JP2010072604A - Method of manufacturing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing toner, manufacturing toner in which a high quality image having high image quality and high resolution with reduced amount of transfer residual toner is obtained, power consumption is small, which has high transfer properties and OHP transmittance required for a color image, and which improves manufacturing efficiency by reducing the time of solvent removal process, in a device obtaining high reliability in cleaning, having superior charging stability, low temperature fixability, and transfer efficiency, and using a cleaning blade. <P>SOLUTION: In the method of manufacturing the toner, the relation among heat transfer area S (m<SP>2</SP>) of a pipe, a supply rate A (kg/min) of an emulsion to the pipe, and an organic solvent content B(%) in the emulsion satisfies 0.5≤S/(A×B×0.01)≤25. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner manufacturing method, and more particularly, to a method for manufacturing a toner for developing an electrostatic image used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like. Relates to a method for producing toner for electrophotography used in copiers, laser printers, plain paper fax machines and the like using a direct or indirect electrophotographic developing system.

In recent years, the strong demand for higher image quality from the market has spurred the development of an electrophotographic apparatus suitable for it and a toner developer used therefor. As a toner corresponding to high image quality, it is essential that the toner has a uniform particle size. When the toner particle size is uniform and the particle size distribution becomes sharp, the behavior of individual toner particles during development is aligned, and the reproducibility of minute dots is remarkably improved.
However, a toner having a smaller particle size and a uniform particle size is more difficult to clean than before. In particular, in blade cleaning, it is impossible to stably clean toner having a uniform and small particle diameter. Under such circumstances, various methods for improving the cleaning property by devising the toner have been proposed. One of them is a method of changing the toner from a spherical shape to a different shape. By changing the shape of the toner, the powder fluidity of the toner is lowered, and it is easy to stop by blade cleaning. However, if the degree of toner irregularity is too large, the behavior of the toner becomes unstable during development and the like, and the fine dot reproducibility deteriorates.

As described above, by changing the shape of the toner, the reliability of the toner with respect to cleaning is certainly improved, but on the other hand, a problem in terms of fixing has occurred. In other words, if the shape of the toner is irregular, the toner filling density in the toner layer on the transfer material before fixing becomes small, the thermal conductivity in the toner layer becomes slow during fixing, and the low-temperature fixability deteriorates. Resulting in. In particular, when the pressure at the time of fixing is smaller than that in the prior art, the thermal conductivity further deteriorates and the low-temperature fixing is hindered.
For example, Patent Document 1 proposes a toner made of polyester having a Wadell practical sphericity of 0.90 to 1.00. However, since the toner is substantially spherical, the above-described problem of toner cleaning performance is solved. It has not been.

  In addition to suspension polymerization, there are emulsion polymerization methods and dissolution suspension methods that are relatively easy to modify, but also in the emulsion polymerization method, complete removal of styrene monomers and removal of emulsifiers and dispersants are possible. It is difficult, and nowadays, the problem for toner is increasing more and more, especially when environmental problems are being highlighted. Also, in the toner shape, the contamination of the photoreceptor due to the toner is caused by the fact that the concave portion of the silica added as a fluidizing agent is weakly adhered to the concave portion and the silica moves to the concave portion during use. And the problem of toner adhesion to the fixing roller are likely to occur. In addition, the dissolution suspension method has the advantage that a polyester resin that can be fixed at low temperature can be used, but in order to achieve oil-less fixing, the polymer and color are controlled during production and control of the polymer to widen the mold release width. Since the high molecular weight component is added in the step of dissolving or dispersing the agent in the solvent, the viscosity of the liquid rises and productivity problems are likely to occur. And those problems are not solved yet. In particular, in the solution suspension method, for example, in Patent Document 2, the toner surface shape is made spherical and uneven to improve the cleaning. A high-molecular-weight design for ensuring stability and further ensuring basic durability and releasability has not been achieved, and toner of satisfactory quality has not been obtained.

  In recent years, Patent Document 3 proposes to obtain resin particles for toner having a shape excellent in blade cleaning property and a wide fixing temperature range. However, in actuality, both cleaning property and low temperature fixing property are insufficient. is there.

  In addition, in the production methods described in Patent Documents 1 to 3, there is always a solvent removal step, but generally the solvent removal under reduced pressure by a batch type evaporator. Considering industrial continuous production, it is necessary to increase the efficiency of the process.

Japanese Patent Laid-Open No. 11-133665 JP 9-15903 A JP 2005-49858 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention provides high reliability in cleaning, excellent charging stability, low-temperature fixability, and transfer efficiency, and high quality images with high image quality and high resolution with little residual toner in an apparatus using blade cleaning. Production method that can produce a toner with low power consumption, high transferability and OHP permeability necessary for color images, and can improve production efficiency by shortening the time of the solvent removal step The purpose is to provide.

Means for solving the problems are as follows. That is,
<1> An oil comprising a dissolving and dispersing step of dissolving or dispersing a kneaded body containing a binder resin, a colorant, a release agent, and a modified layered inorganic mineral in an organic solvent, and a solution or dispersion of the kneaded body An emulsifying and dispersing step of emulsifying and dispersing the phase in an aqueous medium, and an organic solvent removing step of obtaining toner particles by removing the organic solvent from the emulsion obtained by emulsifying and dispersing the oil phase in the aqueous medium. In the emulsification dispersion step, the emulsion has a viscosity measurement value at a rotation speed of 60 rpm of a Brookfield viscometer at 25 ° C. of 100 mPa · s to 1,000 mPa · s. The liquid is supplied to a heated and depressurized tube, and the supplied emulsion is stirred to form a thin film on the inner wall of the tube. In the organic solvent removing step, the emulsion is used as a toner glass. The temperature is controlled below the transition temperature, the organic solvent in the emulsion is discharged from the tube, the organic solvent is removed by removing the emulsion remaining in the tube from the tube, and the heat transfer area S of the tube The relationship between (m ² ), the feeding rate A (kg / min) of the emulsion to the tube, and the organic solvent content B (%) in the emulsion is 0.5 ≦ S / (A × B × 0.01) ≦ 25 is satisfied.
<2> Dissolution for dissolving or dispersing a kneaded body containing a polymer having a site capable of reacting with a compound having an active hydrogen group, a binder resin, a colorant, a release agent, and a modified layered inorganic mineral in an organic solvent A dispersion step, an emulsification dispersion step of emulsifying and dispersing an oil phase comprising a solution or dispersion of the kneaded body in an aqueous medium, and a polymer having a site capable of reacting with the compound having an active hydrogen group. Or an organic solvent removal step of removing the organic solvent while reacting, in the emulsification dispersion step, in the emulsion dispersion step, the rotational speed of a Brookfield viscometer at 25 ° C. of 60 ° C. The measured viscosity of the liquid is 100 mPa · s to 1,000 mPa · s, and the emulsion is supplied to the heated and depressurized tube, and the supplied emulsion is stirred to thin the inner wall of the tube. A film is formed, and in the organic solvent removal step, the temperature of the emulsion is controlled to be equal to or lower than the glass transition temperature of the toner, the organic solvent in the emulsion is discharged from the tube, and the emulsion remaining in the tube is discharged. The organic solvent is removed by taking out from the tube, the heat transfer area S (m ² ) of the tube, the supply rate A (kg / min) of the emulsion to the tube, and the content of the organic solvent in the emulsion The toner manufacturing method is characterized in that the relationship of B (%) satisfies 0.5 ≦ S / (A × B × 0.01) ≦ 25.
<3> The oil phase has a volume average particle diameter Dv of the modified layered inorganic mineral in the kneaded body of 0.1 μm to 0.55 μm, and the modified layered inorganic mineral having a particle diameter of 1 μm or more in the kneaded body is 15% by volume or less. The toner production method according to any one of <1> to <2>, wherein the toner satisfies the following condition.
<4> The method for producing a toner according to any one of <1> to <3>, wherein the toner contains 0.1% by mass to 5% by mass of a modified layered inorganic mineral.
<5> The method for producing a toner according to any one of <1> to <4>, wherein in the modified layered inorganic mineral, at least a part of the metal cation is modified with an organic cation, and the organic cation is a quaternary ammonium ion. It is.
<6> The method for producing a toner according to any one of <1> to <5>, wherein the volume average particle diameter of the toner is 3 μm to 7 μm.
<7> The toner production method according to any one of <1> to <6>, wherein the volume average particle diameter Dv / number average particle diameter Dn of the toner is 1.00 to 1.30.
<8> The toner production method according to any one of <1> to <7>, wherein the toner has an average circularity of 0.94 to 0.99.
<9> The toner production method according to any one of <1> to <8>, wherein the toner particles having a size of 2 μm or less are 10% by number or less with respect to the total number of toner particles.
<10> The method for producing a toner according to any one of <1> to <9>, wherein the shape factor SF-1 of the toner is 110 to 200, and the shape factor SF-2 of the toner is 110 to 300. .
<11> The method for producing a toner according to any one of <1> to <10>, wherein the binder resin contains a polyester resin.
<12> The toner production method according to <11>, wherein the content of the polyester resin in the binder resin is 50% by mass to 100% by mass.
<13> The toner production method according to any one of <11> to <12>, wherein the polyester resin has a THF-soluble component having a weight average molecular weight of 1,000 to 30,000.
<14> The toner production method according to any one of <11> to <13>, wherein the acid value of the polyester resin is 1.0 KOHmg / g to 50.0 KOHmg / g.
<15> The method for producing a toner according to any one of <11> to <14>, wherein the glass transition point of the polyester resin is 35 ° C to 65 ° C.
<16> The method for producing a toner according to any one of <2> to <15>, wherein the polymer having a site capable of reacting with the compound having an active hydrogen group has a weight average molecular weight of 3,000 to 20,000. It is.
<17> The method for producing a toner according to any one of <1> to <16>, wherein the toner has an acid value of 0.5 KOH mg / g to 40.0 KOH mg / g.
<18> The method for producing a toner according to any one of <1> to <17>, wherein the glass transition point of the toner is 40 ° C to 70 ° C.
<19> The method for producing a toner according to any one of <1> to <18>, wherein the toner is a toner used for a two-component developer.

  According to the present invention, conventional problems can be solved, high reliability can be obtained in cleaning, charging stability, low-temperature fixability and transfer efficiency are excellent, and low residual toner is high in an apparatus using blade cleaning. High-quality images with high image quality and high resolution can be obtained, low power consumption, toner with high transferability and OHP permeability required for color images can be manufactured, and the production efficiency is improved by shortening the time of the solvent removal process A toner production method that can be improved can be provided.

(Toner production method)
The toner production method of the present invention includes at least a dissolution / dispersion step, an emulsification / dispersion step, and an organic solvent removal step, and further includes other steps appropriately selected as necessary.

<Dissolution dispersion process>
The dissolution and dispersion step is a step of dissolving or dispersing the kneaded body in an organic solvent.

<< Organic solvent >>
There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, The volatile organic solvent whose boiling point is less than 100 degreeC is preferable from the point that removal is easy. Examples of the organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, and ethyl acetate. , Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. Of these, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable.
Furthermore, in order to lower the viscosity of the dispersion medium containing the toner composition, a solvent (organic solvent) in which a polyester such as a urea-modified polyester described later or a prepolymer (A) described later is soluble can be used. The use of an organic solvent is preferable in that the particle size distribution becomes sharp.
The usage-amount of the organic solvent with respect to 100 parts of prepolymer (A) mentioned later is 0-300 parts normally, Preferably it is 0-100 parts, More preferably, it is 25-70 parts. When an organic solvent is used, the organic solvent is removed from the obtained reaction product under normal pressure or reduced pressure after elongation and / or crosslinking reaction of the modified polyester (prepolymer) with an amine.

<< Kneaded body >>
In the first embodiment of the present invention, the kneaded body includes at least a binder resin, a colorant, a release agent, and a modified layered inorganic mineral, and further includes other components as necessary.
In the second embodiment of the present invention, the kneaded body includes a polymer having a site capable of reacting with a compound having an active hydrogen group, a binder resin, a colorant, a release agent, and a modified layered inorganic mineral. And, if necessary, other components.

<<< Binder resin >>>
The binder resin is not particularly limited and can be appropriately selected according to the purpose. However, the polyester resin effectively exhibits low-temperature fixability while maintaining heat resistant storage stability, and is based on a prepolymer. It is preferable at the point which can provide the offset resistance after modification | denaturation.
The content of the polyester resin in the binder resin is preferably 50% by mass to 100% by mass. When the content is less than 50% by mass, the low-temperature fixing function cannot be sufficiently exhibited.
The polyester resin preferably has a weight average molecular weight of 1,000 to 30,000 in THF-soluble matter. This is because when the amount is less than 1,000, the oligomer component increases, the heat-resistant storage stability is deteriorated, and when it exceeds 30,000, the modification with the prepolymer is insufficient due to steric hindrance and the offset resistance is deteriorated.

The weight average molecular weight is measured by GPC (gel permeation chromatography) as follows. The column was stabilized in a 40 ° C. heat chamber, THF as a solvent was passed through the column at this temperature at a flow rate of 1 mL / min, and the concentration of the sample was adjusted to 0.05% to 0.6% by weight. Measurement is performed by injecting 50 μL to 200 μL of the sample solution. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the prepared calibration curve and the count using several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Or molecular weight made by Toyo Soda Industry Co., Ltd. is 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9. ^{× 10 5, 8.6 × 10 5} , 2 × 10 6, used as a 4.48 × 10 ^6, it is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

  In addition, by adjusting the acid value of the polyester resin to 1.0 KOHmg / g to 50.0 KOHmg / g, grain size control by adding a base compound, low temperature fixability, high temperature offset resistance, heat resistant storage stability, charging stability, etc. The toner characteristics of the toner can be made higher. 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. When the acid value is less than 1.0 KOHmg / g, the basic compound at the time of production is obtained. This is because the dispersion stabilizing effect due to the above cannot be obtained, and the extension or crosslinking reaction of the modified polyester tends to proceed, resulting in problems in production stability.

The acid value of the polyester resin is measured by a method based on JIS K0070. However, when the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.
The acid value is specifically determined by the following procedure.
Measuring apparatus: automatic potentiometric titrator DL-53 Titrator (manufactured by METTLER TOLEDO)
Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
Analysis software: LabX Light Version 1.00.000
Calibration of apparatus: Use a mixed solvent of 120 mL of toluene and 30 mL of ethanol.
Measurement temperature: 23 ° C
The measurement conditions are as follows.
Stirring conditions
Stirring speed [%]: 25
Stirring time [s]: 15
Equilibrium titration conditions
Titration solution: CH ₃ ONa
Concentration [mol / L]: 0.1
Electrode: DG115
Unit of measurement: mV
Before titration drop before measurement Drop volume [mL]: 1.0
Waiting time [s]: 0
Titration drop mode: Dynamic
dE (set) [mV]: 8.0
dV (min) [mL]: 0.03
dV (max) [mL]: 0.5
Measurement mode: equilibrium titration dE [mV]: 0.5
dt [s]: 1.0
t (min) [s]: 2.0
t (max) [s] 20.0
Recognition conditions
Threshold: 100.0
Maximum rate of change only: No
Range: No
Frequency: None
Measurement end condition
Maximum dripping amount [mL]: 10.0
Potential: No
Gradient: No
After the equivalence point: Yes
n number: 1
Combination of end conditions: No
Evaluation conditions
Procedure: Standard
Potential 1: No
Potential 2: No
Stop for re-evaluation: No

The measurement method of the oxidation of the polyester resin is measured under the following conditions based on the measurement method described in JIS K0070-1992. Sample preparation: 0.5 g of polyester (0.3 g in the case of ethyl acetate-soluble component) is added to 120 mL of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 mL of ethanol is added to prepare a sample solution.
The measurement can be calculated by the above apparatus, and specifically, the calculation is performed as follows. Titrate with a pre-standardized N / 10 potassium hydroxide (caustic potash) to alcohol solution, and determine the acid value from the consumption of alcohol potash solution by the following calculation.
Acid value = KOH (mL) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

  Since the heat-resistant storage performance of the main component of the polyester resin after the modification, that is, the binder resin depends on the glass transition point of the polyester resin before the modification, it is preferable to design the glass transition point of the polyester resin at 35 ° C. to 65 ° C. . That is, if it is less than 35 ° C., the heat-resistant storage stability is insufficient, and if it exceeds 65 ° C., it adversely affects low-temperature fixing.

The glass transition point of the polyester resin is measured with a Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation at a temperature increase rate of 10 ° C./min.
A method for measuring Tg will be 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 temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, the sample was cooled to room temperature and left for 10 min, and the temperature rising 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.

  In this invention, the glass transition point (Tg) of binder resin is 40 to 70 degreeC normally, Preferably it is 40 to 60 degreeC. If it is less than 40 ° C., the heat resistance of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of a modified polyester such as a urea-modified polyester resin, the dry toner tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with a known polyester-based toner.

<<< Colorant >>>
The colorant is not particularly limited, and 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 Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faisa Red, Lachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin 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, 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 , Pyrazolone red, polyazo red, chrome vermilion, 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, Indanthrene blue (RS, BC), indigo, ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Mention may be made of green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof. The content of the colorant is usually 1% by mass to 15% by mass with respect to the toner, and preferably 3% by mass to 10% by mass.

  The colorant 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 resin, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and its substituted polymers; styrene-p- Chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-acrylic Acid butyl copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate Copolymer, styrene Acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid Styrenic copolymers such as ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacryl Acid resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be used, and these can be used alone or in combination.

  The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant with a high shear force to obtain a masterbatch. 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, a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components, is also a colorant wet cake. 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.

  In order to adhere and immobilize a charge control agent, which will be described later, on the surface of toner particles, an electrophotographic toner in which particles comprising a colorant and a resin and particles comprising at least charge control agent particles are mixed in a container using a rotating body. Although a manufacturing method is known, this method includes a step of mixing at a peripheral speed of a rotating body of 40 m / sec to 150 m / sec in a container without a fixing member protruding from the inner wall of the container. Toner particles are obtained.

<<< release agent >>>
The release agent (wax) is not particularly limited and may be appropriately selected depending on the intended purpose. However, a low melting point wax having a melting point of 50 ° C. to 120 ° C. is more preferable in dispersion with the binder resin. It is preferable in that it works effectively between the fixing roller and the toner interface as a release agent, and thereby exhibits an effect on high temperature offset resistance without applying a release agent such as oil to the fixing roller.
The melting point of the release agent (wax) was the maximum endothermic peak measured by a differential scanning calorimeter (DSC). The following materials can be used as the wax component that functions as the release agent. That is, as specific examples, waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, And petroleum waxes such as paraffin, microcrystalline, and 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, and chlorinated hydrocarbon, and poly n-stearyl methacrylate and poly n-lauryl methacrylate which are low molecular weight crystalline polymer resins A crystalline polymer having a long alkyl group in the side chain, such as a polyacrylate homopolymer or copolymer (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used.

<<< Modified layered inorganic mineral >>>
The modified layered inorganic mineral is not particularly limited and may be appropriately selected depending on the intended purpose, but has a smectite basic crystal structure, and at least a part of the metal cation is modified with an organic cation. Are preferred. Examples of the layered inorganic mineral in which at least a part of the metal cation is modified with an organic cation include montmorillonite or bentonite, beidellite, nontronite, saponite, hectorite and the like.
Examples of the organic cation modifier for the modified layered inorganic mineral include quaternary alkyl ammonium salts, phosphonium salts, imidazolium salts, and the like, among which quaternary alkyl ammonium salts are preferable. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.

  Examples of the modified layered inorganic mineral include BENTONE 34, BENTONE 52, BENTONE 38, BENTONE 27, BENTONE 57, BENTONE SD, BENTONE CRYTONE 34, CENTONE 34, CENTONE 34, CENTONE 34 , CRAYTONE HY, etc., made by HOJUN, such as Esben, Esben E, Esben C, Esben NZ, Esben NZ70, Esven W, Esben N400, Esven NX, Esven NX80, Esven NO12S, Esven NEZ, Esven NO12, Esben WX, Esben NE, etc. Kunibis 110 manufactured by Kunimine Industry Co., Ltd. Kunibisu 120, Kunibisu 127, and the like.

  A kneaded body of the modified layered inorganic mineral and the binder resin, that is, the master batch is obtained by mixing and kneading the binder resin and the modified layered inorganic mineral modified with an organic cation with high shear force to obtain a master batch. Can do. At this time, an organic solvent can be used in order to enhance the interaction between the modified layered inorganic mineral and the binder resin. In addition, an aqueous paste containing the modified layered inorganic mineral and water is mixed and kneaded with a resin and an organic solvent before the so-called flushing method, and the modified layered inorganic mineral is transferred to the resin side to remove moisture and organic solvent components. Since the wet cake can be used as it is, the method 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.

In the kneaded body of the modified layered inorganic mineral and the binder resin, that is, in the master batch, the volume average particle diameter Dv of the modified layered inorganic mineral is 0.1 μm to 0.55 μm and the volume average particle diameter is 1 μm or more. It is necessary for the modified layered inorganic mineral to satisfy 15% by volume or less.
When the volume average particle diameter Dv exceeds 0.55 μm or the modified layered inorganic mineral having a volume average particle diameter of 1 μm or more exceeds 15% by volume, the effect on the toner shape and toner charging performance is lowered.
The modified layered inorganic mineral is preferably contained in the toner in an amount of 0.1% by mass to 5% by mass. If it is less than 0.1% by mass, the effect on the toner shape and the toner charging performance is reduced, and if it exceeds 5% by mass, the fixing performance is deteriorated.

<<< Polymer having a site capable of reacting with a compound having an active hydrogen group >>>
The polymer having a site capable of reacting with the compound having an active hydrogen group is an important binder resin component for realizing low-temperature fixability and high-temperature offset resistance, and has a weight average molecular weight of 3,000-20. 1,000 is preferred. That is, when the weight average molecular weight is less than 3,000, it becomes difficult to control the reaction rate, and problems in production stability begin to occur. On the other hand, when the weight average molecular weight exceeds 20,000, sufficient modified polyester cannot be obtained and the offset resistance starts to be affected.

Examples of the polymer having a site capable of reacting with the compound having an active hydrogen group include a reactive modified polyester resin (RMPE) capable of reacting with active hydrogen. For example, a polyester prepolymer (A) having an isocyanate group Etc. Examples of the prepolymer (A) include a polycondensate of a polyol (PO) and a polycarboxylic acid (PC) and a polyester having active hydrogen further reacted with a polyisocyanate (PIC). Examples of the group containing active hydrogen in the polyester include a hydroxyl group (alcoholic hydrogen group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable. An amine is used as a crosslinking agent for the reactive modified polyester resin, and a diisocyanate compound (diphenylmethane diisocyanate or the like) is used as an extender. The amines described in detail later act as a crosslinking agent and an extender for the modified polyester capable of reacting with active hydrogen.
Modified polyesters such as urea-modified polyester obtained by reacting the polyester prepolymer (A) having an isocyanate group with an amine (B) can easily adjust the molecular weight of the polymer component, and can be used for dry toners, particularly oilless low temperature. It is convenient to ensure fixing characteristics (a wide range of releasability and fixability without a mechanism for applying a release oil to a fixing heating medium). In particular, urea-modified polyester prepolymer ends can suppress adhesion to the fixing heating medium while maintaining high fluidity and transparency in the fixing temperature range of the unmodified polyester resin itself. it can.

  The polyester prepolymer is preferably a polyester having an active hydrogen group such as an acid group or a hydroxyl group at a terminal and a functional group such as an isocyanate group that reacts with the active hydrogen introduced therein. A modified polyester (MPE) such as urea-modified polyester can be derived from this prepolymer, but in the case of the present invention, the modified polyester used as a toner binder is crosslinked to the polyester prepolymer (A) having an isocyanate group. A urea-modified polyester obtained by reacting amines (B) as an agent and / or extender is preferred. The polyester prepolymer (A) having an isocyanate group is obtained by further reacting a polyester having an active hydrogen group, which is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), with a polyisocyanate (PIC). Can do. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

  Examples of the polyol (PO) include diol (DIO) and trivalent or higher polyol (TO), and (DIO) alone or a mixture of (DIO) and a small amount of (TO) is preferable. Diol (DIO) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, Bisphenol S etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide etc.) adduct of the alicyclic diol; bis Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. Examples of the trivalent or higher polyol (TO) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or higher phenols (Tris) Phenol PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent polyphenols and the like.

  Examples of the polycarboxylic acid (PC) include dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC), and DIC alone or a mixture of DIC and a small amount of (TC) is preferable. Dicarboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalene) Dicarboxylic acid and the like). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (PC), you may make it react with a polyol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.). The ratio of the polyol (PO) and the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably 1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

Examples of the polyisocyanate (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; phenols, oximes, caprolactam And a combination of two or more of these.
The ratio of the polyisocyanate (PIC) is usually 5/1 to 1/1, preferably 4 as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. / 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a modified polyester is used, the urea content in the ester becomes low and the hot offset resistance deteriorates. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5% by mass to 40% by mass, preferably 1% by mass to 30% by mass, and more preferably 2%. It is mass%-20 mass%. If it is less than 0.5% by mass, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by mass, the low-temperature fixability deteriorates.

  The isocyanate group contained per molecule in the prepolymer (A) having the isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  As the amines (B), the diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and amino groups of B1 to B5 were blocked. (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the compound (B6) obtained by blocking the amino group of B1 to B5 include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

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

The ratio of the amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] in the prepolymer (A) having an isocyanate group and the amino group [NHx] in the amine (B). Is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the polyester is lowered and the hot offset resistance is deteriorated.
In the present invention, the polyester resin (polyester) preferably used as the binder resin is a urea-modified polyester (UMPE), but this polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

  The modified polyester such as urea-modified polyester (UMPE) is manufactured by a one-shot method or the like. The weight average molecular weight of the modified polyester such as urea-modified polyester (UMPE) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of a modified polyester such as a urea-modified polyester is not particularly limited when an unmodified polyester (PE) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. In the case of a modified polyester such as UMPE alone, the number average molecular weight is usually 2,000 to 15,000, preferably 2,000 to 10,000, more preferably 2,000 to 8,000. If it exceeds 20,000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.

  The modified polyester such as polyester modified with urea bond (UMPE) is not only used alone, but also with this, unmodified polyester (PE) can be contained as a binder resin component. The combined use of PE improves low-temperature fixability and gloss when used in a full-color device, and is preferable to single use. Examples of PE include polycondensates of polyol PO and polycarboxylic acid PC similar to the polyester component of UMPE, and preferred ones are also the same as in UMPE. The weight average molecular weight (Mw) of PE is 10,000 to 300,000, preferably 14,000 to 200,000. Its Mn (number average molecular weight) is 1,000 to 10,000, preferably 1,500 to 6,000. For UMPE, not only unmodified polyesters but also those modified with chemical bonds other than urea bonds, such as those modified with urethane bonds, can be used in combination. UMPE and PE are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, the polyester component of UMPE and PE are preferably similar in composition. The mass ratio of UMPE to PE when PE is contained is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, and particularly preferably 7/93. ~ 20/80. If the mass ratio of UMPE is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The hydroxyl value (mgKOH / g) of PE is preferably 5 or more, and the acid value (mgKOH / g) of PE is usually 1 to 30, preferably 5 to 20. By giving an acid value, it tends to be negatively charged, and further, the affinity between the paper and the toner is good when fixing to paper, and the low-temperature fixability is improved. However, when the acid value exceeds 30, there is a tendency to deteriorate with respect to the stability of charging, particularly the environmental fluctuation. In the polymerization reaction, if the acid value is touched, it will lead to shaking in the emulsification dispersion process (granulation process), making it difficult to control the emulsification.

Specifically, the hydroxyl value and acid value of PE are determined by the following procedure.
Measuring device: potentiometric automatic titrator DL-53 Titoror (Metler Toledo)
Electrode used: DG113-SC (Metler Toledo)
Analysis software: LabX Light Version 1.00.000
Calibration of apparatus: Use a mixed solvent of 120 mL of toluene and 30 mL of ethanol.
Measurement temperature: 23 ° C
The measurement conditions are as follows.
Stirring conditions
Stirring speed [%]: 25
Stirring time [s]: 15
Equilibrium titration conditions
Titration solution: CH ₃ ONa
Concentration [mol / L]: 0.1
Electrode: DG115
Unit of measurement: mV
Before titration drop before measurement Drop volume [mL]: 1.0
Waiting time [s]: 0
Titration drop mode: Dynamic
dE (set) [mV]: 8.0
dV (min) [mL]: 0.03
dV (max) [mL]: 0.5
Measurement mode: equilibrium titration dE [mV]: 0.5
dt [s]: 1.0
t (min) [s]: 2.0
t (max) [s] 20.0
Recognition conditions
Threshold: 100.0
Maximum rate of change only: No
Range: No
Frequency: None
Measurement end condition
Maximum dripping amount [mL]: 10.0
Potential: No
Gradient: No
After the equivalence point: Yes
n number: 1
Combination of end conditions: No
Evaluation conditions
Procedure: Standard
Potential 1: No
Potential 2: No
Stop for re-evaluation: No

The acid value of PE is measured under the following conditions based on the measurement method described in JIS K0070-1992. Sample preparation: 0.5 g of polyester (0.3 g in the case of ethyl acetate-soluble component) is added to 120 mL of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 mL of ethanol is added to prepare a sample solution.
The measurement can be calculated by the above apparatus, but specifically, it is calculated as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (mL) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

The measuring method of a hydroxyl value is performed as follows.
Weigh accurately 0.5 g of sample into a 100 mL volumetric flask, and add 5 mL of acetylating reagent correctly. Then, it is immersed in a bath at 100 ° C. ± 5 ° C. and heated. After 1-2 hours, the flask is removed from the bath, allowed to cool, water is added and shaken to decompose acetic anhydride. To complete the decomposition, the flask is again heated in a bath for 10 minutes or more, allowed to cool, and the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to determine the OH value (according to JISK0070-1966).

  The resin for toner binder can be produced by the following method. Polyol (PO) and polycarboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc., and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (PIC) at 40 to 140 ° C. to obtain a polyester prepolymer (A) having an isocyanate group. Further, this A is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester (UMPE) modified with a urea bond. The number average molecular weight of the modified polyester is 1,000 to 10,000, preferably 1,500 to 6,000. When reacting PIC and when reacting A and B, a solvent can be used if necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to isocyanates (PIC), such as tetrahydrofuran (such as tetrahydrofuran). When polyester (PE) that is not modified with a urea bond is used in combination, PE is produced in the same manner as the polyester having a hydroxyl group, and this is dissolved in the solution after completion of the UMPE reaction and mixed.

<<< Other ingredients >>>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a charge control agent (charge control agent), an external additive, etc. are mentioned.

<<<<< Charge Control Agent >>>>
Known charge control agents can be used such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84, phenolic condensate E-89 (above, Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary Copy charge PSY VP2038 of ammonium 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- which is a boron complex 147 (manufactured by Nippon Carlit), copper phthalocyanine, perylene, quinaclide , Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  The amount of the 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 not uniquely limited. However, Preferably, it is used in 0.1 mass part-10 mass parts with respect to 100 mass parts of binder resin. Preferably, the range of 0.2 mass part-5 mass parts is good. When the amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is reduced, and the image density Incurs a decline. These charge control agents and release agents can be melt-kneaded together with the masterbatch and the resin, and of course, they may be added when dissolved and dispersed in an organic solvent.

<<<<< External additive >>>>
An external additive is used to assist the fluidity, developability and chargeability of the obtained colored particles, and inorganic fine particles can be preferably used as the external additive. The primary particle diameter of the inorganic fine particles is preferably 0.005 μm to 2 μm, and more preferably 0.005 μm to 0.5 μm. In addition, the specific surface area by BET method ^is preferably 20m ² / g~500m 2 / g. The use ratio of the inorganic fine particles is preferably 0.01% by mass to 5% by mass of the toner, and more preferably 0.01% by mass to 2.0% by mass. 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, silica sand, clay, mica, wollastonite, Examples thereof include diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, as the fluidity imparting agent, it is preferable to use hydrophobic silica fine particles and hydrophobic titanium oxide fine particles in combination. In particular, when stirring and mixing are performed using an average particle size of both fine particles of 0.05 μm or less, the electrostatic force and van der Waals force with the toner are remarkably improved, thereby obtaining a desired charge level. For this reason, even if mixing and mixing is performed inside the developing machine, the fluidity imparting agent is not detached from the toner, a good image quality that does not cause firefly and the like is obtained, and the residual toner is further reduced. Became clear.

  Titanium oxide fine particles are excellent in environmental stability and image density stability, but have a tendency to deteriorate the charge rising characteristics, and therefore, if the amount of titanium oxide fine particles added is larger than the amount of silica fine particles added, the side effect of It can be considered large. However, when the addition amount of the hydrophobic silica fine particles and the hydrophobic titanium oxide fine particles is in the range of 0.3 wt% to 1.5 wt%, the charge rise characteristics are not greatly impaired, and the desired charge rise characteristics can be obtained. It was found that stable image quality can be obtained and toner blowing can be suppressed even when repeated.

<Emulsification dispersion step and organic solvent removal step>
The emulsification dispersion step is a step of emulsifying and dispersing an oil phase composed of a solution or dispersion of a kneaded body in an aqueous medium. In the emulsification dispersion step, particles are granulated.
In the emulsification dispersion step, the viscosity of the emulsion is measured at a viscosity of 60 rpm of a Brookfield viscometer at 25 ° C. of 100 mPa · s to 1,000 mPa · s, and the oil phase is emulsified and dispersed in an aqueous medium. The emulsion obtained by the above is supplied to a heated and decompressed tube, and the supplied emulsion is stirred to form a thin film on the inner wall of the tube.

  If the viscosity of the emulsion is less than 100 mPa · s when the viscosity of the Brookfield viscometer at 25 ° C. is less than 100 mPa · s, a thin film is not uniformly formed on the inner wall of the tube. On the other hand, if the measured viscosity value of the emulsified liquid at a rotation speed of 60 rpm of a Brookfield viscometer at 25 ° C. exceeds 1,000 mPa · s, the film thickness increases and the organic solvent removal efficiency deteriorates.

In the first embodiment of the present invention, the organic solvent removing step is a step of obtaining toner particles by removing the organic solvent from an emulsion obtained by emulsifying and dispersing an oil phase in an aqueous medium. .
In the second embodiment of the present invention, the organic solvent removing step removes the organic solvent after reacting with or reacting with a polymer having a site capable of reacting with the compound having an active hydrogen group. It is a process to do.
In the organic solvent removal step, the temperature of the emulsion is controlled to be equal to or lower than the glass transition temperature of the toner, the organic solvent in the emulsion is discharged from the tube, and the emulsion remaining in the tube is removed from the tube. To remove the organic solvent.

Specifically, as shown in FIG. 1, the emulsified liquid is supplied from a raw material inlet 13 into an inner pipe whose wall surface 12 is heated by a heat medium in the outer pipe 11 and decompressed by a vacuum pump, A thin film is formed on the inner pipe wall surface 12 by agitating the supplied emulsion with the rotor blades 14 (emulsification dispersion step). Further, the temperature is controlled to be equal to or lower than the glass transition temperature of the toner, the organic solvent in the emulsion is discharged from the vapor outlet 15, and the emulsion remaining in the inner tube is taken out from the residual liquid outlet 16 to remove the organic solvent. (Organic solvent removal step).
Here, the heat transfer area S (m ² ) of the inner tube, the supply rate A (kg / min) of the emulsion into the inner tube, and the organic solvent content B (%) in the emulsion Must be controlled to satisfy 0.5 ≦ S / (A × B × 0.01) ≦ 25. If S / (A × B × 0.01) is less than 0.5, the organic solvent removal efficiency deteriorates. When S / (A × B × 0.01) exceeds 25, the organic solvent removal efficiency deteriorates and toner modification occurs due to thermal overload.

  As an apparatus as shown in FIG. 1, there is a control system manufactured by Hitachi Plant Technology.

  For example, when ethyl acetate is used as the organic solvent, the concentration of ethyl acetate in the dispersed particles in the emulsion is specifically determined by the following procedure.

<< Measurement equipment conditions >>
Measuring device: GC-2010 (Gas Chromatograph manufactured by Shimadzu Corporation)
Injection volume: 2.0 μL

Sample vaporization chamber injection mode: split vaporization chamber temperature: 180 ° C
Carrier gas: He
Pressure: 40.2kPa
Total flow rate: 56.0 mL / min
Column flow rate: 1.04 mL / min
Linear velocity: 20.0 cm / sec
Purge flow rate: 3.0 mL / min
Split ratio: 50.0

Column Column name: ZB-50
Liquid phase film thickness 0.25μm
Length 30.0m
Inner diameter: 0.32 mm ID
Maximum column temperature: 340 ° C

Column oven Column temperature: 60 ° C
Column oven temperature program:
60 ° C hold 6 min → temperature rise rate 60 ° C / min → 230 ° C hold 5 min

Detector Detector temperature: 250 ° C
Make-up gas: N ₂ / Air
Makeup flow rate: 30.0 mL / min
H2 flow rate: 47.0 mL / min
Air flow rate: 400 mL / min

Measurement method Preparation of internal standard solution: 4 g of toluene is weighed into a volumetric flask and diluted to 500 mL with DMF.
Preparation of measurement sample: After 1.5 g of the emulsion to be measured is diluted to about 50 mL with DMF, 10 mL of the internal standard solution is collected with a whole pipette and charged. After stirring the measurement sample with a stirrer at 400 rpm for 4 minutes, the sample is set in the autosampler of the measuring instrument GC and measurement is performed. After the measurement, the amount of ethyl acetate in the emulsion is calculated by the internal standard method from the ratio of toluene and ethyl acetate as the internal standard substance.

<< Aqueous medium >>
As the aqueous medium, water alone may be used, but 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 present invention, a urea-modified polyester (UMPE) or the like can be obtained by reacting a reactive modified polyester such as a polyester prepolymer (A) having an isocyanate group with an amine (B) in an aqueous medium. As a method for stably forming a dispersion comprising a modified polyester such as urea-modified polyester or a reactive modified polyester such as prepolymer (A) in an aqueous medium, a modified polyester such as urea-modified polyester or a pre-polymer can be used in an aqueous medium. Examples thereof include a method in which a composition of a toner raw material composed of reactive modified polyester such as polymer (A) is added and dispersed by shearing force. Reactive modified polyester such as prepolymer (A) and other toner composition (hereinafter referred to as toner raw material), colorant, colorant masterbatch, release agent, charge control agent, unmodified polyester resin, etc. Although mixing may be performed when forming the dispersion in the medium, it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles not containing a colorant, the colorant can be added by a known dyeing method.

<< dispersion >>
The dispersion method is not particularly limited, and known equipment such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 μm to 20 μm, the high speed shearing method is preferable. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1,000 rpm to 30,000 rpm, preferably 5,000 to 20,000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 minutes to 5 minutes. The temperature at the time of dispersion is usually 0 ° C. to 150 ° C. (under pressure), preferably 40 ° C. to 98 ° C. Higher temperatures are preferred in that the dispersion of the urea-modified polyester or prepolymer (A) has a low viscosity and is easy to disperse.

  The amount of the aqueous medium used is usually 50 to 2,000 parts by weight, preferably 100 to 1,000 parts by weight, based on 100 parts of the toner composition containing a polyester such as urea-modified polyester or prepolymer (A). It is. If the amount is less than 50 parts by mass, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle size cannot be obtained. If it exceeds 20,000 parts by mass, 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.

Various dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed are used in the liquid containing water. Such a dispersant includes a surfactant, an inorganic fine particle dispersant, a polymer fine particle dispersant and the like.
Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphates, 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 salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyvalent Nonionic surfactants such as alcohol 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- [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) 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) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.

Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), MegaFuck 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 Fgentent F-100, F150 (manufactured by Neos). In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C 6 -C 10) sulfonamidopropyltrimethylammonium salt which right the fluoroalkyl group, Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (manufactured by Daikin Industries, Ltd.) ), Megafuck F-150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and Footgent F-300 (manufactured by Neos).
Moreover, tricalcium phosphate, calcium carbonate, acid value titanium, colloidal silica, hydroxyapatite, etc. can be used as an inorganic compound dispersant which is hardly soluble in water.

Further, the same effect as that of the inorganic dispersant was confirmed for the resin fine particles. For example, MMA polymer fine particles 1 μm and 3 μm, styrene fine particles 0.5 μm and 2 μm, styrene-acrylonitrile fine particle polymer 1 μm, (PB-200H (Kao) SGP (Soken), Technopolymer SB (Sekisui Plastics), SGP-3G (Soken) Micropearl (Sekisui Fine Chemical)).
Further, as a dispersant that can be used in combination with the inorganic dispersant and the resin fine particles, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, pinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Polyoxyethylenes such as, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  The elongation and / or crosslinking reaction time is selected, for example, depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 hours to 24 hours. The reaction temperature is generally 0 ° C to 150 ° C, preferably 40 ° C to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate. In addition, as an extender and / or a crosslinking agent, the above-described amines (B) are used.

<Toner manufactured by toner manufacturing method>
The toner produced by the toner production method of the present invention can be used as a two-component developer. In this case, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier and the toner in the developer is preferably 1 part by mass to 10 parts by mass of the toner with respect to 100 parts by mass of the carrier. 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 μm 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 produced by the toner production method 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.

  In the toner manufactured by the toner manufacturing method of the present invention, the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.00 to 1.30. This makes it possible to obtain high-resolution and high-quality toner. Furthermore, in the case of a two-component developer, even if a long-term balance of the toner is performed, fluctuations in the particle size of the toner in the developer are reduced, and good and stable developability even with long-term stirring in the developing device. Is possible. If Dv / Dn exceeds 1.30, the variation in particle size of individual toner particles is large, and the behavior of the toner varies during development and the like, and the reproducibility of minute dots is impaired. Therefore, a high-quality image cannot be obtained. Dv / Dn is more preferably in the range of 1.00 to 1.20, and a better image can be obtained.

  In the toner manufactured by the toner manufacturing method of the present invention, the volume average particle diameter Dv is preferably 3.0 to 7.0 μm. 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. When the volume average particle diameter is smaller than the above range, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced. When it is used, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur. These phenomena are greatly related to the content of fine powder. In particular, the number of particles having a particle diameter of 2 μm or less is preferably 10% by number or less with respect to the total number of toner particles. If the number of particles having a particle diameter of 2 μm or less exceeds 10% by number with respect to the total number of toner particles, this may hinder the adhesion to the carrier and the high level of charging stability. Conversely, when the toner particle size is larger than the above range, it becomes difficult to obtain a high-resolution and high-quality image, and the toner particle size when the balance of the toner in the developer is performed. In many cases, fluctuations of It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.30.

<< Circularity >>
It is important that the toner produced by the toner production method of the present invention has a specific shape, and the toner with an irregular shape that has an average circularity of less than 0.94 and is too far from a spherical shape is satisfactory. High quality images with no characteristics or dust cannot be obtained. When the average circularity exceeds 0.99, in a system employing blade cleaning or the like, poor cleaning occurs on the photosensitive member and the transfer belt, and stains on the image occur.

As described above, a toner having a small particle size and a uniform particle size is difficult to clean. Therefore, the toner shape factor SF-1 ranges from 110 to 200, and SF-2 ranges from 110 to 300. It is preferable.
First, the relationship between toner shape and transferability will be described. When using a full-color copier that transfers images with multi-color development, the amount of toner on the photoconductor increases compared to the case of one-color black toner used in black-and-white copiers. It is difficult to improve transfer efficiency. In addition, when ordinary irregular toner is used, a shearing force or friction between the photosensitive member and the cleaning member, between the intermediate transfer member and the cleaning member, and / or between the photosensitive member and the intermediate transfer member. Due to the force, toner fusing or filming occurs on the surface of the photoreceptor or the intermediate transfer member, and the transfer efficiency tends to deteriorate. When generating a full-color image, it is difficult to transfer the four-color toner images uniformly. Furthermore, when an intermediate transfer member is used, problems are likely to occur in terms of color unevenness and color balance, and high-quality full-color images are stabilized. Output is not easy.

  From the viewpoint of the balance between blade cleaning and transfer efficiency, the toner shape factor SF-1 is 110 to 200, preferably 120 to 180, so that both cleaning and transferability can be achieved. Cleaning and transferability are greatly related to the material of the blade and how to apply the blade, and transfer is also different depending on the process conditions. Therefore, the design according to the process can be performed within the range of SF-1. However, when SF-1 falls below 110, cleaning with a blade becomes difficult. On the other hand, when SF-1 exceeds 200, the aforementioned transferability is deteriorated. This phenomenon is caused by the shape of the toner being deformed and the movement of toner during transfer (photosensitive member surface to transfer paper, photosensitive member surface to intermediate transfer belt, first intermediate transfer belt to second intermediate transfer belt, etc.) Since the toner particles are not smooth and the behavior of the toner particles varies, uniform and high transfer efficiency cannot be obtained. In addition, unstable charging and brittleness of particles begin to appear. Furthermore, it becomes a fine phenomenon in the developer, which causes a decrease in the durability of the developer.

  In the case of the pulverized toner, the toner is indefinite shape (a shape that is not a specific and well-rounded shape) and the toner has a shape factor SF-1 exceeding 140. However, since the particle size distribution of the toner is generally broad, In order to make Dv / Dn 1.30 or less, this is an inefficient method. When a toner is obtained by a polymerization method, for example, suspension polymerization or emulsion polymerization makes it difficult to make a polyester toner, and it cannot cope with further low-temperature fixing. In a dry toner comprising a toner binder obtained by subjecting an isocyanate group-containing prepolymer to an extension reaction and / or a cross-linking reaction in JP-A-11-149180 and JP-A-2000-292981, and a colorant, the dry toner comprises the prepolymer. A dry toner characterized by comprising particles formed by elongation reaction and / or cross-linking reaction of the polymer (A) with an amine (B) in an aqueous medium has been proposed. Since the toner shape is not obtained, both transferability and cleaning property cannot be achieved.

  Therefore, in the present invention, in the toner production method using the reaction of the prepolymer (A) and the amines (B), the layered inorganic mineral obtained by modifying at least part of the ions of the layered inorganic mineral with organic ions is contained in the toner. By adding a kneading composite step of the modified layered inorganic mineral and the binder resin and a step of dissolving or dispersing the kneaded body to obtain an appropriate dispersion state, the shape factor SF-1 is 110 to 200, A toner having SF-2 of 110 to 300 can be easily obtained. In suspension polymerization and emulsion polymerization that have been conventionally performed, shape control is difficult unlike the case of the present invention.

Hereafter, the measuring method regarding the property of the toner of this invention is shown.
<< Circularity and particles of 2 μm or less >>
In the present invention, a flow type particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation) is used to measure toner having a particle size of 2 μm or less, and analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10) is measured. ) Was used for analysis. Specifically, 0.1 mL to 0.5 mL of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku Co., Ltd.) is added to a glass 100 mL beaker, and each toner 0.1 g to 0 g. 0.5 g was added and stirred with a microspatel, and then 80 mL of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured using the FPIA-2100 until the concentration of the dispersion was 5,000 / μL to 15,000 / μL. In this measurement method, it is important that the concentration of the dispersion is 5,000 / μL to 15,000 / μL from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. Similar to the measurement of the toner particle size described above, the required amount of the surfactant varies depending on the hydrophobicity of the toner. If it is added in a large amount, noise due to bubbles is generated. It will be enough. Further, the toner addition amount differs from the particle size, and it is small for small particle sizes and needs to be increased for large particle sizes. When the toner particle size is 3 μm to 7 μm, the toner amount is 0.1 g to By adding 0.5 g, the dispersion concentration can be adjusted to 5,000 / μL to 15,000 / μL.

<< Toner Shape >>
The shape factors SF-1 and SF-2 used in the present invention were obtained by randomly sampling 300 SEM images of the toner obtained by measurement using an FE-SEM (S-4200) manufactured by Hitachi, Ltd. Were introduced into an image analysis apparatus (LuzexAP) manufactured by Nireco through an interface and analyzed, and values obtained from the following equations were defined as SF-1 and SF-2. The values of SF-1 and SF-2 are preferably values obtained by the Luzex, but are not particularly limited to the FE-SEM apparatus and the image analysis apparatus as long as similar analysis results can be obtained.

SF-1 = (L2 / A) × (π / 4) × 100
SF-2 = (P2 / A) × (1 / 4π) × 100
(Here, L represents the absolute maximum length of the toner, A represents the projected area of the toner, and P represents the maximum peripheral length of the toner.)
In the case of a true sphere, both SF-1 and SF-2 become 100, and the value becomes larger from 100 and becomes an indeterminate shape. In particular, SF-1 represents the shape of the whole toner (ellipse, sphere, etc.), and SF-2 is a shape factor indicating the degree of surface irregularities.

<< Toner particle size >>
The average particle size and particle size distribution of the toner are determined by the Carcoulter counter method. Examples of the measuring device for the particle size distribution of the toner particles include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). In the present invention, measurement was performed using a Coulter Counter TA-II type connected to an interface (Nichiken Giken) that outputs number distribution and volume distribution and a PC9801 personal computer (manufactured by NEC).

The measurement method is described below.
First, 0.1 mL to 5 mL of a surfactant (preferably alkyl benzene sulfonate) is added as a dispersant to 100 mL to 150 mL of the 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 mg 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 volume and number of toner particles or toner are measured using the 100 μm aperture as the aperture by the measuring device. Calculate volume distribution and number distribution.
The channels include: 2.00 μm to less than 2.52 μm; 2.52 μm to less than 3.17 μm; 3.17 μm to less than 4.00 μm; 4.00 μm to less than 5.04 μm; 5.04 μm to less than 6.35 μm; .35 μm to less than 8.00 μm; 8.00 μm to less than 10.08 μm; 10.08 μm to less than 12.70 μm; 12.70 μm to less than 16.00 μm; 16.00 μm to less than 20.20 μm; The target particle size is 2.00 μm to less than 40.30 μm using 13 channels of less than 40 μm; 25.40 μm to less than 32.00 μm; 32.00 μm to less than 40.30 μm. The volume-based volume average particle diameter (Dv) obtained from the volume distribution according to the present invention and the number average particle diameter (Dn) obtained from the number distribution and the ratio Dv / Dn were obtained.

Further examination revealed that the toner acid value is a more important index than the binder resin acid value for low-temperature fixability and high-temperature offset resistance. The toner acid value is derived from the terminal carboxyl group of the unmodified polyester. The unmodified polyester preferably has a toner acid value of 0.5 KOHmg / g to 40.0 KOHmg / g in order to control low-temperature fixability (fixing lower limit temperature, hot offset occurrence temperature, etc.) as a toner. In other words, if the toner acid value exceeds 40.0 KOHmg / g, the elongation or cross-linking reaction of the modified polyester becomes insufficient, and the high temperature offset resistance is affected. If it is less than 0.5 KOHmg / g, This is because the dispersion stability effect due to the base compound cannot be obtained, and the elongation or cross-linking reaction of the modified polyester tends to proceed, resulting in a problem in production stability.
According to a method based on JIS K0070. However, when the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.

The toner acid value is specifically determined by the following procedure.
Measuring device: potentiometric automatic titrator DL-53 Titoror (Metler Toledo)
Electrode used: DG113-SC (Metler Toledo)
Analysis software: LabX Light Version 1.00.000
Calibration of apparatus: Use a mixed solvent of 120 mL of toluene and 30 mL of ethanol.
Measurement temperature: 23 ° C
The measurement conditions are as follows.
Stirring conditions
Stirring speed [%]: 25
Stirring time [s]: 15
Equilibrium titration conditions
Titration solution: CH ₃ ONa
Concentration [mol / L]: 0.1
Electrode: DG115
Unit of measurement: mV
Before titration drop before measurement Drop volume [mL]: 1.0
Waiting time [s]: 0
Titration drop mode: Dynamic
dE (set) [mV]: 8.0
dV (min) [mL]: 0.03
dV (max) [mL]: 0.5
Measurement mode: equilibrium titration dE [mV]: 0.5
dt [s]: 1.0
t (min) [s]: 2.0
t (max) [s] 20.0
Recognition conditions
Threshold: 100.0
Maximum rate of change only: No
Range: No
Frequency: None
Measurement end condition
Maximum dripping amount [mL]: 10.0
Potential: No
Gradient: No
After the equivalence point: Yes
n number: 1
Combination of end conditions: No
Evaluation conditions
Procedure: Standard
Potential 1: No
Potential 2: No
Stop for re-evaluation: No

The toner acid value is measured according to the measurement method described in JIS K0070-1992 under the following conditions.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate soluble component) is added to 120 mL of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Add 30 mL of ethanol to make a sample solution.
The measurement can be calculated by the above apparatus, but specifically, it is calculated as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (mL) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

  The glass transition point of the toner is preferably 40 ° C. to 70 ° C. in order to obtain low temperature fixability, heat resistant storage stability and high durability. That is, when the glass transition point is less than 40 ° C., blocking in the developing machine and filming to the photoreceptor are liable to occur, and when it exceeds 70 ° C., the low-temperature fixability tends to deteriorate.

  The toner of the present invention can react with a compound having an active hydrogen group by emulsifying and dispersing an oil phase composed of a solution or dispersion of the kneaded composite in an aqueous medium or in the organic solvent. A kneaded body of a polymer, a binder resin, a colorant, a release agent, and a modified layered inorganic mineral having various parts are dissolved or dispersed, and an oil phase composed of the solution or dispersion of the kneaded body is dissolved in an aqueous medium. After the organic solvent is removed, washed and dried, it is emulsified and dispersed and reacted with a polymer having a site capable of reacting with the compound having an active hydrogen group, or while reacting. is there.

<Image forming method>
An image forming apparatus in which an image forming method using a toner manufactured by the toner manufacturing method of the present invention will be described with reference to the drawings.
FIG. 2 is a schematic explanatory view showing an example of an image forming apparatus in which an image forming method using the toner manufactured by the toner manufacturing method of the present invention is carried out.
In FIG. 2, an electrophotographic copying machine is illustrated as an image forming apparatus.
In FIG. 2, reference numeral 1 denotes a photosensitive drum as a latent image carrier, which rotates in the direction of the arrow in the drawing, and a charger 2 is disposed around the photosensitive drum 3, and a laser beam 3 corresponding to an image read from a document. Are irradiated as exposure means. Further, a developing device 4, a paper feeding unit 7, a transfer device 5, a cleaning device 6, and a charge eliminating lamp 9 are disposed around the photoreceptor 1. The developing device 4 further includes developing rollers 41 and 42, a paddle-shaped stirring member 43, a stirring member 44, a doctor 45, a toner supply unit 46, and a supply roller 47. The cleaning means 6 includes a cleaning brush 52 and a cleaning blade 61. Members 81 and 82 arranged above and below the developing device 4 are guide rails for attaching / detaching or supporting the developing device. The life of the cleaning blade 61 of the cleaning device can also be detected. The cleaning blade 61 always abuts on the photoconductor during image formation and wears as the photoconductor rotates. When the cleaning blade is worn, the function of removing the residual toner on the surface of the photoreceptor is lowered, and the copy image quality is deteriorated. Even if the toner is not worn, the transferability is improved when the toner is close to a true sphere and the fluidity is improved as compared with the pulverized toner. However, in cleaning, it is easy to cause defective cleaning through the installed blade. Is done. With respect to this problem, the toner manufactured by the toner manufacturing method of the present invention can be used for good cleaning.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
Hereinafter, a part shows a mass part.
(Production Example 1)
<Production of resin fine particle dispersion>
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of a 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 charged and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [resin fine particle dispersion 1] was obtained. The volume average particle diameter of [resin fine particle dispersion 1] measured with LA-920 was 105 nm. A portion of [resin 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.

<Production of low molecular weight polyester-1>
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propion oxide 3-mole adduct, 208 parts by mass of terephthalic acid, 46 parts by mass of isophthalic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 5 hours under normal pressure. Next, after reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts by weight of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure. Low molecular weight polyester-1] was synthesized. The obtained [low molecular weight polyester-1] had a weight-average molecular weight (Mw) of 5,200, a glass transition temperature (Tg) of 45 ° C., and an acid value of 20 mgKOH / g.

<Prepolymer production>
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 795 parts of bisphenol A ethylene oxide 2-mole adduct, 200 parts of isophthalic acid, 65 parts of terephthalic acid, and 2 parts of dibutyltin oxide were added, and atmospheric pressure nitrogen was added. Under an air stream, the condensation reaction was performed at 210 ° C. for 8 hours. Next, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 mmHg to 15 mmHg, then cooled to 80 ° C., and reacted with 170 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain [Prepolymer-1]. The obtained [Prepolymer-1] had a weight average molecular weight of 5,000.

<Manufacture of masterbatch-1>
1,200 parts by mass of water, 174 parts by mass of BENTONE57 (organic modified bentonite, quaternary ammonium cation modified product) manufactured by ELEMENTIS, and 1,570 parts by mass of [Low Molecular Polyester-1] were added to a Henschel mixer (Mitsui Mining Co., Ltd.). And mixed). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare [Masterbatch-1]. The dispersed particle size in the master batch was 0.4 μm, and the particles having a particle size of 1 μm or more was 2% by volume.

<Toner material oil phase dispersion adjustment>
In a beaker, 23.4 parts of [Prepolymer-1], 123.6 parts of [Low molecular weight polyester-1], 20 parts of [Masterbatch-1] and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 2.9 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Toner Material Oil Phase Dispersion-1].

<Preparation of aqueous dispersion of toner material>
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion-1] and 0.5 part of sodium dodecylbenzenesulfonate were added and stirred with a TK homomixer at 12,000 rpm, [toner material] An aqueous phase dispersion] was obtained.

Example 1
<Manufacture of Toner-1>
4 kg of [Toner Material Oil Phase Dispersion-1] was added to 6 kg of [Toner Material Aqueous Dispersion] and reacted while stirring for 30 minutes to obtain a toner emulsion. The amount of ethyl acetate in the toner emulsion was 20% with respect to 100 parts of the toner emulsion. The viscosity of the toner emulsified liquid measured at a rotation speed of 60 rpm with a Brookfield viscometer at 25 ° C. (manufactured by Brookfield) was 500 mPa · s.
10 kg of this toner emulsified liquid is supplied to a tube as shown in FIG. 1 having a tube wall temperature of 50 ° C., a tube internal pressure of 75 mmHg, and a tube heat transfer area of 0.3 m ² at a supply rate of 3 kg / min. Was taken out. After removing the organic solvent, the slurry was placed in a jacketed 20 L tank, aged at a jacket hot water temperature of 45 ° C., filtered, washed, dried, and then air-classified to obtain a spherical toner base. 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec, and 30 seconds of mixing and rest for 1 minute were carried out for 5 cycles to obtain final [Toner (1)].
The amount of ethyl acetate with respect to 100 parts of the toner emulsified liquid after removal of the organic solvent, and the time until 10 kg of the post-ripening emulsified liquid is supplied into the tube and the organic solvent is removed and removed, that is, the time required for removing the organic solvent. Evaluated.
Using the obtained [Toner (1)], volume average particle size, particle size distribution, low temperature fixability, high temperature offset resistance and image quality were evaluated.

(Example 2)
Except that the supply rate of 10 kg of the toner emulsified liquid was changed to 1.5 kg / min, the same operation as in Example 1 was performed, and the process after removing the organic solvent was the same as in [Toner (1)] [Toner (2)] was obtained and evaluated in the same manner.

(Example 3)
Except that the supply rate of 10 kg of the toner emulsified liquid was changed to 0.5 kg / min, the same operation as in Example 1 was performed, and the steps after removing the organic solvent were the same as in [Toner (1)] [Toner (3)] was obtained and evaluated in the same manner.

Example 4
Except that the supply rate of 10 kg of the toner emulsified liquid was changed to 0.1 kg / min, the same operation as in Example 1 was performed, and the steps after removing the organic solvent were the same as in [Toner (1)] [Toner (4)] was obtained and evaluated in the same manner.

(Example 5)
Except that the supply rate of 10 kg of the toner emulsified liquid was changed to 0.06 kg / min, the same operation as in Example 1 was performed, and the steps after removing the organic solvent were the same as in [Toner (1)] [Toner (5)] was obtained and evaluated in the same manner.

(Example 6)
0.9 kg of [Toner Material Oil Phase Dispersion-1] was added to 9.1 kg of [Toner Material Aqueous Dispersion] and reacted while stirring for 30 minutes to obtain a toner emulsion. The amount of ethyl acetate in the toner emulsion was 4.5% with respect to 100 parts of the toner emulsion. The measured viscosity of the toner emulsion at a rotation speed of 60 rpm with a Brookfield viscometer at 25 ° C. (Brookfield) was 100 mPa · s.
The toner emulsion was supplied to a tube as shown in FIG. 1 at a supply rate of 1.5 kg / min, a tube wall temperature of 50 ° C., a tube pressure of 75 mmHg, and a heat transfer area of the tube of 0.3 m ² . The remaining liquid was taken out.
The process after removing the organic solvent was the same as [Toner (1)], and the final [Toner (6)] was obtained and evaluated in the same manner.

(Example 7)
5 kg of [Toner Material Oil Phase Dispersion-1] was added to 5 kg of [Toner Material Aqueous Dispersion] and reacted while continuing stirring for 30 minutes to obtain a toner emulsion. Subsequently, the contents were transferred to a flask equipped with a cooling pipe and aged using a hot water bath. The amount of ethyl acetate in this toner emulsion was 25% with respect to 100 parts of the emulsion. The viscosity of the toner emulsified liquid measured at a rotation speed of 60 rpm with a Brookfield viscometer (Brookfield) at 25 ° C. was 1,000 mPa · s.
10 kg of the toner emulsion is supplied to a tube as shown in FIG. 1 having a supply speed of 1.5 kg / min, a tube wall temperature of 50 ° C., a tube pressure of 75 mmHg, and a heat transfer area of the tube of 0.3 m ² . The liquid was taken out. The process after removing the organic solvent was carried out in the same manner as in [Toner (1)] to obtain the final [Toner (7)] and evaluated in the same manner.

(Comparative Example 1)
The same operation as in Example 1 was performed except that the supply rate of 10 kg of the emulsified liquid after aging was changed to 4 kg / min. However, the toner aggregated during the aging treatment and could not be converted into a toner (see “Toner in Table 2”). (8) ").

(Comparative Example 2)
The process after removing the organic solvent was carried out in the same manner as in [Toner (1)], except that the supply rate of 10 kg of the emulsified liquid after aging was changed to 0.05 kg / min. The final [Toner (9)] was obtained and evaluated in the same manner.

(Comparative Example 3)
0.8 kg of [Toner Material Oil Phase Dispersion-1] was added to 9.2 kg of [Toner Material Aqueous Dispersion] and reacted while continuing stirring for 30 minutes to obtain a toner emulsion. The amount of ethyl acetate in the toner material emulsion was 4.1% with respect to 100 parts of the toner emulsion. The viscosity of the toner emulsified liquid measured at a rotation speed of 60 rpm using a Brookfield viscometer at 25 ° C. was 90 mPa · s.
The toner emulsion 10kg at a feed rate of 1.5 kg / min, the tube wall temperature of 50 ° C., the internal pressure 75 mmHg, and fed to the tube as shown in FIG. 1 is a heat transfer area 0.3 m ² of the tube, the toner emulsion The remaining liquid was taken out.
The process after removing the organic solvent was the same as [Toner (1)], and the final [Toner (10)] was obtained and evaluated in the same manner.

(Comparative Example 4)
5.5 kg of the [toner material oil phase dispersion-1] was added to 4.5 kg of the above [toner material aqueous phase dispersion] and reacted while stirring for 30 minutes to obtain a toner emulsion. The amount of ethyl acetate in this toner emulsion was 27.4% with respect to 100 parts of the emulsion. The viscosity of the Brookfield viscometer measured at a rotation speed of 60 rpm was 1,200 mPa · s.
The toner emulsion after aging is supplied to a tube as shown in FIG. 1 having a supply rate of 1.5 kg / min, a tube wall temperature of 50 ° C., a tube pressure of 75 mmHg, and a heat transfer area of 0.3 m ² . The remaining liquid was taken out.
Thereafter, the same aging treatment as in Example 1 was performed, but the toner could not be formed because the toner aggregated (“Toner (11)” in Table 2).

(Comparative Example 5)
4 kg of [Toner Material Oil Phase Dispersion-1] was added to 6 kg of [Toner Material Aqueous Dispersion] and reacted while stirring for 30 minutes to obtain a toner emulsion. The amount of ethyl acetate in the toner emulsion was 20% with respect to 100 parts of the toner emulsion. The viscosity measurement value of the Brookfield viscometer at a rotation speed of 60 rpm was 500 mPa · s.
This emulsified liquid was put into a 20 L tank with a jacket, and an organic solvent removal operation was performed for 10 minutes at a jacket temperature of 50 ° C. and a tube pressure of 75 mmHg. However, because the toner melted and aggregated, it could not be converted into a toner (Table 2). "Toner (12)").

(Comparative Example 6)
4 kg of [Toner Material Oil Phase Dispersion-1] was added to 6 kg of [Toner Material Aqueous Dispersion] and reacted while stirring for 30 minutes to obtain a toner emulsion. The amount of ethyl acetate in the toner emulsion was 20% with respect to 100 parts of the toner emulsion. The viscosity measurement value of the Brookfield viscometer at a rotation speed of 60 rpm was 500 mPa · s.
This toner emulsion was put into a 20 L tank with a jacket, and the organic solvent was removed for 210 minutes at a jacket temperature of 25 ° C. and an internal pressure of 0.1 mmHg, and the remaining toner emulsion was taken out.
The process after removing the organic solvent was the same as [Toner (1)], and the final [Toner (13)] was obtained and evaluated in the same manner.

(Comparative Example 7)
In a beaker, 23.4 parts of [Prepolymer-1], 141.6 parts of [Polyester-1], organosilica sol (MEK-ST, solid content concentration 30%, average primary particle size 15 nm, manufactured by Nissan Chemical Industries) 7 And 64 parts of ethyl acetate were added and dissolved with stirring. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 2.9 parts of isophoronediamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12000 rpm using a TK homomixer to obtain [Toner Material Oily Dispersion-2].
4 kg of [Toner Material Oil Phase Dispersion-2] was added to 6 kg of [Toner Material Aqueous Dispersion] and reacted while stirring for 30 minutes to obtain a toner emulsion. The amount of ethyl acetate in the toner emulsion was 19% with respect to 100 parts of the toner emulsion. The viscosity measurement value of the Brookfield viscometer at 60 rpm was 600 mPa · s.
The toner emulsion 10kg at a feed rate of 1.5 kg / min, the tube wall temperature of 50 ° C., the internal pressure 75 mmHg, and fed to the tube as shown in FIG. 1 is a heat transfer area 0.3 m ² of the tube, the toner emulsion The remaining liquid was taken out.
The process after removing the organic solvent was the same as [Toner (1)], and the final [Toner (14)] was obtained and evaluated in the same manner.

  The toners obtained in Examples 1 to 7 and Comparative Examples 1 to 7 were evaluated as follows. The status of the organic solvent removal step and the performance evaluation results are shown in Tables 1 to 3.

  Toner evaluation items and evaluation methods in Examples and Comparative Examples are shown below.

<Amount of residual organic solvent in emulsion after removal of organic solvent>
Specifically, it was determined by the following procedure.
Measuring instrument condition measuring device: GC-2010 (Shimadzu gas chromatograph)
Injection volume: 2.0 μL

Sample vaporization chamber injection mode: split vaporization chamber temperature: 180 ° C
Carrier gas: He
Pressure: 40.2kPa
Total flow rate: 56.0 mL / min
Column flow rate: 1.04 mL / min
Linear velocity: 20.0 cm / sec
Purge flow rate: 3.0 mL / min
Split ratio: 50.0

Column Column name: ZB-50
Liquid phase film thickness 0.25μm
Length 30.0m
Inner diameter: 0.32 mm ID
Maximum column temperature: 340 ° C

Column oven Column temperature: 60 ° C
Column oven temperature program:
60 ° C hold 6 min → temperature rise rate 60 ° C / min → 230 ° C hold 5 min

Detector Detector temperature: 250 ° C
Make-up gas: N2 / Air
Makeup flow rate: 30.0 mL / min
H2 flow rate: 47.0 mL / min
Air flow rate: 400 mL / min

Measurement method Preparation of internal standard solution: 4 g of toluene was weighed into a volumetric flask and diluted to 500 mL with DMF.
Preparation of measurement sample: After 1.5 g of the measurement dispersion slurry was diluted to about 50 mL with DMF, 10 mL of the internal standard solution was collected with a whole pipette and charged. After the measurement sample was stirred for 4 minutes at 400 rpm with a stirrer, the sample was set in the autosampler of the measuring instrument GC and measured. After the measurement, the amount of ethyl acetate in the slurry was calculated by the internal standard method from the ratio of toluene and ethyl acetate as the internal standard material.

<Dispersed particle size (volume average particle size) in the master batch>
<< Measurement sample adjustment >>
The amount of organic cation-modified layered mineral in the masterbatch / the amount of binder resin used in the masterbatch = 1/10 The ratio of the masterbatch and binder resin is 5% by weight of Dispersbyk-167 manufactured by BYK Chemie. In ethyl acetate. At this time, the total amount of the master batch amount and the binder resin amount was adjusted to 5 wt%. The prepared sample was stirred for 12 hours.

<< Measurement of dispersed particle size >>
The prepared sample was measured using a laser Doppler particle size distribution measuring device particle size distribution measuring device.
The measuring method is as follows. Apparatus: nanotrac UPA-150EX (made by Nikkiso Co., Ltd.)
Method:
(1) Measuring conditions of measuring instrument:
Distribution display: Volume Number of channels: 52
Measurement time: 15 sec
Particle refractive index: 1.54
Temperature: 25 ° C
Particle shape: non-spherical viscosity (CP): 0.441
Solvent refractive index: 1.37
Solvent name: ethyl acetate (2) The sample diluent to be measured was added using a dropper or a syringe so as to enter (1 to 100) while looking at the sample loading of the measuring instrument.

<Circularity and particles less than 2 μm>
A toner with a particle size of 2 μm or less is measured using a flow type particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation), and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). Went. Specifically, 0.1 mL to 0.5 mL of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku Co., Ltd.) is added to a glass 100 mL beaker, and each toner 0.1 g to 0 g. 0.5 g was added and stirred with a microspatel, and then 80 mL of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured using the FPIA-2100 until the concentration of the dispersion was 5,000 / μL to 15,000 / μL. In this measurement method, it is important that the concentration of the dispersion is 5,000 / μL to 15,000 / μL from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. Similar to the measurement of the toner particle size described above, the required amount of the surfactant varies depending on the hydrophobicity of the toner. If it is added in a large amount, noise due to bubbles is generated. It will be enough. Further, the toner addition amount differs from the particle size, and it is small for small particle sizes and needs to be increased for large particle sizes. When the toner particle size is 3 μm to 7 μm, the toner amount is 0.1 g to By adding 0.5 g, the dispersion concentration can be adjusted to 5,000 / μL to 15,000 / μL.

<< Toner Shape >>
The shape factors SF-1 and SF-2 are obtained by randomly sampling 300 SEM images of toner obtained by measurement using an FE-SEM (S-4200) manufactured by Hitachi, Ltd., and using the image information via an interface. Introduced into an image analysis apparatus (LuzexAP) manufactured by Nireco Corporation and analyzed, and values obtained from the following formulas were defined as SF-1 and SF-2. The values of SF-1 and SF-2 are preferably values obtained by the Luzex, but are not particularly limited to the FE-SEM device and the image analysis device as long as similar analysis results can be obtained.

SF-1 = (L2 / A) × (π / 4) × 100
SF-2 = (P2 / A) × (1 / 4π) × 100
(Here, L represents the absolute maximum length of the toner, A represents the projected area of the toner, and P represents the maximum peripheral length of the toner.)
In the case of a true sphere, both SF-1 and SF-2 become 100, and the value becomes larger from 100 and becomes an indeterminate shape. In particular, SF-1 represents the shape of the whole toner (ellipse, sphere, etc.), and SF-2 is a shape factor indicating the degree of surface irregularities.

<< Toner particle size >>
The average particle size and particle size distribution of the toner are determined by the Carcoulter counter method. Examples of the measuring device for the particle size distribution of the toner particles include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). In the present invention, measurement was performed using a Coulter Counter TA-II type connected to an interface (Nichiken Giken) that outputs number distribution and volume distribution and a PC9801 personal computer (manufactured by NEC).

The measurement method is described below.
First, 0.1 mL to 5 mL of a surfactant (preferably alkyl benzene sulfonate) is added as a dispersant to 100 mL to 150 mL of the 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 mg 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 volume and number of toner particles or toner are measured using the 100 μm aperture as the aperture by the measuring device. Calculate volume distribution and number distribution.
The channels include: 2.00 μm to less than 2.52 μm; 2.52 μm to less than 3.17 μm; 3.17 μm to less than 4.00 μm; 4.00 μm to less than 5.04 μm; 5.04 μm to less than 6.35 μm; .35 μm to less than 8.00 μm; 8.00 μm to less than 10.08 μm; 10.08 μm to less than 12.70 μm; 12.70 μm to less than 16.00 μm; 16.00 μm to less than 20.20 μm; The target particle size is 2.00 μm to less than 40.30 μm using 13 channels of less than 40 μm; 25.40 μm to less than 32.00 μm; 32.00 μm to less than 40.30 μm. The volume-based volume average particle diameter (Dv) obtained from the volume distribution according to the present invention and the number average particle diameter (Dn) obtained from the number distribution and the ratio Dv / Dn were obtained.

<Acid value (KOHmg / g)>
According to the method specified in JISK0070. However, when the sample did not dissolve, dioxane or tetrahydrofuran was used as the solvent.
The acid value was specifically determined by the following procedure.
Measuring apparatus: automatic potentiometric titrator DL-53 Titrator (manufactured by METTLER TOLEDO)
Electrode used: DG113-SC (Metler Toledo)
Analysis software: LabX Light Version 1.00.000
Calibration of apparatus: A mixed solvent of 120 mL of toluene and 30 mL of ethanol was used.
Measurement temperature: 23 ° C
The measurement conditions were as follows.
Stirring conditions
Stirring speed [%]: 25
Stirring time [s]: 15
Equilibrium titration conditions
Titration solution: CH ₃ ONa
Concentration [mol / L]: 0.1
Electrode: DG115
Unit of measurement: mV
Before titration drop before measurement Drop volume [mL]: 1.0
Waiting time [s]: 0
Titration drop mode: Dynamic
dE (set) [mV]: 8.0
dV (min) [mL]: 0.03
dV (max) [mL]: 0.5
Measurement mode: equilibrium titration dE [mV]: 0.5
dt [s]: 1.0
t (min) [s]: 2.0
t (max) [s] 20.0
Recognition conditions
Threshold: 100.0
Maximum rate of change only: No
Range: No
Frequency: None
Measurement end condition
Maximum dripping amount [mL]: 10.0
Potential: No
Gradient: No
After the equivalence point: Yes
n number: 1
Combination of end conditions: No
Evaluation conditions
Procedure: Standard
Potential 1: No
Potential 2: No
Stop for re-evaluation: No

<< Method for Measuring Acid Value >>
Measurement was performed under the following conditions in accordance with the measurement method described in JIS K0070-1992. Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate soluble component) is added to 120 mL of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Further, 30 mL of ethanol was added to prepare a sample solution.
The measurement can be calculated by the above apparatus, and specifically, the calculation was performed as follows.
Titration was carried out with N / 10 caustic potash-alcohol solution that had been standardized in advance, and the acid value was determined from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (mL) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

<Glass transition point Tg (° C)>
The glass transition point was measured with a Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation at a temperature increase rate of 10 ° C./min.
A method for measuring Tg will be 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 temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, the sample was cooled to room temperature and left for 10 min, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at min. Tg was calculated from the tangent of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

<Image density>
Using a digital full-color copier (imageColor 2800, manufactured by Ricoh Co., Ltd.), after running 150,000 image charts with 50% image area in single color mode, a solid image was output to 6000 paper manufactured by Ricoh Co., and the image density was set to XRite. Measurement was carried out by (manufactured by X-Rite).
This was performed for four colors alone, and the average was obtained. When this value is less than 1.2, “x”, when it is 1.2 or more and less than 1.4, “△”, when it is 1.4 or more and less than 1.8, “◯”, 1.8 or more and 2 If less than 2, “◎” was assigned.

<Image graininess, sharpness>
Using a digital full-color copying machine (imageColor 2800, manufactured by Ricoh), a photographic image was output in a single color, and the degree of graininess and sharpness was visually evaluated. In order from the best, “◎” is equivalent to offset printing, “○” is slightly worse than offset printing, “△” is much worse than offset printing, “×” is about the same as conventional electrophotographic images (very much Bad).

<Soil dirt>
Using a digital full-color copier (imageColor 2800 manufactured by Ricoh Co., Ltd.), running 30,000 image charts with a 50% image area in single-color mode, then stopping the blank image during development, and developing on the photoreceptor after development The agent was transferred to a tape, and the difference from the image density of the untransferred tape was measured with a 938 spectrodensitometer (manufactured by X-Rite). The smaller the difference in image density, the better the background stains.
Ranking was in the order of “△” and “×”.

<Toner scattering>
After continuous printing of 50,000 sheets using a digital full-color copying machine (imageColor 2800 manufactured by Ricoh), the degree of toner contamination in the machine was confirmed. A level where there is no problem is indicated by “◯”, a toner is observed, but a level where there is no problem in use is indicated by “Δ”, and a serious problem is indicated by “X”.

<Cleanability>
The transfer residual toner on the photosensitive member that has passed the cleaning process is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Co., Ltd.), measured with a Macbeth reflection densitometer RD514, and the difference from the blank is 0.01 or less. A product was evaluated as ○ (good), and a product exceeding it was evaluated as × (defect).

<Evaluation of charge amount>
1) Charge amount of stirring for 15 seconds Each toner 10g obtained and 100g of ferrite carrier were put in a stainless steel pot up to 30% of the internal volume in an environment of temperature 28 ° C and humidity 80%, and stirred for 15 seconds at a stirring speed of 100rpm. Then, the charge amount (μC / g) of the developer was measured with [Toshiba Chemical Co., Ltd .: TB-200].
The toner charge amount was measured by the blow-off method.
2) Charge amount stirred for 5 minutes As in 1), the charge amount when stirred for 5 minutes was measured.
3) Charge amount with stirring for 10 minutes The charge amount when stirring for 10 minutes was measured in the same manner as in 1).

<Charging stability>
(1) High-temperature and high-humidity environment charging stability In an environment of 40 ° C and 90% humidity, an image chart with a 7% image area in a monochrome mode is output with 100,000 copies on a digital full-color copier (ImagioColor 2800 manufactured by Ricoh). In the meantime, a part of the developer was sampled every 1,000 sheets, and the charge amount was measured by the blow-off method to evaluate the charging stability. When the change in the charge amount was 5 μc / g or less, it exceeded ◯, 5 μc / g, and when it was 10 μc / g or less, Δ, and when it exceeded 10 μc / g, it was marked as x.
(2) Low-temperature, low-humidity environment charging stability In an environment with a temperature of 10 ° C. and a humidity of 15%, an image chart having a 7% image area is output in a monochrome mode on a digital full-color copier (ImagioColor 2800 manufactured by Ricoh). In the meantime, a part of the developer was sampled every 1,000 sheets, and the charge amount was measured by the blow-off method to evaluate the charging stability. When the change in the charge amount was 5 μc / g or less, it exceeded ◯, 5 μc / g, and when it was 10 μc / g or less, Δ, and when it exceeded 10 μc / g, it was marked as x.
The charge amount measurement by the blow-off method (1) and (2) was performed as follows.
In a test room with a temperature of 20 ° C. and a humidity of 50%, 10 g of each toner and 100 g of ferrite carrier are placed in a stainless steel pot up to 30% of the internal volume, and stirred for 10 minutes at a stirring speed of 100 rpm. g) was measured with [Toshiba Chemical Co., Ltd .: TB-200].

<Fixability evaluation>
Using a device obtained by remodeling the fixing unit MF2200 manufactured by Ricoh Co., Ltd., which uses a Teflon (registered trademark) roller as a fixing roller, type 6200 paper manufactured by Ricoh was set therein, and a copying test was performed. The cold offset temperature (fixing lower limit temperature) and the hot offset temperature (hot offset resistant temperature) were determined by changing the fixing temperature. The fixing minimum temperature of the conventional low-temperature fixing toner is about 140 ° C. to 150 ° C. The evaluation conditions for low-temperature fixing are a paper feed linear velocity of 120 mm / sec to 150 mm / sec, a surface pressure of 1.2 kgf / cm ² , a nip width of 3 mm, and a high temperature offset evaluation condition of a paper feed linear velocity of 50 mm / sec. sec, surface pressure 2.0 kgf / cm ² , and nip width 4.5 mm. The criteria for each characteristic evaluation were as follows.
Low temperature fixability (five-level evaluation)
Good: ◎: Less than 140 ° C, ◯: 140 ° C to 149 ° C, □: 150 ° C to 159 ° C, Δ: 160 ° C to 170 ° C, x: 170 ° C or higher.
Good: ◎: 201 ° C or higher, ○: 200 ° C to 191 ° C, □: 190 ° C to 181 ° C, Δ: 180 ° C to 171 ° C, x: 170 ° C or lower

<Heat resistant storage stability>
After the toner was stored at 50 ° C. for 8 hours, it was sieved with a 42 mesh sieve for 2 minutes, and the residual ratio on the wire mesh was regarded 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 Δ: 20% to less than 30% ○: 10% to less than 20% ◎: less than 10%

FIG. 1 is a schematic explanatory diagram illustrating an example of a manufacturing apparatus in which the toner manufacturing method of the present invention is implemented. FIG. 2 is a schematic explanatory view showing an example of an image forming apparatus in which an image forming method using the toner manufactured by the toner manufacturing method of the present invention is carried out.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photosensitive drum 2 Charger 3 Laser beam 4 Developing device 5 Transfer device 6 Cleaning device 7 Paper feed means 9 Static elimination lamp 11 Outer tube 12 Inner tube wall surface 13 Material inlet 14 Rotary blade 15 Steam outlet 16 Residual liquid outlet 41 Developing roller 42 Developing roller 43 Paddle-shaped stirring member 44 Stirring member 45 Doctor 46 Toner supply part 47 Supply roller 52 Cleaning brush 61 Cleaning blade 81 Guide rail 82 Guide rail

Claims (19)

A dissolution and dispersion step of dissolving or dispersing a kneaded body containing a binder resin, a colorant, a release agent, and a modified layered inorganic mineral in an organic solvent;
An emulsification dispersion step of emulsifying and dispersing an oil phase composed of a solution or a dispersion of the kneaded body;
An organic solvent removing step of removing toner from the emulsion obtained by emulsifying and dispersing the oil phase in an aqueous medium to obtain toner particles,
In the emulsification dispersion step, the measured viscosity of the emulsion at a rotational speed of 60 rpm of a Brookfield viscometer at 25 ° C. is 100 mPa · s to 1,000 mPa · s, and the emulsion is supplied to a tube that has been heated and reduced in pressure. And forming a thin film on the inner wall of the tube by stirring the supplied emulsion.
In the organic solvent removal step, the temperature of the emulsion is controlled to be equal to or lower than the glass transition temperature of the toner, the organic solvent in the emulsion is discharged from the tube, and the emulsion remaining in the tube is removed from the tube. The organic solvent is removed with the heat transfer area S (m ² ) of the tube, the feed rate A (kg / min) of the emulsion to the tube, and the content B (%) of the organic solvent in the emulsion. A toner production method, wherein the relationship satisfies 0.5 ≦ S / (A × B × 0.01) ≦ 25. A dissolution and dispersion step of dissolving or dispersing a kneaded body containing a polymer having a site capable of reacting with a compound having an active hydrogen group, a binder resin, a colorant, a release agent, and a modified layered inorganic mineral in an organic solvent; ,
An emulsification dispersion step of emulsifying and dispersing an oil phase composed of a solution or a dispersion of the kneaded body;
An organic solvent removing step of removing the organic solvent after reacting with or reacting with the polymer having a site capable of reacting with the compound having an active hydrogen group,
In the emulsification dispersion step, the measured viscosity of the emulsion at a rotational speed of 60 rpm of a Brookfield viscometer at 25 ° C. is 100 mPa · s to 1,000 mPa · s, and the emulsion is supplied to a tube that has been heated and reduced in pressure. And forming a thin film on the inner wall of the tube by stirring the supplied emulsion.
In the organic solvent removal step, the temperature of the emulsion is controlled to be equal to or lower than the glass transition temperature of the toner, the organic solvent in the emulsion is discharged from the tube, and the emulsion remaining in the tube is removed from the tube. The organic solvent is removed with the heat transfer area S (m ² ) of the tube, the feed rate A (kg / min) of the emulsion to the tube, and the content B (%) of the organic solvent in the emulsion. A toner production method, wherein the relationship satisfies 0.5 ≦ S / (A × B × 0.01) ≦ 25.   In the oil phase, the volume average particle diameter Dv of the modified layered inorganic mineral in the kneaded body is 0.1 μm to 0.55 μm, and the modified layered inorganic mineral having a particle diameter of 1 μm or more in the kneaded body satisfies 15% by volume or less. Item 3. A method for producing a toner according to any one of Items 1 to 2.   The method for producing a toner according to any one of claims 1 to 3, wherein the toner contains 0.1% by mass to 5% by mass of a modified layered inorganic mineral.   The method for producing a toner according to any one of claims 1 to 4, wherein in the modified layered inorganic mineral, at least a part of the metal cation is modified with an organic cation, and the organic cation is a quaternary ammonium ion.   The toner production method according to claim 1, wherein the toner has a volume average particle diameter of 3 μm to 7 μm.   The toner production method according to claim 1, wherein the volume average particle diameter Dv / number average particle diameter Dn of the toner is 1.00 to 1.30.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the toner has an average circularity of 0.94 to 0.99.   The method for producing a toner according to claim 1, wherein the toner particles having a particle size of 2 μm or less are 10% by number or less with respect to the total number of toner particles.   The method for producing a toner according to claim 1, wherein the toner has a shape factor SF-1 of 110 to 200, and the toner has a shape factor SF-2 of 110 to 300.   The method for producing a toner according to claim 1, wherein the binder resin contains a polyester resin.   The method for producing a toner according to claim 11, wherein the content of the polyester resin in the binder resin is 50% by mass to 100% by mass.   The method for producing a toner according to claim 11, wherein the polyester resin has a THF-soluble component having a weight average molecular weight of 1,000 to 30,000.   The method for producing a toner according to claim 11, wherein the acid value of the polyester resin is 1.0 KOH mg / g to 50.0 KOH mg / g.   The method for producing a toner according to claim 11, wherein the glass transition point of the polyester resin is 35 ° C. to 65 ° C.   The method for producing a toner according to claim 2, wherein the polymer having a site capable of reacting with the compound having an active hydrogen group has a weight average molecular weight of 3,000 to 20,000.   The method for producing a toner according to claim 1, wherein the toner has an acid value of 0.5 KOH mg / g to 40.0 KOH mg / g.   The toner production method according to claim 1, wherein the toner has a glass transition point of 40 ° C. to 70 ° C.   The method for producing a toner according to claim 1, wherein the toner is a toner used for a two-component developer.