JP2005070680A - Continuous emulsification apparatus and method for manufacturing toner by using the apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a granulation method with proper balance of emulsification and unification, to easily manufacture toner having a stable volume average particle size without depending on the process and having sharp distribution of the particle size, and as a result, realizing faithful development of a latent image resulting in reproduction of a full-color image having high image quality, and to provide a method of manufacturing the toner. <P>SOLUTION: The apparatus for manufacturing toner for electrophotographic image formation is equipped with a continuous emulsifying machine and is used for the method of dissolving or dispersing a toner composition, containing at least resin, coloring agents and release agents in an organic solvent and of continuously emulsifying the dissolved product or the dispersion material in an aqueous medium. The apparatus is equipped with a means which can vary the retention volume in the emulsifying mechanism. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a toner for developing an electrostatic charge image and a manufacturing method for developing an electrostatic charge image formed on the surface of a photoreceptor in electrophotography and electrostatic recording.

In the developing process, the developer used in electrophotography, electrostatic recording, electrostatic printing, etc. is once attached to an image carrier such as a photoreceptor on which an electrostatic charge image is formed, and then After being transferred from the photoreceptor to a transfer medium such as transfer paper in the transfer process, it is fixed on the paper surface in the fixing process.
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.

In order to obtain high-quality and high-quality images, improvements have been made by reducing the particle diameter of the toner, but the particle shape is indefinite in the production method using the usual kneading and pulverization methods. Internally, the toner is further pulverized by agitation with the carrier in the developing unit, and when it is used as a one-component developer, contact stress between the developing roller and the toner supply roller, the layer thickness regulating blade, the friction charging blade, etc. Or an additive such as a fluidizing agent fixed on the toner surface is embedded in the surface, resulting in a phenomenon that the image quality is deteriorated.
In addition, because of such an irregular shape, the fluidity as a powder is poor, a large amount of fluidization is required, and the filling rate into the toner bottle is low, which becomes an obstacle to downsizing. Yes. Therefore, the current situation is that the merit of reducing the particle size is not utilized. In addition, the pulverization method has a limit on the particle size and cannot cope with further reduction in the particle size.
In order to compensate for the disadvantages of the irregular shape effect, spherical toner has attracted attention, and various methods for its production have been proposed, and a polymer suspension method is a particularly commonly used method.
In this method, a toner composition such as a colorant such as a resin or a pigment, a wax or the like is dissolved in an organic solvent, and the dispersed oil phase is emulsified in a water phase to a toner size droplet by mechanical emulsification means. . At the time of emulsification, if a solid organic fine particle dispersant is used as a stabilizer for emulsified droplets in the aqueous phase, fine droplets having a relatively narrow particle size distribution (Dv / Dn) can be produced.

  In the conventional general suspension method and emulsification method, in the process of generating droplets of toner size, the particles are repeatedly sheared (micronized) and coalesced within the emulsifying mechanism staying partial volume, and the balance is maintained. The particle size is temporarily determined when it is taken, but depending on the formulation, the rate of shearing and coalescence is different, so there has been a problem that the volume average particle size and particle size distribution are different in the emulsification process . As a result, since a difference also occurs in the final particle diameter of the toner, a process such as fine powder cutting and coarse powder cutting is incorporated in the subsequent process, and the volume average diameter and the particle size distribution are combined.

A rotating shaft suspended in the center of the stirring tank as a technique for solving such problems and producing toner with sharp particle size distribution and extremely uniform characteristics with no variation in performance between toner particles. Using a stirring vessel in which two stirring blades are provided adjacent to each other at the top and bottom, and the upper stirring blade is arranged in advance in the rotational direction at an intersecting angle of less than 90 degrees with respect to the lower stirring blade (for example, ), The tip speed of the stirring blade during the polymerization reaction is specified as the relationship between the depth H from the water surface to the top of the stirring blade and the tank diameter D, and the power required for stirring during the polymerization is A polymerizable monomer is provided in a granulation vessel having a method for sharpening the particle size distribution after polymerization by controlling the range (see, for example, Patent Document 2) and a stirrer having a high shearing force. Liquid composition containing composition and dispersion stabilizer Between the volume V using the (m ³⁾ and stirrer power P (kw), 15 <by having the relationship of P / V <100, a method for efficiently producing a sharp toner (e.g., Patent Documents 3 has been proposed.

However, each of these methods is an attempt to control the shape and arrangement of the agitating blades and the agitation power to create particles to the target value, and even to a unified behavior that is one of the granulation mechanisms. This is not considered.
Furthermore, when there is a prescription change, these methods may cause a broad particle size distribution if the particle size adjustment is only related to the stirring blades, and there is a limit to suppressing the generation of fine and coarse powders. There are problems such as.

JP 2000-321821 A JP 2001-125309 A JP 2002-91071 A

  Accordingly, an object of the present invention is to provide a granulation method balanced with emulsification and a toner having a stable volume average particle size and a sharp particle size distribution regardless of the formulation, in view of the above prior art. It is an object of the present invention to provide a toner and a manufacturing method that can be easily manufactured, and as a result, can faithfully develop a latent image and reproduce a high-quality full-color image.

The present inventors have analyzed the prior art and focused on both the emulsification and coalescence mechanisms, and the particle size is determined when shearing and coalescence are achieved and balanced in the retention volume of the emulsification mechanism part. When producing multi-preparation toners in one production line, the emulsification behavior differs greatly depending on the formulation, and there is an optimum emulsification mechanism partial retention volume in each formulation, so a stable target particle size value, sharp particle size It was confirmed that making the distribution was very difficult.
However, in the case of the present invention, by making the partial retention volume of the emulsification mechanism variable, the coalescence time in each formulation can be controlled, and a granulation method that takes into account the balance between emulsification and coalescence has become possible. .
In the present invention, in order to achieve the above-mentioned problems, a continuous emulsification technique can be adopted and the emulsification mechanism partial retention volume can be changed, so that it is possible to deal with multiple prescriptions and target volume average particles in the emulsification process without depending on the prescription. It is possible to create a toner with a diameter and sharp particle size distribution, and by making the partial retention volume of the emulsification mechanism variable, it is possible to control the coalescence time in each formulation, taking into account the balance between emulsification and coalescence. It was found that a granulating method becomes possible.
That is, the above-mentioned problem is solved by (1) “providing a continuous emulsifier and dissolving or dispersing a toner composition containing at least a resin, a colorant, and a release agent in an organic solvent. An electrophotographic image forming toner manufacturing apparatus used for a method of continuously emulsifying in an aqueous medium, comprising means capable of changing a partial retention volume of an emulsification mechanism " ,
(2) The electrophotographic image according to claim 1, wherein “the emulsification mechanism partial retention volume V (L) that can be changed and the discharge flow rate Q (L / sec) of the emulsifier satisfies the following relationship: Toner forming apparatus for forming;

」、
（３）「乳化機構部分滞留容積の変更手段として、伸縮自在管が具備されることを特徴とする前記第（１）項または第（２）項に記載の電子写真画像形成用トナー製造装置」、
（４）「乳化機構部分滞留容積の変更方法として並列的なバイパス経路を用いることを特徴とする前記第（１）項または第（２）項に記載の製造装置」、
（５）「乳化機構部分滞留容積の変更手段として、滞留容積部にストックタンクが具備されることを特徴とする前記第（１）項乃至第（３）項のいずれかに記載の電子写真画像形成用トナー製造装置」により達成される。
また、上記課題は、本発明の（６）「前記第（１）項乃至第（５）項のいずれかに記載のトナー製造装置を用い、連続乳化機のせん断速度を１０〜２４ｍ／ｓにして行なうことを特徴とする電子写真画像形成用トナーの製造方法」、
（７）「連続乳化時の温度を１６〜２５℃で、乳化機構部分滞留部の温度バラツキが±５℃以内にして行なうことを特徴とする前記第（６）項に記載の電子写真画像形成用トナーの製造方法」、
（８）「乳化機構部分滞留部の平均滞留時間を３０ｍｉｎ以内にして行なうことを特徴とする前記第（６）項または第（７）項に記載の電子写真画像形成用トナーの製造方法」、
（９）「乳化機構部分滞留時間内に乳化機によってせん断を受ける平均回数が２００（回／ｍｉｎ）以内にして行なうことを特徴とする前記第（６）項乃至第（８）項の何れかに記載の電子写真画像形成用トナーの製造方法」により達成される。
また、上記課題は、本発明の（１０）「前記第（６）項乃至第（９）項の何れかに記載の製造方法によって得られる、体積平均粒径（Ｄｖ）が３〜１０μｍであることを特徴とする電子写真画像形成用トナー」、
（１１）「体積平均粒径（Ｄｖ）を個数平均粒径（Ｄｎ）で除した値が、１．０５〜１．２５であることを特徴とする前記第（１０）項に記載の電子写真画像形成用トナー」により達成される。
また、上記課題は、本発明の（１２）「前記第（１０）項または第（１１）項に記載の電子写真画像形成用トナーを用いた電子写真画像形成方法」により達成される。
また、上記課題は、本発明の（１３）「前記第（１０）項または第（１１）項に記載のトナーが搭載された電子写真画像形成装置」、
また、上記課題は、本発明の（１４）「前記第（１０）項または第（１１）項に記載のトナーが収納された容器」により達成される。

"
(3) “Electrophotographic image forming toner production apparatus according to item (1) or (2), wherein an expansion / contraction tube is provided as a means for changing the partial retention volume of the emulsification mechanism”. ,
(4) "The manufacturing apparatus according to (1) or (2), wherein a parallel bypass path is used as a method of changing the emulsification mechanism partial residence volume",
(5) The electrophotographic image as described in any one of (1) to (3) above, wherein a stock tank is provided in the retention volume as a means for changing the emulsification mechanism partial retention volume. This is achieved by the “forming toner manufacturing apparatus”.
In addition, the above-described problem is solved by using the toner production apparatus according to any one of (6) and (1) to (5) of the present invention, and setting the shear rate of the continuous emulsifier to 10 to 24 m / s. A method for producing an electrophotographic image-forming toner characterized by
(7) The electrophotographic image formation described in (6) above, wherein the temperature during continuous emulsification is 16 to 25 ° C. and the temperature variation of the emulsifying mechanism partial staying portion is within ± 5 ° C. Toner production method ",
(8) “The method for producing a toner for forming an electrophotographic image according to the item (6) or (7), wherein the average residence time of the emulsification mechanism partial residence part is within 30 minutes”,
(9) Any one of the above items (6) to (8), wherein the average number of times of shearing by the emulsifier is within 200 (times / min) within the partial residence time of the emulsification mechanism And a process for producing a toner for forming an electrophotographic image described in the above.
Moreover, the said subject is a volume average particle diameter (Dv) obtained by the manufacturing method in any one of (10) "the said (6) term | claim-(9) term" of this invention, and is 3-10 micrometers. An electrophotographic image forming toner characterized by that, "
(11) The electrophotographic image described in (10) above, wherein the value obtained by dividing the volume average particle diameter (Dv) by the number average particle diameter (Dn) is 1.05 to 1.25. Achieved by “image forming toner”.
Further, the above-mentioned object is achieved by (12) “Electrophotographic image forming method using electrophotographic image forming toner according to item (10) or (11)” of the present invention.
In addition, the above-mentioned problem is (13) “electrophotographic image forming apparatus equipped with the toner according to (10) or (11)”,
Further, the above object is achieved by (14) “container containing toner according to item (10) or (11)” of the present invention.

  As will be apparent from the following detailed and specific description, according to the production method of the present invention, the fine powder can be obtained by changing the hold-up volume even if the emulsification / convergence behavior changes due to the change in the prescription or variety. Toner and production that can easily produce toner with stable volume average particle size and sharp particle size distribution that suppresses the generation of coarse powder, and as a result, can reproduce high-quality full-color images that are developed faithfully to latent images A method can be provided.

The present invention is described in detail below.
FIG. 1 is a process conceptual diagram showing an example of the continuous emulsification process of the present invention.
FIG. 2 is a conceptual diagram specifically showing a means for changing the partial retention volume of the emulsifying mechanism provided with a telescopic tube such as a bellows tube.
FIG. 3 is a conceptual diagram using a parallel bypass path as a method of changing the emulsifying mechanism partial retention volume.
FIG. 4 is a conceptual diagram of a storage tank having a stock tank as a means for changing the partial retention volume of the emulsification mechanism. By changing the height of the ceiling plate of the stock tank, the volume in the stock tank can be changed. As a result, the hold-up volume can be changed.
A liquid obtained by dissolving or dispersing a toner composition containing at least two kinds of resins having different molecular weights, a colorant and a release agent in an organic solvent, and an extender (hereinafter referred to as A oil phase); An aqueous medium containing a solid resin fine particle dispersant partially dissolved in an aqueous medium (hereinafter referred to as an aqueous phase) and a prepolymer having an isocyanate bond (hereinafter referred to as B oil phase), The liquid was continuously fed in a certain amount, and the A oil phase and the B oil phase were pre-stirred with a static mixer (hereinafter referred to as STM) (the liquid after pre-stirring is called the oil phase), and then the water phase Mix with. The oil phase and water phase mixed by STM are mixed, and emulsification is performed by shearing by a pipeline homomixer (hereinafter referred to as PLHM) in the partial retention volume of the emulsification mechanism.
Here, the total liquid feed amount, the rotation speed of PLHM, the emulsification temperature, the partial retention volume of the emulsification mechanism (hereinafter referred to as hold-up), the accompanying retention time in the hold-up (hereinafter referred to as retention time), and the emulsifier within the retention time The number of times the shearing is applied (hereinafter referred to as the number of passes), the time from when the shearing is received from the emulsifier within the holdup to the next time (hereinafter referred to as the time between passes), the volume average diameter Dv and particle size distribution of the emulsified particles. It is a factor greatly involved in Dv / Dn.
Especially, the shear rate of PLHM is 10 to 24 m / s, the emulsification temperature is 16 to 25 ° C., and the variation is ± 5 ° C., the emulsification mechanism partial retention volume V (L) that can be changed, the discharge flow rate Q (L / sec) of the emulsifier ), The hold-up volume is defined as Q <V <Q × 30, the residence time is within 30 minutes, and the number of passes is within 200 times. When the volume average particle diameter of the toner obtained is Dv and the number average particle diameter is Dn, when Dv is 3 to 10 μm and Dv / Dn is 1.05 to 1.25, a high-quality and high-quality image is obtained. This is preferable.
If these conditions are prioritized, the PLHM shear rate, the number of passes, the emulsification temperature, the hold-up volume, and the residence time are not limited.

The grounds for these conditions are described below.
1) “Hold-up internal volume is Q <V <Q × 30” If the volume outside this range is outside this range, the emulsified liquid will suffer from problems such as increased energy loss and cavitation due to friction with the piping. come.

2) About “the average residence time of the emulsifying mechanism part is within 30 min” (this is also true for “the hold-up volume is Q <V <Q × 30”)
If the retention time in the hold-up becomes too long (in this case, 30 min or more), the time between the passes may become very long, and the coalescence of the particles proceeds until the next shearing, and the shearing and coalescence The balance is biased, resulting in a disadvantageous condition for particle size control.

3) “PLHM shear rate of 10-24 m / s” This is the most effective factor for the shear energy per unit weight and unit time applied to the emulsion. If the shear rate is outside this range, the particle size will be too small. Or it may become too large.

4) About “Emulsification temperature ga of 16 to 25 ° C., the variation is ± 5 ° C.” The emulsification temperature is a factor related to the collision frequency of particles. When the temperature is high, the particles themselves have high energy, the collision frequency between the particles increases, and the coalescence may progress too much. Therefore, there is a possibility that the particle size cannot be controlled to a target value. On the other hand, when the temperature is too low, the coalescence frequency is extremely reduced, and it is considered that the balance between shearing and coalescence cannot be achieved.

5) About “toner volume average particle diameter (Dv) of 3 to 10 μm” It contains at least a polyester resin as a binder, Dv is 3 to 10 μm, and volume average particle diameter (Dv) is number average particle diameter (Dn). In the case of a dry toner having a value Dv / Dn divided by 1.0 to 1.25, the heat-resistant storage stability, low-temperature fixability, and hot offset resistance are all excellent. In particular, the dry toner is applied to a full-color copying machine or the like. When used in an image, an image having excellent gloss can be obtained.
Further, when the dry toner is used as a two-component developer, even if the toner balance for a long period of time is performed, the fluctuation of the particle diameter of the toner in the developer is reduced. Good and stable developability can be obtained.
Even when the toner is used as a one-component developer, the balance of toner (which means that the toner is circulated in the developing unit many times without actually being transferred to the photosensitive member) is performed. In addition, toner particle diameter fluctuations are reduced, and there is no filming of toner on the developing roller, and there is no toner fusion to a member such as a blade for thinning the toner. Even in the case of stirring, good and stable developability and images can be obtained.
In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there.
In addition, when the volume average particle diameter is smaller than the above range, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the chargeability of the carrier tends to be reduced. The agent tends to easily cause toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner.
Further, these phenomena are the same for a toner having a fine powder content higher than the above range.
On the contrary, when the toner particle diameter is larger than the above range, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the toner particles The variation in diameter often increases. It was also clarified that the same applies when Dv / Dn is larger than 1.25.
Further, when Dv / Dn is smaller than 1.05, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and equalizing the charge amount, but the toner cannot be sufficiently charged or the cleaning property is deteriorated. It is clear that there are cases.

The toner granulation can be classified into the following four patterns depending on the content of the prescription.
1. 1. A formulation that is easy to emulsify and unite. 2. A formulation that is easy to emulsify and difficult to unite. 3. A formulation that is difficult to emulsify and easy to unite. Formulations 1 and 2 that are difficult to emulsify and difficult to unite are easy to emulsify. Therefore, it is necessary to reduce the rotational force of PLHM to reduce the shearing force.
Further, in the case of 1, since the prescription is easy to unite, it is necessary to shorten the time between passes in the hold-up. For this purpose, the hold-up volume must be very small. In the case of 2, since it is difficult to unite, it is preferable to increase the hold-up volume in order to lengthen the time between the passes.
Next, in the cases of 3 and 4, since the prescription is difficult to emulsify, it is necessary to increase the rotational speed of the PLHM to increase the shearing force.
In the case of 3, since the prescription is easy to unite, it is necessary to reduce the hold-up volume as in 1 (the PLHM rotation speed is higher than 1 so that the discharge amount increases, and as a result, the hold is held. Because the pipe flow speed in the up-up becomes faster, the conditions are less than in the case of 1.)
In the case of 4, since the prescription is difficult to unite, it is necessary to increase the hold-up volume as in 2 (because the pipe flow rate is faster than 2), the hold-up volume must be increased from 2 Is preferred).
Next, calculation formulas for factors involved in hold-up will be described.

となる。
乳化後は、脱溶剤、洗浄、乾燥の工程を経てトナー粒子母体が生成される。

It becomes.
After emulsification, a toner particle matrix is produced through steps of solvent removal, washing and drying.

(Particle size distribution measurement method)
The average particle size and particle size distribution of the toner were analyzed using a Coulter Multisizer III (manufactured by Coulter), a personal computer (manufactured by IBM), and data analysis using dedicated analysis software (manufactured by Coulter). The Kd value was set using standard particles of 10 μm, and the aperture current was set at an automatic setting.
As the electrolytic solution, a 1% NaCl aqueous solution is prepared using first grade sodium chloride.
In addition, ISOTON-II (manufactured by Coulter Scientific Japan) can be used.
As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzenesulfonate is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and the volume distribution (Dv) is measured by measuring the volume and number of toners of 2 μm or more using a 100 μm aperture tube. And the number distribution (Dn) were calculated.
Then, the volume-based volume average particle size obtained from the volume distribution according to the present invention and the number-based number average particle size obtained from the number distribution were obtained.
The closer the Dv / Dn is to 1.0, the sharper the particle size distribution.

The binder resin used in the present invention is not particularly limited, and any resin can be used as long as it is a resin used for ordinary toners such as a styrene acrylic resin, a polyol resin, and a polyester resin.
In particular, from the viewpoint of fixability, a polyester resin is suitable for reproducing a full-color image.

The modified polyester resin will be described.
The polyester resin contains a functional group contained in the acid or alcohol monomer unit and a bonding group other than an ester bond, or a resin component having a different structure in the polyester resin is bonded by a covalent bond or an ionic bond. .
For example, the polyester terminal is reacted with something other than an ester bond. Specifically, a functional group such as an isocyanate group that reacts with an acid group or a hydroxyl group is introduced at the terminal and further reacted with an active hydrogen compound to modify the terminal or undergo an extension reaction.
Further, compounds having a plurality of active hydrogen groups include those in which polyester ends are bonded to each other (urea-modified polyester, urethane-modified polyester, etc.).
In addition, a reactive group such as a double bond is introduced into the polyester main chain, radical polymerization is caused therefrom, and a carbon-carbon bond graft component is introduced into the side chain or the double bonds are bridged. Included (styrene modified, acrylic modified polyester, etc.).
In addition, a resin component having a different structure is copolymerized in the polyester main chain or reacted with a terminal carboxyl group or hydroxyl group. For example, those obtained by copolymerization with a silicone resin having a terminal modified with a carboxyl group, a hydroxyl group, an epoxy group, or a mercapto group (such as a silicone-modified polyester) are also included.
This will be specifically described below.

(Urea-modified polyester resin)
Examples of the polyester (i) modified with a urea bond include a reaction product of a polyester prepolymer (A) having an isocyanate group and an amine (B). Examples of the polyester prepolymer (A) having an isocyanate group include a product obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate (3), which is a polycondensate of polyol (1) and polycarboxylic acid (2). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol; bisphenol And alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

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

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

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

The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the polyisocyanate (3) 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. It is.
If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

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

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

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

The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2.
When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low, and the hot offset resistance deteriorates.
In the present invention, the polyester (i) modified with a urea bond may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

The urea-modified polyester (i) of the present invention is produced by a one-shot method or a prepolymer method.
The weight average molecular weight of the urea-modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates.
The number average molecular weight of the urea-modified polyester is not particularly limited when the unmodified polyester (i) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight.
(I) When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

(Unmodified polyester resin)
In the present invention, not only the polyester (i) modified with a urea bond but also the polyester (ii) not modified can be included as a toner binder component together with the (i).
By using (ii) in combination, the low-temperature fixability and glossiness when used in a full-color apparatus are improved, which is preferable to single use.
Examples of (ii) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (i) above, and preferred ones are also the same as (i).
(Ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example.
It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (i) and (ii) preferably have similar compositions.
When (ii) is contained, the weight ratio of (i) and (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. If the weight ratio of (i) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The peak molecular weight of (ii) is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate.
The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The acid value of (ii) is usually 1-30, preferably 5-20. By having an acid value, it tends to be negatively charged.

In the present invention, the glass transition point (Tg) of the toner binder is usually 50 to 70 ° C., preferably 55 to 65 ° C. If the temperature is less than 50 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient.
Due to the coexistence of the urea-modified polyester resin, the dry toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester-based toners.
As the storage elastic modulus of the toner binder, the temperature (TG ′) at which 10000 dyne / cm ² is obtained at a measurement frequency of 20 Hz is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates.
As the viscosity of the toner binder, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or lower, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates.
That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or higher. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited.
Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.

(Coloring agent)
As the colorant used in the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, Yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Parared, Phi Sae Red, Par Chlor ortho nitroaniline red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, In Dunslen Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Tog Lean lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, ritbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

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

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

(Release agent)
Further, a wax may be contained together with the toner binder and the colorant.
Known waxes can be used as the wax of the present invention, for example, polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. Can be mentioned. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecandiol diol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone).
Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.
The melting point of the wax used in the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature.
Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability.
The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary.
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable.
When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density Cause a decline.
These charge control agents and release agents can be melt-kneaded together with the masterbatch and the resin, and of course, they may be added when dissolved and dispersed in an organic solvent.

(Toner production method in aqueous medium)
As an aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination.
Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

The toner binder can be produced by the following method.
The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained.
Subsequently, this is made to react with polyisocyanate (3) at 40-140 degreeC, and the prepolymer (A) which has an isocyanate group is obtained. Further, (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester modified with a urea bond.
When (3) is reacted and (A) and (B) are reacted, a solvent can be used as necessary.
Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to the isocyanate (3), such as tetrahydrofuran (such as tetrahydrofuran).
When polyester (ii) not modified with urea bond is used in combination, (ii) is produced by the same method as polyester having a hydroxyl group, and this is dissolved in the solution after completion of the reaction of (i) and mixed. To do.

In order to lower the viscosity of the oil phase of the toner composition and make it emulsifiable, a volatile solvent in which the modified polyesters (i) and (A) are soluble is used. 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.
In addition, the toner shape can be further adjusted by using a solvent that can be dissolved in an aqueous medium such as alcohol or water.
The amount of solvent used with respect to 100 parts of the toner composition is usually 10 to 900 parts.

The toner particles may be formed by reacting, for example, a dispersion in a volatile organic solvent composed of an isocyanate group-containing prepolymer (A) and other toner compositions in an aqueous medium with (B), A modified polyester (i) produced in advance may be used.
As a method for stably forming a dispersion comprising a modified polyester (i) or prepolymer (A) and a toner composition in an aqueous medium, the urea-modified polyester (i) or prepolymer (A) can be used in an aqueous medium. And a method of adding a toner raw material composition to be dispersed by a shearing force.
The prepolymer (A) and other toner compositions (hereinafter referred to as toner raw materials), a colorant masterbatch, a release agent, a charge control agent, an unmodified polyester resin, etc. are dispersed in an aqueous medium. It is preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium.
For the dispersion, a mixer by ordinary stirring, more preferably a homogenizer having a high-speed rotating body and a stator, a high-pressure homogenizer, a disperser using a medium such as a ball mill, a bead mill, a sand mill, or the like is used.
In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles not containing a colorant, the colorant can be added by a known dyeing method.

The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied.
In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing method is preferable.
The emulsifier having rotating blades is not particularly limited, and any emulsifier and disperser that are generally commercially available can be used.
For example, Ultra Thalax (manufactured by IKA), Polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK pipeline homomixer , TK homomic line flow (manufactured by Special Machine Industries Co., Ltd.), colloid mill (manufactured by Shinko Pantech Co., Ltd.), slasher, trigonal wet pulverizer (manufactured by Mitsui Miike Chemical Co., Ltd.), Cavitron (Eurotech Co., Ltd.) ), Fine flow mill (manufactured by Taiheiyo Kiko Co., Ltd.), and other continuous emulsifiers, CLEARMIX (manufactured by M Technique Co., Ltd.), fill mix (manufactured by Special Machine Industries Co., Ltd.) Etc.
When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm.
The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 10 to 98 ° C. The case where the temperature is high is preferable in that the dispersion made of the modified polyester (i) or the prepolymer (A) has a low viscosity and is easily dispersed.

The amount of the aqueous medium used relative to 100 parts of the toner composition containing the urea-modified polyester (i) and the prepolymer (A) is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical.
Although solid fine particles are dispersed in the aqueous medium, as described above, other dispersants can be used in combination in order to adjust the adsorptivity of the solid dispersant to the droplets. Other dispersants can be added before emulsification of the toner composition or when the volatile components are removed after emulsification.

(Solid fine particle dispersant)
The solid fine particle dispersant is a solid that is hardly soluble in water in an aqueous medium, and is preferably a fine particle having an average particle diameter of 0.01 to 1 μm.
Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
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 a basic condition is preferable.
The organic solid fine particle dispersant is copolymerized with a monomer having a carboxyl group such as methacrylic acid obtained by microcrystals of low molecular weight organic compounds or polymer fine particles such as soap-free emulsion polymerization, suspension polymerization or dispersion polymerization. Examples include polystyrene, methacrylic acid ester, acrylic acid ester copolymer, polycondensation systems such as silicone, benzoguanamine, and nylon, and polymer particles made of thermosetting resin.

After adjusting the solid fine particle dispersant in water, an inorganic substance that can be dissolved in an acid such as tricalcium phosphate is partially dissolved by adding a necessary amount of hydrochloric acid or the like in advance. The addition amount of the acid is preferably 0.01% to 10%, more preferably 0.1% to 5% of the amount capable of completely dissolving the inorganic substance.
When using an alkali-soluble material such as polymer fine particles copolymerized with (meth) acrylic acid having a carboxyl group, a necessary amount of a base such as sodium hydroxide is added and partially dissolved. The amount of alkali added is preferably 0.01% to 10%, more preferably 0.1% to 5% of the amount capable of completely dissolving the inorganic substance.

(Other dispersants used at the time of emulsification or added later)
Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, alkyltrimethylammonium salts, Nonionic interfaces such as dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, quaternary ammonium salt type cationic surfactants such as benzethonium chloride, fatty acid amide derivatives, polyhydric alcohol derivatives, etc. Activators include amphoteric surfactants such as alanine, dodecyl di (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount.
Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6- C11) sodium oxy] -1-alkyl (C3-C4) sulfonate, sodium 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) Carboxylic acid and metal salt, perfluoroalkylcarboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl- N- (2hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-ll0, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF- 102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C6 to C10) sulfonamidopropyltrimethylammonium salt which right the fluoroalkyl group, Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, 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.

The stabilization of the dispersed droplets may be adjusted with a polymer protective colloid.
For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or other (meth) acrylic simple substances containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, acrylic acid 3 -Chloro 2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or esters of compounds containing vinyl alcohol and a carboxyl group, For example, vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Reoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl Polyoxyethylenes such as phenyl esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, after the elongation and / or cross-linking reaction, it is better to dissolve and wash away the remaining solid fine particle dispersant. From the aspect, it is preferable.
The elongation and / or cross-linking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. 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 remove the organic solvent from the obtained emulsified dispersion, a method can be employed in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely evaporated and removed.
Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide, combustion gas, or the like, particularly various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used.
Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer, rotary kiln.
When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying, but it is preferable in the liquid to perform the classification operation. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles.
At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.
By mixing the resulting dried toner powder with dissimilar particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by giving mechanical impact force to the mixed powder By immobilizing and fusing on the surface, it is possible to prevent detachment of the foreign particles from the surface of the resulting composite particle.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there.
As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) is modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron Examples include a system (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic mortar.

(Dry toner manufacturing method)
The dry toner can be produced by the following method, but is not limited thereto.
In addition, when preparing the developer, in order to improve the fluidity, storage stability, developability, and transferability of the developer, the hydrophobic silica fine particles listed above are further listed in the developer produced as described above. Inorganic fine particles such as powder may be added and mixed.
When mixing an additive (referred to as an external additive) to be fixed to the toner surface, a general powder mixer is used, but it is preferable to equip 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 in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. In addition, a strong load may be given first and then a relatively weak load, or 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.
To further adjust the shape of the obtained toner, a toner binder, a method of adjusting the shape mechanically using a hybridizer, mechanofusion, etc. A so-called spray drying method is a method in which a toner material is dissolved and dispersed in a solvent in which a toner binder is soluble, and then a solvent is removed using a spray drying apparatus to obtain a spherical toner.
Moreover, although the method of making it spherical by heating in an aqueous medium is mentioned, it is not limited to this.

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

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

Such a fluidizing agent performs surface treatment to increase hydrophobicity, and can prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, stearic acid and other fatty acid metal salts such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization.
The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

(Carrier for two-component developer)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 weights of toner with respect to 100 parts by weight of carrier. Part is preferred.
As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used.
Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin.
Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resin such as vinyl chloride, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexa Fluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Fluoro such as terpolymers of emission and non-fluoride monomers including, and silicone resins.
Moreover, you may make conductive powder etc. contain in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. Hereinafter, a part shows a weight part.
(Example 1)
<About generation of oil phase A>
First, the synthesis of low molecular weight polyester, MB and ketimine constituting the components of the A oil phase will be described below.
(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 at 10-15 mmHg reduced pressure, then add 44 parts of trimellitic anhydride to the reaction vessel at 180 ° C at normal pressure. The mixture was reacted for 2 hours to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25.

(Synthesis of MB)
Add 1200 parts of water, 540 parts of carbon black (Printex 35 Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], 1200 parts of polyester resin, and mix with a Henschel mixer (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. In addition, PY155 (manufactured by Clariant) was used instead of carbon black, and [Masterbatch 2] was obtained through the same process.

(Synthesis of ketimine (extender))
In a reaction vessel equipped with a stir bar 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, an example of creating the A oil phase is shown.
-About black In a container set 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), 947 parts of ethyl acetate are charged. The temperature was raised to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour.
Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged 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.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 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.
Further, 1324 parts of 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] (solid content of [Pigment / WAX Dispersion 1] The concentration (130 ° C., 30 minutes) was 50%).
[Pigment / WAX Dispersion 1] 749 parts and [Ketimine Compound 1] 2.9 parts are put in a container and mixed with a homodisper (made by Tokushu Kika) at 5,000 rpm for 1 minute to complete the black.
-Yellow Yellow was obtained through the same steps as black except that [Master batch 1] was changed to [Master batch 2].

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

<Adjustment of water phase>
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours.
Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 105 nm.
A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The resin content had a Tg of 59 ° C. and a weight average molecular weight of 150,000.
83 parts of this [fine particle dispersion 1], 990 parts of water, 37 parts of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. As a result, a milky white liquid was obtained. This is designated as [Aqueous Phase 1].

<About the emulsification process>
The prescription using 60.4 parts of the A oil phase, 7.4 parts of the B oil phase, and 101.6 parts of the aqueous phase shown above was emulsified as black A and yellow A. The emulsification conditions are as follows.
・ Black A
Total liquid delivery: 10 kg / min
Hold-up amount: 15L
Emulsifier shear rate: 17m / sec
Emulsification temperature: 21 ° C
・ Yellow A
For Black A, the conditions are the same except that the hold-up amount is changed to 20L.

A toner was obtained by treating each emulsified dispersion obtained under the above conditions as follows.
The solvent removal process was performed by the following method.
That is, the temperature was raised to 45 ° C., and the solvent was removed at an outer peripheral end peripheral speed of 10.5 m / s at atmospheric pressure (101.3 kPa). The solvent removal time required 20 hours. Thereafter, the toner of Example 1 was obtained after filtration, washing, and drying.
Next, 100 parts of the obtained base particles and 0.25 parts of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was adjusted to 50 m / Set to sec, 5 cycles were performed for 2 minutes of operation and 1 minute of rest, and the total processing time was 10 minutes.
Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan Co.) was added, the peripheral speed was 15 m / sec, and 30 seconds of mixing and resting for 1 minute were performed for 5 cycles. Further, 0.5 part of hydrophobic silica and 0.5 part of hydrophobized titanium oxide were mixed with a Henschel mixer, and coarse particles were removed with a screen having an opening of 37 μm to obtain black toner and yellow toner.

(Example 2)
In Example 1, the black A and yellow A oil phases were changed from 60.4 parts to 56.4 parts, and the B oil phase was changed from 7.4 parts to 11.4 parts as black B and yellow B. .
Further, the conditions on the equipment side are the same as those in the first embodiment except that black B has a hold-up amount of 300L and yellow B has a hold-up amount of 250L.

(Example 3)
In Example 1, black C and yellow C were prepared by changing the aqueous phase of black A and yellow A from 101.6 parts to 120 parts.
Further, as conditions on the equipment side, Black C had a hold-up amount of 105 L, Yellow C had a hold-up amount of 70 L, a shear rate of 10 m / sec, and an emulsification temperature of 16 ° C.

Example 4
In Example 1, black D and yellow D were obtained by changing the aqueous phase of black A and yellow A from 101.6 parts to 135 parts.
As the conditions on the equipment side, Black D had a hold-up amount of 150 L, Yellow D had a hold-up amount of 105 L, a shear rate of 24 m / sec, and an emulsification temperature of 25 ° C.

(Comparative Example 1)
The conditions are the same except that the hold-up amount for both Black A used in Example 1 and Black B used in Example 2 is 20L.

(Comparative Example 2)
The conditions are the same except that the hold-up amount for both Yellow A used in Example 1 and Yellow B used in Example 2 is 250L.
Table 1 shows the emulsification conditions and the results of Dv and Dv / Dn in each example.

注）画像評価結果は細線再現性を評価し、１〜５の評価で５が一番良い。

Note) The image evaluation result is an evaluation of fine line reproducibility.

(About evaluation method of fine line reproducibility)
For fine line reproducibility, this developer is placed in a remodeled machine from which the fixing oil part of an intermediate transfer type color copying machine (IMAGIO COLOR 5000; manufactured by Ricoh) is removed, and the image occupancy rate is 7%. Running was performed using 6000 paper. Compare the original 10th image and the 30,000th image of the thin line with the original, zoom in with an optical microscope at a magnification of 100x, and compare the line omission state with the stage sample in 5 stages. evaluated.
From the above test results, it can be seen that there is the following tendency.

(About Black A and Yellow A)
It can be seen that a smaller hold-up volume is more convenient for emulsification conditions. This emulsification system is the above-mentioned prescription “easy to emulsify and unite easily”. As can be seen from the result of Comparative Example 2, the time between passes becomes longer when the hold-up volume increases, and the uniting proceeds too much during that time. Thus, it is considered that the particles cannot be made small by shearing with an emulsifier, and that it is in a state of unity> shearing.

(About Black B and Yellow B)
It can be said that it is more convenient for emulsification conditions to have a larger hold-up volume in a pattern opposite to that of black A and yellow A, and it can be said that “a prescription that is easy to emulsify and difficult to unite”. When the hold-up volume is small, the time between the passes is shortened and shearing is again performed by the emulsifier before coalescence is achieved, so that it can be said that the particles cannot be enlarged. In this case, it can be said that the condition of coalescence <shearing.

(About Black C and Yellow C)
Since the system is very easy to emulsify, the shearing force of the emulsifier is small, and it is understood that the coalescence speed is intermediate between black A / yellow A and black B / yellow B. In addition, this system preferably has a low emulsification temperature.

(About Black D and Yellow D)
Since the system is very difficult to emulsify, it can be seen that the shearing force of the emulsifier is large, and the coalescence speed is in the middle region as in Black C and Yellow C. In addition, this system preferably has a high emulsification temperature.

From the above results, it can be seen that the shear and coalescence behavior during emulsification varies greatly depending on the formulation. Therefore, it turns out that adjustment of the unification speed by adjusting the emulsifier shear force and setting an appropriate hold-up amount according to the prescription is necessary. Further, since the emulsification temperature is a factor that greatly contributes to the volume average particle diameter, it is necessary to set it to an appropriate value in advance.
Regarding image evaluation, good results are obtained when Dv and Dv / Dn satisfy specified values.

It is a schematic process drawing of the continuous emulsification process in the present invention. Specifically, as a means for changing the partial retention volume of the emulsifying mechanism, it is a conceptual view of a device equipped with a telescopic tube such as a bellows tube. It is a conceptual diagram of what used a parallel bypass path as a change method of an emulsification mechanism partial residence volume. It is a conceptual diagram of what the stock tank was comprised in the retention volume part as a change means of the emulsification mechanism partial retention volume.

Claims (14)

It is equipped with a continuous emulsifier and is used in a method in which a toner composition containing at least a resin, a colorant and a release agent is dissolved or dispersed in an organic solvent and the dissolved or dispersed material is continuously emulsified in an aqueous medium. An electrophotographic image forming toner manufacturing apparatus comprising a means capable of changing a partial retention volume of an emulsifying mechanism. The toner production for electrophotographic image formation according to claim 1, wherein the following relationship is satisfied when the emulsification mechanism partial retention volume V (L) and the discharge flow rate Q (L / sec) of the emulsifier are changed. apparatus.

The electrophotographic image forming toner manufacturing apparatus according to claim 1, wherein the emulsifying mechanism partial retention volume is changed by a telescopic tube. The manufacturing apparatus according to claim 1, wherein a parallel bypass path is used as a method of changing the emulsification mechanism partial residence volume. The toner manufacturing apparatus for electrophotographic image formation according to any one of claims 1 to 3, wherein a stock tank is provided in the retention volume as a means for changing the partial retention volume of the emulsification mechanism. 6. A method for producing a toner for electrophotographic image formation, wherein the toner production apparatus according to claim 1 is used and the shear rate of a continuous emulsifier is set to 10 to 24 m / s. 7. The method for producing toner for electrophotographic image formation according to claim 6, wherein the temperature during continuous emulsification is 16 to 25 [deg.] C., and the temperature variation of the emulsifying mechanism partial retention portion is within ± 5 [deg.] C. 8. The method for producing a toner for forming an electrophotographic image according to claim 6, wherein the average residence time of the emulsifying mechanism partial residence part is set to 30 minutes or less. 9. The production of toner for electrophotographic image formation according to claim 6, wherein the average number of times of shearing by the emulsifier within the partial residence time of the emulsifying mechanism is 200 (times / min) or less. Method. An electrophotographic image forming toner obtained by the production method according to claim 6, wherein the volume average particle diameter (Dv) is 3 to 10 μm. The toner for forming an electrophotographic image according to claim 10, wherein a value obtained by dividing the volume average particle diameter (Dv) by the number average particle diameter (Dn) is 1.05 to 1.25. An electrophotographic image forming method using the electrophotographic image forming toner according to claim 10. An electrophotographic image forming apparatus on which the toner according to claim 10 or 11 is mounted. A container in which the toner according to claim 10 is stored.

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