JP5090794B2 - Electrophotographic toner and developer, image forming apparatus, process cartridge, and image forming method - Google Patents

Description

  The present invention relates to a toner used in an electrophotographic image forming apparatus such as a copying machine, a printer, and a facsimile machine, a developer using the toner, an image forming apparatus, a process cartridge (process cartridge for the image forming apparatus), and an image forming apparatus. Regarding the method.

  When fixing toner for electrophotography, if the toner melted on the fixing roller remains in the roller section, when the roller rotates again and the remaining toner comes into contact with the recording medium again, the toner is fixed at a location other than the target location, and the ghost A so-called offset phenomenon that causes an image or the like may occur.

  In order to prevent offset, it is necessary to reduce the adhesive force between the melted toner and the fixing roller, and to provide the releasability so that the toner is successfully fixed to the recording paper from the fixing roller. In various image forming apparatuses, an oil coating and fixing method in which oil is applied to a fixing roller to provide releasability.

  However, this method has a drawback in that, when a color image is formed, excessive gloss may occur in the image, and an appropriate image quality cannot be obtained.

  Against this background, recently, an oilless fixing method in which oil is not applied to the fixing roller is becoming common.

  In oilless fixing, a toner in which wax is used as a release agent in a toner with a fine particle size and dispersed in a base resin together with a colorant and the like in a toner manufacturing process is used.

  Then, when heated, the wax melts and oozes out on the surface of the toner, and a state in which oil is applied between the toner and the fixing roller brings about release properties of the toner, and the toner remains on the fixing roller. The toner can be fixed without any problems.

  Therefore, even in the oilless fixing method, it is possible to realize high-quality image formation in which a ghost image or the like due to an offset of the fixing residual toner does not occur.

  On the other hand, the number of sheets that can be output per unit time required for an image forming apparatus has been increasing year by year, and in accordance with this, technically stricter conditions have been demanded. . In particular, at the time of fixing, the energy that can be applied to the toner per unit time is reduced by increasing the image output speed, so that sufficient heat is not transmitted to the toner and exists on or near the surface of the recording medium. The toner causes poor melting.

  Then, toner that does not have a sufficiently low viscosity to be fixed on the recording medium remains without being fixed from the roller onto the recording medium, causing the same offset as described above, and the image quality of the output image is reduced due to the generation of the ghost image. It was the cause.

  In order to solve the above-described problems, a method is conceivable in which a certain amount of a hydrophobic ionic organic compound capable of having both functions of releasing property and fixing property is contained in a toner.

Therefore, when investigating whether or not there was already one that adopted such a way of thinking, one was related to an elliptical organic polymer having light scattering and light collecting optical characteristics using an ionic organic compound. The other relates to a semiconductive member for electrophotography containing an ionic organic compound in a liquid state at room temperature, for example, a charging member of an electrophotographic apparatus, a transfer roll, etc. (see Patent Document 2) However, there was no example in which the toner was contained in the toner in order to improve the fixability of the image forming apparatus that was developed at a high speed.
Japanese Patent Laid-Open No. 2005-247799 JP 2004-191655 A

  The present invention has been made in view of the above circumstances, and even when the recording medium is fixed by a high-speed fixing roller having a conveyance speed of 150 mm / second or more, the toner is fixed only at the print target position of the recording medium. And an image forming apparatus, a process cartridge, and an image forming method using the toner. The purpose is to provide.

In order to solve the above problems, the invention described in claim 1 is an electrophotographic toner containing at least a colorant and a binder resin and having a weight average particle diameter of 3.5 to 10 μm, In addition, it contains a hydrophobic ionic organic compound consisting of a hydrophobic organic cation with a positively charged atom in the molecule and a hydrophobic anion with a negatively charged atom in the molecule. The atom having the positive charge point is a nitrogen atom (N), and the atom having the negative charge point is a nitrogen atom (N) .

The invention according to claim 2 is the electrophotographic toner according to claim 1 , wherein the hydrophobic organic cation to which the N atom is bonded is imidazolium, pyridinium, pyrrolidinium, piperidinium, or quaternary ammonium. It is either.

The invention according to claim 3 is the electrophotographic toner according to claim 1 or 2 , wherein the hydrophobic anion to which the N atom is bonded is di (fluorocarbonsulfonyl) imide or di (alkylsulfonyl) imide. It is characterized by that.

The invention according to claim 4 is the electrophotographic toner according to any one of claims 1 to 3 , wherein the hydrophobic ionic organic compound is contained in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin. It is characterized by being.

The invention according to claim 5 is characterized in that the electrophotographic toner according to any one of claims 1 to 4 is a polymerized toner granulated in an aqueous solvent.

A sixth aspect of the invention is characterized in that the electrophotographic toner according to any one of the first to fourth aspects is a pulverized and granulated toner.

A seventh aspect of the invention is characterized by a one-component developer comprising only the toner of the first to sixth aspects.

According to an eighth aspect of the invention, there is provided a two-component developer comprising the toner according to any one of the first to sixth aspects and a carrier.

According to a ninth aspect of the present invention, there is provided an image bearing member, an electrostatic latent image forming unit for forming an electrostatic latent image on the image bearing member, and developing the electrostatic latent image with toner to form a visible image. A recording medium on which the transfer image is formed, at least a developing means for forming the transfer image, a transfer means for transferring the visible image to a recording medium, and a fixing means for fixing the transfer image transferred to the recording medium. An image forming apparatus having a conveying speed of 150 mm / second or more when discharged from a fixing unit, wherein the toner is the electrophotographic toner according to any one of claims 1 to 5 .

According to a tenth aspect of the present invention, there is provided a process cartridge that integrally supports at least the image carrier and the developing unit and is detachable from the main body of the image forming apparatus, wherein the toner in the developing unit is defined in the first to fifth aspects . Any one of the electrophotographic toners described above.

According to an eleventh aspect of the present invention, there is provided an electrostatic latent image forming step for forming an electrostatic latent image on an image carrier, and a developing step for developing the electrostatic latent image with toner to form a visible image. And a transfer step of transferring the visible image to a recording medium and a fixing step of fixing the transfer image transferred to the recording medium, and discharging the recording medium on which the transfer image is formed from the fixing unit An image forming method in which the conveying speed is 150 mm / second or more, wherein the toner is the electrophotographic toner according to any one of claims 1 to 5 .

According to the present invention, since the toner contains the hydrophobic ionic organic compound, the fixing roller that rotates at a high speed does not cause an offset phenomenon caused by the residual toner remaining on the fixing roller. Thus, an electrophotographic toner capable of forming a high-quality image can be provided by the excellent releasability and strong fixing to a recording medium.
Further, it is possible to provide a stable image forming apparatus, a process cartridge, and an image forming method in which an offset phenomenon does not occur on a high-speed fixing roller using the toner.

Hereinafter, the present invention will be described in detail.
The hydrophobic ionic organic compound used in the present invention is composed of a hydrocarbon chain or hydrocarbon functional group whose main components are carbon and hydrogen except for the vicinity of the charged element, and therefore exhibits strong hydrophobicity. .

  Further, by adjusting the molecular weight of these hydrocarbon parts, it is possible to easily control a wide range of physical properties such as glass transition point and melting point.

  Hereinafter, as a representative example, a hydrophobic ionic organic compound will be described using 1-ethyl-3-methylimidazolium of FIG. 1 as a cation and hexafluorophosphate of FIG. 2 as an anion.

  As shown in FIG. 1, due to the structure of the cation, an electric bias appears on the nitrogen atom and the electrons inside the cation are localized, so that the whole of the cation is composed of hydrocarbons as a whole. Since it has a positive charge, it can be combined with various anions such as those shown in FIG.

  These cations and anions have polarities generated in the vicinity of the nitrogen atom, so they bind to each other as counterions, resulting in a very high molecular weight organic substance and a salt-like structure. New material is realized. Although depending on the size of the hydrocarbon part, the molecular weight of the hydrophobic part is overwhelmingly higher than that of the polar part.

  As described above, the ionic organic compound is largely characterized in that the ionicity is maintained inside the molecule while maintaining the hydrophobicity that is a characteristic of the organic substance. In addition, in the vicinity of polar atoms, the surroundings are bulky, so the bonding strength between salts is very weak compared to general inorganic salts, and depending on the molecular structure, it becomes liquid even at room temperature. Easily melts at low temperatures. In addition, ionic organic compounds are highly stable against heat and chemical reactions, and are resistant to chemical reaction and heat resistance, especially depending on the type, even at temperatures around 200 ° C, they do not decompose or volatilize and remain liquid. Some exist.

  Note that it is not always necessary that both ions of the cation and the anion have a hydrophobic group bonded thereto, and it is sufficient that at least one of the ions maintains a strong hydrophobic group.

  When such an ionic organic compound is used as an additive to the toner, the following effects can be realized due to the characteristic of having a hydrophobic portion and a polar portion.

  In a toner containing an ionic organic compound, when the temperature becomes higher than the melting point during fixing, the ionic organic compound oozes out on the toner surface like a conventional release agent.

  At this time, the hydrophobic portion functions as a wax, and exhibits an effect of achieving releasability so that the toner does not remain on the fixing roller after fixing.

  On the other hand, the polar portion having a bias in the molecule and having a positive charge or a negative charge has higher hydrophilicity than wax, and therefore, for example, a printing recording medium that absorbs some moisture, such as paper. The binding power of becomes stronger.

  Then, especially when forming and outputting images at a high speed, the fixing roller rotates at a high speed, making it difficult to transfer heat to the entire toner more than before, and even when melting does not occur, Since an attractive force that fixes the toner to the paper surface is generated, it is possible to prevent image quality degradation such as a ghost image due to offset.

  As described above, by adding a hydrophobic ionic organic compound to the toner for electrophotography, the toner can exert both hydrophobic and hydrophilic effects, and releasability at the time of fixing. In addition, a toner having fixability to a recording medium during printing can be obtained.

Hereinafter, embodiments of the present invention will be further described.
In the toner of the present invention, at least a binder resin, a colorant, a hydrophobic ionic organic compound, a charge control agent, and an external additive may be used, and a release agent may be mixed as necessary.

(Binder resin)
As the binder resin, any conventionally used resin can be used. For example, homopolymers of styrene such as polystyrene, polychlorostyrene, and polyvinyltoluene, and substituted products thereof; styrene / p-chlorostyrene copolymer, styrene / propylene copolymer, styrene / vinyltoluene copolymer, styrene / vinyl Naphthalene copolymer, styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, styrene / octyl acrylate copolymer, styrene / methyl methacrylate copolymer, Styrene / ethyl methacrylate copolymer, styrene / butyl methacrylate copolymer, styrene / α-chloromethyl methacrylate copolymer, styrene / acrylonitrile copolymer, styrene / vinyl ethyl ether copolymer, styrene / vinyl methyl Ketone copolymer, styrene / Butadiene copolymer, styrene / isoprene copolymer, styrene / acrylonitrile / indene copolymer, styrene / maleic acid copolymer, styrene copolymer such as styrene / maleic acid ester copolymer; polymethyl methacrylate, Polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyvinyl butyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic Base petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used alone or in admixture of two or more.

(Coloring agent)
As the colorant, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL , Isoindolinone yellow, bengara, red lead, red lead, cadmium red, cadmium mercury red, antimony red, permanent red 4R, para red, phise red, parachlor ortho nitroaniline red, risor fast scarlet G, Reliant 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 Range, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo , Ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, manganese violet, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridiane, emerald green, pigment green B, naphthol green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Oxidized Chi Tan, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

(Hydrophobic ionic organic compounds)
Examples of cationic groups and anionic groups used in hydrophobic ionic organic compounds are shown below, but are not limited to these substances.
Examples of substances that can be used for the cationic group include imidazolium ions: R ¹ R ² R ³ —C ₃ H ₃ N ₂ ⁺ imidazolium group (R ^{1 to} R ³ = C _X H _{2X + 1} , x is 0 or An integer of 1 to 25), pyridinium ion: R—C ₅ H ₅ N ⁺ pyridinium ion group ( _{R═C X} H _{2X + 1} , x is 0 or an integer of 1 to 25), pyrrolidinium ion: R ¹ R ² -C ₄ H ₈ N ⁺ pyrrolidinium ion group _{^{(= R 1 ~R 2 C X}} H 2X + 1, x is an integer of 0 or 1 to 25), a quaternary ammonium ^{ion: R 1 R 2 R 3 R} 4 - N ⁺ (R ^{1 to} R ⁴ = C _X H _{2X +} 1, x is 0 or an integer of 1 to 25), piperidinium ion: R ¹ R ² —C ₅ H ₁₀ N ⁺ piperidinium group (R ^{1 to} R ² = C _X H _{2X +} 1, x is 0 or an integer of 1 to 25).

Examples of substances that can be used for the anionic group include fluorocarbon sulfonate ion C _X F _{2X + 1} SO ₃ ⁻ (x is 0 or an integer of 1 to 25), di (fluorocarbon sulfonyl) imide ion (C _X F _{2X + 1).} SO ₂ ) ₂ N ⁻ (x is 0 or an integer from 1 to 25), tris (fluorocarbonsulfonyl) methide ion (C _X H _{2X + 1} SO ₂ ) ₃ C ⁻ (x is an integer from 0 or 1 to 25), alkyl Sulfate ion C _X H _{2X + 1} SO4 ⁻ (x is an integer of 0 or 1 to 25), di (alkylsulfonyl) imide ion (C _X H _{2X + 1} SO ₂ ) ₂ N ⁻ (x is an integer of 1 to 25 Preferably, a functional group comprising any hydrocarbon such as a methyl group, an ethyl group, or a butyl group can be used), a tris (alkylsulfonyl) methide ion (C _X H _{2X + 1} SO ₂ ) ₃ C ⁻ (x is 1 Is an integer of ˜25, preferably a methyl group, Any functional group consisting of any hydrocarbon such as til group and butyl group can be used), nitrate ion NO ₃ ⁻ , hexafluorophosphate ion PF ₆ ⁻ , trifluoroboron ion BF ₄ ⁻ , fluoride ion F ⁻ , chloride Product ion Cl ⁻ , bromide ion Br ⁻ , iodide ion I ^{− and the} like.

  As the hydrophobic ionic organic compound that can be used in the toner of the present invention, a substance composed of a combination of the above anions and cations is used. In particular, it is important to appropriately design the melting point and hydrophobicity according to these combinations, and the melting point is preferably about 40 to 200 ° C. When the temperature is lower than the melting point, the adsorptive power between the toners increases and causes toner aggregation, which may cause problems such as toner clogging in the image forming apparatus.

  In addition, when an ionic organic compound having low hydrophobicity (showing hydrophilicity) is used, moisture is absorbed during storage of the toner, and in a high-temperature and high-humidity environment, the adsorptive power between the toners increases, and toner aggregation occurs. More preferably, the amount of the ionic organic compound dissolved in 100 g of water is 0 wt% to 1 wt% or less because it causes a series of problems such as deterioration in developability. .

  In general, if an ionic organic compound having a too high molecular weight is used, the viscosity is so high that it is difficult to use, or it does not melt even at the fixing temperature, so that a ghost image may be generated. However, with respect to hydrophobicity, it is preferable that the molecular weight of the hydrocarbon portion is large.

  On the other hand, if the molecular weight is small, the melting point becomes high because it has crystallinity, and it may not melt at the fixing temperature. If it is small, the hydrophobicity becomes weak and the original performance may not be exhibited.

  Therefore, when used in a toner, a hydrophobic ionic organic compound having an appropriate molecular weight must be designed in order to have an appropriate melting point or hydrophobicity. When a 1-ethyl-3-methylimidazolium ion such as 1 or anion having a molecular weight of about hexafluorophosphate anion as shown in FIG. 2 is used, it can be used as a release agent that melts at about 60 ° C.

  When the toner has a core-shell structure and is covered with a hard layer, a liquid ionic organic compound can be dispersed. In such a case, an ionic organic compound that exists in a liquid state at room temperature is used. For example, as a substance having appropriate hydrophobicity, 1-n-butyl-1 as shown in FIG. As the -methylpyrrolidinium ion and anion, bis (trifluoromethylsulfonyl) imide as shown in FIG. 4 is preferable.

  In addition, the ionic organic compound is a 1-ethyl-3-methylimidazolium ion as shown in FIG. 5 as a cation and a 1-butyl-4-methylpyridinium ion as shown in FIG. 6 as an anion. Those that become are also useful.

  In addition, the hydrophobic ionic organic compound is included in the case of a liquid, but may be contained inside the base resin or may be attached to the surface of the base resin in the case of a solid. However, it is particularly preferable that it is contained inside. If it is added externally, it may peel off if mechanical stress is applied to the toner, and there is a risk that it will not be able to exhibit appropriate fixing performance. .

  The content thereof can be used in a wide range of 0.01 to 20 parts by weight when the weight of the base resin of the toner is 100. Furthermore, when considering the fixing temperature of the image forming apparatus, it is particularly preferable to contain 0.1 to 10 parts by weight, but this is particularly suitable because the target fixing temperature varies depending on the type and properties of the image forming apparatus. Thus, the content by weight can be selected from the above range.

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

(External additive)
As the external additive, the following inorganic fine particles are preferably used for the purpose of imparting fluidity, chargeability and developability. The primary particle diameter of the inorganic fine particles is preferably 5 × ¹⁰ -3 ~2μm, it is particularly preferably 5 × ¹⁰ -3 ~0.5μm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The addition amount of the inorganic fine particles is preferably 0.01 to 5 wt% of the whole toner, and particularly preferably 0.01 to 2.0 wt%.

  Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  Such external additives can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

(Release agent)
In the present invention, it is not necessary to use a release agent, but an appropriate amount may be added as necessary. As the release agent, a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent between the fixing roller and the toner interface in the dispersion with the binder resin. The effect on high temperature offset is exhibited without applying a release agent such as oil.

Examples of such a wax component include the following.
Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax and rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, and paraffin, microcrystalline, And petroleum waxes such as petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones, and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. .

(Magnetic powder)
The present invention can also be used for a magnetic one-component toner. When used as a magnetic toner, a known magnetic material can be used. Examples of the magnetic material contained in the magnetic toner include iron oxides such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel, These metals include alloys of metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof. These ferromagnetic materials preferably have an average particle size of about 0.1 to 2 μm. The amount of the ferromagnetic material to be contained in the toner is about 20 to 200 parts by weight, particularly preferably 100 parts by weight of the resin component, with respect to 100 parts by weight of the resin component. 40 to 150 parts by weight per part.

(Career)
The toner of the present invention can also be used as a toner for a two-component developer using a carrier. As the carrier, conventionally known ones for two-component developers can be used. For example, a carrier made of magnetic particles such as iron or ferrite, and a resin obtained by coating such magnetic particles with a resin. A coated carrier or a binder-type carrier in which magnetic fine powder is dispersed in a binder resin can be used. Magnetic materials include iron oxides such as magnetite, hematite, and ferrite, iron, cobalt, and nickel. Such metals or alloys of these metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof, etc. Can be used.

  Among these carriers, a silicone resin, a copolymer resin (graft resin) of an organopolysiloxane and a vinyl monomer, or a resin-coated carrier using a polyester resin can be used as a coating resin. A carrier coated with a resin obtained by reacting an isocyanate with a copolymer resin of an organopolysiloxane and a vinyl monomer is preferable from the viewpoint of durability, environmental stability, and spent resistance. . As the vinyl monomer, it is necessary to use a monomer having a substituent such as a hydroxyl group reactive with isocyanate. In addition, it is preferable to use a magnetic carrier having a volume average particle diameter of 20 to 100 μm, preferably 20 to 60 μm from the viewpoint of ensuring high image quality and preventing carrier fogging.

(Carrier coating material)
In addition to the above, coating materials used for carriers include amino resins such as urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins, and epoxy resins. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene-acrylic copolymer resins, Halogenated olefin resins such as vinyl chloride, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoropropylene Resins, copolymers of vinylidene fluoride and acrylic monomers, copolymers of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinyl Fluoro terpolymers such as terpolymer of vinylidene fluoride and a non-fluorinated monomer, and silicone resins.

(Additive for coating resin)
Moreover, you may make conductive powder etc. contain as a filler in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide, aluminum oxide, silica and the like can be used. These preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it is difficult to control electric resistance in the case of conductive powder.

The method for producing the toner of the present invention will be described below.
(Crush and granulate (melt kneading method))
As a method for producing the toner according to the present invention, first, the binder resin, the pigment or dye as the colorant, the release agent, the charge control agent, and other additives are sufficiently mixed with a mixer such as a Henschel mixer. After mixing, continuous twin screw extruder, for example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd., PCM type twin screw extruder manufactured by Ikegai Iron Works, Kurimoto Iron Works The constituent materials are well kneaded using a KEX type twin-screw extruder manufactured by KK or a continuous uniaxial kneader such as a Kneader manufactured by Buss Co., Ltd. or a KCK kneader. At this time, as a method for increasing the specific energy, a method of decreasing the kneading amount or a method of lowering the kneader setting temperature and kneading the kneaded material in a high viscosity state is used.

  Next, after cooling the kneaded product, it is coarsely pulverized using a hammer mill or the like, and further finely pulverized by a fine pulverizer or mechanical pulverizer using a jet stream. The toner of the present invention is obtained by classifying to a predetermined particle size using a classifier.

  Next, the inorganic fine powder and the toner are sufficiently mixed by a mixer such as a Henschel mixer, and passed through a sieve of 250 mesh or more to remove coarse particles and agglomerated particles.

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

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

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

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

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

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

  As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, fatty acid amide derivatives, polyhydric alcohols Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-Hydroxyethyl) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  In addition, examples of the cationic surfactant include aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. , Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (Daikin Industries) Manufactured), MegaFuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products), Footgent F-300 (Neos), and the like.

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

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

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

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

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

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

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

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

  (5) A charge control agent is injected into the toner base particles obtained above, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are attached to the base particles as external additives to obtain a toner. The charge control agent is injected and the inorganic fine particles are externally added by a known method using a mixer or the like.

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

(Toner particle size)
The weight average particle size of the toner granulated in the present invention is preferably in the range of 3.5 μm to 10 μm. If the particle size is smaller than this range, the fixing is effected by the unevenness of the recording medium, for example, the paper surface. Sometimes, there is a toner that does not sufficiently transfer heat, causing an offset due to the toner that does not melt. If the particle diameter is larger than this range, heat is not transferred due to the thickness of the bundled toner itself, which causes offset due to unmelted toner.

(Measurement method of toner particle size)
As an apparatus for measuring the particle size distribution of toner particles by the Coulter counter method, there are Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). In the present invention, measurement was performed using Coulter Multisizer II. The measurement method is described below.

  First, 0.1 to 5 ml of a surfactant, preferably polyoxyethylene alkyl ether, is added as a dispersant in 100 to 150 ml of an electrolytic aqueous solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter (Dn) of the toner can be obtained.

  As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

  The image forming apparatus using the toner of the present invention described above includes an image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the image carrier, and the electrostatic latent image as a toner. The image forming apparatus includes at least a developing unit that develops a visible image using the developing unit, a transfer unit that transfers the visible image to a recording medium, and a fixing unit that fixes the transferred image transferred to the recording medium. It is desirable that the image forming apparatus has a conveyance speed of 150 mm / second or more when the recording medium on which the transfer image is formed is discharged from the fixing unit.

  In the process cartridge of the present invention, at least the image carrier and the developing means are integrated and detachably mounted on the main body of the image forming apparatus. In the main body of the image forming apparatus, in addition to the image carrier and the developing unit, a charging unit and a cleaning unit are arranged around the image carrier, and an exposure unit and a transfer unit are further arranged. The main body of the image forming apparatus is desirably an image forming apparatus having a conveyance speed of 150 mm / second or more when the recording medium on which the transferred toner image is formed is discharged from the fixing unit.

  As shown in Table 1 of Examples described later, according to the toner of the present invention, a high-quality image can be provided without causing any offset even if the linear velocity of the fixing roller is 150 mm / second or more. . The fixing device includes, for example, a heating roller 20 and a pressure roller 30 as shown in FIG. 7, and the heating roller 20 has an outer diameter of 40 mm and a thickness of 1.5 mm made of silicone rubber on the aluminum core 23. The elastic body layer 21 and the PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) surface layer 22 are provided, and a heater is provided inside the aluminum core bar. The pressure roller 30 has an outer diameter of 35 mm, and has an elastic body layer 31 made of silicone rubber and a PFA surface layer 32 made of silicone rubber on an aluminum core bar 33. The heating roller 20 and the pressure roller 30 have a nip (nip width 7 mm) N formed in the pressure contact portion. Although not shown, the fixing device 10 includes a separation claw for separating the fixed recording medium from the heating roller 20, a cleaning web for cleaning the surface of the heating roller, a web roller around which the cleaning web is wound, It has a configuration including a winding roller for winding the cleaning web, and fixing oil is not used. Further, as shown in FIG. 7, the fixing is performed by passing the recording medium S carrying the toner image T in the press contact portion from the right to the left in the drawing.

  Moreover, the measuring method of Tg (glass transition temperature), melting | fusing point, a hydroxyl value, an acid value, a weight average molecular weight, and a number average molecular weight as described in a postscript Example and a comparative example is as follows.

(Measurement method of Tg)
Measure using a differential scanning calorimeter. Specifically, the measurement was performed under the following measurement conditions using TA-60WS and DSC-60 manufactured by Shimadzu Corporation according to the following procedure.
〔Measurement condition〕
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50ml / min)
(Temperature conditions)
Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Retention time: None
Temperature drop: 10 ° C / min
End temperature: 20 ° C
Retention time: None
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
The measurement results were analyzed using the data analysis software (Ta-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method specifies a range of ± 5 ° C centering on the point showing the maximum peak on the lowest temperature side of the DrDSC curve which is the DSC differential curve of the second temperature rise, and the peak temperature is determined using the peak analysis function of the analysis software. Ask. Next, the maximum endothermic temperature of the DSC curve is obtained using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the glass transition temperature (Tg) of the toner.

(Measuring method of melting point)
A TG-DSC system TAS-100 manufactured by Rigaku Corporation was used to measure the melting point of the ionic organic compound. First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. Heat from room temperature to 180 ° C. at a heating rate of 10 ° C./min. The melting point was calculated from the contact point between the tangent line of the endothermic curve near the melting point and the base line using the analysis system in the TAS-100 system.

(Measurement method of hydroxyl value)
0.5 g of the sample was precisely weighed into a 100 ml volumetric flask, and 5 ml of an acetylating reagent was correctly added thereto. Then, it was heated by being immersed in a bath at 100 ° C. ± 5 ° C. After 1 to 2 hours, the flask was taken out of the bath, allowed to cool, then added with water and shaken to decompose acetic anhydride. Next, in order to complete the decomposition, the flask was again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask was thoroughly washed with an organic solvent. This solution was subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to determine the hydroxyl value (according to JIS K0070-1966).

(Measurement method of acid value)
Weigh accurately 1 to 1.5 g of wax in an Erlenmeyer flask, add 20 ml of xylene, and dissolve with heating. After dissolution, 20 ml of dioxane is added and titrated as soon as possible with 1/10 phenolphthalein solution with N / 10 potassium hydroxide standard methanol solution while the liquid does not become cloudy or hazy. At the same time, perform a blank test.
The calculation formula is as shown in Formula 1 below.

Formula 1
Acid value = [5.61 × (AB) × f] / S
However,
A: ml of N / 10 potassium hydroxide standard methanol solution required for this test
B: Number of ml of N / 10 potassium hydroxide standard methanol solution required for the blank test
f: Factor of N / 10 potassium hydroxide standard methanol solution
S: Sample (g)

(Measurement method of weight average molecular weight)
The mass average molecular weight of the polyester resin was measured by GPC (gel permeation chromatography) under the following conditions.
・ Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
・ Flow rate: 1.0 mL / min
Sample: 0.1 mL of a sample having a concentration of 0.05 to 0.6% was injected.
From the molecular weight distribution of the polyester resin measured under the above conditions, the weight average molecular weight of the polyester resin was calculated using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.

(Measurement method of number average molecular weight)
The number average molecular weight was measured using GPC-150C (manufactured by Waters) and columns KF801 to 807 (manufactured by Shodex). At this time, THF (tetrahydrofuran) was used as a solvent, and measurement was performed at a temperature of 40 ° C. and a flow rate of 1.0 ml / min. As a sample, 0.05 ml to 0.6% by weight of a resin solution was used and 0.1 ml was injected. Further, when the insoluble content when adding 1 g of resin to 100 ml of THF was 75% by weight or more, DMF (dimethylformamide) was used as a solvent. The number average molecular weight was calculated from a molecular weight calibration curve prepared using a monodisperse polystyrene standard sample.

  Examples of the present invention are shown below, but the present invention is not limited thereto. In the following, “parts” means parts by weight, and “%” means percent by weight.

The following is a synthesis example of the binder resin used in the production of the toner of the present invention.
(Synthesis example of polyester resin 1)
443 parts of PO adduct of bisphenol A (hydroxyl value 320), 135 parts of diethylene glycol, 422 parts of terephthalic acid, and 2.5 parts of dibutyltin oxide are placed in a reaction vessel equipped with a thermometer, stirrer, cooler and nitrogen introduction tube. Then, the reaction was carried out at 230 ° C. until the acid value became 7, to obtain [Polyester Resin 1]. The resin had a Tg of 65 ° C. and a peak molecular weight of 16000. Moreover, the grindability index of this resin was 0.89. The grindability index is an index indicating the hardness of the binder resin that is the main component of the toner, and can be measured by the following method.
200 kg of resin is kneaded for 15 minutes with a small two roll (Nishimura Co., Ltd.) heated to 110 ° C., then put into Hosokawa Micron Rotoplex, sifted through coarsely pulverized resin particles for 5 minutes, and passed through 16 mesh Thus, a resin powder that does not pass through 20 mesh is obtained.
10.00 g of this classified resin powder is precisely weighed, pulverized with a mill and mixer MM-I type (manufactured by Hitachi Living Supply Co., Ltd.) for 30 seconds, passed through a 30-mesh sieve, and the weight of resin not passing (B ) G is precisely weighed, the residual ratio is obtained from the value of B according to the following formula 2, and this operation is performed three times and the average is obtained as the grindability index.

Formula 2
Millability index F = ((B) g / resin weight before grinding (10.0 g)) × 100
(same as below).

(Synthesis example of styrene acrylic resin 1)
Further, 646 parts of xylene were placed in an autoclave reaction vessel equipped with a thermometer, a stirrer, and a nitrogen introduction tube, and after nitrogen substitution, a mixed monomer of 200 parts of acrylonitrile, 689 parts of styrene, 114 parts of acrylate-2-ethylhexyl, and xylene 118 An initiator solution of 52 parts of di-t-butyl peroxide was added dropwise at 170 ° C. over 3 hours to remove the solvent, thereby obtaining [styrene acrylic resin 1]. The weight average molecular weight of this resin was 4,700, the number average molecular weight was 2,300, and Tg was 55 ° C. Moreover, the grindability index of this resin was 0.24.

(Example of master batch 1 synthesis)
Hereinafter, a synthesis example of the master batch 1 used in the production of the toner of the present invention will be shown.
Water ・ ・ ・ 25 parts Carbon black (Mitsubishi Chemical # C-44) ・ ・ ・ ・ 50 parts Polyester resin (consisting of PO, EO adduct of bisphenol A and terephthalic acid, Tg60 ℃, Mw25000, Mp115 ℃ linear Polyester) 50 parts The above toner constituent materials were mixed with a Henschel mixer (Henschel 20B manufactured by Mitsui Mining Co., Ltd., 1500 rpm for 3 minutes), and the mixture was kneaded at 120 ° C. for 45 minutes using two rolls. Then, it was cooled and rolled, and pulverized with a pulverizer to obtain [Masterbatch 1].

<Example 1>
Polyester resin 1 ... 47.5 parts Styrene acrylic resin 1 ... 47.5 parts
1-ethyl-3-methylimidazolium hexafluorophosphate, melting point 60 ° C. (hydrophobic ionic organic compound)... 1 part Masterbatch 1... 10 parts Mixing is performed with Henschel 20B manufactured by Mitsui Mining Co., Ltd. at 1500 rpm for 3 minutes, and kneading is performed under the following conditions using a single-screw kneader (Bus Co., a small bus co-kneader) (set temperature: inlet portion 100 ° C., At the outlet 50 ° C., the feed amount: 2 kg / Hr) and [base toner 1] were obtained.

Further, the [base toner 1] was kneaded, cooled by rolling, pulverized by a pulverizer, and further an I-type mill (IDS-2 type manufactured by Nippon Pneumatic Co., Ltd., using a flat impact plate, air pressure: 6.8 atm). / Cm ² , feed amount: 0.5 kg / hr) were further pulverized and further classified (132MP manufactured by Alpine) to obtain [Toner Base Particles 1].

  Thereafter, 100 parts by weight of [toner base particle 1], 1.0 part by weight of hydrophobic silica (external additive A) having a primary particle size of 10 nm as an external additive, a primary particle size of 110 nm produced by a sol-gel method, and substantially spherical. 1.5 parts by weight of hexamethyldisilazane hydrophobized silica (external additive B) and 1.0 part of hydrophobic titanium oxide (external additive C) having a primary particle size of 15 nm were added to a Henschel mixer (Henschel manufactured by Mitsui Mining Co., Ltd.). 20B) to obtain a toner.

  Mixing conditions were set by repeating the set of rotating for 30 seconds and stopping rotation for 60 seconds 5 times at a peripheral speed of 30 m / sec. The toner obtained here is referred to as [Toner 1]. [Toner 1] had a weight average particle diameter (D4) of 3.8 μm and a number average particle diameter (Dn) of 3.1 μm.

  This [Toner 1] was mixed with a carrier using a RICOH copier imagio Neo C325, and the following test was performed. In other words, 6.0mg was transferred to A4 size paper (T6000 70W T, manufactured by Ricoh Co., Ltd.) in a uniform 3cm x 5cm rectangle, and the roller rotation speed could be changed freely. The nip width was 10mm. A φ30 rubber fixing roller was heated to 140 ° C. with a halogen lamp and fixed at a linear speed of 160, 240, or 320 mm / sec. At this time, it was visually confirmed whether or not an offset was caused by the toner not fixed and remaining on the fixing roller. In [Toner 1], no offset was observed at any speed.

<Example 2>
Polyester resin 1 ... 47.5 parts Styrene acrylic resin 1 ... 47.5 parts
1-ethyl-3-methylimidazolium hexafluorophosphate, melting point 60 ° C. (hydrophobic ionic organic compound)... 5 parts Masterbatch 1... 10 parts (Minner Henschel 20B at 1500 rpm for 3 minutes) and kneading under the same conditions as in Example 1 to obtain [Base toner 2]. Thereafter, [Mother toner 2] is finely pulverized and classified by the same method as in Example 1 to obtain [Mother toner particles 2], and then [Mother toner particles 2] are obtained in the same manner as in Example 1. External additives were mixed to obtain [Toner 2]. [Toner 2] had a weight average particle diameter (D4) of 3.6 μm and a number average particle diameter (Dn) of 3.2 μm.

  This [Toner 2] was subjected to a visual confirmation experiment as to whether or not a cold offset occurred under the same conditions and evaluation method as in Example 1. In [Toner 2], no offset was observed at any speed.

<Example 3>
Polyester resin 1 ... 47.5 parts by weight Styrene acrylic resin 1 ... 47.5 parts by weight
1-ethyl-3-methylimidazolium hexafluorophosphate, melting point 60 ° C (hydrophobic ionic organic compound) ··· 20 parts by weight Masterbatch 1 ··· 10 parts by weight (Mitsui Mining Co., Ltd. Henschel 20B at 1500 rpm for 3 minutes) and further kneading under the same conditions as in Example 1 to obtain [Base toner 3]. Thereafter, [Mother toner 3] is finely pulverized and classified by the same method as in Example 1 to obtain [Mother toner particles 3]. Then, [Mother toner particles 3] are obtained in the same manner as in Example 1. External additives were mixed to obtain [Toner 3]. [Toner 3] had a weight average particle diameter (D4) of 3.9 μm and a number average particle diameter (Dn) of 3.1 μm.

  This [Toner 3] was subjected to a visual confirmation experiment as to whether or not a cold offset occurred under the same conditions and evaluation method as in Example 1. In [Toner 3], no offset was observed at any speed.

<Example 4>
Examples of toner granulated with an aqueous solvent are shown below.
(Synthesis of organic fine particle emulsion) (Production Example 1)
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 4] was obtained. The average particle diameter of [fine particle dispersion 4] measured by LA-920 was 105 nm. A portion of [Fine Particle Dispersion 4] was dried to isolate the resin component. The resin content had a Tg of 59 ° C. and a weight average molecular weight of 150,000.

(Preparation of aqueous phase) (Production Example 2)
990 parts of water, 99 parts of [Fine Particle Dispersion 4], 35 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: Sanyo Chemical Industries) and 70 parts of ethyl acetate Obtained liquid. This is referred to as [Aqueous Phase 4].

(Synthesis of low molecular weight polyester) (Production Example 3)
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 8 hours at normal pressure, and then react for 5 hours under reduced pressure of 10-15mmHg, then put 44 parts of trimellitic anhydride into the reaction vessel, at 180 ° C at normal pressure The mixture was reacted for 1.8 hours to obtain [Low molecular weight polyester 4]. [Low molecular polyester 4] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a peak molecular weight of 5000, a Tg of 43 ° C., and an acid value of 25.

(Synthesis of Intermediate Polyester) (Production Example 4)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. at normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 4]. [Intermediate Polyester 4] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.

  Next, 410 parts of [Intermediate Polyester 4], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 4] was obtained. [Prepolymer 4] had a free isocyanate (%) of 1.53%.

(Synthesis of ketimine) (Production Example 5)
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 4]. The amine value of [ketimine compound 4] was 418.

(Synthesis of master batch) (Production Example 6)
Add 1200 parts of water, 540 parts of carbon black (Printex35 manufactured by Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], 1200 parts of low molecular weight polyester resin prepared in Production Example 3 and add Henschel mixer (Mitsui Mining Co., Ltd.) ), And the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 4 (BK)].

(Preparation of oil phase) (Production Example 7)
In a container equipped with a stir bar and thermometer, 378 parts of [Low molecular polyester 4], 31 parts of 1-ethyl-3-methylimidazolium hexafluorophosphate (hydrophobic ionic organic compound, Aldrich), 947 parts of ethyl acetate Was heated to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 4 (BK)] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 4].
[Raw material solution 4] Transfer 1324 parts to a container and use a bead mill (Ultra Visco Mill, manufactured by IMEX) to fill the liquid with a feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 80% by volume of 0.5 mm zirconia beads. Then, carbon black and WAX were dispersed under the condition of 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 4] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 4]. The solid content concentration of [Pigment / WAX Dispersion 4] (130 ° C., 30 minutes) was 50%.

(Emulsification ⇒ Solvent removal) (Production Example 8)
[Pigment / WAX Dispersion 4] 749 parts, [Prepolymer 4] 115 parts, [Ketimine Compound 4] 2.9 parts in a container and mixed for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika) Then, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at a rotation speed of 12,500 rpm for 30 minutes to obtain [Emulsified slurry 4].
[Emulsified slurry 4] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 35 ° C. for 7 hours, aging was performed at 45 ° C. for 4 hours to obtain [Dispersed slurry 4]. In the middle of solvent removal, the sample was transferred to a TK homomixer and stirred for 40 minutes at 12,500 rpm to deform the toner.

(Washing → Drying Production Example 9)
[Dispersion Slurry 4] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2): 1OO parts of 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice to obtain [filter cake 4]. .

   [Filtration cake 4] was dried at 45 ° C. for 48 hours in a circulating drier, sieved with a mesh of 75 μm, and a charge control agent (salicylic acid metal salt E-84 was added to 100 parts by weight of the obtained particles. : Orient Chemical Industry Co., Ltd.) 0.6 parts by weight at 1000 rpm using a Henschel mixer, then mixed at 5500 rpm with a Q-type mixer (Mitsui Kinzoku Kogyo Co., Ltd.) to fix the charge control agent on the toner surface. Base toner 4] was obtained. The toner had a weight average particle diameter (D4) of 4.6 μm and a number average particle diameter (Dn) of 3.9 μm.

(Addition of external additives) (Production Example 10)
Next, 100 parts of [base toner 4] was mixed with 0.7 parts of hydrophobic titanium oxide using a Henschel mixer to complete the production of [toner 4].

  When this [Toner 4] was subjected to a visual confirmation experiment as to whether an offset occurred under the same conditions and evaluation method as in Example 1, in [Toner 4], no offset was observed at any speed. There wasn't.

<Example 5>
1-Ethyl-3-methylimidazolium hexafluorophosphate added during preparation of the oil phase of [Toner 4] (Production Example 7), melting point 60 ° C. (hydrophobic ionic organic compound) was 165 parts, and then [Toner 5] was obtained in the same manner as [Toner 4]. The toner had a weight average particle diameter (D4) of 4.3 μm and a number average particle diameter (Dn) of 4.0 μm.
When this [Toner 5] was subjected to a visual confirmation experiment as to whether or not a cold offset occurred under the same conditions and evaluation method as in Example 1, in [Toner 5], the offset was observed regardless of the fixing speed. Was not.

<Example 6>
1-Ethyl-3-methylimidazolium hexafluorophosphate added during preparation of the oil phase of [Toner 4] (Production Example 7), melting point 60 ° C. (hydrophobic ionic organic compound) is 611 parts, and then [Toner 6] was obtained in the same manner as [Toner 4]. The toner had a weight average particle diameter of 4.5 μm and a number average particle diameter of 3.9 μm.
When this [Toner 6] was subjected to a visual confirmation experiment as to whether or not a cold offset occurred under the same conditions and evaluation method as in Example 1, with [Toner 6], the offset was observed regardless of the fixing speed. Was not.

<Example 7>)
Polyester resin 1 ... 47.5 parts Styrene acrylic resin 1 ... 47.5 parts
1-ethyl-3-methylimidazolium hexafluorophosphate, melting point 60 ° C (hydrophobic ionic organic compound) ··· 5 parts Masterbatch 1 ··· 10 parts (Men Co., Ltd., Henschel 20B at 1500 rpm for 3 minutes) and kneading under the same conditions as in Example 1 to obtain [Mother toner 7]. Thereafter, [Mother toner 7] is finely pulverized and classified in the same manner as in Example 1 to obtain [Mother toner particles 7], and then [Mother toner particles 7] are obtained in the same manner as in Example 1. An external additive was mixed to obtain [Toner 7]. [Toner 7] had a weight average particle diameter (D4) of 3.5 μm and a number average particle diameter (Dn) of 3.1 μm.

  When this [Toner 7] was subjected to a visual confirmation experiment as to whether or not a cold offset occurred under the same conditions and evaluation method as in Example 1, with [Toner 7], the offset was observed regardless of the fixing speed. Was not.

<Example 8>)
Polyester resin 1 ... 47.5 parts Styrene acrylic resin 1 ... 47.5 parts
1-ethyl-3-methylimidazolium hexafluorophosphate, melting point 60 ° C (hydrophobic ionic organic compound) ··· 5 parts Masterbatch 1 ··· 10 parts (Minner Henschel 20B at 1500 rpm for 3 minutes) and kneading under the same conditions as in Example 1 to obtain [Base toner 8]. Thereafter, [Mother toner 8] was finely pulverized and classified in the same manner as in Example 1 except that the air pressure during pulverization was changed to 4.5 atm / cm ² to obtain [Mother toner particles 8]. Thereafter, [Toner Base Particles 8] and external additives were mixed in the same manner as in Example 1 to obtain [Toner 8]. [Toner 8] had a weight average particle diameter (D4) of 9.6 μm and a number average particle diameter (Dn) of 9.0 μm.

  When this [Toner 8] was subjected to a visual confirmation experiment as to whether or not a cold offset occurred under the same conditions and evaluation method as in Example 1, the offset was observed with [Toner 8] regardless of the fixing speed. Was not.

<Example 9>)
Polyester resin 1 ... 47.5 parts Styrene acrylic resin 1 ... 47.5 parts
1-butyl-4-methylpyridinium hexafluorophosphate, melting point 45 ° C (hydrophobic ionic organic compound) ··· 5 parts Master batch 1 ··· 10 parts (Henshell 20B manufactured by KK) at 1500 rpm for 3 minutes, and further kneaded under the same conditions as in Example 1 to obtain [Mother toner 9]. Thereafter, [Mother toner 9] is finely pulverized and classified by the same method as in Example 1 to obtain [Mother toner particles 9]. Then, [Mother toner particles 9] are obtained in the same manner as in Example 1. External additives were mixed to obtain [Toner 9]. [Toner 9] had a weight average particle diameter (D4) of 4.5 μm and a number average particle diameter (Dn) of 3.9 μm.

  When this [Toner 9] was subjected to a visual confirmation experiment as to whether or not a cold offset occurred under the same conditions and evaluation method as in Example 1, with [Toner 9], the offset was observed at any speed. Was not.

<Comparative Example 1>
Polyester resin 1 ... 47.5 parts Styrene acrylic resin 1 ... 47.5 parts Paraffin wax (Nippon Seiki Co., Ltd .: 120) ... 5 parts Masterbatch 1 ... 10 parts by weight The toner constituent materials were mixed with a Henschel mixer (Henschel 20B manufactured by Mitsui Mining Co., Ltd., at 1500 rpm for 3 minutes), and further kneaded under the same conditions as in Example 1 to obtain [Base toner 10]. Thereafter, [Mother toner 10] is finely pulverized and classified in the same manner as in Example 1 to obtain [Mother toner particles 10] (mother toner 10), and then [Toner] in the same manner as in Example 1. Base particles 10] and external additives were mixed to obtain [Toner 10]. [Toner 10] had a weight average particle diameter (D4) of 3.8 μm and a number average particle diameter (Dn) of 3.1 μm.

  This [Toner 10] was subjected to a visual confirmation experiment as to whether or not a cold offset occurred under the same conditions and evaluation method as in Example 1. As a result, [Toner 10] was fixed at a linear speed of 240 and 320 mm / sec. In the case, an offset was observed.

(Comparative Example 2)
Polyester resin 1 ... 47.5 parts Styrene acrylic resin 1 ... 47.5 parts
1-Ethyl-3-methylimidazolium hexafluorophosphate (hydrophobic ionic organic compound) ... 25 parts Masterbatch 1 ... 10 parts The above toner constituent materials are mixed with a Henschel mixer (Mitsui Mining Co., Ltd. Henschel 20B at 1500 rpm for 3 minutes), and further kneaded under the same conditions as in Example 1 to obtain [Base toner 10]. Thereafter, [Mother toner 11] is pulverized and classified by the same method as in Example 1 to obtain [Mother toner particles 11], and then [Mother toner particles 11] are obtained in the same manner as in Example 1. An external additive was mixed to obtain [Toner 11]. [Toner 11] had a weight average particle diameter (D4) of 3.6 μm and a number average particle diameter (Dn) of 3.0 μm.

  When the [Toner 11] was fixed at a linear speed of 240 and 320 mm / sec, a visual confirmation experiment was performed to determine whether or not an offset occurred under the same conditions and evaluation method as in Example 1. An offset was observed.

<Comparative Example 3>
Added 110 parts of carnauba wax in place of 1-ethyl-3-methylimidazolium hexafluorophosphate (hydrophobic ionic organic compound) used in the preparation of [Toner 4] oil phase (Production Example 7) Thereafter, [Toner 12] was obtained in the same manner as [Toner 4]. [Toner 12] had a weight average particle diameter (D4) of 4.6 μm and a number average particle diameter (Dn) of 3.9 μm.

  When this [Toner 12] was subjected to a visual confirmation experiment as to whether or not an offset occurred under the same conditions and evaluation method as in Example 1, when [Toner 12] was fixed at a linear speed of 320 mm / sec, Was observed.

<Comparative Example 4>
When preparing the oil phase of [Toner 4] (Production Example 7), the amount of 1-ethyl-3-methylimidazolium hexafluorophosphate (hydrophobic ionic organic compound) added to 100 parts of the total base resin After adding 25 parts, [Toner 13] was obtained in the same manner as [Toner 4]. [Toner 13] had a weight average particle diameter (D4) of 4.3 μm and a number average particle diameter (Dn) of 3.8 μm.

  When this [Toner 13] was subjected to a visual confirmation experiment as to whether or not an offset occurred under the same conditions and evaluation method as in Example 1, the [Toner 13] was fixed at linear speeds of 160, 240, and 320 mm / sec. In all cases, an offset was observed in all cases.

<Comparative Example 5>
Polyester resin 1 ... 47.5 parts Styrene acrylic resin 1 ... 47.5 parts
1-ethyl-3-methylimidazolium hexafluorophosphate (hydrophobic ionic organic compound) ··· 5 parts Masterbatch 1 ··· 10 parts by weight Henschel mixer (Mitsui Mining Co., Ltd.) Mixing with a Henschel 20B made at 1500 rpm for 3 minutes, and kneading under the following conditions in a single-screw kneader (Bus Co., a small bus co-kneader) (set temperature: inlet 100 ° C., outlet 50 At [° C., feed amount: 2 kg / Hr), [base toner 14] was obtained.

Further, the [base toner 14] was kneaded and then cooled by rolling, pulverized by a pulverizer, and further an I-type mill (IDS-2 type manufactured by Nippon Pneumatic Co., Ltd., using a flat impact plate, air pressure: 7.5 atm) / Cm ² , feed amount: 0.25 kg / hr) was finely pulverized, and further classified (132MP manufactured by Alpine) to obtain [Mother toner particles 14].

  Thereafter, 100 parts by weight of [toner base particle 14], 1.0 part by weight of hydrophobic silica (external additive A) having a primary particle size of 10 nm as an external additive, a primary particle size of 110 nm produced by a sol-gel method, and almost spherical. 1.5 parts by weight of hexamethyldisilazane hydrophobized silica (external additive B) and 1.0 part of hydrophobic titanium oxide (external additive C) having a primary particle size of 15 nm were added to a Henschel mixer (Henschel manufactured by Mitsui Mining Co., Ltd.). 20B) to obtain a toner. Mixing conditions were set by repeating the set of rotating for 30 seconds and stopping rotation for 60 seconds 5 times at a peripheral speed of 30 m / sec. The toner obtained here is referred to as [Toner 14]. [Toner 14] had a weight average particle diameter (D4) of 3.2 μm and a number average particle diameter (Dn) of 2.8 μm.

  When this [Toner 14] was subjected to a visual confirmation experiment as to whether or not an offset occurred under the same conditions and evaluation method as in Example 1, it was found that [Toner 14] was fixed at a linear speed of 320 mm / sec. An offset was observed.

<Comparative Example 6>
Polyester resin 1 ... 47.5 parts Styrene acrylic resin 1 ... 47.5 parts
1-ethyl-3-methylimidazolium hexafluorophosphate (hydrophobic ionic organic compound) ··· 5 parts Masterbatch 1 ··· 10 parts Using the above toner constituent materials, Henschel mixer (Mitsui Mining Co., Ltd.) In Henschel 20B at 1500 rpm for 3 minutes, and kneaded under the following conditions in a single-screw kneader (Bus Co., a small bus co-kneader) (set temperature: inlet 100 ° C., outlet 50 ° C. The feed amount was 2 kg / Hr), and [base toner 15] was obtained.

Further, the [base toner 15] is kneaded, cooled by rolling, pulverized by a pulverizer, and further an I-type mill (IDS-2 type manufactured by Nippon Pneumatic Co., Ltd., using a flat impact plate, air pressure: 4.5 atm). / Cm ² , feed amount: 1.0 kg / hr) was finely pulverized and further classified (132MP manufactured by Alpine Co., Ltd.) to obtain [Mother toner particles 15].

  Thereafter, 100 parts by weight of [toner base particle 15], 1.0 part by weight of hydrophobic silica (external additive A) having a primary particle size of 10 nm as an external additive, a primary particle size of 110 nm produced by a sol-gel method, and substantially spherical. 1.5 parts by weight of hexamethyldisilazane hydrophobized silica (external additive B) and 1.0 part of hydrophobic titanium oxide (external additive C) having a primary particle size of 15 nm were added to a Henschel mixer (Henschel manufactured by Mitsui Mining Co., Ltd.). 20B) to obtain a toner. Mixing conditions were set by repeating the set of rotating for 30 seconds and stopping rotation for 60 seconds 5 times at a peripheral speed of 30 m / sec. The toner obtained here is referred to as [Toner 15]. [Toner 15] had a weight average particle diameter (D4) of 12.1 μm and a number average particle diameter (Dn) of 10.5 μm.

  When this [Toner 15] was subjected to a visual confirmation experiment as to whether or not an offset occurred under the same conditions and evaluation method as in Example 1, fixing was performed at 160, 240, and 320 mm / sec. When done, offsets were observed in all cases.

  Table 1 shows the relationship between the type of release agent used in each Example, the melting point, the molecular weight and the addition amount, the weight average particle diameter of the obtained toner, the linear velocity of the fixing roller, and the presence or absence of offset. Table 2 shows similar data regarding the comparative example.

  From Tables 1 and 2, toners of Examples using a hydrophobic ionic organic compound and having a weight average particle size in the range of 3.5 to 10 μm are linear speeds of 160, 240, and 320 mm / second of the fixing roller. In any of the cases, it is clear that no offset occurred.

It is a figure which shows 1-ethyl-3-methylimidazolium ion as an example of the cation molecular part of a hydrophobic ionic organic compound. It is a figure which shows the hexafluorophosphate anion as an example of the anion molecular part of a hydrophobic ionic organic compound. It is a figure which shows 1-butyl-1-methylpyrrolidinium ion as an example of the cation molecular part of a hydrophobic ionic organic compound. It is a figure which shows the bis (trifluoromethyl sulfonyl) imide anion as an example of the anion molecular part of a hydrophobic ionic organic compound. It is a figure which shows 1-butyl-3-methylimidazolium ion as an example of the cation molecular part of a hydrophobic ionic organic compound. It is a figure which shows 1-butyl-4-methyl pyridilium ion as an example of the cation molecular part of a hydrophobic ionic organic compound. 1 is a schematic diagram illustrating an example of a fixing device used in an image forming apparatus of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Fixing device 20 Heating roller 21 Elastic body layer 22 Surface layer 23 Core metal 30 Pressure roller 31 Elastic body layer 32 PFA surface layer 33 Core metal N nip S Recording medium T Toner image

Claims (11)

An electrophotographic toner containing at least a colorant and a binder resin, and having a weight average particle size of 3.5 to 10 μm, and further comprising a hydrophobic molecule in which atoms having a positive charge point in the molecule are bonded. Contains a hydrophobic ionic organic compound consisting of an organic cation and a hydrophobic anion with an atom having a negative charge point in the molecule ,
The atom having the positive charge point is a nitrogen atom (N);
The toner for electrophotography, wherein the atom having the negative charge point is a nitrogen atom (N) . 2. The electrophotographic toner according to claim 1 , wherein the hydrophobic organic cation to which the N atom is bonded is any one of imidazolium, pyridinium, pyrrolidinium, piperidinium, and quaternary ammonium. The electrophotographic toner according to claim 1, wherein the hydrophobic anion to which the N atom is bonded is di (fluorocarbonsulfonyl) imide or di (alkylsulfonyl) imide. 4. The electrophotographic toner according to claim 1, wherein the hydrophobic ionic organic compound is contained in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin. The toner, toner for electrophotography according to any one of claims 1 to 4, characterized in that a polymerized toner is granulated in an aqueous solvent. The toner, toner for electrophotography according to any one of claims 1 to 4, characterized in that by grinding a toner granulated. A one-component developer comprising only the toner according to claim 1 . A two-component developer comprising the toner according to any one of claims 1 to 6 and a carrier. An image bearing member; an electrostatic latent image forming unit that forms an electrostatic latent image on the image bearing member; a developing unit that develops the electrostatic latent image with toner to form a visible image; A transfer speed for transferring the visual image to the recording medium and a fixing means for fixing the transferred image transferred to the recording medium; An image forming apparatus having an image forming speed of 150 mm / second or more, wherein the toner is the electrophotographic toner according to claim 1 . 6. A process cartridge for an image forming apparatus that supports at least an image carrier and a developing unit integrally and is detachable from an image forming apparatus main body, wherein the toner in the developing unit is defined in any one of claims 1 to 5 . A process cartridge which is an electrophotographic toner. An electrostatic latent image forming step for forming an electrostatic latent image on an image carrier, a developing step for developing the electrostatic latent image with toner to form a visible image, and the visible image on a recording medium At least a transfer step for fixing the transfer image transferred to the recording medium, and a conveyance speed when discharging the recording medium on which the transfer image is formed from the fixing unit is 150 mm / second or more 6. An image forming method according to claim 1, wherein the toner is an electrophotographic toner according to any one of claims 1 to 5 .

Images