JP6018566B2 - Method for producing toner for developing electrostatic image - Google Patents

Description

  The present invention relates to a method for producing an electrostatic charge image developing toner.

In recent years, in the field of toner for electrophotography, with the development of an electrophotographic system, development of a toner corresponding to high image quality and high speed has been demanded. From the viewpoint of high image quality, it is necessary to reduce the particle size of the toner, and in an aqueous medium such as suspension polymerization, emulsion polymerization, emulsion aggregation, and dissolution suspension instead of the conventional melt-kneading method. A so-called chemical toner obtained by the chemical method is disclosed. Further, from the viewpoint of speeding up, a chemical toner having a release agent added therein has been reported to improve low-temperature fixability in fixability.
Unlike the melt-kneading and pulverizing method, when the toner is manufactured by the chemical method, there are no kneading steps. is there.

In order to solve this problem, for example, in Patent Document 1, a dispersion of a release agent having a carboxyl group and an acid value of 0.5 to 20 mgKOH / g and a polymer having an oxazoline group are mixed. A method for producing a release agent dispersion liquid for a toner containing release agent particles is disclosed, which can prevent the release agent particles from being released from the toner composition at the time of toner preparation, and has a low temperature fixability. In addition, it is described that an electrophotographic toner having excellent offset resistance can be obtained.
Patent Document 2 discloses a toner containing at least core particles formed by aggregating resin particles, colorant particles, and wax particles, and used as a dispersant used in a wax particle dispersion in which the wax particles are dispersed. A toner characterized by containing a polypropylene glycol ethylene oxide adduct can produce a toner having a small particle size with a sharp particle size distribution without a classification step, and in oil-less fixing in which no oil is used for a fixing roller. Using a release agent such as wax in the toner, it achieves both low-temperature fixability, high-temperature non-offset properties, paper separation from the fixing roller, etc., and storage stability during storage at high temperatures. It has been disclosed that high transfer efficiency can be obtained by preventing omission and scattering of time.

JP 2009-133946 A JP 2010-169702 A

However, even in the method disclosed in the patent document, the release agent release and exposure are not sufficiently suppressed, and the image quality is insufficient.
SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a toner for developing an electrostatic charge image, in which desorption and exposure of a release agent are suppressed, and image density and fog are suppressed.

The inventor uses a water-soluble polymer containing an oxazoline group capable of reacting with various functional groups to disperse a release agent in an aqueous medium, and further heat-mix the release agent particles and resin particles. The release agent particles to which resin particles are adhered are obtained in advance, and then agglomerated and fused to produce toner, so that release and release of the release agent are suppressed, and the resulting toner has excellent image characteristics I found out that
That is, the present invention is a method for producing an electrostatic charge image developing toner comprising the following steps (1) to (3).
Step (1): Step of obtaining a dispersion of release agent particles (WR) including the following steps (1A) and (1B) Step (1A): Release agent and polymer containing oxazoline group in aqueous medium And obtaining a dispersion of release agent particles (W) having a volume median particle size of 0.05 μm or more and 1.5 μm or less Step (1B): Mold release obtained in Step (1A) The agent particles (W) and the resin particles (A) are at least the lower of the glass transition temperature of the resin constituting the resin particles (A) or the melting point of the release agent constituting the release agent particles (W). Step of obtaining a dispersion of release agent particles (WR) in which the resin particles (A) adhere to the release agent particles (W) Step (2): Release agent particles obtained in Step (1) The dispersion of (WR) and the dispersion of resin particles (B) containing polyester are mixed and aggregated to obtain aggregated particles. Step Step (3): A step of fusing the aggregated particles obtained in step (2) to obtain fused particles.

  According to the present invention, it is possible to provide a method for producing a toner for developing an electrostatic charge image, in which desorption and exposure of a release agent are suppressed and image density and fog are excellently suppressed.

[Toner Production Method]
The method for producing an electrostatic image developing toner of the present invention includes the following steps (1) to (3).
Step (1): Step of obtaining a dispersion of release agent particles (WR) including the following steps (1A) and (1B) Step (1A): Release agent and polymer containing oxazoline group in aqueous medium And obtaining a dispersion of release agent particles (W) having a volume median particle size of 0.05 μm or more and 1.5 μm or less Step (1B): Mold release obtained in Step (1A) The agent particles (W) and the resin particles (A) are at least the lower of the glass transition temperature of the resin constituting the resin particles (A) or the melting point of the release agent constituting the release agent particles (W). Step of obtaining a dispersion of release agent particles (WR) in which the resin particles (A) adhere to the release agent particles (W) Step (2): Release agent particles obtained in Step (1) The dispersion of (WR) and the dispersion of resin particles (B) containing polyester are mixed and aggregated to obtain aggregated particles. Step Step (3): A step of fusing the aggregated particles obtained in step (2) to obtain fused particles.

Step (2) may include the next step (2A), and may further include (2B) after step (2A).
Step (2A): The dispersion of the release agent particles (WR) obtained in Step (1), the dispersion of the resin particles (B), and the flocculant are mixed in an aqueous medium to obtain the aggregated particles (1). Step (2B): The resin particles (B) are further added to the aggregated particles (1) obtained in the step (2A) at one time or divided into a plurality of times to adhere the resin particles (B). The step of obtaining the agglomerated particles (2) is as follows. When the step (2A) and the step (2B) are performed, the “aggregated particles obtained in the step (2)” in the step (3) means “the step The agglomerated particles (2) obtained in (2B) ”. In addition, when step (2A) is performed and step (2B) is not performed, “aggregated particles obtained in step (2)” in step (3) is “obtained in step (2A)”. It means “aggregated particles (1)”.

According to the present invention, it is possible to provide a method for producing a toner for developing an electrostatic charge image, in which release and exposure of a release agent are suppressed, and image density and fog are suppressed. The reason why the toner for developing an electrostatic charge image obtained by the production method of the present invention has such an effect is not clear, but is considered as follows.
By dispersing the release agent with a polymer containing an oxazoline group, release agent particles having oxazoline groups capable of reacting with various functional groups on the surface of the release agent are obtained. When this and the resin particle are heated and mixed, when the resin particle adheres to the surface of the release agent particle, the reaction active site in the resin and the oxazoline group are chemically bonded. It is considered that the resin particles are adhered. When the release agent particles to which the resin particles thus obtained are adhered are further agglomerated and fused with the resin particles as the main component of the toner to form a toner, the resin particles on the surface of the release agent particles and the main toner particles Since the affinity of the resin particles of the component is high, the release agent particles are prevented from being detached from the toner in the toner manufacturing process. Further, since the movement of the release agent particles is suppressed by being surrounded by the resin particles, it is considered that the release agent is held inside the toner and the exposure to the toner surface is suppressed. The toner obtained in this way has a high image density without degrading the performance of the main resin since there is no release of the release agent or exposure to the surface, which tends to adversely affect the developability and chargeability. It is considered that the toner can be achieved and can suppress the occurrence of fog, which is an image defect that occurs when the chargeability and developability are not uniform.

<Step (1)>
Step (1) in the toner production method of the present invention is a step of obtaining a dispersion of release agent particles (WR) including the following steps (1A) and (1B).
Step (1A): A release agent and a polymer containing an oxazoline group are dispersed in an aqueous medium, and a release agent particle (W) having a volume median particle size of 0.05 μm to 1.5 μm. Step (1B): The release agent particles (W) obtained in the step (1A) and the resin particles (A) are converted into the glass transition temperature of the resin constituting the resin particles (A) or Dispersion of the release agent particles (WR) in which the resin particles (A) are adhered to the release agent particles (W) by mixing at a temperature lower than the melting point of the release agent constituting the release agent particles (W). Step of obtaining liquid Next, each component used in step (1), step (1A) and step (1B) will be described.

[Step (1A)]
In the step (1A), a release agent and a polymer containing an oxazoline group are dispersed in an aqueous medium, and release agent particles having a volume median particle size of 0.05 μm or more and 1.5 μm or less (W ) Dispersion.

(Release agent particles)
(Release agent)
Examples of the mold release agent include hydrocarbon wax, silicone wax, fatty acid amide, ester wax and the like. These release agents can be used alone or in combination of two or more, and it is preferable to use in combination of two or more.

From the viewpoint of improving the releasability and low-temperature fixability of the toner and from the viewpoint of improving the dispersibility by the polymer containing an oxazoline group, a hydrocarbon wax and an ester wax are preferable, and a hydrocarbon wax and an ester wax are more preferably used in combination. preferable.
(Hydrocarbon wax)
As the hydrocarbon wax, at least one selected from low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, ceresin and the like can be used. Among these, low molecular weight polypropylene, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax are preferable, and paraffin wax is more preferable from the viewpoint of improving toner releasability.

(Ester wax)
As the ester wax, at least one selected from vegetable waxes, ester waxes having natural or synthetic long-chain aliphatic groups, and esterified products of acid-modified polyethylene waxes can be used. As the plant wax, at least one selected from carnauba wax, rice wax, candelilla wax and the like can be used. Examples of the esterified product of the acid-modified polyethylene wax include a wax obtained by esterifying an acid-modified polyolefin obtained by modifying a polyolefin with a carboxylic acid with an alcohol. Among these, plant-based waxes are preferable from the viewpoint of suppressing release from the toner particles of the release agent and exposure to the surface to suppress fogging, and improving the low-temperature fixability and high-temperature offset resistance of the toner, Carnauba wax is more preferred.
Since the ester wax has a carboxy group, it easily reacts with the oxazoline group of the polymer containing the oxazoline group, and the polymer containing the oxazoline group is likely to exist on the release agent particle. preferable.
The acid value of the ester wax used in the present invention is preferably 0.5 mgKOH / g or more, more preferably 0.7 mgKOH / g or more, and still more preferably, from the viewpoint of improving the reactivity with a polymer containing an oxazoline group. From the viewpoint of improving the charging characteristics of the toner, it is preferably 20 mgKOH / g or less, more preferably 17 mgKOH / g or less, still more preferably 15 mgKOH / g or less, and even more preferably 10 mgKOH / g or less. .

The melting point of the release agent is preferably 50 ° C. or more from the viewpoint of suppressing the release of the release agent from the toner particles and exposure to the surface to suppress fogging, and improving the release property and durability of the toner. More preferably, it is 60 ° C. or more, more preferably 70 ° C. or more. From the viewpoint of improving the low-temperature fixability of the toner, it is preferably 100 ° C. or less, more preferably 95 ° C. or less, and still more preferably 90 ° C. or less. . When using 2 or more types together, it is preferable from the same viewpoint that all melting | fusing point is 50 to 100 degreeC.
In this invention, melting | fusing point of a mold release agent can be measured using a differential scanning calorimeter, and is specifically calculated | required by the method of an Example description. When two or more kinds are used in combination, the melting point of the release agent having the largest mass ratio among the release agents contained in the obtained toner is the melting point of the release agent in the present invention. In addition, when all are the same ratio, let the lowest melting | fusing point be melting | fusing point of the mold release agent in this invention.

  The amount of the release agent used is preferably 1 part by mass or more, more preferably 2 parts by mass or more with respect to 100 parts by mass of the resin in the toner, from the viewpoint of improving the releasability and low-temperature fixability of the toner. The amount is preferably 5 parts by mass or more, and preferably 20 parts by mass from the viewpoint of suppressing the release of the release agent from the toner particles and exposure to the surface to suppress fogging, and improving the image density of the printed matter. Hereinafter, it is more preferably 15 parts by mass or less.

  The mass ratio of the ester wax to the hydrocarbon wax when the hydrocarbon wax and the ester wax are used together is the mass ratio of the ester wax / hydrocarbon wax to suppress release of the release agent from the toner particles and exposure to the surface. From the viewpoint of suppressing fogging, from the viewpoint of improving the image density of the printed matter, and from the viewpoint of improving the low-temperature fixability of the toner, preferably 1/99 or more, more preferably 3/97 or more, and still more preferably 5/95 or more. From the viewpoint of suppressing release of the release agent from the toner particles and exposure to the surface to suppress fogging, and from the viewpoint of improving the releasability of the toner, it is preferably 50/50 or less, more preferably 40 / 60 or less, more preferably 35/65 or less, still more preferably 30/70 or less, and preferably 1/99 to 50/5. , More preferably 3 / 97-40 / 60, more preferably 5 / 95-35 / 65, even more preferably 5 / 95-30 / 70.

  The total amount of the hydrocarbon wax and the ester wax in the release agent is to reduce the release of the release agent from the toner particles and the exposure to the surface to suppress fogging, to improve the image density of the printed matter, and to the toner. From the viewpoint of improving releasability and low-temperature fixability, it is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably substantially 100% by mass, and still more preferably 100% by mass.

(Polymer containing oxazoline group)
The polymer containing an oxazoline group is used from the viewpoint of dispersing a release agent in an aqueous medium. By using a polymer containing an oxazoline group, the polymer main chain is adsorbed to a hydrophobic wax, and the polar oxazoline group becomes a dispersing group in an aqueous medium, so that the release agent can be dispersed in the aqueous medium. It becomes. In the subsequent step (1B), since the reactive site in the resin and the oxazoline group are chemically bonded, it is possible to form particles in which the resin particles are firmly attached to the surface of the release agent particles. In addition, when the release agent contains a functional group such as a carboxy group, it reacts with the oxazoline group, more easily adheres to the surface of the release agent, and improves the dispersion stability of the release agent particles. Conceivable.
The number average molecular weight of the polymer containing an oxazoline group is preferably 1,000 or more, more preferably 5,000 or more, and preferably 1,000 from the viewpoint of increasing the reactivity with the release agent and the resin. 1,000 or less, more preferably 100,000 or less.

The oxazoline group equivalent of the polymer containing the oxazoline group is preferably 50 g- from the viewpoint of suppressing the release of the release agent from the toner particles and exposure to the surface to suppress fogging, and improving the image density of the printed matter. solid / eq. Or more, more preferably 80 g-solid / eq. More preferably, 150 g-solid / eq. Or more, preferably 1000 g-solid / eq. Hereinafter, more preferably 500 g-solid / eq. Hereinafter, more preferably 300 g-solid / eq. It is as follows.
The oxazoline group equivalent means the mass of the polymer per mole of oxazoline group.

The polymer containing an oxazoline group used in the present invention is used by adding to a dispersion of release agent particles in an aqueous medium, so that it is water-dispersible or water-soluble from the viewpoint of reactivity. It is preferable that it is water-soluble. Here, “water-soluble” means that the water can be dissolved without turbidity or precipitation. More specifically, the dissolution amount in 100 g of water at 25 ° C. is 15 g or more, preferably 25 g or more.
Commercially available polymers containing oxazoline groups include “Epocross WS series” such as Epocross (registered trademark) WS-300, WS-500, WS-700 (manufactured by Nippon Shokubai Co., Ltd., water-soluble type, main chain acrylic), “K series” (manufactured by Nippon Shokubai Co., Ltd., emulsion type, main chain styrene / acrylic) and the like.

(Aqueous medium)
As the aqueous medium, those containing water as a main component are preferable. From the viewpoint of environmental properties and the viewpoint of improving the dispersion stability of the release agent particles, the water content in the aqueous medium is preferably 80% by mass or more, More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, More preferably, it is substantially 100 mass%, More preferably, it is 100 mass%. As water, deionized water or distilled water is preferably used.
Components other than water in the aqueous medium include alkyl alcohols having 1 to 5 carbon atoms such as methanol, ethanol, isopropanol and butanol; dialkyl ketones having 3 to 4 carbon atoms such as acetone and methyl ethyl ketone; cyclic ethers such as tetrahydrofuran And an organic solvent that dissolves in water. Among these, alcohols having 1 to 5 carbon atoms, such as methanol, ethanol, isopropanol, and butanol, which are organic solvents that do not dissolve the resin, are preferable from the viewpoint of preventing the organic solvent from being mixed into the toner.

(Manufacture of release agent particles (W))
The release agent particles (W) are obtained as a dispersion of release agent particles (W) by dispersing the release agent in an aqueous medium.
A dispersion of release agent particles (W) is obtained by dispersing a release agent and an aqueous medium in the presence of a polymer containing an oxazoline group at a temperature equal to or higher than the melting point of the release agent using a disperser. It is preferable to obtain. As the disperser to be used, from the viewpoint of improving the dispersion stability of the release agent particles, a homogenizer, a high-pressure disperser, an ultrasonic disperser and the like are preferable, and an ultrasonic disperser is more preferable. What is necessary is just to set dispersion | distribution time suitably with the disperser to be used.
Examples of the ultrasonic disperser include an ultrasonic homogenizer. Examples of the commercially available products include “US-150T”, “US-300T”, “US-600T” (manufactured by Nippon Seiki Seisakusho), SONIFER 4020-400, and SONFIER 4020-800 (manufactured by Branson).
In addition, before using the disperser, it is preferable to preliminarily disperse a release agent, a polymer containing an oxazoline group, and if necessary, an aqueous medium using a mixer such as a homomixer or a ball mill.

  The amount of the polymer containing an oxazoline group is preferably 0 with respect to 100 parts by mass of the release agent from the viewpoint of increasing the reactivity with the release agent and the resin and improving the dispersion stability of the release agent particles. .1 part by mass or more, more preferably 0.3 part by mass or more, further preferably 0.5 part by mass or more, and preferably 10 parts by mass from the viewpoint of improving the productivity of the release agent particle dispersion. Hereinafter, more preferably 5 parts by mass or less, still more preferably 2 parts by mass or less, and still more preferably 1 part by mass or less.

In the present invention, the dispersion of the release agent particles in the aqueous medium improves the dispersion stability of the release agent particles by effectively utilizing the dispersion stabilization by the polymer containing the oxazoline group and the resin particles (A). From the viewpoint of obtaining uniform agglomerated particles in the subsequent aggregating step, the condition in which the surfactant is not added, or the surfactant content is 0.5 parts by mass or less with respect to 100 parts by mass of the release agent. It is preferable to carry out under the following conditions.
As an example of the said surfactant, the same thing as what is illustrated in manufacture of the below-mentioned resin particle (A) is mentioned.

Specifically, the heating temperature at the time of dispersion is preferably at least the melting point of the release agent and at least 80 ° C., more preferably at least 85 ° C., even more preferably from the viewpoint of improving the productivity of the release agent particle dispersion. It is 90 ° C or higher, preferably 100 ° C or lower, more preferably 98 ° C or lower, and further preferably 95 ° C or lower.
Moreover, the heating time at the time of dispersion is preferably 5 minutes or more, more preferably 10 minutes or more, still more preferably 20 minutes or more, and preferably 3 from the viewpoint of improving the productivity of the release agent particle dispersion. It is not more than time, more preferably not more than 2 hours, still more preferably not more than 1 hour.

  The solid content concentration of the dispersion of the release agent particles (W) is preferably 5 from the viewpoints of improving the dispersion stability of the release agent particles, facilitating handling, and improving the productivity of the toner. It is at least 10 mass%, more preferably at least 10 mass%, further preferably at least 15 mass%, preferably at most 40 mass%, more preferably at most 30 mass%, still more preferably at most 25 mass%.

The volume median particle size (D ₅₀ ) of the release agent particles (W) is preferably 0.05 μm from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process and improving the durability of the obtained toner. More preferably, it is 0.20 μm or more, more preferably 0.30 μm or more, preferably 1.00 μm or less, more preferably 0.80 μm or less, still more preferably 0.70 μm or less, and still more preferably 0. .65 μm or less, more preferably 0.60 μm or less.
Here, the volume median particle size (D ₅₀ ) is a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size, and the release agent particles (W) The volume-median particle size (D ₅₀ ) is determined by the method described in the examples.
The coefficient of variation (CV value) (%) of the particle size distribution of the release agent particles (W) is preferably from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process and improving the durability of the obtained toner. Is not more than 50%, more preferably not more than 45%, still more preferably not more than 40%. From the viewpoint of improving the productivity of the release agent particle dispersion, it is preferably not less than 15%, more preferably not less than 20%. More preferably, it is 25% or more. Here, the particle size distribution of the release agent particles is determined by the method described in the examples.

[Step (1B)]
In the step (1B), the release agent particles (W) obtained in the step (1A) and the resin particles (A) are combined with the glass transition temperature of the resin constituting the resin particles (A) or the release agent particles ( Mixing is performed at a temperature not lower than the melting point of the release agent constituting W) to obtain a dispersion of release agent particles (WR) in which the resin particles (A) adhere to the release agent particles (W). More specifically, for example, the dispersion liquid of the release agent particles (W) and the resin particles (A) are mixed at the above temperature, preferably the dispersion liquid of the release agent particles (W) and the resin particles. The dispersion of (A) is mixed at the above temperature.

(Resin particles (A))
The resin particles (A) function as a dispersion stabilizer for the release agent particles, and as an affinity improver between the release agent particles and the resin particles (B) described later, so that the toner particles of the release agent can be used. Controls liberation and exposure to the surface.

The resin that constitutes the resin particles (A) has a viewpoint of suppressing release from the toner particles of the release agent and exposure to the surface to suppress fogging, a viewpoint of improving the reactivity with the oxazoline group-containing polymer, and a printed matter. From the viewpoint of improving the image density, those having a hydrophilic group such as a carboxy group are preferred.
The acid value of the resin constituting the resin particles (A) is preferably 6 mgKOH / g or more, more preferably from the viewpoint of improving the dispersion stability of the resin particle dispersion, and from the viewpoint of suppressing release and release of the release agent. Is 10 mg KOH / g or more, more preferably 15 mg KOH / g or more, still more preferably 20 mg KOH / g or more, preferably 60 mg KOH / g or less, more preferably 55 mg KOH / g or less, and even more preferably 50 mg KOH / g or less. is there. The acid value of the resin constituting the resin particle (A) is preferably a carboxy group.

  The resin constituting the resin particles (A) contains, for example, at least one selected from polyester, vinyl chloride resin, and acrylic resin. Of these, polyester or vinyl chloride resin is preferable, and polyester is more preferable.

(polyester)
The resin particles (A) in the present invention are used in view of improving the dispersion stability of the release agent particles, improving the low temperature fixing property and durability of the toner, releasing the release agent from the toner particles, and exposing the surface to the surface. From the viewpoint of suppressing fog and fog, and from the viewpoint of improving the image density of the printed material, the resin preferably contains 90% by mass or more of polyester.
The polyester content in the resin constituting the resin particle (A) is preferably 95% by mass or more in the resin constituting the resin particle (A) from the same viewpoint and from the viewpoint of improving the productivity of the toner. More preferably, it is 98% by mass or more, still more preferably substantially 100% by mass, and still more preferably 100% by mass.
As the resin constituting the resin particles (A), in addition to polyester, known resins used for toner, for example, styrene-acrylic copolymer, epoxy, polycarbonate, polyurethane and the like can be used.

The raw material monomer of the polyester used in the present invention is not particularly limited, and an arbitrary alcohol component and an arbitrary carboxylic acid component are used.
Examples of the carboxylic acid component include dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, anhydrides thereof, and alkyl esters having 1 to 3 carbon atoms, and among them, dicarboxylic acids are preferable.
Specific examples of the dicarboxylic acid include aromatic dicarboxylic acid and aliphatic dicarboxylic acid. Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like. Examples of the aliphatic dicarboxylic acid include sebacic acid, fumaric acid, maleic acid, adipic acid, succinic acid, cyclohexanedicarboxylic acid, an alkyl group having 1 to 20 carbon atoms, or an succinic group substituted with an alkenyl group having 2 to 20 carbon atoms. An acid etc. are mentioned. Specific examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, and the like. Among these, from the viewpoint of improving the durability and chargeability of the toner, it is preferable to contain an aromatic dicarboxylic acid, and terephthalic acid is more preferable. Further, from the viewpoint of improving the dispersion stability of the release agent particles and from the viewpoint of improving the low-temperature fixability of the toner, it is preferable to contain an aliphatic dicarboxylic acid, fumaric acid, adipic acid, succinic acid, 2 or more carbon atoms. More preferably, at least one selected from the group consisting of succinic acid substituted with an alkenyl group of 20 or less and an acid anhydride thereof is substituted with fumaric acid, adipic acid, succinic acid, and an alkenyl group having 2 to 20 carbon atoms. At least one selected from the group consisting of succinic acid is more preferable, fumaric acid or dodecenyl succinic acid is still more preferable, and fumaric acid is still more preferable.

Examples of the trivalent or higher polyvalent carboxylic acid include aromatic polyvalent carboxylic acid and aliphatic polyvalent carboxylic acid. Specific examples of trivalent or higher aromatic polyvalent carboxylic acids include trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, and the like. Among them, the low-temperature fixability and durability of the toner are improved. Therefore, trimellitic acid and its anhydride are preferable, and trimellitic acid anhydride is more preferable. Specific examples of the trivalent or higher aliphatic polyvalent carboxylic acid include butane-1,2,4-tricarboxylic acid, hexane-1,3,6-tricarboxylic acid, cyclohexane-1,2,3-tricarboxylic acid, and the like. Can be mentioned.
A carboxylic acid component may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the alcohol component include aliphatic diols having 2 to 12 carbon atoms, aromatic diols, alicyclic diols, trivalent or higher polyhydric alcohols, or alkylene oxides having 2 to 4 carbon atoms ( Average addition mole number 1-16) and adducts.
Specific examples of the alcohol component include two or more carbon atoms of bisphenol A such as polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane. 3 or less alkylene oxide (average added mole number 1 to 16) adduct, alicyclic diol such as hydrogenated bisphenol A or alkylene oxides having 2 to 4 carbon atoms (average added mole number 1 to 16) Adduct, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,3-butanediol, aliphatic diol having 2 to 12 main chain carbon atoms such as 1,6-hexanediol or the like Alkylene oxide having 2 to 4 carbon atoms (average added mole number of 1 to 16 ) Adducts, trihydric or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane and sorbitol, or adducts thereof having 2 to 4 carbon atoms of alkylene oxide (average addition mole number of 1 to 16). It is done. You may use the said alcohol component in combination of 2 or more type. Examples of the alcohol component include polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane from the viewpoint of improving the durability of the toner. An alkylene oxide (average addition mole number 1 to 16) adduct of bisphenol A having 2 to 3 carbon atoms is preferred.

Polyester, for example, polycondenses the alcohol component and the carboxylic acid component at a temperature of 180 ° C. or higher and 250 ° C. or lower using an esterification catalyst, a polymerization inhibitor, or the like as necessary in an inert gas atmosphere. Can be manufactured.
As the esterification catalyst, an esterification catalyst such as a tin compound such as dibutyltin oxide or di (2-ethylhexanoic acid) tin or a titanium compound such as titanium diisopropylate bistriethanolamate can be used. The amount of the esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and preferably 1 with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. It is not more than part by mass, more preferably not more than 0.8 part by mass.
Examples of the polymerization inhibitor include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and preferably 0 with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. 0.5 parts by mass or less, more preferably 0.3 parts by mass or less.

The softening point of the polyester is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, from the viewpoint of improving the durability of the toner, and from the viewpoint of improving the low-temperature fixability of the toner. The temperature is preferably 165 ° C. or lower, more preferably 140 ° C. or lower, still more preferably 130 ° C. or lower, and still more preferably 125 ° C. or lower.
From the viewpoint of improving the durability of the toner, the glass transition temperature of the polyester is preferably 50 ° C. or higher, more preferably 53 ° C. or higher, and further preferably 55 ° C. or higher. Further, the viewpoint of improving the low-temperature fixability of the toner. Therefore, it is preferably 85 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower.
The acid value of the polyester improves the dispersion stability of the release agent particles, suppresses release of the release agent from the toner particles and exposure to the surface to suppress fogging, and improves the image density of the printed matter. From the viewpoint, it is preferably 6 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, still more preferably 20 mgKOH / g or more, and preferably 35 mgKOH / g or less, more preferably 30 mgKOH. / G or less, more preferably 25 mgKOH / g or less.
The desired softening point, glass transition temperature, and acid value can be obtained by adjusting the type of alcohol component and carboxylic acid component, the charging ratio, the polycondensation temperature, and the reaction time.

  In the present invention, the polyester includes not only unmodified polyester but also polyester modified to such an extent that the properties are not substantially impaired. Examples of the modified polyester include grafting and blocking with phenol, urethane, epoxy and the like by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. And a composite resin having two or more kinds of resin units including a polyester unit.

  Further, when the resin particles contain a plurality of resins, the softening point, glass transition temperature, and acid value of the resin constituting the resin particles are the softening point, glass transition temperature, acid value as a mixture of each resin. Each value is preferably within a range of values of each characteristic of the polyester. The softening point, glass transition temperature, and acid value as a mixture can be determined by the weighted average of each value, that is, the sum of the product of the characteristic value and the content ratio of each resin.

  The resin constituting the resin particles (A) may contain two types of polyesters having different softening points. From the viewpoint of improving low-temperature fixability and durability of the toner, the softening point of one polyester (I) is preferably 70 ° C. or higher and lower than 115 ° C., and the softening point of the other polyester (II) is 115 ° C. or higher and 165 ° C. or lower. preferable. Moreover, the difference of the softening point of two types of polyester becomes like this from a similar viewpoint, Preferably it is 5 degreeC or more, More preferably, it is 10 degreeC or more, Preferably it is 30 degrees C or less, More preferably, it is 20 degrees C or less. The mass ratio (I / II) between the polyester (I) and the polyester (II) is preferably 10/90 to 90/10, and preferably 50/50 to 90 / from the viewpoint of improving the low-temperature fixability and durability of the toner. 10 is more preferable.

(Vinyl chloride resin)
The vinyl chloride resin preferably includes a resin obtained by polymerization (preferably emulsion polymerization) of a vinyl chloride monomer and, if necessary, at least one monomer capable of copolymerization. Examples of the monomer that can be copolymerized with the vinyl chloride monomer include acrylic monomers and vinyl acetate. In addition, as shown in International Publication No. 2010-140647, a vinyl chloride monomer and at least one copolymerizable monomer are polymerized in the presence of a styrene / acryl oligomer and / or an acrylate oligomer (preferably Or vinyl chloride resin obtained by emulsion polymerization).
A commercially available resin emulsion may be used as the vinyl chloride resin. Examples of commercially available resin emulsions include Viniblanc 700 and Viniblanc 701 (both vinyl chloride copolymer emulsions manufactured by Nissin Chemical Industry Co., Ltd.) that are commercially available as so-called soap-free types that do not use a surfactant.

(Acrylic resin)
As the acrylic resin, it is preferable to include an acrylic resin obtained by polymerization (for example, emulsion polymerization) of an acrylic monomer alone or an acrylic monomer and at least one copolymerizable monomer. Further, a monomer that can be cross-linked by reacting with these acrylic copolymers may be used.
Examples of the acrylic monomer include (meth) acrylic acid or (meth) acrylic acid ester. (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate Hydroxy having 1 to 18 carbon atoms, such as octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc. Examples include alkyl esters of (meth) acrylic acid having an alkyl group that may have a group. Here, (meth) acryl means acryl, methacryl or a mixture thereof.
Examples of monomers that can be copolymerized with acrylic monomers include ethylene, vinyl acetate, vinylidene chloride, maleic anhydride, fumaric anhydride, styrene, 2-methylstyrene, chlorostyrene, acrylonitrile, vinyl toluene, N-methylol acrylamide, Examples thereof include at least one selected from the group consisting of N-methylol methacrylamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide, vinyl pyridine, and N-vinyl pyrrolidone.
As the acrylic resin, an acrylic resin emulsion may be used, an acrylic resin emulsion, a styrene-acrylic copolymer resin emulsion, a vinyl acetate-acrylic copolymer resin emulsion, a silicone-acrylic resin emulsion, a polyester-acrylic resin emulsion. , Urethane-acrylic resin emulsion, modified acrylic resin emulsion, self-crosslinking acrylate resin emulsion, and ethylene-vinyl acetate-acrylic resin emulsion. Among these, from the viewpoint of improving the dispersion stability of the release agent particles, an acrylic resin emulsion and a styrene-acrylic copolymer resin emulsion are preferable.

  The glass transition temperature of the resin constituting the resin particles (A) is preferably 50 ° C. or higher, more preferably 53 ° C. or higher, further preferably 55 ° C. or higher, from the viewpoint of improving the durability of the toner. From the viewpoint of improving the low-temperature fixability, it is preferably 90 ° C. or lower, more preferably 85 ° C. or lower, and still more preferably 80 ° C. or lower.

  The resin particles (A) may contain a colorant, a release agent, and a charge control agent as long as the effects of the present invention are not impaired. Moreover, you may contain additives, such as reinforcement fillers, such as a fibrous material, antioxidant, and anti-aging agent, as needed.

(Production of resin particles (A))
The resin particles (A) are preferably produced by a method in which a resin, a surfactant, and the above optional components are mixed in an aqueous medium to obtain a dispersion of the resin particles (A).

  As the aqueous medium, those containing water as a main component are preferable. The above-mentioned thing is mentioned as an aqueous medium.

In the present invention, when the resin particles (A) are produced as a dispersion, the dispersion stability of the release agent particles is effectively improved by utilizing the dispersion stabilization by the resin particles (A), and the subsequent aggregation From the viewpoint of obtaining uniform agglomerated particles in the process, and from the viewpoint of suppressing the release of the release agent from the agglomerated particles, a condition that does not use a surfactant is preferable, but a viewpoint of improving the dispersion stability of the resin particle dispersion Therefore, a surfactant may be used as long as the effects of the present invention are not impaired.
Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. Among them, nonionic surfactants are preferable, and nonionic surfactants and anionic surfactants are preferred. It is more preferable to use an active agent or a cationic surfactant in combination, and from the viewpoint of improving the dispersion stability of the resin particle dispersion, it is further preferable to use a nonionic surfactant and an anionic surfactant in combination. preferable.
When a nonionic surfactant and an anionic surfactant are used in combination, the mass ratio of the nonionic surfactant to the anionic surfactant (nonionic surfactant / anionic surfactant) is: From the viewpoint of improving the dispersion stability of the resin particle dispersion, it is preferably 0.3 or more, more preferably 0.5 or more, preferably 10 or less, more preferably 5 or less, and still more preferably 2 or less. is there.

Examples of nonionic surfactants include polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene fatty acid esters, oxyethylene / oxypropylene block copolymers, and the like.
Examples of the polyoxyethylene alkyl or alkenyl ether include polyoxyethylene oleyl ether and polyoxyethylene lauryl ether.
Examples of the polyoxyethylene alkyl aryl ether include polyoxyethylene nonyl phenyl ether.
Examples of the polyoxyethylene fatty acid ester include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate and the like.
The nonionic surfactant is preferably polyoxyethylene alkyl or alkenyl ether, more preferably polyoxyethylene oleyl ether, from the viewpoint of improving the dispersion stability of the resin particle dispersion.

Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, etc. From the viewpoint of improving the dispersion stability of the resin particle dispersion, alkylbenzene sulfonate, alkyl ether sulfate. Salts are preferred.
As the alkylbenzene sulfonate, an alkali metal salt of alkylbenzene sulfonic acid is preferable, and sodium alkylbenzene sulfonate is more preferable. The alkyl group is preferably a dodecyl group. As the alkyl benzene sulfonate, dodecyl benzene sulfonate is preferable, an alkali metal salt of dodecyl benzene sulfonic acid is more preferable, and sodium dodecyl benzene sulfonate is more preferable.
As the alkyl sulfate, from the viewpoint of improving the dispersion stability of the resin particle dispersion, an alkali metal salt of alkyl sulfate is preferable, and sodium alkyl sulfate is more preferable. The alkyl group is preferably a dodecyl group. As the alkyl sulfate, an alkali metal salt of dodecyl sulfate is more preferable, and sodium dodecyl sulfate is more preferable.
As the alkyl ether sulfate, an alkali metal salt of alkyl ether sulfate is preferable, and sodium alkyl ether sulfate is more preferable. The alkyl group is preferably a dodecyl group. The alkyl ether sulfate is preferably dodecyl ether sulfate, more preferably an alkali metal salt of dodecyl ether sulfate, and still more preferably sodium dodecyl ether sulfate.
Further, as the anionic surfactant, a polymer compound having a carboxyl group salt in the side chain, such as sodium poly (meth) acrylate and sodium (meth) acrylate-sodium maleate copolymer, can also be used. .

  As an example of the cationic surfactant, a quaternary ammonium salt is preferable, and examples thereof include alkylbenzyldimethylammonium chloride and alkyltrimethylammonium chloride.

  As described above, the total amount of the surfactant used is preferably as small as possible from the viewpoint of suppressing the release of the release agent from the aggregated particles. However, the total amount of the surfactant used is 100 parts by mass of the resin constituting the resin particles (A). On the other hand, from the viewpoint of improving the dispersion stability of the resin particle dispersion, it is preferably at least 0.1 part by mass, more preferably at least 0.5 part by mass, and even more preferably at least 1 part by mass. Further, from the viewpoint of improving the storage stability of the toner, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

  As a method of obtaining a dispersion containing the resin particles (A), a method of adding a resin or the like to an aqueous medium and dispersing using a disperser, a phase inversion emulsification in which an aqueous medium is gradually added to the resin or the like and emulsified Law. Hereinafter, the phase inversion emulsification method will be described.

First, the above-mentioned arbitrary components such as a resin, a surfactant, and a colorant are melted and mixed, or dissolved in an organic solvent to obtain a resin mixture.
When the resin is composed of a plurality of resins, a mixture of a plurality of resins may be used in advance, but when other components are added, they are added at the same time, and are mixed by melting or dissolving. May be obtained.

As a method for obtaining a resin mixture, a method in which the above-described optional components such as a resin, a surfactant, a colorant, and an alkaline aqueous solution are placed in a container and the resin is melted and mixed uniformly while stirring with a stirrer is preferable. . From the viewpoint of improving the affinity of the polyester for the aqueous medium and improving the dispersion stability of the resin particle dispersion, it is preferable to use an alkaline aqueous solution.
Examples of the alkali in the alkaline aqueous solution include hydroxides of alkali metals such as potassium hydroxide and sodium hydroxide, and ammonia. From the viewpoint of improving the dispersion stability of the resin particle dispersion, potassium hydroxide, Sodium hydroxide is preferred. The concentration of alkali in the aqueous alkali solution is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass. It is 7 mass% or less, More preferably, it is 7 mass% or less.

  The temperature at which the resin is melted and mixed is preferably equal to or higher than the glass transition temperature of the resin and is preferably equal to or lower than the boiling point of the aqueous medium from the viewpoint of obtaining homogeneous resin particles. Specifically, it is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, further preferably 90 ° C. or higher, and preferably 100 ° C. or lower, more preferably 98 ° C. or lower.

Next, an aqueous medium is added to the resin mixture and phase inversion is performed to obtain a dispersion containing resin particles (A).
From the viewpoint of obtaining homogeneous resin particles, the temperature at which the aqueous medium is added is preferably not less than the glass transition temperature of the resin and preferably not more than the boiling point of the aqueous medium. Specifically, it is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, further preferably 90 ° C. or higher, and preferably 100 ° C. or lower, more preferably 98 ° C. or lower.

  From the viewpoint of obtaining resin particles having a small particle diameter, the addition rate of the aqueous medium is preferably 0.1 parts by mass / 100 parts by mass of the resin constituting the resin particles (A) until the phase inversion is completed. Min. Or more, more preferably 0.5 mass parts / min or more, preferably 50 mass parts / min or less, more preferably 30 mass parts / min or less, still more preferably 10 mass parts / min or less, and even more. Preferably it is 5 mass parts / min or less. There is no restriction | limiting in the addition speed | rate of the aqueous medium after the resin phase is obtained after phase inversion.

  The amount of the aqueous medium used is 100 parts by mass of the resin constituting the resin particles (A) from the viewpoint of improving the productivity of the toner and from the viewpoint of improving the dispersion stability of the resin particle dispersion and the release agent particle dispersion. On the other hand, it is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, still more preferably 170 parts by mass or more, and preferably 900 parts by mass or less, more preferably 500 parts by mass or less, still more preferably 300 parts by mass. Or less.

(Dispersion of resin particles (A))
The solid content concentration of the resulting dispersion of the resin particles (A) is determined from the viewpoint of improving the dispersion stability of the resin particle dispersion, the ease of handling, the release of the release agent from the toner particles, and the exposure to the surface. From the viewpoint of suppressing fog and fog and improving the toner productivity, it is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 50%. It is not more than mass%, more preferably not more than 40 mass%, still more preferably not more than 35 mass%. The solid content includes nonvolatile components such as resins, pigments, and surfactants.

The volume median particle size (D ₅₀ ) of the resin particles (A) in the dispersion of the resin particles (A) is from the viewpoint of improving the dispersion stability of the release agent particles, and the release agent release from the toner particles. From the viewpoint of suppressing exposure to the surface and suppressing fogging, it is preferably 0.01 μm or more, more preferably 0.02 μm or more, further preferably 0.03 μm or more, and preferably 1.0 μm or less, more preferably Is 0.50 μm or less, more preferably 0.20 μm or less.
Here, the volume-median particle size (D ₅₀ ) is a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size, and is determined by the method described in the examples. Desired.
Further, the coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (A) is preferably 40% or less, more preferably 35% or less, from the viewpoint of improving the dispersion stability of the release agent particles. More preferably, it is 30% or less, and from the viewpoint of improving the productivity of the resin particle (A) dispersion, it is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more. In addition, CV value is a value represented by the following formula, and is calculated | required by the method as described in an Example.
CV value (%) = [standard deviation of particle size distribution (μm) / volume average particle size (μm)] × 100

(Manufacture of dispersion of release agent particles (WR))
From the viewpoint of improving the dispersion stability of the release agent particles, from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process, from the viewpoint of including the release agent in the toner even after heating in the fusing process, durability and low temperature of the toner From the viewpoint of improving fixability, the mass ratio of the resin particles (A) to the mass of the release agent particles (W) in the step (1B) (the mass of the resin particles (A) / the release agent particles (W) The mass) is preferably 1/100 to 50/100, more preferably 5/100 to 45/100, still more preferably 10/100 to 40/100, and still more preferably 15/100 to 36/100.

The stirrer used for a process (1B) is not specifically limited, A general stirrer can be used.
The stirring temperature is mixed at a temperature which is lower than either the glass transition temperature of the resin constituting the resin particles (A) or the melting point of the release agent constituting the release agent particles (W). Preferably, the mixing is performed at a temperature not lower than the glass transition temperature of the resin constituting the resin particles (A) and not lower than the melting point of the release agent constituting the release agent particles (W).
Specifically, the mixing temperature is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 85 ° C. or higher, still more preferably 90 ° C. or higher, and preferably 100 ° C. or lower, more preferably It is 98 degrees C or less.
The mixing time is preferably 5 minutes or more, more preferably 15 minutes or more, and preferably 3 hours or less, more preferably 2 hours or less, from the viewpoint of improving the productivity of the release agent particle dispersion. More preferably, it is 1 hour or less.

  The stirring means used in the step (1B) is, for example, a homomixer, a disper (trade name, manufactured by Primix), Claremix (trade name, manufactured by Mtechnics), and Cavitron (trade name, manufactured by Taihei Koki Co., Ltd.). Nanomizer (trade name, manufactured by Nanomizer) can also be used. In addition, when using a disper, it is preferable to perform stirring for 5 minutes or more in the state in which the whole is mixed uniformly.

  The solid content concentration of the dispersion of the release agent particles (WR) is preferably 5 from the viewpoint of improving the dispersion stability of the release agent particles, facilitating handling, and improving the productivity of the toner. It is at least 10 mass%, more preferably at least 10 mass%, further preferably at least 15 mass%, preferably at most 40 mass%, more preferably at most 30 mass%, still more preferably at most 25 mass%.

The volume median particle size (D ₅₀ ) of the release agent particles (WR) is preferably 0.05 μm from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process and improving the durability of the obtained toner. Or more, more preferably 0.10 μm or more, still more preferably 0.20 μm or more, still more preferably 0.30 μm or more, preferably 1.00 μm or less, more preferably 0.80 μm or less, still more preferably 0. .70 μm or less, more preferably 0.65 μm or less, and still more preferably 0.60 μm or less.
The volume median particle size (D ₅₀ ) of the release agent particles (WR) is determined by the method described in the examples.
The coefficient of variation (CV value) (%) of the particle size distribution of the release agent particles (WR) is preferably from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process and improving the durability of the obtained toner. Is not more than 50%, more preferably not more than 40%, still more preferably not more than 37%. From the viewpoint of improving the productivity of the release agent particle dispersion, it is preferably not less than 15%, more preferably not less than 20%. More preferably, it is 25% or more. Here, the particle size distribution of the release agent particles is determined by the method described in the examples.

<Step (2)>
In step (2), the dispersion of release agent particles (WR) obtained in step (1) and the dispersion of resin particles (B) containing polyester are mixed and agglomerated to form aggregated particles. It is a process to obtain.
Step (2) may include the next step (2A), and may further include (2B) after step (2A).
Step (2A): The dispersion of the release agent particles (WR) obtained in Step (1), the dispersion of the resin particles (B), and the flocculant are mixed in an aqueous medium to obtain the aggregated particles (1). Step (2B): The resin particles (B) are further added to the aggregated particles (1) obtained in the step (2A) at one time or divided into a plurality of times to adhere the resin particles (B). Step of Obtaining Aggregated Particles (2) (Resin Particles (B) Adhered Aggregated Particles) Next, each component used in step (2), step (2A) and step (2B) will be described.

(Resin particles (B))
The resin particles (B) function as a binder resin for the toner.
The resin particles (B) in the present invention contain polyester from the viewpoint of improving the low-temperature fixability and durability of the toner.

From the same viewpoint, the content of the polyester in the resin constituting the resin particles (B) is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, even more preferably, in the resin. Preferably it is 100 mass% substantially, More preferably, it is 100 mass%.
As the resin constituting the resin particles (B), in addition to polyester, known resins used for toner, for example, styrene-acrylic copolymer, epoxy, polycarbonate, polyurethane and the like can be used.

  The polyester used for the resin particles (B) can be produced by a polycondensation reaction between an acid component and an alcohol component in the same manner as the polyester used for the resin particles (A). Specific examples of the preferred acid component and alcohol component are the same as those of the polyester used for the resin particles (A), and are preferably the same as the polyester used for the resin particles (A).

The glass transition temperature, softening point, and acid value of the polyester used for the resin particles (B) are preferably in the same range as the polyester used for the resin particles (A).
Moreover, the polyester used for the resin particles (B) may contain two or more kinds of polyesters having different softening points.

  The resin particles (B) may contain a colorant, a release agent, and a charge control agent as long as the effects of the present invention are not impaired. Moreover, you may contain additives, such as reinforcement fillers, such as a fibrous material, antioxidant, and anti-aging agent, as needed.

(Coloring agent)
The resin particles (B) may be particles made of only a resin, or may be colorant-containing resin particles containing a colorant, but are colored from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step. It is preferable that a colorant-containing resin particle containing a colorant is preferable.
When the resin particles (B) are colorant-containing resin particles, the content of the colorant is a resin 100 constituting the resin particles (B) from the viewpoint of improving the image density of the printed matter and improving the low-temperature fixability. Preferably it is 1 mass part or more with respect to a mass part, More preferably, it is 5 mass parts or more, Preferably it is 20 mass parts or less, More preferably, it is 10 mass parts or less.
As the colorant, pigments and dyes are used, and pigments are preferable from the viewpoint of improving the image density of printed matter.
Specific examples of the pigment include carbon black, inorganic composite oxide, benzidine yellow, brilliantamine 3B, brilliantamine 6B, bengal, aniline blue, ultramarine blue, copper phthalocyanine, and phthalocyanine green. Among these, copper Phthalocyanine is preferred.
Specific examples of the dye include acridine series, azo series, benzoquinone series, azine series, anthraquinone series, indigo series, phthalocyanine series, and aniline black series.
A coloring agent can be used individually by 1 type or in combination of 2 or more types.

(Production of resin particles (B))
The resin particles (B) are produced by a method in which the above-mentioned optional components such as a surfactant and a colorant are mixed in an aqueous medium in addition to a polyester-containing resin to obtain a dispersion of resin particles (B). It is preferable.
As the aqueous medium, the same aqueous medium used for the dispersion of the resin particles (A) is preferably used.
A preferred embodiment of a method for obtaining a dispersion containing resin particles (B) is the same as the method for obtaining a dispersion of resin particles (A).

From the viewpoint of suppressing release from the toner particles of the release agent and exposure to the surface and suppressing fogging, and from the viewpoint of improving the image density of the printed material, it is preferable to crosslink the polyester constituting the resin particles (B). It is more preferable to crosslink with a compound having an oxazoline group.
As the compound having an oxazoline group, a compound containing a plurality of oxazoline groups in the molecule is preferable, and a polymer containing an oxazoline group is more preferable. The weight average molecular weight of the polymer containing an oxazoline group is preferably 1,000 or more, more preferably 5,000 or more, and preferably 1,000,000 or less, from the viewpoint of increasing the reactivity with the polyester. More preferably, it is 100,000 or less.
Examples of commercially available polymers containing oxazoline groups include “Epocross WS Series” (water-soluble type, main chain acrylic), “K Series” (emulsion type, main chain styrene / acrylic) manufactured by Nippon Shokubai Co., Ltd. (All are trade names).
The content or addition amount of the compound having an oxazoline group is such that the solid content with respect to 100 parts by mass of the resin in the dispersion of the resin particles (B) from the viewpoint of improving the crosslinking reactivity with the resin and improving the productivity. Is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 0.8 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, Preferably it is 10 mass parts or less.

  By adding and mixing a compound having an oxazoline group, the polyester contained in the resin particles (B) dispersed in the resin dispersion is crosslinked. The temperature during the crosslinking reaction is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and preferably 100 ° C. or lower, more preferably 98 ° C. or lower. The presence of the crosslinking can be confirmed by analyzing the presence of the amide group by a technique such as infrared absorption spectrum analysis.

  The solid content concentration of the dispersion of the resin particles (B) is preferably 10% by mass from the viewpoint of improving the dispersion stability of the resin particle dispersion, facilitating handling, and improving the productivity of the toner. More preferably, it is 15% by mass or more, more preferably 20% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less. The solid content includes nonvolatile components such as resins, pigments, and surfactants.

The volume median particle size (D ₅₀ ) of the resin particles (B) in the dispersion of the resin particles (B) is the viewpoint of suppressing the release of the release agent from the toner particles and the exposure to the surface to suppress fogging, From the viewpoint of obtaining a toner capable of obtaining a high-quality image, it is preferably 0.02 μm or more, more preferably 0.05 μm or more, still more preferably 0.08 μm or more, still more preferably 0.10 μm or more, and preferably Is not more than 1.00 μm, more preferably not more than 0.50 μm, still more preferably not more than 0.30 μm, still more preferably not more than 0.20 μm, still more preferably not more than 0.15 μm.
Further, the coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (B) is a high-quality image from the viewpoint of suppressing the release of the release agent from the toner particles and the exposure to the surface to suppress fogging. Is preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less, from the viewpoint of obtaining a toner from which the toner particles can be obtained, and from the viewpoint of improving the productivity of the dispersion of the resin particles (B). 5% or more is preferable, 10% or more is more preferable, and 15% or more is still more preferable. In addition, CV value is a value represented by the following formula, and is calculated | required by the method as described in an Example.
CV value (%) = [standard deviation of particle size distribution (μm) / volume average particle size (μm)] × 100

[Step (2A)]
As described above, the step (2) may include the next step (2A), and preferably includes the step (2A). Moreover, although only a process (2A) may be sufficient, a process (2B) may be further included after a process (2A).
In the step (2A), the dispersion of the release agent particles (WR), the dispersion of the resin particles (B), and the aggregating agent are mixed in an aqueous medium to obtain agglomerated particles (1). At this time, the dispersion of the release agent particles (WR), the dispersion of the resin particles (B), the flocculant, and an aqueous medium as necessary are added and mixed to disperse the aggregated particles (1). It is preferable to obtain a liquid.
(Manufacture of agglomerated particles (1))
Aggregated particles (1) are produced by a method in which optional components such as resin particles (B), release agent particles (WR), aggregating agent, and colorant are mixed in an aqueous medium to obtain aggregated particles (1). . Here, when mixing the said component, it is preferable to make it aggregate and obtain as a dispersion liquid of aggregated particle (1).

First, the resin particles (B) and the release agent particles (WR) are mixed in an aqueous medium to obtain a mixed dispersion.
In addition, when a colorant is not mixed in the resin particles (B), it is preferable to mix a colorant in the present mixed dispersion.
Moreover, you may mix resin particles other than resin particle (B) in the mixed dispersion liquid in the range which does not inhibit the effect of this invention.
There is no restriction | limiting in order of mixing, You may add any in order and may add simultaneously.

In the mixed dispersion containing the resin particles (B) and the release agent particles (WR), the content of the resin particles (B) is preferably 10% by mass or more from the viewpoint of improving the low-temperature fixability and productivity of the toner. More preferably, it is 15 mass% or more, preferably 40 mass% or less, more preferably 30 mass% or less.
Further, in the mixed dispersion liquid containing the resin particles (B) and the release agent particles (WR), the content of the aqueous medium is agglomerated particles having a target particle size by controlling the aggregation and the viewpoint of improving the productivity of the toner. From the viewpoint of obtaining the above, it is preferably 50% by mass or more, more preferably 60% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less.
The content of the colorant is preferably 2 parts by mass or more with respect to 100 parts by mass of the resin constituting the resin particles (B) from the viewpoint of improving the toner image density and improving the low-temperature fixability. More preferably, it is 3 mass parts or more, Preferably it is 20 mass parts or less, More preferably, it is 10 mass parts or less.
The content of the release agent particles (WR) is preferably 2 parts by mass or more, more preferably 5 parts by mass with respect to 100 parts by mass of the resin particles (B) from the viewpoint of improving the releasability and chargeability of the toner. Part or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less.
The mixing temperature is preferably 0 ° C. or higher and 40 ° C. or lower from the viewpoint of controlling aggregation and obtaining aggregated particles having a target particle size.

Next, the particles in the mixed dispersion can be aggregated to suitably obtain a dispersion of aggregated particles (1). It is preferable to add a flocculant for efficient aggregation.
Specific examples of the flocculant include quaternary salt cationic surfactants, organic flocculants such as polyethyleneimine; inorganic flocculants such as inorganic metal salts, inorganic ammonium salts, and bivalent metal complexes. It is done.
Examples of inorganic metal salts include metal salts such as sodium sulfate, sodium chloride, calcium chloride, magnesium sulfate, calcium nitrate, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic metals such as polyaluminum chloride and polyaluminum hydroxide. A salt polymer is mentioned. Examples of inorganic ammonium salts include ammonium sulfate, ammonium chloride, and ammonium nitrate.
The flocculant is preferably an electrolyte, and more preferably a salt, from the viewpoint of obtaining a toner having a desired particle size while preventing excessive aggregation. The valence is preferably 1 to 5, more preferably 1 to 2, and even more preferably 1. That is, it is preferable to use a monovalent salt. Here, the monovalent salt means that the valence of the metal ion or cation constituting the salt is 1. Examples of the monovalent salt include the inorganic metal salts, inorganic ammonium salts, and the like, and inorganic ammonium salts are preferable.
The flocculant is preferably an inorganic ammonium salt and more preferably ammonium sulfate from the viewpoint of improving the flocculence and obtaining uniform agglomerated particles.

  The amount of the flocculant used is preferably 50 parts by mass or less, and 40 parts by mass or less with respect to 100 parts by mass of the resin constituting the resin particles (A) and the resin particles (B) from the viewpoint of improving the durability of the toner. Is more preferable, and 35 mass parts or less is still more preferable. Further, from the viewpoint of controlling the aggregation of the resin particles to obtain a target particle size, the amount is preferably 1 part by mass or more with respect to 100 parts by mass of the resin constituting the resin particles (A) and the resin particles (B). The above is more preferable, and 20 mass parts or more is still more preferable.

As an aggregating method, an aggregating agent is preferably dropped into an aqueous medium solution into a container containing a mixed dispersion. From the viewpoint of controlling the aggregation of the resin particles to obtain a desired particle size, it is preferable to drop the solution as an aqueous solution. The concentration of the aqueous solution of the flocculant is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more, from the viewpoint of controlling the aggregation of the resin particles to obtain a desired particle size. Further, it is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less. The flocculant may be added at once, or may be added continuously or intermittently. Moreover, it can also be divided and added. It is preferable to sufficiently stir at the time of adding the flocculant and after completion of the addition.
From the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle diameter and improving the productivity of the toner, the dropping time of the aggregating agent is preferably from 1 minute to 120 minutes. The dropping temperature is preferably 0 ° C. or higher and 50 ° C. or lower from the viewpoint of controlling aggregation and obtaining aggregated particles having a target particle size.
Furthermore, from the viewpoint of promoting aggregation, controlling the particle size of the aggregated particles, and suppressing the formation of coarse particles, it is preferable to increase the temperature of the dispersion after adding the coagulant. As temperature to maintain, 50 to 70 degreeC is preferable. It is preferable to confirm the progress of aggregation by monitoring the volume-median particle size of the aggregated particles. The volume median particle size is measured by the method described in the examples.

  The volume-median particle size of the obtained aggregated particles (1) is preferably 10 μm or less, more preferably 8 μm or less, and even more preferably 6 μm, from the viewpoint of obtaining a toner capable of obtaining a high-quality image and suppressing toner scattering. In addition, it is preferably 1 μm or more, more preferably 2 μm or more, and further preferably 3 μm or more. The volume-median particle size of the aggregated particles (1) is specifically determined by the method described in the examples.

[Step (2B)]
Step (2B) is an aggregate formed by adding resin particles (B) to aggregated particles (1) obtained in step (2A) by adding resin particles (B) at a time or divided into multiple times. This is a step of obtaining particles (2) (resin particles (B) adhered aggregated particles). At this time, the resin particles (B) are adhered to the dispersion liquid of the aggregated particles (1) described in the step (2A) by adding the resin particles (B) at one time or divided into a plurality of times, thereby attaching the resin particles (B). It is preferable to obtain a dispersion of (2) (resin particles (B) adhered and agglomerated particles).
By performing this step (2B), it is possible to better prevent the release agent or the like from flowing out of the toner particles.

In the step (2B), when the resin particles (B) are added in a plurality of divided portions, the amount of each resin particle (B) is preferably the same amount. In addition, when the resin particles (B) are added in a plurality of divided portions, the number of times is not particularly limited, but is preferably twice or more from the viewpoint of controlling the particle size of the formed aggregated particles (2). Moreover, from the viewpoint of improving the productivity of the aggregated particles (2), it is preferably 10 times or less, more preferably 8 times or less.
In the step (2B), the resin particles (B) may be the same as the resin particles (B) in the step (2A) or may be resin particles (B) having a different composition. From the viewpoint of improving low-temperature fixability and durability, and from the viewpoint of improving productivity, the same resin particles (B) are preferred.
The timing of adding the resin particles (B) in the step (2B) is not particularly limited as long as the resin particles (B) can be attached to the aggregated particles (1). It is preferable to be between the end of the addition and the fusing step.
When the resin particle (B) dispersion is added to the aggregated particle (1) dispersion, the aggregating agent may be used in this step in order to efficiently attach the resin particle (B) to the aggregated particle (1). Good.

  The temperature in the system in this step is preferably 50 ° C. or higher and 70 ° C. or lower from the viewpoint of improving the durability of the toner and suppressing fogging and improving the image quality obtained. When the aggregated particles (2) are produced in the temperature range, the durability of the obtained toner and the image quality of the printed matter are improved. The reason for this is not clear, but it is considered that the generation of coarse particles is suppressed and the particle size distribution becomes sharp because fusion of the aggregated particles (2) does not occur.

The mixing ratio (aggregated particles (1) / resin particles (B)) of the aggregated particles (1) in the dispersion of the aggregated particles (2) and the resin particles (B) added in the step (2B) is a low temperature of the toner. From the viewpoint of improving fixability and durability, the mass ratio is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and preferably 5.0 or less. Preferably it is 4.0 or less, More preferably, it is 3.5 or less.
When performing the step (2A) and the step (2B), the mass ratio of the resin particles (B) added in each step, that is, the mass of the resin particles (B) added in the step (2A) / step (2B The mass of the resin particles (B) to be added) is preferably 50 from the viewpoint of suppressing the release of the release agent from the toner particles and the exposure to the surface to suppress fogging, and improving the obtained image quality. / 50 to 95/5, more preferably 55/45 to 90/10, still more preferably 60/40 to 80/20.
The volume median particle size (D ₅₀ ) of the agglomerated particles (2) is preferably 1 μm or more, more preferably 2 μm or more, still more preferably 3 μm or more, and even more preferably, from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Is 4 μm or more, preferably 10 μm or less, more preferably 9 μm or less, still more preferably 8 μm or less, and still more preferably 6 μm or less.

It is preferable to add the resin particles (B) and suppress aggregation when the toner particles have grown to an appropriate particle size.
As a method of suppressing aggregation, a method of rapidly reducing the concentration of aggregated particles and an aggregating agent by diluting the dispersion to further suppress aggregation, a method of cooling the dispersion, a method of adding an aggregation stopper, etc. However, from the viewpoint of improving workability and productivity, a method of suppressing the further aggregation by diluting the dispersion liquid to rapidly reduce the concentration of the aggregated particles and the coagulant is preferable.
As the aqueous medium, for example, the above-described aqueous medium is used.
The solid content concentration in the dispersion after dilution is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and further preferably 1.5% by mass or more from the viewpoint of improving the productivity of the toner. Further, from the viewpoint of obtaining fused particles having a target particle size by suppressing further aggregation, it is preferably 10% by mass or less, more preferably 7.0% by mass or less, and further preferably 5.0% by mass. It is as follows.
Further, from the viewpoint of reliably preventing unnecessary aggregation, an aggregation stopper may be added to stop the aggregation. As the aggregation terminator, a surfactant is preferably used, and an anionic surfactant is more preferably used. Examples of the anionic surfactant include alkyl ether sulfates, alkyl sulfates, linear alkylbenzene sulfonates, and polyoxyethylene alkyl ether sulfates. Polyoxyethylene alkyl ether sulfates are preferable, and polyoxyethylene lauryl is preferable. Sodium ether sulfate is more preferred.
The aggregation terminator may be used singly or in combination of two or more.

  From the viewpoint of stopping the aggregation, the addition amount of the aggregation terminator is the resin constituting the aggregated particles (1) or the resin constituting the aggregated particles (2) (that is, the resin and the resin particles constituting the aggregated particles (1)) (Total amount of resin constituting (B)) The amount is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more with respect to 100 parts by mass. From the viewpoint of reducing the amount, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. The aggregation terminator may be added in any form as long as it is added, but it is preferably added in an aqueous solution from the viewpoint of improving productivity.

  The temperature at which the aggregation terminator is added is preferably the same as the temperature at which the aggregated particle dispersion is retained, and is preferably from 50 ° C. to 70 ° C. from the viewpoint of improving toner productivity.

<Step (3)>
Step (3) is a step of fusing the aggregated particles obtained in step (2) to obtain fused particles.
Here, the “aggregated particles obtained in the step (2)” means the aggregated particles (1) obtained in the step (2A) when the step (2B) is not performed, and the step (2B). In the case of carrying out the step, it means the aggregated particles (2) obtained in the step (2B).
At the time of fusion, the resin particles and release agent particles in the agglomerated particles obtained in the step (2) are mainly physically attached, but are fused and integrated, Presumed to be particles.

The heating temperature at the time of fusing is a temperature that is not less than the glass transition temperature of the resin constituting the agglomerated particles and not more than 100 ° C. from the viewpoint of improving the fusing property of the agglomerated particles and improving the productivity of the toner. Preferably, the temperature is such that the glass transition temperature of the resin constituting the aggregated particles is not lower than 90 ° C., more preferably not lower than the glass transition temperature of the resin constituting the aggregated particles and not higher than 85 ° C. Temperature.
The holding time in this step is preferably 10 minutes or more, more preferably 30 minutes or more, and still more preferably from the viewpoint of improving the fusibility of the aggregated particles and improving the durability, chargeability and productivity of the toner. It is 1 hour or longer, preferably 24 hours or shorter, more preferably 10 hours or shorter, still more preferably 5 hours or shorter, still more preferably 3 hours or shorter.

From the viewpoint of suppressing release from the toner particles of the release agent and exposure to the surface and suppressing fogging, and obtaining a high-quality image, the volume-median particle size of the fused particles obtained in this step is preferably It is 2 μm or more, more preferably 3 μm or more, further preferably 4 μm or more, preferably 10 μm or less, more preferably 8 μm or less, still more preferably 7 μm or less, and even more preferably 6 μm or less.
In addition, it is preferable that the average particle diameter of the fusion | melting particle | grains obtained at this process is below the average particle diameter of aggregated particle (2). That is, in this step, it is preferable that the fused particles do not aggregate and fuse.

[Post-processing process]
In the present invention, a post-treatment step may be performed after step (3), and it is preferable to obtain toner particles by isolating the fused particles.
Since the fused particles obtained in the step (3) are present in the aqueous medium, it is preferable to first perform solid-liquid separation. For solid-liquid separation, a suction filtration method or the like is preferably used.
It is preferable to perform washing after the solid-liquid separation. When a nonionic surfactant is used in the production of the resin particles (A) and resin particles (B), it is preferable to remove the added nonionic surfactant. Washing with an aqueous medium below the cloud point is preferred. The washing is preferably performed a plurality of times.
Next, drying is preferably performed, but the temperature during drying is preferably set so that the temperature of the fused particles themselves is 5 ° C. or more lower than the glass transition temperature of the resin constituting the fused particles. It is more preferable to set the temperature so as to be lower than the temperature.
As a drying method, any method such as a vacuum low temperature drying method, a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be adopted. The water content after drying of the toner particles is preferably adjusted to 1.5% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of improving the chargeability of the toner.

The volume median particle size (D ₅₀ ) of the toner particles or toner described later is from the viewpoint of suppressing the release of the release agent from the toner particles and the exposure to the surface to suppress fogging, and from the viewpoint of obtaining a high-quality image. The thickness is preferably 2 μm or more, more preferably 3 μm or more, further preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, still more preferably 7 μm or less, and even more preferably 6 μm or less.
The CV value of toner particles or toner described later is preferably 30% or less, more preferably 28% or less, and even more preferably 27% or less, from the viewpoint of improving image quality. Further, from the viewpoint of improving the productivity of the toner, it is preferably 5% or more, more preferably 10% or more, and further preferably 15% or more.
The volume median particle size (D ₅₀ ) and CV value of the toner particles are determined by the method described in the examples.

[Toner for electrostatic image development]
Toner particles obtained by drying or the like can be used as the toner of the present invention as they are, but it is preferable to use toner particles whose surface has been treated as described below as toner for developing electrostatic images.
The softening point of the toner for developing an electrostatic charge image of the present invention is preferably 60 ° C. or higher, preferably 140 ° C. or lower, more preferably 130 ° C. or lower, from the viewpoint of improving the low-temperature fixability and durability of the toner. More preferably, it is 120 ° C. or lower.

In the toner for developing an electrostatic charge image obtained by the production method of the present invention, the toner particles may be used as the toner as they are, but an additive such as a fluidizing agent is added to the surface of the toner particles as an external additive. It is preferable to use a toner. Examples of the external additive include silica fine particles whose surfaces are hydrophobized, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferable.
The addition amount of the external additive is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more with respect to 100 parts by mass of the toner particles before the treatment with the external additive. , Preferably 5 parts by mass or less, more preferably 4.7 parts by mass or less.
The electrostatic image developing toner obtained by the present invention can be used as a one-component developer or mixed with a carrier and used as a two-component developer.

In relation to the above-described embodiment, the present invention further discloses the following method for producing a toner for developing an electrostatic image.
<1> A method for producing a toner for developing an electrostatic charge image, comprising the following steps (1) to (3).
Step (1): Step of obtaining a dispersion of release agent particles (WR) including the following steps (1A) and (1B) Step (1A): Release agent and polymer containing oxazoline group in aqueous medium And obtaining a dispersion of release agent particles (W) having a volume median particle size of 0.05 μm or more and 1.5 μm or less Step (1B): Mold release obtained in Step (1A) The agent particles (W) and the resin particles (A) are at least the lower of the glass transition temperature of the resin constituting the resin particles (A) or the melting point of the release agent constituting the release agent particles (W). Step of obtaining a dispersion of release agent particles (WR) in which the resin particles (A) adhere to the release agent particles (W) Step (2): Release agent particles obtained in Step (1) The dispersion of (WR) and the dispersion of resin particles (B) containing polyester are mixed and aggregated to obtain aggregated particles. Step Step (3): A step of fusing the aggregated particles obtained in step (2) to obtain fused particles.

<2> The method for producing a toner for developing an electrostatic charge image according to <1>, wherein the release agent is preferably a hydrocarbon wax or an ester wax, more preferably a hydrocarbon wax or an ester wax.
<3> The hydrocarbon wax is preferably at least one selected from low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, ceresin and the like. More preferably, it is at least one selected from low molecular weight polypropylene, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax, and more preferably paraffin wax, for developing electrostatic images according to <2>. Toner manufacturing method.
<4> The ester wax is preferably at least one selected from a plant wax, an ester wax having a natural or synthetic long-chain aliphatic group, and an esterified product of an acid-modified polyethylene wax, and more preferably. Or at least one selected from carnauba wax, rice wax, candelilla wax, and the like, and more preferably carnauba wax, production of an electrostatic charge image developing toner according to <2> or <3> Method.
<5> The method for producing a toner for developing an electrostatic charge image according to any one of <2> to <4>, wherein the ester wax has a carboxy group.
<6> The acid value of the ester wax is preferably 0.5 mgKOH / g or more, more preferably 0.7 mgKOH / g or more, still more preferably 1 mgKOH / g or more, preferably 20 mgKOH / g or less, more preferably 17 mgKOH. / G or less, More preferably, it is 15 mgKOH / g or less, More preferably, it is 10 mgKOH / g or less, The manufacturing method of the electrostatic image developing toner in any one of <2>-<5>.
<7> The melting point of the release agent is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, preferably 100 ° C. or lower, more preferably 95 ° C. or lower, still more preferably. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <6>, which is 90 ° C. or lower.
<8> The amount of the release agent used is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 5 parts by mass or more, with respect to 100 parts by mass of the resin in the toner. Is 20 parts by mass or less, more preferably 15 parts by mass or less. The method for producing an electrostatic charge image developing toner according to any one of <1> to <7>.
<9> The release agent contains a hydrocarbon wax and an ester wax, and the mass ratio of the ester wax to the hydrocarbon wax is preferably 1/99 or more, more preferably 3 /, as the mass ratio of the ester wax / hydrocarbon wax. 97 or more, more preferably 5/95 or more, preferably 50/50 or less, more preferably 40/60 or less, still more preferably 35/65 or less, still more preferably 30/70 or less, and preferably 1/99 to 50/50, more preferably 3/97 to 40/60, still more preferably 5/95 to 35/65, still more preferably 5/95 to 30/70, <1> to <8 The method for producing a toner for developing an electrostatic charge image according to any one of the above.
<10> The total amount of hydrocarbon wax and ester wax in the release agent is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably substantially 100% by mass, and still more preferably 100% by mass. The method for producing a toner for developing an electrostatic image according to any one of <1> to <9>.

<11> The number average molecular weight of the polymer containing an oxazoline group is preferably 1,000 or more, more preferably 5,000 or more, and preferably 1,000,000 or less, more preferably 100,000 or less. The method for producing an electrostatic charge image developing toner according to any one of <1> to <10>.
<12> The oxazoline group equivalent of the polymer containing an oxazoline group is preferably 50 g-solid / eq. Or more, more preferably 80 g-solid / eq. More preferably, 150 g-solid / eq. Or more, preferably 1000 g-solid / eq. Hereinafter, more preferably 500 g-solid / eq. Hereinafter, more preferably 300 g-solid / eq. The method for producing a toner for developing an electrostatic image according to any one of <1> to <11>, wherein:
<13> The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <12>, wherein the aqueous medium is preferably water-based, and more preferably water.
<14> The water content in the aqueous medium is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably substantially 100% by mass, and even more preferably. Is 100 mass%, The manufacturing method of the electrostatic image developing toner in any one of <1>-<13>.

<15> The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <14>, wherein the temperature of the dispersion treatment in the step (1A) is equal to or higher than the melting point of the release agent.
<16> In the step (1A), the release agent and the aqueous medium are dispersed using a disperser at a temperature equal to or higher than the melting point of the release agent in the presence of a polymer containing an oxazoline group. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <15>, which is a step of obtaining a dispersion of agent particles (W).
<17> The electrostatic charge image according to <16>, wherein the disperser is preferably at least one selected from a homogenizer, a high-pressure disperser, and an ultrasonic disperser, and more preferably an ultrasonic disperser. A method for producing a developing toner.
<18> The amount of the polymer containing an oxazoline group in the step (1A) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more with respect to 100 parts by mass of the release agent. Preferably it is 0.5 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 2 parts by mass or less, still more preferably 1 part by mass or less, <1> ~ <17> A method for producing an electrostatic image developing toner according to any one of the above.
<19> The step (1A) is performed under the condition that the surfactant is not added, or the surfactant content is 0.5 parts by mass or less with respect to 100 parts by mass of the release agent. <1> A method for producing a toner for developing an electrostatic charge image according to any one of <18>.
<20> The heating temperature at the time of dispersion in the step (1A) is preferably not less than the melting point of the release agent and not less than 80 ° C, more preferably not less than 85 ° C, still more preferably not less than 90 ° C, and preferably 100 ° C. Hereinafter, the method for producing a toner for developing an electrostatic charge image according to any one of <1> to <19>, which is more preferably 98 ° C. or lower, and further preferably 95 ° C. or lower.
<21> The heating time during dispersion in step (1A) is preferably 5 minutes or more, more preferably 10 minutes or more, still more preferably 20 minutes or more, and preferably 3 hours or less, more preferably 2 hours. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <20>, further preferably 1 hour or less.
<22> The solid content concentration of the dispersion of the release agent particles (W) obtained in the step (1A) is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more. Also, the method for producing a toner for developing an electrostatic charge image according to any one of <1> to <21>, preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. .
<23> The volume median particle size (D ₅₀ ) of the release agent particles (W) is preferably 0.05 μm or more, more preferably 0.20 μm or more, still more preferably 0.30 μm or more, and preferably Is 1.00 μm or less, more preferably 0.80 μm or less, still more preferably 0.70 μm or less, even more preferably 0.65 μm or less, and even more preferably 0.60 μm or less, from <1> to <22> A method for producing a toner for developing an electrostatic image according to any one of the above.
<24> The coefficient of variation (CV value) (%) of the particle size distribution of the release agent particles (W) is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less, The method for producing an electrostatic charge image developing toner according to any one of <1> to <23>, preferably 15% or more, more preferably 20% or more, and further preferably 25% or more.

<25> In the step (1B), preferably, the dispersion of the release agent particles (W) and the resin particles (A) are mixed at the above temperature, and more preferably, the dispersion of the release agent particles (W). The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <24>, wherein the liquid and a dispersion of the resin particles (A) are mixed at the temperature.
<26> The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <25>, wherein the resin constituting the resin particle (A) preferably has a hydrophilic group.
<27> The acid value of the resin constituting the resin particles (A) is preferably 6 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and still more preferably 20 mgKOH / g or more. In addition, the method for producing a toner for developing an electrostatic charge image according to any one of <1> to <26>, which is preferably 60 mgKOH / g or less, more preferably 55 mgKOH / g or less, and still more preferably 50 mgKOH / g or less. .
<28> The method for producing a toner for developing an electrostatic charge image according to <27>, wherein the acid value of the resin constituting the resin particle (A) is based on a carboxy group.
<29> The resin constituting the resin particle (A) preferably contains at least one selected from polyester, vinyl chloride resin, and acrylic resin, and more preferably contains polyester or vinyl chloride resin. And, more preferably, the method for producing a toner for developing an electrostatic charge image according to any one of <1> to <28>, comprising polyester.
<30> The softening point of the polyester is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, preferably 165 ° C. or lower, more preferably 140 ° C. or lower, still more preferably 130. The method for producing a toner for developing an electrostatic charge image according to <29>, wherein the toner is at a temperature of not higher than ° C, more preferably not higher than 125 ° C.
<31> The glass transition temperature of the polyester is preferably 50 ° C. or higher, more preferably 53 ° C. or higher, still more preferably 55 ° C. or higher, preferably 85 ° C. or lower, more preferably 80 ° C. or lower, still more preferably. The method for producing a toner for developing an electrostatic charge image according to <29> or <30>, which is 70 ° C. or lower.
<32> The acid value of the polyester is preferably 6 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, still more preferably 20 mgKOH / g or more, and preferably 35 mgKOH / g. The method for producing a toner for developing an electrostatic charge image according to any one of <29> to <31>, more preferably 30 mgKOH / g or less, and further preferably 25 mgKOH / g or less.
<33> The glass transition temperature of the resin constituting the resin particles (A) is preferably 50 ° C. or higher, more preferably 53 ° C. or higher, still more preferably 55 ° C. or higher, and preferably 90 ° C. or lower, more preferably. Is a method for producing a toner for developing an electrostatic charge image according to any one of <1> to <32>, which is 85 ° C. or lower, more preferably 80 ° C. or lower.
<34> When the resin particles (A) are produced as a dispersion, the total amount of the surfactant used is preferably 0.1 parts by mass with respect to 100 parts by mass of the resin constituting the resin particles (A). Or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, still more preferably. Is 5 parts by mass or less, The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <33>.
<35> When the dispersion of the resin particles (A) is mixed in the step (1B), the solid content concentration of the dispersion of the resin particles (A) is preferably 10% by mass or more, more preferably 15% by mass or more. More preferably, it is 20% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less, according to any one of <1> to <34>. A method for producing a toner for developing an electrostatic image.
<36> The volume median particle size (D ₅₀ ) of the resin particles (A) in the step (1B) is preferably 0.01 μm or more, more preferably 0.02 μm or more, and further preferably 0.03 μm or more. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <35>, which is preferably 1.0 μm or less, more preferably 0.50 μm or less, and still more preferably 0.20 μm or less.
<37> The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (A) is preferably 40% or less, more preferably 35% or less, still more preferably 30% or less, and preferably The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <36>, which is 5% or more, more preferably 10% or more, and further preferably 15% or more.

<38> The mass ratio of the mass of the resin particles (A) to the mass of the release agent particles (W) in the step (1B) (the mass of the resin particles (A) / the mass of the release agent particles (W)) is preferable. Is 1/100 to 50/100, more preferably 5/100 to 45/100, still more preferably 10/100 to 40/100, still more preferably 15/100 to 36/100, <1> to <37> The method for producing a toner for developing an electrostatic charge image according to any one of the above items.
<39> The solid content concentration of the dispersion of the release agent particles (WR) is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 40% by mass. % Or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less, the method for producing a toner for developing an electrostatic charge image according to any one of <1> to <38>.
<40> The volume median particle size (D ₅₀ ) of the release agent particles (WR) is preferably 0.05 μm or more, more preferably 0.10 μm or more, still more preferably 0.20 μm or more, and even more preferably 0. .30 μm or more, preferably 1.00 μm or less, more preferably 0.80 μm or less, still more preferably 0.70 μm or less, still more preferably 0.65 μm or less, and even more preferably 0.60 μm or less. <1>-<39> The manufacturing method of the electrostatic image developing toner in any one of <39>.
<41> The coefficient of variation (CV value) (%) of the particle size distribution of the release agent particles (WR) is preferably 50% or less, more preferably 40% or less, and even more preferably 37% or less. The method for producing an electrostatic image developing toner according to any one of <1> to <40>, preferably 15% or more, more preferably 20% or more, and further preferably 25% or more.

<42> The process (2) preferably includes the following process (2A), and more preferably includes (2B) after the process (2A), according to any one of <1> to <41>. A method for producing a toner for developing an electrostatic image.
Step (2A): The dispersion of the release agent particles (WR) obtained in Step (1), the dispersion of the resin particles (B), and the flocculant are mixed in an aqueous medium to obtain the aggregated particles (1). Step (2B): The resin particles (B) are further added to the aggregated particles (1) obtained in the step (2A) at one time or divided into a plurality of times to adhere the resin particles (B). Step <43> of obtaining the aggregated particles (2) (resin particles (B) adhered aggregated particles) formed in the resin, the content of the polyester in the resin constituting the resin particles (B) is preferably 90% by mass or more, More preferably 95% by mass or more, more preferably 98% by mass or more, still more preferably substantially 100% by mass, and still more preferably 100% by mass, according to any one of <1> to <42>. A method for producing a toner for developing an electrostatic image.
<44> The method for producing a toner for developing an electrostatic charge image according to <43>, wherein the resin constituting the resin particle (B) preferably contains two kinds of polyesters having different softening points.
<45> The softening point of one polyester (I) is preferably 70 ° C. or higher and lower than 115 ° C., and the softening point of the other polyester (II) is 115 ° C. or higher and 165 ° C. or lower. A method for producing a toner for developing a charge image.
<46> The difference between the softening points of the two types of polyester is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and preferably 30 ° C. or lower, more preferably 20 ° C. or lower, <44> or <45> The method for producing a toner for developing an electrostatic charge image according to <45>.
<47> The mass ratio (I / II) of the polyester (I) to the polyester (II) is preferably 10/90 to 90/10, more preferably 50/50 to 90/10, <44 The method for producing a toner for developing an electrostatic charge image according to any one of> to <46>.
<48> The solid content concentration of the dispersion of the resin particles (B) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 50% by mass or less. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <47>, more preferably 40% by mass or less, and still more preferably 35% by mass or less.
<49> The volume median particle size (D ₅₀ ) of the resin particles (B) is preferably 0.02 μm or more, more preferably 0.05 μm or more, still more preferably 0.08 μm or more, and even more preferably 0.10 μm. In addition, it is preferably 1.00 μm or less, more preferably 0.50 μm or less, further preferably 0.30 μm or less, still more preferably 0.20 μm or less, and still more preferably 0.15 μm or less. The method for producing a toner for developing an electrostatic charge image according to any one of 1> to <48>.
<50> The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (B) is preferably 40% or less, more preferably 35% or less, still more preferably 30% or less, and preferably The method for producing an electrostatic charge image developing toner according to any one of <1> to <49>, which is 5% or more, more preferably 10% or more, and further preferably 15% or more.
<51> In the mixed dispersion containing the resin particles (B) and the release agent particles (WR), the content of the resin particles (B) is preferably 10% by mass or more, more preferably 15% by mass or more. In addition, the method for producing a toner for developing an electrostatic charge image according to any one of <1> to <50>, preferably 40% by mass or less, more preferably 30% by mass or less.
<52> In the mixed dispersion liquid containing the resin particles (B) and the release agent particles (WR), the content of the release agent particles (WR) is preferably 100 parts by mass of the resin particles (B). The electrostatic charge image according to any one of <1> to <51>, which is 2 parts by mass or more, more preferably 5 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less. A method for producing a developing toner.
<53> The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <52>, wherein a flocculant is added in the step (2).
<54> The amount of the flocculant used is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably with respect to 100 parts by mass of the resin constituting the resin particles (A) and the resin particles (B). The method for producing a toner for developing an electrostatic charge image according to <53>, which is 35 parts by mass or less, preferably 1 part by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass or more.
<55> The method for producing a toner for developing an electrostatic charge image according to <53> or <54>, wherein the flocculant is dropped as an aqueous solution.
<56> The concentration of the aqueous solution of the flocculant is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass. % Or less, more preferably 15% by mass or less, The method for producing an electrostatic charge image developing toner according to any one of <53> to <55>.
<57> The volume-median particle size of the agglomerated particles (1) is preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less, and preferably 1 μm or more, more preferably 2 μm or more. Is a method for producing a toner for developing an electrostatic charge image according to any one of <1> to <56>, which is 3 μm or more.
<58> The number of additions of the resin particles (B) is preferably 2 times or more, and is preferably 10 times or less, more preferably 8 times or less, and any one of <1> to <57> A method for producing the toner for developing an electrostatic image according to claim 1.
<59> The mixing ratio (aggregated particles (1) / resin particles (B)) of the agglomerated particles (1) in the dispersion of the agglomerated particles (2) and the resin particles (B) added in the step (2B) is: The mass ratio is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3 The method for producing a toner for developing an electrostatic charge image according to any one of <42> to <58>, which is 0.5 or less.
<60> The mass of the resin particles (B) added in the step (2A) / the mass of the resin particles (B) added in the step (2B) is preferably 50/50 to 95/5, more preferably 55/45. -90/10, More preferably, it is 60 / 40-80 / 20, The manufacturing method of the toner for electrostatic image development in any one of <42>-<59>.
<61> The volume median particle size (D ₅₀ ) of the agglomerated particles (2) is preferably 1 μm or more, more preferably 2 μm or more, still more preferably 3 μm or more, still more preferably 4 μm or more, and preferably The method for producing a toner for developing an electrostatic charge image according to any one of <42> to <60>, wherein the toner is 10 μm or less, more preferably 9 μm or less, still more preferably 8 μm or less, and still more preferably 6 μm or less.

<62> It is preferable that the heating temperature at the time of fusing is a temperature that is not less than the glass transition temperature of the resin constituting the aggregated particles and not more than 100 ° C., more preferably the glass transition temperature of the resin constituting the aggregated particles. The temperature according to any one of <1> to <61>, which is a temperature that is at least 90 ° C and more preferably a temperature that is at least the glass transition temperature of the resin constituting the aggregated particles and at most 85 ° C A method for producing a toner for developing an electrostatic image.
<63> The volume median particle size of the fused particles obtained in the step (3) is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably The method for producing an electrostatic charge image developing toner according to any one of <1> to <62>, wherein the toner is 8 μm or less, more preferably 7 μm or less, and still more preferably 6 μm or less.
<64> The volume median particle size (D ₅₀ ) of the toner is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, even more preferably. Is 7 μm or less, more preferably 6 μm or less, the method for producing a toner for developing an electrostatic charge image according to any one of <1> to <63>.

  Each property value of polyester, resin particles, toner, etc. was measured and evaluated by the following method.

[Acid value of resin]
It measured according to JIS K0070. However, the measurement solvent was a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Softening point of resin and toner]
Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger, and the diameter was 1 mm and the length was 1 mm. Extruded from the nozzle. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.

[Glass transition temperature of resin]
Using a differential scanning calorimeter “Q-20” (manufactured by TA Instruments Japan Co., Ltd.), the temperature was raised to 200 ° C., and the sample cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min was raised. Measurement was performed at a temperature rate of 10 ° C./min. Of the observed peaks, the peak temperature with the maximum peak area was defined as the maximum endothermic peak temperature. The intersection temperature between the extension line of the baseline below the maximum peak temperature of endotherm and the tangent showing the maximum slope from the peak rising portion to the peak apex was defined as the glass transition temperature.

[Melting point of release agent]
Using a differential scanning calorimeter “Q-20” (manufactured by TA Instruments Japan Co., Ltd.), the temperature was raised to 200 ° C., and the sample cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min was raised. The temperature was raised at a temperature rate of 10 ° C./min, and the maximum peak temperature of heat of fusion was taken as the melting point.

[Volume Median Particle Size (D ₅₀ ) and Particle Size Distribution (CV Value) of Resin Particles and Release Agent Particles]
(1) Measuring apparatus: Laser diffraction particle size measuring instrument “LA-920” (manufactured by Horiba, Ltd.)
(2) Measurement conditions: Distilled water was added to the measurement cell, and the volume-median particle size (D ₅₀ ) and the volume average particle size were measured at a temperature at which the absorbance falls within an appropriate range. The CV value (particle size distribution) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Solid content concentration of resin particle and release agent particle dispersion]
Using an infrared moisture meter “FD-230” (manufactured by Kett Science Laboratory), 5 g of a measurement sample was dried at a temperature of 150 ° C. and in a measurement mode 96 (monitoring time 2.5 minutes / variation width 0.05%). The moisture percentage was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (% by mass) = 100-M
M: moisture (%) = [(W−W ₀ ) / W] × 100
W: Sample mass before drying (initial sample mass)
W ₀ : Sample weight after drying (absolute dry weight)

[Volume Median Particle Size (D ₅₀ ) and Particle Size Distribution (CV Value) of Aggregated Particles]
The volume median particle size (D ₅₀ ) of the particles was measured as follows.
・ Measuring machine: "Coulter Multisizer III" (Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
・ Analysis software: “Multisizer III version 3.51” (manufactured by Beckman Coulter)
・ Electrolyte: “Isoton II” (Beckman Coulter, Inc.)
Measurement conditions: 30,000 particles are measured after adjusting the particle size of 30,000 particles to a concentration that can be measured in 20 seconds by adding a sample dispersion containing aggregated particles to 100 mL of the electrolyte. From the particle size distribution, the volume median particle size (D ₅₀ ) and the volume average particle size were determined.
Moreover, CV value (%) was calculated according to the following formula as particle size distribution.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Volume Median Particle Size (D ₅₀ ) and Particle Size Distribution (CV Value) of Toner Particles (Fused Particles)]
The volume median particle size of the toner particles (fused particles) was measured as follows.
The measuring instrument, aperture diameter, analysis software, and electrolyte solution were the same as the volume median particle diameter of the aggregated particles.
Dispersion: Polyoxyethylene lauryl ether “Emulgen 109P” (manufactured by Kao Corporation, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by mass.
-Dispersion condition: 10 mg of a toner measurement sample is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of electrolyte is added, and further dispersed for 1 minute with an ultrasonic disperser. A sample dispersion was prepared.
Measurement conditions: After adding the sample dispersion to 100 mL of the electrolyte solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured. The volume-median particle size (D ₅₀ ) and the volume average particle size were determined from the distribution.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Image density of printed matter]
Using a commercially available printer “Microline 5400” (Oki Data Co., Ltd.) on high quality paper “J paper A4 size” (Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 0.42 to 0.48 mg / cm ^2. A solid image was output to obtain a printed matter.
30 sheets of high-quality paper “Excellent White Paper A4 Size” (Oki Data Co., Ltd.) are laid under the printed material, and the reflected image density of the solid image portion of the output printed material is measured by the colorimeter “SpectroEye” (manufactured by Gretag-Macbeth, (Light emission condition: standard light source D ₅₀ , observation field of view 2 °, density standard DINNB, absolute white standard) The values obtained by measuring any three points on the image were averaged to obtain the image density. The larger the value of the reflected image density, the better the image density.

[Photoreceptor fog]
Toner is mounted on a commercially available printer “Microline 5400” (Oki Data Co., Ltd.), and a white image without image is printed using high quality paper “Excellent White Paper A4 Size” (Oki Data Co., Ltd.), up to half of A4 The machine is stopped at the time of transfer, and a transparent mending tape “Scotch (registered trademark) mending tape 810-3-18” (manufactured by 3M) is applied to the surface of the photoconductor before transfer, and the toner on the surface of the photoconductor is removed. Collect.
A mending tape as a reference and a mending tape obtained by collecting the toner on the photoreceptor are respectively affixed to unused excellent white paper, and a colorimeter “SpectroEye” (manufactured by Gretag-Macbeth, Inc., lighting conditions; CIE L ^* a ^* b ^* is measured using a standard light source D ₅₀ , an observation field of view 2 °, a density reference DINNB, and an absolute white reference). The color difference ΔE = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2 between the mending tape from which the toner on the surface of the photoconductor is collected and the reference is determined, and this value is defined as fog. ΔE indicates that the smaller the value, the smaller the fog.

Production Example 1
(Production of polyester A)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3374 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Put 33 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, 672 g of terephthalic acid, and 10 g of dibutyltin oxide, and raise the temperature to 230 ° C. with stirring in a nitrogen atmosphere. After maintaining for 5 hours, the pressure in the flask was further lowered and maintained at 8.3 kPa for 1 hour. Then, after cooling to 210 ° C. and returning to atmospheric pressure, 696 g of fumaric acid and 0.49 g of tert-butylcatechol were added and maintained at a temperature of 210 ° C. for 5 hours. Polyester A was obtained by maintaining at 3 kPa for 4 hours. Table 1 shows the physical properties of Polyester A.

Production Example 2
(Production of polyester B)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 1750 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, A nitrogen atmosphere containing 1625 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, 1145 g of terephthalic acid, 161 g of dodecenyl succinic anhydride, 480 g of trimellitic anhydride, and 10 g of dibutyltin oxide Under stirring, the temperature was raised to 220 ° C. and maintained for 5 hours. After confirming that the softening point measured in accordance with ASTM D36-86 reached 120 ° C., the reaction was stopped by lowering the temperature. Got. Table 1 shows the physical properties of Polyester B.

[Production of resin particle dispersion]
Production Example 3
(Production of resin particle dispersion A-1)
In a 2 liter stainless steel kettle, 390.0 g of polyester A, 210.0 g of polyester B, 30 g of copper phthalocyanine pigment “ECB-301” (manufactured by Dainichi Seika Kogyo), 15% by weight sodium dodecylbenzenesulfonate aqueous solution “Neopelex” G-15 "(anionic surfactant, Kao Corporation) 40.0 g, polyoxyethylene oleyl ether" Emulgen 430 "(nonionic surfactant, Kao Corporation, HLB: 16.2) 6.0 g, The polyester was melted at 95 ° C. while stirring 278.5 g of 5 mass% potassium hydroxide aqueous solution at 200 r / min (circumferential speed 1.2 m / sec) with a chi-type stirrer. The mixture was held for 2 hours under stirring at 200 r / min (circumferential speed 1.2 m / sec) with a chi-type stirrer. Subsequently, 1222 g of deionized water was added dropwise at 6 g / min while stirring at 200 r / min (circumferential speed 1.2 m / sec) with a chi-type stirrer. The system temperature was maintained at 95 ° C. After dropping, the mixture was cooled to 25 ° C., and 28 g of an oxazoline group-containing polymer aqueous solution “Epocross WS-700” (manufactured by Nippon Shokubai Co., Ltd.) was stirred with a chi-type stirrer at 200 r / min (circumferential speed 1.2 m / sec) After that, the temperature was raised to 95 ° C. and held at 95 ° C. for 1 hour.
After cooling, the resin particle dispersion A-1 was obtained through a 200 mesh (mesh: 105 μm) wire mesh. The volume-average particle size (D ₅₀ ) of the resin particles in the obtained resin particle dispersion A-1 was 0.13 μm, the CV value was 25%, and the solid content concentration was 31% by mass.

Production Example 4
(Production of resin particle dispersion A-2)
In a 2 liter stainless steel kettle, 390.0 g of polyester A, 210.0 g of polyester B, 15% by weight sodium dodecylbenzenesulfonate aqueous solution “Neopelex G-15” (anionic surfactant, manufactured by Kao Corporation) 40.0 g , 6.0 g of polyoxyethylene oleyl ether “Emulgen 430” (nonionic surfactant, manufactured by Kao Corporation, HLB: 16.2) and 278.5 g of 5% by mass potassium hydroxide aqueous solution with a chi-type stirrer While stirring at 200 r / min (circumferential speed 1.2 m / sec), the polyester was melted at 95 ° C. The mixture was held for 2 hours under stirring at 200 r / min (circumferential speed 1.2 m / sec) with a chi-type stirrer. Subsequently, 1222 g of deionized water was added dropwise at 6 g / min while stirring at 200 r / min (circumferential speed 1.2 m / sec) with a chi-type stirrer. The system temperature was maintained at 95 ° C. After dripping, it cooled to 25 degreeC.
After cooling, the resin particle dispersion A-1 was obtained through a 200 mesh (mesh: 105 μm) wire mesh. The resin particles in the obtained resin particle dispersion A-1 had a volume-median particle size (D ₅₀ ) of 0.10 μm, a CV value of 22%, and a solid content concentration of 30% by mass.

[Production of dispersion of release agent particles (W)]
Production Example 5
(Production of release agent particle dispersion W-1)
In a 1 liter beaker, 1.7 g of an oxazoline group-containing polymer aqueous solution “Epocross WS-700” (manufactured by Nippon Shokubai Co., Ltd., nonvolatile content 25 mass%, number average molecular weight 20,000) was dissolved in 200 g of deionized water. Thereafter, 5 g of carnauba wax “Carnauba wax No. 1” (manufactured by Hiroyuki Kato, melting point 83 ° C., acid value 5 mg KOH / g) and 45 g of paraffin wax “HNP-9” (manufactured by Nippon Seiwa Co., Ltd., melting point 75 ° C.) Was added and dispersed. The dispersion was subjected to a dispersion treatment with an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusho) for 30 minutes while maintaining the temperature at 90 to 95 ° C., and then cooled to room temperature. After cooling, after passing through a 200 mesh (mesh: 105 μm) wire mesh, deionized water was added to adjust the solid content concentration to 20% by mass to obtain a release agent particle dispersion W-1.

Production Example 6
(Production of release agent particle dispersion W-2)
In Production Example 5 (Production of W-1), 1.7 g of an aqueous solution of oxazoline group-containing polymer “Epocross WS-700” was added to an aqueous solution of oxazoline group-containing polymer “Epocross WS-500” (manufactured by Nippon Shokubai Co., Ltd., 40 mass% nonvolatile content). The number average molecular weight 20,000) was changed to 1.1 g in the same manner to obtain a release agent particle dispersion W-2.

Production Example 7
(Production of release agent particle dispersion W-3)
In Production Example 5 (Production of W-1), 1.7 g of an aqueous solution of oxazoline group-containing polymer “Epocross WS-700” was added to an aqueous solution of oxazoline group-containing polymer “Epocross WS-300” (produced by Nippon Shokubai Co., Ltd., 10 mass% nonvolatile content). The number average molecular weight 15,000) was changed to 4.3 g in the same manner to obtain a release agent particle dispersion W-3.

Production Example 8
(Production of release agent particle dispersion W-4)
In the same manner as in Production Example 5 (Production of W-1), the release agent was changed except that the paraffin wax “HNP-9” was changed to paraffin wax “HNP-11” (manufactured by Nippon Seiwa Co., Ltd., melting point 68 ° C.). A particle dispersion W-4 was obtained.

Production Example 9
(Production of release agent particle dispersion W-5)
In Production Example 5 (Production of W-1), when the oxazoline group-containing polymer aqueous solution was not added, the release agent could not be dispersed and solidified, so that no dispersion was obtained.

Production Example 10
(Production of release agent particle dispersion W-6)
In Production Example 5 (Production of W-1), 1.7 g of the oxazoline group-containing polymer aqueous solution “Epocross WS-700” was changed to 0.43 g of 2,2′-bis (2-oxazoline). The solution could not be dispersed and solidified, so a dispersion could not be obtained.

Production Example 11
(Production of release agent particle dispersion W-7)
In Production Example 5 (Production of W-1), 1.7 g of an oxazoline group-containing polymer aqueous solution “Epocross WS-700” was dissolved in 10% polyvinyl alcohol aqueous solution in which polyvinyl alcohol (degree of polymerization 1500) was dissolved in deionized water. Except for changing to 3 g, release agent particle dispersion W-7 was obtained in the same manner.

Production Example 12
(Production of release agent particle dispersion W-8)
In a 1 liter beaker, 225 g of deionized water, 5 g of carnauba wax “Carnauba Wax No. 1” (manufactured by Hiroyuki Kato, melting point 83 ° C., acid value 5 mg KOH / g), and paraffin wax “HNP-9” (Japan) 45 g (manufactured by Seiwa Co., Ltd., melting point: 75 ° C.) was added and melted while maintaining the temperature at 90 to 95 ° C. to obtain a molten mixture in which carnauba wax and paraffin wax were fused together. Next, 1.7 g of an oxazoline group-containing polymer aqueous solution “Epocross WS-700” (manufactured by Nippon Shokubai Co., Ltd., non-volatile content 25 mass%, number average molecular weight 20,000) was added and the temperature was maintained at 90 to 95 ° C. Dispersion treatment was performed for 15 minutes using an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusho). To this was added 9.0 g of a vinyl chloride resin emulsion “Vinyl Blanc 701” (manufactured by Nissin Chemical Industry Co., Ltd., solid content 30% by mass, acid value 46 mg KOH / g, glass transition temperature 70 ° C., average particle size 30 nm). The mixture was dispersed for 15 minutes with a sonic homogenizer and then cooled to room temperature. After cooling, after passing through a 200 mesh (mesh: 105 μm) wire mesh, deionized water was added to adjust the solid content concentration to 20% by mass to obtain a release agent particle dispersion W-8.

Production Example 13
(Production of release agent particle dispersion W-9)
In a 1 liter beaker, after dissolving 3.3 g of 15 mass% sodium dodecylbenzenesulfonate aqueous solution “Neopelex G-15” (anionic surfactant, manufactured by Kao Corporation) in 200 g of deionized water, 5 g of Uba wax “Carnauba Wax No. 1” (manufactured by Kato Yoko Co., Ltd., melting point 83 ° C., acid value 5 mg KOH / g) and paraffin wax “HNP-9” (Nippon Seiwa Co., Ltd., melting point 75 ° C.) 45 g were added. , Dispersed. The dispersion was subjected to a dispersion treatment with an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusho) for 30 minutes while maintaining the temperature at 90 to 95 ° C., and then cooled to room temperature. After cooling, after passing through a 200 mesh (mesh: 105 μm) wire mesh, deionized water was added to adjust the solid content concentration to 20 mass% to obtain a release agent particle dispersion W-9.
Table 3 shows the volume median particle size of the release agent particles in the obtained release agent particle dispersions W-1 to W-9.

[Production of dispersion of release agent particles (WR)]
Production Example 14
(Production of release agent particle dispersion WR-1)
250.0 g of the release agent particle dispersion W-1 and 31.3 g of the resin particle dispersion A-2 were placed in a 1 liter beaker, heated to 95 ° C. with stirring by a stirrer, and 95 ° C. After holding for 30 minutes, it was cooled. If necessary, deionized water was added to adjust the solid content concentration to 20% by mass to obtain a release agent particle dispersion WR-1.

Production Example 15
(Production of release agent particle dispersion WR-2)
In Production Example 14 (production of WR-1), 31.3 g of the resin particle dispersion A-2 was added to a vinyl chloride resin emulsion “Vinyl Blanc 701” (manufactured by Nissin Chemical Industry Co., Ltd., solid content: 30% by mass, acid value: 46 mgKOH) / G, glass transition temperature 70 ° C., average particle size 30 nm) Except for changing to 29.3 g, release agent particle dispersion WR-2 was obtained.

Production Example 16
(Production of release agent particle dispersion WR-3)
In Production Example 14 (Production of WR-1), 31.3 g of the resin particle dispersion A-2 was mixed with a commercially available styrene-acrylic copolymer resin emulsion “EF-005” (manufactured by Nippon Shokubai Co., Ltd., 42 mass% solid content). The release agent particle dispersion WR-3 was obtained in the same manner except that the acid value was changed to 41.0 g, acid value 20 mgKOH / g, glass transition temperature 50 ° C., average particle size 0.15 μm.

Production Examples 17-21
(Production of release agent particle dispersion WR-4 to 8)
In the same manner as in Production Example 14 (Manufacture of WR-1), except that the dispersion of the release agent particles (W) was changed to that shown in Table 4, a dispersion of the release agent particles (WR) was obtained. It was.
Table 4 shows the volume median particle size of the release agent particles in the obtained release agent particle dispersions WR-1 to WR-8.

Example 1
(Preparation of Toner 1)
Resin particle dispersion A-1 250 g, deionized water 58 g, and release agent particle dispersion WR-1 (release agent particle dispersion with resin particles attached) 41 g were equipped with a dehydration tube, a stirrer, and a thermocouple. They were placed in four 2-liter flasks and mixed at 25 ° C. Next, 25% aqueous ammonia was added to an aqueous solution in which 27.4 g of ammonium sulfate was dissolved in 331.9 g of deionized water and adjusted to pH 8.0 by stirring with a chi-type stirrer. The solution was added dropwise at 30 ° C. over 30 minutes. Next, the obtained mixed solution was heated to 60 ° C. and held at 60 ° C. to form aggregated particles having a volume median particle size (D ₅₀ ) of 4.7 μm.
Subsequently, a mixed liquid obtained by mixing 75 g of resin particle dispersion A-1 and 17.4 g of deionized water is dropped over 180 minutes, and an aggregated particle dispersion having a volume median particle size (D ₅₀ ) of 5.1 μm is obtained. Obtained.
The obtained aggregated particle dispersion and 4110 g of deionized water were placed in a 5 liter flask, heated to 80 ° C. over 2 hours and held for 2 hours, and then the volume median particle size (D ₅₀ ) was 5.0 μm fused particles were obtained. Then, it cooled to 25 degreeC.
The resulting dispersion containing the fused particles is separated by solid filtration by suction filtration, washed with deionized water, and dried at 33 ° C. with a vacuum low-temperature dryer (ADVANTEC Toyo Co., Ltd., model name: DRV622DA). To obtain toner particles. With respect to 100 parts by mass of the toner particles, 2.5 parts by mass of hydrophobic silica “lRY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle size 0.04 μm), hydrophobic silica “Cabo Seal TS720” (manufactured by Cabot, number average) 1.0 part by mass of particle size 0.012 μm) and 0.8 part by mass of organic fine particles “Finesphere P2000” (manufactured by Nippon Paint Co., Ltd., number average particle size 0.5 μm) were externally treated with a Henschel mixer, and 150 mesh Fine particles that passed through the sieve were used as cyan toner.
Table 5 shows the types and physical properties of the release agent particle dispersion and resin particle dispersion used, and the physical properties and evaluation results of the obtained toner.

Examples 2-6, Comparative Examples 1-4
(Production of toners 2 to 10)
A toner was obtained in the same manner as in Example 1 except that the composite particle dispersion was changed to that shown in Table 5.
Table 5 shows the types and physical properties of the release agent particle dispersion and resin particle dispersion used, and the physical properties and evaluation results of the obtained toner.

  From Table 5, it can be seen that the toners of Examples 1 to 6 are all excellent in the image density of the printed matter and the suppression of the photoreceptor fog as compared with the toners of Comparative Examples 1 to 4.

  According to the production method of the present invention, the release and release of the release agent are suppressed, and the image density and fog are excellently suppressed. Therefore, the method is suitably used for electrophotography, electrostatic recording, electrostatic printing, and the like. A toner for developing an electrostatic image can be obtained.

Claims (8)

A method for producing a toner for developing an electrostatic charge image, comprising the following steps (1) to (3).
Step (1): Step of obtaining a dispersion of release agent particles (WR) including the following steps (1A) and (1B) Step (1A): Release agent and polymer containing oxazoline group in aqueous medium And obtaining a dispersion of release agent particles (W) having a volume median particle size of 0.05 μm or more and 1.5 μm or less Step (1B): Mold release obtained in Step (1A) The agent particles (W) and the resin particles (A) are at least the lower of the glass transition temperature of the resin constituting the resin particles (A) or the melting point of the release agent constituting the release agent particles (W). Step of obtaining a dispersion of release agent particles (WR) in which the resin particles (A) adhere to the release agent particles (W) Step (2): Release agent particles obtained in Step (1) The dispersion of (WR) and the dispersion of resin particles (B) containing polyester are mixed and aggregated to obtain aggregated particles. Step Step (3): A step of fusing the aggregated particles obtained in step (2) to obtain fused particles.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the temperature of the dispersion treatment in the step (1A) is equal to or higher than the melting point of the release agent. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the volume median particle size (D ₅₀ ) of the resin particles (A) in the step (1B) is 0.01 μm or more and 1.0 μm or less.   The mass ratio of the mass of the resin particles (A) to the mass of the release agent particles (W) in the step (1B) (the mass of the resin particles (A) / the mass of the release agent particles (W)) is 1/100 to 50. The method for producing a toner for developing an electrostatic charge image according to claim 1, which is / 100.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 4, wherein the resin constituting the resin particles (A) contains polyester.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 5, wherein the release agent comprises an ester wax having an acid value of 0.5 mgKOH / g or more and 20 mgKOH / g or less.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the resin constituting the resin particles (A) has a hydrophilic group.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 7, wherein an acid value of a resin constituting the resin particles (A) is 6 mgKOH / g or more and 60 mgKOH / g or less.