JP4606212B2 - Toner, toner-containing container, image forming method, image forming apparatus, and process cartridge for image forming apparatus - Google Patents

Description

  The present invention relates to toner, a container containing toner, an image forming method, an image forming apparatus, and a process cartridge for the image forming apparatus.

  In electrophotographic image formation, an electrostatic latent image is generally formed on a photoconductor prepared using a photoconductive substance by various means, and then the electrostatic latent image is developed using a developer. The image formed by the developer is transferred onto paper or the like as necessary, and further fixed by heating, pressurization, solvent vapor or the like.

  The methods for developing electrical latent images can be broadly divided into a liquid development method using a liquid developer in which various pigments and dyes are finely dispersed in an insulating organic liquid, a cascade method, a magnetic brush method, and a powder cloud. There is a dry development method using a dry developer (hereinafter referred to as toner) prepared by dispersing a colorant such as carbon black in a natural or synthetic resin as in the method, etc., and in recent years, the dry development method has been widely used. .

  As a fixing method used in the dry development method, a heating heat roller method is widely used because of its energy efficiency. In recent years, in order to save energy by fixing the toner at a low temperature, the thermal energy given to the toner during fixing tends to be small. The 1999 International Energy Agency (IEA) DSM (Demand-side Management) program includes a technology procurement project for next-generation copiers, the requirements for which were published, and for copiers of 30 cpm and above, It is required to achieve dramatic energy savings compared to conventional copying machines so that the standby time is within 10 seconds and the standby power consumption is 10 to 30 watts or less (differs depending on the copying speed). One method for achieving this requirement is to reduce the heat capacity of a fixing member such as a heated heat roller to improve the temperature responsiveness of the toner, but it is not fully satisfactory.

  In order to achieve the above requirement and minimize the waiting time, it is considered to be an essential technical achievement matter to lower the fixing temperature of the toner itself and lower the toner fixing temperature when it can be used.

  In order to cope with such low-temperature fixing, an attempt has been made to use a polyester resin having excellent low-temperature fixability and relatively good heat-preservability in place of the styrene-acrylic resin that has been widely used in the past (Patent Document 1, Patent). Document 2, Patent Document 3, Patent Document 4, Patent Document 5, Patent Document 6, etc.). In addition, there are attempts to add a specific non-olefinic crystalline polymer in the binder for the purpose of improving low-temperature fixability (Patent Document 7) and attempts to use crystalline polyester (Patent Document 8). It cannot be said that the molecular weight is optimized.

  Further, even if these conventionally known techniques are applied, it is impossible to achieve the specifications of a DSM (Demand-side Management) program, and it is necessary to establish a low-temperature fixing technique that is further advanced than the conventional technical field.

  For further low-temperature fixing, it is necessary to control the thermal characteristics of the resin itself. However, if the glass transition temperature (Tg) is lowered too much, the heat-resistant storage stability is deteriorated, and the resin is reduced by reducing the molecular weight. If the F1 / 2 temperature is lowered too much, there are problems such as lowering the hot offset occurrence temperature. For this reason, by controlling the thermal characteristics of the resin itself, it has not been possible to obtain a toner having excellent low-temperature fixability and a high hot offset occurrence temperature.

  On the other hand, toner production methods used for electrostatic image development are roughly classified into a pulverization method and a polymerization method.

  In the pulverization method, a colorant, a charge control agent, an offset preventive agent, and the like are melt-mixed and uniformly dispersed in the thermoplastic resin described above, and the resulting composition is pulverized and classified to produce a toner. ing. According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment. From this requirement, the melt-mixed composition must be made sufficiently brittle. For this reason, when the above composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, toner weight The average particle size must be reduced, and fine powder with a particle size of 4 μm or less and coarse powder with a particle size of 15 μm or more must be removed by classification, which has the disadvantage that the toner yield becomes very low. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. Such dispersion adversely affects toner fluidity, developability, durability, image quality, and the like.

  In recent years, in order to overcome these problems in the pulverization method, a toner production method by a suspension polymerization method has been proposed and implemented. A technique for producing a toner for developing an electrostatic latent image by a polymerization method is known. For example, toner particles are obtained by a suspension polymerization method or an emulsion polymerization aggregation method (Patent Document 9).

However, in these production methods, a polyester resin superior in low-temperature fixability cannot be used as a toner. In order to solve these problems, a toner obtained by sphering a toner composed of a polyester-based resin using a solvent in water (Patent Document 10), a toner using an isocyanate reaction (Patent Document 11), and the like have been proposed. The low-temperature fixability and toner productivity were not satisfactory.
JP 60-90344 A JP-A 64-15755 Japanese Patent Laid-Open No. 2-82267 JP-A-3-229264 JP-A-3-41470 JP-A-11-305486 JP 62-63940 A Japanese Patent No. 2931899 Japanese Patent No. 2537503 JP-A-9-34167 JP-A-11-149180

  The present invention has been made in view of the above problems, and an object thereof is to provide a toner having better low-temperature fixability.

The invention according to claim 1 is a toner including a binder resin and a colorant, wherein the binder resin includes a resin containing a urea bond and a urethane bond, and the total concentration of the urea bond and the urethane bond is It is 0.010 mmol / g (toner) or more and 0.125 mmol / g (toner) or less.
Furthermore, the invention according to claim 1 is a solution in which a ketimine compound , a polymer containing an isocyanate group, and the colorant are dissolved or dispersed in an organic solvent, and the resulting solution or dispersion is dispersed in an aqueous medium. The toner obtained by reacting the ketimine compound and the polymer containing the isocyanate group, or by removing the organic solvent while reacting, washing and drying the toner, the toner containing the isocyanate group The coalescence is a modified polyester obtained by reacting a polyester obtained by reacting a carboxylic acid and an alcohol having no bisphenol skeleton with isophorone diisocyanate, having a glass transition temperature of 0 ° C. to 60 ° C. and a weight average molecular weight of 10,000. ˜100,000 .

The invention according to claim 2 is the invention according to claim 1, wherein the total concentration of the urea bond and the urethane bond is 0.077 mmol / g (toner) or more and 0.125 mmol / g (toner) or less. It is characterized by that.

According to a third aspect of the present invention, in the toner according to the first or second aspect, the polymer is a modified polyester obtained by reacting a polyester having a neopentyl alcohol group and a compound having an isocyanate group. It is characterized by.

According to a fourth aspect of the present invention, in the toner according to any one of the first to third aspects, the ketimine compound is a compound produced by a reaction of isophoronediamine and a ketone .

According to a fifth aspect of the present invention, in the toner according to any one of the second to fourth aspects, the polymer has a weight average molecular weight of 13,000 or more and 60000 or less.

The compound having an amino group is included in the compound having an active hydrogen group, and the isocyanate group is a site capable of reacting with the compound having the active hydrogen group.

The invention described in claim 6 is the toner according to any one of claims 2 to 5, wherein the glass transition temperature of the polymer is 30 ° C. or higher and 44.2 ° C. or lower.

The toner according to any one of claims 1 to 6, the glass transition temperature is preferably at 40 ° C. or higher 70 ° C. or less.

According to a seventh aspect of the present invention, in the toner according to any one of the first to sixth aspects, the volume average particle size is 3 μm or more and 8 μm or less.

According to an eighth aspect of the present invention, in the toner according to any one of the first to seventh aspects, the ratio of the volume average particle diameter to the number average particle diameter is 1.25 or less.

The toner according to any one of claims 1 to 8, the glass transition temperature of the binder resin is preferably 30 ° C. or higher 50 ° C. or less.

The toner according to any one of claims 1 to 8 ,
The acid value of the binder resin is preferably 1 mgKOH or more and 30 mgKOH or less.

The toner according to any one of claims 1 to 8, hydroxyl value of the binder resin is preferably less than 1 mgKOH 30 mgKOH.

The invention described in claim 9 is characterized in that the toner according to any one of claims 1 to 8 is accommodated in a toner-containing container.

According to a tenth aspect of the present invention, in the image forming method, an image is formed using the toner according to any one of the first to eighth aspects.

According to an eleventh aspect of the present invention, in the image forming apparatus, an image is formed using the toner according to any one of the first to eighth aspects.

According to a twelfth aspect of the present invention, there is provided an image forming apparatus in which at least one means selected from the group consisting of a charging means, a developing means, and a cleaning means and an image carrier are integrated, and are detachable from the main body of the image forming apparatus. An image is formed using the toner according to any one of claims 1 to 8 .

  According to the present invention, it is possible to provide a toner having more excellent low-temperature fixability.

  Next, embodiments of the present invention will be described with reference to the drawings.

  The toner according to the present invention contains a binder resin and a colorant, and the binder resin contains a resin containing urea bonds and / or urethane bonds, and the total concentration of urea bonds and / or urethane bonds is 0.010 mmol / It is not less than g (toner) and not more than 0.125 mmol / g (toner). Here, the urea bond (urea group) is a —NHCONH— bond, and the urethane bond is a —NHCOO— bond. The total concentration (mmol / g) of urea bonds and / or urethane bonds is the number of urea bonds and / or urethane bonds contained in the toner per unit mass.

The total concentration C (mmol / g) of urea bond and / or urethane bond is, for example, in the case where the toner according to the present invention is obtained using a reaction of a polymer having an isocyanate group (—NCO group). Based on the weight ratio A (%) of the polymer having an isocyanate group and the weight ratio B (%) of the isocyanate group contained in the polymer having an isocyanate group,
C (mmol / g) = [{(A / 100) × (B / 100)} / 42] × 2 × 1000
Can be calculated according to The weight ratio B (%) of isocyanate groups contained in the polymer having isocyanate groups is measured in accordance with JIS K1603.

  When the total concentration of urea bonds and / or urethane bonds is less than 0.010 mmol / g (toner), it may be difficult to obtain sufficient offset resistance. Moreover, when the total concentration of urea bonds and / or urethane bonds exceeds 0.125 mmol / g (toner), it may be difficult to obtain sufficient low-temperature fixability. In addition, when the toner has negative chargeability, the negative chargeability of the toner may be reduced. That is, when the total concentration of urea bond and / or urethane bond is 0.010 mmol / g (toner) or more and 0.125 mmol / g (toner) or less, it has sufficient offset resistance and sufficient low-temperature fixability. It becomes possible to obtain a toner, and in particular, it is possible to obtain a toner having better low-temperature fixability as compared with a conventional toner.

  In addition, the compound having a site capable of reacting with a compound having an active hydrogen group, such as a polymer having a site capable of reacting with a compound having an active hydrogen group (for example, an isocyanate group), which does not contain at least a bisphenol skeleton, a compound having an active hydrogen group In the case of a modified polyester obtained by reacting with a polymer, the molecular weight of the polymer having a site capable of reacting with a compound having an active hydrogen group can be 10,000 or more and 100,000 or less, and the above urea bond and / or It is possible to achieve a total concentration of urethane bonds.

  The present inventors dissolve or disperse (containing the composition) a polymer having a site capable of reacting with a compound having an active hydrogen group, a colorant, and a release agent in at least an organic solvent, ) After the solution or dispersion is dispersed in an aqueous medium and the polymer having a site capable of reacting with the compound having an active hydrogen group is reacted, or while reacting, the organic solvent is removed, washed, A dry toner, which contains a blocked isocyanate compound, has a controlled particle size and shape, further satisfies low-temperature fixing, has good offset resistance, and stores toner. It has been found that the toner has good properties and the toner collected on the cleaning roller can be prevented from being melted again, and the image stain can be reduced.

  The embodiment of the present invention, for example, dissolves or disperses a polymer having a site capable of reacting with a compound having an active hydrogen group, a colorant, and a release agent (containing composition) in at least an organic solvent, After the (composition) solution or dispersion is dispersed in an aqueous medium and the polymer having a site capable of reacting with the compound having an active hydrogen group is reacted, or while reacting, the organic solvent is removed. A toner for electrostatic charge development, which is a washed and dried toner, wherein the total concentration of urea groups and urethane groups is 0.010 mmol / g (toner) to 0.125 mmol / g (toner). .

  Preferably, as the polymer, an electrostatic charge development characterized by adding a site capable of reacting with an active hydrogen group to a polyester obtained by polycondensation of an alcohol having no bisphenol skeleton and a carboxylic acid. Toner.

  Preferably, the electrostatic charge developing toner is characterized in that a site to which a site capable of reacting with a compound having an active hydrogen group is added in the polymer is an isocyanate group.

  Also preferred is an electrostatic charge developing toner in which the polymer has a weight average molecular weight of 10,000 to 100,000.

  Also preferably, the toner for electrostatic charge development is characterized in that Tg of the polymer is 0 ° C. to 60 ° C.

  Preferably, the toner is for electrostatic charge development, wherein the functional group having an active hydrogen group in the compound is an amino group.

  The toner for electrostatic charge development is preferably characterized in that the toner particles have a glass transition point of 40 to 70 degrees.

  Preferably, the toner for developing an electrostatic charge image is characterized in that the toner particles have a weight average particle diameter of 3 to 8 μm.

  The toner for developing an electrostatic charge image is preferably characterized in that the toner particles have a weight average particle diameter / number average particle diameter of 1.25 or less.

  Preferably, the toner for developing electrostatic images is characterized in that the toner binder resin has a glass transition point of 30 to 50 ° C.

  The toner for developing an electrostatic charge image is preferably characterized in that the toner binder resin has an acid value of 1 to 30 mgKOH.

  The toner for developing an electrostatic charge image is preferably characterized in that the toner binder resin has a hydroxyl value of 1 to 30 mgKOH.

  According to such an electrostatic charge image developing toner, it is possible to provide a toner that has excellent low-temperature fixability, anti-offset performance, and good high-definition images.

(Dv / Dn (ratio of volume average particle diameter / number average particle diameter))
The toner has a volume average particle diameter (Dv) of 3 to 8 μm and a ratio (Dv / Dn) to the number average particle diameter (Dn) of 1.25 or less, preferably 1.10 to 1.25. The toner has excellent heat resistance, low-temperature fixability, and hot offset resistance, particularly excellent image gloss when used in full-color copiers, etc. Even if the balance is performed, the fluctuation of the toner particle diameter in the developer is reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. Even when used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner is filmed on the developing roller and the toner is made thin. The toner was not fused to a member such as a blade, and good and stable developability and images were obtained even when the developing device was used (stirred) for a long time.

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

  Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention.

  On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high resolution and high quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large. It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25.

  Further, when the volume average particle size / number average particle size is smaller than 1.05, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and equalizing the charge amount, but the toner becomes insufficiently charged. In some cases, it was also found that the cleaning property may be deteriorated.

(Glass transition temperature of toner)
Since the heat-resistant storage performance depends on the glass transition point of the toner particles, it is preferable to design the glass transition point of the toner particles to 40 ° C. to 70 ° C. That is, if it is less than 40 ° C., the heat-resistant storage stability is insufficient, and if it exceeds 70 ° C., it adversely affects low-temperature fixing.

(Binder resin)
By setting the acid value of the toner binder resin to 1.0 to 50.0 (KOHmg / g), the toner properties such as low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and charging stability are improved. Is possible. That is, when the acid value exceeds 50.0 (KOHmg / g), the extension or crosslinking reaction of the modified polyester becomes insufficient, and the high-temperature offset resistance is affected, and when it is less than 1.0 (KOHmg / g) This is because the extension or crosslinking reaction of the modified polyester is likely to proceed, causing problems in production stability.

  Further, by setting the hydroxyl value to 1.0 to 100.0 (KOHmg / g), it is possible to suppress toner dissolution from the cleaning roller. That is, when the hydroxyl value is less than 1.0 (KOHmg / g), the reaction with the blocked isocyanate in the toner becomes insufficient, and there is a concern about toner dissolution from the cleaning roller. On the other hand, if the hydroxyl value exceeds 100.0 (KOHmg / g), the hydrophilicity of the toner is increased and there is a risk of causing problems in charging characteristics under high temperature and high humidity conditions.

  Since the heat-resistant storage performance depends on the glass transition point of the binder resin, it is preferable to design the glass transition point of the binder resin at 30 ° C. to 50 ° C. That is, if it is less than 30 ° C., the heat-resistant storage stability is insufficient, and if it exceeds 50 ° C., it adversely affects low-temperature fixing.

(Organic solvent)
In the present invention, the organic solvent is not particularly limited as long as it is a solvent capable of dissolving and / or dispersing the toner composition. As a preferable thing, it is preferable that the boiling point of this solvent is less than 150 degreeC from the point of being easy to remove. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, methyl acetate, ethyl acetate, methyl ethyl ketone, acetone. , Tetrahydrofuran and the like can be used alone or in combination of two or more. The amount of solvent used is usually 40 to 300 parts, preferably 60 to 140 parts, and more preferably 80 to 120 parts with respect to 100 parts of the toner composition.

(Coloring agent)
As the coloring agent of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide , Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow ( 5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red , Fais red, parachlorol Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

  The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet cake of a coloring agent, is a method of mixing and kneading an aqueous paste containing water of a coloring agent together with a resin and an organic solvent, transferring the coloring agent to the resin side, and removing moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
Further, a wax may be contained together with the toner binder and the colorant. Known waxes can be used as the wax of the present invention, such as polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. It is done. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18 -Octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 1000 cps, as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. Any known charge control agent can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified) Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (above, Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP 1415 (above, Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt. In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they can be added directly when dissolved and dispersed in an organic solvent. May be.

(External additive)
As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 μm to 2 μm, and particularly preferably 5 μm to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, particularly preferably 00.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  Other polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine, nylon, thermosetting resin, etc. Examples include polymer particles.

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

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

  The dry toner of the present invention can be produced by the following method, but is not limited thereto.

(Toner production method in aqueous medium)
The aqueous phase used in the present invention is used by adding resin fine particles in advance. The water used for the aqueous phase may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  In the aqueous phase, the toner particles are reacted with a dispersion composed of a compound (A) having an active hydrogen group and a polymer (B) having a site capable of reacting with an active hydrogen group dissolved or dispersed in an organic solvent. It is obtained by forming. As a method for stably forming a dispersion comprising a polymer (B) in an aqueous phase, a composition of a toner raw material comprising a polymer (B) dissolved or dispersed in an organic solvent in an aqueous phase is added. For example, a method of dispersing by shearing force may be used. The polymer (B) dissolved or dispersed in an organic solvent and other toner compositions (hereinafter referred to as toner raw materials), a colorant masterbatch, a release agent, a charge control agent, a binder resin, etc. It may be mixed when the dispersion is formed in the aqueous phase, but it is more preferable that the toner raw material is mixed in advance and then dissolved or dispersed in an organic solvent, and then the mixture is added and dispersed in the aqueous phase. . In the present invention, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in the aqueous phase. It may be added. For example, after forming particles not containing a colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion made of the polymer (B) has a low viscosity and is easy to disperse.

  The amount of the aqueous phase used relative to 100 parts of the toner composition containing the polymer (B) 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 composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino acids as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in the aqueous phase Alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, quaternary ammonium such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride Nonionic surfactants such as salt-type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N − Amphoteric surfactants such as ammonium betaine.

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- [omega-fluoroalkyl (C6-C11). ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carboxylic acid and Metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- (2 hydroxy ethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned,
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. , DS-102 (manufactured by Taikin Kogyo Co., Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF- 102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C 6 -C 10) sulfonamidopropyltrimethylammonium salt which right the fluoroalkyl group, Benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (manufactured by Daikin Industries) ), Megafuck F-150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and Footgent F1300 (manufactured by Neos).

  Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant which is hardly soluble in water.

  Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro 2-hydroxypropyl, methacrylic acid 3-chloro-2-monohydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N- Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or esters of compounds containing vinyl alcohol and carboxyl groups, such as acetic acid Pinyl, pinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, nitrogen such as pinylviridine, vinylpyrrolidone, vinylimidazole, ethyleneimine Homopolymers or copolymers such as those having atoms or heterocycles thereof, polyoxyethylene, polyoxypropylene, poly Xylethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation.

  When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

  The elongation and / or crosslinking reaction time is selected depending on the structure of the site capable of reacting with the active hydrogen group of the polymer (B) and the reactivity of the compound (A) having an active hydrogen group, but usually 10 minutes. -40 hours, preferably 2-24 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.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

  When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.

  In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.

  The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

  Mixing or giving mechanical impact force to the powder mixture after drying with different types of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles By immobilizing and fusing on the surface, it is possible to prevent detachment of foreign particles from the surface of the resulting composite particle.

  Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 weights of toner with respect to 100 parts by weight of carrier. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

  Further, the toner according to the present invention is contained in a known container. The toner container containing the toner of the present invention has, for example, a bottle shape, and the toner container can be attached to and detached from the image forming apparatus or the process cartridge for the image forming apparatus.

  An image can be formed using the toner according to the present invention in a known image forming method and an electrophotographic apparatus for forming a known image such as an electrophotographic forming method and an electrophotographic apparatus.

  Further, the toner according to the present invention is a known image forming unit in which at least one unit selected from the group consisting of a charging unit, a developing unit, and a cleaning unit and an image carrier are integrated and detachable from the main body of the image forming apparatus. An image can be formed using the process cartridge for an apparatus.

[Examples and Comparative Examples]
EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

~ Synthesis of organic fine particle emulsion ~
Production Example 1
In a reaction vessel equipped with a stirrer 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 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 105 nm. A portion of [Fine Particle Dispersion 1] 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.

-Adjustment of aqueous phase-
Production Example 2
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

~ Synthesis of low molecular weight polyester ~
Production Example 3
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 8 hours at normal pressure, and further react for 5 hours at 10-15 mmHg reduced pressure, then add 44 parts of trimellitic anhydride to the reaction vessel at 180 ° C at normal pressure. The mixture was reacted for 2 hours to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, Tg of 43 ° C., and an acid value of 25 mgKOH.

~ Synthesis of intermediate polyester ~
Production Example 4
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 299.7 parts of neopentyl alcohol and 232.1 parts of terephthalic acid are placed and reacted at 230 ° C. for 8 hours at normal pressure. 1] was obtained. [Intermediate Polyester 1] had a weight average molecular weight of 10,000, Tg of 23 ° C., an acid value of 0.5, and a hydroxyl value of 19. Next, 100 parts of [Intermediate polyester 1], 8.3 parts of isophorone diisocyanate, and 108.3 parts of ethyl acetate were 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. [Prepolymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 0.65%.

Production Example 5
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 299.7 parts of neopentyl alcohol and 232.1 parts of terephthalic acid were placed and reacted at 230 ° C. for 4 hours at normal pressure. 2] was obtained. [Intermediate Polyester 1] had a weight average molecular weight of 6000, Tg of 13 ° C., an acid value of 0.8, and a hydroxyl value of 22. Next, 100 parts of [Intermediate polyester 1], 9.6 parts of isophorone diisocyanate, and 109.6 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. [Prepolymer 2] was obtained. [Prepolymer 2] had a free isocyanate weight% of 0.75%.

Production Example 6
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 299.7 parts of neopentyl alcohol and 232.1 parts of terephthalic acid are placed, reacted at 230 ° C. for 8 hours at normal pressure, and further 10-15 mmHg Was reacted for 5 hours under reduced pressure to obtain [Intermediate Polyester 3]. [Intermediate Polyester 3] had a weight average molecular weight of 17,000, Tg of 45 ° C., an acid value of 0.3, and a hydroxyl value of 15. Next, 100 parts of [Intermediate Polyester 3], 6.5 parts of isophorone diisocyanate, and 106.5 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. [Prepolymer 3] was obtained. [Prepolymer 3] had a free isocyanate weight% of 0.47%.

Production Example 7
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 299.7 parts of neopentyl alcohol and 232.1 parts of fumaric acid are placed, reacted at 230 ° C. for 8 hours at normal pressure, and further 10-15 mmHg [Intermediate polyester 4] was obtained by reaction for 2 hours under reduced pressure. [Intermediate Polyester 4] had a weight average molecular weight of 14,000, Tg of 31 ° C., an acid value of 0.4, and a hydroxyl value of 18. Next, 100 parts of [Intermediate Polyester 4], 67.8 parts of isophorone diisocyanate, and 107.8 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. [Prepolymer 4] was obtained. [Prepolymer 4] had a free isocyanate weight percentage of 0.6%.

Production Example 8
A prepolymer 5 was obtained in the same manner as in Production Example 4 except that 3.5 parts of epichlorohydrin was used instead of 8.3 parts of isophorone diisocyanate in Production Example 4. Prepolymer 5 had an epoxy weight percent of 3.1%.

~ Synthesis of ketimine ~
Production Example 9
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 150 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 416.

~ Synthesis of MB ~
Production Example 10
1200 parts of water, 540 parts of carbon black (made by Printex 35 Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5] and 1200 parts of polyester resin are added and mixed with a Henschel mixer (made by Mitsui Mining Co., Ltd.). After kneading at 150 ° C. for 30 minutes using two rolls, rolling and cooling and pulverizing with a pulverizer, [Masterbatch 1] was obtained.

~ Preparation of oil phase ~
Production Example 11
In a container equipped with a stirrer and a thermometer, 378 parts of [Low molecular weight polyester 1], 110 parts of Carnauba WAX, 22 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industry), and 947 parts of ethyl acetate were charged with stirring. The temperature was raised to 0 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].

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

~ Emulsification⇒Desolvation ~
[Example 1]
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine] 2.1 parts were put in a container and mixed for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika). Thereafter, 1200 parts of [Aqueous Phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsified Slurry 1]. [Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1]. [Dispersion Slurry 1] had a volume average particle size of 5.21 μm and a number average particle size of 4.54 μm (measured with Multisizer II).

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

  (2): 100 parts of distilled water 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): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [Filter cake 1]. It was. [Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with an opening of 75 μm mesh to obtain [Toner 1].

[Example 2]
[Toner 2] was obtained in the same manner as in Example 1 except that [Prepolymer 2] was used instead of [Prepolymer 1] in Example 1, and 2.4 parts instead of 2.1 parts of ketimine were used. It was.

Example 3
[Toner 3] is obtained in the same manner as in Example 1 except that [Prepolymer 3] is used instead of [Prepolymer 1] in Example 1 and 1.5 parts is used instead of 2.1 parts of ketimine. It was.

Example 4
[Toner 4] was obtained in the same manner as in Example 1 except that [Prepolymer 4] was used instead of [Prepolymer 1] in Example 1 and 1.9 parts was used instead of 2.1 parts of ketimine. It was.

Example 5
[Toner 5] was obtained in the same manner as in Example 1 except that [Prepolymer 5] was used in place of [Prepolymer 1] in Example 1 and the part was used in place of 2.1 parts of ketimine.

~ Synthesis of intermediate polyester ~
Production Example 12
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 299.7 parts of neopentyl alcohol and 332.6 parts of terephthalic acid are placed, reacted at 230 ° C. for 8 hours at normal pressure, and further 10-15 mmHg Was reacted for 8 hours under reduced pressure to obtain [Intermediate Polyester 6]. [Intermediate Polyester 6] had a weight average molecular weight of 58000, Tg of 72 ° C., an acid value of 0.1, and a hydroxyl value of 11. Next, 100 parts of [Intermediate polyester 6], 4.8 parts of isophorone diisocyanate, and 104.8 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. [Prepolymer 6] was obtained. [Prepolymer 6] had a free isocyanate weight percent of 0.24%.

Production Example 13
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51. Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

[Comparative Example 1]
[Toner 6] was obtained in the same manner as in Example 1 except that [Prepolymer 6] was used instead of [Prepolymer 1] in Example 1 and 0.8 part was used instead of 2.1 parts of ketimine. It was.

[Comparative Example 2]
[Toner 7] was obtained in the same manner as in Example 1 except that [Prepolymer 7] was used instead of [Prepolymer 1] in Example 1, and 4.8 parts was used instead of 2.1 parts of ketimine. It was.

(Evaluation item)
-Measurement of NCO% The method of measuring NCO% is according to the method specified in JIS K1603.

-Method for calculating the total concentration of urea groups and urethane groups "weight ratio of polymer having a site capable of reacting with a compound having an active hydrogen group in the toner; A (%)"
“NCO% of a polymer having a site capable of reacting with a compound having an active hydrogen group; B (%)”
Where the value calculated by the following formula is “total concentration of urea group and urethane group; C” C (mmol / g) = [{(A / 100) × (B / 100)} / 42] × 2 × 1000
-Method for measuring acid value The method for measuring acid value is as defined in JIS K0070. However, if the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.

-Measuring method of hydroxyl value The measuring method of a hydroxyl value is based on the method prescribed | regulated to JISK0070. However, if the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.

-Particle size The particle size of the toner was measured with a particle size measuring device "Coulter Counter TAII" manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 µm. The volume average particle diameter and the number average particle diameter were determined by the particle size measuring instrument.

-Tg measuring method The measuring method of Tg is outlined. As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.

  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. First, after heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, the sample was cooled to room temperature and allowed to stand for 10 minutes, and the heating rate was again increased to 150 ° C. under a nitrogen atmosphere DSC measurement was performed by heating at / min. Tg was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

-Heat-resistant storage stability After storing the toner at 50 ° C for 8 hours, the toner was screened with a 42 mesh screen for 2 minutes, and the residual rate on the wire mesh was defined as heat-resistant storage stability. A toner having better heat-resistant storage stability has a lower residual ratio. The following four levels were evaluated.

×: 30% or more △: 20-30%
○: 10 to 20%
◎: Less than 10% ・ Fixability Using Ricoh's imgio Neo 450, solid images and thick paper transfer paper (Ricoh type 6200 and NBS Ricoh's copy printing paper <135>) with a solid image of 1.0 ± 0 Adjust so that 1 mg / cm ² of toner is developed, adjust the temperature of the fixing belt to be variable, and measure the temperature at which offset does not occur on plain paper and the minimum fixing temperature on thick paper did. The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.

・ Charging characteristics 1) Stirring for 15 seconds Q / M
Silicon resin-coated ferrite carrier (average particle size 50 μm) 100 parts 4 parts of the test toner was placed in a stainless steel pot up to 30% of the internal volume, stirred for 15 seconds at a stirring speed of 100 rpm, and determined by a blow-off method.

2) 10 minutes stirring Q / M
Charge amount when stirring for 10 minutes as in 1)

以上、本発明の実施の形態及び実施例を具体的に説明してきたが、本発明は、これらの実施の形態及び実施例に限定されるものではなく、これら本発明の実施の形態及び実施例を、本発明の主旨及び範囲を逸脱することなく、変更又は変形することができる。

Although the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to these embodiments and examples, and these embodiments and examples of the present invention are not limited thereto. Can be changed or modified without departing from the spirit and scope of the present invention.

  The present invention can be applied to an electrostatic charge image developing toner for developing an electrostatic charge image formed on the surface of a photoreceptor and a developer using the toner in electrophotography and electrostatic recording. The present invention also relates to an electrostatic image developing toner used for developing an electrostatic latent image such as an electrophotographic method, an electrostatic recording method, and an electrostatic printing method, and more specifically, sufficient low-temperature fixability and wide-range fixing. The present invention can be applied to toner for developing an electrostatic image for the purpose of establishing a temperature region and obtaining a good high-definition image.

Claims (12)

In a toner containing a binder resin and a colorant,
The binder resin includes a resin containing a urea bond and a urethane bond,
Urine total concentration of hydrogen bond and the urethane bond, 0.010 mmol / g (toner) or 0.125 mmol / g (toner) hereinafter der is,
A ketimine compound , a polymer containing an isocyanate group, and the colorant are dissolved or dispersed in an organic solvent, and the resulting solution or dispersion is dispersed in an aqueous medium to contain the ketimine compound and the isocyanate group. A toner obtained by reacting a polymer or removing the organic solvent while reacting, washing and drying the polymer ,
The polymer containing an isocyanate group is a modified polyester obtained by reacting a polyester obtained by reacting a carboxylic acid and an alcohol having no bisphenol skeleton with isophorone diisocyanate, and has a glass transition temperature of 0 ° C to 60 ° C. A toner having a weight average molecular weight of 10,000 to 100,000 at 0 ° C. 2. The toner according to claim 1, wherein the total concentration of the urea bond and the urethane bond is 0.077 mmol / g (toner) or more and 0.125 mmol / g (toner) or less. The toner according to claim 1, wherein the polymer is a modified polyester obtained by reacting a polyester having a neopentyl alcohol group with a compound having an isocyanate group. The toner according to claim 1, wherein the ketimine compound is a compound formed by a reaction of isophoronediamine and a ketone . The toner according to any one of claims 1 to 4, wherein the polymer has a weight average molecular weight of 13,000 or more and 60000 or less. The toner according to claim 1, wherein the polymer has a glass transition temperature of 30 ° C. or higher and 44.2 ° C. or lower.   The toner according to claim 1, wherein the volume average particle diameter is 3 μm or more and 8 μm or less.   The toner according to claim 1, wherein the ratio of the volume average particle diameter to the number average particle diameter is 1.25 or less.   A toner-containing container containing the toner according to claim 1.   An image forming method, wherein an image is formed using the toner according to claim 1.   An image forming apparatus that forms an image using the toner according to claim 1. In a process cartridge for an image forming apparatus in which at least one means selected from the group consisting of a charging means, a developing means, and a cleaning means and an image carrier are integrated and detachable from the main body of the image forming apparatus.
A process cartridge for an image forming apparatus, wherein an image is formed using the toner according to claim 1.