organic ion represented by the following general formula (1) is particularly used. preferable. The following general formula (1) is, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).
Formula (1) R ₁ (OR ₂ ) _n OSO ₃ M
[Wherein, R ₁ represents an alkyl group having 13 carbon atoms, and R ₂ represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element]

  By using a modified layered inorganic mineral, it has moderate hydrophobicity, and therefore tends to be present at the interface of the droplets, so that the surface is unevenly distributed and can exhibit charging properties.

In the present invention, the toner may further contain a colorant, a release agent, a charge control agent, resin fine particles, inorganic fine particles, a fluidity improver, a cleaning property improver, a magnetic material, a metal soap, and the like.
The colorant can be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow ( GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Iso Indolinone Yellow, Bengala, Pangdan, Pepper Red, Cadmium Red, Cadmium Mercury Red, Antimony Zhu, Permanent Red 4R, Para Red, Faise Red, p-Chloro-o-nitroaniline red, Resol Fast Scarlet G, Brilli Fast Scarlet, Brilliant Carmine BS, 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, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon , Oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine oren , Perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, Ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Examples thereof include zinc white, litbon, and mixtures thereof. Colorants that can be used particularly preferably include pigment red such as PR122, PR269, PR184, PR57: 1, PR238, PR146, and PR185; pigment yellow such as PY93, PY128, PY155, PY180, and PY74; PB15: 3 Pigment blue, etc. These may be used alone or in combination of two or more.

The colorant may be used by being dispersed in a solvent together with the binder resin or the like, or may be used as a dispersion of a colorant obtained by dispersing the colorant in the solvent. In addition, when dispersing the colorant, in order to apply an appropriate shearing force, a part of a binder resin or the like may be added to adjust the viscosity.
The dispersed particle diameter of the colorant is preferably 1 μm or less. When a toner produced using a colorant having a dispersed particle diameter exceeding 1 μm is used, the image quality may be easily deteriorated, and in particular, the OHP light transmittance may be easily deteriorated.
The dispersed particle size of the colorant can be measured using a particle size distribution measuring apparatus Microtrac ultrafine particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.) using a laser Doppler method.
The content of the colorant in the toner can be appropriately selected according to the purpose, but is usually 1 to 15% by weight, and preferably 3 to 10% by weight. When the content of the colorant is less than 1% by weight, the coloring power of the toner decreases. When the content of the coloring agent exceeds 15% by weight, poor pigment dispersion occurs in the toner. May be reduced.

  The release agent can be appropriately selected from known ones according to the purpose, and waxes having a carbonyl group, polyolefin waxes, long-chain hydrocarbons, and the like can be used. Waxes having a carbonyl group are preferred. These may be used alone or in combination of two or more.

  Specific examples of the wax having a carbonyl group include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerol tribehenate, 1,18- An ester having a plurality of alkanoic acid residues such as octadecandiol diol stearate; an ester having a plurality of alkanol residues such as tristearyl trimellitic acid and distearyl maleate; a plurality of alkanoic acid residues such as dibehenyl amide Amides; amides having a plurality of monoamine residues such as trimellitic acid tristearyl amide; dialkyl ketones such as distearyl ketone and the like, and esters having a plurality of alkanoic acid residues are particularly preferred. Specific examples of the polyolefin wax include polyethylene wax and polypropylene wax. Specific examples of the long chain hydrocarbon include paraffin wax and sazol wax.

The melting point of the release agent is preferably 40 to 160 ° C, more preferably 50 to 120 ° C, and particularly preferably 60 to 90 ° C. When the melting point is less than 40 ° C., the wax may adversely affect the heat resistant storage stability, and when it exceeds 160 ° C., cold offset may occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps and more preferably 10 to 100 cps at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving the hot offset resistance and the low-temperature fixability may not be obtained.
The content of the release agent in the toner is preferably 0 to 40% by weight, and more preferably 3 to 30% by weight. When the content exceeds 40% by weight, the fluidity of the toner may be lowered.

The inorganic fine particles can be appropriately selected from known ones according to the purpose, and specifically, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide. , Tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride Etc. These may be used alone or in combination of two or more.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method of inorganic fine particles is 20-500 m < ² > / g.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by weight, and more preferably 0.01 to 5.0% by weight.

  When surface treatment is performed using a fluidity improver, the hydrophobicity of the toner surface is improved, and deterioration of fluidity and charging characteristics can be suppressed even under high humidity. Specific examples of fluidity improvers include silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. Etc.

When the cleaning property improving agent is added to the toner, the transferred developer remaining on the photoreceptor or the primary transfer medium is easily removed. Specific examples of cleaning improvers include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, resin particles obtained using soap-free emulsion polymerization such as polymethyl methacrylate particles and polystyrene particles. . The resin particles preferably have a narrow particle size distribution, and preferably have a volume average particle diameter of 0.01 to 1 μm.
The magnetic material can be appropriately selected from known materials according to the purpose, and examples thereof include iron powder, magnetite, and ferrite. Among them, a white magnetic material is preferable in terms of color tone.

  In the present invention, the aqueous medium preferably contains a polymer dispersant. The polymer dispersant is preferably a water-soluble polymer. The water-soluble polymer can be appropriately selected from known ones, and examples thereof include sodium carboxymethyl cellulose, hydroxyethyl cellulose, and polyvinyl alcohol. These may be used alone or in combination of two or more.

When emulsifying or dispersing the toner material in the aqueous medium using the oil phase containing the toner material, it is preferable to disperse the oil phase containing the toner material in the aqueous medium while stirring.
A known disperser or the like can be appropriately used for the dispersion. Specific examples of the disperser include a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser, and an ultrasonic disperser. Especially, since the particle diameter of a dispersion (oil droplet) can be controlled to 2-20 micrometers, a high-speed shearing disperser is preferable.

  When a high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose. The rotation speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. In the case of a batch system, the dispersion time is preferably 0.1 to 5 minutes, and the dispersion temperature is preferably 0 to 150 ° C. and more preferably 40 to 98 ° C. under pressure. In general, the dispersion is easier when the dispersion temperature is higher.

  The method for forming the toner base particles can be appropriately selected from known methods. Specifically, a method for forming toner base particles using a suspension polymerization method, an emulsion polymerization aggregation method, a dissolution suspension method, or the like, or a toner base particle while producing an adhesive substrate (binder resin). Among them, among them, the method of forming toner base particles while producing an adhesive substrate is preferable. Here, the adhesive base material is a base material having adhesiveness to a recording medium such as paper.

  For suspension polymerization, a toner raw material mixture containing a binder resin or a monomer as a raw material thereof, a layered inorganic mineral modified at least partially with organic ions, a colorant, a wax component, a charge control agent, etc. A toner particle having a size suitable as a toner, specifically, a particle diameter of about 3 to 12 μm, is prepared by a granulation step of dispersing in an aqueous dispersion medium and generating particles of the toner raw material mixture. The toner particles are taken out from the aqueous dispersion medium, washed and dried to obtain a toner.

  In the method of directly obtaining toner particles by the suspension polymerization method, the monomer that can be used for forming the binder resin is specifically styrene; o- (m-, p-) methylstyrene, m -Styrenic monomers such as (p-) ethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, (Meth) acrylate such as dodecyl acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate ) Acrylic acid ester monomers; butadiene, isoprene, cyclohexene, (meth) acrylonitrile, acrylic acid Such ene-based monomers bromide is preferably used. These may be used alone or in general so that the theoretical glass transition temperature (Tg) described in the publication Polymer Handbook 2nd edition III-P139-192 (John Wiley & Sons) is 40-75 ° C. It is used by appropriately mixing the monomer. When the theoretical glass transition temperature is less than 40 ° C., problems are likely to occur in terms of storage stability and durability stability of the toner, while when it exceeds 75 ° C., the toner fixing point is increased, and the fixability and color reproduction are increased. It causes sexual deterioration.

Furthermore, in the present invention, it is preferable to use a crosslinking agent during the synthesis of the binder resin in order to increase the mechanical strength and color reproducibility of the toner particles.
Examples of the crosslinking agent used in the toner according to the present invention include divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, , 4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (M NDA Nippon Kayaku), and those obtained by changing the methacrylates of the above acrylate.

  Polyfunctional crosslinkers include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy, polyethoxy Phenyl) propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and triallyl trimellitate.

For the emulsion polymerization aggregation method, emulsion polymerization aggregation is performed by preparing a resin by emulsion polymerization, heteroaggregating it with a dispersion of layered inorganic minerals, pigments, release agents, etc., at least partially modified with organic ions, and then fusing and coalescing them. When manufactured by the fusion method, the effects of the present invention can be easily obtained.
The emulsion polymerization agglomeration and fusion method comprises a resin particle dispersion prepared by an emulsion polymerization method, a layered inorganic mineral obtained by modifying at least a part prepared separately with organic ions, a colorant dispersion, and a release agent dispersion as necessary. A step of preparing an agglomerated particle dispersion (hereinafter referred to as “aggregation step”) by mixing and aggregating at least resin particles and a layered inorganic mineral at least partially modified with organic ions and a colorant to form aggregated particles. And a step of heating and fusing the aggregated particles to form toner particles (hereinafter also referred to as “fusion step”).

  In the aggregating step, the resin particle dispersion, the layered inorganic mineral obtained by modifying at least a part of the organic ions, the colorant dispersion, and if necessary, the release agent dispersion are mixed with each other to aggregate the resin particles. To form agglomerated particles. Aggregated particles are formed by hetero-aggregation, etc., and at that time, for the purpose of stabilizing the aggregated particles and controlling the particle size / particle size distribution, the ionic surfactant having a polarity different from that of the aggregated particles or a monovalent or more metal salt A compound having the following charge can be added. In the fusion step, the resin is melted by heating to a temperature equal to or higher than the glass transition point of the resin in the aggregated particles.

  In the previous stage of the fusing step, there can be provided an attaching step in which other fine particle dispersion is added to and mixed with the aggregated particle dispersion to uniformly attach the fine particles to the surface of the aggregated particles to form adhered particles. Furthermore, a layered inorganic mineral dispersion modified at least partly with organic ions is added to and mixed with the aggregated particle dispersion, and the layered inorganic mineral modified at least partly with organic ions is uniformly attached to the surface of the aggregated particles and adhered particles. An adhesion step for forming the film can be provided. Also, in order to strengthen the adhesion of layered inorganic minerals modified at least partly with organic ions, other fine particle dispersions are added after attaching layered inorganic minerals modified at least partly with organic ions An adhering step can be provided in which fine particles are uniformly adhered to the surface of the aggregated particles to form adhering particles. These adhered particles are formed by heteroaggregation or the like. This adhered particle dispersion is also fused by heating to a temperature equal to or higher than the glass transition point of the resin particles to form fused particles.

The fused particles fused in the fusion step exist as a colored fused particle dispersion in the aqueous medium, and at the same time the fused particles are taken out of the aqueous medium in the washing step, the impurities mixed in the respective steps are removed. The toner is removed and dried to obtain a toner for developing an electrostatic image as powder.
In the washing step, acidic and possibly basic water is added in several times the amount to the fused particles and stirred, followed by filtration to obtain a solid content. The pure water is added several times to the solid content and stirred, followed by filtration. This is repeated several times until the pH of the filtrate after filtration reaches about 7, and colored toner particles are obtained. In the drying step, the toner particles obtained in the washing step are dried at a temperature below the glass transition point. At this time, it is possible to circulate dry air or heat under vacuum as necessary.

In the present invention, a surfactant can be used to stabilize the dispersibility of the resin particle dispersion, the colorant dispersion, and the release agent dispersion.
Examples of such surfactants include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type And nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable. In the toner of the present invention, an anionic surfactant generally has a strong dispersing power and is excellent in the dispersibility of resin particles and a colorant. Therefore, a cationic agent is used as a surfactant for dispersing a release agent. Surfactants are advantageous. The nonionic surfactant is preferably used in combination with an anionic surfactant or a cationic surfactant. Surfactant may be used individually by 1 type and may use 2 or more types together.

  Specific examples of anionic surfactants include fatty acid soaps such as potassium laurate, sodium oleate, and castor oil sodium; sulfate esters such as octyl sulfate, lauryl sulfate, lauryl ether sulfate, and nonyl phenyl ether sulfate; lauryl sulfonate , Dodecylbenzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate, etc. Sulfonates: lauryl phosphate, isopropyl phosphate, nonylphenyl ether phosphate Phosphoric acid esters such as Feto; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate, sulfosuccinic acid salts, such as sodium lauryl sulfosuccinate 2; and the like.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dihydroxyethyl methyl ammonium chloride, oleyl bispolyoxyethylene methyl ammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzene dimethyl Ammonium chloride, alkyltri And quaternary ammonium salts such as chill ammonium chloride.

  Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxy Alkyl phenyl ethers such as ethylene nonyl phenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene Alkylamines such as oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as ethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid Alkanolamides such as diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate Etc.

  The content of the surfactant in each dispersion may be a level that does not impair the characteristics of the present invention, and is generally a small amount. Specifically, in the case of a resin particle dispersion, 0.01 to 1 wt. %, Preferably 0.02 to 0.5% by weight, more preferably 0.1 to 0.2% by weight. When the content is less than 0.01% by weight, aggregation may occur particularly when the pH of the resin particle dispersion is not sufficiently basic. The content in the case of the colorant dispersion and the release agent dispersion is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 0.2% by weight. If the content is less than 0.01% by weight, the stability between the particles is different at the time of agglomeration, which causes problems such as the release of specific particles. If the content exceeds 10% by weight, the particle size distribution of the particles becomes wider. In addition, there are problems such as difficulty in controlling the particle diameter, which is not preferable.

In addition to the resin, colorant, and release agent, the toner of the present invention includes other components such as an internal additive, a charge control agent, inorganic particles, organic particles, a lubricant, and an abrasive depending on the purpose. It is possible to add the fine particles.
As an internal additive, it is used to such an extent that it does not hinder the chargeability as a toner characteristic. For example, a metal such as ferrite, magnetite, reduced iron, cobalt, manganese, nickel, an alloy, or a magnetic compound such as a compound containing these metals The body is used.
The charge control agent is not particularly limited, but in particular for color toners, colorless or light-colored ones are preferably used. For example, quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments are used.

  Examples of the inorganic particles include all particles usually used as an external additive on the toner surface, such as silica, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, and cerium oxide. Examples of the organic particles include all particles usually used as external additives on the toner surface, such as vinyl resins, polyester resins, and silicone resins. In addition, these inorganic particles and organic particles, fluidity aids, cleaning aids and the like can be used. Examples of the lubricant include fatty acid amides such as ethylene bis stearic acid amide and oleic acid amide, and fatty acid metal salts such as zinc stearate and calcium stearate. As an abrasive | polishing agent, the above-mentioned silica, alumina, cerium oxide etc. are mentioned, for example.

  As described above, when the resin particle dispersion, the layered inorganic mineral dispersion modified at least partially with organic ions, the colorant dispersion, and the release agent dispersion are mixed, the content of the colorant is 50% by weight. The following is sufficient, and the range of 2 to 40% by weight is preferable. The content of the layered inorganic mineral at least partially modified with organic ions is preferably in the range of 0.05 to 10% by weight. Further, the content of the other components only needs to be a level that does not hinder the object of the present invention, and is generally extremely small, specifically in the range of 0.01 to 5% by weight, 0.5 A range of ˜2% by weight is preferred.

  In the present invention, as a dispersion medium for the resin particle dispersion, a layered inorganic mineral dispersion at least partially modified with organic ions, a colorant dispersion, a release agent dispersion, and a dispersion of other components, for example, an aqueous medium Is used. Specific examples of the aqueous medium include water such as distilled water and ion exchange water, alcohol, and the like. These may be used individually by 1 type and may use 2 or more types together.

  In the step of preparing the aggregated particle dispersion of the present invention, the aggregated particles can be adjusted by adjusting the emulsifying power of the emulsifier with pH to generate aggregation. At the same time, an aggregating agent may be added in order to stably and rapidly aggregate the particles to obtain aggregated particles having a narrower particle size distribution. As the flocculant, a compound having a monovalent or higher charge is preferable. Specifically, water-soluble surfactants such as the above-mentioned ionic surfactants and nonionic surfactants, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, Acids such as oxalic acid, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate and other inorganic acid metal salts, sodium acetate, potassium formate, sodium oxalate, phthalic acid Aliphatic acids such as sodium and potassium salicylates, metal salts of aromatic acids, metal salts of phenols such as sodium phenolate, metal salts of amino acids, triethanolamine hydrochloride, aniline hydrochloride and other aliphatic and aromatic amines Inorganic acid salts and the like. When considering the stability of the aggregated particles, the stability of the aggregating agent with respect to heat and time, and the removal during washing, a metal salt of an inorganic acid is preferable in terms of performance and use.

  The amount of these flocculants to be added varies depending on the valence of the charge, but all of them are small amounts. It is about 5% by weight or less. A smaller amount of the flocculant is preferable, and a compound having a higher valence is preferable because the amount added can be reduced.

Regarding a method of forming toner base particles while producing an adhesive base material, the toner material contains a binder resin precursor and a compound that extends or crosslinks with the binder resin precursor, and in an aqueous medium. A method of forming toner base particles while producing a binder resin by reacting these may be mentioned. Examples of the binder resin precursor and the compound that extends or crosslinks with the binder resin precursor include polymers having reactivity with active hydrogen groups and compounds having active hydrogen groups.
In addition, the toner material may further contain a known binder resin, a first binder resin, a binder resin precursor, and a compound that extends or crosslinks with the binder resin precursor. Can be used.
The toner thus obtained preferably contains a colorant, and may further contain other components such as a release agent and a charge control agent that are appropriately selected as necessary.

The adhesive substrate is appropriately selected according to the purpose, but a polyester resin or the like is preferably used.
The polyester resin is appropriately selected depending on the purpose, but a urea-modified polyester resin or the like is preferably used.
The urea-modified polyester resin is obtained by reacting an amine as a compound having an active hydrogen group and a polyester prepolymer having an isocyanate group as a polymer having reactivity with the active hydrogen group in an aqueous medium. In addition, when synthesizing the urea-modified polyester resin, a urethane bond may be formed by adding an alcohol in addition to the amine. The molar ratio of the urethane bond to the urea bond thus formed (to distinguish it from the urethane bond of the polyester prepolymer having an isocyanate group) is preferably from 0 to 9, and preferably from 1/4 to 4. Is more preferable, and 2/3 to 7/3 is particularly preferable. If this ratio is greater than 9, the hot offset resistance may decrease.

  Specific examples of the adhesive substrate include a polyester prepolymer obtained by reacting a 2-condensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid with isophorone diisocyanate, and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 Mixtures of polyadducts of molar adducts and isophthalic acid; bisphenol A ethylene oxide 2 molar adducts and polycondensates of isophthalic acid reacted with isophorone diisocyanate and uread with isophorone diamine, and bisphenol A mixture of ethylene oxide 2 mol adduct and terephthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid A mixture of a polyester prepolymer obtained by reacting a condensate with isophorone diisocyanate and uread with isophorone diamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid; Polyester prepolymer prepared by reacting bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate with isophorone diisocyanate, and oleaminated with isophoronediamine, 2 mol of bisphenol A propylene oxide Mixture of adduct and polycondensate of terephthalic acid; bisphenol A ethylene oxide 2-mole adduct and polycondensate of terephthalic acid with isophorone diisocyanate A mixture of a polyester prepolymer obtained by urea formation with hexamethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid; polycondensation of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid A mixture of a polyester prepolymer obtained by reacting the product with isophorone diisocyanate and uread with hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid; A polyester prepolymer obtained by reacting a bicondensate of bisphenol A ethylene oxide 2 mol and a polycondensate of terephthalic acid with isophorone diisocyanate, and urethanized with ethylenediamine, and bisphenol A polyester prepolymer prepared by reacting bisphenol A ethylene oxide 2-mole adduct and isophthalic acid polycondensate with diphenylmethane diisocyanate in urea with hexamethylenediamine Of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride A polyester prepolymer obtained by reacting a polycondensate with diphenylmethane diisocyanate and uread with hexamethylenediamine, and a bisphenol A ethylene oxide 2-mole adduct / bisphenol A mixture of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate reacted with toluene diisocyanate in urea with hexamethylenediamine And a mixture of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate.

The compound having an active hydrogen group acts as an elongation agent, a crosslinking agent or the like when a polymer having reactivity to the active hydrogen group undergoes an elongation reaction, a crosslinking reaction, or the like in an aqueous medium.
Specific examples of the active hydrogen group include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), amino group, carboxyl group, mercapto group and the like. In addition, an active hydrogen group may be individual, and 2 or more types of mixtures may be sufficient as it.
The compound having an active hydrogen group can be appropriately selected according to the purpose. However, when the polymer having reactivity to the active hydrogen group is a polyester prepolymer having an isocyanate group, an elongation reaction with the polyester prepolymer. Amines are preferred because they can have a high molecular weight by a crosslinking reaction or the like.

The amines can be appropriately selected depending on the purpose, and specific examples include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. Diamines and mixtures of diamines and small amounts of trivalent or higher amines are preferred. These may be used alone or in combination of two or more.
Examples of diamines include aromatic diamines, alicyclic diamines, and aliphatic diamines. Specific examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, and the like. Specific examples of the alicyclic diamine include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane, isophorone diamine and the like. Specific examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, hexamethylene diamine and the like. Specific examples of the trivalent or higher amine include diethylenetriamine and triethylenetetramine. Specific examples of amino alcohols include ethanolamine and hydroxyethylaniline. Specific examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan. Specific examples of amino acids include aminopropionic acid and aminocaproic acid. Specific examples of those in which the amino group is blocked include ketimine compounds and oxazolidone compounds obtained by blocking the amino group with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

  In addition, a reaction terminator can be used in order to stop the elongation reaction, the crosslinking reaction, and the like of the compound having an active hydrogen group and a polymer having reactivity with the active hydrogen group. When a reaction terminator is used, the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Specific examples of the reaction terminator include monoamines such as diethylamine, dibutylamine, butylamine and laurylamine, and ketimine compounds in which these amino groups are blocked.

  The ratio of the equivalent of the isocyanate group of the polyester prepolymer to the equivalent of the amino group of the amine is preferably 1/3 to 3, more preferably 1/2 to 2, and particularly preferably 2/3 to 1.5. . If this ratio is less than 1/3, the low-temperature fixability may be lowered. If it exceeds 3, the molecular weight of the urea-modified polyester resin may be lowered, and the hot offset resistance may be lowered.

  The polymer having reactivity to active hydrogen groups (hereinafter sometimes referred to as “prepolymer”) can be appropriately selected from known resins and the like, and can be selected from polyol resins, polyacrylic resins, polyester resins, and epoxy resins. And derivatives thereof. Among them, it is preferable to use a polyester resin in terms of high fluidity and transparency at the time of melting. These may be used alone or in combination of two or more.

The functional group capable of reacting with the active hydrogen group of the prepolymer includes isocyanate group, epoxy group, carboxyl group, chemical structural formula -COCl
In particular, an isocyanate group is preferable. The prepolymer may have one of such functional groups or two or more kinds.
As a prepolymer, the molecular weight of the polymer component can be easily adjusted, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. Since it can ensure, it is preferable to use the polyester resin which has an isocyanate group etc. which can produce | generate a urea bond.

  The polyester prepolymer containing an isocyanate group can be appropriately selected depending on the purpose. Specific examples include a reaction product of a polyester resin having an active hydrogen group obtained by polycondensation of a polyol and a polycarboxylic acid, and a polyisocyanate.

  The polyol can be appropriately selected according to the purpose, and a diol, a trihydric or higher alcohol, a mixture of a diol and a trihydric or higher alcohol, etc. can be used, but the diol or the diol and a small amount of a trihydric or higher alcohol. Is preferred. These may be used alone or in combination of two or more.

  Specific examples of the diol include alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol; diethylene glycol, triethylene glycol, dipropylene Diols having an oxyalkylene group such as glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols including ethylene oxide and propylene oxide , With addition of alkylene oxide such as butylene oxide; bisphenols such as bisphenol A, bisphenol F and bisphenol S; bisphenols with ethyleneoxy , Propylene oxide, alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide. In addition, it is preferable that carbon number of alkylene glycol is 2-12. Among these, alkylene glycols having 2 to 12 carbon atoms or alkylene oxide adducts of bisphenols are preferred, alkylene oxide adducts of bisphenols or alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbons. The mixture of is particularly preferred.

Examples of trihydric or higher alcohols include trihydric or higher aliphatic alcohols, trihydric or higher polyphenols, and alkylene oxide adducts of trihydric or higher polyphenols. Specific examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Specific examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak and the like. Specific examples of adducts of trivalent or higher polyphenols with alkylene oxides include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to trihydric or higher polyphenols.
When a diol and a trihydric or higher alcohol are mixed and used, the weight ratio of the trihydric or higher alcohol to the diol is preferably 0.01 to 10%, more preferably 0.01 to 1%.

  The polycarboxylic acid can be appropriately selected according to the purpose, and dicarboxylic acid, trivalent or higher carboxylic acid, a mixture of dicarboxylic acid and trivalent or higher carboxylic acid, and the like can be used. And a small amount of a trivalent or higher polycarboxylic acid mixture is preferred. These may be used alone or in combination of two or more.

  Specific examples of the dicarboxylic acid include divalent alkanoic acid, divalent alkenoic acid, and aromatic dicarboxylic acid. Specific examples of the divalent alkanoic acid include succinic acid, adipic acid, sebacic acid and the like. The number of carbon atoms of the divalent alkenoic acid is preferably 4 to 20, and specific examples include maleic acid and fumaric acid. The aromatic dicarboxylic acid preferably has 8 to 20 carbon atoms, and specific examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Among these, a divalent alkenoic acid having 4 to 20 carbon atoms or an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable.

As the trivalent or higher carboxylic acid, trivalent or higher aromatic carboxylic acid or the like can be used. The carbon number of the trivalent or higher aromatic carboxylic acid is preferably 9 to 20, and specific examples thereof include trimellitic acid and pyromellitic acid.
As the polycarboxylic acid, an acid anhydride or lower alkyl ester of any of dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid can be used. Specific examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.
In the case of using a mixture of dicarboxylic acid and trivalent or higher carboxylic acid, the weight ratio of trivalent or higher carboxylic acid to dicarboxylic acid is preferably 0.01 to 10%, more preferably 0.01 to 1%. preferable.

  As for the mixing ratio at the time of polycondensation of the polyol and the polycarboxylic acid, the equivalent ratio of the hydroxyl group of the polyol to the carboxyl group of the polycarboxylic acid is usually preferably 1 to 2, more preferably 1 to 1.5, 1.02-1.3 is particularly preferred.

  The content of the structural unit derived from the polyol in the polyester prepolymer having an isocyanate group is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight, and particularly preferably 2 to 20% by weight. When this content is less than 0.5% by weight, the hot offset resistance is lowered, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by weight. In this case, the low-temperature fixability may be lowered.

  The polyisocyanate can be appropriately selected depending on the purpose, but it is blocked with an aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, an araliphatic diisocyanate, an isocyanurate, or the like, blocked with a phenol derivative, oxime, caprolactam, or the like. And the like.

  Specific examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetra And methyl hexane diisocyanate. Specific examples of the alicyclic diisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Specific examples of the aromatic diisocyanate include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanatodiphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl. 4,4′-diisocyanato-3-methyldiphenylmethane, 4,4′-diisocyanato-diphenyl ether, and the like. Specific examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Specific examples of the isocyanurates include tris (isocyanatoalkyl) isocyanurate, tris (isocyanatocycloalkyl) isocyanurate, and the like. These may be used alone or in combination of two or more.

When the polyisocyanate and the polyester resin having a hydroxyl group are reacted, the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyester resin is usually preferably 1 to 5, more preferably 1.2 to 4, more preferably 1 .5-3 are particularly preferred. When the equivalent ratio exceeds 5, the low-temperature fixability may decrease, and when it is less than 1, the offset resistance may decrease.
The content of the structural unit derived from polyisocyanate in the polyester prepolymer containing an isocyanate group is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight, further 2 to 20% by weight. preferable. When this content is less than 0.5% by weight, the hot offset resistance may be lowered, and when it exceeds 40% by weight, the low-temperature fixability may be lowered.

  The average number of isocyanate groups that the polyester prepolymer has per molecule is preferably 1 or more, more preferably 1.2 to 5, and even more preferably 1.5 to 4. When the average number is less than 1, the molecular weight of the urea-modified polyester resin is lowered, and the hot offset resistance may be lowered.

3000-30,000 are preferable and, as for the weight average molecular weight of the polymer which has the reactivity with respect to an active hydrogen group, 5000-25,000 are more preferable. When the weight average molecular weight is less than 1000, the heat resistant storage stability may be lowered, and when it exceeds 30,000, the low temperature fixability may be lowered. In addition, a weight average molecular weight is obtained by measuring tetrahydrofuran soluble part using a gel permeation chromatography (GPC).
The GPC measurement can be performed as follows, for example. First, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran is used as a column solvent at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran solution adjusted to a sample concentration of 0.05 to 0.6% by weight is injected and measured. In measuring the molecular weight, the molecular weight is calculated from the relationship between the logarithmic value of the calibration curve prepared from several kinds of standard samples and the count number. As a standard sample for preparing a calibration curve, the molecular weight is 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ and 4.48 × 10 ⁶ monodisperse polystyrene (manufactured by Pressure Chemical or Toyo Soda Industry Co., Ltd.) can be used. At this time, it is preferable to use about 10 kinds of standard samples. A refractive index detector can be used as the detector.

In the present invention, the binder resin used as the toner material can be appropriately selected according to the purpose, and a polyester resin or the like can be used, but an unmodified polyester resin is preferable. The content of the polyester resin component contained in the binder resin in the binder resin is preferably 50 to 100% by weight. Thereby, low temperature fixability and glossiness can be improved.
Examples of the unmodified polyester resin include a polycondensate of a polyol and a polycarboxylic acid. The non-modified polyester resin is preferably partially compatible with the urea-modified polyester resin, that is, has a similar structure compatible with each other in terms of low-temperature fixability and hot offset resistance. .
The weight average molecular weight of the unmodified polyester resin is preferably 1000 to 30000, and more preferably 1500 to 15000. When the weight average molecular weight is less than 1000, the heat resistant storage stability may be lowered. For this reason, it is preferable that content of the component whose weight average molecular weight is less than 1000 is 8-28 weight%. On the other hand, if the weight average molecular weight exceeds 30000, the low-temperature fixability may be lowered.

The glass transition temperature of the unmodified polyester resin is usually 30 to 70 ° C, more preferably 40 to 55 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 70 ° C., the low-temperature fixability may be lowered.
The glass transition temperature can be measured as follows using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner is put in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, the glass transition temperature can be calculated from the contact point between the tangent line and the base line of the endothermic curve near the glass transition temperature using the analysis system in the TG-DSC system.

The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g or more, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. When the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1.0 to 50.0 mgKOH / g, and more preferably 1.0 to 30.0 mgKOH / g. Thereby, the toner is easily negatively charged.

  When the toner contains an unmodified polyester resin, the weight ratio of the polyester prepolymer having an isocyanate group to the unmodified polyester resin is preferably 5/95 to 25/75, more preferably 10/90 to 25/75. preferable. When the weight ratio is less than 5/95, the hot offset resistance may be lowered, and when it exceeds 25/75, the low-temperature fixability and the glossiness of the image may be lowered.

The aqueous medium preferably contains resin particles.
The resin particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. A thermosetting resin may be used. Specific examples include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins, and the like. Among these, one or more resins selected from the group consisting of vinyl resins, polyurethane resins, epoxy resins, and polyester resins are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained. These may be used alone or in combination of two or more.
The vinyl resin is a resin obtained by homopolymerizing or copolymerizing a vinyl monomer. Specifically, a styrene- (meth) acrylic acid ester copolymer, a styrene-butadiene copolymer, (meth) Acrylic acid-acrylic acid ester polymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

  Moreover, as the resin particles, a copolymer obtained by polymerizing a monomer having a plurality of unsaturated groups can also be used. The monomer having a plurality of unsaturated groups can be appropriately selected according to the purpose. Specifically, sodium salt eleminol RS-30 of methacrylic acid ethylene oxide adduct sulfate (manufactured by Sanyo Chemical Industries), divinylbenzene 1,6-hexanediol diacrylate and the like.

  The resin particles can be obtained by polymerization using a known method, but are preferably used as an aqueous dispersion of resin particles. As a method for preparing an aqueous dispersion of resin particles, in the case of a vinyl resin, an aqueous dispersion of resin particles is obtained by polymerizing a vinyl monomer using a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, or a dispersion polymerization method. In the case of polyaddition or condensation resins such as polyester resins, polyurethane resins, and epoxy resins, a precursor such as a monomer or oligomer or a solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant. After that, heating or adding a curing agent to cure, a method for producing an aqueous dispersion of resin particles, a precursor such as a monomer or oligomer, or an appropriate emulsifier is dissolved in the solution, and then water is added. Method of phase inversion emulsification: Resin is pulverized and classified using a mechanical pulverizer or jet pulverizer to obtain resin particles, which are then dispersed in water in the presence of an appropriate dispersant. After obtaining resin particles by spraying a resin solution in the form of a mist, the resin particles are dispersed in water in the presence of an appropriate dispersant, a poor solvent is added to the resin solution, or the solvent is heated. By cooling the dissolved resin solution, the resin particles are precipitated, and after removing the solvent to obtain resin particles, a method of dispersing the resin particles in water in the presence of an appropriate dispersant, a resin solution, Disperse in an aqueous medium in the presence of an appropriate dispersant, then remove the solvent by heating, reduced pressure, etc., dissolve an appropriate emulsifier in the resin solution, and then add water to emulsify the phase. Methods and the like.

As an example of a toner production method, a method for forming toner base particles while producing an adhesive substrate will be described below. In such a method, preparation of an aqueous medium phase, preparation of an oil phase containing a toner material, emulsification or dispersion of the toner material, formation of an adhesive substrate, removal of the solvent, heavy weight having reactivity with active hydrogen groups. Synthesis of a compound, synthesis of a compound having an active hydrogen group, and the like are performed.
The aqueous medium can be prepared by dispersing the resin particles in the aqueous medium. The addition amount of the resin particles in the aqueous medium is preferably 0.5 to 10% by weight.

The oil phase containing the toner material is prepared in a solvent by a compound having an active hydrogen group, a polymer having reactivity to the active hydrogen group, a rheology additive, a colorant, a release agent, a charge control agent, an unmodified material. The toner material such as polyester resin can be dissolved or dispersed.
In the toner material, components other than the polymer having reactivity with the active hydrogen group may be added and mixed in the aqueous medium when the resin particles are dispersed in the aqueous medium, or the toner material contains the toner material. When the oil phase is added to the aqueous medium, it may be added to the aqueous medium.

  The emulsification or dispersion of the toner material can be performed by dispersing an oil phase containing the toner material in an aqueous medium. Then, when the toner material is emulsified or dispersed, an adhesive base is formed by subjecting a compound having an active hydrogen group and a polymer having reactivity to the active hydrogen group to an extension reaction and / or a crosslinking reaction.

  Adhesive substrates such as urea-modified polyester resins contain, for example, a liquid containing a polymer having reactivity with active hydrogen groups such as polyester prepolymers having isocyanate groups, and active hydrogen groups such as amines. The oil phase containing the toner material may be preliminarily produced by emulsifying or dispersing in an aqueous medium together with the compound, and by subjecting both to an extension reaction and / or a crosslinking reaction in the aqueous medium. May be produced by emulsifying or dispersing in an aqueous medium to which the toner is added, and subjecting both to an extension reaction and / or a crosslinking reaction in the aqueous medium, and emulsifying or dispersing the oil phase containing the toner material in the aqueous medium. After that, a compound having an active hydrogen group is added, and an extension reaction and / or a cross-linking reaction are performed on both from the particle interface in an aqueous medium. It may be. When both are subjected to an extension reaction and / or a crosslinking reaction from the particle interface, a urea-modified polyester resin is preferentially formed on the surface of the toner to be produced, and a concentration gradient of the urea-modified polyester resin can be provided in the toner.

  The reaction conditions for producing the adhesive substrate can be appropriately selected according to the combination of the polymer having reactivity with active hydrogen groups and the compound having active hydrogen groups. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours. The reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

  In a water-based medium, a method for stably forming a dispersion containing a polymer capable of reacting with an active hydrogen group such as a polyester prepolymer having an isocyanate group includes a reaction with an active hydrogen group in the aqueous medium phase. Examples thereof include a method in which a liquid prepared by dissolving or dispersing a toner material such as a polymer, a colorant, a release agent, a charge control agent, and an unmodified polyester resin in a solvent is added and dispersed by shearing force.

Dispersion can be performed using a known disperser, and examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, a friction disperser, a high-pressure jet disperser, and an ultrasonic disperser. Although mentioned, since the particle diameter of a dispersion can be controlled to 2-20 micrometers, a high-speed shearing disperser is preferable.
When a high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose. The rotation speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. In the case of a batch system, the dispersion time is preferably 0.1 to 5 minutes, and the dispersion temperature is preferably 0 to 150 ° C., more preferably 40 to 98 ° C. under pressure. The dispersion temperature is generally easier to disperse when the temperature is higher.

The amount of the aqueous medium used when emulsifying or dispersing the toner material is preferably 50 to 2000 parts by weight, and more preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the toner material. If the amount used is less than 50 parts by weight, the dispersion state of the toner material may be deteriorated, and toner base particles having a predetermined particle size may not be obtained. May be.
In the step of emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoints of stabilizing the dispersion such as oil droplets to obtain a desired shape and sharpening the particle size distribution.

The dispersant can be appropriately selected according to the purpose, and examples thereof include surfactants, sparingly water-soluble inorganic compound dispersants, and polymeric protective colloids, and surfactants are preferred. These may be used alone or in combination of two or more.
As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like can be used.

  Examples of the anionic surfactant include alkylbenzene sulfonate, α-olefin sulfonate, phosphate ester, and the like, and those having a fluoroalkyl group are preferably used. As an anionic surfactant having a fluoroalkyl group, a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (C6-C11) oxy ] Sodium 1-alkyl (C3-C4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) carboxylic acid or Its metal salt, perfluoroalkylcarboxylic acid (C7 to C13) or its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid or its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2 -Hydroxyethyl) perfluorooctance Examples include sulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, and the like. Commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (manufactured by Asahi Glass Co., Ltd.), Fluorard FC-93, FC-95, FC-98, FC-129. (Above, manufactured by Sumitomo 3M), Unidyne DS-101, DS-102 (above, manufactured by Daikin Industries, Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F- 833 (above, manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (above, manufactured by Tochem Products), Footage 100, 150 (above, manufactured by Neos).

  As cationic surfactants, amine salt type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline; alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts And quaternary ammonium salt type surfactants such as alkylisoquinolinium salts and benzethonium chloride. Among them, aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, benzalkonium salts, benzethonium chloride, Examples include pyridinium salts and imidazolinium salts. Commercially available cationic surfactants include Surflon S-121 (Asahi Glass Co., Ltd.); Florard FC-135 (Sumitomo 3M Co., Ltd.); Unidyne DS-202 (Daikin Kogyo Co., Ltd.), MegaFuck F-150, F -824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products);

Examples of nonionic surfactants include fatty acid amide derivatives and polyhydric alcohol derivatives.
Specific examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine.

Specific examples of the hardly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Polymeric protective colloids include monomers having carboxyl groups, alkyl (meth) acrylates having hydroxyl groups, vinyl ethers, vinyl carboxylates, amide monomers, acid chloride monomers, monomers having nitrogen atoms or heterocyclic rings thereof, and the like. Examples thereof include homopolymers or copolymers obtained by polymerization, polyoxyethylene resins, and celluloses. In addition, the homopolymer or copolymer obtained by polymerizing the above monomers includes those having a structural unit derived from vinyl alcohol.

Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride and the like. Specific examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. Is mentioned. Specific examples of vinyl ether include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether and the like. Specific examples of vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl butyrate and the like. Specific examples of the amide monomer include acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like. Specific examples of the acid chloride monomer include acrylic acid chloride and methacrylic acid chloride. Specific examples of the monomer having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethyleneimine. Specific examples of polyoxye and BR> `len-based resins include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl Examples thereof include phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene phenyl stearate, and polyoxyethylene pelargonate phenyl. Specific examples of celluloses include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.
When using an acid such as calcium phosphate salt or a material that can be dissolved in alkali as a dispersant, use a method such as dissolving the calcium salt with hydrochloric acid, washing with water, or decomposing with an enzyme. Can be removed.

  A catalyst can be used for the elongation reaction and / or the crosslinking reaction in producing the adhesive substrate. Specific examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

As a method for removing the organic solvent from the dispersion liquid such as an emulsified slurry, the temperature of the entire reaction system is gradually raised to evaporate the organic solvent in the oil droplets, and the dispersion liquid is sprayed in a dry atmosphere to obtain the oil. Examples include a method of removing the organic solvent in the droplets.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. Classification may be performed by removing fine particle portions by a cyclone, decanter, centrifugation, or the like in the liquid, or classification may be performed after drying.

The obtained toner base particles may be mixed with particles such as a colorant, a release agent, and a charge control agent. At this time, by applying a mechanical impact force, it is possible to prevent particles such as a release agent from detaching from the surface of the toner base particles.
As a method of applying mechanical impact force, a method of applying impact force to a mixture using a blade rotating at a high speed, throwing the mixture into a high-speed air current, and accelerating the particles or particles to an appropriate collision plate The method of making it collide etc. is mentioned. As an apparatus used in this method, an Ong mill (manufactured by Hosokawa Micron Corporation), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure were lowered, and a hybridization system (manufactured by Nara Machinery Co., Ltd.) Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

The toner of the present invention is manufactured using the toner manufacturing method of the present invention.
Since the toner of the present invention has a smooth surface, it has excellent properties such as transferability and chargeability, and can form a high-quality image. Further, when the toner of the present invention contains an adhesive substrate obtained by reacting a compound having an active hydrogen group with a polymer having reactivity to the active hydrogen group in an aqueous medium, the transferability and fixability are improved. Further excellent properties such as Therefore, the toner of the present invention can be used in various fields and can be suitably used for image formation by electrophotography.

  The volume average particle diameter of the toner of the present invention is preferably 3 to 8 μm, and more preferably 4 to 7 μm. When the volume average particle diameter is less than 3 μm, in the two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. In the case of a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner may occur. When the volume average particle diameter exceeds 8 μm, it becomes difficult to obtain a high-resolution and high-quality image, and when the toner in the developer is balanced, the fluctuation of the toner particle diameter may increase. .

  The ratio of the volume average particle diameter to the number average particle diameter of the toner of the present invention is preferably 1.00 to 1.30, and more preferably 1.20 or less. As a result, in the two-component developer, even if the toner balance for a long period of time is performed, the toner particle diameter in the developer is little changed, and good and stable developability can be obtained even in the case of long-term stirring in the developing device. . In the case of 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 on a member such as a blade for thinning the toner Therefore, even when the developing device is used (stirred) for a long time, good and stable developability can be obtained, so that a high-quality image can be obtained. When this ratio exceeds 1.30, it is difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the toner particle diameter may increase. is there.

  The ratio of the volume average particle diameter to the volume average particle diameter and the number average particle diameter can be measured as follows using a particle size measuring device Multisizer III (manufactured by Beckman Coulter, Inc.). First, 0.1 to 5 ml of a surfactant such as alkyl benzene sulfonate is added as a dispersant to 100 to 150 ml of an aqueous electrolyte solution such as an about 1 wt% sodium chloride aqueous solution. Next, about 2 to 20 mg of a measurement sample is added. The aqueous electrolyte solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and then the volume and number of toners are measured using a 100 μm aperture to determine the volume distribution and number distribution. calculate. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.

  The toner of the present invention preferably contains 20 to 80% of all toner particles having a circularity of 0.950 or less. The circularity is a value obtained by dividing the circumference of a circle having an area equal to the projected area of the sample by the circumference of the sample. If particles having a circularity of 0.950 or less in the toner exceed 80%, a satisfactory transferability and a high-quality image free from dust may not be obtained. If it is less than%, an image forming apparatus employing blade cleaning or the like may cause poor cleaning on the photosensitive member or the transfer belt, and stains on the image may occur. For example, when forming an image with a high image area ratio, such as a photographic image, toner that has formed an untransferred image due to poor paper feed or the like accumulates on the photoconductor, causing image smudges or touching the photoconductor The charging roller or the like to be charged may be contaminated and the original charging ability may not be exhibited.

The average circularity can be measured by an optical detection band method in which a suspension containing toner is passed through an imaging unit detection band on a flat plate, a particle image is optically detected by a CCD camera, and analyzed. It can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation).
The toner of the present invention preferably contains 1 to 20% by number of particles having a particle size of 2 μm or less. Phenomenon such as filming of toner on the developing roller and fusion of toner to a member such as a blade for thinning the toner is greatly related to the content of fine powder. If it exceeds the number%, it will be an obstacle to adhesion to the carrier and stability of charging at a high level.

The toner has a shape factor SF1 of 115 or more and 130 or less. In addition, SF1 is the formula SF1 = π (L / 2) ² / A × 100
Defined by Here, L is an average value of the maximum length of the toner, and A is an average value of the projected area of the toner. The true sphere SF1 is 100, and the shape changes from spherical to indefinite as SF1 becomes larger than 100. In addition, L and A sample 100 images of the carrier expanded 300 times using FE-SEM S-800 (manufactured by Hitachi, Ltd.), for example. It is obtained by introducing into an analysis device Luzex AP (manufactured by Nireco) and analyzing.

The specific surface area of the toner of the present invention is preferably ^{0.5~3.0m 2 / g, 0.5~2.5m 2 /} g is more preferable. When the specific surface area is less than 0.5 m ² / g, the effect of the external additive added to the toner cannot be obtained, and the fluidity and chargeability of the toner may deteriorate, exceeding 3.0 m ² / g. If so, the transferability may deteriorate. The specific surface area can be measured using the BET method. Specifically, nitrogen gas can be adsorbed on the surface of the sample using a specific surface area measuring device Tristar 3000 (manufactured by Shimadzu Corporation), and measurement can be performed using the BET multipoint method.

The penetration of the toner of the present invention is preferably 15 mm or more, and more preferably 20 to 30 mm. When the penetration is less than 15 mm, the heat resistant storage stability may be deteriorated. The penetration can be measured by a penetration test (JIS K2235-1991).
Specifically, the toner is filled in a 50 ml glass container and left in a thermostat at 50 ° C. for 20 hours, and then the toner is cooled to room temperature and a penetration test is performed. In addition, it has shown that heat resistance preservability is excellent, so that the value of penetration is large.

  The toner of the present invention preferably has a low fixing minimum temperature and a high offset non-occurrence temperature from the viewpoint of achieving both low-temperature fixability and offset resistance. For this purpose, it is preferable that the minimum fixing temperature is less than 140 ° C. and the temperature at which no offset occurs is 200 ° C. or more. Here, the lower limit fixing temperature is the lower limit of the fixing temperature at which the residual ratio of the image density after a copy test using an image forming apparatus and rubbing the obtained image with a pad is 70% or more. The offset non-occurrence temperature can be obtained by measuring a temperature at which no offset occurs using an image forming apparatus adjusted to be developed with a predetermined amount of toner.

  The thermal characteristics of the toner, also called flow tester characteristics, are evaluated as a softening temperature, an outflow start temperature, a 1/2 method softening point, and the like. These thermal characteristics can be measured by an appropriately selected method, and can be measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).

The softening temperature of the toner of the present invention is preferably 30 ° C. or higher, and more preferably 50 to 90 ° C. When the softening temperature is less than 30 ° C., the heat resistant storage stability may be deteriorated.
The outflow start temperature of the toner of the present invention is preferably 60 ° C. or higher, and more preferably 80 to 120 ° C. When the outflow start temperature is less than 60 ° C., at least one of heat resistant storage stability and offset resistance may be deteriorated.

  The 1/2 method softening point of the toner of the present invention is preferably 90 ° C. or higher, more preferably 100 to 170 ° C. When the 1/2 method softening point is less than 90 ° C., the offset resistance may be deteriorated.

  The glass transition temperature of the toner of the present invention is preferably 40 to 70 ° C, more preferably 45 to 65 ° C. When the glass transition temperature is less than 40 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient. The glass transition temperature can be measured using a differential scanning calorimeter DSC-60 (manufactured by Shimadzu Corporation) or the like.

The density of an image formed using the toner of the present invention is preferably 1.40 or more, more preferably 1.45 or more, and further preferably 1.50 or more. If the image density is less than 1.40, the image density may be low and high image quality may not be obtained. The image density was determined by using a tandem color electrophotographic apparatus “Imagio Neo 450” (manufactured by Ricoh), setting the surface temperature of the fixing roller to 160 ± 2 ° C. A solid image of 1.00 ± 0.1 mg / cm ² was formed, and the image density at any five positions in the obtained solid image was measured using a spectrometer 938 spectrodensitometer (manufactured by X-Light). It can be obtained by measuring and calculating the average value.

  The color of the toner of the present invention can be appropriately selected according to the purpose, and can be one or more selected from the group consisting of black toner, cyan toner, magenta toner, and yellow toner. It can be obtained by appropriately selecting a colorant.

  The developer of the present invention contains the toner of the present invention, and may further contain other components appropriately selected such as a carrier. For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably. The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like that supports an increase in information processing speed in recent years, the lifetime is shortened. A two-component developer is preferred because it improves.

When the developer of the present invention is used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, the blade for thinning the toner, etc. Therefore, good and stable developability and images can be obtained even with long-term stirring in the developing device.
When the developer of the present invention is used as a two-component developer, there is little fluctuation in the particle diameter of the toner even if the toner balance is maintained over a long period of time, and good and stable developability even with long-term agitation in the developing device. An image is obtained.

The carrier can be appropriately selected according to the purpose, but a carrier having a core material and a resin layer covering the core material is preferable.
The material of the core material can be appropriately selected from known materials, and examples thereof include 50 to 90 emu / g manganese-strontium-based material, manganese-magnesium-based material, and the like. In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 to 120 emu / g. In addition, it is preferable to use a low-magnetization material such as 30-80 emu / g of copper-zinc system because it can reduce the impact of the developer in a spiked state on the photoconductor and is advantageous for high image quality. . These may be used alone or in combination of two or more.

  The volume average particle diameter of the core material is preferably 10 to 150 μm, and more preferably 40 to 100 μm. If the volume average particle size is less than 10 μm, fine particles are increased in the carrier, and magnetization per particle may be reduced to cause carrier scattering. If it exceeds 150 μm, the specific surface area is decreased, and In the case of a full color with many solid portions, the reproduction of the solid portions may be deteriorated.

  The material of the resin layer can be appropriately selected from known resins according to the purpose, but amino resin, polyvinyl resin, polystyrene resin, polyhalogenated olefin, polyester resin, polycarbonate resin, polyethylene , Polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Examples include fluoroterpolymers such as copolymers of monomers having no fluoro group, silicone resins, and the like. These may be used alone or in combination of two or more.

  Specific examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Specific examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral. Specific examples of the polystyrene resin include polystyrene and styrene-acrylic copolymer. Specific examples of the polyhalogenated olefin include polyvinyl chloride. Specific examples of the polyester resin include polyethylene terephthalate and polybutylene terephthalate.

The resin layer may contain conductive powder or the like as necessary. Specific examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of the conductive powder is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control the electric resistance.
The resin layer can be formed by preparing a coating solution by dissolving a silicone resin or the like in a solvent, and then applying and drying the coating solution on the surface of the core using a known coating method, followed by baking. it can. As a coating method, a dip coating method, a spray method, a brush coating method, or the like can be used. The solvent can be appropriately selected depending on the purpose, and examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and butyl cellosolve. The baking may be an external heating method or an internal heating method, a method using a fixed electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, a method using a microwave, or the like. Is mentioned.

The content of the resin layer in the carrier is preferably 0.01 to 5.0% by weight. When this content is less than 0.01% by weight, a uniform resin layer may not be formed on the surface of the core material. May occur, and the uniformity of the carrier may be reduced.
The content of the carrier in the two-component developer is preferably 90 to 98% by weight, and more preferably 93 to 97% by weight.
The developer of the present invention can be used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

The toner-containing container of the present invention has the toner of the present invention. The toner-containing container of the present invention includes the case of having the developer of the present invention.
The container of the toner container can be appropriately selected from known containers, and those having a container body and a cap are preferably used.
The size, shape, structure, material and the like of the container body can be appropriately selected according to the purpose.
The shape is preferably cylindrical or the like, and preferably has spiral irregularities formed on the inner peripheral surface, and part or all of the spiral portion has a bellows function. By rotating such a container main body, the toner as the contents can be transferred to the discharge port side.
The material of the container body is preferably a material with good dimensional accuracy, and examples thereof include resins such as polyester resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylic acid, polycarbonate resin, ABS resin, and polyacetal resin.
The toner-containing container of the present invention can be easily stored and transported, has excellent handleability, and can be removably attached to a process cartridge, an image forming apparatus or the like to supply toner.

The process cartridge of the present invention has a developing means and an image carrier having the developer of the present invention, and may further have other means appropriately selected as necessary. As a result, the electrostatic latent image carried on the image carrier can be developed using the developer to form a visible image.
The developing means preferably includes the toner-containing container of the present invention and a developer carrier for carrying and transporting the developer, and further includes a layer thickness regulating member for regulating the thickness of the toner layer to be carried. May be.
The process cartridge of the present invention can be detachably attached to the image forming apparatus main body.

The image forming method of the present invention forms an image using the developer of the present invention. For this reason, high image quality can be obtained efficiently.
The image forming method of the present invention preferably includes an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step. If necessary, a static elimination step, a cleaning step, a recycling step, a control step, etc. You may have a process further.

An image forming apparatus for forming an image using the developer of the present invention includes an image carrier, an electrostatic latent image forming unit, a developing unit having the developer of the present invention, a transfer unit, and a fixing unit. Preferably, it may further include means such as a static elimination means, a cleaning means, a recycling means, and a control means as necessary.
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the image carrier. The material, shape, structure, size and the like of the image carrier can be appropriately selected from known ones. Examples of the material include inorganic substances such as amorphous silicon and selenium, and organic substances such as polysilane and phthalopolymethine. Amorphous silicon is preferable because of its long life. Further, the shape is preferably a drum shape. The electrostatic latent image can be formed by uniformly charging the surface of the image carrier and then exposing it imagewise, and can be performed by an electrostatic latent image forming unit. The electrostatic latent image forming means preferably has a charger that uniformly charges the surface of the image carrier and an exposure device that exposes the surface of the image carrier.

Charging can be performed by applying a voltage to the surface of the image carrier using a charger. The charger can be appropriately selected according to the purpose, but a known contact charger equipped with a conductive or semiconductive roll, brush, film, rubber blade, etc., or corona discharge such as corotron or scorotron is used. Non-contact chargers and the like.
The exposure can be performed by exposing the surface of the image carrier using an exposure device. The exposure device can be appropriately selected according to the purpose, but various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used. It should be noted that an optical back side system in which exposure is performed from the back side of the image carrier may be adopted.

  The development step is a step of forming a visible image by developing the electrostatic latent image using the developer of the present invention. The visible image can be formed using a developing unit. The developing means can be appropriately selected from known ones, and preferably has a developing device that accommodates the developer of the present invention and can apply the developer to the electrostatic latent image in a contact or non-contact manner. As the developing device, it is preferable to use a developing device provided with the toner container of the present invention. The developing device may be a dry development system or a wet development system. Further, it may be a single color developer or a multicolor developer. Specifically, a stirrer for charging the developer by friction stirring and a developer having a rotatable magnet roller can be used. The developer accommodated in the developing device is the developer of the present invention, but may be a one-component developer or a two-component developer.

  In a developing device having a two-component developer, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the image carrier by an electric attractive force. As a result, the electrostatic latent image is developed with toner, and a visible image is formed with toner on the surface of the image carrier.

The transfer step is a step of transferring a visible image to a recording medium. The intermediate transfer member is used to primarily transfer the visible image onto the intermediate transfer member, and then the secondary transfer of the visible image onto the recording medium. It is preferable. At this time, the toner used is usually two or more colors, and it is preferable to use a full-color toner. For this reason, it is more preferable to have a primary transfer process in which a visible image is transferred onto an intermediate transfer member to form a composite transfer image, and a secondary transfer process in which the composite transfer image is transferred onto a recording medium.
The transfer can be performed by charging the image carrier using a transfer unit. The transfer means preferably has a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. The intermediate transfer member can be appropriately selected from known transfer members according to the purpose, and a transfer belt or the like can be used.

The transfer means preferably has a transfer device that peels and charges the visible image formed on the image carrier to the recording medium side. There may be one transfer means or a plurality of transfer means. Specific examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. The recording medium can be appropriately selected from known recording media, and recording paper or the like can be used. The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit. The toner may be fixed each time the toner of each color is transferred to the recording medium, or may be fixed at once in a state where the toner of each color is laminated. The fixing unit can be appropriately selected according to the purpose, but a known heating and pressing unit can be used. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. The heating in the heating and pressurizing means is usually preferably 80 ° C to 200 ° C. A known optical fixing device may be used together with or instead of the fixing unit depending on the purpose.

The neutralization step is a step of neutralizing by applying a neutralization bias to the image carrier, and can be performed using a neutralization unit. The neutralization means can be appropriately selected from known neutralizers, and a neutralization lamp or the like can be used.
The cleaning step is a step of removing toner remaining on the image carrier, and can be performed using a cleaning unit. The cleaning means can be appropriately selected from known cleaners, and a magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, web cleaner, or the like can be used.

The recycling process is a process in which the toner removed by the cleaning process is recycled by the developing unit, and can be performed using the recycling unit. The recycling means can be appropriately selected according to the purpose, and a known conveying means or the like can be used.
The control means is a process for controlling each process, and can be performed using the control means. The control means can be appropriately selected according to the purpose, and devices such as a sequencer and a computer can be used.

  FIG. 1 shows an example of an image forming apparatus used in the present invention. The image forming apparatus 100A includes a drum-shaped photosensitive member 10 as an additional carrier, a charging roller 20 as a charging unit, an exposure device 30 as an exposure unit, a developing device 40 as a developing unit, and an intermediate transfer member 50. And a cleaning device 60 as a cleaning means and a static elimination lamp 70 as a static elimination means.

  The intermediate transfer member 50 is an endless belt, and is stretched by three rollers 51 so as to be movable in the direction of the arrow. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. A cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50. In addition, a transfer roller 80 serving as a transfer unit capable of applying a transfer bias for transferring (secondary transfer) a visible image (toner image) to a recording sheet 95 serving as a recording medium is disposed to face the recording paper 95. . Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is in contact with the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. And the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as a developer carrying member, and a black developing device 45K, a yellow developing device 45Y, a magenta developing device 45M, and a cyan developing device 45C provided around the developing belt 41. The black developing device 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing device 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developer 45M includes a developer container 42M, a developer supply roller 43M, and a developer roller 44M. The cyan developer 45C includes a developer container 42C, the developer supply roller 43C, and a developer. A roller 44C is provided. The developing belt 41 is an endless belt, is stretched by a plurality of belt rollers so as to be movable in the direction of the arrow, and a part of the developing belt 41 is in contact with the photoreceptor 10.

  In the image forming apparatus 100A, the charging roller 20 uniformly charges the photoconductor 10, and then exposes the photoconductor 10 using the exposure device 30 to form an electrostatic latent image. Next, the electrostatic latent image formed on the photoreceptor 10 is developed by supplying a developer from the developing device 40 to form a toner image. Further, the toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied by the roller 51, and further transferred (secondary transfer) onto the recording paper 95. As a result, a transfer image is formed on the recording paper 95. The toner remaining on the photoconductor 10 is removed by a cleaning device 60 having a cleaning blade, and the charged charge on the photoconductor 10 is removed by a static elimination lamp 70.

  FIG. 2 shows another example of the image forming apparatus used in the present invention. The image forming apparatus 100B does not include the developing belt 41, except that a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C are arranged around the photoconductor 10 so as to face each other. It has the same configuration as that of the image forming apparatus 100A and exhibits the same function and effect. In FIG. 2, the same components as those in FIG. 1 are denoted by the same reference numerals.

FIG. 3 shows another example of the image forming apparatus used in the present invention. The image forming apparatus 100C is a tandem color image forming apparatus. The image forming apparatus 100 </ b> C includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder 400. The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16 so as to be able to move clockwise in the drawing. An intermediate transfer body cleaning device 17 for removing toner remaining on the intermediate transfer body 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched by the support rollers 14 and 15 is provided with a tandem developing device in which image forming means 18 of four colors of yellow, cyan, magenta, and black are opposed to each other along the conveying direction. 120 is arranged. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 can contact each other. It is. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the image forming apparatus 100C, a sheet reversing device 28 for reversing the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Thereby, images can be formed on both sides of the recording paper.

Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. First, a document is set on the document table 130 of the automatic document feeder 400, or the automatic document feeder 400 is opened to set a document on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed.
When a start switch (not shown) is pressed, when an original is set on the automatic document feeder 400, after the original is conveyed onto the contact glass 32, on the other hand, when an original is set on the contact glass 32, Immediately, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, the reflected light from the original surface of the light irradiated by the first traveling body 33 is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35. As a result, a color original (color image) is read and used as image information for each color of black, yellow, magenta, and cyan. The image information of each color is transmitted to the image forming means 18 of each color in the tandem developing device 120, and a toner image of each color is formed.

  The toner image on the black photoconductor 10K, the toner image on the yellow photoconductor 10Y, the toner image on the magenta photoconductor 10M, and the toner image on the cyan photoconductor 10C are sequentially transferred onto the intermediate transfer member 50. (Primary transfer). Then, the toner images of the respective colors are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  As shown in FIG. 4, the image forming means 18 for each color in the tandem developing device 120 includes a photosensitive member 10, a charger 59 for uniformly charging the photosensitive member 10, and a photosensitive device based on image information of each color. By exposing the body 10 (L in the figure), an exposure device 21 that forms an electrostatic latent image on the photoreceptor 10, and developing the electrostatic latent image using toner of each color, the photoreceptor 10 A developing unit 61 that forms toner images of the respective colors, a transfer charger 62 that transfers the toner images of the respective colors onto the intermediate transfer member 50, a photoconductor cleaning device 63, and a static eliminator 64 are provided.

On the other hand, in the paper feed table 200, one of the paper feed rollers 142a is selectively rotated to feed recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145a. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the paper feed roller 142b is rotated to feed out the recording paper on the manual feed tray 52, separated one by one by the separation roller 145b, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in time with the color transfer image formed on the intermediate transfer member 50, and the recording paper is fed between the intermediate transfer member 50 and the secondary transfer device 22, thereby being recorded on the recording paper. A color transfer image is formed. The toner remaining on the intermediate transfer member 50 after the transfer is cleaned by the intermediate transfer member cleaning device 17.

  The recording paper on which the color transfer image is formed is conveyed to the fixing device 25 by the secondary transfer device 22, and the color transfer image is fixed on the recording paper by heat and pressure. Thereafter, the recording paper is switched by the switching claw 55 and discharged by the discharge roller 56 and is stacked on the discharge tray 57. Alternatively, the sheet is switched by the switching claw 55, reversed by the sheet reversing device 28, led to the transfer position again, and after the image is formed on the back surface, the sheet is discharged by the discharge roller 56 and stacked on the discharge tray 57.

Examples of the present invention will be described below, but the present invention is not limited to the following examples. In addition, a part means a weight part in an Example.
Example 1
229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propion oxide 3-mole adduct, 208 parts of terephthalic acid, 46 parts of adipic acid and dibutyltin oxide 2 parts were added and reacted at 230 ° C. under normal pressure for 8 hours. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure, (unmodified polyester resin 1) Was synthesized.
The obtained (unmodified polyester resin 1) had a number average molecular weight of 2500, a weight average molecular weight of 6700, a glass transition temperature of 43 ° C., and an acid value of 25 mgKOH / g.

  1200 parts of water, 540 parts of carbon black Printex 35 (manufactured by Dexa; DBP oil absorption = 42 ml / 100 mg, pH = 9.5) and 1200 parts of unmodified polyester resin were mixed using a Henschel mixer (manufactured by Mitsui Mining). . The resulting mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare (Masterbatch 1).

In a reaction vessel equipped with a stir bar and a thermometer, 378 parts of unmodified polyester resin, 110 parts of carnauba wax, and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and held at 80 ° C. for 5 hours. Then, it cooled to 30 degreeC over 1 hour. Next, 500 parts of a master batch and 500 parts of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain a raw material solution.
1324 parts of the obtained raw material solution was transferred to a reaction vessel, and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill Ultra Visco Mill (manufactured by Imex Co., Ltd.). 3 passes under the condition of 6 m / sec. I. Pigment Red and carnauba wax were dispersed to obtain a wax dispersion.

Next, 1324 parts of a 65 wt% ethyl acetate solution of unmodified polyester resin was added to the wax dispersion. As a charge control agent, 2.0 parts of Clayton APA (manufactured by Southern Clay Products) is added to 200 parts of a dispersion obtained by one pass using Ultraviscomil under the same conditions as described above. K. Using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred at 7000 rpm for 60 minutes to obtain a toner material dispersion.
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 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 and reacted at 230 ° C. for 8 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester resin was synthesize | combined.
The obtained intermediate polyester resin had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition temperature of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g.

Next, 410 parts of the intermediate polyester resin, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Was synthesized. The free isocyanate content of the obtained prepolymer was 1.53% by weight.
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound. The amine value of the obtained ketimine compound was 418 mgKOH / g.
In a reaction vessel, 749 parts of a dispersion of toner material, 115 parts of a prepolymer and 2.9 parts of a ketimine compound are charged and mixed at 5,000 rpm for 1 minute using a TK homomixer (manufactured by Tokushu Kika). A mixture was obtained.

In a reaction vessel equipped with a stir bar and thermometer, 683 parts of water, 11 parts of reactive emulsifier (sodium salt of methacrylic acid ethylene oxide adduct) Eleminol RS-30 (manufactured by Sanyo Chemical Industries), styrene 83 Parts, 83 parts of methacrylic acid, 110 parts of butyl acrylate and 1 part of ammonium persulfate were stirred at 400 rpm for 15 minutes to obtain an emulsion. The emulsion was heated, heated to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% by weight aqueous ammonium persulfate solution was added and aged at 75 ° C. for 5 hours to prepare a resin particle dispersion.
The volume average particle size of the resin particles contained in the obtained resin particle dispersion was measured using a particle size distribution measuring apparatus Microtrac Ultra Fine Particle Size Distribution Meter UPA-EX150 (made by Nikkiso Co., Ltd.) using a laser Doppler method. However, it was 105 nm. Further, a part of the resin particle dispersion was dried to isolate the resin, and the glass transition temperature of the resin was measured. As a result, it was 59 ° C. and the weight average molecular weight was 150,000.

990 parts of water, 83 parts of resin particle dispersion, 37 parts of a 48.5% by weight aqueous solution of dodecyl diphenyl ether disulfonate, Eleminol MON-7 (manufactured by Sanyo Kasei Kogyo Co., Ltd.), 1% by weight aqueous solution of sodium carboxymethylcellulose polymer dispersant 135 parts of BS-H-3 (Daiichi Kogyo Seiyaku Co., Ltd.) and 90 parts of ethyl acetate were mixed and stirred to obtain an aqueous medium.
To 1200 parts of the aqueous medium, 867 parts of the oil phase mixed liquid was added and mixed for 20 minutes at 13000 rpm using a TK homomixer to prepare a dispersion (emulsified slurry).

Next, the emulsified slurry was charged into a reaction vessel in which a stirrer and a thermometer were set, and after removing the solvent at 30 ° C. for 8 hours, aging was performed at 45 ° C. for 4 hours to obtain a dispersed slurry.
The obtained dispersion slurry was measured using Multisizer III (manufactured by Beckman Coulter, Inc.). The volume average particle size was 5.1 μm and the number average particle size was 4.3 μm.
After 100 parts by weight of the dispersion slurry was filtered under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, mixed at 12000 rpm for 10 minutes using a TK homomixer, and then filtered.
The obtained filter cake was added with 10% by weight phosphoric acid to adjust the pH to 3.7, mixed at 12000 rpm for 10 minutes using a TK homomixer, and then filtered.

Furthermore, 300 parts of ion-exchanged water was added to the obtained filter cake, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice to obtain a final filter cake.
The obtained final filter cake was dried at 45 ° C. for 48 hours using a circulating drier, and sieved with a mesh having an opening of 75 μm to obtain (toner mother particles 1).
To 100 parts of the obtained toner base particles, 1.0 part of hydrophobic silica as an external additive and 0.5 part of hydrophobic titanium oxide are added and mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). (Toner 1) was produced.

(Example 2)
(Toner base particle 2) (toner 2) was produced in the same manner as in Example 1 except that the amount of Kraton APA used as the charge control agent was changed from 2.0 parts to 1.0 part. .
(Example 3)
(Toner base particles 3) (toner 3) were produced in the same manner as in Example 1 except that the addition amount of Clayton APA was changed from 2.0 parts to 0.15 parts.
Example 4
(Toner base particles 4) (toner 4) were produced in the same manner as in Example 1 except that the addition amount of Clayton APA was changed from 2.0 parts to 4.0 parts.
(Example 5)
Toner mother particles 5 (toner 5) were produced in the same manner as in Example 1 except that Clayton APA was changed to Clayton HY (manufactured by Southern Clay Products).
(Example 6)
Toner mother particles 6 (toner 6) were manufactured in the same manner as in Example 1 except that Clayton APA was changed to Clayton AF (manufactured by Southern Clay Products).

(Example 7)
-Preparation of colorant dispersion (1)-
Carbon black (Degussa: Printex 35) 125 parts Azisper PB821 (Azinomoto Finetech) 18.8 parts Ethyl acetate (Wako Pure Chemical Industries, Ltd .: Special grade) 356.2 parts Ultraviscomyl ( A colorant dispersion liquid (1) was prepared by dissolving / dispersing using an Imex Corporation and dispersing a colorant (black pigment).

(Preparation of release agent dispersion)
-Preparation of release agent dispersion (1) (wax component A)-
Carnauba wax (melting point: 83 ° C., acid value 8 mg KOH / g, saponification value 80 mg KOH / g) 30 parts Ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd .: special grade) 270 parts Ultraviscomil (made by IMEX) Was used for wet pulverization to prepare a release agent dispersion (1).

-Preparation of a layered compound modified with an organic cation (a deforming agent dispersion A)-
・ Clayton APA (manufactured by Southern Clay Products) 30 parts ・ Ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd .: special grade) 270 parts or more Wet-pulverize with Ultraviscomyl (manufactured by Imex) to disperse the deforming agent Liquid A was prepared.
・ Polyester (1)
Polyester resin composed of bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, terephthalic acid derivative (Mw 50,000, Mn 3,000, acid value 15 mgKOH / g, hydroxyl value 27 mg
KOH / g, Tg 55 ° C, softening point 112 ° C)
350 parts-Colorant dispersion (1) 237 parts-Release agent dispersion (1) 72 parts-Profiler dispersion A 304 parts-Hydrophobic silicon oxide fine particles (Aerosil R972) 17.8 parts The mixture was mixed and stirred well until uniform (this solution was designated as solution A).

  On the other hand, 100 parts of calcium carbonate dispersion in which 40 parts of calcium carbonate fine particles were dispersed in 60 parts of water, 200 parts of 1% aqueous solution of Serogen BS-H (Daiichi Kogyo Seiyaku Co., Ltd.), and 157 parts of water were added. K. The mixture was stirred for 3 minutes using a homodisper fmodel (manufactured by Primix) (this solution was designated as solution B). In addition, T.W. K. Using a homomixer mark2 fmodel (manufactured by Primix), 345 parts of the solution B and 250 parts of the solution A were stirred at 10,000 rpm for 2 minutes to suspend the mixed solution, and then propeller type at room temperature and normal pressure for 48 hours. The solvent was removed by stirring with a stirrer. Next, hydrochloric acid was added to remove calcium carbonate, followed by washing with water, drying and classification to obtain toner base particles 7 (toner 7). The average particle size of the toner was 6.2 μm.

(Example 8)
-Preparation of solvent-free resin-
Monomer mixed solution in which 100 parts by weight of styrene and 0.7 parts by weight of di-tertiary butyl peroxide are uniformly mixed in an autoclave equipped with a stirrer, a heating device and a cooling device controlled at 215 ° C. Was continuously added in 30 minutes, and further maintained at 215 ° C. for 30 minutes to obtain a solventless resin. The resulting solventless resin had a molecular weight peak Mp of 4,150 and a weight average molecular weight Mw of 4,800.

(Adjustment of resin emulsion dispersion)
A container equipped with a stirrer and a dropping pump was charged with 27 parts by weight of deionized water and 1 part by weight of an anionic emulsifier (Daiichi Kogyo Seiyaku Co., Ltd .: trade name Neogen SC-A). A monomer mixture composed of parts by weight, 25 parts by weight of butyl acrylate, and 0.05 parts by weight of divinylbenzene was added dropwise with stirring to obtain a monomer emulsified dispersion.
Next, in a pressure-resistant reaction vessel equipped with a stirrer, a pressure gauge, a thermometer, and a dropping pump, 120 parts by weight of deionized water was charged and purged with nitrogen, and then the temperature was raised to 80 ° C. 5% by weight was added to a pressure resistant reactor, and 1 part by weight of a 2% by weight aqueous potassium persulfate solution was further added, and initial polymerization was performed at 80 ° C. After completion of the initial polymerization, the temperature was raised to 85 ° C. and the remaining monomer emulsified dispersion and 4 parts by weight of 2% by weight potassium persulfate were added over 3 hours, and then maintained at the same temperature for 2 hours. A styrene-based resin emulsion dispersion having a solid content concentration of 0.15 μm was obtained. The obtained resin emulsion dispersion had a high polymerization conversion rate and could be polymerized stably. As a result of analyzing the molecular weight after separating the resin with an ultracentrifuge, the weight average molecular weight Mw was 950,000 and the molecular weight peak Mp was 700,000.
100 parts by weight of the above solvent-free resin and 135 parts by weight of the above resin emulsified dispersion are continuously mixed and heated at a jacket temperature of 215 ° C. with a continuous kneader (manufactured by Kurimoto Kakosho: trade name KRC Kneader). Then, a water removal treatment was performed to obtain an evaporative dehydration kneaded product having a water content of 0.1% or less. The residual monomer content in the obtained evaporative dehydration kneaded product was 80 ppm. The evaporative dehydrated kneaded product was cooled and then roughly crushed with a hammer mill and then finely pulverized with a jet mill to obtain a styrene acrylic resin (1).
A toner base particle 8 (toner 8) was obtained in the same manner as in Example 7 except that the polyester (1) in Example 7 was changed to the styrene acrylic resin (1).

Example 9
After introducing 5 parts by mass of Na ₃ PO ₄ into 500 parts by mass of ion-exchanged water and heating to 60 ° C., a Claremix high-speed stirrer (manufactured by M Technique, peripheral speed 22 m / s) is installed and stirred. did. To this, an aqueous solution in which ₂ parts by mass of CaCl ₂ was dissolved in 15 parts by mass of ion exchange water was quickly added to obtain an aqueous dispersion medium containing Ca ₃ (PO ₄ ) ₂ .
Polymerizable monomer Styrene 85 parts by mass n-butyl acrylate 20 parts by mass Colorant C.I. I. Pigment Blue 15: 3 7.5 parts by mass / charge control agent E-88 (manufactured by Orient Chemical Industries) 1 part by mass / polar resin saturated polyester 5 parts by mass (acid value 10 mgKOH / g, peak molecular weight: 7,500)
Release agent Ester wax (Maximum endothermic peak temperature in DSC: 72 ° C.) 15 parts by mass Clayton APA (manufactured by Southern Clay Products) 15 parts by mass Each material was uniformly dissolved or dispersed in the monomer. To this was added 3 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator to prepare a polymerizable monomer composition.
The polymerizable monomer composition is introduced into the aqueous dispersion medium, and then at a temperature of 60 ° C. and N ₂ atmosphere for 15 minutes with a CLEARMIX high-speed stirrer (manufactured by M Technique, peripheral speed 22 m / s). Stirring to produce particles of the polymerizable monomer composition in the aqueous dispersion medium. After the dispersion, the stirring apparatus was stopped and introduced into a polymerization apparatus equipped with a full zone stirring blade (manufactured by Shinko Pantech Co., Ltd.). In the polymerization apparatus 11, the polymerizable monomer was reacted for 5 hours while stirring the stirring blade at a maximum stirring peripheral speed: 3 m / s under a temperature of 60 ° C. and an N ₂ atmosphere. Thereafter, the temperature was raised to 80 ° C., and the polymerizable monomer was further reacted for 5 hours. After the completion of the polymerization reaction, toner mother particles 9 (toner 9) were obtained by washing with water, drying and classification. The average particle size of the toner was 5.8 μm.

(Example 10)
Toner mother particles 10 (toner 10) were produced in the same manner as in Example 1 except that Clayton APA was changed to Bentone SD-2 (Elementis).

(Comparative Example 1)
Preparation of unmodified polyester In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propion oxide 3-mole adduct, 208 parts of terephthalic acid, isododecenyl anhydride 80 parts of oxalic acid, 44 parts of trimellitic anhydride and 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 10 hours under normal pressure to synthesize an unmodified polyester resin.
The obtained unmodified polyester resin had a number average molecular weight of 7200, a weight average molecular weight of 16000, a glass transition temperature of 65 ° C., and an acid value of 15 mgKOH / g. (Unmodified polyester 2)
Preparation of toner Unmodified polyester 2 85 parts Masterbatch 1 15 parts Clayton APA 1 part The above materials were sufficiently stirred and mixed with a Henschel mixer, and then kneaded for 1 hour with two rolls with a roll surface of 100 degrees, 5 degrees After rolling and cooling at / min and coarse pulverization, pulverization and classification were performed using an I-2 type mill (manufactured by Nippon Pneumatic Kogyo Co., Ltd.) and a DS classifier (manufactured by Nippon Pneumatic Co., Ltd.). Toner mother particles 6 were obtained.
To 100 parts of the obtained toner base particles, 1.0 part of hydrophobic silica as an external additive and 0.5 part of hydrophobized titanium oxide are added and mixed using a Henschel mixer (Mitsui Mining Co., Ltd.). Thus, toner mother particles 11 (toner 11) were produced.

(Comparative Example 2)
(Toner base particles 12) (toner 12) were produced in the same manner as in Comparative Example 1, except that the amount of Kraton APA used as the charge control agent was changed from 1.0 part to 2.0 parts. .
(Comparative Example 3)
(Toner base particle 13) (toner 13) was produced in the same manner as in Comparative Example 1 except that the amount of Kraton APA used as the charge control agent was changed from 1.0 part to 4.0 parts. .
(Comparative Example 4)
(Toner base particle 14) (toner 14) Manufactured.

The toner was evaluated.
(XPS)
Equipment used: PHI 1600S type X-ray photoelectron spectrometer Usage conditions: X-ray source MgKα (100 W)
Analysis area 0.8 × 2.0mm
The sample is measured by placing a toner on a carbon sheet on a sample holder.
The toner is melt-kneaded by batch-type kneading using a lab plast mill 4C150 (manufactured by Toyo Seiki Co., Ltd.). The toner amount is 45 g, the heating temperature is 130 ° C., and the rotation speed is 50 rpm. The subsequent block was roughly crushed and similarly placed on a carbon sheet for measurement.
The surface atomic concentration was calculated from the peak intensity of each atomic concentration measured using a relative sensitivity factor provided by PHI, and the surface atomic concentration was estimated.
In this measurement, since the layered inorganic compound contains Al, the atomic concentration% of Al was measured.

The measurement results are shown.

比較例となる粉砕トナーについては、混練後も値が変わらない。
また実施例６、実施例９ではＡ＞Ｂ×１．４が成立しない。 Similarly, the kneaded product was measured by XPS. Of the results, the surface atomic concentration of Al before and after kneading in Table 2 is shown.

The value of the pulverized toner as a comparative example does not change even after kneading.
In the sixth and ninth embodiments, A> B × 1.4 does not hold.

The toner mother particles or toners obtained in Examples 1 to 10 and Comparative Examples 1 to 4 were evaluated as follows.
(Quantification of layered inorganic mineral in toner)
The addition amount of the layered inorganic mineral was determined by fluorescent X-ray.
A calibration curve was prepared by preparing a toner in which a predetermined amount of a layered inorganic mineral was added to the toner in advance.
The sample was prepared by 3 g of toner obtained after drying, an automatic pressure molding machine (manufactured by T-BRB-32 Maekawa), a load of 6.0 t, a pressurization time of 60 sec (manufacturer and conditions) to a diameter of 3 mm and a thickness of 2 mm. The pellets were molded, and the layered inorganic mineral in the toner was measured by quantitative analysis with a fluorescent X-ray apparatus (ZSX-100e, manufactured by Rigaku Denki).

(Chargeability)
9 g of carrier and 1 g of toner base particles were placed in a stainless steel cylindrical pot having a diameter of 30 mm and a width of 30 mm, and stirred at 600 rpm.
Stirring time was 60 sec, 10 min, 24 hours, and charging property at 3 points was confirmed.
After stirring, 1 g of the stirred developer was measured using a blow-off device manufactured by Toshiba Chemical Corporation. Further, after measuring the charge amount after stirring for 24 hours, the blown carriers were collected again, new toner base particles were added, and the charge amount was confirmed again after stirring for 10 minutes.
Here, stirring for 60 seconds is used as an index for determining the rising property of the charging property, and it is preferable that the stirring amount is approximately equal to the charging amount after 10 minutes.
In addition, the chargeability needs to be flat when stirring for 10 minutes and stirring for one day. If the charge amount after one day is lowered, the influence of spent or the like, the influence of leakage of chargeability, etc. can be considered.
Furthermore, the chargeability is measured again after blowing, and the chargeability after 10 minutes is confirmed (comparison is the charge after a new 10 minutes). The toner base particle component adheres to the carrier surface, and the new toner enters. However, it is confirmed that the charging ability does not decrease. If this charge is lower than the new combination, there is an effect of spent etc., and it can be determined that it cannot withstand long-term use.

(Skin cover)
After running 10,000 sheets with the Ricoh ipsio Color 8100, the sheet was stopped when the white paper was developed, and the soiled portion on the photoreceptor was transferred, and the id was measured. If it is 0.03 or more, it becomes a background contamination danger area, and if it is 0.05 or more, it becomes background contamination, which is a level that appears in the image.

(Fixability)
Remodel the fixing machine with Ricoh ipsio color 8100, adjust the hot water to develop 1.0 ± 0.1mg / cm ² of toner on solid images, and fix the temperature at which no offset occurs with Ricoh type6200 paper Temperature and fixing minimum temperature were measured with RICOH TYPE6000 / 90W paper. The minimum fixing temperature was determined as the minimum fixing temperature, which was the roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad was 70% or more.
When the lower limit fixing temperature is 150 ° C. or more, it is determined that the margin is not sufficient and it cannot be used (×). If it was 140 degrees C or less, it was judged that there was a margin ((circle)), and 140-150 degreeC was ((triangle | delta)) in the meantime.
Further, with respect to the fixing width, those having 50 degrees or more were judged as ◯, 40 to 50 degrees as Δ, and 40 degrees or less as x.

The evaluation results are shown in Table 3.

It is a schematic explanatory drawing which shows an example of the image forming apparatus used by this invention. It is a schematic explanatory drawing which shows the other example of the image forming apparatus used by this invention. It is a schematic explanatory drawing which shows the other example of the image forming apparatus used by this invention. FIG. 4 is a schematic explanatory view showing a part of the image forming apparatus shown in FIG. 3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Photoconductor 10K Black photoconductor 10Y Yellow photoconductor 10M Magenta photoconductor 10C Cyan photoconductor 14, 15, 16 Support roller 17 Intermediate transfer body cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer Device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing Belt 42K, 42Y, 42M, 42C Developer container 43K, 43Y, 43M, 43C Developer supply roller 44K, 44Y, 44M, 44C Developer roller 45K Black developer 45Y Yellow developer 45M Magenta developer 45C Cyan Present Device 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Manual feed tray 53 Manual feed path 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona charger 59 Charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Static eliminator 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Recording paper 100A, 100B, 100C Image forming device 110 Belt type fixing device 120 Tandem type developer 130 Document table 142a, 142b Paper feed roller 143 Paper bank 144 Paper feed cassette 145a, 145b Separating roller 146 Feeding path 147 Conveying roller 148 Feeding path 150 Copier main body 200 Feeding table 300 Scanner 400 Automatic document feeder

Claims (33)

In a toner in which an oil phase containing at least a binder resin and / or a binder resin precursor and a layered inorganic mineral in which at least some of the ions between layers are modified with organic ions is dispersed and / or emulsified in an aqueous medium and granulated. When the atomic concentration% of the specific element constituting the layered inorganic mineral when the toner is measured by XPS is A, and the atomic concentration% of the specific element when the toner is measured by XPS after melting and kneading is B , A> B. Toner.   The toner according to claim 1, wherein A> B × 1.4.   The toner according to claim 1, wherein the specific element is Al and A> 0.5 atomic%.   The toner according to claim 1, wherein the modified layered inorganic mineral is a layered inorganic mineral obtained by modifying at least a part of cations between layers with an organic cation. To any one of claims 1 to 4, the amount of the layered inorganic mineral at least part of the interlayer ions contained modified with organic ions in the toner is characterized in that 0.05 to 5.0 wt% The toner described. To any one of claims 1 to 5, the amount of the layered inorganic mineral at least part of the interlayer ions contained modified with organic ions in the toner is characterized in that 0.05 to 2.0 wt% The toner described. The toner according to any one of claims 1-6, characterized in that it contains at least two binder resins. The toner according to claim 3 , wherein the first binder resin contained in the binder resin is a resin having a polyester skeleton. The toner according to claim 8 , wherein the first binder resin is a polyester resin. The toner according to claim 9 , wherein the polyester resin is an unmodified polyester resin. 11. The toner according to claim 3 , wherein the content of the polyester resin component contained in the binder resin in the binder resin is 50 to 100% by weight. The toner according to any one of claims 3 to 11 , wherein the polyester resin component contained in the binder resin has a THF-soluble weight average molecular weight of 1,000 to 30,000 . The toner according to claim 8 , wherein the acid value of the first binder resin is 1.0 to 50.0 (KOH mg / g). The toner according to any one of claims 8 to 13 , wherein the glass transition point of the first binder resin is 30 to 70 ° C. The binder resin precursor toner according to any one of claims 3 to 14, which is a modified polyester resin. Dissolve or disperse the first binder resin, the binder resin precursor, a compound that extends or crosslinks with the binder resin precursor, a colorant, a release agent, and the modified layered inorganic mineral in at least an organic solvent. The solution or dispersion obtained by subjecting the solution or dispersion to a crosslinking reaction and / or extension reaction in an aqueous medium, and removing the solvent from the obtained solution or dispersion. The toner according to any one of 8 to 15 . The binder resin precursor has a site capable of reacting with a compound having an active hydrogen group, and the binder resin precursor has a weight average molecular weight of 3,000 to 30,000. The toner according to 16 . A ratio Dv / Dn of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner is 1.00 to 1.30, and particles having a circularity of 0.950 or less are 20% of all toner particles. the toner according to any one of claims 1 to 17, characterized in that contained 80%. The toner according to any one of claims 1 to 18 volume particle diameter Dv / number average particle diameter Dn of the toner is equal to or 1.20 or less. The toner according to any one of claims 1 to 19, wherein the particle size of the toner is from 1 to 20% by number or less of particles 2 [mu] m. The toner according to any one of claims 1 to 20, acid value of the toner is characterized in that it is a 0.5~40.0 (KOHmg / g). The toner according to any one of claims 1 to 21 , wherein the toner has a glass transition point of 40 to 70 ° C. The toner according to any one of claims 1 to 22 , wherein the toner is used for a two-component developer. Toner container, characterized in that it comprises a toner according to any one of claims 1 to 23. Developing agent characterized by containing the toner according to any one of claims 1 to 23. An image forming apparatus that forms an image using the developer according to claim 25 . An image forming method comprising forming an image using the developer according to claim 25 . 26. A process cartridge comprising a developing unit having the developer according to claim 25 and an image carrier. A toner that is granulated by dispersing and / or emulsifying in a water-based medium an oil phase containing at least a binder resin and / or a binder resin precursor and a layered inorganic mineral in which at least some of the ions between layers are modified with organic ions . In the manufacturing method,
When the atomic concentration% of the specific element constituting the layered inorganic mineral when the toner is measured by XPS is A, and the atomic concentration% of the specific element when the toner is measured by XPS after melt-kneading is B, A method for producing a toner, comprising granulating so that A> B.   At least a binder resin, a binder resin precursor, a compound that extends or crosslinks with the binder resin precursor, a colorant, a release agent, and a layered layer in which at least part of ions between layers is modified with organic ions in an organic solvent A method for producing a toner, comprising dissolving or dispersing an inorganic mineral, subjecting the solution or dispersion to a crosslinking reaction and / or elongation reaction in an aqueous medium, and removing the solvent from the obtained solution or dispersion. When the atomic concentration% of the specific element constituting the layered inorganic mineral when the toner is measured by XPS is A, and the atomic concentration% of the specific element when the toner is measured by XPS after melt-kneading is B, A method for producing a toner, comprising granulating so that A> B. The toner production method according to claim 29 or 30 , wherein the toner contains at least two kinds of binder resins. 31. The method for producing a toner according to claim 30 , wherein the first binder resin among the binder resins is a resin having a polyester skeleton. The toner production method according to claim 32 , wherein the first binder resin is a polyester resin.

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