JP6446914B2 - Toner for electrostatic image development - Google Patents

Description

  The present invention relates to an electrostatic image developing toner excellent in high image quality, low-temperature fixability and blocking resistance.

The toner for developing an electrostatic charge image is used for image formation for visualizing an electrostatic charge image in a printer, a copying machine, a facsimile, or the like. For example, when an image is formed by electrophotography, an electrostatic latent image is first formed on a photosensitive drum, then developed with toner, transferred to transfer paper, and fixed by heat or the like. Image formation is performed.
As a toner for developing an electrostatic image, usually, a binder resin and a colorant are mixed with a charge control agent, a release agent, a magnetic material, etc., if necessary, and then melt-kneaded with an extruder or the like, and then pulverized. For the purpose of imparting various properties such as fluidity to the toner particles obtained by the so-called melt-kneading and pulverizing method, for example, solid fine particles such as silica are attached to the surface as external additives Is used.

In recent years, high-definition image quality has been demanded in image formation for copying machines and printers,
Polymerization methods such as a suspension polymerization method, an emulsion aggregation method, and a dissolution suspension method that easily control the particle size and particle size distribution of toner particles have been proposed.
Furthermore, with the recent spread of copiers and printers, in addition to demands for image quality, toners that are particularly excellent in high-speed printing and low-energy fixability have become desirable, and the low-temperature fixability of toner has been improved. Has been tried. In order to achieve low-temperature fixing, a method of lowering the glass transition point of the binder resin and a method of using a crystalline resin are often used, but the low-temperature fixing property, blocking resistance and high-temperature offset resistance are usually There is a contradictory relationship and it is hoped that they will be compatible.

To solve these problems, a core-shell structure in which a shell layer having a high glass transition temperature (Tg) having excellent heat resistance is formed on the surface of a core composed of a resin having excellent low-temperature fixability and low melt viscosity. A method of maintaining blocking resistance while maintaining low-temperature fixability has been performed.
When forming the core-shell structure, if the shell particles are attached and heated at a high temperature, the core particles and the shell particles are fused, and at the same time, the shell particles are buried, resulting in an uncoated portion. It is known that blocking resistance is insufficient. On the other hand, if the shell component is too much, the low-temperature fixing property of the toner will be hindered. Conversely, if the shell component is too little, a non-coated part will be formed and the core component will be exposed on the toner surface, and the expected anti-blocking performance will not be obtained. It has been known.

  In Patent Document 1, the core mainly includes a crystalline resin, and the shell is 15% by mass to 120% by mass with respect to the core, more preferably 25-100% by mass, and further preferably 35-80% by mass. The shell has hemispherical protrusions with a step difference of 0.3 μm or more, thereby trying to achieve both low-temperature fixability and cleanability. In Patent Document 2, an intermediate layer composed of inorganic fine particles or organic fine particles is formed on the surface of toner inner core particles, and an outer shell layer is formed on the surface, thereby attempting to achieve both fixing properties and heat resistance. In Patent Document 3, a core-shell type consisting of a core layer, a resin particle layer A for obtaining heat-resistant storage stability, and a shell layer including a resin particle layer B for obtaining emulsion stability outside the core particle, Attempts to achieve both low-temperature fixability and heat-resistant storage stability. In Patent Document 4, a positively chargeable compound is held on the surface of base particles, and negative charge control resin fine particles are fixed to the surface of the base particle, thereby allowing the charge control agent or charge control resin to adhere uniformly to the toner surface. Are trying.

JP 2005-274964 A JP 2003-91093 A JP2013-109142A JP 2009-244494 A

  However, in Patent Document 1, the condition that the aggregate of the resin fine particles for forming a shell is attached as a shell on the core is preferable, and the ratio of the shell to the core is consequently changed because of the necessity of covering the entire surface of the core. It can be inferred that it is set high, but as will be described later, if the ratio of the shell to the core is increased, the low-temperature fixability of the core tends to be lost, which is disadvantageous.

In addition, Patent Document 2 shows an example in which a benzoguanamine resin or tricalcium phosphate is used for the intermediate layer. However, since the intermediate layer contains a component having no softening property, as shown in a comparative example described later, the temperature is low. It is disadvantageous to obtain fixing ability.
In Patent Document 3, since both the resin particle layer A and the resin particle layer B require an amount sufficient to cover the core particles, the ratio of the total amount of the shell to the core tends to increase. If the ratio of the shell to is high, the low-temperature fixability of the core tends to be lost, which is disadvantageous.

In Patent Document 4, it is necessary that there is almost no difference between the glass transition temperature of the mother particle corresponding to the core particle and the glass transition temperature of the negative charge control resin fine particle corresponding to the shell particle. It is disadvantageous to achieve both anti-blocking properties.
The present invention has been made in view of the above problems, and provides an electrostatic charge image developing toner that can achieve both low-temperature fixability and blocking resistance and is excellent in image quality.

  The most effective form for achieving both low temperature fixability and blocking resistance is that the shell particles are thinly coated on the surface of the core particles having low temperature fixability at a high coverage. In addition, the shell particles are uniformly and thinly coated by providing a resin coating layer made of a water-soluble resin on the surface of the core particles as an intermediate layer as a means for that. I found that it was possible.

This invention is based on the knowledge mentioned above, and the summary of this invention is as follows.
<1> An electrostatic charge image developing toner having toner base particles containing at least a binder resin and a colorant and an external additive,
The toner base particles have a core-shell structure having core particles and a shell layer;
The toner base particles have a resin coating layer made of a water-soluble resin on the surface of the core particles,
And having the shell layer on the resin coating layer,
The shell layer is made of particles mainly composed of a resin,
The electrostatic charge image developing toner satisfying the following relationship, wherein the glass transition temperature of the polymer primary particles constituting the core particles is Tg1, and the glass transition temperature of the particles constituting the shell layer is Tg2. .
25 ° C ≦ Tg1 ≦ 45 ° C
55 ° C ≦ Tg2 ≦ 100 ° C
Tg2-Tg1 ≧ 20

<2> The electrostatic image developing toner according to <1>, wherein the particles constituting the shell layer contain a resin having a sulfonic acid group.
<3> The electrostatic image developing toner according to <1> or <2>, wherein the core particles are obtained by a polymerization method.
<4><1> to <3, wherein the chargeability of the core particle and the resin coating layer is opposite to each other, and the chargeability of the resin coating layer and the shell layer is opposite to each other > The toner for developing an electrostatic charge image according to any one of the above items.
<5> The toner for developing an electrostatic charge image according to any one of <1> to <4>, wherein the core particle has a capsule structure.
<6> The wax contained in the core layer of the core particles having a capsule structure is a wax that uses a thermogravimetric apparatus, and the time for the weight loss at 200 ° C. to reach 0.1% is 15 minutes or more, The electrostatic charge according to any one of <1> to <5>, wherein the wax contained in the shell layer of the core particle having a capsule structure is a wax having a melting point of 70 ° C. or higher. Toner for image development.

<7> After the aqueous solution containing the water-soluble resin is mixed with the dispersion of the core particles and the water-soluble resin is adhered to the surface of the core particles, the dispersion of the particles constituting the shell layer is further mixed. The toner for developing an electrostatic charge image according to any one of <1> to <6>, wherein toner mother particles are obtained through a step of attaching particles constituting the shell layer.
<8> An aqueous solution containing a water-soluble resin having a chargeability opposite to that of the core particles is mixed with the dispersion of the core particles to adhere the water-soluble resin to the surface of the core particles, and then the water-soluble resin and <1> to <6>, wherein toner mother particles are obtained through a step of adhering the particles constituting the shell layer by mixing a dispersion of the particles constituting the shell layer having reverse charging properties. The toner for developing an electrostatic image according to any one of the above items.

According to the present invention, it is possible to provide a toner for developing an electrostatic image having both low-temperature fixability and blocking resistance.
This effect is obtained by providing a resin coating layer made of a water-soluble resin on the surface of core particles having low temperature fixability, and then attaching shell particles having high blocking resistance at a high coverage. This new core-shell structure realizes more effective low-temperature fixability.

FIG. 1 is a SEM photograph of core particles in Example 8 at a magnification of 3000 times. FIG. 2 is a SEM photograph of the core particles in Example 8 at a magnification of 1000 times. FIG. 3 is an SEM photograph of the water-soluble resin coating layer-forming particles in Example 8 at a magnification of 3000 times. FIG. 4 is a SEM photograph of the water-soluble resin coating layer-forming particles in Example 8 at a magnification of 1000 times. FIG. 5 is an SEM photograph of the toner base particles (after shell layer formation) in Example 8 at a magnification of 10,000. FIG. 6 is an SEM photograph at a magnification of 10,000 times of the toner base particles of the present invention after washing. FIG. 7 is an SEM photograph of the toner base particles of the present invention after cleaning at a magnification of 10,000.

In the present invention, a state before having a resin coating layer and a shell layer made of a water-soluble resin is referred to as a core particle. Further, after the resin coating layer made of a water-soluble resin is provided on the surface of the core particle, a shell layer is further provided, and the one before having an external additive is referred to as toner mother particle. A toner having an external additive on the surface of the toner base particles is referred to as toner.
Here, in the present specification, “mass%” and “weight%”, and “part by mass” and “part by weight” have the same meaning.
The toner of the present invention contains at least a binder resin and a colorant, and may contain a wax, a charge control agent, and the like as necessary.

<1. Core particle>
(1-1. Configuration of core particles)
The core particle contains at least a binder resin and a colorant, and may contain a wax, a charge control agent, and the like as necessary.
The binder resin is not particularly limited as long as it is generally used as a binder resin in the production of toner. For example, polystyrene resin, poly (meth) acrylic resin, polyolefin resin, epoxy resin Examples thereof include thermoplastic resins such as resins and polyester resins, and mixtures of these resins.

As the monomer component used for producing the binder resin, a monomer generally used in producing a toner binder resin can be appropriately used.
For example, a polymerizable monomer having an acidic group (hereinafter sometimes simply referred to as an acidic monomer), a polymerizable monomer having a basic group (hereinafter simply referred to as a basic monomer). ), Any polymerizable monomer having no acidic group or basic group (hereinafter sometimes referred to as other monomer) can be used.

When a polystyrene copolymer resin and a poly (meth) acrylic resin are used as the binder resin, the following monomers are listed as examples.
As the acidic monomer, a polymerizable monomer having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, cinnamic acid, a polymerizable monomer having a sulfonic acid group such as sulfonated styrene, Examples thereof include polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide.

Basic monomers include aromatic vinyl compounds having amino groups such as aminostyrene, nitrogen-containing heterocyclic-containing polymerizable monomers such as vinylpyridine and vinylpyrrolidone, amino acids such as dimethylaminoethyl acrylate and diethylaminoethyl methacrylate. (Meth) acrylic acid ester etc. which have group are mentioned.
These acidic monomers and basic monomers contribute to the dispersion stabilization of the core particles. It may be used singly or as a mixture of plural kinds, and may exist as a salt with a counter ion.

  Other monomers include styrenes such as styrene, methylstyrene, chlorostyrene, dichlorostyrene, pt-butylstyrene, pn-butylstyrene, pn-nonylstyrene, methyl acrylate, acrylic acid Acrylic esters such as ethyl, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate , Methacrylates such as isobutyl methacrylate, hydroxyethyl methacrylate, 2-ethylhexyl methacrylate, acrylamide, N-propylacrylamide, N, N-dimethylacrylamide, N, N-dipropylacrylamide, N, N Dibutyl acrylamide, and the like. Other monomers may be used alone or in combination of two or more.

  When the binder resin is a cross-linked resin, a polyfunctional monomer is used together with the above-mentioned polymerizable monomer. For example, divinylbenzene, hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Examples include dimethacrylate, tetraethylene glycol dimethacrylate, hexaethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, diallyl phthalate, and the like.

Among these, a bifunctional polymerizable monomer is preferable, and divinylbenzene and hexanediol diacrylate are particularly preferable. These polyfunctional polymerizable monomers may be used alone or as a mixture of plural kinds.
It is also possible to use a polymerizable monomer having a reactive group in a pendant group, such as glycidyl methacrylate, methylol acrylamide, acrolein and the like.

A known chain transfer agent can be used as necessary. Specific examples of the chain transfer agent include t-dodecyl mercaptan, dodecanethiol, diisopropyl xanthogen, carbon tetrachloride, trichlorobromomethane, and the like. The chain transfer agent may be used alone or in combination of two or more, and is used in an amount of 0 to 5% by weight based on the polymerizable monomer.
When a polystyrene copolymer resin and a poly (meth) acrylic resin are used as a binder resin, the number average molecular weight in gel permeation chromatography (hereinafter referred to as GPC) is preferably 2000 or more, more preferably It is 2500 or more, more preferably 3000 or more, preferably 50,000 or less, more preferably 40,000 or less, and further preferably 35,000 or less. The weight average molecular weight determined in the same manner is preferably 20,000 or more, more preferably 30,000 or more, preferably 500,000 or less, more preferably 450,000 or less. When the number average molecular weight and the weight average molecular weight of the binder resin are in the above ranges, it is preferable because the durability, storage stability, and fixability of the toner are improved.

  When a polyester resin is used as the binder resin, examples of the divalent alcohol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neo Diols such as pentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A, etc. Examples of the divalent acid include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and cyclohexanedi. Rubonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, anhydrides of these acids, lower alkyl esters, or alkenyl succinic acids such as n-dodecenyl succinic acid, n-dodecyl succinic acid or alkyl succinic acids, Other divalent organic acids can be mentioned.

When the binder resin is a cross-linked resin, a polyfunctional monomer is used together with the above-described polymerizable monomer. For example, trihydric or higher polyhydric alcohols include, for example, sorbitol, 1, 2, 3, 6 -Hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, and the like. Examples of the trivalent or higher acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1 ,
2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8- Examples include octanetetracarboxylic acid and anhydrides thereof.

These polyester resins can be synthesized by a usual method. Specifically, conditions such as reaction temperature (170 to 250 ° C.), reaction pressure (5 mmHg to normal pressure) and the like are determined according to the reactivity of the monomer, and the reaction is terminated when predetermined physical properties are obtained. .
When a polyester resin is used as the binder resin, the number average molecular weight in GPC is preferably 2000 to 20000, and more preferably 3000 to 12000.

The glass transition temperature (Tg) of the binder resin is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 30 ° C. or higher, preferably 80 ° C. or lower, more preferably 60 ° C. or lower. More preferably, it is 55 ° C. or lower.
Wax can be used as an anti-offset agent. Low temperature fixability, blocking resistance, and high temperature offset resistance are in a trade-off relationship. To achieve both, it is preferable to use a wax as an anti-offset agent at the same time as the toner has a core-shell structure.
Also, a wax can be used to improve the low-temperature fixability.

  As the wax used in the toner of the present invention, known waxes can be arbitrarily used. Specifically, olefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, copolymer polyethylene, paraffin wax, and behenyl behenate. , Ester waxes having a long chain aliphatic group such as montanic acid ester and stearyl stearate, plant waxes such as hydrogenated castor oil and carnauba wax, ketones having a long chain alkyl group such as distearyl ketone, having an alkyl group Examples include higher fatty acids such as silicone and stearic acid, long-chain fatty acid polyhydric alcohols such as long-chain fatty acid alcohols and pentaerythritol, and partial ester forms thereof, higher fatty acid amides such as oleic acid amide and stearic acid amide, etc. Paraffin wax Other hydrocarbons such as Fischer-Tropsch wax, ester wax, and silicone waxes. Waxes may be used alone or in combination.

  During operation of a printer or the like, ultrafine particles are discharged from the apparatus together with ozone, dust, and VOC. The ultrafine particles are considered to have been rapidly cooled down into particles by chemical substances volatilized from toner, fixing members, paper, etc. involved in the fixing process. As one of the methods for reducing ultrafine particles, it is effective to select a wax with less chemical volatilization during fixing. Examples thereof include neopentyl polyol ester represented by the following general formula (1).

In formula (1), R ¹ is a divalent to octavalent neopentyl polyol residue, R ² is a linear alkyl group having 13 to 25 carbon atoms, and p is an integer of 2 to 8.
Among the neopentyl polyol esters represented by the formula (1), a wax that uses a thermogravimetric measuring device and has a time for a weight loss at 200 ° C. to reach 0.1% is 15 minutes or more. More preferably, the wax has an arrival time of 17 minutes or more, and more preferably 19 minutes or more. In general, since the temperature of the fixing roller of the printer is 200 ° C. or less, the temperature that is actually given at the time of fixing in the printer by selecting a wax having a small volatile component when heated at 200 ° C., that is, a slow weight reduction rate. , It can be expected that there are few volatile components from the wax. As a result, discharge of ultrafine particles during printer operation can be reduced.

The melting point of the wax is preferably 120 ° C. or less, more preferably 110 ° C. or less, still more preferably 100 ° C. or less, preferably 40 ° C. or more, and more preferably 50 ° C. or more. If the melting point is too high, the effect of reducing the fixing temperature may be poor, and if the melting point is too low, problems may arise in blocking resistance and storage stability.
The amount of the wax is preferably 1 part by mass or more with respect to 100 parts by mass of the toner, more preferably 2 parts by mass or more, and further preferably 5 parts by mass or more. Moreover, it is preferable that it is 40 mass parts or less, More preferably, it is 35 mass parts or less, More preferably, it is 30 mass parts or less. If the wax content in the toner is too low, performance such as high-temperature offset resistance may not be sufficient, and if it is too high, blocking resistance may not be sufficient, or the wax may leak from the toner and contaminate the device. Sometimes.

  A known colorant can be arbitrarily used as the colorant. Specific examples of the colorant include carbon black, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow, rhodamine dyes, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo, Any known dyes and pigments such as disazo dyes and condensed azo dyes can be used alone or in combination. In the case of a full color toner, it is preferable to use benzidine yellow for yellow, monoazo and condensed azo dyes, magenta for quinacridone and monoazo dyes, and cyan for phthalocyanine blue. The colorant is preferably used in an amount of 3 to 20 parts by mass with respect to 100 parts by mass of the toner.

  Any known charge control agent can be used. Specific examples of charge control agents include nigrosine dyes, amino group-containing vinyl copolymers, quaternary ammonium salt compounds, polyamine resins and the like for positive chargeability, and chromium, zinc, iron and cobalt for negative chargeability. And metal-containing azo dyes containing metals such as aluminum, salts of salicylic acid or alkylsalicylic acid with the aforementioned metals, metal complexes, and the like. The amount of the charge control agent is preferably 0.1 to 25 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the toner. The charge control agent may be blended in the core particles, or may be used in a form adhered to the surface of the toner base particles.

(1-2. Formation method of core particle)
The core particles of the present invention may be produced by any known method and are not particularly limited.
(1-2-1. Method for Aggregating Particles Smaller than Core Particle Size to Create Core Particles)
A method of obtaining core particles by preparing each raw material as particles smaller than the core particle size and mixing and aggregating them can be used.
There are several methods for preparing the binder resin in the polymer primary particle dispersion smaller than the core particle size as described below.

(1-2-1-1. Emulsion polymerization)
Polymer primary particles containing styrene or (meth) acrylic monomers as constituents are emulsified with an emulsifier using the aforementioned styrene or (meth) acrylic monomers and, if necessary, a chain transfer agent. Obtained by polymerization.
Known emulsifiers can be used, but one or more emulsifiers selected from cationic surfactants, anionic surfactants, and nonionic surfactants can be used in combination.

  Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide, and examples of the anionic surfactant include And fatty acid soap such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate and the like. Nonionic surfactants include, for example, polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl sucrose, etc. Is mentioned.

  The amount of the emulsifier used is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. In addition, these emulsifiers can be used as protective colloids, for example, one or more of partially or completely saponified polyvinyl alcohols such as polyvinyl alcohol and cellulose derivatives such as hydroxyethyl cellulose.

  Moreover, a well-known polymerization initiator can be used 1 type or in combination of 2 or more types as needed. For example, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, and the like, and redox initiators combining these persulfates as a component with a reducing agent such as acidic sodium sulfite, hydrogen peroxide, 4,4 '-Azobiscyanovaleric acid, t-butyl hydroperoxide, cumene hydroperoxide, and other water-soluble polymerization initiators, and redox in which these water-soluble polymerization initiators are combined with reducing agents such as ferrous salts as one component Initiators, benzoyl peroxide, 2,2′-azobis-isobutyronitrile, and the like are used. These polymerization initiators may be added to the polymerization system before, simultaneously with, or after addition of the polymerizable monomer, and these addition methods may be combined as necessary.

In order to disperse the wax with a suitable dispersed particle size in the toner, it is preferable to use so-called seed polymerization in which the wax is added as a seed during emulsion polymerization. By adding as a seed, the wax is finely and uniformly dispersed in the toner, so that deterioration of the chargeability and heat resistance of the toner can be suppressed.
Also, a wax / long-chain polymerizable monomer prepared by previously dispersing a wax in a water-based dispersion medium with a long-chain polymerizable monomer such as stearyl acrylate is prepared. The polymerizable monomer can also be polymerized in the presence of.

  Emulsion polymerization is possible using a colorant as a seed, but if a polymerizable monomer is polymerized in the presence of the colorant, the metal in the colorant affects radical polymerization, making it difficult to control the molecular weight and rheology of the resin. Therefore, it is preferable to add the colorant dispersion in the next step without adding the colorant during the emulsion polymerization.

(1-2-1-2. Method of emulsifying resin)
After obtaining the resin by a method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., mix it with an aqueous medium and heat it to a temperature higher than either the melting point of the resin or the glass transition temperature to increase the viscosity of the resin. The polymer primary particles are obtained by lowering and emulsifying by applying a shearing force.
Examples of the emulsifier for applying a shearing force include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser.
If the viscosity of the resin during emulsification is high and does not decrease to the desired particle size, increase the temperature using an emulsifier capable of pressurization to atmospheric pressure or higher, and emulsify with the resin viscosity lowered to obtain the desired particle size. Polymer primary particles having a diameter can be obtained.

  As another method, an organic solvent may be mixed with the resin in advance to reduce the viscosity of the resin. The organic solvent used is not particularly limited as long as it dissolves the resin, but is not limited to ketone solvents such as tetrahydrofuran (THF), methyl acetate, ethyl acetate, and methyl ethyl ketone, and benzene solvents such as benzene, toluene, and xylene. Etc. can be used. Furthermore, an alcohol solvent such as ethanol or isopropyl alcohol may be added to water or a resin for the purpose of improving the affinity with an aqueous medium and controlling the particle size distribution. When an organic solvent is added, it is necessary to remove the organic solvent from the emulsion after the emulsification is completed. As a method of removing the organic solvent, there is a method of volatilizing the organic solvent while reducing the pressure at room temperature or under heating.

For the purpose of controlling the particle size distribution, a salt such as sodium chloride or potassium chloride, ammonia or the like may be added.
For the purpose of controlling the particle size distribution, an emulsifier or a dispersant may be added. For example, water-soluble polymers such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, and sodium polyacrylate; the aforementioned emulsifiers; inorganic compounds such as tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate, and barium carbonate. Can be mentioned. As a usage-amount, 0.01-20 mass parts is preferable with respect to 100 mass parts of resin.

When a resin containing an acidic group or a basic group is used, the amount of emulsifier or dispersant added can be reduced, but the hygroscopicity of the resin increases and the chargeability may deteriorate.
Further, a phase inversion emulsification method may be used. In the phase inversion emulsification method, an organic solvent, a neutralizing agent, and a dispersion stabilizer are added to the resin as necessary, and an aqueous medium is dropped under stirring to obtain emulsified particles. In this method, an organic solvent is removed to obtain an emulsion. As the organic solvent, the same organic solvents as those described above can be used. As the neutralizing agent, general acids such as nitric acid, hydrochloric acid, sodium hydroxide and ammonia, and alkalis can be used.

(1-2-1-3. Formation of Core Particles)
In any of the above preparation methods for emulsion polymerization and resin emulsification, the volume average particle diameter of the obtained polymer primary particles is usually 0.02 μm or more, preferably 0.05 μm or more, and more preferably 0.8 μm. It is 1 μm or more, usually 3 μm or less, preferably 2 μm or less, and more preferably 1 μm or less. When the volume average particle size of the polymer primary particles is smaller than the above range, it may be difficult to control the aggregation rate in the aggregation process. On the other hand, when larger than the said range, the particle size of the core particle obtained by aggregation may become large easily, and it may become difficult to obtain the core particle of the target particle size.

In any preparation method, Tg of the polymer primary particles is 25 ° C. or higher and 45 ° C. or lower.
In the aggregation step, the polymer primary particles, the colorant particles, and, if necessary, the blending components such as the charge control agent and the wax are mixed simultaneously or sequentially. First, a dispersion of each component, that is, a polymer primary particle dispersion, a colorant particle dispersion, a charge control agent dispersion and a wax fine particle dispersion, if necessary, are mixed and mixed to obtain a dispersion mixture. Is preferable from the viewpoint of the uniformity of the composition and the uniformity of the particle diameter.

The colorant is preferably used in the state of being dispersed in water in the presence of an emulsifier, and the volume average particle diameter of the colorant particles is 0.01 μm or more, more preferably 0.05 μm or more, and more preferably 3 μm or less. 1 μm.
In the emulsion aggregation method, aggregation is usually performed in a tank equipped with a stirrer, but there are a heating method, a method of adding an electrolyte, and a method of combining them. When polymer primary particles are agglomerated with stirring to obtain particle aggregates of the desired size, the particle size of the particle aggregates is controlled based on the balance between the agglomeration force between the particles and the shearing force due to agitation. However, the cohesive force can be increased by heating or adding an electrolyte.

The electrolyte in the case of adding the electrolyte to be agglomerated may be any of acid, alkali, salt, organic, and inorganic. Specifically, the acid may be hydrochloric acid, nitric acid, sulfuric acid, citric acid. Etc., as alkali, sodium hydroxide, potassium hydroxide, aqueous ammonia, etc., as salt, NaCl, KCl, LiCl, Na ₂ SO ₄ , K ₂ SO ₄ , Li ₂ SO ₄ , MgCl ₂ , CaCl ₂ , MgSO ₄ , _{CaSO 4, ZnSO 4, Al 2} (SO 4) 3, Fe 2 (SO 4) 3, CH 3 COONa, C 6 H 5 SO 3 Na and the like. Of these, inorganic salts having a divalent or higher polyvalent metal cation are preferred.

  The amount of electrolyte added varies depending on the type of electrolyte, the target particle size, etc., but is preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the solid component of the mixed dispersion. preferable. Further, it is preferably 25 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less. If the amount added is too small, the progress of aggregation may be delayed, and fine particles of 1 μm or less may remain after aggregation, or the average particle size of the obtained particle aggregate may not reach the target particle size. If the amount is too large, rapid agglomeration tends to occur and it becomes difficult to control the particle size, and the obtained agglomerated particles may cause problems such as inclusion of coarse particles or irregular shapes. When the aggregation is performed by adding an electrolyte, the aggregation temperature is 20 ° C. or higher, more preferably 30 ° C. or higher, 80 ° C. or lower, more preferably 70 ° C. or lower.

The time required for agglomeration is optimized depending on the shape of the apparatus and the processing scale, but in order for the core particle size to reach the target particle size, it is usually held at the aforementioned predetermined temperature for at least 30 minutes or more. Is desirable. The temperature rise until reaching the predetermined temperature may be raised at a constant rate, or may be raised stepwise.
Rather than mixing all the raw material dispersions first to form particle aggregates, a part of the raw material dispersions are added after the particle aggregates are formed, so that there is a difference in composition between the inside and the surface of the core particles. You can turn it on. The raw material to be added may be the same as or different from the raw material to be mixed first. That is, the core particle itself may have a so-called capsule structure. Specifically, when the particle constituting the core layer of the core particle having the capsule structure is the core particle c and the particle constituting the shell layer of the core particle having the capsule structure is the shell particle s, the core particle c After the formation of the particle aggregate, the shell particles s are additionally added, and after undergoing a fusion process or the like, core particles having a capsule structure are obtained.

  For example, when a polymer primary particle (corresponding to the shell particle s) having a higher Tg than the polymer primary particle (corresponding to the core particle c) to be mixed first is added, during the subsequent aging step Core particles having a structure in which the ratio of the resin having a low Tg is high and the ratio of the resin having a high Tg is high on the inside, although the structure is not formed in which the additive particles are embedded and the surface is completely covered with the additive particles Is obtained. In the present invention, the anti-blocking property is improved by coating the shell particles and forming the shell layer by the method described later in (3. Shell layer). Furthermore, it becomes easy to obtain good blocking resistance.

When the core particle having a capsule structure is used, the wax can be changed between the inside and the surface of the core particle by making the wax contained in the raw material to be mixed first and the wax contained in the additional raw material different.
In this case, it is preferable to select a wax having a high compatibility with the resin as the wax to be mixed first, and a wax having a low compatibility with the resin as the wax to be added additionally.

The wax having high compatibility with the resin lowers the viscosity of the resin during fixing heating and improves the low-temperature fixing performance.
On the other hand, the wax having low compatibility with the resin exhibits a releasing effect by melting and exuding from the toner during fixing heating, and contributes to prevention of hot offset. By disposing it at a position close to the toner surface, a release effect can be efficiently exhibited.

  The compatibility between the resin and the wax can be inferred from a change in the free energy of the polymer mixing, and specifically, it is determined by the difference in the solubility parameter between the constituent resin and the wax and the molecular weight. That is, it is considered that the closer the solubility parameter value of the wax to be used is to the constituent resin, and the lower the molecular weight, the better the compatibility. On the other hand, when a plurality of chemical species constituting the wax are included or when the crystallinity is low due to impurities or the like, the compatibility cannot be simply estimated. In that case, the dispersed particle diameter in the resin can be directly observed with TEM or the like, or can be inferred from the degree of decrease in Tg of the resin containing wax.

  When the core particle having a capsule structure is used, the shell layer, that is, the wax contained outside the core particle is different from the core layer, ie, the wax contained inside the core particle, and It is preferable from the viewpoint of fixing performance that the melting point of the contained wax is higher than the melting point of the wax contained inside. The difference between the melting point of the wax contained on the outside and the melting point of the wax contained on the inside is preferably 5 ° C. or more, and the upper limit is preferably 30 ° C. or less, and 20 ° C. or less. Is more preferable, and it is still more preferable that it is 15 degrees C or less.

When the core particle having a capsule structure, the wax contained in the core layer of the core particle is highly compatible with the resin, the wax contained in the shell layer of the core particle is low in compatibility with the resin, Furthermore, it is preferable that the wax content of the core layer of the core particle is larger than the wax content of the shell layer of the core particle. Specifically, when the amount of the wax contained in the core layer of the core particle having the capsule structure is Wcc and the amount of the wax contained in the shell layer of the core particle having the capsule structure is Wcs, Wcc: Wcs is It is preferable that it is 99: 1-80: 20, and it is more preferable that it is 99: 1-90: 10.
In this case, the wax contained in the core layer of the core particles is preferably a wax having a weight loss at 200 ° C. reaching 0.1% for 15 minutes or longer. A wax having a time when the weight loss at 200 ° C. reaches 0.1% is more preferably 17 minutes or more, more preferably 19 minutes or more. Choosing a wax with a low content of volatile components for a wax with a high content is effective in reducing the discharge of ultrafine particles during printer operation. In this case, it is preferable that the wax contained in the shell layer of the core particles has a low compatibility with the constituent resin as described above and has a melting point of 70 ° C. or higher.

Conditions for attaching the additional particles to the particle aggregate are as follows.
The temperature is preferably a temperature equal to or lower than the Tg of the polymer primary particles in the particle aggregate and in the additional particles. In this case, the additional particles are easily attached to the particle aggregate, and as a result, the formed attached particles are easily stabilized. Since the treatment time depends on the temperature, it cannot be defined unconditionally, but is usually about 5 minutes to 2 hours. This operation may be performed while standing or may be stirred by a mixer or the like. The latter is advantageous in that the additional particles can be uniformly attached.

The operation of adding additional particles may be performed once or a plurality of times. The first additional particles and the subsequent additional particles may be in any combination, and can be appropriately selected according to the use and purpose of the electrostatic image developing toner.
In order to increase the stability of the particle aggregate obtained in the aggregation step, it is preferable to perform fusion in the aggregated particles in the aging step after the aggregation step. The temperature of the ripening step is preferably not less than Tg of the polymer primary particles, more preferably not less than 5 ° C higher than Tg, and preferably not more than 80 ° C higher than Tg, more preferably 60 ° C higher than Tg. It is as follows. Further, the time required for the aging step varies depending on the shape of the target core particle, but is usually 0.1 to 10 hours, preferably 0.5 to 5 hours after reaching the Tg or more of the polymer primary particles. It is desirable.

  It is preferable to add a surfactant, adjust the pH, or use both in combination after the aggregation step, preferably before the aging step or during the aging step. As the surfactant used here, one or more emulsifiers can be selected from the emulsifiers that can be used when producing the polymer primary particles. In particular, the emulsifiers used when producing the polymer primary particles. It is preferable to use the same. The addition amount in the case of adding the surfactant is not limited, but is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and preferably with respect to 100 parts by mass of the solid component of the mixed dispersion. Is 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less. After the aggregation process, before the completion of the aging process, by adding a surfactant or adjusting the pH, aggregation of the particle aggregates obtained in the aggregation process can be suppressed. The generation of coarse particles may be suppressed.

  The particle aggregate before the aging step is considered to be an aggregate due to electrostatic or physical aggregation of the polymer primary particles, but after the aging step, the polymer primary particles constituting the particle aggregate are fused to each other. doing. By controlling the temperature and time of this ripening process, various shapes can be selected depending on the purpose, such as a cocoon shape in which polymer primary particles are aggregated, a potato type in which fusion has progressed, and a sphere in which fusion has further progressed. Core particles can be produced.

(1-2-2. Method for Creating Core Particle Size)
After mixing each raw material, the method of obtaining a core particle can be used by atomizing the mixture to the size of the core particle.

(1-2-2-1. Suspension polymerization)
Add colorants, polymerization initiators, and additives such as waxes, polar resins, charge control agents and crosslinking agents to the above styrene or (meth) acrylic monomers, and dissolve or disperse them uniformly. A monomer composition is prepared. This monomer composition is dispersed in an aqueous medium containing a suspension stabilizer or the like as necessary. Granulation is performed by adjusting the stirring speed and time so that the droplets of the monomer composition have the desired core particle size. Thereafter, the particles are maintained by the action of the dispersion stabilizer, and stirring is performed to such an extent that sedimentation of the particles is prevented, and the core particles can be obtained by performing polymerization.

  Specific examples of the suspension stabilizer include calcium phosphate, magnesium phosphate, calcium hydroxide, magnesium hydroxide and the like. These may be used alone or in combination of two or more, and an amount of 1 part by mass or more and 10 parts by mass or less is preferable with respect to 100 parts by mass of the polymerizable monomer. The suspension stabilizer may be added to the polymerization system before, simultaneously with, or after the addition of the polymerizable monomer, and these addition methods may be combined as necessary.

When the polar resin is contained in the monomer composition, the polar resin tends to move to the vicinity of the droplet surface after the monomer composition is dispersed in the aqueous medium to form droplets. By performing polymerization in this state, core particles having a difference in composition between the inside and the surface can be obtained. For example, if a polar resin having a Tg higher than the Tg after polymerization of the monomer is selected, the inside of the core particle has a low Tg and the surface has a Tg of Tg.
A structure in which a high proportion of resin is present in a high ratio is obtained. In the present invention, the blocking resistance is enhanced by coating the shell particles. However, when this method is used in combination, it becomes easier to obtain good blocking resistance.
In addition, a pH adjusting agent, a polymerization degree adjusting agent, an antifoaming agent, etc. can be suitably added to the reaction system.

(1-2-2-2. Dissolution suspension)
An oily dispersion is prepared in which at least a binder resin and a colorant, and, if necessary, a wax and a charge control agent are dissolved or dispersed in an organic solvent, and this is dispersed in an aqueous medium. Next, the organic solvent is removed from the dispersion to obtain core particles.
As an aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination.

  If necessary, a dispersant can be used. The use of a dispersant is preferable because the particle size distribution becomes sharp and the dispersion is stable. As the dispersant, the same emulsifiers as those used in the above emulsion polymerization can be used. In addition, various hydrophilic polymer substances that form a polymeric protective colloid in an aqueous medium can be present. In addition, inorganic fine particles and / or polymer fine particles can be used. As the inorganic fine particles, various conventionally known inorganic compounds that are insoluble or hardly soluble in water are used. Examples of such materials include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite. As the polymer fine particles, various conventionally known fine particles that are insoluble or hardly soluble in water are used.

When the oil dispersion is dispersed in an aqueous medium, a known dispersing machine such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, or an ultrasonic wave can be applied as a dispersing device.
An oil-based dispersion liquid may be prepared using a prepolymer having a reactive group instead of the binder resin, and the resin may be elongated by dispersing it in an aqueous medium and then reacting the reactive group. In this method, since the prepolymer has a relatively low molecular weight, the viscosity of the oil-based dispersion is difficult to increase, and dispersion in an aqueous medium becomes easy.

In order to facilitate uniform dispersion of the colorant in the oil-based dispersion, the colorant may be prepared in advance as a master batch combined with a resin and dispersed in an organic solvent.
As a method of removing the organic solvent, there is a method of volatilizing the organic solvent while reducing the pressure at room temperature or under heating.
When a highly polar resin and a low polarity resin are used in combination as the binder resin, after the monomer composition is dispersed in the aqueous medium to form droplets, the highly polar resin is in the vicinity of the droplet surface, The resin with low polarity moves to the vicinity of the droplet center. Then, by removing the organic solvent, core particles having a difference in composition between the inside and the surface can be obtained.

  When preparing an oily dispersion using a prepolymer capable of reacting with an active hydrogen group-containing compound, after dispersing the oily dispersion in an aqueous medium, the active hydrogen group-containing compound is added and the aqueous dispersion is added in the aqueous medium. By subjecting both to an extension reaction or a cross-linking reaction from the droplet surface, an extension or cross-linking resin is preferentially generated on the droplet surface. Then, by removing the organic solvent, core particles having a difference in composition between the inside and the surface can be obtained.

By selecting a raw material in consideration of Tg by these methods, a structure in which the inside of the core particle has a low Tg and the surface has a high ratio of a high Tg resin can be obtained.
Further, even when polymer fine particles having a high Tg are used as the dispersant, a structure in which the inside of the core particle has a low Tg and a high ratio of a resin having a high Tg is obtained on the surface.
In the present invention, the blocking resistance is enhanced by coating the shell particles. However, if these methods are used in combination, good blocking resistance can be more easily obtained.

(1-2-3. Treatment of the obtained core particles, etc.)
When core particles are prepared by polymerization methods such as emulsion aggregation method, suspension polymerization method, dissolution suspension method, etc., the core particles are dispersed within the same range as in the slurry liquid at the time of core particle production. The dispersant, emulsifier, etc. present in the liquid are removed by washing and used in the next step.
For washing, for example, filtration, decantation, etc., separate the aqueous medium containing the dispersant / emulsifier from the core particles, and add the aqueous medium to the core particles obtained as a thick slurry or wet cake to disperse. The method of repeating operation is mentioned.

<2. Resin coating layer made of water-soluble resin>
In the toner of the present invention, a resin coating layer made of a water-soluble resin (hereinafter sometimes referred to as a water-soluble resin coating layer) is formed on the core particle surface. This water-soluble resin coating layer serves as a foundation for uniformly coating the outermost shell particles. By designing the water-soluble resin coating layer and the shell particles to have opposite charging characteristics, the shell particles are water-soluble. A thin and dense shell layer is formed by adhering to any part of the surface of the resin coating layer, and as a result, good blocking resistance can be obtained without impairing the low-temperature fixability.

  In the present invention, the resin coating layer made of a water-soluble resin means a layer of a film having a substantially smooth surface although it has unevenness derived from the unevenness of the core particle surface. This water-soluble resin coating layer may contain a plurality of water-soluble resins as long as the effects of the present invention are not significantly impaired. Here, the water solubility means that the solubility in water at 25 ° C. is 1 g / 100 ml or more.

The thin water-soluble resin coating layer means that the particles before coating of the water-soluble resin coating layer, that is, SEM photographs of the core particles (FIGS. 1 and 2), and SEM photographs of the water-soluble resin coating layer-forming particles (FIGS. 3 and 3). 4) can be compared and confirmed from the fact that the particle size does not change. Thus, since there is no change in the particle diameter of the particles before and after the formation of the water-soluble resin coating layer, the thickness of the water-soluble resin coating layer formed on the core particles is estimated to be 10 nm or less.
It can also be confirmed that the water-soluble resin coating layer is a film layer having a substantially smooth surface because the particle shape does not change in the comparison of the same figure.

(2-1. Configuration of resin coating layer made of water-soluble resin)
As the resin constituting the water-soluble resin coating layer, when the core particles are negatively charged, it is preferable to use a positively charged resin because a thin and uniform water-soluble resin coating layer can be easily formed. The positively chargeable resin is not particularly specified, but —NH ₂ , —NHCH ₃ , —N (CH ₃ ) ₂ , —NHC ₂ H ₅ , —N (C ₂ H ₅ ) ₂ , —NHC ₂ H ₄ OH, etc. And a resin containing a quaternary ammonium salt in which they are ammonium chloride. Among these, a resin containing a quaternary ammonium salt is preferable. In particular, when the negatively chargeable core particles contain sulfonic acid groups or sulfonate groups, and the positively chargeable water-soluble resin contains quaternary ammonium salts, the sulfonic acid groups or sulfonate groups and quaternary ammonium salts are used. Reacting with each other to form an insoluble salt is preferable because the water-soluble resin coating layer is firmly fixed on the surface of the core particles. A resin containing a quaternary ammonium salt can be obtained by subjecting a polymer containing an amino group to ammonium chloride. It can also be obtained by polymerizing a monovinyl monomer containing an ammonium salt group. Moreover, you may make it copolymerize with the monomer generally used for binder resin. However, the method for producing the positively chargeable resin is not limited to these methods.

  Among resins containing a quaternary ammonium salt, a resin having a structural unit represented by any of the following structural formulas (2) to (5) is preferable.

In the structural formulas (2) to (5), R ³ is a hydrogen atom or a methyl group, R ⁴ is an alkylene group, and R ^{5 to} R ⁹ are each independently a hydrogen atom or a carbon number. 1 to 6 linear, branched or cyclic alkyl groups, and X < ^- > is a halogen ion, an alkyl sulfate ion, a benzene sulfonate ion or an alkyl benzene sulfonate ion.

In the quaternary ammonium salts shown in the structural formulas (2) to (5), X ⁻ is preferably a chloride ion or a toluene sulfonate ion, and R ³ is a hydrogen atom or a methyl group. Preferably, R ⁴ is an alkylene group having 1 to 3 carbon atoms such as CH ₂ , C ₂ H ₄ , C ₃ H ₆ and derivatives thereof, and R ^{5 to} R ⁹ are each independently CH ₃ , An alkyl group such as C ₂ H ₅ or C ₃ H ₇ is preferred.

Examples of amino group-containing (meth) acrylate monomers include dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, dipropylaminomethyl (meth) acrylate, diisopropylaminomethyl (meth) acrylate, and ethylmethylamino. Methyl (meth) acrylate, methylpropylaminomethyl (meth) acrylate, dimethylamino-1-ethyl (meth) acrylate, diethylamino-1-ethyl (meth) acrylate, dipropylamino-1-ethyl (meth) acrylate, diisopropylamino -1-ethyl (meth) acrylate, ethylmethylamino-1-ethyl (meth) acrylate, methylpropylamino-1-ethyl (meth) acrylate, dimethylamino-2-ethyl (meth) Chlorate, diethylamino-2-ethyl (meth) acrylate, dipropylamino-2-ethyl (meth) acrylate, diisopropylamino-2-ethyl (meth) acrylate, ethylmethylamino-2-ethyl (meth) acrylate, methylpropylamino 2-ethyl (meth) acrylate, dimethylamino-1-propyl (meth) acrylate, diethylamino-1-propyl (meth) acrylate, dipropylamino-1-propyl (meth) acrylate, diisopropylamino-1-propyl (meth) ) Acrylate, ethylmethylamino-1-propyl (meth) acrylate, methylpropylamino-1-propyl (meth) acrylate, dimethylamino-2-propyl (meth) acrylate, diethylamino-2-propi (Meth) acrylate, dipropylamino-2-propyl (meth) acrylate, diisopropylamino-2-propyl (meth) acrylate, ethylmethylamino-2-propyl (meth) acrylate, methylpropylamino-2-propyl (meth) Examples include N, N-disubstituted aminoalkyl (meth) acrylate compounds such as acrylate.

Examples of the quaternizing agent used for converting an amino group into an ammonium salt include alkyl halides such as methyl iodide, ethyl iodide, methyl bromide, and ethyl bromide, methyl paratoluenesulfonate, and paratoluenesulfone. Examples thereof include ethyl acid and paratoluenesulfonic acid alkyl esters such as propylparatoluenesulfonic acid propyl.
When the core particles are positively charged, it is preferable to use a negatively charged resin because a thin and uniform water-soluble resin coating layer can be easily formed. The negatively chargeable resin is not particularly specified, and examples thereof include a resin having a carboxyl group, a resin having a sulfonic acid group, and a resin having a sulfonamide group. Moreover, you may make it copolymerize with the monomer generally used for binder resin. However, the method for producing the negatively chargeable resin is not limited to these methods.

Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and cinnamic acid. Examples of the sulfonic acid group-containing monomer include sulfonated styrene and acrylamide sulfonic acid. Examples of the sulfonamide group-containing monomer include styrene sulfonamide.
Although the molecular weight of resin used for a water-soluble resin coating layer is not specifically limited, The weight average molecular weight in GPC is 3000 or more, and it is desirable that it is 1 million or less. If the weight average molecular weight is 3000 or less, the adsorptive power to the core particle surface may be weak, and if it exceeds 1,000,000, the polymer chain becomes long, so that it can be adsorbed to multiple core particles in a bridging manner. There is sex.

  The content of the water-soluble resin coating layer is not particularly limited as long as the effect of the present invention is not impaired, but is usually preferably 0.01 parts by mass or more, more preferably 0.05 with respect to 100 parts by mass of the core particles. It is not less than 3 parts by mass and usually not more than 3 parts by mass. When the amount is less than 0.01 parts by mass, it is difficult to obtain a target water-soluble resin coating layer as a uniform layer, and when the amount exceeds 3 parts by mass, toner fixability tends to deteriorate.

(2-2. Method of forming a resin coating layer made of a water-soluble resin on the core particles)
When forming a water-soluble resin coating layer on the core particle surface, it is preferable from the viewpoint of operability to prepare and use a water-soluble resin as an aqueous solution as a component of the water-soluble resin coating layer. Further, various commercially available resin aqueous solutions such as PAS-H, PAS-J (manufactured by Nitto Bo Medical Co., Ltd.), Jurimer AC-103 (manufactured by Toagosei Co., Ltd.) and the like can also be used.

A water-soluble resin coating layer can be formed by adding and mixing a water-soluble resin coating layer resin aqueous solution to the core particle dispersion.
The mixing temperature of the core particles and the resin aqueous solution at the time of forming the resin layer is not particularly limited. However, if the mixing is performed at a temperature 10 ° C. or more lower than the Tg of the core particles, the generation of core particle aggregates is prevented, and the core particles and the resin aqueous solution are uniformly distributed Since it can mix, it is preferable.

  After uniform mixing, the pH, electrolyte concentration, and temperature of the mixed solution can be adjusted. When either or both of the core particle and the water-soluble resin coating layer component have the property that the chargeability changes depending on the pH, the pH of the mixed solution is adjusted to a region where the chargeability of the both indicates the opposite sign. It is preferable. Usually, if the core particle surface and the water-soluble resin coating layer component are adjusted to a pH range in which the chargeability is reversed, the formation of the water-soluble resin coating layer proceeds, but the electrolyte concentration may be adjusted supplementarily. As the electrolyte, inorganic or organic acids, alkalis and salts can be used. The temperature is preferably adjusted at Tg + 20 ° C. or lower of the core particles in order to prevent aggregation between the core particles.

After forming the water-soluble resin coating layer, it is preferable to remove excess water-soluble resin that does not adhere to the surface of the core particles remaining in the aqueous medium by washing. As a specific method, a method similar to the cleaning of the core particles can be used.
Alternatively, the ratio of the core particles to the water-soluble resin can be strictly adjusted so that excess resin that does not adhere to the core particle surfaces does not remain in the aqueous medium. In this case, cleaning can be omitted.

As a method for confirming that the water-soluble resin coating layer has been formed, the sign of the ζ potential of the dispersion before and after the formation of the water-soluble resin coating layer is reversed, or the dispersion before and after the water-soluble resin coating layer is formed. This can be confirmed by reversing the sign of the charge amount of the washed and dried powder.
Although it is possible to prepare a water-soluble resin coating layer component as a fine particle dispersion instead of an aqueous solution and coat the surface of the core particles with fine particles, it is possible to form a water-soluble resin coating layer, but the layer is thicker than the method using an aqueous solution. Therefore, the low-temperature fixability tends to deteriorate. As can be seen from the comparative examples described later, in the case of fine particles of hard material, the deterioration of the low-temperature fixability is more remarkable.

  Further, when the water-soluble resin coating layer component is prepared as a fine particle dispersion, it is difficult to coat the shell particles thinly and uniformly on the surface of the water-soluble resin coating layer in the next step. The part which does not coat may occur. The reason for this is not clear, but it is presumed that the water-soluble resin coating layer formed by the fine particles has irregularities on the surface and the state is not uniform, so that the adhesion of the shell particles varies. If an attempt is made to cover the entire surface of the water-soluble resin coating layer by increasing the amount of shell particles added to compensate for the non-uniform coating, the shell layer becomes thick and the low-temperature fixability is impaired.

<3. Shell layer>
In the present invention, the form of the shell layer is not particularly limited, but is preferably formed of particles. Hereinafter, the case of forming the shell layer using particles will be described as an example of the shell layer of the present invention. The particles forming the shell layer are called shell particles.
Moreover, although the material which comprises a shell layer is not specifically limited, It is preferable that the shell layer contains resin and it is more preferable that resin is a main component. Here, the main component is a component mainly responsible for the performance of the shell, excluding substances used auxiliary in the production of main components such as emulsifiers and dispersants, and additives such as preservatives. Preferably there is.

(3-1. Configuration of Shell Particles)
The shell particles to be coated on the surface of the water-soluble resin coating layer may be inorganic particles or resin fine particles, and are not particularly limited. However, from the viewpoints of particle production, controllability of particle performance, and low-temperature fixability, the shell particles are preferably resin fine particles.
When the shell particles are resin fine particles, the resin component is not particularly specified, but for example, a resin generally used as a binder resin such as a styrene type, an acrylic type or an ester type, or a copolymer type or a blend type thereof may be used.

  The weight average molecular weight of the resin shell particles is preferably 10,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 10,000 to 300,000. If the weight average molecular weight of the resin shell particles is too low, the blocking resistance of the toner may be deteriorated and the durability in the cartridge may be deteriorated. On the other hand, if the resin shell particles are too high, the low-temperature fixability may be deteriorated.

  The Tg of the resin shell particles is 55 ° C. or higher, preferably 60 ° C. or higher. The upper limit is not particularly limited as long as the effect of the present invention is not impaired, but is 100 ° C. or lower, preferably 80 ° C. It is below, More preferably, it is 75 degrees C or less. Further, it is necessary to be higher than the Tg of the polymer primary particles in the core particles, and specifically, (Tg + 20 of the polymer primary particles in the core particles) ° C. or more. The upper limit is not particularly limited, but is (Tg + 50 of core particles) ° C. or less, and (Tg + 40 of core particles) ° C. or less is preferable. If the Tg of the resin shell particles is too low, the resin shell particles are softened or the external additive is embedded in the shell particles, so that the blocking resistance is deteriorated. On the other hand, if the Tg of the resin shell particles is too high, the low-temperature fixability may decrease.

  The content of the shell particles is not particularly limited as long as the effects of the present invention are not impaired. Usually, the content is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more with respect to 100 parts by mass of the core particles. Moreover, Preferably it is 8 mass parts or less, More preferably, it is 6 mass parts or less. If the amount is less than 0.5 parts by mass, the intended shell layer is difficult to obtain as a uniform layer, so that the storage stability is deteriorated. If the amount exceeds 8 parts by mass, the toner fixing property tends to be deteriorated.

  When the water-soluble resin coating layer is positively charged, it is preferable to use a negatively charged resin for the shell particles because a thin and uniform shell layer can be easily formed. The negatively chargeable resin is not particularly specified, but a resin obtained by copolymerizing a monomer having a carboxyl group; a sulfonic acid group; a sulfonamide group and a monomer generally used for a binder resin is preferable. In particular, when the water-soluble resin contains a quaternary ammonium salt and the negatively-charged shell particles contain a sulfonic acid group or a sulfonic acid group, the quaternary ammonium salt reacts with the sulfonic acid group or the sulfonic acid group and is insoluble. It is preferable to form the salt because the shell particles are firmly fixed to the surface of the water-soluble resin coating layer. Among these, a resin having a sulfonic acid group is preferable. However, the method for producing the negatively chargeable resin is not limited to these methods.

  A water-soluble resin coating layer is formed using the resin having the structural unit represented by the structural formula (4) or (5) described above, and the resin having the structural unit represented by the following structural formula (6) is formed on the shell particles. When used, it is preferable because the charge amount can stably maintain high chargeability from the beginning.

In the structural formula (6), R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, and M is a hydrogen atom or an alkali metal. It is.
When the water-soluble resin coating layer is negatively charged, it is preferable to use a positively charged resin for the shell particles because a thin and uniform shell layer can be easily formed. Although the positively chargeable resin is not particularly specified, such as —NH ₂ , —NHCH ₃ , —N (CH ₃ ) ₂ , —NHC ₂ H ₅ , —N (C ₂ H ₅ ) ₂ , —NHC ₂ H ₄ OH, etc. A monomer containing an amino group; a resin obtained by copolymerizing a monomer containing a quaternary ammonium salt obtained by ammonium chloride and a monomer generally used for a binder resin is preferable. These monomers impart positive chargeability to the shell particles, and at the same time, impart emulsion stability of the shell particles, so that aggregation of the shell particles is less likely to occur when the shell layer is formed. Among these, a resin containing a quaternary ammonium salt is preferable. However, the method for producing the positively chargeable resin is not limited to these methods.

  The lower limit of the amount of the monomer unit having a functional group imparting charging property in the binder resin of the shell particles is usually 0.5% by mass or more, preferably 1% by mass or more, more preferably. On the other hand, the upper limit is usually 15% by mass or less, preferably 12% by mass or less, and more preferably 10% by mass or less. If the amount of the functional group-providing monomer having the functional group is too small, the chargeability of the toner after the shell layer is formed may be insufficient. There is a case where the decrease in the charge amount becomes large and fogging occurs.

The resin shell particles may be prepared by dispersing or emulsifying a resin in an aqueous medium, and may be prepared by a polymerization method such as emulsion polymerization, soap-free polymerization, suspension polymerization, etc. From the viewpoint of easiness, a polymerization method is preferred.
When the resin shell particles are prepared by emulsion polymerization, they can be prepared in the same manner as (1-2-1-1. Emulsion polymerization) in the above-mentioned core particle section.

The volume average particle diameter of the shell particles is not particularly limited as long as the effects of the present invention are not impaired, but 20 nm or more is preferable. Moreover, 500 nm or less, Furthermore, 150 nm or less is preferable.
Various commercially available products can be used for the shell particles. Examples thereof include FCA-207P (: trade name, styrene / acrylic resin), FCA-201-PS (: trade name, styrene / acrylic resin) manufactured by Fujikura Kasei Co., Ltd., and the like.

By selecting the particle size, particle size distribution, shape, etc. of the shell particles, the BET specific surface area of the toner base particles after the shell layer is formed can be adjusted. For example, when shell particles having a volume average particle size of 40 nm or less are selected, the BET specific surface area of the toner base particles can be reduced.
(3-2. Method of coating shell particles on water-soluble resin coating layer)
As a method for producing a toner having a core-shell structure, there are a method of forming a core-shell structure by mixing the shell particles in the latter half of the core particle forming step and a method of coating the surface of the completed core particles with shell particles.

In the former case, which is a conventional embodiment, the shell particles are embedded in the core particles during the manufacturing process, so that the core particle component is exposed on the surface of the toner base particles. In order to completely coat the core particles, it is necessary to coat a large amount of shell particles, and as a result, the low-temperature fixability is impaired.
On the other hand, in the latter case, which is an embodiment for realizing the present invention, the surface of the finished core particle is coated with the water-soluble resin coating layer and the shell particle, so that the shell particle is not embedded in the core particle during the manufacturing process. The core particles can be completely covered with a small number of shell particles. In addition, the chargeability of the water-soluble resin coating layer and the shell particles is opposite, and the wettability of both resins is not high, which also has the effect of making it difficult for the shell particles to be embedded.

In addition, since the chargeability of the water-soluble resin coating layer and the shell particles is opposite, shell particles are likely to adhere to the surface of the water-soluble resin coating layer, but since the shell particles have the same chargeability, after the shell layer is formed, The shell particles are less likely to adhere to the top. Therefore, a thin and uniform shell layer can be easily formed.
As described above, even when the shell layer is thin, it is possible to maintain blocking resistance, and as a result, the toner has excellent low-temperature fixability.

The step of coating the shell particles on the water-soluble resin coating layer is performed by adding the shell particles to the water-soluble resin coating layer-forming particle dispersion and mixing them.
The mixing temperature of the water-soluble resin coating layer-forming particles and the shell particles is not particularly limited, but the temperature lower by 10 ° C. or more than the lowest Tg among the Tg of the core particles, the water-soluble resin coating layer and the shell particles is not limited. This is preferable because uniform mixing can be performed while preventing generation of aggregates.

  After uniform mixing, the pH, electrolyte concentration, and temperature of the mixed solution can be adjusted. When either or both of the core particle surface and the water-soluble resin coating layer component have the property that the chargeability varies depending on the pH, the pH should be adjusted to a pH range in which both exhibit opposite chargeability. Is preferred. Usually, if the water-soluble resin coating layer-forming particles and the shell particles are adjusted to a pH range in which the chargeability is reversed, the formation of the shell layer proceeds, but the electrolyte concentration may be further adjusted. As the electrolyte, inorganic or organic acids, alkalis and salts can be used.

The temperature adjustment is preferably performed at Tg + 20 ° C. or less of the core particle in order to prevent aggregation between particles.
As a method for confirming that the shell layer has been formed, the sign is reversed when the ζ potential of the dispersion liquid before and after the shell layer formation is measured, or the charge amount after washing and drying the dispersion liquid before and after the shell layer formation is measured. When measured, it can be confirmed by reversing the sign.

<4. Cleaning and drying of toner base particles>
The toner base particles coated with the shell particles are separated from the aqueous solvent, washed, dried, subjected to external addition treatment as necessary, and used as an electrostatic image developing toner.
Water is used as the liquid used for washing, but washing with an acid or alkali aqueous solution is also possible. Moreover, it can also wash | clean with warm water or hot water, and these methods can also be used together. Through such a washing step, suspension stabilizers, emulsifiers, unreacted monomers and the like can be reduced and removed. In the washing step, for example, it is preferable to repeat the operation of dispersing the toner base particles by adding a liquid for cleaning to the toner base particles into a thick slurry or wet cake by filtering, decanting, or the like. The toner base particles after washing are preferably collected in the form of a wet cake in terms of handling in the subsequent drying process.

In the drying process, a fluidized drying method such as a vibration type fluidized drying method or a circulation type fluidized drying method, an air flow drying method, a vacuum drying method, a freeze drying method, a spray drying method, a flash jet method, or the like is used. Operating conditions such as temperature, air volume, and degree of reduced pressure in the drying step are appropriately optimized based on the Tg of the colored particles, the shape, mechanism, size, etc. of the apparatus used.
The volume average particle size of the toner of the present invention is preferably 3 μm or more, and more preferably 5 μm or more. Moreover, 15 micrometers or less are preferable, and also 10 micrometers or less are more preferable. Further, the shape has an average circularity measured by using a flow type particle image analyzer FPIA-3000, preferably 0.90 or more, more preferably 0.92 or more, further preferably 0.94 or more, preferably Is 0.99 or less. If the average circularity is too small, the image density may be lowered due to deterioration of charging due to poor adhesion of the external additive to the toner base particles, and if it is too large, the cleaning may be poor due to the shape.

<Adjustment of ζ potential>
Hereinafter, the adjustment of the ζ potential will be described using a negatively chargeable toner as an example.
The core particle and the shell particle have the same polarity, the water-soluble resin coating layer has a ζ potential opposite to that of the core particle and the shell particle, and the ζ potential at pH 3 has the following relationships (I) to (V): It is preferable to satisfy.
(I) ζ potential of core particles: −20 mV to −70 mV
(II) ζ potential of water-soluble resin coating layer forming particles: +40 mV to +120 mV
(III) ζ potential of shell particles: −40 mV to −100 mV
(IV) ζ potential of toner base particles: −30 mV to −90 mV
(V) 1.0 ≦ ζ potential of toner mother particles / ζ potential of core particles ≦ 5.0
The negatively charged toner of the present invention uniformly coats the core particles by using as little shell particles and positively chargeable water-soluble resin as possible with respect to the negatively charged core particles. For this purpose, the zeta potential of the core particles, water-soluble resin coating layer forming particles, shell particles, and toner base particles is preferably in the above range.

The core particle has a ζ potential (I) of preferably −20 mV to −70 mV, more preferably −20 mV to −50 mV.
If the ζ potential of the core particles is less than −20 mV, the water-soluble resin having the opposite polarity becomes difficult to adhere or adsorb, and / or the amount or amount of the water-soluble resin adhering or adsorbing is reduced, or the adhesion becomes uneven. There is a risk that the coating of shell particles, which is a process, is insufficient.

On the other hand, when the ζ potential of the core particle is larger than −70 mV, the water-soluble resin is easily attached or adsorbed. However, a large amount of the water-soluble resin is used in order to keep the ζ potential of the water-soluble resin coating layer-forming particle within the appropriate range. Need to adhere or adsorb. When the amount of water-soluble resin adhering or adsorbing is too large, the charging characteristics, environmental characteristics, and low-temperature fixing performance of the toner tend to deteriorate.
In order for the ζ potential of the core particle to satisfy the above condition (I), the means is not particularly limited, but the content of the basic monomer is preferably 10 wt% or less based on the entire resin in the core particle. . When more than 10 wt% of basic monomer is used, it is necessary to use a large amount of acidic monomer in the resin in the core particle in order to adjust the ζ potential to the above range, resulting in deterioration of environmental characteristics. There is a risk.

The total content of acidic monomers and basic monomers with respect to the entire resin in the core particles is preferably 20 wt% or less, more preferably 10 wt% or less, and particularly preferably 5 wt% or less.
Next, the ζ potential (II) of the water-soluble resin-coated layer-forming particles. Since the water-soluble resin is positively charged, the ζ potential range (condition (II)) is reached when a suitable amount of the water-soluble resin is coated. The water-soluble resin coating layer, particularly when the resin constituting the water-soluble resin coating layer contains a basic monomer as a constituent component, has a ζ potential that depends on pH and does not exhibit sufficient positive chargeability in the alkaline region. Therefore, the ζ potential is also lowered. On the other hand, in the acidic region, sufficient positive chargeability is exhibited and the ζ potential is also increased.

  The ζ potential of the water-soluble resin coating layer-forming particles is preferably +40 mV to +120 mV, more preferably +50 to +90 mV. If the ζ potential of the water-soluble resin coating layer-forming particles is smaller than +40 mV, the shell particles are not sufficiently adhered and uniform coating cannot be performed. On the other hand, if it is higher than +120 mV, a large amount of shell may be covered and fixing property may be deteriorated, or if an appropriate amount of shell is covered, charging property and environmental characteristics may be deteriorated.

In order to adjust the ζ potential of the water-soluble resin coating layer forming particles to an appropriate range, the means is not particularly limited, but after adjusting the ζ potential to the appropriate range by the above-mentioned method, the water-soluble resin is adjusted. It is preferable to adjust the content of the basic monomer, which is a constituent component of the resin constituting the resin, to 20 wt% to 100 wt% of the entire water-soluble resin.
The ζ potential (condition (III)) of the shell particles is preferably −40 mV to −100 mV. More preferably, it is −40 mV to −80 mV.

It is desirable that the shell particles have a high ζ potential from the viewpoint of selectively adhering to the surface of the water-soluble resin coating layer-forming particles without causing aggregation of the shells when the shell is added. However, if the ζ potential of the shell particles is too high, the coating amount of the shell particles is insufficient or the coating becomes non-uniform, which is not desirable.
In order to ensure a sufficient coating amount of the shell particles, there is a method of increasing the coating amount of the water-soluble resin and making the ζ potential of the water-soluble resin coating layer forming particles higher than the above range. As described above, there is a possibility that the charging characteristics and the environmental characteristics may be deteriorated when used for the above. In addition, in order to increase the ζ potential of the water-soluble resin coating layer-forming particles, it is necessary to use a large amount of a basic monomer, which may similarly cause deterioration of environmental characteristics.

  In order to make the coating of the shell particles uniform and appropriate, it is preferable that the ζ potential of the shell particles and the ζ potential of the water-soluble resin coating layer forming particles are in the ranges described above. The means for adjusting the ζ potential of the shell particle is not particularly limited, but can be adjusted by the content of the acidic monomer in the resin in the shell particle, and the content is 0.5 wt% or more and 20 wt% or less of the entire resin. Preferably there is.

  When the content of the acidic monomer is less than 0.5 wt%, the ζ potential of the shell particles becomes low, and when the shell particles are added, the shell particles adhere to the water-soluble resin coating layer forming particles and at the same time Agglomeration may occur. On the other hand, if the content of the acidic monomer is more than 20 wt%, the ζ potential becomes too high, and there is a risk that the adhesion amount of the shell is not sufficient or the environmental characteristics are deteriorated.

Although it does not specifically limit as an acidic monomer, The thing containing a sulfonic acid group and a sulfonate group is preferable.
After coating the core particles with the water-soluble resin, it is desirable that the pH of the dispersion of the water-soluble resin coating layer-forming particles is once in the alkaline region. Accordingly, it is important that the ζ potential of the water-soluble resin coating layer forming particles becomes negative. Since the water-soluble resin itself does not exhibit sufficient positive chargeability under alkaline conditions, and the core particles exhibit high negative chargeability under alkaline conditions, they become negative in the alkaline region.

  This phenomenon can be explained by the respective pKa and pKb when an acidic monomer is used for the core particle and a basic monomer is used for the water-soluble resin. Designed so that the water-soluble resin coating layer-forming particles exhibit strong negative chargeability, that is, a high negative polarity ζ potential under alkalinity, shell particles are added to the water-soluble resin coating layer-forming particles under alkalinity, and then the pH is adjusted. It is a more preferable manufacturing method to set it as an acidic region.

  When shell particles are added to water-soluble resin coating layer-forming particles under acidic conditions, the adhesion of shell particles to water-soluble resin coating layer-forming particles is faster than the diffusion of shell particles, and toner base particles (negatively charged), partially In this case, toner mother particles (positively chargeable) having a shell attached thereto and water-soluble resin coating layer forming particles (positively charged) are mixed. For this reason, the negatively charged toner base particles and the positively charged toner base particles partially having a shell attached thereto or the positively charged water-soluble resin coating layer forming particles may aggregate to deteriorate the particle size distribution.

On the other hand, such problems can be prevented by adding shell particles under alkalinity and acidifying the shell particles after sufficiently diffusing and homogenizing. The pH adjustment during the production is carried out by adding an acid or a base, but it is presumed that the above problem does not occur because the acid diffuses and homogenizes much faster than the shell particles after the addition.
In addition, the water-soluble resin-coated layer-forming particles may not exhibit sufficient negative polarity in the alkaline region due to insufficient adhesion or adsorption of the water-soluble resin to the core particles. In this case, the addition of shell particles tends to cause aggregation at the same time, which is not preferable.

For this reason, the ζ potential of the water-soluble resin coating layer forming particles is preferably −20 mV to −100 mV at pH 11.
If the ζ potential of the water-soluble resin coating layer-forming particles is lower than −20 mV at pH 11, as described above, aggregation tends to occur when shell particles are added under alkalinity. On the other hand, if the design and adhesion amount of the core particles and the water-soluble resin are appropriate, it will not exceed -100 mV.

The ζ potential of the toner base particles is preferably −30 mV to −90 mV, and 1.0 ≦ the ζ potential of the toner base particles / the ζ potential of the core particles ≦ 5.0.
When the ζ potential of the core particles, the ζ potential of the water-soluble resin coating layer forming particles, and the ζ potential of the shell particles are appropriately adjusted by the above-described method, and the uniform coating can be performed, the ζ potential of the toner base particles falls within the above range. When the ζ potential of the toner base particles is smaller than −30 mV and / or when the ζ potential of the toner base particles / the ζ potential of the core particles is less than 1.0, the adhesion amount of the shell particles is insufficient or non-uniform. There is a possibility that some trouble has occurred. Further, when the value is larger than −90 mV and / or the ζ potential of the toner base particles / the ζ potential of the core particles is larger than 5.0, the adhesion amount of the shell particles is excessive or the shells are aggregated. There is a possibility that the problem of.

<5. External additive>
(5-1. External additives)
In the present invention, an external additive can be added as necessary to improve the fluidity of the toner and charge control. The external additive can be appropriately selected from various inorganic or organic fine particles. Two or more kinds of external additives may be used in combination.

  Inorganic fine particles include silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, and other carbides, boron nitride, titanium nitride. , Various nitrides such as zirconium nitride, various borides such as zirconium boride, various oxides such as titanium oxide, calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, cerium oxide, silica, colloidal silica, titanium Various titanate compounds such as calcium oxide, magnesium titanate and strontium titanate, phosphate compounds such as calcium phosphate, sulfides such as molybdenum disulfide, fluorides such as magnesium fluoride and fluorocarbon, aluminum stearate, stearin Calcium, zinc stearate, can be used various metal soaps such as magnesium stearate, talc, bentonite, various carbon black or conductive carbon black, magnetite, ferrite or the like. As the organic fine particles, fine particles such as styrene resin, acrylic resin, epoxy resin, and melamine resin can be used. In addition, charging stability can be improved by using fine particles containing fluorine atoms.

  Among these external additives, silica, titanium oxide, alumina, zinc oxide, various carbon blacks, conductive carbon blacks, and the like are preferably used. In addition, the external additive is prepared by applying the surface of the inorganic or organic fine particles to a silane coupling agent such as hexamethyldisilazane (HMDS) or dimethyldichlorosilane (DMDS), a titanate coupling agent, silicone oil, or dimethyl silicone oil. Hydrophobic by treating agents such as silicone oil treating agents such as modified silicone oil and amino-modified silicone oil, silicone varnish, fluorine-based silane coupling agent, fluorine-based silicone oil, coupling agent having amino group or quaternary ammonium base What was surface-treated, such as chemical conversion, can also be used. Two or more kinds of the treatment agents can be used in combination.

The content of the external additive is preferably 0.5 parts by mass or more, more preferably 0.8 parts by mass or more, preferably 5 parts by mass or less, more preferably 4 parts by mass with respect to 100 parts by mass of the toner base particles. It is below mass parts.
Generally, when the blocking resistance is improved by increasing the content of the external additive, the low-temperature fixability tends to deteriorate. However, in the toner of the present invention, the content of the external additive should be increased. The blocking resistance is easily improved, while the low-temperature fixability is hardly deteriorated.

  The reason for this is not clear, but is estimated as follows. Since most of the external additive is located on the shell particles, when the amount of the external additive is increased, the amount of the external additive is increased on the outermost surface of the toner, and the blocking resistance can be effectively improved. In addition, since the shell is composed of particles, there is a gap between the shell particles, and at the time of fixing, it is thought that the core component moves from the gap to the outside, and low temperature fixability is expressed. It is estimated that even when the amount of the additive is increased, the gap is not completely closed and the gap remains, and as a result, the low-temperature fixability can be maintained.

  In the toner of the present invention, conductive fine particles may be used as an external additive from the viewpoint of charge control. The upper limit of the resistance of the conductive fine particles is usually 400 Ω · cm or less, preferably 200 Ω · cm or less, more preferably 100 Ω · cm or less, and further preferably 60 Ω · cm or less. On the other hand, the lower limit is usually 0.1 Ω · cm or more, preferably 1 Ω · cm or more, more preferably 5 Ω · cm or more, and further preferably 15 Ω · cm. Examples of the conductive fine particles include metal oxides such as conductive titanium oxide, silica, and magnetite, or those doped with a conductive substance, conjugated double bonds such as polyacetylene, polyphenylacetylene, and poly-p-phenylene. Examples include organic fine particles obtained by doping a conductive material such as metal to a polymer having carbon, carbon typified by carbon black and graphite, etc., but from the viewpoint that conductivity can be imparted without impairing the fluidity of the toner, conductive oxidation What doped titanium or its electroconductive substance is more preferable. The lower limit of the content of the conductive fine particles is usually 0.05 parts by mass or more, preferably 0.1 parts by mass or more, and preferably 0.2 parts by mass or more with respect to 100 parts by mass of the toner base particles. It is more preferable that On the other hand, the upper limit of the content of the conductive fine particles is usually 3 parts by mass or less, preferably 2 parts by mass or less, and more preferably 1 part by mass or less.

(5-2. External additive method)
Examples of the method for adding the external additive include a method using a high-speed stirrer such as a Henschel mixer, a method using an apparatus capable of applying a compressive shear stress, and the like.
The external toner can be prepared by a one-stage external addition method in which all the external additives are added to the toner base particles at the same time, or can be prepared by a separate external addition method in which each external additive is externally added.
In order to prevent a temperature increase during external addition, it is preferable to install a cooling device in the container or to add externally in stages.

(6. Others)
The toner for developing an electrostatic image of the present invention may be used in any form of a two-component developer using the toner together with a carrier or a magnetic or non-magnetic one-component developer not using a carrier. When used as a two-component developer, the carrier may be a magnetic substance such as iron powder, magnetite powder, ferrite powder or the like, or a known material such as a resin-coated surface or a magnetic carrier. As the coating resin of the resin coating carrier, generally known styrene resin, acrylic resin, styrene acrylic copolymer resin, silicone resin, modified silicone resin, fluororesin, or a mixture thereof can be used.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the following examples, “part” means “part by mass”.
Each particle diameter, circularity, electrical conductivity, thermal characteristics, etc. were measured as follows.

<Medium diameter measurement (D50)>
The median diameter (D50) of particles having a median diameter (D50) of less than 1 micron is obtained by using Nikkiso Co., Ltd. model Microtrac Nanotrac 150 (hereinafter abbreviated as “Nanotrack”) and analysis software Microtrac Particle Analyzer Ver10.1.2-019EE. The method described in the instruction manual using the ion-exchange water having an electric conductivity of 0.5 μS / cm as the solvent, the solvent refractive index: 1.333, the measurement time: 120 seconds, and the number of measurements: 5 times. The average value was obtained. Other setting conditions were particle refractive index: 1.59, transparency: transmission, shape: true sphere, density: 1.05.

<Volume Median Particle Size Measurement (Dv50)>
The volume median particle size (Dv50) of the particles having a volume median particle size (Dv50) of 1 micron or more is obtained by using Multisizer III (aperture diameter 100 μm: hereinafter abbreviated as Multisizer) manufactured by Beckman Coulter, It was measured by isoton II as a dispersion medium and dispersed to a dispersoid concentration of 0.03%.

<Average circularity measurement>
The average circularity is determined by dispersing the dispersoid in a dispersion medium (Cell Sheath: Sysmex) at 5720-7140 / μl, and using a flow particle analyzer (FPIA 3000: Sysmex) to analyze the amount of HPF. It measured by HPF mode on 0.35 microliters and HPF detection amount 2000-2500 conditions.

<Electrical conductivity measurement>
The electrical conductivity was measured using a conductivity meter (CyberScanCON100 manufactured by ASONE Corporation).

<Weight average molecular weight (Mw)>
The THF soluble components of the dried polymer primary particle dispersion and shell particle dispersion were measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC apparatus HLC-8020 manufactured by Tosoh Corporation, column: PL-gelMixed-B 10μ manufactured by Polymer Laboratory, solvent: THF, sample concentration: 0.1% by weight, calibration curve: standard polystyrene water-soluble resin coating layer aqueous solution D1 Measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC apparatus HLC-8010 manufactured by Tosoh Corporation, column: TSKgel GMPWx1 manufactured by Tosoh Corporation, solvent: 0.5 M acetic acid + 0.5 M sodium acetate aqueous solution, sample concentration: 0.2 wt%, calibration curve: polyethylene glycol

<Measurement of glass transition temperature (Tg)>
Using a differential thermal analyzer (DSC200) manufactured by Seiko Denshi Kogyo Co., Ltd., the temperature was measured at a temperature rising rate of 10 ° C./min. Tg was determined from the intersection of the base line extension of the DSC curve and the tangent line showing the maximum slope in the endothermic curve.

<Charge amount measurement>
F-80 manufactured by Powdertech Co., Ltd. is used as a carrier, and 10 g of a 1:24 weight ratio with the carrier is placed in a glass sample bottle with a capacity of 30 ml, and the frequency is 600 rpm with a mixer mill manufactured by Mitamura Riken Kogyo. Then, the amount of charge was measured by the suction blow-off method using 0.1 g of the blow-off charge amount measuring device manufactured by Toshiba Chemical Co., Ltd.
Blow condition: 0.05kgf x 3 seconds
Suction pressure: 350-400 mmH ₂ O
Screen: 400 mesh

<Measurement of zeta potential>
The zeta potential is measured by diluting the core particle dispersion, the water-soluble resin coating layer forming particle dispersion, and the shell particle dispersion to 1/1000 each with pure water using Zetasizer Nano (Malvern). did.

<Weight reduction of wax at 200 ° C.>
The weight loss at 200 ° C. of the wax was measured using TG / DTA6200 and EXSTAR6000 manufactured by Hitachi High-Tech Science Co., Ltd. The time for the weight loss to reach 0.1% was determined based on the maximum weight.
Sample container: Platinum sample pan Reference: Sample pan only Sample amount: 30-31mg
Atmosphere: Nitrogen (flow rate 200ml / min)
Temperature conditions Starting temperature: 28 ° C
Temperature increase rate: 10 ° C / min
Holding temperature: 200 ° C

[Example 1]
<Preparation of black colorant dispersion>
Carbon black (Mitsubishi Chemical Corporation, Mitsubishi Carbon Black) manufactured by a furnace method in which a toluene extract has an ultraviolet absorbance of 0.02 and a true density of 1.8 g / cm ³ is placed in a stirrer vessel equipped with a propeller blade. MA100S) 20 parts, 20% sodium dodecylbenzenesulfonate aqueous solution (hereinafter abbreviated as 20% DBS aqueous solution) 1 part, 4 parts of nonionic surfactant (Emulgen 120, manufactured by Kao Corporation), ion exchange with 2 μS / cm conductivity 75 parts of water was added and predispersed to obtain a pigment premix solution. The volume cumulative 50% diameter Dv50 of the carbon black in the dispersion after the premix was about 90 μm. The premix solution was supplied as a raw material slurry to a wet bead mill and subjected to one-pass dispersion. Note that zirconia beads (true density of 6.0 g / cm ³ ) having a diameter of 120 mmφ, a separator having a diameter of 60 mmφ, and a diameter of 50 μm were used as a dispersion medium. Since the effective internal volume of the stator is about 2 liters and the media filling volume is 1.4 liters, the media filling rate is 70%. When the rotational speed of the rotor is constant (the peripheral speed at the tip of the rotor is about 11 m / sec), the premix slurry is supplied from the supply port by a non-pulsating metering pump at a supply speed of about 40 liters / hr and reaches a predetermined particle size. The product was acquired from the outlet. During operation, cooling was performed while circulating cooling water at about 10 ° C. from the jacket to obtain a black colorant dispersion.

<Preparation of wax dispersion A1>
Paraffin wax (melting point 75 ° C., 0.1% weight loss time 14 minutes) 27.2 parts, stearyl acrylate 2.8 parts, 20% DBS aqueous solution 1.9 parts, demineralized water 68.1 parts heated to 90 ° C. Then, the mixture was stirred for 10 minutes using a homomixer (Mark IIf model manufactured by Tokushu Kika Kogyo Co., Ltd.). Next, under 90 ° C. heating, circulating emulsification is started under a pressure of 20 MPa using a high pressure emulsifier, the particle diameter is measured with Nanotrac, and dispersed until the median diameter (D50) is 250 nm or less. Dispersion A1 was produced. The final particle size (D50) was 244 nm.

<Preparation of polymer primary particle dispersion B1>
A reactor equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device was charged with 36.3 parts of wax dispersion A1 and 260 parts of demineralized water, and a nitrogen stream while stirring. The temperature was raised to 90 ° C.
Thereafter, the following mixture of monomers and emulsifier solution was added over 300 minutes while stirring was continued. The time when the addition of the monomer / emulsifier aqueous solution started to be added was regarded as polymerization start, and the following initiator aqueous solution 1 was added over 270 minutes after 30 minutes from the start of polymerization. Thereafter, the initiator aqueous solution 2 was added over 120 minutes. Thereafter, the inner temperature was maintained at 90 ° C. for 60 minutes under stirring.

[Monomers]
Styrene 67.8 parts Butyl acrylate 32.2 parts Acrylic acid 1.5 parts Trichlorobromomethane 1.0 part Hexanediol diacrylate 1.2 parts

[Emulsifier aqueous solution]
20% DBS aqueous solution 1.0 part Demineralized water 67.5 parts

[Initiator aqueous solution 1]
8% aqueous hydrogen peroxide solution 15.5 parts 8% L-(+) ascorbic acid aqueous solution 15.5 parts

[Initiator aqueous solution 2]
8% L-(+) ascorbic acid aqueous solution 14.2 parts After the completion of the polymerization reaction, the mixture was cooled to obtain a milky white primary polymer particle dispersion B1. The median diameter (D50) measured using Nanotrac was 265 nm. The weight average molecular weight (Mw) was 44000. Tg was 36 ° C.

<Preparation of core particle dispersion C1>
100 parts of polymer primary particle dispersion B1 (solid content) is charged into a mixer equipped with a stirrer, heating and cooling device, and each raw material / auxiliary charging device, and 7.5 parts of black colorant dispersion (solid content) ) Was added over 5 minutes and mixed uniformly, and then 0.31 part (solid content) of 0.5% aluminum sulfate aqueous solution was added over 15 minutes. The temperature was further increased to 45 ° C. over 150 minutes. Here, the volume-median particle size (Dv50) was measured using a multisizer and found to be 6.1 μm. Then, after adding 4.1 parts (solid content) of 20% DBS aqueous solution, the temperature was raised to 96 ° C. over 50 minutes, maintained for 50 minutes, and then cooled to 30 ° C. The ζ potential at pH 1.9 was −30.2 mV.

  The obtained dispersion was extracted and suction filtered with an aspirator using 5 types C (No. 5C manufactured by Toyo Roshi Kaisha, Ltd.) filter paper. The cake remaining on the filter paper was transferred to a stainless steel container equipped with a stirrer (propeller blade), and ion-exchanged water having an electric conductivity of 1 μS / cm was added and stirred uniformly, and then stirred for 30 minutes. This process is repeated until the electric conductivity of the filtrate reaches 10 μS / cm, and then ion-exchanged water having an electric conductivity of 1 μS / cm is added to the cake remaining on the filter paper so that the dispersion concentration becomes 20% and stirred. As a result, a core particle dispersion C1 was obtained.

<Reference example>
A core particle dispersion was obtained in the same manner as in C1, except that the number of parts of acrylic acid was changed to 1.2 parts. Washing was repeated until the electrical conductivity of the filtrate reached 2 μS / cm, and then the obtained cake was dried in an air dryer set at 40 ° C. for 48 hours, and the charge amount was measured to be −1 μC.

<Preparation of water-soluble resin coating layer aqueous solution D1>
480 parts of demineralized water was charged into a reactor equipped with a stirring device (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device, and the temperature was raised to 70 ° C. in a nitrogen stream while stirring.
Thereafter, the initiator aqueous solution 1 was added, and further 5 minutes later, the following monomers and the initiator aqueous solution 2 were added over 60 minutes while stirring was continued. Thereafter, the aqueous initiator solution 3 was added over 60 minutes, and the temperature was raised to 90 ° C. simultaneously with the start of the addition. After the initiator aqueous solution 3 was added, the inner temperature was maintained at 90 ° C. for 90 minutes under stirring.

[Monomers]
Blemmer QA (manufactured by NOF Corporation, (2-hydroxy-3-methacryloxypropyl) trimethylammonium chloride, 50% aqueous solution) 10.0 parts

[Initiator aqueous solution 1]
8.0% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride
3.0 parts [Initiator aqueous solution 2]
8.0% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride
3.0 parts [Initiator aqueous solution 3]
8.0% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride
3.0 parts It cooled after completion | finish of a polymerization reaction, and water-soluble resin coating layer aqueous solution D1 was obtained. The weight average molecular weight (Mw) was 7600.

<Preparation of shell particle dispersion E1>
A reactor equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device was charged with 2.0 parts of a 20% DBS aqueous solution and 323 parts of demineralized water, and a nitrogen stream while stirring. The temperature was raised to 80 ° C.
Thereafter, the initiator aqueous solution was added while stirring was continued, and further 5 minutes later, the following mixed emulsion of monomers 1 and emulsifier solution and monomers 2 were added over 210 minutes. Thereafter, the inner temperature was maintained at 80 ° C. for 90 minutes under stirring.

[Monomers 1]
Styrene 83.5 parts Butyl acrylate 16.5 parts [Emulsifier aqueous solution]
20% DBS aqueous solution 1.0 part demineralized water 71.4 parts [Monomers 2]
20% sodium parastyrene sulfonate aqueous solution 12.5 parts [initiator aqueous solution]
4.0% aqueous potassium persulfate solution 6.4 parts Cooled after completion of the polymerization reaction to obtain milky white shell particle dispersion E1. The median diameter (D50) measured using Nanotrac was 63 nm. The weight average molecular weight (Mw) was 242,000. Tg was 72 ° C. The ζ potential at pH 2.8 was −55.2 mV.

<Manufacture of toner mother particles F1>
A reactor equipped with a stirrer and a heating / cooling device was charged with 100 parts (solid content) of the core particle dispersion C1, and 0.15 part (solid content) of the water-soluble resin coating layer aqueous solution D1 was added while stirring at room temperature. Stir at room temperature for 30 minutes. Then, after adding in the addition amount of 1N-NaOH aqueous solution 7.5g / 1L dispersion volume, it heated up to 50 degreeC of internal temperature, hold | maintained for 60 minutes, and then cooled to 30 degreeC. The ζ potential at pH 2.9 was +53.5 mV.

The obtained dispersion was extracted and suction filtered with an aspirator using 5 types C filter paper. Ion exchange water having an electric conductivity of 1 μS / cm was applied to the cake remaining on the filter paper until the electric conductivity of the filtrate reached 10 μS / cm. To the cake remaining on the filter paper, ion exchange water having an electric conductivity of 1 μS / cm was added to a dispersion concentration of 20% and stirred to disperse.
A portion of the dispersion was repeatedly washed until the electrical conductivity of the filtrate reached 2 μS / cm, and the resulting cake was dried in a blow dryer set at 40 ° C. for 48 hours. The charge amount was measured to be +6 μC. there were.

  A reactor equipped with a stirrer and a heating / cooling device was charged with 100 parts (solid content) of the above dispersion, and 3 parts (solid content) of the shell particle dispersion E1 was added dropwise with stirring at an internal temperature of 20 ° C., and stirred at room temperature. did. Then, after dripping at the addition amount of 1N-HCl aqueous solution 10g / 1L dispersion volume, the dispersion liquid was heated up to the internal temperature of 50 degreeC, hold | maintained for 120 minutes, and then cooled to 30 degreeC. The volume median particle size (Dv50) measured using Multisizer III was 8.3 μm, and the average circularity measured by a flow particle analyzer was 0.947. The ζ potential at pH 3.0 was −68.1 mV.

The obtained dispersion was extracted and suction filtered with an aspirator using 5 types C filter paper. The cake remaining on the filter paper was transferred to a stainless steel container equipped with a stirrer (propeller blade), ion-exchanged water having an electric conductivity of 1 μS / cm was added, and the mixture was uniformly dispersed by stirring at 50 rpm, and then stirred for 30 minutes.
This process was repeated until the electric conductivity of the filtrate reached 2 μS / cm, and then the obtained cake was dried in an air dryer set at 40 ° C. for 48 hours to obtain toner mother particles F1. When the charge amount was measured, it was −2 μC.

<Manufacture of developing toner G1>
In a sample mill KR-3 manufactured by Kyoritsu Riko Co., 100 parts of toner base particles F1 were added, and then 0.5 parts of silica fine particles having a volume average primary particle size of 0.03 μm were added and stirred and mixed for a total of 2 minutes. . Thereafter, 1.0 part of silica fine particles having a volume average primary particle size of 0.01 μm was added, stirred for 2 minutes in total, mixed, and sieved to obtain a developing toner G1.

[Example 2]
<Preparation of polymer primary particle dispersion B2>
Polymer primary particle dispersion B2 was obtained in the same manner as in B1, except that the monomers were changed as follows. The weight average molecular weight (Mw) was 48,000. Tg was 33 ° C.
[Monomers]
Styrene 65.5 parts Butyl acrylate 34.5 parts Acrylic acid 1.5 parts Trichlorobromomethane 1.0 part Hexanediol diacrylate 1.2 parts

<Preparation of core particle dispersion C2>
A core particle dispersion C2 was obtained in the same manner as C1, except that B2 was used instead of B1 as the polymer primary particle dispersion.

<Manufacture of toner mother particles F2>
Instead of water-soluble resin coating layer aqueous solution D1, 0.07 part (solid content) of PAS-H-10L (manufactured by Nitto Bo Medical Co., Ltd., 28% aqueous solution of diallyldimethylammonium chloride polymer, weight average molecular weight (Mw) 200,000) Toner mother particles F2 were obtained in the same manner as F1, except that it was used. The volume median particle size (Dv50) measured using Multisizer III before washing was 7.7 μm, and the average circularity measured by a flow type particle analyzer was 0.951.

<Manufacture of developing toner G2>
A developing toner G2 was obtained by the same method as G1, except that F2 was used instead of the toner base particles F1.

[Comparative Example 1]
<Manufacture of toner mother particles F3>
Toner base particles F3 were obtained in the same manner as F1, except that 0.15 part (solid content) of Blemmer QA was used instead of the water-soluble resin coating layer aqueous solution D1. The volume median particle size (Dv50) measured using Multisizer III before washing was 12.0 μm.

<Manufacture of developing toner G3>
A developing toner G3 was obtained by the same method as G1, except that F3 was used instead of the toner base particles F1.

[Comparative Example 2]
<Manufacture of toner mother particles F4>
Toner base particles F4 are obtained in the same manner as F2 except that 3.0 parts (solid content) of AERODIS W440 (manufactured by Nippon Aerosil Co., Ltd., 40% aqueous dispersion of alumina) is used instead of the water-soluble resin coating layer aqueous solution D1. It was. The volume median particle size (Dv50) of F4 before washing measured using Multisizer III was 6.9 μm, and the average circularity measured by a flow particle analyzer was 0.951.

<Manufacture of developing toner G4>
A developing toner G4 was obtained in the same manner as in G1, except that F4 was used instead of the toner base particles F1.
The developing toners obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated by the following methods.

<Blocking resistance>
5 g of developing toner is put in a cylindrical container having an inner diameter of 3 cm and a height of 6 cm, and a load of 40 g is put on it and left in an environment of temperature 50 ° C. and humidity 40% for 24 hours. The degree of aggregation was confirmed by applying a load.
○: It collapses with a load of less than 200 g.
Δ: collapses with a load of less than 500 g.
X: Aggregates and does not collapse unless a load of 500 g or more is applied.

<Fixing test>
The fixing machine is a hot roll fixing system. The heating roller of the fixing machine has a heater on the upper roller, the release layer is made of PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), and silicone oil. Evaluation was carried out without coating. Prepare recording paper (FC Dream made by Kishu Paper) carrying an unfixed toner image with an adhesion amount of about 0.7 mg / cm ² ), and change the surface temperature of the heating roller from 100 ° C to 210 ° C in 5 ° C increments. Then, the sheet was conveyed to the fixing nip portion, and the fixing state when being discharged at a speed of 195 mm / sec was observed. The temperature range in which toner offset or paper wrapping did not occur on the heating roller during fixing and the toner on the recording paper after fixing was sufficiently adhered to the recording paper was determined as the fixing temperature range ΔT as follows.

○ ΔT ≧ 50 ℃
△ 50 ℃> ΔT ≧ 30 ℃
× ΔT <30 ° C

As shown in Table 1, in Examples 1 and 2, the surface of a thin water-soluble resin coating layer is thinly and uniformly coated with shell particles, so that high blocking resistance and low-temperature fixability can be realized. It was.
In Comparative Example 1, when the surface of the toner base particles was observed with a scanning electron microscope, only a small amount of shell particles were observed. This is because the monomer was used as the water-soluble resin coating layer component, so that the water-soluble resin coating layer was not formed on the surface of the core, and thus the shell particles were not attached. Since no shell was formed, the blocking resistance was insufficient.

  In Comparative Example 2, the blocking resistance was good, but the fixability was insufficient. This is because the water-soluble resin coating layer is formed with fine particles, so that the water-soluble resin coating layer becomes thicker, and the ratio of the total amount of the water-soluble resin coating layer and the shell layer in the entire toner increases. It is thought that the fixing property was impaired. If the ratio of the water-soluble resin coating layer is further increased, it is presumed that the low-temperature fixability is hardly obtained. Similarly, it can be presumed that low-temperature fixability is hardly obtained when the ratio of the shell layer is increased.

The weight average molecular weight (Mw) and glass transition temperature (Tg) were measured as follows, and other items were measured in the same manner as described above.
<Weight average molecular weight (Mw)>
The THF soluble components of the dried polymer primary particle dispersion and shell particle dispersion were measured by gel permeation chromatography (GPC) under the following conditions.

Apparatus: GPC apparatus HLC-8320 manufactured by Tosoh Corporation, column: TOSOH TSKgel
SuperHM-H (2), solvent: THF, sample concentration: 0.1% by weight, calibration curve: standard polystyrene <Glass transition temperature (Tg)>
Using a differential thermal analyzer (DSC220) manufactured by Seiko Denshi Kogyo Co., Ltd., the temperature was measured at a temperature rising rate of 10 ° C./min. Tg was determined from the intersection of the base line extension of the DSC curve and the tangent line showing the maximum slope in the endothermic curve.

[Example 3]
<Preparation of polymer primary particle dispersion B3>
A polymer primary particle dispersion B3 was obtained in the same manner as in B1, except that the monomers were changed as follows. The median diameter (D50) measured using Nanotrac was 258 nm. The weight average molecular weight (Mw) was 114,000. Tg was 36 ° C.

[Monomers]
Styrene 67.8 parts Butyl acrylate 32.2 parts Acrylic acid 1.5 parts Trichlorobromomethane 1.0 part Hexanediol diacrylate 0.7 part

<Preparation of core particle dispersion C3>
The polymer primary particle dispersion is B3 instead of B1, and 7.6 parts (solid content) of EP-700 (manufactured by Dainichi Seika Co., Ltd., PB15: 3 dispersion) is used instead of the black colorant dispersion. Obtained a core particle dispersion C3 by the same method as C1.

<Manufacture of toner mother particles F5>
70 parts (solid content) of core particle dispersion C3 and 30 parts of demineralized water were charged into a reactor equipped with a stirrer and a heating / cooling device, and 0.15 part of water-soluble resin coating layer aqueous solution D1 (solid content) while stirring at room temperature. ) And stirred at room temperature for 15 minutes. Then, after adding by the addition amount of 1N-NaOH aqueous solution 7.5g / 1L dispersion volume, stirring was continued for 15 minutes. 3 parts (solid content) of shell particle dispersion E1 was added dropwise and stirred at room temperature for 15 minutes. Thereafter, the dispersion was added dropwise at an addition amount of 10 g / 1 L dispersion volume of 1N HCl aqueous solution, and stirring was continued for 15 minutes. Then, the dispersion was heated to an internal temperature of 45 ° C., held for 60 minutes, and then cooled to 30 ° C. . The volume median particle size (Dv50) measured using Multisizer III was 7.5 μm, and the average circularity measured by a flow particle analyzer was 0.964.

The obtained dispersion was extracted and suction filtered with an aspirator using 5 types C filter paper. The cake remaining on the filter paper was transferred to a stainless steel container equipped with a stirrer (propeller blade), demineralized water having an electric conductivity of 1 μS / cm was added, and the mixture was uniformly dispersed by stirring at 50 rpm, and then stirred for 60 minutes.
This process was repeated until the electric conductivity of the filtrate reached 2 μS / cm, and then the obtained cake was dried in an air dryer set at 40 ° C. for 48 hours to obtain toner mother particles F5.

<Manufacture of developing toner G5>
Into sample mill KR-3 manufactured by Kyoritsu Riko Co., Ltd., 100 parts of toner base particles F5 are charged, followed by 0.8 parts of silica fine particles PDMS-treated with a volume average primary particle diameter of 0.1 μm, and a volume average primary particle diameter. 0.8 parts of silica fine particles treated with PDMS at 0.12 μm were added and stirred and mixed for a total of 1.5 minutes. Thereafter, 0.3 part of titania fine particles treated with alkylsilane with a volume average primary particle size of 0.014 μm, 0.4 part of silica fine particles treated with PDMS with a volume average primary particle size of 0.015 μm, and a volume average primary particle size of 0.1 parts. 0.2 parts of silica fine particles treated with PDMS / aminosilane at 01 μm were added and stirred and mixed for a total of 1.5 minutes. Thereafter, 0.2 parts of resin beads having a volume primary particle size of 0.2 μm were stirred for 1.5 minutes, mixed, and sieved to obtain a developing toner G5.

[Example 4]
<Preparation of core particle dispersion C4>
A core particle dispersion C4 was obtained in the same manner as C3 except that EP-700 was changed to 6.6 parts.
<Manufacture of toner mother particles F6>
C4 was used instead of the core particle dispersion C3, and PAS-J-81 (manufactured by Nitto Bo Medical, 25% aqueous solution of diallyldimethylammonium chloride / acrylamide copolymer, catalog value weight average) instead of the water-soluble resin coating layer aqueous solution D1 Using 0.075 parts (molecular weight (Mw) 870,000) (solid content), water dispersion of styrene / 2-ethylhexyl acrylate / 2-acrylamido-2-methylpropanesulfonic acid copolymer in place of shell particle dispersion E1 Liquid (containing 2-2.7% by weight of 2-acrylamido-2methylpropanesulfonic acid, polymerization average molecular weight (Mw): 14,200, Tg: 70 ° C., median diameter measured using Nanotrac (D50): 24 nm, Toner base particles in the same manner as F5 except that 3.5 parts (solid content) (solid content concentration: 20% by weight) is used. To give the F6. The volume median particle size (Dv50) measured using Multisizer III before washing was 7.4 μm, and the average circularity measured by a flow particle analyzer was 0.969.

<Manufacture of developing toner G6>
A developing toner G6 was obtained in the same manner as G5 except that F6 was used instead of the toner base particles F5.

[Example 5]
<Preparation of wax dispersion A2>
Ester wax Nissan Electol WE-10 (manufactured by NOF Corporation, catalog value melting point 69 ° C., 0.1% weight loss time 19 minutes) 29.8 parts, decaglycerin dekabehenate (acid value 3.2 mg KOH / g, Hydroxyl value 27 mg KOH / g) 0.24 parts, 20% DBS aqueous solution 2.75 parts, demineralized water 67.25 parts were heated to 90 ° C. and stirred for 20 minutes. Next, under 100 ° C. heating, circulation emulsification is started using a high-pressure emulsifier under a pressure of 30 MPa, the particle diameter is measured with Nanotrac, and dispersed until the median diameter (D50) is 245 nm or less. Dispersion A2 was prepared. The final particle size (D50) was 232 nm.

<Preparation of polymer primary particle dispersion B4>
A polymer primary particle dispersion B4 was obtained in the same manner as in B1, except that the wax dispersion A1 was changed to 41.6 parts of A2 and the monomers were changed as follows. The median diameter (D50) measured using the nanotrack was 210 nm. The weight average molecular weight (Mw) was 264000. Tg was 38 ° C.

[Monomers]
Styrene 69.1 parts Butyl acrylate 30.9 parts Acrylic acid 1.5 parts Trichlorobromomethane 1.0 part Hexanediol diacrylate 0.7 part <Preparation of polymer primary particle dispersion B5>
A polymer primary particle dispersion B5 was obtained in the same manner as in B1, except that the monomers were changed as follows. The weight average molecular weight (Mw) was 92,000. Tg was 48 ° C.

[Monomers]
Styrene 76.8 parts Butyl acrylate 23.2 parts Acrylic acid 1.5 parts Trichlorobromomethane 1.0 part Hexanediol diacrylate 0.7 part

<Preparation of core particle dispersion C5>
A mixer equipped with a stirrer, a heating / cooling device, and a raw material / auxiliary charging device was charged with 97 parts (solid content) of polymer primary particle dispersion B4, and further, 6.6 parts of EP-700 was added over 5 minutes. After adding and mixing uniformly, 0.31 part (solid content) of 0.5% aluminum sulfate aqueous solution was added over 15 minutes. The temperature was further increased to 44 ° C. over 170 minutes. Here, the volume-median particle size (Dv50) was measured using a multisizer and found to be 6.4 μm. Thereafter, 3 parts (solid content) of polymer primary particle dispersion B5 was added over 3 minutes, and then stirring was continued for 30 minutes. Then, after adding 4.1 parts (solid content) of 20% DBS aqueous solution, the temperature was raised to 84 ° C. over 50 minutes, maintained for 60 minutes, and then cooled to 30 ° C. Thereafter, filtration, washing, and dispersion were performed in the same manner as C3 to obtain a core particle dispersion C5.

<Preparation of shell particle dispersion E2>
A shell particle dispersion E2 was obtained in the same manner as E1, except that the monomers 1 were changed as follows. The median diameter (D50) measured using the nanotrack was 58 nm. The weight average molecular weight (Mw) was 57000. Tg was 75 ° C.

[Monomers 1]
Styrene 88.0 parts Butyl acrylate 12.0 parts 1-Dodecanethiol 0.5 parts

<Manufacture of toner mother particles F7>
Toner mother particles F7 were obtained in the same manner as F5 except that C5 was used instead of the core particle dispersion C3 and E2 was used instead of the shell particle dispersion E1. The volume median particle size (Dv50) measured using Multisizer III before washing was 6.8 μm, and the average circularity measured by a flow particle analyzer was 0.970.

<Manufacture of developing toner G7>
A developing toner G7 was obtained in the same manner as G5 except that F7 was used instead of the toner base particles F5.

[Example 6]
<Preparation of polymer primary particle dispersion B6>
A polymer primary particle dispersion B6 was obtained in the same manner as in B4 except that the monomers were changed as follows. The median diameter (D50) measured using nanotrack was 205 nm. The weight average molecular weight (Mw) was 269000. Tg was 36 ° C.

[Monomers]
Styrene 68.2 parts Butyl acrylate 31.8 parts Acrylic acid 1.5 parts Trichlorobromomethane 1.0 part Hexanediol diacrylate 0.8 part

<Preparation of core particle dispersion C6>
Disperse core particles in the same manner as C5 except that 83 parts (solid content) of B6 is used instead of polymer primary particle dispersion B4 and 17 parts (solid content) of B3 is used instead of polymer primary particle dispersion B5. A liquid C6 was obtained.

<Manufacture of toner mother particles F8>
F6 except that C6 is used instead of the core particle dispersion C4, and the aqueous dispersion of styrene / 2-ethylhexyl acrylate / 2-acrylamido-2-methylpropanesulfonic acid copolymer is 3.0 parts (solid content). In the same manner, toner mother particles F8 were obtained. The volume median particle size (Dv50) measured using Multisizer III before washing was 7.3 μm, and the average circularity measured by a flow particle analyzer was 0.968.

<Manufacture of developing toner G8>
A developing toner G8 was obtained in the same manner as G5 except that F8 was used instead of the toner base particles F5.

[Example 7]
<Preparation of core particle dispersion C7>
A core particle dispersion C7 was obtained in the same manner as C6 except that the polymer primary particle dispersion B6 was changed to 90 parts (solid content) and the polymer primary particle dispersion B3 was changed to 10 parts (solid content).

<Manufacture of toner mother particles F9>
Toner mother particles F9 were obtained in the same manner as F6 except that C7 was used instead of the core particle dispersion C4. The volume median particle diameter (Dv50) measured using Multisizer III before washing was 6.9 μm, and the average circularity measured by a flow particle analyzer was 0.966.
<Manufacture of developing toner G9>
A developing toner G9 was obtained in the same manner as G5 except that F9 was used instead of the toner base particles F5.

[Example 8]
<Preparation of polymer primary particle dispersion B7>
A polymer primary particle dispersion B7 was obtained in the same manner as in B4 except that the monomers were changed as follows. The median diameter (D50) measured using the nanotrack was 203 nm. The weight average molecular weight (Mw) was 403000. Tg was 37 ° C.

[Monomers]
Styrene 69.1 parts Butyl acrylate 30.9 parts Acrylic acid 1.5 parts Trichlorobromomethane 1.0 part Hexanediol diacrylate 0.5 part <Preparation of wax dispersion A3>
Wax dispersion in the same manner as A2 except that Nissan Electol WEP-5 (manufactured by NOF Corporation, catalog value melting point 82 ° C., 0.1% weight reduction time 55 minutes) is used instead of Nissan Electol WE-10. A3 was produced. The final particle size (D50) was 238 nm.

<Preparation of polymer primary particle dispersion B8>
A polymer primary particle dispersion B8 was obtained in the same manner as in B4 except that the wax dispersion A2 was changed to A3 and the monomers were changed as follows. The median diameter (D50) measured using nanotrack was 205 nm. The weight average molecular weight (Mw) was 304000. Tg was 38 ° C.

[Monomers]
Styrene 65.5 parts Butyl acrylate 34.5 parts Acrylic acid 1.5 parts Trichlorobromomethane 1.0 part Hexanediol diacrylate 0.7 part

<Preparation of core particle dispersion C8>
The core is the same as C5 except that 85 parts (solid content) of B7 is used instead of the polymer primary particle dispersion B4 and 15 parts (solid content) of B8 is used instead of the polymer primary particle dispersion B5. A particle dispersion C8 was obtained.

<Manufacture of toner mother particles F10>
Toner base particles F10 were obtained in the same manner as F6 except that C8 was used instead of the core particle dispersion C4. The volume median particle diameter (Dv50) measured using Multisizer III before washing was 7.7 μm, and the average circularity measured by a flow particle analyzer was 0.973.
<Manufacture of developing toner G10>
A developing toner G10 was obtained in the same manner as G5 except that F10 was used instead of the toner base particles F5.

[Example 9]
<Preparation of magenta colorant dispersion>
A magenta colorant dispersion was obtained in the same manner as the black colorant dispersion, except that Pigment Red 122 was used instead of carbon black.

<Preparation of core particle dispersion C9>
Core particle dispersion C9 was obtained in the same manner as C8, except that 12.1 parts of magenta colorant dispersion was used instead of EP-700.
<Manufacture of toner mother particles F11>
Toner mother particles F11 were obtained in the same manner as F6 except that C9 was used instead of the core particle dispersion C4. The volume median particle size (Dv50) measured using Multisizer III before washing was 7.0 μm, and the average circularity measured by a flow particle analyzer was 0.969.

<Manufacture of developing toner G11>
Into sample mill KR-3 manufactured by Kyoritsu Riko Co., Ltd., 100 parts of toner base particles F11 are added, followed by 1.8 parts of silica fine particles PDMS-treated with a volume average primary particle size of 0.1 μm, and a volume average primary particle size. 0.3 parts of silica fine particles treated with PDMS at 0.06 μm were added and stirred and mixed for a total of 1.5 minutes. Thereafter, 0.6 parts of titania fine particles treated with alkylsilane with a volume average primary particle size of 0.014 μm, 0.6 parts of silica fine particles treated with PDMS with a volume average primary particle size of 0.015 μm, and a volume average primary particle size of 0.1 parts. 0.1 parts of silica fine particles treated with PDMS / aminosilane at 01 μm were added and stirred and mixed for a total of 1.5 minutes. Thereafter, 0.2 parts of resin beads having a volume primary particle size of 0.2 μm were stirred and mixed for 1.5 minutes and sieved to obtain a developing toner G11.

[Comparative Example 3]
<Manufacture of toner mother particles F12>
The polymer primary particle dispersion is agglomerated in the same manner as C3 except that B5 is used instead of B3, and then filtered, washed and dried in the same manner as F5 without forming the water-soluble resin coating layer and the shell layer. Thus, toner mother particles F12 were obtained. The volume median particle diameter (Dv50) measured using Multisizer III before filtration was 6.8 μm, and the average circularity measured by a flow type particle analyzer was 0.972.
<Manufacture of developing toner G12>
A developing toner G12 was obtained in the same manner as G5 except that F12 was used instead of the toner base particles F5.

[Comparative Example 4]
<Preparation of wax dispersion A4>
Instead of Nissan Electol WE-10, HiMic-1090 (manufactured by Nippon Seiwa Co., Ltd .: catalog value melting point 89 ° C.) 29.7 parts, except that decaglycerin decabehenate is changed to 0.3 parts, it is the same as A2 Thus, a wax dispersion A4 was produced.

<Preparation of polymer primary particle dispersion B9>
A polymer primary particle dispersion B9 was obtained in the same manner as in B3 except that the wax dispersion A1 was changed to 35.0 parts of the wax dispersion A4 and the monomers were changed as follows. The weight average molecular weight (Mw) was 81000.
[Monomers]
Styrene 75.9 parts Butyl acrylate 24.1 parts Acrylic acid 1.2 parts Trichlorobromomethane 1.0 part Hexanediol diacrylate 0.7 part

<Manufacture of toner mother particles F13>
Aggregation is carried out in the same manner as in C5 except that 80 parts (solid content) of B980 is used instead of the polymer primary particle dispersion liquid B4 and 20 parts (solid content) of the polymer primary particle dispersion liquid B5 is used. By performing filtration, washing, and drying in the same manner as F5 without forming a coating layer and a shell layer, toner mother particles F13 were obtained. The volume median particle diameter (Dv50) measured using Multisizer III before filtration was 7.3 μm, and the average circularity measured by a flow particle analyzer was 0.963.

<Manufacture of developing toner G13>
A developing toner G13 was obtained in the same manner as G5 except that F13 was used instead of the toner base particles F5.
The developing toners obtained in Examples 3 to 9 and Comparative Examples 3 to 4 were used and evaluated by the following methods. The results are shown in Table 2.

[Fixing test]
Recording paper carrying an unfixed toner image (Excellent White manufactured by Oki Data Co., Ltd.) was prepared and tested as follows using two types of heat roll fixing type fixing machines.
Fixing machine A
The roller diameter is 27 mm, the nip width is 9 mm, the fixing speed is 229 mm / sec, the upper roller has a heater, the roller surface is composed of PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), Not applied.

Fixing machine B
The roller diameter is 34 mm, the nip width is 7 mm, the fixing speed is 195 mm / sec, the upper roller has a heater, the roller surface is composed of PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), Not applied.

<Low temperature fixability test by tape peeling>
The surface temperature of the roller was lowered from 170 ° C. in increments of 5 ° C., and a recording paper carrying an unfixed toner image having an adhesion amount of about 0.4 mg / cm ² was conveyed to the fixing nip portion to obtain a fixed image. A mending tape was applied to the fixed image, and a 2 kg weight was passed over the fixed image to bring the tape and the fixed image into close contact with each other. The mending tape was peeled off, and the degree to which the fixed image transferred to the tape was visually determined.
Fixing machines A and B
A: Fixing at 140 ° C. or lower ◯: Fixing at 145 ° C. Δ: Fixing at 150 ° C. x: Fixing at 150 ° C. or higher

<Low-temperature fixability test by bending>
The surface temperature of the roller was lowered from 170 ° C. in increments of 5 ° C., and a recording paper carrying an unfixed toner image having an adhesion amount of about 1.0 mg / cm ² was conveyed to the fixing nip portion to obtain a fixed image. The fixed image was folded in half with the inside, and a 2 kg weight was passed over the fold. The fixed image was expanded, and the degree of toner peeling at the bent portion was visually judged.
Fixing machine A
A: Fixing at 140 ° C. or lower ◯: Fixing at 145 ° C. Δ: Fixing at 150 ° C. x: Fixing machine B that does not fix unless it is 155 ° C. or higher
◎: Fix at 135 ° C. or lower ◯: Fix at 140 ° C. Δ: Fix at 145 ° C. ×: Fix at 150 ° C. or higher

<Hot offset resistance test>
The surface temperature of the roller was increased from 175 ° C. in increments of 5 ° C., the recording paper carrying the unfixed toner image was conveyed to the fixing nip portion, and the state when discharged was observed.
Fixing machine A
A: No offset at 195 ° C. ○: Offset at 195 ° C. Δ: Offset at 190 ° C. x: Fixing machine B offset at 185 ° C. or less
A: Not offset at 210 ° C. ○: Offset at 200 to 210 ° C. Δ: Offset at 180 to 195 ° C. x: Offset at 175 ° C. or less

[Blocking resistance]
10 g of developing toner is put into a cylindrical container having an inner diameter of 3 cm and a height of 6 cm, a load of 20 g is put on it, and left in an environment of a temperature of 50 ° C. and a humidity of 55% for 48 hours. The degree of aggregation was confirmed by applying a load.
◎: collapses with a load of less than 100 g ○: collapses with a load of 100 g or more and less than 200 g Δ: collapses with a load of 200 g or more and less than 300 g ×: does not collapse unless a load of 300 g or more is applied

[Chargeability]
FMU65 manufactured by Kanto Denka Kogyo Co., Ltd. was used as a carrier, 10 g of a mixture of developing toner and carrier in a weight ratio of 1:24 was placed in a glass sample bottle and shaken with NR-1 manufactured by Taitec Co., Ltd. Using 0.1 g, a charge amount was measured by a suction blow-off method using a blow-off charge amount measuring device manufactured by Toshiba Chemical Corporation.
Blowing conditions: 0.05 kgf / cm ² × 3 seconds
Suction pressure: 350-400 mmH ₂ O
Screen: 400 mesh Measurement was performed 3 times with shaking time of 1 minute, 5 minutes, and 30 minutes, and the charge amount was determined as Q, and determined as follows.
A: Q ≦ −18 (μC / g) in all three times
Δ: Q ≦ −13 (μC / g) in all three times,
At least one of the three times is 18 <Q ≦ −13 (μC / g) ×: At least one of the three times is 13 <Q (μC / g)

[Generated amount of ultrafine particles]
A recording paper (excellent white manufactured by Oki Data Co., Ltd.) carrying an unfixed toner image having a length of 4 cm and a width of 20 cm and an adhesion amount of about 1.0 mg / cm ² is prepared. sec, fixing was performed at a fixing temperature of 170 ° C. At that time, the number of ultrafine particles leaked from the exhaust was measured using a P-Trac ultra particle counter Model 8525 manufactured by TSI Incorporated. The same measurement was performed on a blank paper not carrying a toner image. A value obtained by subtracting the number of detections when passing through blank paper from the number of detections when passing through unfixed toner was determined as follows, with the amount of ultrafine particles generated.
◎: Less than 50,000 ○: 50,000 to 100,000 △: 100,000 to 200,000 ×: 200,000 or more

[BET specific surface area]
The BET specific surface area of the toner base particles and the developing toner is determined by Macsorb manufactured by Mountec Co., Ltd.
Measurement was performed by a one-point method using model-1208.
Measurement sample amount: about 0.5g
Measurement gas: 30% nitrogen / 70% helium mixed gas Flow rate: 25 mL / min

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2013-178429 filed on August 29, 2013, the contents of which are incorporated herein by reference.

Claims (8)

An electrostatic charge image developing toner having toner base particles containing at least a binder resin and a colorant and an external additive,
The toner base particles have a core-shell structure having core particles and a shell layer;
The toner base particles have a resin coating layer made of a water-soluble resin on the surface of the core particles,
And having the shell layer on the resin coating layer,
The shell layer is made of particles mainly composed of a resin,
The electrostatic charge image developing toner satisfying the following relationship, wherein the glass transition temperature of the polymer primary particles constituting the core particles is Tg1, and the glass transition temperature of the particles constituting the shell layer is Tg2. .
25 ° C ≦ Tg1 ≦ 45 ° C
55 ° C ≦ Tg2 ≦ 100 ° C
Tg2-Tg1 ≧ 20 2. The electrostatic image developing toner according to claim 1, wherein the particles constituting the shell layer contain a resin having a sulfonic acid group. The electrostatic charge image developing toner according to claim 1, wherein the core particle is a polymer. The charge property of the said core particle and the said resin coating layer has a reverse relationship, and the charge property of the said resin coating layer and the said shell layer is a reverse relationship, The any one of Claim 1 thru | or 3 characterized by the above-mentioned. The toner for developing an electrostatic charge image according to the item. The electrostatic image developing toner according to claim 1, wherein the core particles have a capsule structure. The wax contained in the core layer of the core particle having a capsule structure is a wax in which the time for the weight loss at 200 ° C. to reach 0.1% is 15 minutes or more using a thermogravimetric apparatus, and the capsule 6. The electrostatic image developing toner according to claim 1, wherein the wax contained in the shell layer of the core particle having a structure is a wax having a melting point of 70 ° C. or higher. After the aqueous solution containing the water-soluble resin is mixed with the dispersion of the core particles to attach the water-soluble resin to the surface of the core particles, the dispersion of the particles constituting the shell layer is further mixed with the shell. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 6, wherein toner mother particles are obtained through a step of attaching particles constituting the layer. The core particle dispersion is mixed with an aqueous solution containing a water-soluble resin having a chargeability opposite to that of the core particles, and the water-soluble resin is adhered to the surface of the core particles. 7. The toner base particles according to claim 1, wherein a toner mother particle is obtained through a step of mixing a dispersion liquid of particles constituting the shell layer having a property and adhering the particles constituting the shell layer. A method for producing the toner for developing an electrostatic image according to claim 1.