JP3428364B2 - Colorant dispersion, method for producing toner for developing electrostatic image, toner for developing electrostatic image, developer for electrostatic image, and image forming method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for efficiently producing a toner for developing an electrostatic charge image, which is excellent in light transmittance, colorability, etc. and is suitably used in image formation by electrophotography and the like. The present invention relates to a colorant dispersion suitable for use in a method, an electrostatic charge image developing toner produced by the method, an electrostatic charge image developer using the electrostatic charge image developing toner, and an image forming method.

[0002]

2. Description of the Related Art A method of visualizing image information through an electrostatic charge image, such as electrophotography, is currently widely used in various fields. In the electrophotographic method, a charging step,
An electrostatic charge image is formed on the photoreceptor through an exposure step, and the electrostatic charge image is developed using a developer containing toner particles,
The electrostatic charge image is visualized through a transfer process, a fixing process, and the like.

By the way, as the developer, a two-component developer containing toner particles and carrier particles and a one-component developer containing magnetic toner particles or non-magnetic toner particles are known. ing. The toner particles in the developer are usually produced by a kneading and pulverizing method. In this kneading and pulverizing method, a thermoplastic resin and the like are melt-kneaded together with a pigment, a charge control agent, a release agent such as wax, and the like, and after cooling, the melt-kneaded product is finely pulverized and classified to obtain desired toner particles. It is a manufacturing method. The toner particles produced by the kneading and pulverizing method may further have inorganic and / or organic fine particles added to the surface of the toner particles for the purpose of improving fluidity and cleaning property.

In the case of the toner particles produced by the above kneading and pulverizing method, the shape thereof is usually irregular and the surface composition is not uniform. Although the shape and surface composition of the toner particles are slightly changed depending on the pulverizability of the materials used and the conditions of the pulverization process, it is difficult to intentionally control them to a desired degree. Further, in the case of toner particles produced by the kneading and pulverizing method using a material having particularly high pulverizability, the toner particles are further pulverized or changed in shape by mechanical force such as various shearing forces in the developing machine. Often happens. As a result, in the two-component developer, finely divided toner particles adhere to the carrier surface to accelerate the charge deterioration of the developer, and in the one-component developer, the particle size distribution is expanded. However, there arises a problem that the finely divided toner particles are scattered or the developing property is deteriorated due to the change of the toner shape and the image quality is deteriorated.

When the shape of the toner particles is irregular, the fluidity is not sufficient even if a fluidity aid is added, and the fine particles of the fluidity aid may be formed by the mechanical force such as shearing force during use. There is a problem that the particles move to the concave portions and are buried in the concave portions, so that the fluidity decreases with time, and the developability, transferability, cleaning property, etc. deteriorate. Further, when such toner is collected by a cleaning process and returned to the developing machine for reuse, there is a problem that image quality is likely to deteriorate. In order to prevent these problems, it is possible to further increase the amount of fluidity aid, but in this case,
There arises a problem that black spots are generated on the photoconductor and particles of the fluidity aid are scattered.

On the other hand, in the case of a toner having a release agent such as wax internally added, the release agent may be exposed on the surface of toner particles depending on the combination with a thermoplastic resin. In particular, in the case of a toner obtained by combining a resin, which has elasticity imparted by a high molecular weight component and is not easily pulverized, and a brittle wax such as polyethylene, polyethylene is often exposed on the surface of toner particles. Although such a toner is advantageous in releasability at the time of fixing and cleaning of untransferred toner from the photosensitive member, polyethylene on the surface of the toner particles causes mechanical force such as shearing force in the developing device. Since they are detached from the toner particles and are easily transferred to the developing roll, the photosensitive member, the carrier, etc., they are liable to be contaminated and the reliability as a developer is lowered.

Under such circumstances, in recent years, as means for producing a toner in which the shape and surface composition of particles are controlled, for example, JP-A-63-282752 and JP-A-6-25 are available.
Japanese Patent No. 0439 proposes a method for producing a toner by an emulsion polymerization aggregation method. The method proposed in these publications is to prepare a resin particle dispersion liquid by emulsion polymerization or the like, prepare a colorant dispersion liquid in which a colorant is dispersed in an aqueous medium (solvent), and mix them to obtain toner particles. This is a method for producing a toner by forming agglomerated particles corresponding to the diameter and heating and fusing.

However, in the case of these methods, it is necessary to prepare a colorant dispersion liquid in which the colorant is dispersed in an aqueous solvent, but the average particle diameter of the colorant in the colorant dispersion liquid is controlled. However, it is difficult to produce a toner having desired characteristics. In order to control the average particle size of the colorant in the colorant dispersion, the colorant is dispersed in the aqueous medium (solvent) to a desired particle size without agglomeration and sedimentation or precipitation, and the resin A colorant dispersion liquid is required so that the colorants do not aggregate even when forming aggregated particles together with the particles, but such a colorant dispersion liquid is not easy to prepare. That is, when the average particle size of the colorant in the colorant dispersion is large, the colorant is settled or precipitated, the colorants are aggregated with the coarse particles as the core, and the colorant is formed when the aggregated particles are formed together with the resin particles. Various problems occur such as liberation, deterioration of chargeability due to exposure of the colorant on the toner surface, and deterioration of toner light transmittance due to coarse particles. In addition, when the average particle diameter of the colorant in the colorant dispersion is small, problems such as insufficient colorability of the obtained toner occur.

On the other hand, in recent years, the demand for higher image quality has increased,
In particular, in color image formation, in order to realize a high-definition image, there is a marked tendency for the toner to have a smaller diameter and a uniform particle diameter. When an image is formed using a toner having a wide particle size distribution,
Due to the toner on the fine powder side in the particle size distribution, the problems of contamination of the developing roll, charging roll, charging blade, photoconductor, carrier, etc. and toner scattering become significant, making it difficult to simultaneously realize high image quality and high reliability. is there. Further, such a toner having a wide particle size distribution has a problem that it is inferior in reliability even in a system having a cleaning function or a toner recycling function. In order to achieve high image quality and high reliability at the same time, it is necessary to sharpen the particle size distribution of the toner, reduce the particle size, and make the particle size uniform.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the various problems in the prior art and achieve the following objects. That is, the present invention is: 1. An electrostatic charge image development which is excellent in various characteristics such as charging property, developing property, transfer property, fixing property and cleaning property, particularly excellent in light transmittance and coloring property, and which satisfies high image quality and high reliability. And an electrostatic charge image developer using the toner for developing an electrostatic charge image. (2) An object of the present invention is to provide an electrostatic charge image developing toner suitable for a two-component type electrostatic charge image developer having high transfer efficiency, low toner consumption, and long life. (3) A method for producing an electrostatic charge image developing toner capable of easily and simply producing an electrostatic charge image developing toner excellent in the above various properties without causing release of a colorant, a release agent, etc., and the electrostatic charge It is an object of the present invention to provide a colorant dispersion liquid having excellent dispersibility of a colorant, which is preferably used in a method for producing an image developing toner. (4) An object of the present invention is to provide an image forming method capable of easily and easily forming a high-saturation full-color image on paper and OHP. (5) An object of the present invention is to provide an image forming method which is highly suitable for a so-called toner recycling system in which toner collected from a cleaner is reused and which can obtain high image quality excellent in light transmittance and colorability.

[0011]

Means for solving the above-mentioned problems are as follows. That is, <1> a resin particle dispersion liquid in which resin particles are dispersed,
A step of mixing a colorant dispersion liquid obtained by dispersing a colorant in an aqueous medium, aggregating the resin particles and the colorant to form aggregated particles to prepare an aggregated particle dispersion liquid, and the aggregated particles In the method for producing a toner for developing an electrostatic charge image, which comprises the step of heating and fusing to form toner particles.
And a particle size of 84% of the cumulative volume of the colorant in the colorant dispersion is at most 500 nm, and
After the step of preparing the aggregated particle dispersion,
Add a fine particle dispersion that is made by dispersing fine particles into the dispersion liquid.
Adhering particles by mixing and adhering the fine particles to the agglomerated particles
A method for producing a toner for developing an electrostatic charge image, which further comprises a step of forming a child . <2> The method for producing an electrostatic image developing toner according to <1>, wherein the aqueous medium contains at least one of an anionic surfactant, a cationic surfactant and a nonionic surfactant. <3> The electrostatic image development according to <1> or <2>, in which the colorant dispersion is prepared by dispersing the colorant in an aqueous medium using either an ultrasonic disperser or a high-pressure impact disperser. It is a method of manufacturing toner for use. <4> The method for producing an electrostatic charge image developing toner according to any one of <1> to <3>, wherein the colorant dispersion contains at least two types of colorants. <5> The method for producing an electrostatic charge image developing toner according to any one of <1> to <4>, wherein the average particle diameter of the resin particles is at most 1 μm. <6> The method for producing an electrostatic charge image developing toner according to any one of <1> to <5>, wherein the aggregated particles include a release agent.

<7> An electrostatic charge image developing toner produced by the method for producing an electrostatic charge image developing toner according to any one of <1> to <6> .

<8> An electrostatic charge image developer containing a carrier and a toner, wherein the toner is the electrostatic charge image developing toner according to <7>. . <9> The above <8 > in which the carrier has a resin coating layer.
The electrostatic charge image developer described in <> .

<10> A step of forming an electrostatic latent image on an electrostatic latent image carrier, a step of developing the electrostatic latent image with a developer layer on a developer carrier to form a toner image, In the image forming method, which includes a transfer step of transferring a toner image onto a transfer body and a cleaning step of removing toner for developing an electrostatic charge image remaining on the electrostatic latent image carrier, the developer layer may have the above-mentioned <7. The image forming method is characterized by containing the toner for developing an electrostatic charge image as described in <1> .

<11> A method for producing the toner according to <1>
Used in the method, a colorant dispersion liquid in which the colorant is dispersed in an aqueous medium, wherein the average particle diameter of the colorant in the colorant dispersion liquid is at most 350 nm, and the cumulative volume is 8
A colorant dispersion is characterized in that the particle size of 4% is at most 500 nm. <12> The colorant dispersion liquid according to <11> , wherein the aqueous medium contains at least one of an anionic surfactant, a cationic surfactant and a nonionic surfactant. <13> The above <11> or <12>, wherein the dispersion is performed using either an ultrasonic disperser or a high-pressure impact disperser.
The colorant dispersion described in 1. <14> The above < comprising at least two colorants.
The colorant dispersion according to any one of 11> to <13> .

[0016]

DETAILED DESCRIPTION OF THE INVENTION

-Colorant Dispersion Liquid-The colorant dispersion liquid of the present invention comprises a colorant dispersed in an aqueous medium. The average particle size of the colorant in the colorant dispersion (including both primary particles and secondary particles) is generally preferably half the wavelength of light or less, but in the present invention, at most 350 nm (ie 3
50 nm or less), preferably 50 to 350 nm,
50 to 300 nm is more preferable, and 50 to 250 nm is particularly preferable. In the present invention, as the average particle diameter of the colorant in the colorant dispersion, any one of the lower limit value or the upper limit value of the numerical range or the colorant in the colorant dispersion liquid used in Examples described later is used. Any one of the values of the average particle size is set as the lower limit, and any one of the lower limit value or the upper limit value of the above numerical range or the value of the average particle size of the colorant in the colorant dispersion liquid used in Examples described later is used. A numerical range of the upper limit is also preferable. If the average particle size of the colorant in the colorant dispersion exceeds 350 nm, the average particle size of the colorant dispersed in the toner cannot be reduced, and the toner may not have sufficient light transmittance. OHP
In the above, a high-saturation full-color image cannot be obtained, the toner particle size distribution is widened, the colorant particles are exposed on the toner surface, and the colorant particles do not form aggregates with the resin particles and are released. It is easy to cause deterioration of performance and reliability, such as being lost. On the other hand, the average particle diameter of the colorant in the colorant dispersion is 5
When it is less than 0 nm, the coloring property may not be sufficient. The average particle size of the colorant in the colorant dispersion can be measured using, for example, Microtrac.

The particle size (including both primary particles and secondary particles) having a cumulative volume of 84% of the colorant in the colorant dispersion is 500 nm or less, and 200 to 30.
0 nm is preferred. In the present invention, as the particle size of the cumulative volume of 84%, the lower limit value or the upper limit value of any of the numerical ranges or the value of the particle size of the cumulative volume of 84% used in Examples described later is used. A lower limit is also preferable, and a lower limit or an upper limit of any of the above numerical ranges or a numerical range having an upper limit of any cumulative volume of 84% adopted in the examples described later is also preferable. If the value of the cumulative volume of the colorant in the colorant dispersion liquid of 84% exceeds 500 nm,
The pigment content of the toner is reduced, and the toner is easily exposed on the surface of the toner, and charging and powder characteristics are easily deteriorated. In the present invention, the particle size of the colorant in the colorant dispersion having a cumulative volume of 84% means that the total volume of the particles is 100%.
When the cumulative curve is calculated as, the cumulative curve is 50
The particle size at the time of% is the volume average particle size, and the point of 84% also means the particle size of the cumulative volume of 84%. For example, a laser scattering / diffraction type particle sizer, a centrifugal sedimentation type particle sizer etc. It is possible to measure, but since there is a machine difference in the value of the average particle size of the cumulative volume of 84% depending on the type of these measuring machines, the “average particle size of the cumulative volume of 84%” of the colorant in the present invention is It indicates the value measured using Microtrac (Microtrac UPA9340, manufactured by Nikkiso Co., Ltd.).

Examples of the colorant include carbon black, chrome yellow, Hansa yellow, benzidine yellow, thren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliant carmine 3B, Brilliant Carmine 6B, DuPont Oil Red, Pyrazolone Red, Resole Red, Rhodamine B Lake, Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride,
Various pigments such as phthalocyanine blue, phthalocyanine green, and malachite green oxalate; acridine-based, xanthene-based, azo-based, benzoquinone-based, azine-based, anthraquinone-based, dioxazine-based, thiazine-based, azomethine-based, indico-based, thioindico-based, phthalocyanine And various dyes such as aniline black, polymethine, triphenylmethane, diphenylmethane, thiazine, thiazole and xanthene. These colorants may be used alone or in combination of at least two (two or more). In the latter case, the color of the toner can be arbitrarily adjusted by changing the type and mixing ratio of the colorant (pigment).

In the present invention, as the colorant,
It may be surface-modified with rosin, polymer or the like. The surface-modified colorant is sufficiently stabilized in the colorant dispersion, and after the colorant is dispersed in the colorant dispersion to a desired average particle size, resin particles are dispersed. This is advantageous in that the colorants do not aggregate even in the aggregating step during mixing with the liquid, and a good dispersed state can be maintained. On the other hand, the colorant that has been subjected to excessive surface modification treatment,
In the aggregating step, the resin particles may be released without aggregating. Therefore, the surface modification treatment is performed under optimal conditions that are appropriately selected. As the polymer,
Examples thereof include acrylonitrile polymer and methyl methacrylate polymer. As the conditions for the surface modification, generally, a polymerization method in which a monomer is polymerized in the presence of a colorant (pigment), a colorant (pigment) is dispersed in a polymer solution, and the solubility of the polymer is lowered to reduce the colorant ( It is possible to use a phase separation method in which the pigment is deposited on the surface.

Suitable examples of the aqueous medium include water and alcohol to which at least one kind of surfactant is added. Examples of the surfactants include anionic surfactants such as sulfate ester type, sulfonate type, phosphoric acid ester type and soap type; amine salt type, quaternary ammonium salt type and the like cationic surfactants; polyethylene. Preferable examples include nonionic surfactants such as glycol type, alkylphenol ethylene oxide adduct type and polyhydric alcohol type. Among these, ionic surfactants are preferable, and anionic surfactants and cationic surfactants are more preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The surfactants may be used alone or in combination of two or more.

Specific examples of the anionic surfactant include fatty acid soaps such as potassium laurate, sodium oleate and sodium castor oil; sulfates such as octyl sulfate, lauryl sulfate, lauryl ether sulfate and nonylphenyl ether sulfate. Lauryl sulfonate, dodecyl sulfonate, dodecyl benzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate, etc. sodium alkylnaphthalene sulfonate, naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric amide sulfonate, olein Sulfonates such as acid amide sulfonate; lauryl phosphate, isopropyl Dialkyl sodium sulfosuccinates, such as sodium dioctyl sulfosuccinate, lauryl disodium sulfosuccinate; Sufeto, phosphoric acid esters such as nonyl phenyl ether phosphate
Sulfosuccinates such as polyoxyethylene disodium lauryl sulfosuccinate; and the like.

Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride,
Amine salts such as oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate; lauryltrimethylammonium chloride, dilauryldimethylammonium chloride, distearylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleyl Quaternary ammonium salts such as bispolyoxyethylenemethylammonium chloride, lauroylaminopropyldimethylethylammonium ethosulfate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzenedimethylammonium chloride and alkyltrimethylammonium chloride; and the like.

Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl. Alkyl phenyl ethers such as ether and polyoxyethylene nonyl phenyl ether; polyoxyethylene laurate, polyoxyethylene stearate,
Alkyl esters such as polyoxyethylene oleate;
Alkylamines such as polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; polyoxyethylene lauric acid amide, polyoxyethylene Alkyl amides such as stearic acid amide and polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide Alkanolamides of polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethyl Nso sorbitan monostearate,
Sorbitan ester ethers such as polyoxyethylene sorbitan monooleate; and the like.

The colorant can be dispersed in the aqueous medium by using a known disperser such as a media type disperser. Regarding which disperser to use,
The colorant can be appropriately selected according to the type of the colorant, but in the present invention, it is preferable to use either an ultrasonic disperser or a high-pressure impact disperser. When the colorant is dispersed in the aqueous medium, if a binder resin is used in addition to the colorant, the slurry has an appropriate viscosity, and therefore a sufficient shearing force can be obtained even by dispersion with a media type disperser such as a sand mill or a ball mill. The average particle diameter of the colorant in the colorant dispersion can be 300 nm or less. However, when only the colorant is used, the viscosity of the slurry is low, and therefore dispersion by the media-type disperser is sufficient. It may not be possible to apply a strong shearing force,
It is not easy to make the average particle diameter of the colorant in the colorant dispersion liquid 300 nm or less.

Therefore, when the media type disperser is used to disperse the colorant in the aqueous medium, the colorant cannot be dispersed to a sufficient particle size, and even with a weak shearing force. It is necessary to select a dispersible and easily dispersible colorant, and only a toner having a limited hue can be obtained, and reproduction of intermediate colors may be insufficient. Further, for the dispersion of the hardly dispersible colorant, it is possible to increase the shearing force by using a medium having a small diameter or increasing the filling rate of the medium. However, in most cases, the slurry is thixotropic under a continuous high shearing condition. Therefore, the dispersion stability becomes insufficient, and as a result, the average particle size of the colorant in the colorant dispersion cannot be 300 nm or less. Furthermore, it is difficult to sharpen the particle size distribution of the colorant in the colorant dispersion by the dispersion using the media type disperser, and the crushed material of the media is mixed in the colorant dispersion, the dispersion time is long, etc. I have a problem. When using the media type disperser, these problems must be avoided, and it is necessary to optimally control the mechanical dispersion conditions such as the type and amount of the dispersant, the media diameter and the shear rate. On the other hand, it is inconvenient, but using either the ultrasonic disperser or the high-pressure impact disperser is advantageous in that the above problems do not occur.

Therefore, in the present invention, a media-type disperser can be used for the easily dispersible colorant, but an ultrasonic disperser and high-pressure impact which can give impact to the particles of the colorant without using a medium. Any of the formula dispersers can be suitably used. When either the ultrasonic disperser or the high-pressure impact disperser is used, strict control of mechanical conditions such as shear rate becomes unnecessary, and the type / amount / dispersibility of the colorant and the type of the aqueous medium. It is advantageous in that the average particle diameter of the colorant in the colorant dispersion can be easily set to 300 nm or less without depending on the amount or the like. In particular, in the case of a high-pressure impact disperser, it is possible to give an impact sufficient to destroy the hardly dispersible colorant, and it is possible to instantly disperse the hardly dispersible colorant. It is very advantageous because impurities are not mixed in.

The colorant dispersion of the present invention, since the dispersibility of the colorant is very good, but can be widely used in various fields of the aqueous ink, the ink jet recording ink such as the beginning, the following the present invention For electrostatic image development
It is used in a toner manufacturing method .

-Method for producing toner for developing electrostatic image-The method for producing toner for developing electrostatic image of the present invention comprises a resin particle dispersion liquid in which resin particles are dispersed, and a colorant in which a colorant is dispersed. A step of mixing a dispersion liquid, aggregating the resin particles and the colorant to form agglomerated particles to prepare an agglomerated particle dispersion liquid (hereinafter sometimes referred to as "aggregating step"), and the agglomerated particles And the step of fusing to form toner particles (hereinafter sometimes referred to as “fusing step”). The method for producing a toner for developing an electrostatic charge image of the present invention further comprises: after the aggregating step and before the fusing step.
Fine particles obtained by dispersing fine particles in the aggregated particle dispersion liquid
Add and mix dispersion to attach the fine particles to the aggregated particles
To form adhering particles (hereinafter referred to as “adhering step”)
May be included) .

In the aggregating step, the resin particles and the colorant dispersed in the resin particle dispersion and the colorant dispersion, which are mixed with each other, aggregate to form aggregated particles. The agglomerated particles are formed by heteroaggregation or the like, and, for example, the polarities / amounts of the ionic surfactants contained in the added dispersion liquid and the added dispersion liquid are preliminarily shifted, and the balance deviation is caused. It is formed by adding an ionic surfactant in a polarity and amount that compensates for In the fusing step, the resin in the aggregated particles is melted, the resin particles and the colorant are fused, and toner particles for electrostatic image development are formed.

In the adhering step, the agglomerated particles are used as mother particles, and the fine particles in the fine particle dispersion liquid added and mixed in the agglomerated particle dispersion liquid in which the agglomerated particles are dispersed are uniformly adhered to the surface of the agglomerated particles. Is formed. The adhered particles are formed by heteroaggregation or the like, and, for example, the polarities / amounts of the ionic surfactants contained in the dispersion liquid to be added and the dispersion liquid to be added are preliminarily shifted, and the deviation of the balance is caused. It is formed by adding an ionic surfactant in a polarity and amount that compensates for The attaching step is
By being performed , in the fusing step, the resin in the adhered particles is melted and fused to form toner particles for electrostatic image development.

(Aggregating Step) In the aggregating step, the resin particles and the colorant are aggregated in a dispersion liquid obtained by mixing the resin particle dispersion liquid and the colorant dispersion liquid to form aggregated particles to disperse the aggregated particles. This is a step of preparing a liquid.

The resin particle dispersion liquid comprises at least resin particles dispersed therein. Examples of the resin in the resin particles include a thermoplastic binder resin and the like. Specifically, styrene, parachlorostyrene, homopolymers or copolymers of styrenes such as α-methylstyrene (styrene-based resin). Resin); methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylate
Homopolymers or copolymers of vinyl group-containing esters such as propyl, lauryl methacrylate and 2-ethylhexyl methacrylate (vinyl resins); Homopolymers or copolymers of vinyl nitriles such as acrylonitrile and methacrylonitrile. Polymer (vinyl resin); homopolymer or copolymer of vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether (vinyl resin); vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone Polymer or copolymer (vinyl resin); Homopolymer or copolymer of olefins such as ethylene, propylene, butadiene, isoprene (olefin resin); Epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose Resin, polyether Non-vinyl condensation resin of butter, and the like, and the like graft polymer of these non-vinyl condensation resin and a vinyl monomer and the like. These resins have 1
They may be used alone or in combination of two or more.

Of these resins, vinyl resins are particularly preferable. The vinyl-based resin is advantageous in that the resin particle dispersion can be easily prepared by emulsion polymerization or seed polymerization using an ionic surfactant or the like. Examples of the vinyl-based monomer include vinyl-based polymer acids and vinyl-based polymer bases such as acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, vinyl sulfonic acid, ethyleneimine, vinyl pyridine, and vinylamine. Examples include monomers that are raw materials. In the present invention, it is preferable that the resin particles contain the vinyl monomer as a monomer component. In the present invention, among these vinyl-based monomers, a vinyl-based polymer acid is more preferable in terms of easiness of reaction for forming a vinyl-based resin, and specifically, acrylic acid, methacrylic acid, maleic acid, cinnamic acid. A dissociative vinyl-based monomer having a carboxyl group as a dissociative group, such as acid or fumaric acid, is particularly preferable from the viewpoint of controlling the degree of polymerization and the glass transition point.

The concentration of the dissociative group in the dissociative vinyl monomer is, for example, as described in Chemistry of Polymer Latex (Polymer Publishing Association), when particles such as toner particles are dissolved from the surface. It can be determined by a quantification method or the like. The molecular weight of the resin and the glass transition point from the surface to the inside of the particles can be determined by the above method and the like.

The average particle size of the resin particles is usually
At most 1 μm (1 μm or less), 0.01 to 1
It is preferably μm. When the average particle diameter exceeds 1 μm, the particle size distribution of the finally obtained toner for developing an electrostatic image is widened or free particles are generated, which tends to deteriorate the performance and reliability. On the other hand, when the average particle diameter is within the above range, the above-mentioned defects are not present, and uneven distribution among toner particles is reduced,
This is advantageous in that the dispersion in the toner becomes good and the variations in performance and reliability are reduced. The average particle size of the previous term is
For example, it can be measured using a micro track or the like.

The colorant dispersion liquid is the same as that of the present invention.
A colorant dispersion is used . The combination of the resin of the resin particles and the colorant is not particularly limited and can be freely selected according to the purpose.

In the present invention, a release agent, an internal additive, a charge control agent, an inorganic particle, an organic particle, a lubricant is added to at least one of the resin particle dispersion and the colorant dispersion according to the purpose. Other components (particles) such as an abrasive can be dispersed. In that case, other components (particles) may be dispersed in at least one of the resin particle dispersion liquid and the colorant dispersion liquid, or the resin particle dispersion liquid and the colorant dispersion liquid are mixed. You may mix the dispersion liquid which disperse | distributes other components (particles) in a mixed liquid.

Examples of the releasing agent include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; silicones having a softening point by heating; oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide and the like. Fatty acid amides; carnauba wax, rice wax, candelilla wax,
Plant waxes such as wood wax and jojoba oil; animal waxes such as beeswax; mineral and petroleum waxes such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax; and their modified products. Can be mentioned. In the present invention, among these release agents, those used in Examples described later are particularly preferable. These releasing agents may be used alone or in combination of two or more.

The content of the releasing agent in the toner for developing an electrostatic charge image is preferably 0.5 to 50% by weight, and 1
-40% by weight is more preferable, and 1-30% by weight is particularly preferable. If the content is less than 0.5% by weight, the releasability is insufficient and the toner tends to adhere to the fixing roll during high-temperature fixing, so-called offset easily occurs, and if it exceeds 50% by weight. However, the toner becomes brittle, and the toner particles are easily crushed by stirring in the developing machine, which is not preferable. The melting point of the release agent is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher, from the viewpoint of toner storage stability.

These waxes are dispersed in a water-based medium such as water together with a polymer electrolyte such as an ionic surfactant, a polymer acid and a polymer base, and heated to a temperature higher than the melting point to give a strong shearing force. When it is processed using an applicable homogenizer or a pressure discharge type disperser, fine particles of 1 μm or less are easily prepared.

Examples of the internal additive include magnetic materials such as ferrite, magnetite, reduced iron, cobalt, nickel, manganese, and other metals, alloys, and compounds containing these metals.

Examples of the charge control agent include quaternary ammonium salt compounds, nigrosine compounds, aluminum,
Examples thereof include dyes composed of complexes of iron and chromium, triphenylmethane-based pigments, and the like. The charge control agent in the present invention is preferably a material which is hardly dissolved in water from the viewpoint of controlling the ionic strength which affects the stability at the time of aggregation and fusion and reducing the pollution of wastewater.

Examples of the inorganic particles include silica,
Examples thereof include alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, and cerium oxide, and all particles usually used as external additives on the surface of toner. Examples of the organic particles include all particles such as vinyl resins, polyester resins, and silicone resins which are usually used as external additives on the surface of toner. In addition, these inorganic particles and organic particles can be used as a fluidity aid, a cleaning aid, and the like. Examples of the lubricant include, for example, ethylenebisstearyl amide,
Examples thereof include fatty acid amides such as oleic acid amide, and fatty acid metal salts such as zinc stearate and calcium stearate. Examples of the abrasive include silica described above,
Examples thereof include alumina and cerium oxide.

The average particle size of the other components (particles) is usually at most 1 μm (that is, 1 μm or less), and preferably 0.01 to 1 μm. When the average particle diameter exceeds 1 μm, the particle size distribution of the finally obtained toner for developing an electrostatic image is widened or free particles are generated, which tends to deteriorate the performance and reliability. On the other hand, when the average particle diameter is within the above range, the above-mentioned drawbacks are eliminated, uneven distribution between toner particles is reduced, dispersion in the toner is improved, and variations in performance and reliability are reduced, which is advantageous. In addition,
The average particle diameter can be measured by using, for example, Microtrac.

Examples of the dispersion medium in the resin particle dispersion liquid, the colorant dispersion liquid and the dispersion liquid in which the other components (particles) are dispersed include an aqueous medium. Examples of the aqueous medium include distilled water, water such as ion-exchanged water, alcohols and the like. These may be used alone or in combination of two or more.

In the present invention, it is preferable to add and mix a surfactant to the aqueous medium. Examples of the surfactant include the same as those exemplified in the description of the colorant dispersion liquid of the invention.

When the resin particle dispersion liquid and the colorant dispersion liquid are mixed, the content of the resin particles may be 40% by weight or less, preferably about 2 to 20% by weight. . The content of the colorant may be 50% by weight or less, preferably about 2 to 40% by weight. Further, the content of the other components (particles) may be such that the object of the present invention is not impaired, and is generally extremely small, specifically about 0.01 to 5% by weight. And is preferably about 0.5 to 2% by weight.

The method for preparing the resin particle dispersion is not particularly limited, and a method appropriately selected according to the purpose can be adopted. For example, it can be prepared as follows. The resin in the resin particles is an ester having the vinyl group, the vinyl nitriles,
In the case of a homopolymer or a copolymer (vinyl resin) of vinyl monomers such as the vinyl ethers and the vinyl ketones, the vinyl monomers are subjected to emulsion polymerization in an ionic surfactant or By carrying out seed polymerization or the like, it is possible to prepare a dispersion liquid in which resin particles made of a vinyl monomer homopolymer or copolymer (vinyl resin) are dispersed in an ionic surfactant. When the resin in the resin particles is a resin other than the homopolymer or copolymer of the vinyl-based monomer, if the resin is soluble in an oily solvent having relatively low solubility in water, , The resin is dissolved in the oily solvent, the dissolved product is added to water together with the ionic surfactant and the polyelectrolyte, fine particles are dispersed using a disperser such as a homogenizer, and then heated or depressurized. Thus, it can be prepared by evaporating the oily solvent.

The colorant dispersion can be prepared, for example, by dispersing the colorant in an aqueous medium such as the surfactant. For example, when the other component (particle) is a release agent, the dispersion liquid in which the other component (particle) is dispersed is a high amount of an ionic surfactant, a polymer acid, a polymer base, or the like. Disperse in water with molecular electrolyte. This can be prepared by heating the temperature above the melting point of the release agent and applying strong shearing using a homogenizer or a pressure discharge type disperser to atomize the release agent. When the other component (particle) is an inorganic particle or the like, it can be prepared by dispersing the inorganic particle or the like in an aqueous medium such as the surfactant.

When the resin particles dispersed in the resin particle dispersion liquid are composite particles containing a component other than the resin particles, the dispersion liquid in which these composite particles are dispersed is, for example, as follows. Can be prepared in this manner.
For example, a method in which each component of the composite particles is dissolved and dispersed in a solvent, then dispersed in water together with a suitable dispersant as described above, and the solvent is removed by heating or depressurizing, or emulsion polymerization. It can be prepared by mechanically shearing or electrically adsorbing the surface of the latex produced by the seed polymerization or seed polymerization and immobilizing it.

The dispersing means is not particularly limited, and examples thereof include known dispersing devices such as a ball mill, a sand mill and a dyno mill having a rotary shearing homogenizer and a media.

The aggregated particles are prepared, for example, as follows. An ionic surfactant having a polarity opposite to that of the ionic surfactant is added to a first dispersion (at least one of a resin particle dispersion and a colorant dispersion) containing an aqueous medium to which the ionic surfactant is added and mixed. (), Or an aqueous medium () to which it is added and mixed, or a second dispersion liquid (at least one of a resin particle dispersion liquid and a colorant dispersion liquid) () containing the aqueous medium is mixed. When this mixed solution is stirred using a stirring means, the action of the ionic surfactant causes
The resin particles and the like are aggregated in the dispersion liquid, aggregated particles are formed by the resin particles and the like, and the aggregated particle dispersion liquid is prepared. The stirring means is not particularly limited and may be appropriately selected from known stirring devices and the like according to the purpose. The mixing is preferably carried out at a temperature below the glass transition point of the resin contained in the mixed solution. When the mixing is performed under this temperature condition, the aggregation can be performed in a stable state.

In the above or case, aggregated particles are formed by aggregating at least one of the resin particles and the colorant dispersed in the first dispersion liquid. In the above case,
Aggregated particles formed by aggregating at least one of resin particles and a colorant dispersed in the second dispersion and at least one of resin particles and a colorant dispersed in the first dispersion. It is formed.

When the aggregated particles are formed, the ionic surfactant contained in the dispersion liquid on the addition side and the ionic surfactant contained in the addition side are set to have opposite polarities, Shift the polarity balance in advance,
It is preferable to compensate for this balance deviation. That is, it is preferable to add the ionic surfactant contained in the liquid on the side of addition to the ionic surfactant contained in the liquid on the side of addition so as to compensate for this balance deviation. Generally, depending on the type of the resin and the colorant of the resin particles, their polarities, etc., it may be difficult to agglomerate, and specific material particles may be liberated during agglomeration, and a desired toner composition may not be obtained. . When the release agent or the like is released, various properties inherent to the toner are impaired, and the released release agent overflows from the developing machine during development to contaminate the inside of the developing machine, or the released release agent is released in the developing machine. Due to the mechanical stress, the problem may occur such that the developing sleeve is broken or adhered and filming is performed on the developing sleeve. However, when the aggregated particles are formed as described above, such a problem does not occur. For example, even if the resin in the resin particles and the colorant have the same polarity, a surfactant having an opposite polarity is used. Addition is advantageous in that uniform agglomerated particles can be easily formed by the resin particles and the colorant.

The average particle size of the aggregated particles formed in this aggregating step is not particularly limited, but is usually controlled so as to be about the same as the average particle size of the electrostatic image developing toner to be obtained. It The control can be easily performed, for example, by appropriately setting / changing the temperature and the mixing / stirring condition. Through the above aggregation step, aggregated particles having an average particle diameter approximately the same as the average particle diameter of the electrostatic image developing toner are formed, and an aggregated particle dispersion liquid in which the aggregated particles are dispersed is prepared. The content of aggregated particles in the aggregated particle dispersion is usually 40% by weight or less. In the present invention, the aggregated particles may be referred to as “mother particles”.

(Adhering Step) In the adhering step, a step of adding and mixing a fine particle dispersion liquid in which fine particles are dispersed in the aggregated particle dispersion liquid to adhere the fine particles to the aggregated particles to form adhered particles Is.

Examples of the fine particles include, for example, those mentioned above.
Examples include resin fine particles of the resin particles, colorant fine particles of the coloring agent, and fine particles of the other components (particles). Examples thereof include a colorant dispersion liquid in which an agent is dispersed, and a dispersion liquid in which other components (particles) are dispersed. These fine particle dispersions are
They may be used alone or in combination of two or more. Fine particles such as the resin particles are uniformly adhered to the surface of the agglomerated particles to form adhered particles, and when the adhered particles are heated and fused in a fusion step described below, the agglomerated particles form a coloring agent or a release agent. When they are contained, their surfaces are covered with the material of the fine particles (shells are formed), so that the exposure of these release agents and the like from the toner particles can be effectively prevented.

In this adhesion step, when the resin fine particles are used, for example, in the case of producing a toner for developing a multicolor electrostatic image, a layer of the resin fine particles is formed on the surface of the aggregated particles. The influence of the coloring agent contained in the aggregated particles on the charging behavior can be minimized, and the difference in charging characteristics depending on the type of the coloring agent can be suppressed. Further, when a resin having a high glass transition point is selected as the resin in the resin fine particles, it is possible to produce a toner for developing an electrostatic charge image, which has both heat storability and fixability and is excellent in charging property. Further, in this adhesion step, a release agent fine particle dispersion liquid in which a release agent such as wax is dispersed as the fine particles is added and mixed, and then a resin having a high hardness or an inorganic particle is dispersed as the fine particles. By adding and mixing the fine particle dispersion liquid, a shell made of a resin or inorganic particles having high hardness can be formed on the outermost surface of the toner particles.
In this case, the exposure of the wax can be suppressed, and the wax can effectively act as a release agent during fixing. As described above, for example, the surface of the toner particles can be coated with a resin, a charge control agent, or the like, and the colorant or the release agent can be present near the surface of the toner particles.

The average particle size of the fine particles is usually at most 1 μm (that is, 1 μm or less), and 0.01 to 1
It is preferably μm. When the average particle diameter exceeds 1 μm, the particle size distribution of the finally obtained toner for developing an electrostatic image is widened or free particles are generated, which tends to deteriorate the performance and reliability. On the other hand, when the average particle diameter is within the above range, it is advantageous in that the above-mentioned drawbacks are eliminated and a layered structure of fine particles is formed. The average particle size can be measured by using, for example, Microtrac.

The volume of the fine particles depends on the volume fraction of the obtained electrostatic charge image developing toner, and is preferably 50% or less of the volume of the obtained electrostatic charge image developing toner. When the volume of the fine particles exceeds 50% of the volume of the toner for developing an electrostatic image to be obtained, the fine particles do not adhere to or aggregate on the aggregated particles, and new aggregated particles are formed by the fine particles. The composition distribution and particle size distribution of the toner for developing an electrostatic charge image may significantly change, and desired performance may not be obtained.

In the fine particle dispersion, one kind of these fine particles may be dispersed alone to prepare a fine particle dispersion, or two or more kinds of fine particles may be dispersed together to prepare a fine particle dispersion. May be. In the latter case, the combination of fine particles to be used in combination is not particularly limited and can be appropriately selected according to the purpose.

Examples of the dispersion medium in the fine particle dispersion include the above-mentioned aqueous media. In the present invention, it is preferable to add and mix at least one of the above-mentioned surfactants to the aqueous medium.

The content of the fine particles in the fine particle dispersion is usually 5 to 60% by weight, preferably 10 to 40% by weight. If the content is out of the above range, the structure and composition of the electrostatic charge image developing toner from the inside to the surface may not be sufficiently controlled.

The fine particle dispersion is prepared, for example, by dispersing at least one kind of the fine particles in an aqueous medium to which an ionic surfactant or the like is added and mixed. In addition, it can be prepared by mechanically shearing or electrically adsorbing and immobilizing it on the latex surface prepared by emulsion polymerization or seed polymerization.

In this adhesion step, the fine particle dispersion liquid is added and mixed into the agglomerated particle dispersion liquid prepared in the agglomeration step, whereby the fine particles adhere to the surface of the agglomerated particles to form adhered particles. It The fine particles are
Since it corresponds to particles newly added from the viewpoint of the aggregated particles, it may be referred to as “additional particles” in the present invention.

The method of addition and mixing is not particularly limited, and may be, for example, gradually and continuously, or may be divided into a plurality of times and stepwise. In this way, by adding and mixing the fine particles (additional particles), generation of fine particles can be suppressed, and the particle size distribution of the obtained electrostatic image developing toner can be made sharp. Further, the composition and physical properties of the obtained electrostatic charge image developing toner from the surface to the inside can be changed stepwise, and the structure of the electrostatic charge image developing toner can be easily controlled.

In the above, when the resin in the resin particles and the fine particles is selected so that the glass transition point of the resin existing outside the toner is higher than the glass transition point of the resin existing inside the toner, It is possible to achieve both the storage stability and fluidity of the toner and the minimum fixing temperature. Further, by increasing the molecular weight of the resin on the polymer side and increasing the elasticity in the molten state, offset to the heat roll at high temperatures can be prevented. This effect is an extremely effective means especially when oil is not applied.

Furthermore, when the molecular weight of the resin existing outside the toner (that is, the resin in the fine particles) is selected to be smaller than the molecular weight of the resin existing inside the toner (that is, the resin in the agglomerated particles). Since the surface smoothness of the obtained toner particles is enhanced, the fluidity and the transfer performance are easily improved. However, when the aggregated particles are not formed of one type of resin fine particles, that is, when two or more types of resin particles are aggregated, the resin existing inside the toner (that is, The molecular weight of (resin) means the average value of the molecular weights of all resins contained in the aggregated particles.

The molecular weight of the resin existing outside the toner,
When the molecular weight of the resin present inside the toner is extremely different, the adhesive force between the core portion and the coating layer portion of the obtained toner particles may be reduced, and the toner particles may not be adhered to the inside of the developing machine. When the toner is subjected to mechanical stress such as stirring or mixing with a carrier, the toner particles may be destroyed. Therefore, when the fine particles are attached to the aggregated particles, resin fine particles having an intermediate molecular weight and / or glass transition point between the resin inside the toner and the resin inside the toner are first used and It can be attached to the agglomerated particles and then the selected resin particles.

When the addition and mixing are carried out stepwise by dividing into a plurality of times, a layer of the fine particles is laminated stepwise on the surface of the agglomerated particles, and the particles of the toner for developing an electrostatic image are spread from the inside to the outside. It can have structural changes and composition gradients, can change physical properties, can improve surface hardness of particles, and can maintain particle size distribution during fusion in the fusion process and suppress fluctuations It is possible to eliminate the need to add a stabilizer such as a surfactant or a base or an acid for enhancing stability during fusion,
It is advantageous in that the added amount thereof can be suppressed to the minimum limit, and the cost can be reduced and the quality can be improved.

The conditions for adhering the fine particles to the aggregated particles are as follows. That is, the temperature is equal to or lower than the glass transition point of the resin in the resin particles in the aggregating step, and is preferably about room temperature. When heated at a temperature equal to or lower than the glass transition point, the aggregated particles and the fine particles are easily attached to each other, and as a result, the formed attached particles are easily stabilized. The treatment time cannot be unconditionally specified because it depends on the temperature, but it is usually about 5 minutes to 2 hours. At the time of the adhesion, the dispersion liquid containing the aggregated particles and the fine particles may be allowed to stand or may be gently stirred by a mixer or the like.
The latter case is advantageous in that uniform adhered particles are likely to be formed.

In the present invention, the number of times of this adhesion step may be once or plural times. In the former case, only one layer of the fine particles (additional particles) is formed on the surface of the aggregated particles,
In the latter case, if two or more kinds of fine particle dispersions are prepared, a layer of fine particles (additional particles) contained in these fine particle dispersions is laminated on the surface of the aggregated particles. The latter case is advantageous in that a toner for developing an electrostatic charge image having a complicated and precise hierarchical structure can be obtained, and a desired function can be imparted to the toner for developing an electrostatic charge image.

When the attaching step is performed a plurality of times, any combination of the fine particles (additional particles) to be attached first and the fine particles (additional particles) to be attached subsequently to the agglomerated particles (mother particles) is any combination. However, it may be appropriately selected depending on the application of the electrostatic image developing toner.

When the adhering step is carried out a plurality of times, each time the fine particles are added and mixed, the dispersion liquid containing the fine particles and the agglomerated particles is treated at a temperature not higher than the glass transition point of the resin in the resin particles in the aggregating step. It is preferable to heat at
It is more preferable that the heating temperature is increased stepwise. This is advantageous in that the adhered particles can be stabilized and the generation of free particles can be suppressed.

By the above-mentioned attaching step, the attached particles are formed by attaching the fine particles to the aggregated particles prepared in the aggregating step. When the attaching step is performed a plurality of times, the attached particles are formed by attaching the fine particles a plurality of times to the aggregated particles prepared in the aggregating step. Therefore,
By attaching appropriately selected fine particles to the aggregated particles in the attaching step, a toner for developing an electrostatic image having desired characteristics can be freely designed and manufactured. Since the distribution of the colorant in the adhered particles finally becomes the distribution of the colorant in the toner particles, the finer and more uniform the dispersion of the colorant in the adhered particles is, the more electrostatic image development is obtained. The coloring property of the toner for use is improved.

(Fusing Step) The fusing step is a step of heating and fusing the adhered particles to form toner particles.

Regarding the heating temperature, the adhesion step
The glass transition temperature of the resin contained in the adhered particles to the decomposition temperature of the resin may be used. Therefore, the temperature of the heating varies depending on the type of the resin of the fine particles, can not be indiscriminately specified, the adhesion step
The glass transition temperature of the resin contained in the adhered particles is 180 ° C to 180 ° C. By appropriately selecting the heating temperature, the shape of the obtained toner particles can be arbitrarily controlled from an irregular shape to a spherical shape. The heating can be performed using a heating device / tool known per se.

As the fusion time, a shorter time is required if the heating temperature is high, and a longer time is required if the heating temperature is low. That is, the fusion time cannot be unconditionally specified because it depends on the heating temperature, but it is generally 30 minutes to 10 hours. In the present invention, the electrostatic image developing toner obtained after the completion of the fusing step can be washed and dried under appropriate conditions. On the surface of the obtained toner for developing an electrostatic image, inorganic particles such as silica, alumina, titania and calcium carbonate, and resin particles such as vinyl resin, polyester resin and silicone resin are sheared in a dry state. May be applied to add. These inorganic particles and resin particles function as external additives such as a fluidity aid and a cleaning aid.

By the above-mentioned fusing step, the agglomerated particles (mother particles) are fused, and the adhering particles prepared in the adhering step are obtained in a state where the fine particles (additional particles) are attached to the surface of the agglomerated particles. The toner is fused to produce an electrostatic image developing toner.

In the method for producing a toner for developing an electrostatic charge image of the present invention, since fine powder is not generated during the production of toner particles, it occurs during pulverization in the kneading pulverization method or during material dispersion in the suspension polymerization method. It is advantageous in that fine powder need not be removed and the process can be simplified. Further, since at least the resin particles and the colorant are uniformly dispersed or aggregated in a state where they are intentionally localized, the aggregates are fused to form toner particles. Can be controlled uniformly or intentionally.
Further, since a highly hydrophobic material such as a release agent can be selectively present inside the toner particles, the amount of the release agent on the surface of the toner particles can be reduced.

-Toner for developing electrostatic image-The toner for developing electrostatic image of the present invention obtained by the above-mentioned method for producing the toner for developing electrostatic image of the present invention is the above-mentioned aggregate.
It has a structure in which particles are used as mother particles, and a coating layer of the fine particles (additional particles) is formed on the surface of the mother particles . The layer of the fine particles (additional particles) may be one layer,
The number of layers may be two or more, and generally, the number of layers is the same as the number of times the adhesion step is performed in the method for producing an electrostatic image developing toner of the present invention.

In the electrostatic image developing toner of the present invention,
The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography is 4 to 30.
Is preferred, 4-20 is more preferred, and 5-15 is particularly preferred. When the molecular weight distribution represented by the ratio (Mw / Mn) exceeds 30, the light transmittance and the coloring property are insufficient,
In particular, when the toner for developing an electrostatic image is developed or fixed on the film, the image projected by light transmission becomes an unclear and dark image or a non-transparent and non-colored projection image, and a temperature of less than 4 is high. At the time of fixing, the viscosity of the toner is remarkably reduced, and offset easily occurs. On the other hand, when the molecular weight distribution represented by the ratio (Mw / Mn) is within the above numerical range, the light transmittance and the colorability are sufficient, and the viscosity of the toner for developing an electrostatic charge image at the time of fixing at a high temperature is lowered. And the occurrence of offset can be effectively suppressed.

The electrostatic image developing toner is excellent in various properties such as charging property, developing property, transfer property, fixing property and cleaning property, particularly in light transmittance and colorability in an image. Further, since the above-mentioned various performances are stably exhibited and maintained without being affected by environmental conditions, the reliability is high. Since the toner for developing an electrostatic image is produced by the method for producing a toner for developing an electrostatic image of the present invention, it has a small average particle size and a small particle size, unlike the case where it is produced by a kneading and pulverizing method. The distribution is sharp.

The particle size distribution of the electrostatic image developing toner is
As described above. The average particle diameter of the toner for developing an electrostatic image is preferably 2 to 9 μm, more preferably 3 to 8 μm. If the average particle size is less than 2 μm, the chargeability tends to be insufficient, and the developability may decrease.
If it exceeds 9 μm, the resolution of the image may deteriorate.

The charge amount of the electrostatic image developing toner is preferably 10 to 40 μC / g, and preferably 15 to 35 μC / g.
g is more preferred. If the charge amount is less than 10 μC / g, background stains are likely to occur, and if it exceeds 40 μC / g, the image density is apt to decrease. The ratio of the charge amount in the summer and the charge amount in the winter of the toner for developing an electrostatic image is preferably 0.5 to 1.5,
0.7 to 1.3 is preferable. If the ratio is out of the preferred range, the toner is highly dependent on the environment and lacks stability in charging property, which may be not preferable in practical use.

—Electrostatic Image Developer— The electrostatic image developer of the present invention is not particularly limited except that it contains the toner for developing an electrostatic image of the present invention, and an appropriate component composition depending on the purpose. Can be taken. The electrostatic charge image developer of the present invention is prepared as a one-component electrostatic charge image developer when the toner for developing an electrostatic charge image of the present invention is used alone, and is also a two-component system when used in combination with a carrier. Is prepared as an electrostatic charge image developer. The carrier is not particularly limited and may be a carrier known per se. For example, known carriers such as resin-coated carriers described in JP-A-62-39879 and JP-A-56-11461 are known. A carrier can be used. The mixing ratio of the electrostatic image developing toner of the present invention and the carrier in the electrostatic image developer is not particularly limited and may be appropriately selected depending on the purpose.

-Image Forming Method- The image forming method of the present invention includes an electrostatic latent image forming step, a toner image forming step, a transferring step, and a cleaning step.
Each of the above steps is a general step in itself, for example,
JP-A-56-40868, JP-A-49-9123
It is described in Japanese Patent Publication No. 1 and the like. The image forming method of the present invention can be carried out using an image forming apparatus such as a copying machine or a facsimile machine known per se.

The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier. The toner image forming step is a step of developing the electrostatic latent image with a developer layer on a developer carrier to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developing toner of the present invention. The transfer step is a step of transferring the toner image onto a transfer body. The cleaning step is a step of removing the electrostatic image developer remaining on the electrostatic latent image carrier.

In the image forming method of the present invention, it is preferable that the image forming method further includes a recycling step. The recycling step is a step of transferring the electrostatic charge image developing toner collected in the cleaning step to a developer layer. The image forming method including the recycling step can be carried out using an image forming apparatus such as a toner recycling system type copier or facsimile machine. Further, the present invention can be applied to a recycling system in which the cleaning step is omitted and the toner is collected simultaneously with the development.

[0090]

EXAMPLES Examples of the present invention will be described below.
The invention is in no way limited to these examples. In addition, below, the particle size of the cumulative volume of the colorant of 84% was measured using Microtrac (manufactured by Nikkiso Co., Ltd., Microtrac UPA9340). The glass transition point of the resin in the resin particles and toner particles was measured using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-50) at a heating rate of 3 ° C./min.

(Example 1) -Preparation of colorant dispersion liquid (1) -Magenta pigment: 10 g (manufactured by Dainichiseika Co., Ltd .: CI Pigment Red) 57:
1) Anionic surfactant: 1.5 g (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) ion-exchanged water: 88.5 g or more mixed Then, a colorant dispersion liquid (1) was prepared in which the colorant (magenta pigment) was dispersed by dissolving and dissolving for 2 hours using a sand mill. The average particle diameter of the colorant in the colorant dispersion liquid (1) was 300 nm, and the cumulative volume was 84%.
Had a particle size of 450 nm.

-Preparation of Resin Particle Dispersion Liquid (1) -Styrene: 370 g n-Butyl acrylate: 30 g Acrylic acid:・ ・ ・ ・ ・ ・ ・ ・ ・ 6g Dodecanethiol ・ ・ ・ ・ ・ ・ ・ ・ ・ 24g Carbon tetrabromide ・ ・ ・ ・ ・ ・ ・ 4g , 6 g of nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Nonipol 400) and 10 g of anionic surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: Neogen R) 10
50 g of ion-exchanged water in which 550 g of ion-exchanged water was dispersed in a flask, emulsified in a flask, and slowly mixed for 10 minutes while adding 4 g of ammonium persulfate (manufactured by Tokai Denka Co., Ltd.) After purging with nitrogen, the content in the flask was heated in an oil bath until the temperature reached 70 ° C. with stirring, and emulsion polymerization was continued for 5 hours. Then, the reaction solution was cooled to room temperature and then left to stand in an oven at 80 ° C. to remove water, so that the average particle size was 155 nm and the glass transition point was 59.
A resin particle dispersion liquid (1) was prepared in which resin particles having a weight average molecular weight (Mw) of 12,000 were dispersed.

-Preparation of Resin Particle Dispersion (2) -Styrene: 280 g n-Butyl acrylate: 120 g Acrylic acid:・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 8 g or more of the mixture and dissolved is mixed with 6 g of a nonionic surfactant (Nanipol 400 manufactured by Sanyo Kasei Co., Ltd.) and an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.). Company: Neogen R)
Disperse 12 g in 550 g of ion-exchanged water, disperse in a flask, emulsify, and slowly mix for 10 minutes while adding 50 g of ion-exchanged water in which 3 g of potassium persulfate (manufactured by Kanto Chemical Co., Inc.) was dissolved. Then, after purging with nitrogen, the content in the flask was heated in an oil bath until the temperature reached 70 ° C. with stirring, and emulsion polymerization was continued for 5 hours. Then, the reaction solution was cooled to room temperature and then left in an oven at 80 ° C. to remove water, whereby the average particle size was 105 nm, the glass transition point was 53 ° C.,
A resin particle dispersion liquid (2) was prepared by dispersing resin particles having a weight average molecular weight (Mw) of 550,000.

<Aggregating Step> Colorant Dispersion Liquid (1) ... 50 g Resin Particle Dispersion Liquid (1) ... 120 g Resin Particle Dispersion Liquid (2) ...・ ・ ・ 80 g Cationic surfactant ・ ・ ・ ・ 1.5 g (Kao Corp .: Sanizol B50) The above components were placed in a round stainless steel flask, and a homogenizer (manufactured by IKA: After dispersing using Ultra Turrax T50), the mixture was heated to 48 ° C. in a heating oil bath. The obtained agglomerated particles were measured with a Coulter counter (TA2 type, manufactured by Coulter, Inc.) and found to be 5.4 μm.

<Adhesion Step> -Preparation of Adhered Particles-After holding this aggregated particle dispersion for 30 minutes at 48 ° C., the resin particle dispersion (1) as a resin particle dispersion is added to this aggregated particle dispersion. After slowly adding 60 g, the temperature of the heating oil bath was further raised and the temperature was maintained at 50 ° C. for 1 hour.
The obtained adhered particles were measured with a Coulter counter (TA2 type, manufactured by Coulter Co.) to give 5.9.
was μm.

<Fusing Step> After adding 3 g of an anionic surfactant (Neogen R, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), the mixture was heated to 97 ° C. with continuous stirring and kept for 4 hours. Then, it was cooled, filtered, washed with ion-exchanged water, and then dried using a vacuum dryer to obtain agglomerated particles. The obtained toner particles were measured with a Coulter counter (TA2 type, manufactured by Coulter Co.), and the result was 5.9 μm.

When the cross section of the toner particles is observed with an electron microscope, the particle size of the colorant (magenta pigment) is the same as the average particle size of the colorant (magenta pigment) in the colorant dispersion liquid (1). The colorant was uniformly dispersed in the toner particles.

-Production of Electrostatic Image Developer-The obtained toner for developing an electrostatic image and ferrite with polymethylmethacrylate (manufactured by Soken Chemical Co., Ltd., molecular weight 9.5)
10%) was mixed with a ferrite carrier having an average particle diameter of 50 μm to prepare a two-component electrostatic image developer having a toner concentration of 8% by weight. -Image formation-Using this electrostatic image developer, a fixed image was formed on OHP by an image forming apparatus (A Color remodeling machine manufactured by Fuji Xerox Co., Ltd.), and the HAZE value of the fixed image was measured to be 15%. Shows sufficient transparency, and the electrostatic charge image developer containing the toner for developing an electrostatic charge image was excellent in light transmittance and colorability.

(Comparative Example 1) In Example 1, the dispersion time of the colorant (magenta pigment) was changed from 2 hours to 1 hour, and the average particle diameter of the colorant (magenta pigment) in the colorant dispersion liquid (1) was changed. Toner particles were produced in the same manner as in Example 1 except that the thickness was changed from 300 nm to 500 nm.
When a fixed image was formed on the sample, and the fixed image was evaluated, the HAZE value was 25%, and the transparency deteriorated.
Due to the presence of a coarse colorant (magenta pigment) which is not taken into the agglomerated particles in the aggregating process due to the deterioration of the light transmittance, the colorant (magenta pigment) is contained in the agglomerated particle dispersion liquid.
Was released, the concentration of the colorant (magenta pigment) in the toner particles was lowered, and the coloring property was lowered.

(Comparative Example 2) -Preparation of colorant dispersion liquid (comparative) -Cyan pigment ..... (Copper phthalocyanine)) Anionic surfactant: 1.5 g (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) ion exchanged water: 88.5 g A colorant dispersion liquid (comparative) obtained by mixing and dissolving the above and dispersing the colorant (cyan pigment) for 5 minutes using an ultrasonic disperser (RUS-600CCVP manufactured by Nippon Seiki Seisakusho Co., Ltd.) Prepared. The average particle diameter of the colorant in the colorant dispersion (comparison) was 250 nm, and the cumulative volume was 84%.
Had a particle size of 2000 nm (note that the particle size distribution graph had two peaks).

Toner particles were produced in the same manner as in Example 1 except that the colorant dispersion liquid (1) in Example 1 was replaced with the colorant dispersion liquid (comparison). Coarse colorant that is not incorporated (cyan pigment)
Due to the presence of, the colorant (cyan pigment) is liberated in the aggregated particle dispersion, the concentration of the colorant (cyan pigment) in the toner particles is extremely lowered, and the coloring property is extremely lowered. occured.

(Example 2) -Preparation of colorant dispersion liquid (2) -Cyan pigment: 10 g (Dainichiseika Co., Ltd., copper phthalocyanine) Anion interface Activator: 1.5 g (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) Ion-exchanged water: 88.5 g Mix and dissolve the above A colorant dispersion liquid (1) was prepared by dispersing the colorant (cyan pigment) for 20 minutes by using an ultrasonic disperser (RUS-600CCVP manufactured by Nippon Seiki Seisakusho Co., Ltd.). The average particle size of the colorant in the colorant dispersion liquid (1) was 170 nm, and the particle size with a cumulative volume of 84% was 270 nm.

-Preparation of Release Agent Dispersion (1)-Wax: 600 g (Mitsui Petrochemical Co., Ltd., 100P wax) Anionic surfactant ... 25g (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) Ion-exchanged water 1700g After heating above to 130 ° C and predispersing by stirring A pressure release homogenizer (Gorin homogenizer manufactured by Doei Shoji Co., Ltd.) was used for dispersion treatment to prepare a release agent dispersion liquid in which a release agent having an average particle diameter of 170 nm was dispersed.

<Aggregating Step> Colorant Dispersion Liquid (2) ... 50 g Resin Particle Dispersion Liquid (1) ... 120 g Resin Particle Dispersion Liquid (2) ... ...... 80 g Release agent dispersion liquid (1) ・ ・ ・ ・ ・ ・ 50 g Cationic surfactant ・ ・ ・ ・ ・ ・ ・ ・ 1.8 g (Kao Corporation: Sanizole B50) The above materials were placed in a round stainless steel flask, dispersed using a homogenizer (Ultra Turrax T50 manufactured by IKA), and then heated to 48 ° C. in a heating oil bath. The obtained agglomerated particles were measured with a Coulter counter (TA2 type, manufactured by Coulter, Inc.) and found to be 5.2 μm.

<Adhesion Step> -Preparation of Adhered Particles-To this aggregated particle dispersion liquid, 60 g of resin particle dispersion liquid (1) as a resin fine particle dispersion liquid was slowly added, and the temperature of the heating oil bath was further raised. And kept at 50 ° C. for 1 hour. When the obtained adhered particles are measured using a Coulter counter (TA2 type manufactured by Coulter Inc.),
It was 5.8 μm.

<Fusing Step> After adding 3 g of an anionic surfactant (Neogen R manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), the mixture was heated to 97 ° C. with continuous stirring and kept for 4 hours. Then, it was cooled, filtered, washed with ion-exchanged water, and then dried using a vacuum dryer to obtain agglomerated particles. The obtained toner particles were measured with a Coulter counter (TA2 type, manufactured by Coulter Co.), and the result was 5.9 μm.

When the cross section of the toner particles is observed with an electron microscope, the particle size of the colorant (cyan pigment) is the same as the average particle size of the colorant (cyan pigment) in the colorant dispersion liquid (2). The colorant was uniformly dispersed in the toner particles.

-Production of Electrostatic Image Developer- The two-component system electrostatic charge in which the toner for developing an electrostatic image thus obtained and the ferrite carrier used in Example 1 are mixed and the toner concentration is 8% by weight. An image developer was prepared. -Image formation-Using this electrostatic image developer, a fixed image was formed on OHP with an image forming apparatus (A Color remodeling machine manufactured by Fuji Xerox Co., Ltd.), and the HAZE value of the fixed image was measured to be 13%. Shows sufficient transparency, and the electrostatic charge image developer containing the toner for developing an electrostatic charge image was excellent in light transmittance and colorability.

(Example 3) -Preparation of colorant dispersion liquid (3) -Magenta pigment: 1 kg (manufactured by Dainichiseika Co., Ltd., Pigment Red 57: 1) ) Anionic surfactant: 150 g (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) Ion-exchanged water: 9 kg or more, mixed and dissolved Then, a high-pressure impact disperser ULTIMIZER (manufactured by Sugino Machine Ltd., HJP30006) was used to disperse the colorant (magenta pigment) for about 1 hour to prepare a colorant dispersion (3). The average particle diameter of the colorant (magenta pigment) in the colorant dispersion liquid (3) is
150 nm, the particle size with a cumulative volume of 84% is 320 n
It was m.

Example 1 using this colorant dispersion (3)
Toner particles were produced in the same manner as in Example 1, and image formation was performed in the same manner as in Example 1 to form a fixed image on OHP. The HAZE value of the fixed image was measured and was 10%, which was a very good transparency. The electrostatic charge image developer containing the toner for developing an electrostatic charge image was excellent in light transmittance and colorability. Also,
When the cross section of the toner particles for electrostatic image development is observed by TEM, the colorant (magenta pigment) retains the average particle size of the colorant (magenta pigment) in the colorant dispersion liquid (3). Were uniformly dispersed in the toner particles for developing an electrostatic image.

(Example 4) -Preparation of colorant dispersion liquid (4) -Magenta pigment: 1 kg (manufactured by Dainichiseika Co., Ltd., CI Pigment Red 57: 1 (Carmin 6
B)) Anionic surfactant: 150 g (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) Ion-exchanged water :: Mix 9 kg or more. A colorant dispersion liquid (4) prepared by dissolving and dissolving the colorant (magenta pigment) for about 1 hour using a high-pressure impact disperser Ultimaizer (HJP30006 manufactured by Sugino Machine Co., Ltd.) is prepared. did. The average particle diameter of the colorant (magenta pigment) in the colorant dispersion liquid (4) is
150 nm, the particle size with a cumulative volume of 84% is 320 n
It was m.

—Preparation of Colorant Dispersion Liquid (5) — Magenta Pigment ・ ・ ・ ・ ・ ・ ・ ・ 1 kg (PR122 (Quinacridone Red) manufactured by Dainichiseika Co., Ltd.) Anion Surfactant: 150 g (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) ion-exchanged water: 9 kg or more, mixed and dissolved, A high-pressure impact disperser ULTIMIZER (manufactured by Sugino Machine Ltd., HJP30006) was used to disperse the colorant (magenta pigment) for about 30 minutes to prepare a colorant dispersion (5). The average particle size of the colorant (magenta pigment) in the colorant dispersion liquid (5) is 70 nm, and the particle size with a cumulative volume of 84% is 240.
was nm.

Colorant dispersion (1) in Example 1
Except that 25 g of each of these colorant dispersions (4) and (5) were used, toner particles were produced in the same manner as in Example 1, and image formation was performed in the same manner as in Example 1. When a fixed image was formed on the OHP,
Pigment Red 57: 1 (Carmine 6B) and P.P. R. 122
An intermediate color of two magenta pigments with (quinacridone red) was obtained, and when the HAZE value of the fixed image was measured, it showed a very good transparency of 12%, and the toner for developing an electrostatic charge image was contained. The electrostatic image developer was excellent in light transmittance and colorability.

[0114]

According to the present invention, it is possible to solve the various problems in the prior art. Further, according to the present invention, electrostatic charge image development which is excellent in various characteristics such as charging property, developing property, transfer property, fixing property and cleaning property, particularly excellent in light transmittance and coloring property, and which satisfies high image quality and high reliability. And an electrostatic charge image developer using the electrostatic charge image developing toner. Further, according to the present invention, it is possible to provide an electrostatic charge image developing toner suitable for a two-component type electrostatic charge image developer having high transfer efficiency, low toner consumption, and long life. Further, according to the present invention, a toner for developing an electrostatic charge image capable of easily and simply producing a toner for developing an electrostatic charge image excellent in the above-mentioned various properties without inviting release of a colorant, a releasing agent, etc. Method and preparation of toner for developing electrostatic image
It is possible to provide a colorant dispersion having excellent dispersibility of the colorant used in the manufacturing method . Further, according to the present invention,
It is possible to provide an image forming method capable of easily and easily forming a high-saturation full-color image on paper and OHP. Further, according to the present invention, there is provided an image forming method which is highly suitable for a so-called toner recycling system in which toner collected from a cleaner is reused and which can obtain high image quality excellent in light transmittance and colorability. be able to.

Front page continued (72) Inventor Masaaki Suwabe 1600 Takematsu, Minamiashigara City, Kanagawa Prefecture, Fuji Zelocks Co., Ltd. (72) Inventor Shuji Sato 1600 Takematsu, Minami Ashigara City, Kanagawa Prefecture, (72) Inventor, Kakukura Yasuo 1600 Takematsu, Minamiashigara-shi, Kanagawa Fuji Zelocks Co., Ltd. (72) Inventor Takeshi Shoko 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Fuji Zelocks Co., Ltd. (72) Hisao Morishiri, 1600 Takematsu, Minamiashigara-shi, Kanagawa Fujize Locks Co., Ltd. (72) Inventor Junichi Tomonaga 1600 Takematsu, Minamiashigara-shi, Kanagawa Fuji Ze Rocks Co., Ltd. (56) References JP-A-4-324868 (JP, A) JP-A-7-261453 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03G 9/08

Claims (14)

(57) [Claims] 1. A resin particle dispersion liquid in which resin particles are dispersed and a colorant dispersion liquid in which a colorant is dispersed in an aqueous medium are mixed, and the resin particles and the colorant are aggregated and aggregated. In the method for producing a toner for developing an electrostatic charge image, which comprises the steps of forming particles to prepare an aggregated particle dispersion, and heating the aggregated particles to fuse them to form toner particles, coloring in the colorant dispersion The average particle size of the agent is at most 350 nm, and the particle size of 84% of the cumulative volume of the colorant in the colorant dispersion is at most 500 nm, and after the step of preparing the aggregated particle dispersion , The aggregation
Fine particle dispersion prepared by dispersing fine particles in the particle dispersion.
Add and mix to attach the fine particles to the aggregated particles
A method for producing a toner for developing an electrostatic charge image , further comprising the step of forming adhered particles . 2. The aqueous medium is at least one of an anionic surfactant, a cationic surfactant and a nonionic surfactant.
The method for producing an electrostatic charge image developing toner according to claim 1, further comprising a seed. 3. The electrostatic charge image developing according to claim 1, wherein the colorant dispersion is prepared by dispersing the colorant in an aqueous medium using either an ultrasonic disperser or a high-pressure impact disperser. Toner manufacturing method. 4. The method for producing an electrostatic charge image developing toner according to claim 1, wherein the colorant dispersion contains at least two types of colorants. 5. The average particle diameter of the resin particles is at most 1 μm.
5. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 4. 6. The aggregated particle comprises a release agent.
6. The method for producing a toner for developing an electrostatic charge image according to any one of 1 to 5. 7. A toner for developing electrostatic images which is characterized in that it is manufactured by the manufacturing method of the electrostatic image developing toner according to any one of claims 1 6. 8. An electrostatic charge image developer containing a carrier and a toner, wherein the toner is the electrostatic charge image developing toner according to claim 7 . 9. A contract comprising a carrier having a resin coating layer.
The electrostatic image developer according to claim 8 . 10. A step of forming an electrostatic latent image on an electrostatic latent image carrier, a step of developing the electrostatic latent image with a developer layer on a developer carrier to form a toner image, the toner. transfer step for transferring an image onto a transfer member, and an image forming method including a cleaning step of removing the toner for developing an electrostatic image remaining on the electrostatic latent image bearing member, the developer layer is 請
An image forming method comprising the electrostatic charge image developing toner according to claim 7 . 11. The method for producing a toner according to claim 1.
A colorant dispersion liquid comprising a colorant dispersed in an aqueous medium, wherein the colorant dispersion liquid has an average particle diameter of at most 350 nm and a cumulative volume of 84%.
A colorant dispersion having a particle size of at most 500 nm. 12. The colorant dispersion according to claim 11 , wherein the aqueous medium contains at least one of a nonionic surfactant, an anionic surfactant and a cationic surfactant. 13. The dispersion according to claim 11 or 12, wherein the dispersion is performed using either an ultrasonic disperser or a high-pressure impact disperser.
The colorant dispersion described in 1. 14. Comprising at least two colorants
The colorant dispersion liquid according to claim 11 .