JP2006078972A - Method for manufacturing toner for electrostatic image development and toner, developer, process cartridge and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for easily and profitably manufacturing a toner having an always stable volume average particle diameter and a sharp particle size distribution. <P>SOLUTION: A granulating apparatus with an emulsification dispersing machine and an emulsified liquid circulating/retaining section used in an emulsifying step of toner manufacture is preliminarily filled with an emulsified and/or dispersion liquid in which droplets have a volume average particles diameter D<SB>p</SB>v adjusted to 2-7 μm and a D<SB>p</SB>v to number average particle diameter D<SB>p</SB>n ratio (D<SB>p</SB>v)/(D<SB>p</SB>n) adjusted to 1.05-1.30. An oily phase containing at least a binder resin and a colorant in an organic solvent and an aqueous phase are continuously fed into the apparatus and granulated into particles, and the particles are treated to manufacture the objective toner. A polyester resin is used as the binder resin. The toner has a volume average particles diameter D<SB>t</SB>v adjusted to 3-6 μm and a D<SB>t</SB>v to number average particle diameter D<SB>t</SB>n ratio (D<SB>t</SB>v)/(D<SB>t</SB>n) adjusted to 1.05-1.25. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing an electrostatic charge image developing toner for visualizing an electrostatic charge image formed on the surface of a latent image carrier such as a photoreceptor in electrophotography and electrostatic recording, and the like. The present invention relates to a manufactured toner, a developer using the toner, a process cartridge using the developer, and an image forming apparatus.

  In the developing process, a developer used in electrophotography, electrostatic recording, electrostatic printing, and the like is once attached to an image carrier such as a photoreceptor on which an electrostatic charge image is formed, and then transferred to a transfer process. After being transferred from the photoconductor to a transfer medium such as transfer paper, the toner is fixed on the paper surface in a fixing step. At that time, as a developer for developing the electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer that does not require a carrier (magnetic toner, Non-magnetic toners are known. Conventionally, as dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like, toner binders such as styrene resins and polyesters are melt-kneaded together with colorants and finely pulverized.

As a countermeasure for obtaining a high-quality, high-quality image, a method of improving by reducing the particle diameter of the toner is used. However, in the production method by the usual kneading and pulverization methods, the particle shape is indefinite, and when used as a one-component developer, stirring with a carrier in the developing section of the apparatus, a developing roller and a toner supply roller, The toner is further pulverized by contact stress with a layer thickness regulating blade, a frictional charging blade, or the like, and extremely fine particles are generated or a fluidizing agent is embedded in the toner surface, resulting in a decrease in image quality.
In addition, since the shape is irregular, the fluidity of the powder is poor, requiring countermeasures to enhance fluidization, and the filling rate into the toner bottle is low, which is an obstacle to downsizing. ing. Therefore, the current situation is that the merit of reducing the particle size is not utilized.

In addition, there is a limit to the particle size that can be produced by the pulverization method, and it is not possible to cope with further reduction in particle size. Various spherical toner manufacturing methods such as suspension polymerization and emulsion aggregation have been devised to compensate for the disadvantages of the irregular shape effect and to obtain a small toner particle size and sharp particle size distribution. Yes.
However, in general, when the binder resin component is obtained by the suspension polymerization method and the emulsion aggregation method, generally, a batch reaction, for example, a reaction such as radical polymerization of styrene-acryl, is involved. In addition, there is a problem that it takes time until the particles are formed including cooling, and further, a fixed matter is generated in the reaction tank, and there are many problems in terms of productivity. Furthermore, when the binder resin component is a styrene-acrylic resin, there remains a problem with respect to a high level of low-temperature fixability.

  On the other hand, an organic solvent solution of a mixture containing a colorant and a binder resin as essential components and an aqueous medium are emulsified using a continuous emulsifying disperser to form colored resin fine particles, and then the organic solvent is removed, aqueous A method of taking out colored resin fine particles dispersed in a solvent as a dry powder has been proposed (see, for example, Patent Document 1).

  However, in the above transfer emulsification, it is difficult to form particles having a sharp particle size distribution, and in order to obtain particles having a sharp particle size distribution, a plurality of emulsifiers or a series of emulsifiers are connected in series. These are not preferable methods from the viewpoints of cost and maintainability.

  In addition, when the toner composition mixed solution in which the binder resin and the colorant are dissolved or dispersed in the solvent and the aqueous medium are continuously supplied to the emulsifier to form a suspension, the toner composition mixed liquid and the aqueous medium are mixed. The toner is manufactured so that the ratio (B / A) between the total supply amount A and the suspension amount B per unit time passing through the stirring section of the emulsifier obtained by a separate experiment is 5 or more and 500 or less. Has been proposed (see, for example, Patent Document 2).

  However, if the toner composition mixture and the aqueous medium are continuously supplied and suspended in the stirring section, the suspension staying in the emulsifier becomes non-uniform, and it takes time to obtain uniform particles. There's a problem. Further, in order to obtain particles having a sharp particle size distribution, it is considered that a non-uniform suspension at the initial stage of suspension needs to be discarded.

Japanese Patent Laid-Open No. 9-297431 JP 2001-255695 A

  The present invention has been made in view of the above-described prior art, and an easy and lean manufacturing method of a toner having a stable volume average particle diameter and a sharp particle size distribution, and a long-term obtained by the manufacturing method. Another object of the present invention is to provide a toner having a good developability and capable of forming a high-quality image, a developer, a process cartridge, and an image forming apparatus. Furthermore, the toner in the present invention is intended to be compatible with an energy-saving fixing device.

As a result of intensive studies, the present inventors have previously determined a volume average particle diameter (D _p v) of droplets in a granulator equipped with an emulsifying disperser and an emulsion circulation / retention unit used in an emulsification process of toner production. , and _{D p} v and the number average particle diameter _(D p n) ratio _{(D p v / D p n} ) a predetermined value to separately adjust prepare emulsified and / or dispersion (hereinafter the "emulsion-dispersion The oil phase and water phase that have been fully filled in advance by liquid feeding are emulsified and / or dispersed (hereinafter referred to as “emulsification / dispersion”). After the droplet diameter is adjusted in the same manner, the oil phase and the aqueous phase are fed to dispose of the non-uniform emulsification / dispersion at the initial stage of emulsification / dispersion. The present invention has been found out that continuous emulsification and dispersion are possible without any problems, and the above-mentioned problems can be solved. Hereinafter, the present invention will be specifically described.

That is, the granulating apparatus provided with an emulsifying disperser and an emulsified liquid circulation / retention part used in the emulsification process of toner production comprises at least a binder resin and / or a resin precursor, an oil phase containing a colorant and an aqueous medium. In the method for producing a toner for developing an electrostatic image in which an aqueous phase is fed to form droplets,
In said granulator, pre volume average particle diameter of the droplets _(D p v) is at 2-7 [mu] m, said _{D p} v and the ratio _(D p of the number average particle diameter _{(D p n) v / D} p n ) Is fully charged with the emulsified and / or dispersed liquid adjusted to 1.05-1.30, and then the oil phase and the aqueous phase are continuously fed. This is a method for producing an image developing toner.

In addition, the granulator equipped with an emulsifying disperser used in the emulsification step of toner production and an emulsion circulation / retention part is composed of an oil phase containing at least a binder resin and / or a resin precursor and a colorant and an aqueous medium. In the method for producing a toner for developing an electrostatic image in which an aqueous phase is fed to form droplets,
In the granulator, the oil phase and the aqueous phase in a full amount are fed in advance and emulsified and dispersed. The volume average particle diameter (D _p v) of the droplets is 2 to 7 μm, and D _p v and after the ratio of the number average particle diameter _{(D p n) (D p} v / D p n) is obtained by the emulsification and / or dispersion of 1.05 to 1.30, the liquid feed of the oil and water phases A method for producing a toner for developing an electrostatic charge image, which is continuously performed.

Furthermore, the present invention relates to an oil phase and an aqueous medium containing at least a binder resin and a colorant in an organic solvent in a granulating apparatus provided with an emulsifying disperser and an emulsion circulation / retention part used in an emulsification step of toner production. In the method for producing a toner for developing an electrostatic image in which droplets are formed by feeding a water phase comprising:
In said granulator, pre volume average particle diameter of the droplets _(D p v) is at 2-7 [mu] m, said _{D p} v and the ratio _(D p of the number average particle diameter _{(D p n) v / D} p n ) Is fully charged with the emulsified and / or dispersed liquid adjusted to 1.05-1.30, and then the oil phase and the aqueous phase are continuously fed. This is a method for producing an image developing toner.

Further, the present invention provides an oil phase and an aqueous medium containing at least a binder resin and a colorant in an organic solvent in a granulating apparatus provided with an emulsifying disperser and an emulsion circulation / retention unit used in an emulsification step of toner production. In the method for producing a toner for developing an electrostatic image in which droplets are formed by feeding a water phase comprising:
In the granulator, the oil phase and the aqueous phase in a full amount are fed in advance and emulsified and dispersed. The volume average particle diameter (D _p v) of the droplets is 2 to 7 μm, and D _p v and after the ratio of the number average particle diameter _{(D p n) (D p} v / D p n) is obtained by the emulsification and / or dispersion of 1.05 to 1.30, a liquid feed of said oil and water phases A method for producing a toner for developing an electrostatic charge image, which is continuously performed.

  Here, in any one of the above methods for producing a toner for developing an electrostatic image, it is preferable that the binder resin contains a polyester resin.

  The present invention also relates to an electrostatic image developing toner obtained by any one of the production methods described above.

  Here, the acid value of the toner is preferably 0.5 to 40.0 (KOH mg / g).

  In any of the above toners, the toner preferably has a glass transition point of 40 to 65 ° C.

Then, the in any one of the toner, the toner having a volume average particle diameter (D t _v) is preferably a 3 to 8 [mu] m.

Further, it is preferable that the ratio of the toner having a volume average particle diameter _(D t v) and number average particle diameter _{(D t n) (D t} v / D t n) is 1.05 to 1.25.

  In any one of the toners, the average circularity of the toner is preferably 0.92 to 1.00.

Furthermore, in any one of the toners, it is preferable that the BET specific surface area of the toner is 1.0 to 6.0 m ² / g.

  The present invention is a developer for developing an electrostatic latent image formed on a latent image carrier, and the developer is a single component using any one of the electrostatic image developing toners described above. The present invention relates to a developer characterized by being a developer.

  The present invention also relates to a developer for developing an electrostatic latent image formed on a latent image carrier, the developer comprising a magnetic carrier and the electrostatic image developing toner described above. The present invention relates to a developer characterized by being a two-component developer.

  Further, the present invention is a developing device for developing and developing an electrostatic latent image on a latent image carrier by carrying and transporting the developer by the developer carrier and forming an electric field at a position facing the latent image carrier. The developer is one of the above-described developers, and relates to a developing device.

  The present invention also includes at least a latent image carrier that carries a latent image, and a developing unit that supplies toner to the electrostatic latent image formed on the surface of the latent image carrier to visualize the latent image. The process cartridge is supported by the image forming apparatus and is detachably formed on the main body of the image forming apparatus, wherein the developing means is the developing apparatus described above.

  According to another aspect of the present invention, there is provided an image forming apparatus including a process cartridge which is detachably attached to the main body of the image forming apparatus, wherein the process cartridge is the process cartridge described above. The present invention relates to an image forming apparatus.

According to the production method of the present invention, the volume average particle diameter (D _p v) of the droplets, D _p v and the number average particle diameter (D _p n) are previously added to the granulator used in the emulsification step of toner production. continuous oil phase and the aqueous phase is fed by a state ratio _{(D p v / D p n} ) is emulsified adjusted to a predetermined value and / or dispersion (emulsion-dispersion) is satisfied in) In this case, since emulsification and / or dispersion (emulsification / dispersion) is performed, it is not necessary to discard a non-uniform emulsification / dispersion liquid at the initial stage of emulsification / dispersion, and waste and efficiency reduction are avoided.
The granulator can easily and efficiently produce a toner having a stable volume average particle size and a sharp particle size distribution, and can form a high-quality image with good developability over the long term. Toner can be provided. The obtained toner is suitable for a fixing device capable of achieving energy saving, and a high-quality image can be formed by a developing device using the toner, a process cartridge, and an image forming apparatus equipped with the developing device.

As described above, in the present invention, the granulation apparatus used in the emulsification step of toner production is preliminarily provided with a volume average particle diameter (D _p v) of droplets, and D _p v and number average particle diameter (D _p n). feeding ratio of _{(D p v / D p n} ) were adjusted to a predetermined value, so-called in at least an emulsified state or dispersed state in advance satisfy the emulsification and / or dispersion, thereafter in the oil phase and water phase To produce a toner having a volume average particle size and a sharp particle size distribution.
The resin precursor used in the present invention may be a monomer component, and “emulsification” includes “emulsion polymerization”.

Preferred embodiments of the present invention will be described below with reference to the drawings.
FIG. 1 is a schematic configuration diagram showing an example of a granulating apparatus used in an emulsification step of toner production according to the present invention. In FIG. 1, the granulating device 4 is composed of an emulsifier-dispersing machine (PLHM) 2 and an emulsion liquid circulation / retention unit 3. That is, in the granulating device 4, the oil phases 7, 8 and the aqueous phase 9 supplied from the supply tanks 17, 18, 19 of each phase are mixed and stirred to be emulsified and dispersed to form droplets (granulate). The

The A oil phase 7 and the B oil phase 8 are pre-stirred with an STM (static mixer) 5 before being mixed with the aqueous phase 9. The liquid after the pre-stirring is called an oil phase. The oil phase mixed in STM 5 and the aqueous phase 9 are mixed, and the volume of the emulsion circulation / retention part 3 of the granulating device 4, the so-called area where the emulsion / dispersion stays (hereinafter referred to as hold-up). The emulsifying and dispersing machine (PLHM) 2 installed in the inside is subjected to shearing to emulsify and disperse.
Here, the oil phase is a dissolved or dispersed dispersion in which toner components (binder resin, colorant, etc.) are dissolved in an organic solvent, and the aqueous phase is, for example, an aqueous system containing a solid resin fine particle dispersant. It is a medium. Note that PLHM is an abbreviation for pipeline homomixer. Reference numeral 6 denotes a solvent removal tank for removing the organic solvent in the emulsified / dispersed liquid.

In the embodiment of FIG. 1, an example is shown in which the binder resin raw material corresponding to the toner composition is supplied separately to the A oil phase 7 and the B oil phase 8. Here, the A oil phase 7 is an active hydrogen that undergoes an addition reaction with a prepolymer of the B oil phase 8 in a liquid in which a toner composition containing at least a binder resin and a colorant is dissolved or dispersed in an organic solvent. Compound B), and the B oil phase 8 is, for example, a prepolymer having an isocyanate bond. In addition, the aqueous phase 9 is an aqueous medium in which a solid resin fine particle dispersing agent partially dissolved in an aqueous medium is present, for example. Details of each oil phase composition and water phase will be described later.
However, when the oil phase and the aqueous phase 9 are continuously metered, and the emulsification / dispersion liquid (PLHM) 2 is applied with a shearing force to emulsify and disperse, the emulsification / dispersion liquid staying in the hold-up is obtained. Since it becomes non-uniform and it takes time to obtain uniform particles, the non-uniform emulsification / dispersion at the initial stage of emulsification / dispersion must be discarded.

Therefore, in the present invention, in a hold-up, pre volume average particle diameter of the droplets _(D p v) is at 2-7 [mu] m, and _{D p} v and the number average particle diameter _(D p n) of the ratio _(D p v / _D p n) satisfies fills the emulsification and dispersion that satisfies 1.05 to 1.30 (full fill) or the amount that can be charged in the hold-up the oil phase and the aqueous phase 9 ( (Full filling), and after adjusting the emulsion / dispersion liquid droplets with the emulsifier-dispersing machine (PLHM) 2, each phase is continuously quantitatively fed to receive a new shearing force with the PLHM 2. oil phase and a mixture of water phase 9, that is, quickly generated new emulsification and dispersion stable and the volume average particle diameter of the droplets (D _e v) is 3~8μm next, D _e v and the number the ratio of the average particle diameter _{(D e n) (D e} v / D e n) is found to be a 1.05-1.25.

The emulsion or dispersion obtained as described above becomes toner base particles through the steps of solvent removal, washing and drying.
The toner obtained through these steps is in the range volume average particle size of interest _(D t v) is _{3~8μm, D t v / D t} n is uniform 1.05-1.25 It is a particle and is suitable for a fixing device that can achieve energy saving, and can form a high-quality image with good developability over the long term.

In addition, the resin precursor contained in the oil phase in the toner for developing an electrostatic charge image of the present invention may be a monomer component as described above, or may be resinized by a reaction such as emulsion polymerization. In order to obtain a toner having excellent low-temperature fixability, hot offset resistance, and heat-resistant storage stability, it is preferable to use a polyester resin as the binder resin.
In order to maintain heat-resistant storage stability while having low-temperature fixability and hot offset resistance, it is important to adjust the weight average molecular weight (Mw) of the polyester resin. The weight average molecular weight of the minute is preferably designed to be 1,000 to 30,000, and the weight average molecular weight when the low temperature fixability is more important is more preferably in the range of 1,000 to 20,000. That is, if it is less than 1,000, the oligomer component increases, so that the heat-resistant storage stability is deteriorated, and if it exceeds 30,000, the melting temperature becomes high and the low-temperature fixability is deteriorated.

The molecular weight of the polyester resin is measured by GPC (gel permeation chromatography) as follows.
<Measurement method>
Stabilize the column in a heat chamber at 40 ° C., flow THF at a flow rate of 1 ml / min through the column at this temperature, and prepare a THF sample solution of resin prepared at a sample concentration of 0.05 to 0.6% by weight. Is measured by injecting 50 to 200 μl. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the prepared calibration curve and the number of counts using several types of monodisperse polystyrene standard samples.

Examples of the standard polystyrene sample for creating the calibration curve include, for example, Pressure Chemical Co. Alternatively Toyo Soda Kogyo Co., Ltd. having a molecular weight of ^{6 × 10 2, 2.1 × 10} 3, 4 × 10 3, 1.75 × 10 4, 5.1 × 10 4, 1.1 × 10 5, 3.9 It is appropriate to use x10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

  In the toner of the present invention, the above polyester resin is used as a binder resin, and a polymer having a site capable of reacting with a compound having an active hydrogen group, which will be described in detail later (hereinafter referred to as “prepolymer”), is mixed. Can be manufactured. By mixing this prepolymer with a compound having an active hydrogen group, an elongation or a crosslinking reaction can be performed in the toner production process, and the above-described toner characteristics can be improved.

According to a further study of the present invention, the acid value of the toner is important for low-temperature fixability and hot offset resistance. The acid value of the toner is preferably 0.5 to 40.0 (KOH mg / g). When the acid value of the toner exceeds 40.0 (KOHmg / g), the prepolymer elongation or crosslinking reaction becomes insufficient, affecting the hot offset resistance, and less than 0.5 (KOHmg / g). In this case, the elongation or crosslinking reaction of the prepolymer is likely to proceed, causing a problem in production stability.
In addition, the measuring method of the acid value of a polyester resin is based on the method based on JISK0070. However, if the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.

The glass transition point of the toner is preferably 40 to 65 ° C. in order to obtain low temperature fixability, heat resistant storage stability and high durability. If the glass transition point is less than 40 ° C., toner blocking and filming on the photoreceptor are likely to occur in the developing machine, and if it exceeds 65 ° C., the low-temperature fixability tends to deteriorate.
The glass transition point (Tg) is measured with a Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation at a temperature increase rate of 10 ° C./min.

Toner having a volume average particle diameter of the present invention _(D t v) is preferably from 3 to 8 [mu] m, The ratio of the number average particle diameter and volume average particle diameter _{(D t v) (D t} n) (D _t v _{/ D t} n) is in the range of 1.05 to 1.25, further preferred.
By defining the D t _{v /} D t _n Thus, it is possible to obtain high resolution, the toner of high quality. In order to obtain a higher quality image, the _{D t} v and 3 to 7 [mu] _m, the _{D t} v / D t n to 1.05 to 1.20, and the following particle 3μm in% by number from 1 to 10 well to the number%, more preferably, the _{D t} v and 3 to 6 [mu] _m, it is preferable to _{D t} v / D t n to 1.05 to 1.15.

  The toner whose particle size has been adjusted as described above is excellent in all of heat-resistant storage, low-temperature fixability, and hot offset resistance, and particularly excellent in image gloss when used in a full-color copying machine. In the developer, even if the toner balance for a long period of time is performed, fluctuations in the particle size of the toner in the developer are reduced, and good and stable developability can be obtained even with long-term stirring in the developing device.

  For the average particle size and particle size distribution of the toner, a Coulter Counter TA-II type was used, and an interface (manufactured by Nikka Giken) that outputs the number distribution and volume distribution was connected to a PC 9801 personal computer (manufactured by NEC). It is a measured value.

  The toner of the present invention preferably has an average circularity of 0.92 to 1.00. Thereby, a high-definition image with an appropriate image density can be formed with good reproducibility. If the average circularity is less than 0.92, it is difficult to obtain a satisfactory transferability and a high-quality image free from dust.

The average circularity of the toner can be measured by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.).
<Measurement method>
As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkyl benzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and a measurement sample is further added. About 0.1 to 0.5 g. The suspension in which the sample is dispersed is obtained by performing a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

The toner of the present invention preferably has a BET specific surface area of 1.0 to 6.0 (m ² / g). If the BET specific surface area is less than 1.0 (m ² / g), the image quality deteriorates due to the presence of coarse particles and inclusion of additives. On the other hand, if it exceeds 6.0 (m ² / g), the image quality deteriorates due to the presence of fine particles, the emergence of additives, and surface irregularities.

  Note that the BET specific surface area of the toner is measured using a device capable of complying with JIS standards (Z8830 and R1626) such as NOVA series manufactured by Yuasa Ionics.

Next, materials used for the toner of the present invention will be described in detail.
The polyester resin is obtained by polycondensation of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC). Examples of the polyhydric alcohol (PO) include dihydric alcohol (DIO) and trihydric or higher polyhydric alcohol (TO). (DIO) alone or a mixture of (DIO) and a small amount of (TO) is preferable. .

  As the dihydric alcohol (DIO), alkylene glycol (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (Eg, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (eg, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenol (Eg, bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxides of the above alicyclic diols (eg, ethylene oxide, propylene oxide) De, butylene oxide) adducts, alkylene oxide of the bisphenols (e.g., ethylene oxide, propylene oxide, and the like butylene oxide, etc.) adducts.

  The trihydric or higher polyhydric alcohol (TO) is a trihydric or higher polyhydric aliphatic alcohol (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); Phenols (for example, trisphenol PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or higher polyphenols and the like.

  Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC). (DIC) alone and (DIC) with a small amount of (TC) Mixtures are preferred.

  Divalent carboxylic acids (DIC) include alkylene dicarboxylic acids (eg, succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (eg, maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (eg, phthalic acid) , Isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). 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 polyvalent carboxylic acid (TC) include aromatic polyvalent carboxylic acids having 9 to 20 carbon atoms (for example, trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the acid anhydride or lower alkyl ester (For example, methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing. .

  The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  The prepolymer used in the present invention is preferably a polyester-based prepolymer (A) containing an isocyanate group, and is a polycondensate of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC) and having an active hydrogen group. Can be obtained by further reacting with polyisocyanate (PIC). In this case, examples of the active hydrogen group of the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

  Examples of the polyhydric alcohol (PO) include the same compounds as those used in the production of the polyester resin. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols. Particularly preferred are alkylene oxide adducts of bisphenols and combinations of these with alkylene glycols having 2 to 12 carbon atoms.

  Examples of the polyvalent carboxylic acid (PC) include the same compounds as those used in the production of the polyester resin. Among these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatics having 8 to 20 carbon atoms. Group dicarboxylic acid.

  The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyvalent isocyanate (PIC) include aliphatic polyisocyanates (eg, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate); alicyclic polyisocyanates (eg, isophorone diisocyanate, cyclohexyl). Aromatic diisocyanates (eg, tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (eg, α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; What blocked polyisocyanate with a phenol derivative, oxime, caprolactam, etc .; and these 2 or more types combined use is mentioned.

  When the polyester-based prepolymer (A) having an isocyanate group is obtained, the ratio of the polyvalent isocyanate (PIC) to the polyester-based resin (PE) having active hydrogen is determined by the ratio of the isocyanate group [NCO] and the hydroxyl group of the polyester having a hydroxyl group. The equivalent ratio [NCO] / [OH] to [OH] is usually 5/1 to 1/1, preferably 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 /. 1. The content of the polyvalent isocyanate (PIC) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. %.

  Next, polyamines and / or amines having active hydrogen groups are used as the amines (B), which are compounds having active hydrogen groups, which are reacted with the prepolymer (A). The active hydrogen group in this case includes a hydroxyl group and a mercapto group. Examples of such amines (B) include diamine (B1), trivalent or higher polyvalent amine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and amino acids B1 to B5. What blocked the group (B6) etc. are mentioned.

  Examples of the diamine (B1) include aromatic diamines (eg, phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane); alicyclic diamines (eg, 4,4′-diamino-3,3′-dimethyl). Dicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc.); and aliphatic diamines (eg, ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.).

  Examples of the trivalent or higher polyvalent amine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.

  Examples of the B1-B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1-B5 amines and ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). . Among these amines (B), preferred are (B1) and a mixture of (B1) and a small amount of (B2).

  Furthermore, when making a prepolymer (A) and amines (B) react, the molecular weight of the isocyanate modified polyester produced | generated using an elongation terminator can be adjusted if necessary. Examples of the elongation terminator include monoamines having no active hydrogen groups (for example, diethylamine, dibutylamine, butylamine, laurylamine), and those in which they are blocked (for example, ketimine compounds). The addition amount is appropriately selected in relation to the molecular weight desired for the urea-modified polyester to be produced.

  The ratio of the amines (B) and the prepolymer (A) having an isocyanate group is such that the isocyanate group [NCO] in the prepolymer (A) having an isocyanate group and the amino group [NHx] in the amine (B). The equivalent ratio [NCO] / [NHx] (where x is a number from 1 to 2) is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1 2/1 to 1 / 1.2.

In the present invention, if the acid value and glass transition point (Tg) of the toner are within the specified ranges, resins other than the polyester resin can be used as the binder resin in blend use.
Examples of usable resins other than polyester resins include the following.

  Polystyrene, chloropolystyrene, poly α-methylstyrene, styrene / chlorostyrene copolymer, styrene / propylene copolymer, styrene / butadiene copolymer, styrene / vinyl chloride copolymer, styrene / vinyl acetate copolymer, styrene / Maleic acid copolymer, styrene / acrylic acid ester copolymer (for example, styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, styrene / octyl acrylate) Copolymer, styrene / phenyl acrylate copolymer, etc.), styrene / methacrylate copolymer (eg, styrene / methyl methacrylate copolymer, styrene / ethyl methacrylate copolymer, styrene / butyl methacrylate copolymer). Polymer, Styrene / Phenol methacrylate Copolymer), styrene resins such as styrene / α-chloroacrylate copolymer, styrene / acrylonitrile / acrylate ester copolymer (for example, homopolymer or copolymer containing styrene or styrene-substituted product) Etc.), vinyl chloride resin, styrene / vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyethylene resin, polypropylene resin, ionomer resin, polyurethane resin, silicone resin, ketone resin, ethylene / ethyl acrylate Polymers, xylene resins, polyvinyl butyral resins, etc., petroleum resins, hydrogenated petroleum resins, and the like. The method for producing these resins is not particularly limited, and any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used.

  As the colorant, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, Yellow lead, Titanium yellow, Polyazo yellow, Oil yellow, Hansa yellow (GR, A, RN, R), Pigment yellow L, Benzidine yellow (G, GR), Permanent yellow (NCG), Vulcan fast yellow (5G, R) ), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Se Red, Parachlor Ortonito Aniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min 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, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red Polyazo Red, Chrome Vermillion, 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, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Lid Russian nin green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

The colorant used in the present invention can also be used as a master batch combined with a resin.
As a binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the above-mentioned polyester resin, styrene such as polystyrene, poly p-chlorostyrene and polyvinyltoluene, and a polymer of its substitution product; styrene-p-chloro Styrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-acrylic acid Butyl copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer Polymer, styrene-a Lilonitrile 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, polyester, 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 used, and these can be used alone or in combination.

  The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant under high shear. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. A so-called flushing method in which an aqueous paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, the colorant is transferred to the resin side, and moisture and organic solvent components are removed is also known as a colorant. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

  Further, a wax can be contained together with the binder resin and the colorant. As the wax used in the present invention, known waxes can be used, for example, polyolefin wax (for example, polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (for example, paraffin wax, sazol wax, etc.); carbonyl group Examples thereof include waxes.

  Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (for example, carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1 , 18-octadecane diol distearate); polyalkanol esters (eg, tristearyl trimellitic acid, distearyl maleate); polyalkanoic acid amides (eg, ethylenediamine dibehenyl amide); polyalkylamides (eg, Trimellitic acid tristearyl amide, etc.); and dialkyl ketones (eg, distearyl ketone, etc.).

Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C.
A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps (5 to 1000 mPa · s), more preferably 10 to 100 cps (10 to 100 mPa · s) as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cp (1000 mPa · s) s are poor in improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

The toner of the present invention may contain a charge control agent as necessary.
Any known charge control agent can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified) Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives.

  Specifically, 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, LR-147 which is a boron complex (Nippon Carlit) ), Copper phthalocyanine, perylene, quinacridone, a Zeo pigments and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

  In the present invention, the amount of charge control agent used is determined uniquely by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. Although it is not a thing, Preferably it is used in 0.1-10 weight part with respect to 100 weight part of binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline.

As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 × 10 ^-3 ~2μm, it is particularly preferably 5 × 10 ^-3 ~0.5μm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.

The use ratio of the inorganic fine particles used as the external additive is preferably 0.01 to 5 wt%, and particularly preferably 0.01 to 2.0 wt% of the toner.
Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, Examples thereof include diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  In addition, polymer fine particles, for example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, methacrylate ester, acrylate ester copolymer, polycondensation system such as silicone, benzoguanamine, nylon, heat Examples thereof include polymer particles made of a curable resin.

  Such a fluidizing agent increases the hydrophobicity by performing a surface treatment, and can prevent the deterioration of the flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. It is done. In particular, it is preferable to use hydrophobic silica and hydrophobic titanium oxide obtained by subjecting silica and titanium oxide to the above surface treatment.

  Examples of the method for producing a toner for developing an electrostatic charge image according to the present invention are illustrated below, but the present invention is not limited to these methods.

(Production of polyester resin)
The above-mentioned polyhydric alcohol (PO) and polycarboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc., and are produced while reducing the pressure as necessary. Water is distilled off to obtain a polyester resin.

(Prepolymer production)
Polyester having a hydroxyl group obtained by the same method as the above polyester resin is reacted with polyvalent isocyanate (PIC) at 40 to 140 ° C. to obtain a polyester prepolymer (A) having an isocyanate group. When reacting polyvalent isocyanate (PIC), a solvent can be used as necessary.
Usable solvents include aromatic solvents that are inert to isocyanate compounds (eg, toluene, xylene, etc.); ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (eg, acetic acid) Ethyl etc.); amides (for example, dimethylformamide, dimethylacetamide, etc.) and ethers (for example, tetrahydrofuran etc.) etc. are mentioned.

(Production of modified polyester resin)
The reaction between the polyester prepolymer (A) and the amines (B) may be carried out by mixing with other toner constituent materials, or may be prepared in advance. In the case of producing in advance, the polyester prepolymer (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a urea-modified polyester resin. Also in the case of reacting the polyester prepolymer (A) and the amines (B), a solvent can be used as necessary, as in the case of the prepolymer (A). Solvents that can be used are as described above.

  Further, in order to improve the fluidity, storage stability, developability, and transferability of the toner, inorganic fine particles such as the above-mentioned hydrophobic silica fine powder can be added and mixed with the toner. For mixing external additives, a general powder mixer is used, but it is preferable to use a jacket equipped with a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added midway or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, then a relatively weak load, and vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, and the like.

(Toner production method in aqueous medium)
As shown in FIG. 1, the toner production in the aqueous medium according to the present invention is carried out in advance by adding a volume average of droplets to a granulating device 4 equipped with an emulsifying / dispersing machine (PLHM) 2 and an emulsion circulation / retention unit 3. particle size _(D p v), and _{D p} v leave satisfied and the number average particle diameter _(D p n) of the ratio _{(D p v / D p n} ) consists adjusted droplet emulsion-dispersion, Thereafter, the oil phase and the aqueous phase are continuously fed.

  The aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (eg, methanol, isopropyl alcohol, ethylene glycol), dimethylformamide, tetrahydrofuran, cellosolves (eg, methyl cellosolve), lower ketones (eg, acetone, methyl ethyl ketone, etc.), and the like. Can be mentioned.

In order to form droplets of the emulsified / dispersed liquid, a dispersion composed of a polyester prepolymer (A) having an isocyanate group in an aqueous medium may be formed by reacting with an amine (B). You may use the produced modified polyester resin.
That is, if necessary, the oil layer is, for example, a solution (A oil phase 7) in which at least a binder resin, a colorant, and an extender (active hydrogen compound) that undergoes addition reaction with a prepolymer are dissolved or dispersed in an organic solvent, and for example, It is also possible to divide into prepolymers (B oil phase 8) having an isocyanate bond that reacts with the extender, mix them at the time of feeding, and supply them to the granulator 4.

  Other toner constituent materials such as wax and charge control agent may be mixed when forming the dispersion in the aqueous medium. However, after these toner constituent materials are mixed in advance, the toner constituent materials are mixed in the aqueous medium. More preferably, the mixture is added and dispersed. In the present invention, toner constituent materials such as wax and charge control agent do not necessarily have to be mixed when forming droplets (granulation) in an aqueous medium. After the particles are formed, It may be added.

(Solid fine particle dispersant)
Further, by adding a solid fine particle dispersant in advance to the aqueous medium, the dispersion of oil droplets in the aqueous phase is made uniform. This is because the solid fine particle dispersant is arranged on the surface of the oil droplets at the time of dispersion, and the dispersion of the oil droplets is made uniform, and at the same time, coalescence of the oil droplets is prevented and the particle size distribution is sharp. Toner can be obtained. The solid fine particle dispersant is present in a solid state hardly soluble in water in an aqueous medium, and is preferably inorganic fine particles having an average particle diameter of 0.01 to 1 μm.

  Specific examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, Examples thereof include diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. More preferably, tricalcium phosphate, calcium carbonate, colloidal titanium oxide, colloidal silica, hydroxyapatite and the like can also be used. In particular, hydroxyapatite synthesized by reacting sodium phosphate and calcium chloride in water under basic conditions is preferable.

  The dispersion method is not particularly limited, but a high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but usually the shear rate is 8 to 30 m / s, preferably 10 to 24 m / s. Note that known equipment such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied depending on the properties of the oil phase including the binder resin.

  The amount of the aqueous medium used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts by weight of the toner composition containing the polyester resin and the prepolymer (A). If it is less than 50 parts by weight, the toner composition is poorly emulsified and dispersed, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. The use of a dispersant is preferable in that the particle size distribution becomes sharp and the emulsification / dispersion is stable.

  Dispersants for emulsifying and dispersing the oil phase in which the toner composition is dispersed in an aqueous medium include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters, and alkylamines. Amine salts such as salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, nonionic surfactants such as polyhydric alcohol derivatives such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl- N Amphoteric surfactants such as N- dimethyl ammonium betaine.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be increased in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11). ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts thereof, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2-Hide Xylethyl) perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphoric acid Examples include esters.

  As a trade name of the surfactant having the fluoroalkyl group, for example, Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC- l29 (manufactured by Sumitomo 3M), Unidyne DS-101, DS-102, (manufactured by Taikin Kogyo Co., Ltd.), Megafac F-l0, F-l20, F-113, F-191, F-812, F-833 ( Dainippon Ink Co., Ltd.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), Footent F-100, F150 (Neos) Manufactured).

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

  Further, the dispersed droplets may be stabilized by a polymer protective colloid. Examples of such polymeric protective colloids include acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or (Meth) acrylic monomers containing hydroxyl groups such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, methacryl Acid γ-hydroxypropyl, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylate, N-methylolacrylamide, N-methylolmethacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or vinyl alcohol and carboxyl group Esters of contained compounds, such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl Homopolymers or copolymers such as those having nitrogen atoms such as pyrrolidone, vinylimidazole, ethyleneimine, or heterocyclic rings thereof, poly Xylethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl Polyoxyethylenes such as esters and polyoxyethylene nonylphenyl esters, and celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

Furthermore, in order to lower the viscosity of the toner composition, a solvent in which the polyester resin or the polyester prepolymer (A) is soluble can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable.
The usage-amount of the solvent with respect to 100 weight part of polyester prepolymers (A) is 0-300 weight part normally, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after elongation and / or crosslinking reaction.

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

  In order to obtain the desired shape of the toner, a stirrer equipped with a stirrer (eg, homomixer, Ebara milder) prior to removing the solvent from the obtained emulsified / dispersed liquid after the elongation and / or crosslinking reaction Etc., and applying a shearing force to the emulsified / dispersed liquid to transform the particles having a substantially spherical shape into a spindle shape, and then removing the solvent from the emulsified / dispersed liquid at a Tg or less of the binder resin. By providing the toner, particles can be fixed and a toner having a desired shape can be produced.

  Examples of the method for adjusting the shearing force include the processing time and number of processing of the apparatus, the temperature and viscosity of the emulsified / dispersed liquid, and the concentration of the organic solvent in the particles. In addition, the degree of deformation due to the shearing force is different depending on the coverage of the resin fine particles on the particle surface, the degree of reactivity with the compound having an active hydrogen group, etc., and the shape of the particle itself is different.

In order to remove the organic solvent from the obtained emulsified / dispersed liquid, a method of gradually elevating the temperature of the entire system and completely evaporating and removing the organic solvent in the droplets can be employed. Alternatively, the emulsified / dispersed liquid can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation. is there.
As a dry atmosphere in which the emulsification / dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various airflows heated to a temperature higher than the boiling point of the highest boiling solvent used are generally used. . A spray dryer, belt dryer, rotary kiln, etc. can provide the desired quality in a short time.

The obtained dried toner powder is mixed with different particles such as charge control agent, fluidizing agent, colorant, etc., or fixed and fused on the surface by applying mechanical impact force to the mixed powder. In addition, it is possible to prevent the detachment of the foreign particles from the surface of the obtained composite particle.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

Furthermore, the toner of the present invention can be used as a magnetic toner containing a magnetic substance. Examples of magnetic materials contained in the toner include iron oxides such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel, Alternatively, alloys of these metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof are included. . In particular, magnetite is preferable in terms of magnetic properties.
These ferromagnetic materials desirably have an average particle diameter of about 0.1 to 2 μm, and the amount contained in the toner is about 15 to 200 parts by weight, particularly preferably 100 parts by weight of the binder resin component. Is 20 to 100 parts by weight with respect to 100 parts by weight of the binder resin component.

  The toner of the present invention can be used as a one-component developer or a two-component developer combined with a magnetic carrier. As the magnetic carrier when the toner of the present invention is used as a two-component developer, all known carriers can be used, for example, magnetic powder such as iron powder, ferrite powder, nickel powder, glass beads, etc. And those whose surfaces are treated with a resin or the like.

  Examples of the resin powder that can be coated on the magnetic carrier in the present invention include a styrene-acrylic copolymer, a silicone resin, a maleic acid resin, a fluorine resin, a polyester resin, and an epoxy resin. In the case of a styrene-acrylic copolymer, those having a styrene content of 30 to 90% by weight are preferred. In this case, when the styrene content is less than 30% by weight, the development characteristics are low, and when it exceeds 90% by weight, the coating film becomes hard and easily peeled, and the life of the carrier is shortened. Moreover, the resin coating of the carrier in the present invention may contain an adhesion-imparting agent, a curing agent, a lubricant, a conductive material, a charge control agent and the like in addition to the resin.

An image forming apparatus using the toner of the present invention as a developer will be described.
FIG. 2 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present invention. In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which the copying apparatus is placed, 300 is a scanner mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) mounted thereon.

The copying apparatus main body 100 has a tandem type in which four image forming units 18 each having various units for performing an electrophotographic process such as charging, developing, and cleaning are arranged in parallel around a photosensitive member 40 as a latent image carrier. An image forming apparatus 20 is provided.
Above the tandem type image forming apparatus 20, there is provided an exposure apparatus 21 that exposes the photoreceptor 40 with laser light based on image information to form a latent image. Further, an intermediate transfer belt 10 made of an endless belt member is provided at a position facing each photoreceptor 40 of the tandem type image forming apparatus 20.

  A primary transfer unit 62 for transferring the toner images of the respective colors formed on the photoconductor 40 to the intermediate transfer belt 10 is disposed at a position facing the photoconductor 40 via the intermediate transfer belt 10. A secondary transfer device 22 that collectively transfers the toner images superimposed on the intermediate transfer belt 10 onto transfer paper conveyed from the paper feed table 200 is disposed below the intermediate transfer belt 10.

  The secondary transfer device 22 is configured by spanning a secondary transfer belt 24 that is an endless belt between two rollers 23, and is disposed by pressing against the support roller 16 via the intermediate transfer belt 10. The toner image on 10 is transferred onto a transfer sheet. A fixing device 25 for fixing the image on the transfer paper is provided beside the secondary transfer device 22.

The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt. The secondary transfer device 22 described above also has a sheet transport function for transporting the transfer paper after image transfer to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveyance function together.
In the illustrated example, a reversing device 28 for reversing the transfer paper so as to record images on both sides of the transfer paper is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 20 described above. .

  The developing device 4 of the image forming unit 18 uses a developer containing the above toner. In the developing device 4, the developer carrying member carries and conveys the developer, and an alternating electric field is applied at a position facing the photoconductor 40 to develop the latent image on the photoconductor 40. By applying the alternating electric field, the developer is activated, the charge amount distribution of the toner can be narrowed, and the developability can be improved.

  Further, the developing device 4 can be a process cartridge that is integrally supported together with the photoreceptor 40 and is detachably formed on the main body of the image forming apparatus. In addition, the process cartridge may include a charging unit and a cleaning unit.

  The operation of the image forming apparatus is as follows. First, a document is set on the document table 30 of the automatic document feeder 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed. Hold it down. 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 other contact glass 32. At that time, the scanner 300 is immediately driven to travel the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34 and reflects by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.

  When a start switch (not shown) is pressed, one of the support rollers 14, 15, 16 is rotated by a drive motor (not shown), the other two support rollers are driven to rotate, and the intermediate transfer belt 10 is rotated and conveyed. To do. At the same time, the individual image forming means 18 rotates the photoconductors 40 to form black, yellow, magenta, and cyan monochrome images on the photoconductors 40, respectively. Then, along with the conveyance of the intermediate transfer belt 10, the monochrome images are sequentially transferred to form a composite color image on the intermediate transfer belt 10.

  On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, and the sheet is fed out from one of the paper feed cassettes 44 provided in multiple stages in the paper bank 43, and the separation roller 45. Then, the sheets are separated one by one into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying machine main body 100, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 50 is rotated to feed out the sheets on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer belt 10, the sheet is fed between the intermediate transfer belt 10 and the secondary transfer device 22, and is transferred by the secondary transfer device 22. A color image is recorded on the sheet.

The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching roller 55 is used to switch the discharge image. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and the image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.
On the other hand, the intermediate transfer belt 10 after image transfer is removed by the intermediate transfer belt cleaning device 17 to remove residual toner remaining on the intermediate transfer belt 10 after image transfer, and is prepared for re-image formation by the tandem image forming apparatus 20.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to this. Hereinafter, a part shows a weight part.

Example 1
First, low molecular polyester, MB, and ketimine, which are components of the oil phase A, were synthesized as follows.
(Synthesis of low molecular weight polyester)
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 put 44 parts of trimellitic anhydride into the reaction vessel at 180 ° C, normal pressure For 2 hours to obtain [Low molecular polyester 1]. [Low molecular polyester 1] had a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25.

  Further, 670 parts of bisphenol A ethylene oxide 2-mole adduct and 335 parts of terephthalic acid were charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and the reaction was carried out at 210 ° C. under a normal pressure nitrogen stream. A time condensation reaction was performed. Next, the reaction was continued for 3 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, followed by cooling to obtain [Low Molecular Polyester 2]. [Low molecular polyester 2] had a weight average molecular weight of 6,000, a Tg of 52 ° C., and an acid value of 35.

  Also, 73 parts of bisphenol A ethylene oxide 2-mole adduct, 590 parts of bisphenol A propylene oxide 2-mole adduct, 254 parts of terephthalic acid, and 46 parts of isophthalic acid were added in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. The mixture was subjected to a condensation reaction at 210 ° C. for 10 hours under a normal pressure nitrogen stream. Subsequently, 38 parts of 4-t-butylbenzoic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 0 to 15 mmHg, followed by cooling to obtain [Low Molecular Polyester 3]. [Low molecular weight polyester 3] had a weight average molecular weight of 4,200, a Tg of 45 ° C., and an acid value of 8.

  Further, 670 parts of bisphenol A propylene oxide 2-mol adduct and 310 parts of terephthalic acid were charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and the mixture was added at 230 ° C. under a normal pressure nitrogen stream. A time condensation reaction was carried out. Next, the reaction was continued for 1 hour while dehydrating under reduced pressure of 10 to 15 mmHg, followed by cooling to obtain [Low Molecular Polyester 4]. [Low molecular polyester 4] had a weight average molecular weight of 6,000, a Tg of 57 ° C., and an acid value of 51.

[Synthesis of MB]
1200 parts of water, 540 parts of carbon black (made by Printex 35 Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5] and 1200 parts of polyester resin are added, and the mixture is mixed with a Henschel mixer (made by Mitsui Mining Co., Ltd.). After kneading at 150 ° C. for 30 minutes using two rolls, rolling and cooling and pulverizing with a pulverizer, [Masterbatch 1] was obtained. Moreover, [Masterbatch 2] was obtained through the same process using PY155 (manufactured by Clariant) instead of carbon black.

[Synthesis of ketimine]
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

Next, production examples of the A oil phase will be described.
[Production Example of Black Oil Phase A-1]
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 (salicylic acid metal complex E-84: Orient Chemical Industry), and 947 parts of ethyl acetate were charged and stirred. The temperature was raised to 80 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1].

  [Raw Material Solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed is 1 kg / hr, disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and wax were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, 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%.

  [Pigment / Wax Dispersion 1] 749 parts, [Ketimine Compound 1] 2.9 parts are put in a container and mixed for 1 minute at 5000 rpm using a homodisper (manufactured by Tokushu Kika), [Black Oil Phase A-1 ]

[Production Example of Yellow Oil Phases A-1 to A-3]
Except for changing [Low molecular polyester 1] to [Low molecular polyester 2] and [Masterbatch 1] to [Masterbatch 2], the same procedure as for [Black oil phase A-1] is followed to [Yellow oil Phase A-1] was obtained. Except for changing [Low molecular polyester 1] to [Low molecular polyester 3] and [Masterbatch 1] to [Masterbatch 2], the same procedure as [Black oil phase A-1] Phase A-2] was obtained. Except for changing [Low Molecular Polyester 1] to [Low Molecular Polyester 4] and [Master Batch 1] to [Master Batch 2], the same procedure as for [Black Oil Phase A-1] is followed to obtain [Yellow Oil Phase A-3] was obtained.

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

Next, an example of adjusting the aqueous phase will be described.
[Examples of water phase production]
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system temperature was raised to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt) A dispersion [fine particle dispersion 1] was obtained.
The volume average particle size of [Fine Particle Dispersion 1] was 105 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 59 ° C., and the weight average molecular weight was 150,000.

  83 parts of this [fine particle dispersion 1], 990 parts of water, 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred to give a milky white color Obtained liquid. This is designated as [Aqueous Phase 1].

Each oil layer and water phase prepared as described above is used, and after performing emulsification and dispersion under the conditions of each of the following production examples, using a granulation apparatus having the same configuration as shown in FIG. To produce a toner. In addition, the liquid feeding conditions, hold-up capacity, and emulsifier shear rate in the emulsification step were fixed under the following conditions.
<Emulsification process conditions>
A oil phase feed rate: 3560 g / min
B oil phase feed rate: 440 g / min
Aqueous liquid feed rate: 6000 g / min
Hold-up capacity: 15L
Emulsifier shear rate: 17m / sec

[Production Example 1]
In advance, 15 L of an emulsion / dispersion liquid having a volume average particle diameter of 4.8 μm and Dv / Dn of 1.20 prepared using the black oil phase A-1, the prepolymer 1, and the aqueous phase 1 was filled in the holdup and filled. Subsequently, the black oil phase A-1, the prepolymer 1, and the aqueous phase 1 are quantitatively supplied for 10 minutes under the emulsification conditions defined above, and the emulsification / dispersion for 0 to 5 minutes and the emulsification / dispersion for 5 to 10 minutes. A liquid was obtained. Each obtained emulsification / dispersion was processed as follows to obtain a toner. The solvent removal process was performed by the following method.

The temperature was raised to 45 ° C., and the solvent was removed under an atmospheric pressure (101.3 kPa) at an outer peripheral edge peripheral speed of 10.5 m / sec. The solvent removal time required 5 hours. Thereafter, after filtration, washing and drying, two types of toner base particles were obtained.
Next, 100 parts of the obtained toner base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were mixed using a Q-type mixer (manufactured by Mitsui Mining Co., Ltd.). Furthermore, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. Further, 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide were mixed with a Henschel mixer, and coarse particles were removed with a screen having an opening of 37 μm to obtain two types of black toners. The toner obtained from the emulsion / dispersion for 0 to 5 minutes was used as toner (A), and the toner obtained from the emulsion / dispersion for 5 to 10 minutes was used as toner (a).

[Production Example 2]
In advance, black oil phase A-1, prepolymer 1, and aqueous phase 1 are supplied to the hold-up according to the determined feed amount, and the black oil phase A-1, prepolymer 1, and water phase 1 are contained in the hold-up. Filled with mixture. Subsequently, the emulsification / dispersion liquid was adjusted within the hold-up by operating the granulator with the liquid feeding stopped. The volume average particle diameter of the prepared emulsified / dispersed liquid was 5.1 μm, and Dv / Dn was 1.15. Subsequently, two types of black toners were obtained in the same manner as in Production Example 1 under fixed emulsification conditions. The toner obtained from the emulsion / dispersion for 0 to 5 minutes was used as toner (B), and the toner obtained from the emulsion / dispersion for 5 to 10 minutes was used as toner (b).

[Production Example 3]
In advance, yellow oil phase A-1, prepolymer 1, and aqueous phase 1 are supplied to the hold-up according to the determined liquid feed amount, and the yellow oil phase A-1, prepolymer 1, and water phase 1 are contained in the hold-up. Filled and filled with mixture. Subsequently, the emulsification / dispersion liquid was adjusted within the hold-up by operating the granulator with the liquid feeding stopped. The volume average particle diameter of the prepared emulsified / dispersed liquid was 6.2 μm, and Dv / Dn was 1.20. Subsequently, two types of yellow toners were obtained in the same manner as in Production Example 1 under fixed emulsification conditions. The toner obtained from the emulsion / dispersion for 0 to 5 minutes was used as toner (C), and the toner obtained from the emulsion / dispersion for 5 to 10 minutes was used as toner (c).

[Production Example 4]
In advance, yellow oil phase A-2, prepolymer 1, and water phase 1 are supplied to the hold-up according to the determined liquid feed amount, and the yellow oil phase A-2, prepolymer 1, and water phase 1 are contained in the hold-up. Filled and filled with mixture. Subsequently, the emulsification / dispersion liquid was adjusted within the hold-up by operating the granulator with the liquid feeding stopped. The volume average particle diameter of the prepared emulsified / dispersed liquid was 4.3 μm, and Dv / Dn was 1.12. Subsequently, two types of yellow toners were obtained in the same manner as in Production Example 1 under fixed emulsification conditions. The toner obtained from the emulsion / dispersion for 0 to 5 minutes was used as toner (D), and the toner obtained from the emulsion / dispersion for 5 to 10 minutes was used as toner (d).

The volume average particle diameter of the toner obtained by the above _{(A) ~ (d) (} D t v), the ratio of _{D t} v to the number average particle diameter _{(D t n) (D t} v / D t n), The values relating to the acid value, Tg, average circularity, and BET specific surface area are shown in Table 1 below.

[Production Example 5]
In advance, yellow oil phase A-1, prepolymer 1, and aqueous phase 1 are supplied to the hold-up according to the determined liquid feed amount, and the yellow oil phase A-1, prepolymer 1, and water phase 1 are contained in the hold-up. Filled and filled with mixture. Subsequently, simultaneously with the operation of the granulator, the yellow oil phase A-1, the prepolymer 1 and the aqueous phase 1 are quantitatively supplied for 10 minutes, and the emulsion / dispersion liquid for 0 to 5 minutes and the emulsion / dispersion for 5 to 10 minutes are supplied. A liquid was obtained. Production of toner from the resulting emulsified / dispersed liquid was carried out in the same manner as in Production Example 1 to obtain two types of yellow toner. The toner obtained from the emulsion / dispersion for 0 to 5 minutes was used as toner (E), and the toner obtained from the emulsion / dispersion for 5 to 10 minutes was used as toner (e).

[Production Example 6]
In advance, yellow oil phase A-3, prepolymer 1, and aqueous phase 1 are supplied to the hold-up according to the determined liquid feed amount, and the inside of the hold-up contains yellow oil phase A-3, prepolymer 1, and water phase 1. Filled and filled with mixture. Subsequently, simultaneously with the operation of the granulator, the yellow oil phase A-3, the prepolymer 1 and the aqueous phase 1 are quantitatively supplied for 10 minutes, and the emulsion / dispersion liquid for 0 to 5 minutes and the emulsion / dispersion for 5 to 10 minutes are supplied. A liquid was obtained. Production of toner from the resulting emulsified / dispersed liquid was carried out in the same manner as in Production Example 1 to obtain two types of yellow toner. The toner obtained from the emulsion / dispersion for 0 to 5 minutes was used as toner (F), and the toner obtained from the emulsion / dispersion for 5 to 10 minutes was used as toner (f).

The volume average particle diameter of the toner obtained by the above _{(E) ~ (f) (} D t v), the ratio of _{D t} v to the number average particle diameter _{(D t n) (D t} v / D t n), Table 2 shows values relating to acid value, Tg, average circularity, and BET specific surface area.

  Each of the toners (A) to (d) obtained above was evaluated for low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and image quality. For comparison, the same evaluation was performed using the toners (E) to (f). The evaluation items and evaluation methods of the toner are as follows. The evaluation results are shown in Table 3 below.

<Fixability evaluation>
Ricoh Co., Ltd. Copier using Teflon (registered trademark) roller as the fixing roller MF2200 Using a modified machine, a Ricoh type 6200 paper was set on this, and a copying test was performed. The cold offset temperature (fixing lower limit temperature) and the hot offset resistant temperature were determined by changing the fixing temperature. The minimum fixing temperature of the conventional low-temperature fixing toner is about 140 to 150 ° C. The evaluation conditions for low-temperature fixability are 120 to 150 mm / sec for the paper feed linear velocity, the surface pressure is 1.2 kgf / cm ² , the nip width is 3 mm, and the evaluation conditions for the hot offset are 50 mm / sec for the paper feed linear velocity. sec, a surface pressure of 2.0 kgf / cm ² , and a nip width of 4.5 mm.
The criteria for each characteristic evaluation are as follows.

[Cold offset temperature] (5-level evaluation)
A: Less than 140 ° C., ○: 140-150 ° C., □: 150-160 ° C., Δ: 160-170 ° C., x: over 170 ° C.

[Hot offset resistance] (5-level evaluation)
A: 201 ° C. or higher, ○: 200 to 191 ° C., □: 190 to 181 ° C., Δ: 180 to 171 ° C., x: over 170 ° C.

<Evaluation of heat-resistant storage stability>
20g of toner sample is put into a 20ml glass bottle, and the glass bottle is tapped about 50 times to harden the sample tightly, then left in a high temperature bath at 50 ° C for 24 hours, and then the penetration is measured using a penetration tester. It calculated | required as follows.

[Heat resistant storage stability] (5-level evaluation)
◎: penetration, ○: ~ 25mm, □ 25-20mm, △: 20-15mm, x: more than 15mm

<Image quality evaluation>
Fog, toner scattering, and background contamination were evaluated, and when satisfactory results were obtained for each evaluation item, it was determined that the image quality was good. The evaluation method for each item is as follows.
(Image density): After outputting a solid image, the image density is measured by X-Rite (manufactured by X-Rite). This was measured at five points for each color alone, and the average was obtained for each color.
(Fog): The degree of toner contamination on the transfer paper upper surface was visually evaluated.
(Toner scattering): Toner contamination in the copying machine was visually evaluated.
In addition, fog and toner scattering were evaluated using a Ricoh IPSIO color 8000 remodeling machine using each toner after an image area ratio 5% chart continuous 50000 sheet output durability test.

  As can be seen from Table 1, Table 2, and Table 3, in the examples using the toners (A) to (d) according to the present invention, the toner obtained in 0 to 5 minutes and the toner obtained in 5 to 10 minutes were obtained. The same physical properties were obtained in the toner, and excellent results were obtained in all of low-temperature fixability, hot offset resistance, heat-resistant storage stability, and image quality. On the other hand, in the comparative examples using the toners (E) to (f), a remarkable difference was observed in the particle size distribution between the toner obtained in 0 to 5 minutes and the toner obtained in 5 to 10 minutes. Further, in terms of quality, the toner obtained in 0 to 5 minutes was fogged and scattered, resulting in inferior image quality.

It is a schematic block diagram which shows an example of the emulsification dispersion | distribution apparatus used for the emulsification process of toner manufacture in this invention. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present invention.

Explanation of symbols

2 Emulsifier / Disperser (PLHM)
3 Emulsified liquid circulation / retention section 4 Granulator 5 STM (Static mixer)
6 Desolvation tank 7 A oil phase 8 B oil phase 9 Water phase 17 A oil phase supply tank 18 B oil phase supply tank 19 Water phase supply tank

Claims (17)

An aqueous phase comprising an oil phase containing at least a binder resin and / or a resin precursor and a colorant and an aqueous medium in a granulator equipped with an emulsifying disperser and an emulsion liquid circulation / retention section used in an emulsification process of toner production In the manufacturing method of the electrostatic image developing toner,
In said granulator, pre volume average particle diameter of the droplets _(D p v) is at 2-7 [mu] m, said _{D p} v and the ratio _(D p of the number average particle diameter _{(D p n) v / D} p n ) Is fully charged with the emulsified and / or dispersed liquid adjusted to 1.05-1.30, and then the oil phase and the aqueous phase are continuously fed. A method for producing a toner for image development. An aqueous phase comprising an oil phase containing at least a binder resin and / or a resin precursor and a colorant and an aqueous medium in a granulator equipped with an emulsifying disperser and an emulsion liquid circulation / retention section used in an emulsification process of toner production In the manufacturing method of the electrostatic image developing toner,
In the granulator, the oil phase and the aqueous phase in a full amount are fed in advance and emulsified and dispersed. The volume average particle diameter (D _p v) of the droplets is 2 to 7 μm, and D _p v and after the ratio of the number average particle diameter _{(D p n) (D p} v / D p n) is obtained by the emulsification and / or dispersion of 1.05 to 1.30, the liquid feed of the oil and water phases A method for producing a toner for developing an electrostatic charge image, characterized in that the toner is continuously formed. In an emulsification disperser used in an emulsification process of toner production and a granulation apparatus equipped with an emulsion circulation / retention unit, an oil phase containing at least a binder resin and a colorant in an organic solvent and an aqueous phase composed of an aqueous medium are provided. In the method of producing a toner for developing an electrostatic image in which liquid droplets are sent to form droplets,
In said granulator, pre volume average particle diameter of the droplets _(D p v) is at 2-7 [mu] m, said _{D p} v and the ratio _(D p of the number average particle diameter _{(D p n) v / D} p n ) Is fully charged with the emulsified and / or dispersed liquid adjusted to 1.05-1.30, and then the oil phase and the aqueous phase are continuously fed. A method for producing a toner for image development. In an emulsification disperser used in an emulsification process of toner production and a granulation apparatus equipped with an emulsion circulation / retention unit, an oil phase containing at least a binder resin and a colorant in an organic solvent and an aqueous phase composed of an aqueous medium are provided. In the method of producing a toner for developing an electrostatic image in which liquid droplets are sent to form droplets,
In the granulator, the oil phase and the aqueous phase in a full amount are fed in advance and emulsified and dispersed. The volume average particle diameter (D _p v) of the droplets is 2 to 7 μm, and D _p v and after the ratio of the number average particle diameter _{(D p n) (D p} v / D p n) is obtained by the emulsification and / or dispersion of 1.05 to 1.30, the liquid feed of the oil and water phases A method for producing a toner for developing an electrostatic charge image, characterized in that the toner is continuously formed.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the binder resin contains a polyester resin.   An electrostatic charge image developing toner obtained by the production method according to claim 1.   The toner for developing an electrostatic charge image according to claim 6, wherein the toner has an acid value of 0.5 to 40.0 (KOH mg / g).   The toner for developing an electrostatic charge image according to claim 6 or 7, wherein the toner has a glass transition point of 40 to 65 ° C. The toner according to any one of claims 6-8, wherein the toner having a volume average particle diameter (D t _v) is 3 to 8 [mu] m. Claims the ratio of Volume average particle diameter of said toner _(D t v) and number average particle diameter _{(D t n) (D t} v / D t n) is characterized by a 1.05-1.25 The toner for developing an electrostatic image according to 9.   11. The electrostatic image developing toner according to claim 6, wherein the toner has an average circularity of 0.92 to 1.00. The electrostatic image developing toner according to claim 6, wherein the toner has a BET specific surface area of 1.0 to 6.0 m ² / g.   A developer for developing an electrostatic latent image formed on a latent image carrier, wherein the developer is a one-component development using the electrostatic charge image developing toner according to any one of claims 6 to 12. A developer characterized by being a developer.   A developer for developing an electrostatic latent image formed on a latent image carrier, the developer comprising a magnetic carrier and the electrostatic image developing toner according to any one of claims 6 to 12. A developer characterized by being a two-component developer.   A developing device for carrying and transporting a developer by a developer carrying member, forming an electric field at a position facing the latent image carrying member, and developing an electrostatic latent image on the latent image carrying member, wherein the developer 15. A developing device comprising the developer according to claim 13.   A latent image carrier that carries the latent image and a developing unit that supplies toner to the electrostatic latent image formed on the surface of the latent image carrier to visualize the latent image are integrally supported to form an image. 16. A process cartridge formed detachably on the apparatus main body, wherein the developing means is the developing apparatus according to claim 15. 17. An image forming apparatus having a process cartridge which is detachable from a main body of the image forming apparatus, wherein the process cartridge is the process cartridge according to claim 16. .

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