JP5233574B2 - Method for producing toner for developing electrostatic image - Google Patents

Description

The present invention relates to a copying machine, a printer, a manufacturing method of preparative toner for developing electrostatic images used like a facsimile.

  In general, an electrophotographic image forming method generally uses a developer to develop an electrostatic image formed on a photoreceptor prepared using a photoconductive substance using various means. A method in which the developed image is transferred to paper or the like as necessary and fixed by heating, pressing, solvent vapor, or the like is performed.

  Methods for developing electrostatic images can be broadly divided into liquid development methods that use liquid developers in which various pigments and dyes are dispersed in an insulating organic liquid, cascade methods, magnetic brush methods, powder cloud methods, etc. As described above, there is a dry development method using a dry developer (hereinafter referred to as toner) in which a colorant such as carbon black is dispersed in a natural or synthetic resin, and the dry development method has been widely used in recent years.

  As a fixing method used in the dry development method, a heating heat roller method is generally used because of its energy efficiency. In recent years, in order to save energy by fixing toner at low temperature, the thermal energy given to the toner during fixing tends to be small. In 1999, the International Energy Agency (IEA) Demand-side Management (DSM) program has a technology procurement project for next-generation copiers, and the required specifications have been published. Is required to achieve dramatic energy saving compared to conventional copying machines so that the power consumption during standby is 10 to 30 W (depending on the copying speed). One method for achieving this requirement is to reduce the heat capacity of a fixing member such as a heated heat roller to improve the temperature responsiveness of the toner, but it is not fully satisfactory.

  In order to achieve this requirement and minimize the waiting time, it is considered that lowering the toner fixing temperature is an essential technical achievement. In order to cope with such low-temperature fixing, a polyester resin having excellent low-temperature fixability and relatively good heat storage stability is used in place of the styrene-acrylic resin that has been widely used. In order to improve low-temperature fixability, a method of adding a specific non-olefinic crystalline polymer as a binder resin and a method of using a crystalline polyester are known, but the molecular structure and molecular weight are optimized. I can't say. Even if these methods are applied, it is impossible to achieve the above-mentioned DSM program specifications.

  Therefore, in order to further fix at a low temperature, it is necessary to control the thermal characteristics of the binder resin. However, if the glass transition temperature is lowered too much, there is a problem that the heat resistant storage stability is lowered. In addition, if the molecular weight is reduced and the melting start temperature of the resin is lowered too much, there is a problem that the hot offset occurrence temperature is lowered. For this reason, a toner excellent in low-temperature fixability and offset resistance has not been obtained by controlling the thermal characteristics of the binder resin.

  On the other hand, a method for producing a toner used for developing an electrostatic charge image is roughly classified into a pulverization method and a polymerization method. In the pulverization method, a colorant, a charge control agent, an offset preventive agent and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner. When the pulverization method is used, a toner having some excellent characteristics can be produced, but the toner material is limited. For example, the composition obtained by melt mixing must be capable of being pulverized and classified using equipment that can be used economically. For this reason, the composition obtained by melt mixing must be made sufficiently brittle. Further, when the obtained composition is pulverized, the particle size distribution tends to be widened. At this time, in order to obtain a copy image having good resolution and gradation, for example, it is necessary to reduce the weight average particle diameter of the toner, and classify fine powder having a particle diameter of 4 μm or less and coarse powder having a particle diameter of 15 μm or more. If it is removed by this, there is a problem that the yield of toner decreases. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent and the like in the thermoplastic resin. This adversely affects toner fluidity, developability, durability, image quality, and the like.

  In order to overcome these problems in the pulverization method, a toner production method by a polymerization method is known. For example, a toner is obtained by using a suspension polymerization method or an emulsion polymerization aggregation method (see, for example, Patent Document 1). Is manufactured.

  However, in these production methods, a polyester resin superior in low-temperature fixability cannot be used as a toner. Therefore, in order to solve these problems, a toner made of a polyester resin is spheroidized in water using an organic solvent (see, for example, Patent Document 2), a prepolymer having an isocyanate group and an amine are reacted. (See, for example, Patent Document 3) obtained by the above method, but further reduction in manufacturing time is required from the viewpoint of economy.

  Further, for example, Patent Document 4, Patent Document 5 and the like have been proposed as the following to solve offset resistance or low-temperature fixability and high-temperature offset resistance by toner granulated in an aqueous medium. Both still have room to consider.

(Patent Document 4)
At least an organic solvent is dissolved or dispersed in a composition containing a polymer having a site capable of reacting with a compound having an active hydrogen group, a colorant, and a release agent, and a solution or dispersion comprising the composition is prepared. A toner obtained by dispersing in an aqueous medium and reacting the polymer with a compound having an active hydrogen group, or by reacting the polymer, removing the organic solvent, washing and drying the toner, And the compound having an active hydrogen group, the reaction temperature is in the range of 10 ° C. to X ° C. so that the solubility of water in the organic solvent is 0.04 to 30% by weight (where X ° C. = organic And the solubility of water in the organic solvent at 20 ° C. is 0.04 to 10% by weight.

(Patent Document 5)
Dissolve at least a polymer having a site capable of reacting with a compound having an active hydrogen group, an acidic group-containing binder resin, a colorant, a release agent, and a tertiary amine in an organic solvent or an organic dispersion medium. Alternatively, after the dispersed solution or dispersion is dispersed in a resin fine particle-containing aqueous medium and the polymer having a site capable of reacting with the compound having an active hydrogen group is reacted or reacted, the organic solvent or An electrostatic charge image developing toner produced by removing an organic dispersion medium, washing, and drying, wherein the solution or dispersion has an acid number A in the range of 15 to 30, and the solution or dispersion The ratio B / A of the acid number A to the base number B of the liquid is in the range of 1/5 to 1/1, and the particle ratio of 2 μm or less of the toner particle diameter is 5% by number or less.

Japanese Patent No. 2537503 JP-A-9-34167 JP-A-11-149180 JP 2005-122073 A JP 2007-183341 A

The present invention has been made in view of the above-described problems of the prior art, and is a toner that is excellent in low-temperature fixability and offset resistance and capable of forming a high-definition image. It reduces the time, and an object thereof is to provide a method of manufacturing a preparative toner that can be efficiently manufactured.

In order to solve the above problems, the invention according to claim 1 is a polymer having a binder resin, a compound having an active hydrogen group, and a site capable of reacting with a compound having an active hydrogen group in at least an organic solvent. A composition containing a colorant and a release agent is dissolved or dispersed, and the solution or dispersion is dispersed in an aqueous medium so that the compound having the active hydrogen group can react with the compound having the active hydrogen group. after reacting the polymer having a site or while the reaction, the organic solvent was removed, washed, a manufacturing method of the electrostatic image developing preparative toner obtained by drying the organic After removing the solvent and before washing, the reaction product is ripened, and in the ripening step, 30 to 70% mol of a tertiary amine compound is added to the acid value of the reaction product after removal of the organic solvent. It is characterized by that.

Invention according to claim 2, that Oite the production method of the electrostatic image developing preparative toner according to claim 1, wherein the polymer capable of reacting sites with a compound having an active hydrogen group is an isocyanate group Features.

The invention according to claim 3, Oite the manufacturing method of the electrostatic image developing preparative toner according to claim 1 or 2, wherein the binder resin is characterized in that it is a polyester resin.

The invention according to claim 4, and characterized in that Oite the production method of the electrostatic image developing preparative toner according to claim 3, the glass transition temperature of the polyester resin (Tg) of a 30 to 50 ° C. To do.

Invention of claim 5, Oite the production process of claims 1 to either preparative for developing electrostatic images according to toner of 4, an acid value of the reaction product after the organic solvent removed 1～30MgKOH / g.

The invention according to claim 6, Oite the process according to claim 1 to the electrostatic image developing preparative toner according to any one of 5, glass transition temperature of the toner (Tg) of is 40 to 70 ° C. It is characterized by that.

Wherein the billing invention according to claim 7, Oite to the manufacturing method of claims 1 to electrostatic image developing preparative toner according to any one of 6, weight average particle size of the toner is 3~8μm And

The invention according to claim 8, Oite the manufacturing method of the electrostatic image developing preparative toner according to claim 7, a weight average particle diameter / number average particle diameter of the toner is 1.25 or less Features.

The invention according to claim 9, Oite the process according to claim 1 to the electrostatic image developing preparative toner according to any one of 8, the average circularity of the toner is 1.00 to 0.90 It is characterized by that.

  According to the present invention, a toner that is excellent in low-temperature fixability and anti-offset property and can form a high-definition image, the time until obtaining the physical properties is shortened, and a toner that is efficiently manufactured is obtained. Can be provided.

Hereinafter, the best mode for carrying out the present invention will be described.
The present invention dissolves a composition containing a binder resin, a compound having an active hydrogen group, a polymer having a site capable of reacting with a compound having an active hydrogen group, a colorant, and a release agent in at least an organic solvent. Or after dispersing, dispersing the solution or dispersion in an aqueous medium and reacting the compound having an active hydrogen group with a polymer having a site capable of reacting with the compound having an active hydrogen group, or while the reaction, the organic solvent was removed, washed, a process for the preparation of a dry electrostatic image developing preparative toner obtained, after removal of the organic solvent, prior to washing, a step of aging the reaction In the aging step, 30 to 70% mol of a tertiary amine compound is added with respect to the acid value of the reaction product after removal of the organic solvent.

  Here, “adding 30 to 70% mol of a tertiary amine compound with respect to the acid value of the reaction product after removal of the organic solvent” is added depending on the acid value of the reaction product after removal of the organic solvent. It means that the amount of the tertiary amine compound is determined in the range of 30 to 70% mol. The acid value (mgKOH / g) of the reaction product after removal of the organic solvent needs to be converted to mol / g, and using the conversion formula = (0.001 gKOH / g) /56.1, the acid value per 1 g (Mol) is calculated.

  As described above, the organic solvent is removed by removing the organic solvent after reacting or reacting the compound having the active hydrogen group with the polymer having a site capable of reacting with the compound having the active hydrogen group. By adding and aging a tertiary amine compound in the range of 30 to 70% mol with respect to the acid value of the subsequent reaction product, the reaction rate of the reaction product increases, and the desired physical properties of the toner are obtained. Time can be shortened. This is presumably because the tertiary amine compound acts as a catalyst in the reaction between the compound having the active hydrogen group and the polymer having a site capable of reacting with the compound having the active hydrogen group, thereby promoting the reaction.

(Tertiary amine compound)
The tertiary amine compound added in the reaction step is premised on the addition to the granulated particle-water dispersion, and therefore needs to have water solubility, but the others are not particularly limited. Specifically, a tertiary amine catalyst or the like used in the synthesis of polyurethane is suitable from the viewpoint of safety and reaction rate improvement. Examples of commercially available products include U-CAT660M (manufactured by San Aho Pro), ZF-20 (manufactured by Huntsman), and trimethylamine.
Moreover, as an addition amount of a tertiary amine compound, it is preferable that it is 30-70% mol with respect to the acid value of the reaction material after the said organic solvent removal, and 40-50% mol is more preferable. When the added amount of the tertiary amine compound is less than 30% mol of the acid value of the reaction product, the reaction rate is hardly improved. When the added amount exceeds 70% mol, the tertiary amine compound adsorbed on the toner surface is obtained. Removal becomes difficult and negative chargeability deteriorates.

(Acid value of the reaction product after removal of the organic solvent)
The acid value of the reaction product after removal of the organic solvent is preferably set to an acid value of 1 to 30 (mgKOH / g) in order to control the fixing characteristics (fixing lower limit temperature, hot offset generation temperature, etc.). 30 (mgKOH / g) is more preferable. That is, when the acid value of the reaction product after removal of the organic solvent exceeds 30 (mgKOH / g), the extension or crosslinking reaction of the modified polyester becomes insufficient, and the high temperature offset resistance is affected, and 1 (mgKOH / If it is less than g), the extension or crosslinking reaction of the modified polyester is likely to proceed, causing a problem in production stability.
In order to keep the acid value of the reaction product after removal of the organic solvent within the range of 1 to 30 mg KOH / g, it is necessary to control the acid value of the toner constituting material so as to have such an acid value.

The acid value of the reaction product after removal of the organic solvent 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 Titoror (Metler Toledo)
Electrode used: DG113-SC (Metler Toledo)
Analysis software: LabX Light Version 1.00.000
Calibration of the 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 during titration
Speed [%] 25
Time [second] 15
・ Titration conditions
Titration solution CH ₃ ONa
Concentration [mol / L] 0.1
Electrode DG115
Unit of measure mV
Add titrant before measurement
Additional amount [mL] 1.0
Wait time [s] 0
Titration drop mode: Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measurement mode: Equivalent measurement
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Stop measurement
Maximum dripping volume [mL] 10.0
End potential No
Equivalent display Yes

(Polymer having a site capable of reacting with a compound having an active hydrogen group)
Although it does not specifically limit as a polymer site | part of the polymer which reacts with an active hydrogen group, A polyester resin is preferable from a viewpoint of binder resin.
The site that reacts with the active hydrogen group is most preferable from the viewpoint of reactivity and economy of the isocyanate group, and a polymer that reacts with the active hydrogen group can be synthesized from the aforementioned polymer and an isocyanate compound. In the synthesis, the site that reacts with the isocyanate compound is not particularly limited as long as it is a functional group having an active hydrogen group, but a hydroxyl group is preferred from the viewpoint of reaction controllability and versatility, and an alcoholic hydroxyl group is most preferred.

  As said polyester resin, the polyester prepolymer (A) which has an isocyanate group is used suitably. This prepolymer (A) is a polycondensate of polyol (1) and polycarboxylic acid (2), and is obtained by reacting polyisocyanate with polyester having active hydrogen. As the active hydrogen group possessed by the polyester, an alcoholic hydroxyl group is preferably used as described above.

  Examples of the polyol (1) include a diol (1-1) and a trihydric or higher polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among these, 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 (1-2) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); aromatic aliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates as phenol derivatives, oximes, caprolactam And a combination of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.

  The content of the polyisocyanate (3) component in the polyester prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. . If it is less than 0.5 wt%, 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 wt%, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 2 or more, preferably 2 to 3 on average, more preferably 2 to 2.5 on average. . If it is less than 2 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

(Binder resin)
In the present invention, a resin is used in addition to a polymer having a site capable of reacting with an active hydrogen group, and all these resins are expressed as a “binder resin”. And it is preferable that all these resin is a polyester resin.

(Compound having an active hydrogen group)
As described above, in the present invention, the active hydrogen group that reacts with the isocyanate group is preferably a hydroxyl group. A polyester resin is preferably used as the compound having a hydroxyl group. Since this polyester resin also has a role as a binder resin for toner, it preferably has the following glass transition temperature.

(Glass transition temperature (Tg) of polyester resin)
The glass transition temperature of the polyester resin is preferably 30 ° C to 50 ° C. When it is less than 30 ° C., offset resistance and heat-resistant storage stability may be deteriorated, and when it exceeds 50 ° C., low-temperature fixability may be deteriorated. The glass transition temperature can be measured using, for example, a TG-DSC system TAS-100 manufactured by Rigaku Corporation.

(Glass transition temperature of toner)
The glass transition temperature of the toner of the present invention is preferably designed to be 40 to 70 ° C. That is, if it is less than 40 ° C., the heat resistant storage stability is insufficient, and if it exceeds 70 ° C., the low-temperature fixability is adversely affected.

(Ratio of (Dv) to weight average particle diameter (Dv) and number average particle diameter (Dn) of toner)
The toner of the present invention preferably has a weight average particle diameter (Dv) of 3 to 8 μm, and the ratio (Dv / Dn) of the weight average particle diameter (Dv) to the number average particle diameter (Dn) is 1.00. It is preferably 1.25, more preferably 1.10 to 1.25. Thereby, a toner excellent in heat-resistant storage stability, low-temperature fixability and offset resistance can be obtained. At this time, when such a toner is used in a full-color copying machine or the like, an image having excellent gloss can be obtained. In addition, when such a toner is used for a two-component developer, even if the toner balance is maintained over a long period of time, the variation in the particle diameter of the toner in the developer can be reduced. In this stirring, good and stable developability can be obtained. Further, when such a toner is used as a one-component developer, fluctuations in the particle diameter of the toner can be reduced even if the toner is balanced. Furthermore, it is possible to suppress toner filming on the developing roller and fusion of toner to a member such as a blade for thinning the toner on the developing roller. ), Good and stable developability and images can be obtained.

  In general, it is said that the smaller the particle size of the toner, the more advantageous it is for high-resolution and high-quality image formation, but it is disadvantageous for transferability and cleaning properties. When the weight average particle size of the toner is smaller than 3 μm, in the two-component developer, the toner may be fused to the surface of the magnetic carrier due to long-term stirring in the developing device, and the charging ability of the magnetic carrier may be lowered. Further, when such a toner is used as a one-component developer, filming of the toner on the developing roller and fusion of the toner to a member such as a blade for thinning the toner on the developing roller occur. Sometimes.

  Further, when the weight average particle diameter of the toner is larger than 8 μm, it becomes difficult to form a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, Variations in particle size can be large. The same applies when Dv / Dn is greater than 1.25.

In the present invention, the weight average particle diameter and number average particle diameter of the toner are measured with a particle size measuring device Multisizer III (manufactured by Beckman Coulter, Inc.) at an aperture diameter of 100 μm, and analysis software Beckman Coulter Mutizer 3 Version 3.51 is used. It is obtained by analyzing using. The specific measurement method is shown below.
To a glass 100 ml beaker, 0.5 ml of a 10% by weight aqueous solution of an alkylbenzene sulfonate neogen SC-A (Daiichi Kogyo Seiyaku Co., Ltd.) and 0.5 g of toner are added as a surfactant. Stir in. Next, 80 ml of ion-exchanged water is added and then dispersed for 10 minutes with an ultrasonic disperser W-113MK-II (manufactured by Honda Electronics Co., Ltd.), and the resulting toner dispersion is measured using Multisizer III. At this time, Isoton III (manufactured by Beckman Coulter) is used as the measurement solution. During the measurement, the toner dispersion is dropped so that the concentration indicated by Multisizer III is 8 ± 2%. Thereby, the error of the obtained particle diameter can be made small.

(Average circularity of toner)
The average circularity of the toner particles in the present invention is preferably 0.90 to 1.00. With an irregularly shaped toner that is too far from the sphere, such as an average circularity of less than 0.90, satisfactory transferability and high-quality images without dust cannot be obtained. If the value exceeds 1.00, in a system that employs blade cleaning or the like, poor cleaning occurs on the photosensitive member and the transfer belt, causing stain on the image. For example, development / transfer with a low image area ratio results in a small amount of residual toner and poor cleaning does not become a problem. The image-formed toner may be generated as a transfer residual toner on the photosensitive member, and if accumulated, the image may be soiled. In addition, the charging roller that contacts and charges the photosensitive member may be contaminated, and the original charging ability may not be exhibited.
The average circularity can be measured using a flow type particle image analyzer (Flow Particle Image Analyzer).

(Organic solvent)
In the present invention, the organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner composition, but the boiling point is preferably less than 150 ° C. because it is easy to remove. Examples of such organic solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, methyl acetate, ethyl acetate, methyl ethyl ketone. , Acetone, tetrahydrofuran and the like, and can be used alone or in combination of two or more. The amount of the organic solvent used relative to 100 parts by weight of the toner composition is usually 40 to 300 parts by weight, preferably 60 to 140 parts by weight, and more preferably 80 to 120 parts by weight.

(Coloring agent)
In the present invention, known dyes and pigments can be used as the colorant. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow Iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sayred, p- Rollo-o-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 red, Lazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bituminous, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Gree Lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and the like, and these can be used alone or in combination of two or more.

  The content of the colorant in the toner is usually 1 to 15% by weight, and preferably 3 to 10% by weight.

  In the present invention, the colorant can also be used as a master batch combined with a resin. Examples of the resin used in the masterbatch or the resin kneaded with the masterbatch include a modified or unmodified polyester resin; a polymer of styrene such as polystyrene, poly (p-chlorostyrene), polyvinyltoluene, and the like; a styrene-p -Chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene- Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethacrylic acid Methyl copolymer, styrene-acrylic Ronitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid Resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination of two or more.

  The master batch is obtained by mixing and kneading the resin and the colorant under a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method in which an aqueous paste containing a colorant and water is mixed and kneaded together with a resin and an organic solvent, the colorant is transferred to the resin side, and the water and the organic solvent are removed, uses the wet cake of the colorant as it is. Can do. When mixing and kneading, a high shearing dispersion device such as a three-roll mill can be used.

(Release agent)
In the present invention, known release agents can be used, for example, polyolefin waxes such as polyethylene wax and polypropylene wax; long-chain hydrocarbons such as paraffin wax and sazol wax; having a carbonyl group A wax etc. are mentioned. Among these, a wax having a carbonyl group is preferable.
Examples of the wax having a carbonyl group include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecanediol diester. Polyalkanoic acid esters such as stearate; Polyalkanol esters such as tristearyl trimellitic acid and distearyl maleate; Polyalkanoic acid amides such as ethylenediamine dibehenyl amide; Polyalkylamides such as trimellitic acid tristearyl amide; Distearyl Examples thereof include dialkyl ketones such as ketones. Of these, polyalkanoic acid esters are preferred.
In this invention, melting | fusing point of a mold release agent is 40-160 degreeC normally, 50-120 degreeC is preferable and 60-90 degreeC is still more preferable. When the melting point is less than 40 ° C., the heat-resistant storage stability may be lowered, and when it exceeds 160 ° C., cold offset may occur during fixing at a low temperature.
Further, the melt viscosity of the release agent is preferably 5 to 1000 mPa · sec, and more preferably 10 to 1000 mPa · sec, as a measured value at a temperature 20 ° C. higher than the melting point. When the melt viscosity exceeds 1000 mPa · sec, the effect of improving offset resistance and low-temperature fixability may be reduced. The content of the release agent in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

(Charge control agent)
In the present invention, the toner may contain a charge control agent as required. As the charge control agent, known ones can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium Examples thereof include salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus or phosphorus compounds, tungsten or tungsten compounds, fluorine-based surfactants, 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, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (made of Hodogaya Chemical Co., Ltd.), quaternary ammonium salt Copy charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, boron complex LR-147 (Nippon Carlit) Made), copper phthalocyanine, perylene, quinacridone, azo face Other, sulfonic acid group, a carboxyl group, and a polymer compound having a quaternary ammonium salt or the like.

  In the present invention, the amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, the toner production method including the dispersion method, etc., and is not uniquely limited. It is preferable that it is 0.1 to 10 weight% with respect to resin, and 0.2 to 5 weight% is still more preferable. When the amount of the charge control agent used is less than 0.1% by weight, the chargeability of the toner is small, and the amount of adhesion to the electrostatic caustic image due to development is reduced, leading to a decrease in image density. On the other hand, if it exceeds 10% by weight, the chargeability of the toner increases and the effect of the main charge control agent may be diminished. Furthermore, the electrostatic attractive force with the developing roller increases, which may cause a decrease in developer fluidity and a decrease in image density. The charge control agent may be melt-kneaded with the master batch and the resin and then dissolved and dispersed, or may be added when dissolved or dispersed in an organic solvent, or may be fixed on the surface of the toner base particles. Good.

(External additive)
The toner of the present invention preferably contains inorganic particles as an external additive in order to assist fluidity, developability and chargeability. The primary particle diameter of the inorganic particles is preferably 5 nm to 2 μm, and particularly preferably 5 to 500 nm. Moreover, it is preferable that the specific surface area by BET method of an inorganic particle is 20-500 m < ² > / g. The amount of the inorganic particles used is preferably 0.01 to 5% by weight, particularly preferably 0.01 to 2% by weight, based on the toner base particles.
Specific examples of inorganic particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. , Chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like.
Examples of other external additives include polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylate ester copolymer, acrylate ester copolymer, silicone resin, benzoguanamine resin, nylon and the like. Examples thereof include polymer particles such as condensation systems and thermosetting resins.

When such an external additive is subjected to a surface treatment, the hydrophobicity of the surface can be improved, and a decrease in toner fluidity and chargeability can be suppressed even under high humidity. Examples of the surface treatment agent include silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. Can be mentioned.
The toner of the present invention can contain a cleaning property improving agent in order to easily remove the developer after transfer remaining on the photosensitive member or the primary transfer medium. Examples of the cleaning property improver include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, polymer particles produced by soap-free emulsion polymerization such as polymethyl methacrylate and polystyrene, and the like. The polymer particles preferably have a volume average particle size of 0.01 to 1 μm, and more preferably have a narrow particle size distribution.

(Toner production method)
In the present invention, the toner can be produced by the following method, but is not limited thereto.
First, a solution or dispersion obtained by dissolving or dispersing a composition containing a polyester resin, a polymer having a functional group capable of reacting with an active hydrogen group, a colorant, and a release agent in an organic solvent. After the liquid is dispersed in an aqueous medium, the polymer is subjected to an extension reaction and / or a crosslinking reaction to obtain a dispersion of toner base particles.

  The aqueous medium may be water alone, or a solvent miscible with water may be used in combination. Examples of such solvents include alcohols such as methanol, isopropanol and ethylene glycol, cellosolves such as dimethylformamide, tetrahydrofuran and methyl cellosolve, and lower ketones such as acetone and methyl ethyl ketone.

  The toner base particles are obtained by reacting a polymer having a site capable of reacting with an active hydrogen group in an aqueous phase. As a method for stably forming a dispersion containing a polyester resin and a polymer having a site capable of reacting with an active hydrogen group in an aqueous phase, a polyester resin dissolved or dispersed in an organic solvent, an active hydrogen group, Examples thereof include a method in which a polymer having a reactive site is added to an aqueous phase and dispersed by shearing force. Other toner compositions (hereinafter referred to as toner raw materials), a colorant, a colorant master batch, a release agent, a charge control agent, a binder resin, and the like are mixed when forming a dispersion in an aqueous phase. However, it is preferable that the toner raw materials are mixed in advance and dissolved or dispersed in an organic solvent, and then added to the aqueous phase and dispersed. In the present invention, the toner raw material is not necessarily mixed when forming the toner base particles in the aqueous phase, and may be added after the toner base particles are formed. For example, after forming toner base particles containing no colorant, the colorant can be added by a known dyeing method.

  A dispersion method is not particularly limited, and a known method such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, or an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing method is preferable. When using a high-speed shearing type disperser, the number of rotations is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but is usually 0.1 to 5 minutes in the case of a batch method. The temperature during dispersion (under pressure) is usually 0 to 150 ° C, preferably 40 to 98 ° C. If the temperature is less than 0 ° C., the toner composition viscosity may be increased and dispersion may become difficult.

  The amount of the aqueous medium used is usually 50 to 2000 parts by weight and preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the toner composition. When the amount of the aqueous medium used is less than 50 parts by weight, the dispersion state of the toner composition may be deteriorated. Moreover, when the usage-amount of an aqueous medium exceeds 20000 weight part, it is not economical. In the present invention, the aqueous medium preferably contains a dispersant as required. Thereby, the particle size distribution can be narrowed and the dispersion stability can be improved.

  Dispersing agents include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters, alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and amine salt type positive ions such as imidazoline. Ionic surfactant, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, quaternary ammonium salt type cationic surfactant such as benzethonium chloride, Nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, bis (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine Agent And the like.

In addition, it is preferable to use a surfactant having a fluoroalkyl group as the dispersant because the amount added can be reduced.
Examples of the anionic surfactant having a fluoroalkyl group include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonylglutamate, 3- (ω-fluoroalkyl (C6 to C11) oxy). -1-alkyl (C3-C4) sodium sulfonate, 3- (ω-fluoroalkanoyl (C6-C8) -N-ethylamino) -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carboxylic acid and its Metal salts, perfluoroalkyl carboxylic acids (C7 to C13) and their metal salts, perfluoroalkyl (C4 to C12) sulfonic acids and their metal salts, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- (2- Hydroxyethyl) perfluorooctance Examples include sulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, and the like. Commercially available products include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by DIC), Xtop EF-102, 103 , 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products Co., Ltd.), Footgent F100, F150 (manufactured by Neos), and the like.

  Examples of the cationic surfactant having a fluoroalkyl group include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. Group quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products include Surflon S-121 (manufactured by Asahi Glass Co., Ltd.), Florard FC-135 (manufactured by Sumitomo 3M Company), Unidyne DS-202 (manufactured by Daikin Industries, Ltd.), MegaFuck F-150, F-824 (manufactured by DIC Corporation). ), Ectop EF-132 (manufactured by Tochem Products), and Footgent F-300 (manufactured by Neos).

  As the dispersant, inorganic particles that are hardly soluble in water, such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite, can be used.

  Further, resin particles may be used as the dispersant. Examples of the resin particles include acrylic acids, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and other acids; β-hydroxyethyl acrylate , Β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, methacrylic acid 3 Hydroxy acids such as chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin monoacrylate, glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide (Meth) acrylic monomer having a group; vinyl alcohol such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether or ethers with vinyl alcohol; vinyl alcohol such as vinyl acetate, vinyl propionate, vinyl butyrate and carboxyl Esters of compounds having a group; acrylamide, methacrylamide, diacetone acrylamide and their methylol compounds; acid chlorides such as acrylic acid chloride and methacrylic acid chloride; vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine, etc. Having a nitrogen atom or a heterocyclic ring thereof, such as homo- or copolymers; polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene amine Polyamides such as kill amide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester; methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose And the like.

In the case where a compound that is soluble in an acid or alkali such as calcium phosphate is used as the dispersant, for example, the calcium phosphate is dissolved in an acid such as hydrochloric acid and then washed with water to form calcium phosphate from the toner base particles. Can be removed. In addition, it can also be removed by enzymatic degradation.
When a dispersant is used, it can be used as a toner in a state where the dispersant remains on the surface of the toner base particles. However, it is more preferable to remove the polyester resin by washing after removing the polyester resin from an elongation reaction and / or a crosslinking reaction. It is preferable from the viewpoint of the charging property.

  In order to remove the organic solvent from the dispersion of toner base particles, a method of gradually raising the temperature of the entire system and evaporating and removing the organic solvent in the droplets can be used. It is also possible to spray the dispersion of toner base particles in a dry atmosphere to remove the organic solvent in the droplets to form toner base particles and to evaporate and remove the dispersant. Examples of the dry atmosphere include heated gases such as air, nitrogen, carbon dioxide, and combustion gas, and various airflows heated to a temperature equal to or higher than the boiling point of the organic solvent used are generally used. By using a spray dryer, belt dryer, rotary kiln or the like, the desired quality can be obtained in a short time.

  In the present invention, when the particle size distribution of the toner base particles is wide and the washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying the toner base particles into a desired particle size distribution. Examples of the classification method before the drying treatment include a cyclone, a decanter, and centrifugal separation. Thereby, the fine particles can be removed. Further, the toner base particles may be classified after the drying treatment, but classification is preferably performed before the drying treatment in terms of efficiency.

  In the present invention, the dispersant is preferably removed from the dispersion of the toner base particles, but it is preferably performed simultaneously with the classification.

The toner of the present invention can be produced by mixing the toner base particles with different particles such as release agent particles, charge control agent particles, fluidizing agent particles, and colorant particles. At this time, by applying a mechanical impact force to the obtained mixture, it is possible to immobilize and coalesce foreign particles on the surface of the toner base particles, and to suppress detachment of the foreign particles from the toner surface. be able to.
Specific means include a method of applying an impact force to the mixture with blades rotating at high speed, a method of injecting and accelerating the mixture into a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. It is done. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron system (Manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

  In the present invention, the toner base particles can be used as they are.

The toner of the present invention can be used as a two-component developer by mixing with a magnetic carrier, and the content of the toner in the developer is 1 to 10 parts by weight with respect to 100 parts by weight of the magnetic carrier. It is preferable that
As a magnetic carrier, well-known things, such as iron powder with an average particle diameter of 20-200 micrometers, ferrite powder, and magnetite powder, can be used, and resin may be coat | covered on the surface.

  Coating resins include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, epoxy resin and other amino resins; acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral Polyvinyl and polyvinylidene resins such as polystyrene resins, polystyrene resins such as styrene acrylic copolymer resins, halogenated olefin resins such as polyvinyl chloride, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resins, polyethylene ; Polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, a copolymer of vinylidene fluoride and an acrylic monomer, Kka vinylidene copolymer of vinyl fluoride, fluorine-based resin terpolymers, etc. of tetrafluoroethylene and vinylidene fluoride and non-fluorinated monomer; and silicone resins.

  Further, the coating resin may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. In addition, it is preferable that the average particle diameter of electroconductive powder is 1 micrometer or less. When the average particle size is larger than 1 μm, it may be difficult to control electric resistance.

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

(Image forming method)
Next, an image forming method using the toner of the present invention will be described.
The image forming method of the present invention has at least an electrostatic charge image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, a recycling step, You may have a control process etc. further.

  The electrostatic charge image forming step is a step of forming an electrostatic charge image on the photoreceptor. The electrostatic charge image can be formed, for example, by charging the surface of the photosensitive member uniformly by applying a voltage using a charging device and then performing imagewise exposure using an exposure device. it can.

  The material, shape, structure, size and the like of the photoreceptor are not particularly limited and can be appropriately selected from known ones, but the shape is preferably a drum shape. Examples of the photoreceptor include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors (OPC) such as polysilane and phthalopolymethine. Amorphous silicon photoreceptors are preferable in terms of long life. .

The charging device is not particularly limited and can be appropriately selected depending on the purpose. For example, a known contact charger including a conductive or semiconductive roll, brush, film, rubber blade, Examples thereof include a non-contact charger using corona discharge such as corotron and scorotron. The charging device is preferably arranged in contact or non-contact with the photoreceptor, and charges the surface of the photoreceptor by applying a DC voltage and an AC voltage in a superimposed manner.
The charging device is a charging roller that is disposed in close proximity to the photoconductor via a gap tape, and charges the surface of the photoconductor by applying a DC voltage and an AC voltage superimposed on the charging roller. Those that do are preferred.

  The exposure apparatus is not particularly limited as long as it can image-wise expose the surface of the photoreceptor charged by the charging apparatus, and can be appropriately selected according to the purpose. Examples thereof include a rod lens array system, a laser optical system, and a liquid crystal shutter optical system. In addition, you may employ | adopt the light back system which performs imagewise exposure from the back surface side of a photoreceptor.

  The developing step is a step of forming a visible image by developing the electrostatic image with the toner of the present invention using a developing device.

  The developing device is not particularly limited as long as it can be developed using the toner of the present invention, and can be appropriately selected from known ones. For example, the developing device contains a developer composed of the toner of the present invention, Examples include those having at least a developer-carrying body capable of bringing a developer into contact or non-contact with an electrostatic charge image, and preferably including a developer-containing container in a detachable manner. The developing device may be either a single-color developing device or a multi-color developing device, and examples thereof include a stirrer that charges a developer by frictional stirring and a rotatable magnet roller. In the developing device, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. Since the magnet roller is disposed in the vicinity of the photoconductor, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the photoconductor by an electric attractive force. As a result, the electrostatic charge image is developed with toner, and a visible image is formed on the surface of the photoreceptor. Note that an alternating electric field is preferably applied when the toner is moved to the surface of the photoreceptor.

  The transfer process is a process in which a visible image (toner image) is transferred to a transfer medium using a transfer device. The transfer process is possible after first transferring the visible image onto the intermediate transfer body using an intermediate transfer body. A mode in which the visual image is secondarily transferred onto the transfer target is preferable. In addition, a primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer member using two or more colors, preferably full color toner, as the toner, and the composite transfer image on the transfer target An embodiment having a secondary transfer step of transferring is preferable. The visible image can be transferred by charging the photoconductor using, for example, a transfer charger.

  The transfer device preferably has a primary transfer device that transfers a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer device that transfers the composite transfer image onto a transfer target. The transfer device (primary transfer device, secondary transfer device) preferably has at least a transfer device that peels and charges the visible image formed on the photosensitive member toward the transfer target. There may be one transfer device or two or more transfer devices. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

  The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. Examples thereof include a transfer belt.

  The transfer target is not particularly limited, and can be appropriately selected from known recording media (recording paper, synthetic paper, resin film, etc.).

  The fixing step is a step of fixing the visible image transferred to the transfer target using a fixing device, and may be fixed for each color toner each time it is transferred to the transfer target. The toners may be fixed simultaneously at the same time in a state where the toners are laminated.

  The fixing device is not particularly limited and may be appropriately selected according to the purpose. However, a fixing device that is heat-pressed and fixed using a known fixing member is preferable. The fixing member is preferably in the form of a roller or a belt, and examples thereof include a combination of a heating roller and a pressure roller, and a combination of a heating roller, a pressure roller and an endless belt. At this time, it is preferable that heating temperature is 80-200 degreeC normally.

  In the present invention, the fixing device includes a heating body having a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film. It is possible to use means for heating and press-fixing by passing the transfer body on which the received image is formed.

  Depending on the purpose, for example, a known optical fixing device may be used together with the fixing device or instead of the fixing device.

  The neutralization step is a step of performing neutralization by applying a neutralization bias to the photoconductor using a neutralization device.

  The neutralization device is not particularly limited, and may be any one as long as it can apply a neutralization bias to the photosensitive member, and can be appropriately selected from known neutralization devices. Examples thereof include a neutralization lamp.

  The cleaning step is a step of removing toner remaining on the photoreceptor using a cleaning device.

  The cleaning device is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected from known cleaners. For example, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller A cleaner, a blade cleaner, a brush cleaner, a web cleaner, etc. are mentioned.

  The recycling process is a process in which the toner removed in the cleaning process is recycled to the developing device using a recycling apparatus.

  There is no restriction | limiting in particular in a recycling apparatus, For example, a well-known conveyance means etc. are mentioned.

  A control process is a process of controlling each process using a control device.

  The control device is not particularly limited as long as the movement of each step can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  Next, the image forming method of the present invention will be described with reference to FIG. The image forming apparatus shown in FIG. 1 includes a photosensitive member 10, a charging device 20, an exposure device 30, a developing device 40, an intermediate transfer member 50, a cleaning device 60 having a cleaning blade, a charge eliminating device 70, a transfer device. A device 80 is provided. Note that a charging roller is used as the charging device 20, a static elimination lamp as the static elimination device 70, and a transfer roller as the transfer device 80.

The intermediate transfer member 50 is an endless belt, and is designed to be stretched by three support rollers 51 arranged on the inner side thereof so as to be movable in the arrow direction. A part of the three support rollers 51 also functions as a transfer bias roller capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer member 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof. Further, a transfer device 80 capable of applying a secondary transfer bias for transferring a visible image (secondary transfer) to the transfer target 95 is disposed opposite to the transfer device 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the visible image on the intermediate transfer member 50 is in contact with the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. And the contact portion between the intermediate transfer body 50 and the transfer body 95.
Note that transfer paper is used as the transfer target 95.

  The developing device 40 includes a developing belt 41 as a developer carrier, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. ing. The developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K, and the developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The developing unit 45M includes a developer accommodating portion 42M, a developer supply roller 43M, and a developing roller 44M. The developing unit 45C includes a developer accommodating portion 42C, the developer supplying roller 43C, and the developing roller 44C. Yes. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

In this image forming apparatus, after the charging device 20 uniformly charges the photoconductor 10, the exposure device 30 exposes the photoconductor 10 imagewise to form an electrostatic image. Next, the developing device 40 supplies the developer to develop the electrostatic charge image formed on the photoconductor 10 to form a visible image.
The visible image is transferred (primary transfer) onto the intermediate transfer body 50 by the voltage applied from the support roller 51 and further transferred (secondary transfer) onto the transfer body 95. As a result, a transfer image is formed on the transfer target 95. The toner remaining on the photoconductor 10 is removed by the cleaning device 60, and the charge of the photoconductor 10 is removed by the charge eliminating lamp 70.

Next, another aspect of the image forming method of the present invention will be described with reference to FIG. The image forming apparatus shown in FIG. 2 has a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan around the photosensitive member 10, instead of the developing device 40 in the image forming apparatus shown in FIG. The developing unit 45C has the same configuration as that of the image forming apparatus shown in FIG.
In FIG. 2, the same components as those in the image forming apparatus shown in FIG. The same applies to FIGS. 3 and 4 described later.

  Next, another aspect of the image forming method of the present invention will be described with reference to FIG. The image forming apparatus shown in FIG. 3 is a tandem type color image forming apparatus. The image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

  The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15, and 16 and can rotate clockwise in FIG. 3. A cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. On the intermediate transfer member 50 stretched by the support roller 14 and the support roller 15, four image forming units 18 of yellow, cyan, magenta, and black are arranged opposite to each other along the conveying direction. A means 120 is arranged. An exposure device 21 is disposed in the vicinity of the image forming unit 120. The secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the image forming unit 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of support rollers 23, and the recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 are mutually connected. It is possible to touch. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt and a pressure roller 27 that is pressed against the fixing belt 26. A reversing device 28 for reversing the recording paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25 in order to form images on both sides of the recording paper.

  Next, formation of a full-color image (color copy) using the image forming unit 120 will be described. First, an original document is set on the document table 130 of the automatic document feeder (ADF) 400 or the automatic document feeder 400 is opened, and the original document is set on the contact glass 32 of the scanner 300. Close.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. When this happens, the scanner 300 is immediately driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33, and reflected light from the document surface is reflected by a mirror in the second traveling body 34. Further, the image is received by the reading sensor 36 through the imaging lens 35, and the original is read to obtain image information of black, yellow, magenta and cyan. Next, each image information is transmitted to each image forming unit 18 in the image forming means 120, and a visible image of each color of black, yellow, magenta and cyan is formed.

  As shown in FIG. 4, the image forming unit 18 includes a photoconductor 10, a charging device (no reference) for uniformly charging the photoconductor 10, and an exposure device 21, based on each image information. A developing device that develops an electrostatic charge image formed by exposing the photoconductor 10 to each other using each toner (black toner, yellow toner, magenta toner, and cyan toner) to form a visible image using each toner. (No code), a transfer charger (no code) for transferring a visible image onto the intermediate transfer member 50, a cleaning device (no code), and a charge eliminating device (no code) are provided, based on each image information Thus, a visible image of each color can be formed. Next, the visible images of the respective colors are sequentially transferred (primary transfer) onto the intermediate transfer body 50 that is rotated and moved by the support rollers 14, 15 and 16, and the visible images of the respective colors are superimposed to form a composite transfer image. It is formed.

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed the recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the paper feed roller 142 is rotated to feed out the recording paper on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual paper feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the recording paper. Then, the registration roller 49 is rotated in synchronization with the composite transfer image formed on the intermediate transfer member 50, and the recording paper is sent between the intermediate transfer member 50 and the secondary transfer device 22, so that the secondary transfer device. By transferring the composite transfer image onto the recording paper (secondary transfer) by 22, a color image is formed on the recording paper. The toner remaining on the intermediate transfer member 50 is removed by the cleaning device 17.

  The recording paper on which the color image is formed is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the composite transfer image is heated and pressed and fixed on the recording paper. Thereafter, the recording paper is switched by the switching claw 55 and discharged by the discharge roller 56 and is stacked on the discharge tray 57. Alternatively, it is switched by the switching claw 55 and reversed by the reversing device 28 and led to the transfer position again. After an image is formed also on the back surface, the sheet is discharged by the discharge roller 56 and stacked on the discharge tray 57.

(Process cartridge)
The process cartridge of the present invention includes an electrostatic charge image carrier on which an electrostatic charge image is formed, and a developing device that develops the electrostatic image formed on the electrostatic charge image carrier using the toner of the present invention. It is integrally supported and is detachable from the image forming apparatus main body. It should be noted that the process cartridge of the present invention may further support other means appropriately selected as needed.

  FIG. 5 shows an example of the process cartridge of the present invention. The process cartridge includes a photosensitive member 101 and includes a charging device 102, an exposure device 103, a developing device 104, a transfer device 106, and a cleaning device 107. These members can be the same as those used in the image forming apparatus described later.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In addition, a part means a weight part.

(Measuring method)
-Isocyanate group content The isocyanate group content was measured using the method defined in JIS K1603.
Specifically, after about 2 g of the modified polyester is precisely weighed, 5 ml of dry toluene is quickly added to completely dissolve the sample. Thereafter, 5 ml of a 0.1 M, n-dibutylamine / toluene solution is added using a pipette, and then gently stirred for 15 minutes. Further, 5 ml of isopropanol was added and stirred, and potentiometric titration was performed using a 0.1 M ethanolic hydrochloric acid standard solution. From the obtained titration value, the amount of dibutylamine consumed is calculated, and the isocyanate group content is calculated.

-Acid value The acid value was measured using the method prescribed | regulated to JISK0070. However, when the sample does not dissolve, a solvent such as dioxane or THF can be used as the solvent.

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

-Molecular weight The molecular weight of resin was measured on condition of the following using GPC (gel permeation chromatography).
Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
Temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 ml / min Sample: Using a molecular weight calibration curve created from a monodisperse polystyrene standard sample from the molecular weight distribution of a resin measured under conditions of 0.1 ml injection or more of a 0.05 to 0.6 wt% sample. The weight average molecular weight of the toner was calculated.
In addition, when measuring the molecular weight of the prepolymer having an isocyanate group, a sample in which the isocyanate group was sealed was prepared by adding 3-fold equivalent of dibutylamine to the isocyanate group, and used for GPC measurement. .

・ Glass transition temperature Tg
Tg was measured using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation).
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. Next, after heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, cooled to room temperature, left for 10 minutes, and again heated to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at ° C / 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.

Aging condition The reaction product after removing the organic solvent was changed at 45 ° C. by changing the amount of the tertiary amine compound added and the aging time with respect to the acid value of the reaction product after removing the organic solvent.

Production Example 1
(Synthesis of organic fine particles)
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of a sodium salt of sulfate ester of methacrylic acid ethylene oxide adduct (Eleminol RS-30, Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid Parts, 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. Next, the temperature in the system was raised to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% by weight 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, and a sodium salt of a sulfate ester of an ethylene oxide adduct of methacrylic acid). A dispersion (resin particle dispersion) was obtained. The volume average particle size of the resin particles obtained by measuring the resin particle dispersion with LA-920 (manufactured by Horiba, Ltd., laser diffraction particle size distribution analyzer) was 105 nm. When a part of the resin particle dispersion was dried to isolate the resin component, the glass transition temperature of the resin component was 59 ° C., and the weight average molecular weight was 150,000.

Production Example 2
(Preparation of aqueous phase)
By mixing and stirring 990 parts of water, 83 parts of a resin particle dispersion, 37 parts of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries) and 90 parts of ethyl acetate, milky white An aqueous medium ([aqueous phase 1]) was obtained.

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

Production Example 4
(Synthesis of intermediate polyester)
463 parts of propylene glycol, 657 parts of terephthalic acid, 96 parts of trimellitic anhydride and 2 parts of titanium tetrabutoxide are placed in a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe. The reaction was continued for 5 hours, and further [Intermediate Polyester 1] was reacted for 5 hours at a reduced pressure of 10-15 mmHg. [Intermediate Polyester 1] had a weight average molecular weight of 28000, Tg of 36 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 16.5 mgKOH / g.

(Prepolymer synthesis)
Next, 250 parts of [Intermediate polyester 1], 16.7 parts of isophorone diisocyanate, and 250 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. The isocyanate weight percent of [Prepolymer 1] was 0.52%.

Production Example 6
(Manufacture of master batch)
Add 1200 parts of water, 540 parts of carbon black (Printex 35, manufactured by Degussa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], 1200 parts of [low molecular weight polyester 1], Henschel mixer (manufactured by Mitsui Mining) The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

Production Example 7
(Production of oil phase)
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular polyester 1], 110 parts of Carnauba WAX, 22 parts of CCA (charge control agent, salicylic acid metal complex E-84: manufactured by Orient Chemical Industries), 947 parts of ethyl acetate Was heated to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw Material Solution 1] Transfer 1324 parts to a container and use a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.) and fill with 80% by volume of 0.5 mm zirconia beads using a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec. Carbon black and WAX were dispersed under conditions of 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50% by weight.

[Example 1]
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, and isophorone diamine 1.2 parts are put in a container and mixed with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at 5000 rpm for 1 minute. 1,200 parts of [Aqueous Phase 1] was added, and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsified Slurry 1]. [Emulsified slurry 1] was put into a container in which a stirrer and a thermometer were set, and after removing the solvent for 8 hours at 30 ° C., 20 parts of [U-CAT660M] (tertiary amine compound, manufactured by San Aho Pro Co., Ltd.) (50 % Mol) and aging was carried out at 45 ° C. for 3 hours to obtain [Dispersion Slurry 1]. [Dispersion Slurry 1] had a volume average particle size of 5.1 μm and a number average particle size of 4.4 μm (measured with Multisizer III).
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(2): 100 parts of distilled water was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(4): 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered twice to obtain [filter cake 1]. [Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved toner base 1 was obtained with a mesh opening of 75 μm. The acid value of the reaction product after removing the solvent was 19.4 mgKOH / g.
To 100 parts of the obtained toner base, 0.5 part of hydrophobic silica (R972, manufactured by Nippon Aerosil Co., Ltd.) and 0.5 part of hydrophobic titanium oxide (MT150AI, manufactured by Titanium Industry Co., Ltd.) were mixed with a Henschel mixer. Toner 1 was obtained.

[Example 2]
Toner base 2 in the same manner as in Example 1 except that 20 parts of [U-CAT660M] in Example 1 was changed to 13 parts (50% mol) of ZF-20 (tertiary amine compound, manufactured by Huntsman). Subsequently, toner 2 was obtained.

Example 3
A toner base 3 and then toner 3 were obtained in the same manner as in Example 1 except that 20 parts of [U-CAT660M] in Example 1 was changed to 5 parts (50% mol) of trimethylamine.

Example 4
A toner base 4 and then a toner 4 were obtained in the same manner as in Example 1 except that aging at 45 ° C. for 3 hours in Example 1 was performed for 2 hours.

Example 5
A toner base 5 and then a toner 5 were obtained in the same manner as in Example 1 except that 20 parts of [U-CAT660M] was changed to 15 parts (40% mol) in Example 1.

Example 6
In Example 1, the toner base 6 was obtained in the same manner as in Example 1 except that 20 parts of [U-CAT660M] was changed to 12 parts (30% mol) and aged for 3 hours at 45 ° C. for 5 hours. Toner 6 was obtained.

Example 7
In Example 1, a toner base 7 and then toner 7 were obtained in the same manner as in Example 1 except that 20 parts of U-CAT660M] were changed to 27 parts (70% mol).

[Comparative Example 1]
A toner base 8 and then a toner 8 were obtained in the same manner as in Example 1 except that 20 parts of [U-CAT660M] was changed to 8 parts (20% mol) in Example 1.

[Comparative Example 2]
A toner base 9 and then toner 9 were obtained in the same manner as in Example 1 except that 20 parts of [U-CAT660M] was changed to 40 parts (100% mol) in Example 1.

[Comparative Example 3]
A toner base 10 and then toner 10 were obtained in the same manner as in Example 1 except that 20 parts of [U-CAT660M] was changed to 0 part (0% mol) in Example 1.
In Comparative Example 3, aging for 10 hours was required to obtain a toner base equivalent to that in Example 1.

(Evaluation method)
-Heat-resistant storage stability After storing the toner at 50 ° C for 8 hours, the toner was sieved with a 42-mesh sieve for 2 minutes, and the residual ratio on the wire mesh was measured to evaluate the heat-resistant storage stability. In addition, the thing whose residual rate on a wire net is less than 10% is ◎, the thing which is 10% or more and less than 20% is ◯, the thing which is 20% or more and less than 30% is △, and the thing which is 30% or more is x. Judged.

・ Fixability Using an image forming apparatus imagio Neo 450 (manufactured by Ricoh), a solid image and a thick paper on a transfer paper type 6200 (manufactured by Ricoh) and copy printing paper <135> (manufactured by NBS Ricoh), Adjustment was made so that a toner of 0.0 ± 0.1 mg / cm ² was developed, and the fixing upper limit temperature at which no offset occurred on plain paper and the fixing lower limit temperature on thick paper were measured. The minimum fixing temperature is the temperature of the fixing roll at which the residual ratio of the image density after rubbing the developed image with a pad is 70% or more.

Charge amount Charge amount after charging 100 parts of a silicone resin coated ferrite carrier with an average particle size of 50 μm and 4 parts of toner up to 30% of the internal volume of the stainless steel pot and stirring at 100 rpm for 60 seconds and 10 minutes (charge amount 1 And 2) were determined by the blow-off method.

·strange picture
5 parts of the produced toner and 95 parts of the carrier described above were mixed in a blender for 10 minutes to produce a developer.
The developer was placed in a commercially available color copying machine (PRETER 550; manufactured by Ricoh Co., Ltd.), and after running 100,000 sheets of 6000 paper manufactured by Ricoh Co. at a printing ratio of 5%, the temperature was 30 ° C. and the humidity was 90%. %, An image for fine line evaluation was output, and filming due to inorganic fine particles on the photoreceptor was judged based on the degree of reproduction of the fine line. The higher the number of ranks, the better.
Rank 1 ··· Fine lines overlap and cannot be separated and identified Rank 2 ··· Fine lines overlap but can be separated and identified Rank 3 ··· Fine lines can be separated and identified but lines blur ： Bokeh can be seen Rank 4 ・ ・ ・ ・ Thin lines can be separated and identified, no blurring of lines, no blurring

(Evaluation results)
Table 1 shows the types of tertiary amine catalysts used for the production of the toner.

  Table 2 shows the evaluation results of the toner.

(Note) In the table, TMA in the row of added amine species represents trimethylamine.

From Table 2, it can be seen that the toner of the example in which the tertiary amine compound is added in a specific process has only a low fixing minimum temperature or a high fixing maximum temperature, and has good low-temperature fixability and hot offset resistance. It can also be seen that the charge amount is high and the fine line reproducibility is excellent, so that a high-quality image can be obtained.
On the other hand, when the tertiary amine compound is not added in the specific step, not only the fixing maximum temperature is low, but also the fine line reproducibility is not good, and even if the tertiary amine compound is added, If the amount added is too small, the upper limit temperature of fixing does not increase, or the reproducibility of fine lines is not good. If the amount is too large, the charge amount is low and the reproducibility of fine lines is not good. Is clear.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus in which a toner of the present invention is used. It is a schematic block diagram which shows the other example of the image forming apparatus in which the toner of this invention is used. 1 is a schematic configuration diagram illustrating an example of a tandem type image forming apparatus in which a toner of the present invention is used. FIG. 5 is a partially enlarged view of the tandem type image forming apparatus of FIG. 4. FIG. 3 is a schematic configuration diagram illustrating an example of a process cartridge in which the toner of the present invention is used.

Explanation of symbols

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 discharge tray 58 corona charger 60 cleaning device 61 developing device 62 transfer charger 63 photoconductor cleaning device 64 discharger 70 discharger lamp 80 transfer roller 90 cleaning device 95 transfer paper 100 image forming device 101 photoconductor 102 charging means 103 exposure 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 14 Feeding path 147 transport rollers 148 feed path 150 copier main body 200 feeder table 300 Scanner 400 automatic document feeder (ADF)

Claims (9)

At least in an organic solvent, a binder resin, a compound having an active hydrogen group, a polymer having a site capable of reacting with a compound having an active hydrogen group, a colorant, and a composition containing a release agent are dissolved or dispersed. The solution or dispersion is dispersed in an aqueous medium and the compound having the active hydrogen group is reacted with the polymer having a site capable of reacting with the compound having the active hydrogen group, or while reacting, the organic solvent was removed, washed, a manufacturing method of the electrostatic image developing preparative toner obtained by drying,
After removal of the organic solvent and before washing, the reaction product is ripened, and in the aging step, the tertiary amine compound is added in an amount of 30 to 70% mol based on the acid value of the reaction product after the organic solvent removal. method of producing an electrostatic charge image developing preparative toner which comprises adding. The manufacturing method of the electrostatic image developing preparative toner according to claim 1, wherein the polymer capable of reacting sites with a compound having an active hydrogen group is an isocyanate group. According to claim 1 or 2 The manufacturing method of the electrostatic image developing preparative toner according to, wherein said binder resin is a polyester resin. The manufacturing method of the electrostatic image developing preparative toner according to claim 3, wherein the glass transition temperature of the polyester resin (Tg) of a 30 to 50 ° C.. The process according to claim 1 to any electrostatic image developing preparative toner according to the 4 acid value of the reaction product after the organic solvent removal, characterized in that a 1~30mgKOH / g. The process according to claim 1 to the electrostatic image developing preparative toner according to any one of 5, wherein the glass transition temperature (Tg) of the toner is 40 to 70 ° C.. The process according to claim 1 to the electrostatic image developing preparative toner according to any one of 6, wherein the weight average particle size of the toner is 3 to 8 [mu] m. The manufacturing method of the electrostatic image developing preparative toner according to claim 7, wherein the weight-average particle diameter / number average particle diameter of the toner is 1.25 or less. The process according to claim 1 to the electrostatic image developing preparative toner according to any one of 8, wherein an average circularity of the toner is 1.00 to 0.90.

Images