JP6373048B2 - Aqueous dispersion of binder resin composition for toner - Google Patents

Description

  The present invention relates to an aqueous dispersion of a binder resin composition for a toner used for developing a latent image formed in an electrophotographic method, a method for producing the same, and an electrophotographic toner obtained using the aqueous dispersion.

  In the field of electrophotography, with the development of electrophotographic systems, development of toner for electrophotography corresponding to high image quality is required.

  Corresponding to high image quality, a method of obtaining a toner having a narrow particle size distribution and a small particle size is obtained by aggregating and fusing fine resin particles in an aqueous medium to obtain a toner. A toner is manufactured by an aggregation method or an aggregation fusion method.

For example, Patent Document 1 discloses that a polyester resin is graft-copolymerized with a polymerizable vinyl monomer for the purpose of obtaining a toner capable of obtaining excellent storage stability and excellent crush resistance while achieving low-temperature fixability. Fine particles containing the graft copolymer and wax obtained by the above, or the fine particles containing the graft copolymer obtained by graft copolymerization of a polymerizable vinyl monomer to the polyester resin and the fine particles containing the wax are agglomerated. A step of forming aggregated particles by
An addition step of adding a wax stabilizer to the aqueous medium in which the aggregated particles are formed; and
There is described a method for producing a toner for developing an electrostatic charge image, which comprises a step of heating an aqueous medium to which the wax stabilizer is added.

JP 2012-088345 A

  Polyester resins and waxes are very different in polarity and are difficult to mix. In particular, in the production of toner by the emulsion aggregation method in which shearing force cannot be applied, poor wax dispersion becomes remarkable. In the method described in Patent Document 1, the dispersion of the wax in the resin is still not sufficient.

  The present invention provides an aqueous dispersion of a binder resin composition for a toner capable of obtaining a toner excellent in filming resistance, low-temperature fixability and hot offset resistance, a method for producing the same, and an aqueous dispersion obtained using the aqueous dispersion. The present invention relates to an electrophotographic toner.

  The present inventor considered that the factors affecting filming resistance, low-temperature fixability, and hot offset resistance are the dispersion state of the wax, and as a result of examination, the wax was an ester wax and / or a hydrocarbon wax. It is obtained by agglomerating an aqueous dispersion of a binder resin in which (A) is finely dispersed in a polyester resin containing a structural unit derived from a hydrocarbon wax (B) having a specific hydroxyl group and / or carboxy group. The present inventors have found that the toner can solve the above problems and have completed the present invention.

The present invention
[1] An aqueous dispersion of a binder resin composition for toner comprising a polyester resin and a wax (A),
The wax (A) is at least one selected from the group consisting of an ester wax and a hydrocarbon wax, and the content of the wax (A) is 3 to 50 mass with respect to 100 mass parts of the polyester resin. Department,
The polyester-based resin has a component part derived from a hydrocarbon wax (B) having a hydroxyl group and / or a carboxy group having a melting point of 60 to 110 ° C. and a molecular weight of 400 or more,
An aqueous dispersion of a binder resin composition for toner,
[2] Step 1: Polyester resin raw material monomer is polycondensed in the presence of hydrocarbon wax (B) to obtain a polyester resin, and Step 2: Polyester resin obtained in Step 1 is added to an aqueous medium. In which a wax (A) is added in Step 1 and / or Step 2, wherein the wax (A) is added in Step 1 and / or Step 2. And a method for producing an aqueous dispersion of the binder resin composition for toner according to [3], and [3] Step A: Aggregated particles obtained by subjecting the aqueous dispersion of the binder resin composition for toner according to [1] to an aggregation step. The present invention relates to an electrophotographic toner obtained by a method comprising a step of obtaining a water-based dispersion of, and Step C: a step of fusing the aggregated particles.

  The electrophotographic toner obtained using the aqueous dispersion of the binder resin composition for toner of the present invention exhibits excellent effects in filming resistance, low-temperature fixability and hot offset resistance.

  The aqueous dispersion of the binder resin composition for toner of the present invention includes a polyester resin and a wax (A), and the wax (A) is at least one selected from the group consisting of an ester wax and a hydrocarbon wax. The polyester-based resin has a component derived from a hydrocarbon wax (B) having a hydroxyl group and / or a carboxy group having a specific melting point and molecular weight.

  The reason why the electrostatic charge image developing toner obtained using the aqueous dispersion of the binder resin composition of the present invention is excellent in filming resistance, low-temperature fixability and hot offset resistance is not clear. I think so.

  In the aqueous dispersion of the binder resin composition of the present invention, the hydrocarbon wax (B) bonded to the polyester resin can enhance the dispersibility of the wax (A) and can be included in the resin. The exposure of the wax (A) to the resin surface is suppressed, and the aqueous dispersion is agglomerated and fused to obtain a toner, whereby the finely dispersed state of the wax (A) in the binder resin composition is reduced. While maintaining, the exposure of the wax (A) to the surface of the toner particles can also be suppressed, so that the obtained toner is considered to be excellent in filming resistance and low-temperature fixability.

  Further, at the time of fixing the toner, it is considered that the wax (A) is finely dispersed in the resin, and the wax (A) bleeds out to uniformly cover the image surface. .

  The polyester resin can be obtained by polycondensation of raw material monomers in the presence of the hydrocarbon wax (B).

  As a raw material monomer for the polyester resin, an alcohol component and a carboxylic acid component are used.

  Examples of the alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, and the like (I ):

(In the formula, RO is an alkylene oxide, R is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers indicating the average added mole number of alkylene oxide, and the sum of x and y is 1 to 16) (Preferably 1.5 to 5.0)
Divalent alcohols such as alkylene oxide adducts of bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A and the like A trihydric or higher polyhydric alcohol such as sorbitol, pentaerythritol, glycerin, trimethylolpropane and the like;

  The alkylene oxide adduct of bisphenol A represented by the formula (I) has a high affinity with the wax (A) and can finely disperse the wax (A), so that it is preferable as an alcohol component. The content of the alkylene oxide adduct of bisphenol A represented by the formula (I) is preferably 80 mol% or more from the viewpoint of improving filming resistance, hot offset resistance and low temperature fixability in the alcohol component, 90 mol% or more is more preferable, 95 mol% or more is more preferable, substantially 100 mol% is further more preferable, and 100 mol% is further more preferable.

  On the other hand, in the carboxylic acid component, divalent carboxylic acid compounds include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutacone An aliphatic dicarboxylic acid such as succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms such as acid, succinic acid, adipic acid, dodecenyl succinic acid, octyl succinic acid; Examples include anhydrides and alkyl (C1-3) esters of these acids.

  The aromatic dicarboxylic acid compound has high affinity with the wax (A), can finely disperse the wax (A), is preferred as the carboxylic acid component, more preferably terephthalic acid and isophthalic acid, and even more preferably terephthalic acid. .

  The content of the aromatic dicarboxylic acid compound is preferably 50 mol% or more, more preferably 60 mol% or more, from the viewpoint of improving filming resistance, hot offset resistance and low-temperature fixability in the carboxylic acid component. More preferably, it is at least mol%. Further, from the viewpoint of low-temperature fixability of the toner, 90 mol% or less is preferable, and 80 mol% or less is more preferable.

  Moreover, from the viewpoint of enhancing the emulsifying property of the resin and suppressing the exposure of the wax (A) to the resin surface, an aliphatic dicarboxylic acid compound is preferable, and fumaric acid is more preferable.

  The content of the aliphatic dicarboxylic acid compound is preferably 10 mol% or more, more preferably 20 mol% or more in the carboxylic acid component, from the viewpoint of heat-resistant storage stability, durability and low-temperature fixability of the toner. Moreover, 80 mol% or less is preferable, 70 mol% or less is more preferable, and 60 mol% or less is more preferable.

  The carboxylic acid component preferably contains both an aromatic dicarboxylic acid compound and an aliphatic dicarboxylic acid compound, and the molar ratio of the aliphatic dicarboxylic acid compound (aliphatic dicarboxylic acid compound / aromatic dicarboxylic acid compound) is From the viewpoint of heat-resistant storage stability, durability and low-temperature fixability of the toner, it is preferably 20/80 to 80/20, more preferably 50/50 to 80/20, and further preferably 60/40 to 80/20. .

  The total amount of the aliphatic dicarboxylic acid compound and the aromatic dicarboxylic acid compound in the carboxylic acid component is preferably 85 mol% or more, more preferably 90 mol%, from the viewpoint of heat resistant storage stability, durability, and low-temperature fixability of the toner. That's it.

  Examples of the trivalent or higher polyvalent carboxylic acid compound include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid and acid anhydrides thereof, lower alkyl (C1-C3) ester etc. are mentioned.

  The content of the trivalent or higher polyvalent carboxylic acid compound is preferably 1 mol% or more, and more preferably 3 mol% or more from the viewpoint of the durability of the toner in the carboxylic acid component. Further, from the viewpoint of low-temperature fixability of the toner, it is preferably 15 mol% or less, and more preferably 10 mol% or less.

  The alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate.

  In addition, in this invention, polyester-type resin contains polyester modified | denatured to such an extent that the characteristic is not impaired substantially besides polyester resin. Examples of the modified polyester include a urethane-modified polyester in which the polyester is modified with a urethane bond, an epoxy-modified polyester in which the polyester is modified with an epoxy bond, and two or more resin components including a polyester component and an addition polymerization resin component. And composite resins having

  The wax (B) is a hydrocarbon wax having a hydroxyl group and / or a carboxy group.

  In the present invention, the wax (B) may have either one of a hydroxyl group and a carboxy group, or may have both a hydroxyl group and a carboxy group. From the viewpoint of high humidity storage stability, a hydrocarbon wax having a hydroxyl group and a carboxy group is preferred. Hereinafter, the “hydrocarbon wax having a hydroxyl group” includes a wax having a carboxy group in addition to a hydroxyl group, but having a hydroxyl value based on a hydroxyl group higher than an acid value based on the carboxy group. The “hydrocarbon wax having a carboxy group” includes a wax having a hydroxyl group in addition to the carboxy group, but having an acid value based on the carboxy group higher than the hydroxyl value based on the hydroxyl group.

  A wax having a hydroxyl group and a wax having a carboxy group may be used at the same time, but a wax having a hydroxyl group is preferred from the viewpoint of polycondensation reactivity.

  The hydrocarbon wax having a hydroxyl group is obtained by modifying a hydrocarbon wax such as paraffin wax, Fischer-Tropsch wax, microcrystalline wax, polyethylene wax, etc. by oxidation treatment. Examples of the oxidation treatment method include the methods described in JP-A Nos. 62-79267 and 2010-197979. Specifically, there is a method of oxidizing a hydrocarbon wax by liquid phase oxidation with a gas containing oxygen in the presence of boric acid.

  Examples of commercially available hydrocarbon waxes having a hydroxyl group include Unilin 700, Unilin 425, Unilin 550 (manufactured by Baker Petrolite), Paracoll 6420, Paracol 6470, Paracol 6490 (manufactured by Nippon Seiwa Co., Ltd.), and the like.

  The hydroxyl value of the hydrocarbon wax having a hydroxyl group is preferably 40 mgKOH / g or more, more preferably 55 mgKOH / g or more, and further preferably 65 mgKOH / g or more, from the viewpoint of low-temperature fixability and high-humidity storage stability of the toner. Further, from the viewpoint of heat resistant storage stability of the toner, 180 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, 120 mgKOH / g or less is more preferable, and 110 mgKOH / g or less is more preferable.

  Examples of the hydrocarbon wax having a carboxy group include an acid-modified wax, which can be obtained by introducing a carboxy group into a wax such as polyethylene wax or polypropylene wax.

  Examples of the acid modification method include the methods described in JP-A-2006-328388 and JP-A-2007-84787. Specifically, introducing a carboxyl group into a hydrocarbon wax melt by adding an organic peroxide compound (reaction initiator) such as DCP (dicumyl peroxide) and a carboxylic acid compound to cause a reaction. Can do.

  Specific examples of the hydrocarbon wax used as a reaction raw material include paraffin wax, Fischer-Tropsch wax, olefin, microcrystalline wax, polyethylene wax and the like, and paraffin wax and Fischer-Tropsch wax are preferable. Examples of commercially available paraffin waxes and Fischer-Tropsch waxes used as reaction raw materials include HNP-11, HNP-9, HNP-10, FT-0070, HNP-51, and FNP-0090 manufactured by Nippon Seiwa.

  Examples of the hydrocarbon wax having a carboxy group include high wax 1105A (maleic anhydride-modified ethylene / propylene copolymer, manufactured by Mitsui Chemicals, Inc.).

  The acid value of the hydrocarbon wax having a carboxy group is preferably 40 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 55 mgKOH / g or more, from the viewpoint of low-temperature fixability and high-humidity storage stability of the toner. Further, from the viewpoint of heat resistant storage stability of the toner, 180 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, 120 mgKOH / g or less is more preferable, and 110 mgKOH / g or less is more preferable.

  The sum of the acid value and the hydroxyl value of the hydrocarbon wax (B) increases the reactivity between the polyester resin raw material monomer and the hydrocarbon wax (B), increases the dispersibility of the wax (A), and prevents filming. From the viewpoint of excellent hot offset resistance and low-temperature fixability, preferably 40 mgKOH / g or more, preferably 50 mgKOH / g or more, more preferably 60 mgKOH / g or more, more preferably 70 mgKOH / g or more, 90 mgKOH / g or more Is more preferable. Moreover, 200 mgKOH / g or less is preferable and 180 mgKOH / g or less is more preferable from the viewpoint of improving affinity with wax (A), improving dispersibility, and being excellent in filming resistance, hot offset resistance and low-temperature fixability. Preferably, it is 160 mgKOH / g or less, more preferably 140 mgKOH / g or less, and further preferably 130 mgKOH / g or less.

  The melting point of the hydrocarbon wax (B) is 60 ° C. or higher, preferably 65 ° C. or higher, more preferably 70 ° C. or higher, and 72 ° C. or higher from the viewpoints of filming resistance, hot offset resistance and low-temperature fixability. Further preferred. Further, from the viewpoint of improving filming resistance, hot offset resistance and low-temperature fixability by improving the emulsifiability of the polyester-based resin and encapsulating the wax (A) in the binder resin, the temperature is 110 ° C. or less. Yes, it is preferably 105 ° C or lower, more preferably 90 ° C or lower, and further preferably 80 ° C or lower.

  The molecular weight of the hydrocarbon wax (B) is 400 or more from the viewpoint of excellent filming resistance, hot offset resistance and low temperature fixability by finely dispersing and stabilizing the wax (A) in the resin. 500 or more, more preferably 600 or more, and even more preferably 720 or more. Further, from the same viewpoint, 3000 or less is preferable, 2500 or less is more preferable, 2000 or less is further preferable, 1500 or less is further preferable, and 1000 or less is more preferable.

  The temperature during the polycondensation reaction of the alcohol component and the carboxylic acid component is preferably 200 ° C. or higher, more preferably 225 ° C. or higher, from the viewpoint of reactivity. Further, from the viewpoint of thermal decomposability, 250 ° C. or lower is preferable. The temperature during the polycondensation reaction is preferably 200 to 250 ° C, more preferably 225 to 250 ° C.

The polycondensation reaction may be performed in the presence of an esterification catalyst, an esterification cocatalyst, a polymerization inhibitor, or the like, if necessary.
Examples of esterification catalysts include tin catalysts and titanium catalysts. Examples of the tin catalyst include dibutyltin oxide and tin (II) 2-ethylhexanoate. From the viewpoints of reactivity, molecular weight adjustment and resin physical property adjustment, Sn such as tin (II) 2-ethylhexanoate is used. Tin (II) compounds having no —C bond are preferred. Examples of the titanium catalyst include titanium diisopropylate bistriethanolamate. The amount of the esterification catalyst used is preferably 0.01 to 1.5 parts by mass, more preferably 0.1 to 1.0 part by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.
Examples of the esterification promoter include gallic acid. The amount of the esterification cocatalyst used is preferably 0.001 to 0.5 parts by mass, more preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.
Examples of the polymerization inhibitor include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 to 0.5 parts by mass and more preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

The amount of the component derived from the hydrocarbon wax (B) contained in the polyester resin is stabilized by finely dispersing the wax (A) in the polyester resin and stabilizing it in the binder resin composition. From the viewpoint of excellent heat resistance, hot offset resistance and low-temperature fixability, it is 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 7% by mass or more. Further, from the viewpoint of suppressing a decrease in glass transition temperature and excellent in filming resistance, hot offset resistance and low-temperature fixability, it is 20% by mass or less, preferably 15% by mass or less, and more preferably 12% by mass or less. .
Therefore, the amount of the component derived from the hydrocarbon wax (B) contained in the polyester resin is 1 part by mass or more, preferably 3 parts by mass or more, from the above viewpoint, in 100 parts by mass of the polyester resin. More preferred is at least 7 parts by mass, still more preferred is at least 7 parts by mass, is at most 20 parts by mass, is preferably at most 15 parts by mass, and is more preferably at most 12 parts by mass.

  The amount of the hydrocarbon wax (B) can be adjusted by the amount used for the polycondensation reaction, and the amount of the hydrocarbon wax (B) used is 100 parts by weight of the raw material monomer of the polyester resin. In view of the above, it is 1 part by mass or more, preferably 3 parts by mass or more, more preferably 5 parts by mass or more, more preferably 7 parts by mass or more, 20 parts by mass or less, preferably 15 parts by mass or less, 12 parts by mass Part or less is more preferable.

  The reaction rate of the hydrocarbon wax (B) is preferably 70% or more, more preferably 90% or more, from the viewpoint of excellent filming resistance, hot offset resistance and low-temperature fixability. The reaction rate of the wax can be calculated from the endothermic amount of the unreacted wax part, as will be described later. Since the unreacted hydrocarbon wax also functions as a release agent, it may remain in the polyester resin.

The structural site derived from the hydrocarbon wax (B) contained in the polyester-based resin is a site where the wax is ester-bonded, and the amount thereof is, for example, nuclear magnetic resonance spectroscopy using the measurement nucleus as a proton. Measured by ( ¹ H-NMR), and can be calculated from the integrated value of peaks characteristic of polyester and hydrocarbon wax.

  The wax (A) is at least one selected from the group consisting of ester wax and hydrocarbon wax.

  The ester wax refers to a wax having an ester group, and includes natural ester wax and synthetic ester wax. From the viewpoint of improving the heat resistant storage stability of the toner, natural ester wax is preferred.

  Examples of the natural ester wax include carnauba wax, rice wax, and candelilla wax. Examples of the synthetic ester wax include montan ester wax, but the toner of the present invention may be any one. In the present invention, carnauba wax is preferred from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner.

  Synthetic ester wax is an ester compound obtained by reacting carboxylic acid and alcohol.

  Examples of the hydrocarbon wax include hydrocarbon waxes such as low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax, and oxides thereof. Among these, low molecular weight polypropylene and paraffin wax are preferable from the viewpoint of improving the high temperature offset resistance of the toner. Furthermore, paraffin wax is more preferable from the viewpoint of improving the low-temperature fixability of the toner.

  The melting point of the wax (A) is preferably 50 ° C. or higher, and more preferably 60 ° C. or higher, from the viewpoint of hot offset resistance of the toner. Further, from the viewpoint of low-temperature fixability of the toner, 130 ° C. or lower is preferable, and 120 ° C. or lower is more preferable.

  The content of the wax (A) improves the releasability and is excellent in hot offset resistance and low-temperature fixability with respect to 100 parts by mass of the polyester resin (including the structural unit derived from the hydrocarbon wax (B)). From the viewpoint, 3 parts by mass or more is preferable, 5 parts by mass or more is more preferable, and 7 parts by mass or more is more preferable. Further, from the viewpoint of filming resistance and hot offset resistance, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, further preferably 30 parts by mass or less, and further preferably 20 parts by mass or less.

  The mass ratio of wax (A) to hydrocarbon wax (B) (the amount of wax (A) relative to 100 parts by mass of polyester resin / the amount derived from hydrocarbon wax (B) in 100 parts by mass of polyester resin) From the viewpoint of improving the filming resistance, hot offset resistance and low temperature fixability according to (A), 0.2 or more is preferable, 0.5 or more is more preferable, and 0.7 or more is more preferable. Further, from the viewpoint of improving the dispersibility of the wax (A) and improving the filming resistance and hot offset resistance, it is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, and further preferably 5 or less. 3 or less is more preferable.

  The binder resin composition for toner may be obtained by mixing a polyester resin and a wax (A). However, in the present invention, the wax (A) is more finely dispersed in the binder resin composition. From the viewpoint of improving filming resistance, hot offset resistance and low-temperature fixability, in the production of the polyester-based resin, a resin composition obtained using wax (A), that is, wax (A) and carbonization A resin composition obtained by polymerizing a raw material monomer of a polyester resin in the presence of the hydrogen wax (B) is preferable.

  The softening point of the binder resin composition is preferably 80 ° C. or higher, and more preferably 90 ° C. or higher, from the viewpoint of toner storage stability. Further, from the viewpoint of low-temperature fixability of the toner, 170 ° C. or lower is preferable, 150 ° C. or lower is more preferable, and 130 ° C. or lower is further preferable. When the polyester resin is composed of two or more kinds of polyesters, it is preferable that the weighted average value is within the above range.

  The glass transition temperature of the binder resin composition is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, from the viewpoint of toner storage stability. Further, from the viewpoint of low-temperature fixability of the toner, it is preferably 70 ° C. or lower, more preferably 60 ° C. or lower, and further preferably 50 ° C. or lower.

  The acid value of the binder resin composition is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, from the viewpoint of low-temperature fixability of the toner. Further, from the viewpoint of toner storage stability, it is preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, and more preferably 20 mgKOH / g or less.

The aqueous dispersion of the binder resin composition of the present invention is preferably a method in which the aqueous dispersion of the present invention is obtained by adding the binder resin to an aqueous medium and performing phase inversion emulsification. That is, the method for producing an aqueous dispersion of the binder resin composition of the present invention is preferably a method including the following Step 1 and Step 2, and the wax (A) is added in Step 1 and / or Step 2. Is preferred.
Step 1: Polyester resin raw material monomers are polycondensed in the presence of hydrocarbon wax (B) to obtain a polyester resin Step 2: An aqueous medium is added to the polyester resin obtained in Step 1, Phase emulsification process

  Step 1 is a process for producing the polyester resin. When the wax (A) is used, the raw material monomer of the polyester resin is polycondensed in the presence of the wax (A) and the hydrocarbon wax (B). The amount of wax (A) and hydrocarbon wax (B) used is as described above. The obtained polyester resin is subjected to Step 2 as a binder resin composition.

  Step 2 is a step in which an aqueous medium is added to the polyester resin obtained in Step 1 for phase inversion emulsification. A surfactant may be added as necessary. By phase inversion emulsification, the wax (A) can be more finely dispersed, and the filming resistance, hot offset resistance and low-temperature fixability can be further improved.

  In the phase inversion emulsification step, by adding an aqueous medium to the polyester resin, first, the W / O phase is formed, and then the phase is inverted to the O / W phase. Whether or not phase inversion has occurred can be confirmed, for example, by visual observation or electrical conductivity.

  The phase inversion step can be adjusted by the addition rate and amount of the aqueous medium as described later.

  In step 2, the polyester resin preferably contains at least one of an organic solvent and a neutralizing agent, more preferably contains a neutralizing agent, and further preferably contains an organic solvent and a neutralizing agent. Moreover, you may add surfactant as needed.

  Specific examples of the organic solvent from the viewpoint of dissolving the polyester resin include alcohol solvents such as isopropanol and isobutanol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone; ethers such as dibutyl ether and dioxane. System solvents: Examples include acetate solvents such as ethyl acetate and isopropyl acetate. Among these, ketone solvents are preferable, and methyl ethyl ketone is more preferable.

  The mass ratio of the organic solvent to the polyester resin (organic solvent / polyester resin) is preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and preferably 5 or less, more preferably 1.5. Hereinafter, it is more preferably 1 or less, further preferably 0.8 or less, and further preferably 0.6 or less.

  Examples of the neutralizing agent used in the present invention include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonia; organics such as trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine, and tributylamine. A base.

The degree of neutralization of the polyester resin by the neutralizing agent is preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and still more preferably 95 mol%. % Or more, more preferably 99 mol% or more, and preferably 150 mol% or less. In addition, the neutralization degree (mol%) of resin can be calculated | required by a following formula.
Degree of neutralization = {[mass of neutralizer (g) / equivalent of neutralizer] / [[acid value of resin (mgKOH / g) × mass of resin (g)] / (56 × 1000)]} × 100

  As the aqueous medium, those mainly containing water are preferable. The content of water is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and further preferably 100% by mass from the viewpoint of improving the emulsion stability of the resin in the aqueous medium. . The water is preferably deionized water or distilled water.

  Examples of components other than water include organic solvents that dissolve in water, such as methanol, ethanol, acetone; and cyclic ethers such as tetrahydrofuran.

  The temperature at which the aqueous medium is added is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, from the viewpoint of improving the emulsion stability of the resin. Further, it is preferably 75 ° C. or lower, more preferably 70 ° C. or lower, further preferably 65 ° C. or lower, and further preferably 60 ° C. or lower.

  From the viewpoint of obtaining resin composition particles having a small particle size, the addition rate of the aqueous medium is preferably 0.1 parts by mass / 100 parts by mass of the binder resin composition or the polyester resin until phase inversion is completed. min or more, more preferably 0.5 parts by mass / min or more, further preferably 1 part by mass / min or more, still more preferably 3 parts by mass / min or more, and even more preferably 4 parts by mass / min or more. Also, preferably 50 parts by mass / min or less, more preferably 30 parts by mass / min or less, more preferably 20 parts by mass / min or less, still more preferably 10 parts by mass / min or less, and even more preferably 8 parts by mass / min. Less than min. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.

  The use amount of the aqueous medium is preferably 100 parts by mass or more, more preferably 150 parts by mass with respect to 100 parts by mass of the binder resin composition or the polyester resin from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process. More preferably, it is 200 parts by mass or more, more preferably 300 parts by mass or more, and still more preferably 400 parts by mass or more. Further, it is preferably 2000 parts by mass or less, more preferably 1500 parts by mass or less, further preferably 1000 parts by mass or less, still more preferably 700 parts by mass or less, and still more preferably 500 parts by mass or less.

  Surfactants include nonionic surfactants, anionic surfactants and cationic surfactants. Among these, from the viewpoint of dispersibility of the binder resin composition or the polyester resin, nonionic surfactants and / or anionic surfactants are preferable, and anionic surfactants are more preferable.

  Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene lauryl ether or polyoxyethylene alkyl ethers, polyethylene glycol monolaurate, Examples include polyoxyethylene fatty acid esters such as polyethylene glycol monostearate and polyethylene glycol monooleate, and oxyethylene / oxypropylene block copolymers. Among these, from the viewpoint of emulsion stability of the resin, polyoxyethylene alkyl ethers Is preferred.

  Examples of the anionic surfactant include alkylbenzene sulfonates such as sodium alkylbenzene sulfonate, alkyl sulfates such as sodium alkyl sulfate, and alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate. From the viewpoint of emulsion stability, sodium alkylbenzene sulfonate and alkyl ether sulfate are preferable, and alkyl ether sulfate is preferable.

  Examples of the cationic surfactant include alkyltrimethylammonium chloride and dialkyldimethylammonium chloride.

  Among the surfactants, polyoxyethylene alkyl ethers and alkyl ether sulfates are preferable, and alkyl ether sulfates are more preferable from the viewpoint of the dispersibility of the binder resin composition or the polyester-based resin and the emulsion stability of the resin. .

From the viewpoint of toner productivity, the volume median particle diameter (D ₅₀ ) of the particles of the binder resin composition for toner in the aqueous dispersion of the binder resin composition for toner obtained in step 2 is preferably It is 50 nm or more, more preferably 100 nm or more, and further preferably 200 nm or more. Further, it is preferably 450 nm or less, more preferably 400 nm or less, and further preferably 350 nm or less. In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size.

  When the aqueous dispersion contains an organic solvent, it is preferable to perform Step 3 of removing the organic solvent from the obtained aqueous dispersion after Step 2.

  The method for removing the organic solvent is not particularly limited, and any method can be used. However, since it is dissolved in water, it is preferably distilled. Further, the organic solvent may not be completely removed and may remain in the aqueous dispersion. In this case, the residual amount of the organic solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0% in the aqueous dispersion.

  When removing the organic solvent by distillation, it is preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be used while stirring. Further, from the viewpoint of maintaining the dispersion stability of the binder resin composition, it is more preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be used under reduced pressure and distill off. Note that the temperature may be increased after the pressure is reduced, or the pressure may be decreased after the temperature is increased. From the viewpoint of maintaining the dispersion stability of the binder resin composition, it is preferable to distill off at a constant temperature and pressure.

  Furthermore, after Step 2 or Step 3, Step 4 of mixing a surfactant with the aqueous dispersion obtained in Step 2 or Step 3 may be performed.

  The amount of the surfactant added in the step 4 is preferably 50% by mass or more of the total amount of the surfactant added in the steps 1 to 4 from the viewpoint of heat resistant storage stability, durability and low-temperature fixability of the toner. 100% by mass or less, more preferably 60% by mass or more and 100% by mass or less, further preferably 70% by mass or more and 100% by mass or less, still more preferably 80% by mass or more and 100% by mass or less, and still more preferably 90% by mass or more. 100% by mass or less.

  Further, the amount of the surfactant to be added in Step 4 is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the binder resin composition from the viewpoint of heat resistant storage stability, durability and low-temperature fixability of the toner. Preferably it is 1 part by mass or more, more preferably 1.5 parts by mass or more. Further, it is preferably 6 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 4.5 parts by mass or less.

  When the surfactant is added, it is preferable to stir with a commonly used mixing and stirring device such as an anchor blade or an external circulation stirring device.

  When a mixing stirring device such as an anchor blade is used, the peripheral speed of stirring is preferably 20 m / min or more, more preferably 40 m / min or more, more preferably 60 m / min or more, and further preferably from the viewpoint of dispersibility. 80m / min or more. Further, it is preferably 200 m / min or less, more preferably 150 m / min or less, and further preferably 100 m / min or less.

  The temperature at the time of adding the surfactant in step 4 is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher from the viewpoint of the dispersibility of the surfactant in water. Further, it is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and further preferably 35 ° C. or lower.

  The solid content concentration of the aqueous dispersion obtained through the production process of the aqueous dispersion including Step 1 to Step 4 is preferably 3 by appropriately adding water from the viewpoints of stability of the dispersion and ease of handling. It is at least 5% by mass, more preferably at least 5% by mass, even more preferably at least 15% by mass. Further, it is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.

The preferred volume-median particle diameter (D ₅₀ ) of the particles of the binder resin composition for toner in the aqueous dispersion of the binder resin composition for toner obtained in steps 1 to 4 is the same as that for the toner obtained in step 2. The same as the preferred volume-median particle diameter (D ₅₀ ) of the particles of the binder resin composition for toner in the aqueous dispersion of the binder resin composition, as described above.

  In addition to the phase inversion emulsification method, the aqueous dispersion of the binder resin composition for toner of the present invention may be emulsified by physical force such as ultrasonic waves. However, what is obtained by emulsification by the phase inversion emulsification method can increase the dispersibility of the wax (A) and can be included in the resin, thereby suppressing the exposure of the wax (A) to the resin surface. This is preferable from the viewpoint of excellent filming resistance, hot offset resistance, and low-temperature fixability of the toner.

The electrophotographic toner of the present invention using the aqueous dispersion of the binder resin composition is obtained by a method including the following steps A and C.
Step A: Step of obtaining an aqueous dispersion of aggregated particles by subjecting the aqueous dispersion of the binder resin composition for toner of the present invention to an aggregation step Step C: Step of fusing the aggregated particles

Moreover, the method for producing an electrophotographic toner of the present invention includes the following step B, and in step C, the aggregated particles obtained in step B may be fused. That is, the method for producing an electrostatic charge image developing toner according to the present invention may include the following steps A, B and C.
Step A: An aqueous dispersion of the binder resin composition for toner of the present invention is subjected to an aggregation step to obtain an aqueous dispersion of aggregated particles. Step B: An aqueous system of a polyester resin is added to the dispersion obtained in Step A. Step C for mixing and agglomerating the dispersion to obtain aggregated particles C: Step for fusing the aggregated particles

  Hereinafter, steps A to C will be described.

  Step A is a step of obtaining aggregated particles by aggregating the aqueous dispersion of the binder resin composition for toner of the present invention. By this step A, a dispersion in which aggregated particles are dispersed in a medium is obtained.

  In Step A, it is preferable to add a flocculant in order to efficiently perform the aggregation.

  As the flocculant, a quaternary salt cationic surfactant, an organic flocculant such as polyethyleneimine; and an inorganic flocculant such as inorganic metal salt and inorganic ammonium salt are used. From the viewpoint of the particle size distribution of the toner, heat resistant storage stability and gloss of printed matter, an inorganic flocculant is preferable, and an inorganic metal salt is particularly preferable.

  Examples of the inorganic metal salt include sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, and aluminum chloride. The valence of the central metal of the inorganic metal salt is preferably 2 or more from the viewpoint of the particle size distribution of the toner, heat resistant storage stability, and gloss of the printed matter.

  When the flocculant is added, the addition amount is preferably 0.001 part by mass or more, more preferably 100 parts by mass with respect to 100 parts by mass of the binder resin composition, from the viewpoint of heat resistant storage stability, durability and low-temperature fixability of the toner. 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.2 parts by mass or more. Further, it is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, further preferably 1 part by mass or less, still more preferably 0.8 parts by mass or less, and further preferably 0.5 parts by mass or less.

  The flocculant is preferably added after being dissolved in an aqueous medium, and it is preferable that the flocculant is sufficiently stirred at the time of addition of the flocculant and after completion of the addition.

  In the aggregation step, the solid content concentration in the system is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more in order to cause uniform aggregation. Further, it is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

  In the aggregation process, from the viewpoint of uniformly dispersing the flocculant and causing uniform aggregation, the temperature at the time of addition of the flocculant is preferably 10 ° C or higher, more preferably 15 ° C or higher, and further preferably 18 ° C or higher. is there. Further, it is preferably 40 ° C. or lower, more preferably 35 ° C. or lower, and further preferably 30 ° C. or lower. The holding temperature after adding the flocculant is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, and further preferably 47 ° C. or higher. Further, it is preferably 65 ° C. or lower, more preferably 60 ° C. or lower, and further preferably 55 ° C. or lower.

  In Step A, the colorant, the charge control agent, the release agent, the conductivity adjusting agent, the reinforcing filler such as a fibrous substance, the antioxidant, and the anti-aging agent are added and then agglomerated. May be.

  There is no restriction | limiting in particular as a coloring agent, A well-known coloring agent is mentioned, According to the objective, it can select suitably. Specifically, carbon black, inorganic composite oxide, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, Vulcan orange, watch young red, permanent red, brilliantamine 3B, Brilliantamine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, etc. Various pigments: acridine, xanthene, azo, benzoquinone, azine, anthraquinone, indico, thio Njiko type, phthalocyanine type, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, thiazine, and include various dyes of thiazole, and the like. These can be used alone or in combination of two or more.

  The addition amount of the colorant is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 1.0 parts by mass or more, with respect to 100 parts by mass of the binder resin composition from the viewpoint of improving the image quality. More preferably, it is 2.0 parts by mass or more. Further, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, further preferably 8 parts by mass or less, and further preferably 5 parts by mass or less.

The colorant may be added as a colorant dispersion containing colorant fine particles. The volume median particle size (D ₅₀ ) of the colorant fine particles is preferably 50 nm or more, more preferably 100 nm or more. Further, it is preferably 200 nm or less, more preferably 150 nm or less.

  Examples of charge control agents include chromium azo dyes, iron azo dyes, aluminum azo dyes, and salicylic acid metal complexes. Various charge control agents may be used alone or in combination of two or more.

  When a charge control agent is added, the addition amount is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and further preferably from 100 parts by mass of the binder resin composition from the viewpoint of improving image quality. Is 0.5 parts by mass or more, more preferably 0.6 parts by mass or more. Further, it is preferably 8 parts by mass or less, more preferably 7 parts by mass or less, further preferably 5 parts by mass or less, and further preferably 2 parts by mass or less.

The charge control agent may be added as a charge control agent dispersion containing charge control agent fine particles. The volume median particle size (D ₅₀ ) of the charge control agent fine particles is preferably 100 nm or more, more preferably 300 nm or more. Moreover, it is preferably 800 nm or less, more preferably 500 nm or less.

  Further, additives such as a colorant and a charge control agent may be premixed in the binder resin composition when preparing the resin particles, or a dispersion in which each additive is separately dispersed in a dispersion medium such as water. A liquid may be prepared, mixed with an aqueous dispersion of the binder resin composition, and subjected to an aggregation step.

  When the additive is added to the binder resin composition in advance when preparing the resin particles, it is preferable to melt-knead the binder resin composition and the additive in advance.

  For melt kneading, it is preferable to use an open roll type biaxial kneader. An open roll type biaxial kneader is a kneader in which two rolls are arranged close to each other in parallel, and a heating function or a cooling function can be imparted by passing a heat medium through each roll. Therefore, the open roll type biaxial kneader is an open type part to be melt kneaded, and is provided with a heating roll and a cooling roll, so that it occurs during melt kneading unlike a normal biaxial kneader. The kneading heat can be easily dissipated.

  In addition, an aqueous dispersion of each additive can be obtained by mixing each additive, a surfactant, and water and dispersing the mixture with a disperser.

  Step B is a step in which an aqueous dispersion of a polyester resin is mixed with the dispersion obtained in Step A and aggregated to obtain aggregated particles. By performing Step B, a core-shell type toner can be obtained through Step C described later. That is, the aggregate portion obtained in the step A mainly constitutes the core portion, and the portion aggregated in the step B mainly constitutes the shell portion. The “dispersion obtained in step A” means a dispersion obtained by aggregating the aqueous dispersion of the binder resin composition and having the aggregated particles dispersed in a medium.

  The polyester resin constituting the aqueous dispersion of the polyester resin used in the step B is not particularly limited as long as it is a polyester resin for toners having physical properties generally used for toners. Obtained by polycondensation with an acid component.

  The kind and content of the alcohol component which is the raw material of the polyester resin are the same as the alcohol component of the polyester resin.

  From the viewpoint of improving the heat resistance storage stability, durability, and low-temperature fixability of the toner by making the heat resistance of the toner shell higher than that of the core, the softening point of the polyester resin is higher than the softening point of the binder resin composition. Is preferably high. From this viewpoint, the temperature difference between the softening points of the polyester resin and the binder resin composition is preferably 2 ° C. or higher, more preferably 4 ° C. or higher, further preferably 5 ° C. or higher, more preferably 8 ° C. or higher, and still more preferably. Is above 10 ° C. Further, it is preferably 35 ° C. or lower, more preferably 30 ° C. or lower, further preferably 25 ° C. or lower, more preferably 20 ° C. or lower, and further preferably 15 ° C. or lower.

  The softening point of the polyester resin constituting the aqueous dispersion of the polyester resin is preferably 95 ° C. or higher, more preferably 100 ° C. or higher, further preferably 105 ° C. or higher, more preferably 110 ° C. or higher, more preferably 115 ° C. or higher. is there. Further, it is preferably 140 ° C. or lower, more preferably 135 ° C. or lower, further preferably 130 ° C. or lower, further preferably 125 ° C. or lower, and further preferably 123 ° C. or lower.

  Further, the glass transition temperature of the polyester resin constituting the aqueous dispersion of the polyester resin is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, more preferably, from the viewpoint of heat resistant storage stability, durability and low-temperature fixability of the toner. Is 55 ° C. or higher, more preferably 60 ° C. or higher. Further, it is preferably 85 ° C. or lower, more preferably 80 ° C. or lower, further preferably 75 ° C. or lower, and further preferably 70 ° C. or lower.

  The acid value of the polyester resin constituting the aqueous dispersion of the polyester resin is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, and still more preferably, from the viewpoint of heat resistant storage stability, durability and low-temperature fixability of the toner. 10 mgKOH / g or more, more preferably 12 mgKOH / g or more. Further, it is preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, further preferably 20 mgKOH / g or less, and further preferably 18 mgKOH / g or less.

  The softening point, glass transition temperature, and acid value of the polyester resin can be easily adjusted by adjusting the raw material monomer composition, molecular weight, catalyst amount, etc., or by selecting reaction conditions.

  Preferred types of the carboxylic acid component that is a raw material of the polyester resin constituting the aqueous dispersion of the polyester resin are the same as the carboxylic acid component of the polyester resin, and include an aliphatic dicarboxylic acid compound and an aromatic dicarboxylic acid compound. It is more preferable that terephthalic acid and fumaric acid are included.

  In the carboxylic acid component, the content of the aliphatic dicarboxylic acid compound is such that the heat resistance of the shell portion of the toner is higher than that of the core portion, and the heat resistant storage stability, durability, and low-temperature fixability of the toner are improved. It is preferable that the content of the aliphatic dicarboxylic acid in the raw material carboxylic acid component of the polyester resin is smaller. From the viewpoint, the content is preferably 5 mol% or more, more preferably 8 mol% or more, and further preferably 10 mol% or more in the carboxylic acid component. Further, it is preferably 25 mol% or less, more preferably 20 mol% or less, and still more preferably 15 mol% or less.

  Further, the content of the aromatic dicarboxylic acid compound in the carboxylic acid component is such that the heat resistance of the toner shell part is made higher than that of the core part to improve the heat resistant storage stability, durability and low-temperature fixability of the toner. Therefore, the content of the aromatic dicarboxylic acid compound in the raw material carboxylic acid component of the polyester resin is preferably larger than the content. From this viewpoint, the content is preferably 75 mol% or more, more preferably 80 mol% or more, and still more preferably 85 mol% or more in the carboxylic acid component. Further, it is preferably 98 mol% or less, more preferably 95 mol% or less, and still more preferably 90 mol% or less.

The volume median particle diameter (D ₅₀ ) of the polyester resin particles in the aqueous dispersion is preferably 50 nm or more, more preferably 100 nm or more, from the viewpoint of toner productivity. Further, it is preferably 400 nm or less, more preferably 350 nm or less, further preferably 300 nm or less, further preferably 250 nm or less, and further preferably 200 nm or less.

The volume median particle diameter (D ₅₀ ) of the aggregated particles obtained in the step B is preferably 3.0 μm or more, more preferably 3.5 μm or more, further preferably 4.0 μm or more, further preferably from the viewpoint of low-temperature fixability of the toner. Is 4.5 μm or more. Further, it is preferably 8.5 μm or less, more preferably 8.0 μm or less, further preferably 7.5 μm or less, further preferably 7.0 μm or less, and further preferably 6.5 μm or less.

  In Step C, after adding an aggregation terminator as necessary to the aqueous dispersion of aggregated particles obtained in Step A or Step B, the fused particles are obtained by heating as necessary.

  The temperature in the system in the fusing process is determined from the viewpoints of the intended toner particle size, particle size distribution, shape control and particle fusing property, and from the viewpoint of enhancing the heat-resistant storage stability, durability and low-temperature fixability of the toner. The softening point of the resin composition is preferably −40 ° C. or higher, more preferably softening point −35 ° C. or higher, softening point + 10 ° C. or lower is more preferable, softening point or lower is more preferable, softening point −10 ° C. or lower is preferable, A softening point of −15 ° C. or lower is preferable, and a softening point of −20 ° C. or lower is preferable. Specifically, it is preferably 70 ° C or higher, more preferably 75 ° C or higher. Further, it is preferably 100 ° C. or lower, more preferably 90 ° C. or lower. The stirring speed is preferably a speed at which the aggregated particles do not settle.

  In addition, when using an aggregation terminator, it is preferable to use a surfactant as the aggregation terminator, and it is more preferable to use an anionic surfactant. Of the anionic surfactants, it is more preferable to use at least one selected from the group consisting of alkyl ether sulfates, alkyl sulfates, and linear alkylbenzene sulfonates, and it is more preferable to use alkyl ether sulfates. .

  The electrophotographic toner of the present invention can be suitably obtained by subjecting the fused particles obtained in Step C to a solid-liquid separation step such as filtration, a washing step, and a drying step as appropriate.

  In the washing step, it is preferable to completely remove the added nonionic surfactant by washing, and washing with an aqueous solution below the cloud point of the nonionic surfactant is preferred. The washing is preferably performed a plurality of times.

  In the drying step, any method such as a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be employed. The water content after drying of the toner is preferably adjusted to 1.5% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of chargeability.

  An external additive may be used in the toner of the present invention in order to improve transferability. As the external additive, inorganic fine particles are preferably used. Examples of the inorganic fine particles include silica, alumina, titania, zirconia, tin oxide and zinc oxide, and silica is preferable.

  Silica is preferably hydrophobic silica that has been subjected to a hydrophobic treatment, from the viewpoint of toner transferability.

  Examples of the hydrophobizing agent for hydrophobizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Of these, hexamethyldisilazane is preferred.

  The average particle diameter of the external additive is preferably 10 nm or more, and more preferably 15 nm or more, from the viewpoint of the chargeability, fluidity, and transferability of the toner. Further, it is preferably 250 nm or less, more preferably 200 nm or less, and further preferably 90 nm or less.

  The content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.3 parts by mass or more with respect to 100 parts by mass of the toner before being processed with the external additive. Moreover, 5 mass parts or less are preferable, and 3 mass parts or less are more preferable.

The volume median particle diameter (D ₅₀ ) of the toner obtained by the production method of the present invention is preferably 3.0 μm or more, more preferably 3.5 μm or more, further preferably 4.0 μm or more, from the viewpoint of low-temperature fixability of the toner. More preferably, it is 4.5 μm or more. Further, it is preferably 8.5 μm or less, more preferably 8.0 μm or less, further preferably 7.5 μm or less, further preferably 7.0 μm or less, and further preferably 6.5 μm or less.

  The electrophotographic toner of the present invention can be used as a one-component developing toner or as a two-component developer mixed with a carrier.

  In relation to the above-described embodiment, the present invention further discloses the following binder resin composition for toner, a method for producing the same, and a toner for electrophotography containing the binder resin composition.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The physical properties of the resin and the like were measured by the following method.

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

[Glass transition temperature of resin composition and resin]
Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of sample is weighed into an aluminum pan, heated to 200 ° C., and from that temperature Cool to 0 ° C at a temperature drop rate of 10 ° C / min. Next, the sample is heated at a heating rate of 10 ° C / min, and the temperature at the intersection of the base line extension below the endothermic peak temperature and the tangent that indicates the maximum slope from the peak rise to the peak apex is measured. The glass transition temperature is assumed.

[Acid value of resin composition and resin]
Measured according to the method of JIS K 0070. However, only the measurement solvent is changed from the ethanol / ether mixed solvent specified in JIS K 0070 to the acetone / toluene mixed solvent (acetone: toluene = 1: 1 (volume ratio)).

[Melting point of wax]
Using a differential scanning calorimeter “DSC210” (manufactured by Seiko Denshi Kogyo Co., Ltd.), the sample was heated up to 200 ° C and cooled to 0 ° C at a rate of temperature decrease of 10 ° C / min. The melting point is the maximum peak temperature of the heat of fusion.

[Molecular weight of wax]
Using the following measuring device and analytical column, chloroform is flowed as an eluent at a flow rate of 1 ml per minute, and the column is stabilized in a constant temperature bath at 40 ° C. Measurement is performed by injecting 100 μl of the sample solution. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. At this time, several types of monodisperse polystyrene (A-500 (5.0 × 10 ² ), A-1000 (1.01 × 10 ³ ), A-2500 (2.63 × 10 ³ ), A- 5000 (5.97 × 10 ³ ), F-1 (1.02 × 10 ⁴ ), F-2 (1.81 × 10 ⁴ ), F-4 (3.97 × 10 ⁴ ), F-10 (9.64 × 10 ⁴ ), F- 20 (1.90 × 10 ⁵ ), F-40 (4.27 × 10 ⁵ ), F-80 (7.06 × 10 ⁵ ), F-128 (1.09 × 10 ⁶ )) prepared as standard samples are used.
Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation)
Analytical column: GMHXL + G3000HXL (manufactured by Tosoh Corporation)

[Acid value and hydroxyl value of wax]
Measured by the method of JIS K0070. However, only the measurement solvent is changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of xylene and ethanol (xylene: ethanol = 3: 5 (volume ratio)).

[Reaction rate of hydrocarbon wax (B)]
Using a differential scanning calorimeter “DSC210” (manufactured by Seiko Denshi Kogyo Co., Ltd.), the melting point of the wax is determined by comparing the endothermic area of the resin produced without using the wax (A) and the endothermic area of the hydrocarbon wax (B) before the reaction. The reaction rate (100-unreacted rate,%) is calculated from the unreacted rate (%) calculated according to the following formula. Resin and hydrocarbon wax (B) are measured using the same mass.

(In the formula, X represents the mass ratio of the hydrocarbon wax (B) used in the reaction with respect to 100 parts by mass of the raw material monomer of the polyester resin.)

[Volume Median Particle Size (D ₅₀ ) of Resin Composition Particles, Resin Particles, Colorant Particles, and Charge Control Agent Particles]
(1) Measuring device: Laser diffraction particle size measuring instrument “LA-920” (manufactured by HORIBA, Ltd.)
(2) Measurement conditions: Distilled water is added to the measurement cell, and the volume-median particle diameter is measured at a temperature at which the absorbance falls within an appropriate range.

[Solid content concentration of resin composition aqueous dispersion, resin aqueous dispersion, colorant dispersion, and charge control agent dispersion]
Using an infrared moisture meter “FD-230” (manufactured by Kett Science Laboratory Co., Ltd.), measure the moisture content of a 5 g measurement sample at a drying temperature of 150 ° C. and a measurement mode of 96 (monitoring time 2.5 min / variation width 0.05%). To do. The solid content concentration is calculated according to the following formula.
Solid content concentration (% by mass) = 100-M
M: Water content (% by mass)

[Volume Median Particle Size of Aggregated Particles (D ₅₀ )]
Measuring instrument: "Coulter Multisizer III" (Beckman Coulter, Inc.)
Aperture diameter: 50μm
Analysis software: "Multisizer III version 3.51" (Beckman Coulter, Inc.)
Electrolyte: “Isoton II” (Beckman Coulter, Inc.)
Dispersion: Polyoxyethylene lauryl ether “Emulgen 109P” (manufactured by Kao Corporation, HLB: 13.6) is dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by mass.
Dispersion conditions: Add 10 mg of sample (converted to solid content) to 5 mL of the above dispersion, disperse for 1 minute with an ultrasonic disperser, then add 25 mL of electrolyte, and further disperse for 1 minute with an ultrasonic disperser Sample dispersion.
Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic 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, Determine the volume-median particle size.

[Number average particle diameter of external additives]
The number average value of the particle diameter of 500 particles measured from a scanning electron microscope (SEM) photograph of the external additive. When there is a major axis and a minor axis, the major axis is indicated.

[Production Example of Binder Resin Composition]
Ingredients for polyester resin other than fumaric acid, trimellitic anhydride and wax (B) shown in Tables 1 and 2, esterification catalyst and esterification co-catalyst, thermometer, stainless steel stirring rod, flow-down condenser and nitrogen introduction The flask was placed in a 10-liter four-necked flask equipped with a tube, and heated to 235 ° C. over 2 hours in a mantle heater in a nitrogen atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or more at 235 ° C. After cooling to 180 ° C, trimellitic anhydride, fumaric acid, wax (B), wax (A) "HNP-9" (manufactured by Nippon Seiwa Co., Ltd., paraffin wax, melting point: 78 ° C) and 4-tert-butyl Catechol was added and the temperature was raised to 210 ° C. over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was performed at 8 kPa until the softening points shown in Tables 1 and 2 were reached, and resin compositions A, B, and D to I were obtained.

[Production example of polyester resin]
A resin C was obtained in the same manner as in the resin composition A except that the wax (A) was not used.

[Production example of polyester resin]
Raw material monomer of polyester resin other than fumaric acid shown in Table 2, esterification catalyst and esterification co-catalyst are added to a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring bar, a flow-down condenser and a nitrogen inlet tube. The mixture was heated in a mantle heater in a nitrogen atmosphere to 235 ° C. over 2 hours. Thereafter, it was confirmed that the reaction rate reached 95% or more at 235 ° C. Thereafter, the mixture was cooled to 180 ° C., trimellitic anhydride, fumaric acid and 4-tert-butylcatechol were added, and the temperature was raised to 210 ° C. over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was performed at 8 kPa until the softening point shown in Table 2 was reached, to obtain Resin J.

  Details of the wax used are shown in Table 3.

[Production Example 1 of aqueous dispersion of binder resin or binder resin composition]
Into a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube, 150 g of the resin or resin composition (when containing wax (A)) shown in Table 4 and 75 g of methyl ethyl ketone were charged. It was dissolved at 73 ° C. over 2 hours. The obtained solution was neutralized by adding a 5% by mass sodium hydroxide aqueous solution so that the neutralization degree was 100 mol% with respect to the acid value of the resin, and stirred for 30 minutes. After cooling, 675 g of ion-exchanged water (30 ° C.) was added over 77 minutes while stirring at 280 r / min (peripheral speed 88 m / min) while maintaining the temperature at 30 ° C. Subsequently, after heating up to 50 degreeC over 30 minutes, methyl ethyl ketone was distilled off under reduced pressure. After that, the aqueous dispersion was cooled to 30 ° C. while stirring at 250 r / min (peripheral speed 88 m / min), and then the anionic surfactant “Emar E27C” (sodium polyoxyethylene lauryl ether sulfate, Kao Corporation) 16.7 g) was mixed and completely dissolved. Thereafter, the solid content concentration of the dispersion was measured, and ion-exchanged water was added so as to be 20% by mass to obtain dispersions a-1, b, c-1, dl, and j.

[Production Example 2 of aqueous dispersion of binder resin composition]
In a 3L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, 150g of resin c-2, 75g of methyl ethyl ketone, "HNP-9" (manufactured by Nippon Seiwa Co., Ltd., paraffin wax, melting point) : 78 ° C.) 13.7 g was charged and dissolved at 73 ° C. over 2 hours. The obtained solution was neutralized by adding a 5% by mass sodium hydroxide aqueous solution so that the neutralization degree was 100 mol% with respect to the acid value of the resin, and stirred for 30 minutes. Thereafter, 675 g of ion-exchanged water was added over 77 minutes while stirring at 280 r / min (peripheral speed 88 m / min) while maintaining the temperature at 30 ° C. Subsequently, after heating up to 50 degreeC over 30 minutes, methyl ethyl ketone was distilled off under reduced pressure. After that, the aqueous dispersion was cooled to 30 ° C. while stirring at 250 r / min (peripheral speed 88 m / min), and then the anionic surfactant “Emar E27C” (sodium polyoxyethylene lauryl ether sulfate, Kao Corporation) 16.7 g) was mixed and completely dissolved. Thereafter, the solid content concentration of the dispersion was measured, and ion-exchanged water was added so as to be 20% by mass to obtain Dispersion c-2.

[Production Example 3 of aqueous dispersion of binder resin composition]
Dispersion c-2 was prepared in the same manner as in the production of Dispersion c-2 except that “HNP-9” was changed to “WEP-8” (manufactured by Nippon Seiwa Co., Ltd., ester wax, melting point: 80 ° C.). 3 was obtained.

[Production of aqueous dispersion of binder resin composition]
150 g of Resin Composition A, 75 g of ethyl acetate, 16.7 g of anionic surfactant (trade name: “Emar E27C” manufactured by Kao Corporation) are dissolved at 25 ° C. and dissolved at 73 ° C. over 2 hours. It was. To the obtained solution, 5% by mass sodium hydroxide aqueous solution was added so that the neutralization degree was 70 mol% with respect to the acid value of the resin, and then 600 g of ion-exchanged water was mixed, and an ultrasonic homogenizer ( 30 dispersion treatment was performed at an output of 350 W using a doctor Heelscher Co., Ltd. (trade name: “UP-400S”). Thereafter, ethyl acetate was distilled off under reduced pressure at 73 ° C. to obtain dispersion a-2.

[Production Example of Colorant Dispersion]
Mixing 50g of copper phthalocyanine "ECB-301" (manufactured by Daiichi Seika Kogyo Co., Ltd.), 5g of nonionic surfactant "Emulgen 150" (polyoxyethylene lauryl ether, Kao Corporation) and 200g of ion-exchanged water Then, it was dispersed for 10 minutes using a homogenizer to obtain a colorant dispersion containing colorant fine particles. The volume median particle size (D ₅₀ ) of the colorant fine particles was 120 nm, and the solid content concentration was 22% by mass.

[Production example of charge control agent dispersion]
Mixing 50 g of salicylic acid compound “Bontron E-84” (made by Orient Chemical Co., Ltd.) as a charge control agent, 5 g of “Emulgen 150” (made by Kao Corporation) and 200 g of ion-exchanged water as a nonionic surfactant Then, glass beads were used and dispersed for 10 minutes using a sand grinder to obtain a charge control agent dispersion containing charge control agent fine particles. The volume median particle size (D ₅₀ ) of the charge control agent fine particles was 400 nm, and the solid content concentration was 22% by mass.

[Manufacture of toner for electrophotography]
Examples 1-7 and Comparative Examples 1-5
300 g of the core aqueous dispersion shown in Table 5, 8 g of the colorant dispersion, 2 g of the charge control agent dispersion, and 52 g of deionized water were placed in a 2 L container, and 100 r / min (peripheral speed 31 m / min) with an anchor-type stirrer. min), 150 g of a 0.1 mass% calcium chloride aqueous solution was added dropwise at 30 ° C. over 30 minutes. Then, it heated up to 50 degreeC, stirring. It was held at 50 ° C. until the volume median particle size was 5 μm. At 3 hours, the volume median particle size reached 5 μm. Thereafter, 75 g of an aqueous dispersion for shell (dispersion j) was added and dispersed by stirring. Thereafter, a dilute solution obtained by diluting 4.2 g of anionic surfactant “Emar E27C” (manufactured by Kao Corporation, solid content: 28% by mass) with 37 g of deionized water was added as an aggregation terminator. Next, the temperature was raised to 80 ° C, and after the temperature reached 80 ° C, the temperature was maintained at 80 ° C for 1 hour, and then the heating was terminated. As a result, fused particles were formed, and then slowly cooled to 20 ° C., filtered through a 150 mesh (mesh 150 μm) wire mesh, suction filtered, washed, and dried to obtain toner particles.

(External addition process)
To 100 parts by mass of the obtained toner particles, hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: HMDS, number average particle size 40 nm) 1.0 part by mass, hydrophobic silica “R972” ”(Manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: DMDS, number average particle size 16 nm) 0.6 parts by mass, and titanium oxide“ JMT-150IB ”(manufactured by Teika Co., Ltd., number average particle size 15 nm) 0.5 parts by mass Was added to a 10 L Henschel mixer (Mitsui Mining Co., Ltd.) equipped with ST and Ao stirring blades, and stirred at 3000 r / min for 2 minutes to obtain a toner (volume-median particle size: about 5 μm). .

Example 8
375 g of the core aqueous dispersion shown in Table 5, 8 g of the colorant dispersion, 2 g of the charge control agent dispersion, and 52 g of deionized water are placed in a 2 L container, and 100 r / min (peripheral speed 31 m / min) with an anchor-type stirrer. min), 150 g of a 0.1 mass% calcium chloride aqueous solution was added dropwise at 30 ° C. over 30 minutes. Then, it heated up to 50 degreeC, stirring. It was held at 50 ° C. until the volume median particle size was 5 μm. At 3 hours, the volume median particle size reached 5 μm. Thereafter, a dilute solution obtained by diluting 4.2 g of anionic surfactant “Emar E27C” (manufactured by Kao Corporation, solid content: 28% by mass) with 37 g of deionized water was added as an aggregation terminator. Next, the temperature was raised to 80 ° C, and after the temperature reached 80 ° C, the temperature was maintained at 80 ° C for 1 hour, and then the heating was terminated. As a result, fused particles were formed, and then slowly cooled to 20 ° C., filtered through a 150 mesh (mesh 150 μm) wire mesh, suction filtered, washed, and dried to obtain toner particles.

Test Example 1 [filming resistance]
Toner is mounted on a non-magnetic one-component development system printer "OKI Microline 18" (Oki Data Co., Ltd.), and an oblique stripe pattern with a blackening rate of 5.5% is obtained at a temperature of 30 ° C and a humidity of 80%. Continuous printing was performed. On the way, a solid image was printed every 500 sheets, and streaks on the image were confirmed. The number of printed sheets up to the time when the streak was visually observed on the image was defined as the number of printed sheets. The results are shown in Table 5. The larger the number of printing sheets, the better the filming resistance. The number of printing sheets is preferably 4500 sheets or more, more preferably 5500 sheets or more, further preferably 6000 sheets or more, and further preferably 6800 sheets or more. The results are shown in Table 5.

Test Example 2 [Low-temperature fixability and hot offset resistance]
Toner was mounted on a device that improved the fixing machine of the copier “AR-505” (manufactured by Sharp Corporation) so that fixing was possible outside the device, and printed matter was obtained in an unfixed state (printing area: 2cm × 12cm, adhesion amount: 0.5mg / cm ² ). Then, using a fixing machine (fixing speed 300mm / sec) adjusted so that the total fixing pressure is 40kgf, the fixing roll temperature is increased from 80 ° C to 240 ° C in 5 ° C increments, and unfixed at each temperature. A fixing test of the printed matter in the state was performed. A cellophane adhesive tape “UNICEF Cellophane” (Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z 1522) is attached to the image portion of the printed matter, and the tape is passed through a fixing roller set at 30 ° C. I peeled it off. As the fixing paper, “CopyBond SF-70NA” (manufactured by Sharp Corporation, 75 g / m ² ) was used.
The optical reflection density before and after applying the tape was measured using a reflection densitometer “RD-915” (manufactured by Gretag Macbeth Co.), and the ratio between the two (after peeling / before sticking × 100) was initially 90%. The temperature of the fixing roller exceeding the temperature was set as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixing property. The minimum fixing temperature is preferably 115 ° C. or lower, more preferably 110 ° C. or lower, and even more preferably 108 ° C. or lower.
Further, the fixed image obtained above was judged visually, and the lowest temperature of the fixing roll where hot offset was observed was defined as the hot offset temperature. The higher the hot offset temperature, the better the hot offset resistance. The hot offset temperature is preferably 170 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 185 ° C. or higher. The results are shown in Table 5.

  From the above results, it can be seen that the toners of the examples all have better filming resistance, hot offset resistance, and low-temperature fixability than the toners of the comparative examples.

  In the following, among the examples, Example 1, which is particularly good, is compared with other examples and comparative examples.

In Example 2, the content ratio [(A) / (B)] of the wax (A) to the wax (B) is 4, which is higher than 1 in Example 1, and is resistant to filming and hot offset. Sex is slightly decreased.
In Example 3, the molecular weight of the wax (B) is 470, which is smaller than 800 in Example 1, and the filming resistance, hot offset resistance and low-temperature fixability are slightly lowered.
In Example 4, the molecular weight of the wax (B) is 1500, which is larger than 800 in Example 1, and the filming resistance, hot offset resistance and low-temperature fixability are slightly lowered.
In Example 5, since the wax (A) was not present during the polymerization of the binder resin and the wax (A) was added during the emulsification of the binder resin composition, the filming resistance, hot offset resistance and Low temperature fixability is slightly reduced.
In Example 6, the wax (A) was not present during the polymerization of the binder resin, the wax (A) was added during the emulsification of the binder resin composition, and the wax (A) was further added to the paraffin used in Example 1. The wax is replaced with an ester wax, and although the low-temperature fixability is improved, the filming resistance and the hot offset resistance are slightly lowered.
In Example 7, unlike the phase inversion emulsification of Example 1, a binder resin obtained by emulsification with ultrasonic waves is used, and the filming resistance, hot offset resistance and low temperature fixability are slightly lowered. ing.
In Example 8, since there is no shell layer, the filming resistance and the hot offset resistance are slightly deteriorated.

In Comparative Example 1, the wax (B) is not used, the dispersibility of the wax (A) is poor, and the filming resistance, hot offset resistance, and low-temperature fixability are reduced.
In Comparative Example 2, the wax (A) is not used, and although the filming resistance is good, the hot offset resistance and the low-temperature fixability are deteriorated.
In Comparative Example 3, the filming resistance and the low-temperature fixability are lowered, and the hot offset resistance is slightly lowered. This is because the melting point of the wax (B) is 119.4 ° C. (76.1 ° C. in Example 1). This is probably because the emulsifiability of the polyester-based resin was lowered because it was too high.
In Comparative Example 4, the filming resistance and the hot offset resistance are lowered, and the low-temperature fixability is slightly lowered. This is because the content of the wax (B) in 100 parts by mass of the polyester resin is 23.1 masses. This is probably because the amount is too large (9.1 parts by mass in Example 1).
In Comparative Example 5, the filming resistance, the hot offset resistance and the low-temperature fixability are lowered. This is because the molecular weight of the wax (B) is too small (270 in Example 1). This is probably because the dispersion power of A) was lowered.

  The aqueous dispersion of the binder resin composition for toner of the present invention is suitably used for the production of a toner used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method and the like. Is.

Claims (7)

Step A: a step of subjecting an aqueous dispersion of a binder resin composition for a toner containing a polyester resin and wax (A) to an aggregation step to obtain an aqueous dispersion of aggregated particles; and
Step C: Step of fusing the aggregated particles
A method for producing an electrophotographic toner comprising :
The wax (A) is at least one selected from the group consisting of an ester wax and a hydrocarbon wax, and the content of the wax (A) is 3 to 50 mass with respect to 100 mass parts of the polyester resin. Department,
The polyester-based resin has a component part derived from a hydrocarbon wax (B) having a hydroxyl group and / or a carboxy group having a melting point of 60 to 110 ° C. and a molecular weight of 400 or more,
A method for producing an electrophotographic toner . The production method according to claim 1, wherein the total value of the hydroxyl value and the acid value of the hydrocarbon wax (B) is 40 to 200 mgKOH / g. The mass ratio of wax (A) to hydrocarbon wax (B) (amount of wax (A) with respect to 100 parts by mass of polyester resin / amount derived from hydrocarbon wax (B) in 100 parts by mass of polyester resin) is 0.2. The manufacturing method of Claim 1 or 2 which is -20. The binder resin composition for a toner is a resin composition obtained by polymerizing a raw material monomer of a polyester resin in the presence of a wax (A) and a hydrocarbon wax (B). Manufacturing method . The alcohol component which is a raw material monomer of the polyester resin is represented by the formula (I):

(In the formula, RO is an alkylene oxide, R is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers indicating the average added mole number of alkylene oxide, and the sum of x and y is 1 to 16) Is)
The manufacturing method in any one of Claims 1-4 which contains 80 mol% or more of alkylene oxide adducts of bisphenol A represented by these in an alcohol component. The manufacturing method in any one of Claims 1-5 in which the carboxylic acid component which is a raw material monomer of a polyester-type resin contains 50 mol% or more of aromatic dicarboxylic acid compounds in a carboxylic acid component. further,
Step B: The dispersion obtained in Step A is mixed with an aqueous dispersion of a polyester resin and aggregated to obtain aggregated particles. In Step C, the aggregated particles obtained in Step B are fused. The manufacturing method in any one of Claims 1-6 obtained by the method containing a process .