JP7001223B2 - Manufacturing method of toner for static charge image development - Google Patents

Description

The present invention relates to a method for producing a toner for developing an electrostatic charge image used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like.

In the field of electrophotographic, with the development of electrophotographic systems, there is a demand for the development of toners for electrophotographics that can achieve high image quality and high speed. As a method for obtaining toner having a narrow particle size distribution and a small particle size in response to higher image quality, a coagulation fusion method (emulsification) in which fine resin particles and the like are aggregated and fused in an aqueous medium to obtain toner. The so-called chemical toner is manufactured by the agglomeration method and the agglomeration union method).

Patent Document 1 contains agglomerated particles containing the resin particles (A) and the release agent particles, and an anionic surfactant having a polyethylene glycol moiety having an average number of moles of ethylene oxide added of 1 or more and less than 8. An electrostatic charge image comprising the step of fusing the aggregated particles in the aqueous mixture under the pH after and / or adjusting the pH of the aqueous mixture at 25 ° C. to 5.1-6.1. A method for manufacturing a developing toner is described. According to the manufacturing method, it is described that a toner for static charge image development can be obtained, which has both good low-temperature fixability and heat-resistant storage stability and less toner scattering.

Patent Document 2 describes a toner containing a polyester resin, a colorant and a mold release agent, having an average circularity of 0.95 to 0.985, a turbidity measured under certain conditions of 35 to 60, and a supernatant. Described is a static charge image developing toner characterized in that a fatty acid metal salt having an average particle size of 2 to 4 μm and resin particles having an average particle size of 180 nm to 320 nm are contained in the liquid. It is stated that it is excellent in low temperature fixing property, cleaning property, and image quality.

In Patent Document 3, latex resin, wax and colorant are aggregated to obtain particles having an average particle size of about 3.5 to about 7 microns, diluted with a liquid and then fused to prepare toner particles. Toners with a roundness of about 0.945 to about 0.998 are described. As a result, it is said that a toner having a high pigment content can be obtained.

In Patent Document 4, agglomerated particles are formed from an emulsion containing a resin latex, a colorant, a wax, and an additive, and by further adding the resin latex, a shell is formed on the surface of the agglomerates and agglomerated. After stopping the aggregation of the particles by raising the pH of the mixture of particles to a pH at which aggregation stops, the mixture is heated to a temperature adjusted to a predetermined fusion pH, and then the pH of the mixture is raised to a predetermined fusion pH. A method for producing toner particles to be fused by lowering the temperature and heating and maintaining the fusion temperature is described.

Japanese Unexamined Patent Publication No. 2014-6453 Japanese Unexamined Patent Publication No. 2010-102057 Japanese Unexamined Patent Publication No. 2015-11346 Japanese Unexamined Patent Publication No. 2012-14169

Compared with pulverized toner, general chemical toner has a high circularity and is inferior in cleaning property. More recently, the speed of electrophotographic systems has increased, and the cleanability of the photoconductor drum may become a more prominent issue.
In addition, unlike pulverized toner that is continuously produced, batch production is common for chemical toner, so it is required to efficiently produce toner with excellent cleaning properties.
The present invention relates to a method for producing a toner for developing an electrostatic charge image, which exhibits excellent cleaning properties.

In order to solve such a problem, the present inventor has focused on a step of fusing agglomerated particles in a method for producing a chemical toner. As a result, the fusion is advanced by adjusting the pH in the system during the fusion step, and the basic compound is added again after the fusion is advanced especially under acidic conditions, so that the cleaning property is excellent. It was found that the toner can be obtained.
The present invention
A method for producing a toner for static charge image development, which comprises a step of fusing agglomerated particles, which are agglomerates of polyester-based resin particles, in an aqueous medium.
In the process of fusing,
An acidic substance is added at a temperature equal to or higher than the glass transition temperature of the polyester resin of the agglomerated particles, and the pH in the aqueous medium is lowered by 0.1 or more and 3.0 or less from that before the addition of the acidic substance. The pH should be in the range of 4.0 or more and 7.0 or less after the substance is added.
After that, a basic substance is added at a temperature equal to or higher than the glass transition temperature of the polyester resin of the aggregated particles, and the pH in the aqueous medium is raised by 0.1 or more and less than 1.0 from before the addition of the basic substance. The present invention relates to a method for manufacturing a toner for developing an electrostatic charge image.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing a toner for developing an electrostatic charge image, which exhibits excellent cleaning properties.
According to the present invention, in addition to the above-mentioned effects, it is possible to provide a method for producing a toner for static charge image development, which exhibits excellent fog suppression, chargeability and heat-resistant storage stability.

[Manufacturing method of toner for static charge image development]
The method for producing a toner for static charge image development of the present invention (hereinafter, also simply referred to as “toner”) is a step of fusing agglomerated particles, which are agglomerates of polyester-based resin particles, in an aqueous medium (hereinafter, “fusing”). Also called "process").
In the step of fusing, the temperature in the aqueous medium is 0.1 or more and 3.0 or less than before the addition of the acidic substance by adding the acidic substance at a temperature equal to or higher than the glass transition temperature of the polyester resin of the aggregated particles. The temperature is lowered to a range of pH 4.0 or more and 7.0 or less after the addition of the acidic substance.
Then, after that, at a temperature equal to or higher than the glass transition temperature of the polyester resin of the agglomerated particles and adding a basic substance, the pH in the aqueous medium is 0.1 or more and less than 1.0 than before the addition of the basic substance. Raise it.
By the above method, a toner showing excellent cleaning property can be obtained.

The reason is not clear, but it can be considered as follows.
In the fusion step, the fusion of agglomerated particles is promoted by raising the temperature to a temperature higher than the glass transition temperature of the resin. At this time, by adjusting the pH to the acidic side, the dissociation of acid groups such as carboxy groups is dissociated. By suppressing and reducing the electrical repulsion, the fusion of the agglomerated particles can proceed rapidly, and the desired fused particles can be obtained in a shorter time.
However, it has been clarified that even after the fused particles are obtained under such acidic conditions, the fusion is likely to proceed and the circularity is increased, which causes a problem in cleanability.
Therefore, after adding an acidic substance and rapidly obtaining fused particles, a basic substance is immediately added and the conditions are changed to basic conditions to stop the progress of the fused particles to maintain low circularity. can do.
However, when the polyester-based resin is contained, the polyester-based resin is hydrolyzed under basic conditions, so that the particles on the toner surface may be redispersed or the molecular weight of the resin on the surface may be lowered. Therefore, it is considered that a toner having excellent cleaning property can be obtained by adding a basic substance but not making it basic and changing the pH to 0.1 or more and less than 1.0.

Definitions of various terms in the present specification are shown below.
Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio of the softening point of the resin to the maximum endothermic temperature (softening point (° C.) / maximum endothermic peak temperature (° C.)) in the measurement method described in Examples described later. The crystalline resin has a crystallinity index of 0.6 or more and 1.4 or less. Amorphous resins have a crystallinity index of less than 0.6 or more than 1.4. The crystallinity index can be appropriately adjusted depending on the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate.
In the specification, the carboxylic acid component of the polyester resin includes not only the compound but also an anhydride that decomposes during the reaction to generate an acid, and an alkyl ester of each carboxylic acid (alkyl group having 1 or more and 3 or less carbon atoms). Is also included.
As used herein, the term "binding resin" means a resin component contained in a toner including a polyester resin A, a polyester resin B, and a crystalline polyester resin C.
"Volume medium particle size D ₅₀ " is a particle size in which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size.
The coefficient of variation of the particle size distribution (hereinafter, also simply referred to as “CV value”) is a value expressed by the following formula. The volume average particle size in the following formula is the particle size obtained by multiplying the particle size measured on a volume basis by the proportion of particles having that particle size value and dividing the value obtained by that by the number of particles. be.
CV value (%) = [standard deviation of particle size distribution (μm) / volume average particle size (μm)] × 100

<Fusing process>
The method for producing a toner of the present invention includes a step of fusing agglomerated particles, which are agglomerates of polyester-based resin particles, in an aqueous medium. By this step, the physically aggregated polyester resin particles are fused.
In the fusion step, the agglomerated particles preferably have agglomerated particles 1 which are aggregates of the resin particles a containing the polyester-based resin A, and resin particles b containing the polyester-based resin B adhering to the surface thereof. Particle 2.
The polyester-based resin A, the resin particles a, the agglomerated particles 1, the polyester-based resin B, the resin particles b, and the agglomerated particles 2 will be described in detail later.

The volume median particle size (D ₅₀ ) of the agglomerated particles 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, still more preferably 6 μm. It is as follows. The volume median particle size (D ₅₀ ) of the agglomerated particles is determined by the method described in Examples described later.

In the fusion step, the temperature at which the agglomerated particles are fused (hereinafter, also referred to as “temperature T ₁ ”) has a viewpoint of obtaining a toner exhibiting excellent cleaning property, as well as excellent fog suppression, chargeability and heat storage property. From the viewpoint of obtaining the indicated toner, the temperature is equal to or higher than the glass transition temperature of the polyester resin of the aggregated particles.
The temperature T ₁ means the temperature of the aqueous medium containing the agglomerated particles, and means, for example, the temperature measured by inserting a thermometer into the mixed solution to be fused.
When a plurality of polyester-based resins are contained, the temperature T ₁ is preferably equal to or higher than the glass transition temperature of all polyester-based resins having the glass transition temperature contained in the aggregated particles, and more specifically, described above. In the agglomerated particles 2, the temperature is equal to or higher than the glass transition temperature of the polyester resin A and higher than the glass transition temperature of the polyester resin B.
The temperature T ₁ is preferably 2 from the glass transition temperature of the polyester resin of the aggregated particles from the viewpoint of further improving the cleaning property of the toner and from the viewpoint of further improving the fog suppression, chargeability and heat storage stability of the toner. ° C. Higher temperature or higher, more preferably 5 ° C. higher than the glass transition temperature of the agglomerated particles polyester resin, still more preferably 8 ° C. higher than the glass transition temperature of the aggregated particles polyester resin, and preferably. Is 30 ° C. or lower than the glass transition temperature of the agglomerated polyester resin, more preferably 20 ° C. or higher than the glass transition temperature of the agglomerated polyester resin, and more preferably the glass transition of the agglomerated polyester resin. The temperature is 15 ° C. higher than the temperature.
The above-mentioned temperature T ₁ is a preferable range based on the resin having the highest glass transition temperature when two or more kinds of polyester resins are contained.
The temperature T ₁ is preferably 65 ° C. or higher, more preferably 68 ° C. or higher, still more preferably 68 ° C. or higher, from the viewpoint of further improving the cleaning property of the toner and further improving the fog suppression, chargeability and heat-resistant storage property. It is 70 ° C. or higher, preferably 95 ° C. or lower, more preferably 90 ° C. or lower, still more preferably 85 ° C. or lower.
_In the present production method, it is preferable that the temperature at the time of adding the acidic substance and the time of adding the basic substance is within the above range of T1.

[Acid substances]
Examples of the acidic substance include inorganic acids and organic acids.
Examples of the inorganic acid include nitric acid, sulfuric acid, hydrochloric acid and phosphoric acid.
Examples of the organic acid include carboxylic acid compounds such as carboxylic acid, dicarboxylic acid and tricarboxylic acid, sulfonic acid compounds such as methanesulfonic acid, benzenesulfonic acid and toluenesulfonic acid, ascorbic acid, phenol and cresol. Of these, carboxylic acid compounds are preferred.
Examples of the carboxylic acid compound include acetic acid, lactic acid, tartaric acid, propionic acid, benzoic acid, oxalic acid, terephthalic acid, fumaric acid, succinic acid, acrylic acid and adipic acid.
Among these, inorganic acids are preferable, and sulfuric acid is more preferable, from the viewpoint of further improving the cleaning property of the toner, and from the viewpoint of further improving fog suppression, chargeability, and heat-resistant storage stability.

The acidic substance is preferably added into the system as an aqueous solution of the acidic substance from the viewpoint of further improving the cleaning property and further improving the fog suppression, chargeability and heat storage property.
When added as an aqueous solution of an acidic substance, the concentration of the acidic substance is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more in the aqueous solution of the acidic substance. Yes, and preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less. Is.

The method for adding the acidic substance may be any of a method of adding all at once, a method of adding the whole amount in two or more portions, and a method of continuously adding the acidic substance over a certain period of time. From the viewpoint of suppressing further aggregation of the particles, either a method of adding the particles in portions or a method of continuously adding the particles over a certain period of time is preferable.

As the water-based medium, a medium containing water as a main component is preferable.
Examples of water include deionized water and distilled water.
The content of water 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 98% by mass or more, still more preferably 100% by mass.
As a component other than water that can form an aqueous medium together with water, an alkyl alcohol having 1 or more and 5 or less carbon atoms; a dialkyl ketone having 3 or more and 5 or less carbon atoms such as acetone and methyl ethyl ketone; and dissolved in water such as a cyclic ether such as tetrahydrofuran. Organic solvent is used. Among these, from the viewpoint of preventing the organic solvent from being mixed into the toner, an alkyl alcohol having 1 or more and 5 or less carbon atoms that does not dissolve the polyester resin is preferable, and methanol, ethanol, isopropanol, and butanol are more preferable.

The pH in the aqueous medium is set before the addition of the acidic substance by adding the acidic substance from the viewpoint of obtaining a toner exhibiting excellent cleaning property and obtaining a toner exhibiting excellent fog suppression, chargeability and heat storage property. It is lowered by 0.1 or more and 3.0 or less.
The pH in the aqueous medium means the pH of the aqueous medium containing the aggregated particles, and is, for example, the pH measured by immersing the electrode of the pH meter in the dispersion liquid to be fused using a pH meter.
The pH lowered by the addition of an acidic substance (hereinafter, also referred to as “ΔpH”) is preferably 0. 15 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and preferably 2.5 or less, more preferably 2.0 or less, still more preferably 1.0 or less, still more preferably 0. It is 0.8 or less.

The pH in the aqueous medium before the addition of the acidic substance (hereinafter, also referred to as "pH in the initial aqueous medium") is from the viewpoint of further improving the cleaning property, and further improves the fog suppression, the chargeability and the heat-resistant storage property. From the viewpoint, it is preferably 6.0 or more, more preferably 6.5 or more, still more preferably 6.8 or more, and preferably 12.0 or less, more preferably 10.0 or less, still more preferably 8. It is 5 or less, more preferably 7.5 or less.

The pH in the aqueous medium after the addition of the acidic substance (hereinafter, also referred to as “pH after the addition of the acidic substance”) is from the viewpoint of further improving the cleaning property, and further improves the fog suppression, the chargeability and the heat-resistant storage property. From the viewpoint, it is preferably 4.0 or more, more preferably 5.0 or more, still more preferably 6.0 or more, still more preferably 6.2 or more, and preferably 7.0 or less, more preferably 6. It is 8 or less, more preferably 6.7 or less.

After the addition of the acidic substance, it is preferable to keep the temperature within the range of the temperature _T1 .
It is preferable to maintain the temperature within the range of the temperature _T1 until the following circularity is reached.

The circularity of the fused particles at the start of addition of the basic substance is preferably 0.950 or more from the viewpoint of further improving the cleaning property, and from the viewpoint of further improving the fog suppression, chargeability and heat storage stability. It is more preferably 0.955 or more, still more preferably 0.960 or more, and preferably 0.965 or less.
The circularity of the fused particles is determined by the method described in Examples.
For fusion, it is preferable to monitor the circularity of the fused particles and start adding the basic substance when the degree is in an appropriate range.

[Basic substance]
Examples of the basic substance include alkali metal hydroxides, carbonates, bicarbonates, and nitrogen-containing basic substances.
Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and lithium hydroxide.
Examples of the carbonate include sodium carbonate and potassium carbonate.
Examples of the hydrogen carbonate include sodium hydrogen carbonate and potassium hydrogen carbonate.
Examples of the nitrogen-containing basic substance include ammonia, trimethylamine, and diethanolamine.
Among these, alkali metal hydroxides are preferable, and potassium hydroxide is more preferable, from the viewpoint of further improving the cleaning property of the toner, and from the viewpoint of further improving fog suppression, chargeability and heat storage stability.

The basic substance is preferably added into the system as an aqueous solution of the basic substance from the viewpoint of further improving the cleaning property and further improving the fog suppression, chargeability and heat storage property.
When added as an aqueous solution of a basic substance, the concentration of the basic substance is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more in the aqueous solution of the basic substance. And, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less.

The pH in the aqueous medium can be adjusted by adding a basic substance from the viewpoint of obtaining a toner exhibiting excellent cleaning properties and from the viewpoint of obtaining a toner exhibiting excellent fog suppression, chargeability and heat storage resistance. Increase by 0.1 or more and less than 1.0 from before addition. At this time, by using a specific basic substance and raising the pH, excessive fusion treatment is suppressed and the circularity of the toner particles is suppressed from becoming excessively high.
The pH increased by the addition of a basic substance (hereinafter, also referred to as “ΔpH”) is preferably 0 from the viewpoint of further improving the cleaning property, and from the viewpoint of further improving the fog suppression, chargeability and heat storage property. .1 or more, more preferably 0.2 or more, and preferably 0.8 or less, more preferably 0.5 or less, still more preferably 0.3 or less.

The pH in the aqueous medium after the addition of the basic substance (hereinafter, also referred to as "pH after the addition of the basic substance") is from the viewpoint of further improving the cleaning property, as well as the fog suppression, the chargeability and the heat-resistant storage property. From the viewpoint of improvement, it is preferably 5.0 or more, more preferably 6.0 or more, still more preferably 6.2 or more, still more preferably 6.5 or more, and preferably 6.9 or less, more preferably. It is 6.8 or less, more preferably 6.7 or less.

The circularity of the fused particles after the addition of the basic substance is preferably 0.950 or more, more preferably 0.955 or more, still more preferably 0.960 or more, and preferably 0.970 or less. It is preferably 0.967 or less, more preferably 0.965 or less.
The circularity of the fused particles is determined by the method described in Examples.

The difference between the circularity of the fused particles after the addition of the basic substance and the circularity of the fused particles at the start of the addition of the basic substance [after the addition of the basic substance-at the start of the addition of the basic substance] is cleanability. From the viewpoint of further improving fog suppression, chargeability and heat storage stability, preferably 0.007 or less, more preferably 0.005 or less, still more preferably 0.003 or less, still more preferable. Is less than or equal to 0.002 and more than or equal to 0.000.

A method for producing a toner according to an embodiment of the present invention is, for example, a step of aggregating resin particles a containing a polyester resin A to obtain agglomerated particles 1 (hereinafter, also referred to as “step (1)”).
A step of adhering the resin particles b containing the polyester-based resin B to the agglomerated particles 1 to obtain the agglomerated particles 2 (hereinafter, also referred to as “step (2)”), and a step of fusing the agglomerated particles 2 in an aqueous medium. (Hereinafter, also referred to as "process (3)")
including.
Hereinafter, the present invention will be described by taking the embodiment as an example.

<Process (1)>
In step 1, the resin particles a containing the polyester-based resin A are aggregated to obtain the aggregated particles 1.
[Resin particles a]
In step 1, it is preferable that the resin particles a contain the crystalline polyester resin C, or the resin particles c containing the crystalline polyester resin C are aggregated together with the resin particles a.

≪Polyester resin A≫
Examples of the polyester resin A include a polyester resin and a composite resin containing a polyester resin segment and an addition polymerization resin segment. Of these, composite resins are preferred.
The polyester-based resin A is preferably an amorphous polyester-based resin A.

（式中、ＯＲ¹及びＲ²Ｏはオキシアルキレン基であり、Ｒ¹及びＲ²はそれぞれ独立にエチレン基又はプロピレン基であり、ｘ及びｙはアルキレンオキサイドの平均付加モル数を示し、それぞれ正の数であり、ｘとｙの和の値は、１以上、好ましくは１．５以上であり、１６以下、好ましくは８以下、より好ましくは４以下である）で表されるビスフェノールＡのアルキレンオキサイド付加物である。
ビスフェノールＡのアルキレンオキサイド付加物としては、例えば、ビスフェノールＡ〔２，２－ビス（４－ヒドロキシフェニル）プロパン〕のプロピレンオキサイド付加物、ビスフェノールＡのエチレンオキサイド付加物が挙げられる。これらは１種又は２種以上を用いてもよい。
これらの中でも、ビスフェノールＡのプロピレンオキサイド付加物が好ましい。
ビスフェノールＡのアルキレンオキサイド付加物の含有量は、アルコール成分中、好ましくは７０モル％以上、より好ましくは９０モル％以上、更に好ましくは９５モル％以上であり、そして、１００モル％以下であり、更に好ましくは１００モル％である。 The polyester resin is, for example, a polycondensate of an alcohol component and a carboxylic acid component.
Examples of the alcohol component include aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Among these, aromatic diols are preferable.
The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of the formula (I) :.

(In the formula, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are independently ethylene groups or propylene groups, and x and y indicate the average number of adducts of the alkylene oxide, respectively, which are positive. The value of the sum of x and y is 1 or more, preferably 1.5 or more, 16 or less, preferably 8 or less, and more preferably 4 or less). It is an oxide adduct.
Examples of the alkylene oxide adduct of bisphenol A include a propylene oxide adduct of bisphenol A [2,2-bis (4-hydroxyphenyl) propane] and an ethylene oxide adduct of bisphenol A. These may be used alone or in combination of two or more.
Among these, a propylene oxide adduct of bisphenol A is preferable.
The content of the alkylene oxide adduct of bisphenol A is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less in the alcohol component. More preferably, it is 100 mol%.

Examples of the linear or branched aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , 2,3-Butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1, , 12-Dodecanediol.
Examples of the alicyclic diol include hydrogenated bisphenol A [2,2-bis (4-hydroxycyclohexyl) propane] and an alkylene oxide adduct having 2 or more and 4 or less carbon atoms of hydrogenated bisphenol A (average number of added moles 2). 12 or less).
Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
These alcohol components may be used alone or in combination of two or more.

Examples of the carboxylic acid component include a dicarboxylic acid and a trivalent or higher valent carboxylic acid.
Examples of the dicarboxylic acid include aromatic dicarboxylic acids, linear or branched aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Among these, at least one selected from aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids is preferable.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
The amount of the aromatic dicarboxylic acid is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, still more preferably 50 mol% or more, and preferably 50 mol% or more in the carboxylic acid component. It is 90 mol% or less, more preferably 80 mol% or less, still more preferably 75 mol% or less.

The linear or branched aliphatic dicarboxylic acid has preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less.
Examples of the linear or branched aliphatic dicarboxylic acid include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedic acid, and azelaic acid. , Succinic acid substituted with an alkyl group having 1 or more and 20 or less carbon atoms or an alkenyl group having 2 or more and 20 or less carbon atoms. 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, and octenyl succinic acid. Of these, fumaric acid and sebacic acid are preferable.
The amount of the linear or branched aliphatic dicarboxylic acid is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, and preferably 80 mol% or more in the carboxylic acid component. Below, it is more preferably 70 mol% or less, still more preferably 50 mol% or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, and examples thereof include trimellitic acid.
When a trivalent or higher polyvalent carboxylic acid is contained, the amount of the trivalent or higher polyvalent carboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% in the carboxylic acid component. And more, preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 15 mol% or less.
As these carboxylic acid components, one kind or two or more kinds may be used.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group / OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less. It is preferably 1.2 or less.

(Manufacturing method of polyester resin)
The polyester resin is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component.
The polyester resin is prepared by using an esterification catalyst such as di (2-ethylhexanoic acid) tin (II), dibutyltin oxide, and titanium diisopropyrate bistriethanol aminate as necessary, and the total amount of the alcohol component and the carboxylic acid component is 100. 0.01 part by mass or more and 5 parts by mass or less with respect to parts by mass; an esterification auxiliary catalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) is used as a total amount of 100 parts by mass of the alcohol component and the carboxylic acid component. Polycondensation may be carried out by using 0.001 part by mass or more and 0.5 part by mass or less with respect to the parts.
When a monomer having an unsaturated bond such as fumaric acid is used for polycondensation, it is preferably 0.001 part by mass or more with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component, if necessary. A radical polymerization inhibitor of 0.5 parts by mass or less may be used. Examples of the radical polymerization inhibitor include 4-tert-butylcatechol.
The temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, further preferably 180 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower. The polycondensation may be carried out in an inert gas atmosphere.

The composite resin in the above embodiment includes a polyester resin segment and an addition polymerization resin segment. The polyester resin constituting the polyester resin segment is the same as the polyester resin described above.

The addition polymerized resin segment is, for example, an addition polymer of a raw material monomer containing a styrene compound.
Examples of the styrene-based compound include unsubstituted or substituted styrene. Examples of the substituent substituted with styrene include an alkyl group having 1 or more and 5 or less carbon atoms, a halogen atom, an alkoxy group having 1 or more and 5 or less carbon atoms, a sulfonic acid group or a salt thereof.
Examples of the styrene-based compound include styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid or salts thereof. Among these, styrene is preferable.
The content of the styrene-based compound in the raw material monomer of the addition polymerization resin segment is preferably 50% by mass or more, more preferably 65% by mass or more, further preferably 75% by mass or more, and 100% by mass or less. It is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.

Examples of the raw material monomers other than the styrene compound include (meth) acrylic acid esters such as alkyl (meth) acrylate, benzyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate; ethylene, propylene, and butadiene. Olefins; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether; vinylidene halide such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone can be mentioned. .. Among these, (meth) acrylic acid ester is preferable, and (meth) acrylic acid alkyl is more preferable.
The number of carbon atoms of the alkyl group in the alkyl (meth) acrylate is preferably 1 or more, more preferably 6 or more, still more preferably 10 or more, and preferably 24 or less, more preferably 22 or less, still more preferably 20. It is as follows.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) propyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, and (meth). ) Acrylic acid (iso) amyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid (iso) octyl, (meth) acrylic acid (iso) decyl, (meth) acrylic acid ( Examples thereof include (iso) dodecyl, (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, (meth) acrylic acid (iso) behenyl, and (meth) acrylic acid 2-ethylhexyl or (meth). Stearyl acrylate is preferred, and stearyl (meth) acrylate is more preferred.
In addition, "(iso or tertiary)" and "(iso)" mean both the case where these prefixes exist and the case where these prefixes do not exist, and when these prefixes do not exist, they indicate normal. Further, "(meth) acrylic acid" indicates acrylic acid or methacrylic acid.

The content of the (meth) acrylic acid ester in the raw material monomer of the addition polymerization resin segment is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or more. It is mass% or less, more preferably 35% by mass or less, still more preferably 25% by mass or less.

The total amount of the styrene compound and the (meth) acrylic acid ester in the raw material monomer of the addition polymerization resin segment 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. Is 100% by mass.

The composite resin preferably has a structural unit derived from a bireactive monomer bonded to the polyester resin segment and the addition polymerization resin segment via a covalent bond.
The “constituent unit derived from the bireactive monomer” means a unit on which the functional group and the addition polymerizable group of the bireactive monomer have reacted.
Examples of the addition polymerizable group include a carbon-carbon unsaturated bond.
Examples of the bireactive monomer include an addition-polymerizable monomer having at least one functional group selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group in the molecule. .. Among these, from the viewpoint of reactivity, an addition-polymerizable monomer having at least one functional group selected from a hydroxyl group and a carboxy group is preferable, and an addition-polymerizable monomer having a carboxy group is more preferable.
Examples of the addition polymerizable monomer having a carboxy group include acrylic acid, methacrylic acid, fumaric acid, and maleic acid. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable, from the viewpoint of reactivity of both the polycondensation reaction and the addition polymerization reaction.
The amount of the structural unit derived from the bireactive monomer is preferably 1 mol part or more, more preferably 5 mol part or more, still more preferably 8 mol part or more with respect to 100 mol part of the alcohol component of the polyester resin segment of the composite resin. And preferably 30 mol parts or less, more preferably 25 mol parts or less, still more preferably 20 mol parts or less.

The content of the polyester resin segment in the composite resin is preferably 35% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or more. It is mass% or less, more preferably 75 mass% or less.

The content of the addition polymerized resin segment in the composite resin is preferably 5% by mass or more, more preferably 15% by mass or more, still more preferably 25% by mass or more, and preferably 60% by mass or less, more preferably. It is 55% by mass or less, more preferably 45% by mass or less.

The amount of the structural unit derived from the bireactive monomer in the composite resin is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, and preferably. Is 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.

The total amount of the constituent units derived from the polyester resin segment, the addition polymerization resin segment and the bireactive monomer in the composite resin is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more. And, 100% by mass or less, and more preferably 100% by mass.

The composite resin may be produced, for example, by a method including a step A of polycondensing an alcohol component and a carboxylic acid component, and a step B of addition polymerization of the raw material monomer and the bireactive monomer of the addition polymerization resin segment.
The process B may be performed after the process A, the process A may be performed after the process B, or the process A and the process B may be performed at the same time.
In step A, a part of the carboxylic acid component is subjected to a polycondensation reaction, then step B is carried out, and then the rest of the carboxylic acid component is added to the polymerization system, and the polycondensation reaction of step A and, if necessary, both reactions. A method of further advancing the reaction with the sex monomer is preferable.

The conditions for polycondensation are the same as those illustrated in the above-mentioned method for synthesizing polyester resin.
Examples of the radical polymerization initiator for addition polymerization include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile). Can be mentioned.
The amount of the radical polymerization initiator used is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the raw material monomer of the addition polymerization resin segment.
The temperature of the addition polymerization is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, and preferably 230 ° C. or lower, more preferably 220 ° C. or lower, still more preferably 210 ° C. or lower.

(Physical characteristics of polyester resin A)
The softening point of the polyester-based resin A is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher, and further improves low-temperature fixability, from the viewpoint of further improving heat-resistant storage stability. From the viewpoint, it is preferably 140 ° C. or lower, more preferably 130 ° C. or lower, still more preferably 125 ° C. or lower.
The glass transition temperature of the polyester resin A is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, still more preferably 40 ° C. or higher, and further improves low-temperature fixability, from the viewpoint of further improving heat-resistant storage stability. From the viewpoint of the temperature, it is preferably 80 ° C. or lower, more preferably 70 ° C. or lower, and further preferably 60 ° C. or lower.

The acid value of the polyester resin A is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less. , More preferably 30 mgKOH / g or less.
The softening point, glass transition temperature, and acid value of the polyester resin A can be appropriately adjusted depending on the type and amount of the raw material monomer used, and the production conditions such as reaction temperature, reaction time, and cooling rate, and they can be appropriately adjusted. The value of is obtained by the method described in Examples.
When two or more kinds of polyester resins A are used in combination, it is preferable that the softening point, the glass transition temperature and the acid value obtained as a mixture thereof are within the above-mentioned ranges.

The content of the polyester-based resin A is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and 100% by mass, based on the total amount of the resin components of the aggregated particles 1. It is 9% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less.

≪Crystalline polyester resin C≫
The crystalline polyester resin C is a polycondensate of an alcohol component and a carboxylic acid component.
As the alcohol component, α, ω-aliphatic diol is preferable.
The number of carbon atoms of the α, ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less. be.
Examples of the α, ω-aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol Can be mentioned. Among these, 1,6-hexanediol, 1,10-decanediol, and 1,12-dodecanediol are preferable, and 1,10-decanediol is more preferable.

The amount of α, ω-aliphatic diol is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 in the alcohol component. It is less than or equal to mol%, more preferably 100 mol%.

The alcohol component may contain other alcohol components different from the α, ω-aliphatic diol. Examples of other alcohol components include aliphatic diols other than α and ω-aliphatic diols such as 1,2-propanediol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; glycerin and penta. Examples thereof include trihydric or higher alcohols such as erythritol and trimethylol propane. These alcohol components may be used alone or in combination of two or more.

As the carboxylic acid component, an aliphatic dicarboxylic acid is preferable.
The aliphatic dicarboxylic acid has preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
Examples of the aliphatic dicarboxylic acid include fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, sebacic acid and dodecanedioic acid are preferable, and sebacic acid is more preferable. As these carboxylic acid components, one kind or two or more kinds may be used.

The amount of the aliphatic dicarboxylic acid is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol in the carboxylic acid component. % Or less, more preferably 100 mol%.

The carboxylic acid component may contain another carboxylic acid component different from the aliphatic dicarboxylic acid. Examples of other carboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and polyvalent carboxylic acids having a valence of 3 or more. As these carboxylic acid components, one kind or two or more kinds may be used.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group / OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less. It is preferably 1.2 or less.

Examples of the method for producing the crystalline polyester resin C include the same examples as the above-mentioned method for producing the polyester resin of the polyester resin A.

(Physical characteristics of crystalline polyester resin C)
The softening point of the crystalline polyester resin C is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, and further improves low-temperature fixability, from the viewpoint of further improving heat-resistant storage stability. From the viewpoint of the temperature, it is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 100 ° C. or lower.

The melting point of the crystalline polyester resin C is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, and further improves low-temperature fixability, from the viewpoint of further improving heat-resistant storage stability. From the viewpoint, it is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, still more preferably 80 ° C. or lower.

The acid value of the crystalline polyester resin C is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and preferably 35 mgKOH / g or less, more preferably 25 mgKOH / g or less, still more preferably 20 mgKOH / g. It is as follows.

The softening point, melting point, and acid value of the crystalline polyester resin C can be appropriately adjusted depending on the type and amount of the raw material monomer used, and the production conditions such as reaction temperature, reaction time, and cooling rate. It is obtained by the method described in. When two or more kinds of crystalline polyester resin C are used in combination, it is preferable that the values of the softening point, the melting point, and the acid value obtained as a mixture thereof are within the above ranges.

The content of the crystalline polyester resin C is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and more preferably 20% by mass or more, based on the total amount of the resin components of the aggregated particles 1. It is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less.

The mass ratio of the polyester resin A to the crystalline polyester resin C [polyester resin A / crystalline polyester resin C] is preferably 40/60 or more, more preferably 50/50 or more, still more preferably 60/40 or more. And preferably 95/5 or less, more preferably 90/10 or less, still more preferably 80/20 or less.

The total amount of the polyester resin A and the crystalline polyester resin C is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass, based on the total amount of the resin components of the aggregated particles 1. As mentioned above, it is more preferably 95% by mass or more, and 100% by mass or less, and further preferably 100% by mass.

<< Manufacturing method of resin particles a >>
The dispersion liquid of the resin particles a is obtained by dispersing the polyester resin A in an aqueous medium. When the toner contains the crystalline polyester resin C, the crystalline polyester resin C may be dispersed at the same time to form the resin particles a containing the crystalline polyester resin C, or the crystals may be separated from the resin particles a. Resin particles c containing the sex polyester resin C may be used. The dispersion liquid of the resin particles c can also be obtained by the same method as the method for producing the dispersion liquid of the resin particles a.
The aqueous medium preferably contains water as a main component, and the content of water in the aqueous medium is preferably 80% by mass from the viewpoint of improving the dispersion stability of the dispersion liquid of the resin particles and from the viewpoint of environmental friendliness. % Or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, and 100% by mass or less, still more preferably 100% by mass. As the water, deionized water or distilled water is preferable. Examples of components other than water that can be contained in the aqueous medium include alkyl alcohols having 1 or more and 5 or less carbon atoms; dialkyl ketones having 3 or more and 5 or less carbon atoms such as acetone and methyl ethyl ketone; and soluble in water such as cyclic ethers such as tetrahydrofuran. Organic solvent to be used. Among these, methyl ethyl ketone is preferable.

The dispersion can be carried out by a known method, but it is preferably dispersed by a phase inversion emulsification method. Examples of the phase inversion emulsification method include a method of adding an aqueous medium to an organic solvent solution of a resin or a molten resin to invert phase emulsification.

The organic solvent used for phase inversion emulsification is not particularly limited as long as the resin is dissolved, and examples thereof include methyl ethyl ketone.
It is preferable to add a neutralizing agent to the organic solvent solution. Examples of the neutralizing agent include basic substances. Examples of the basic substance include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; and nitrogen-containing basic substances such as ammonia, trimethylamine and diethanolamine.
The equivalent amount (mol%) of the neutralizing agent to the acid group of the resin contained in the resin particles a is preferably 10 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, and It is preferably 150 mol% or less, more preferably 100 mol% or less, still more preferably 70 mol% or less.
The equivalent amount (mol%) of the neutralizing agent used can be calculated by the following formula. When the equivalent amount of the neutralizing agent is 100 mol% or less, it is synonymous with the degree of neutralization.
Equivalent to use of neutralizer (mol%) = [{mass of neutralizer added (g) / equivalent of neutralizer} / [{weighted average acid value of resin constituting resin particles a (mgKOH / g) × Mass of resin constituting resin particles a (g)} / (56 × 1000)]] × 100

While stirring the organic solvent solution or the melted resin, an aqueous medium is gradually added to invert the phase.
The temperature of the organic solvent solution when the aqueous medium is added is preferably at least the glass transition temperature of the resin constituting the resin particles a, more preferably 50 ° C. or higher, still more preferably, from the viewpoint of improving the dispersion stability of the resin particles a. Is 60 ° C. or higher, preferably 85 ° C. or lower, and more preferably 80 ° C. or lower.

After the phase inversion emulsification, if necessary, the organic solvent may be removed from the obtained dispersion by distillation or the like. 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, still more preferably substantially 0% in the aqueous dispersion.

The content of the polyester-based resin A is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass, based on the total amount of the resin components of the resin particles a. % Or more, and 100% by mass or less, more preferably 100% by mass.

When the resin particles a contain the crystalline polyester resin C, the content of the polyester-based resin A is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total amount of the resin components of the resin particles a. It is more preferably 65% by mass or more, and preferably 95% by mass or less, preferably 90% by mass or less, and preferably 80% by mass or less.
When the resin particles a contain the crystalline polyester resin C, the content of the crystalline polyester resin C is preferably relative to the total amount of the resin components of the resin particles a from the viewpoint of improving the low temperature fixability of the toner. It is 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less.

The volume median particle size (D ₅₀ ) of the resin particles a in the dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more, and more preferably 0.08 μm or more, from the viewpoint of obtaining a toner that can obtain a high-quality image. It is preferably 0.8 μm or less, more preferably 0.4 μm or less, still more preferably 0.3 μm or less.
The CV value of the resin particles a in the dispersion is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, more preferably, from the viewpoint of obtaining a toner that can obtain a high-quality image. Is 35% or less, more preferably 30% or less.
The volume median particle size (D ₅₀ ) and CV value of the resin particles are determined by the method described in Examples described later.

When the resin particles c containing the crystalline polyester resin C are used, the resin particles c can be obtained by the same method as described above.
The amount of the resin particles a and the resin particles c added is preferably an amount that is the content of the polyester-based resin A and the crystalline polyester-based resin C described above.

〔Release agent〕
The agglomerated particles 1 may contain a mold release agent.
Examples of the mold release agent include polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax; hydrocarbon waxes such as microcrystallin wax, paraffin wax, Fishertropch wax, and sazole wax, or oxides thereof; carnauba wax. , Montan wax or ester waxes such as deoxidizing waxes and fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like. These may be used alone or in combination of two or more.

The melting point of the release agent is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and preferably 160 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 140 ° C. or lower.
The content of the release agent is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, still more preferably 5 parts by mass or more, and preferably 20 parts by mass with respect to 100 parts by mass of the binder resin. By mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.

(Dispersion of mold release agent particles)
It is preferable that the release agent is contained in the agglomerated particles 1 by mixing with the resin particles a and aggregating the release agent as a dispersion liquid of the release agent particles.
The dispersion liquid of the release agent particles can be obtained by using a surfactant, but it is preferably obtained by mixing the release agent and the resin particles z described later. By preparing the release agent particles using the release agent and the resin particles z, the release agent particles are stabilized by the resin particles z, and the release agent can be placed in the aqueous medium without using a surfactant. It becomes possible to disperse. It is considered that the release agent particles have a structure in which a large number of resin particles z are attached to the surface of the release agent particles in the dispersion liquid.

The resin constituting the resin particles z in which the release agent is dispersed is preferably a polyester resin, and has a polyester resin segment and an addition polymerization resin segment from the viewpoint of improving the dispersibility of the release agent in an aqueous medium. It is more preferable to use the composite resin D.
The softening point of the composite resin D is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and preferably 140 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower.
The preferred range of other resin properties of the composite resin D, the preferred examples of the raw material monomers constituting the resin, and the like are the same as the examples shown in the polyester resin A. The dispersion liquid of the resin particles z can be obtained, for example, by the above-mentioned phase inversion emulsification method.
The volume median particle diameter (D ₅₀ ) of the resin particles z is preferably 0.01 μm or more, more preferably 0.03 μm or more, and preferably 0. It is 3 μm or less, more preferably 0.2 μm or less.
The CV value of the resin particles z is preferably 10% or more, more preferably 15% or more, and preferably 40% or less, more preferably 35% or less, from the viewpoint of dispersion stability of the release agent particles. More preferably, it is 30% or less.

The release agent particle dispersion liquid is, for example, a homogenizer, a high-pressure disperser, an ultrasonic disperser, etc. It is obtained by dispersing using a disperser.
The heating temperature at the time of dispersion is preferably equal to or higher than the melting point of the mold release agent and 80 ° C. or higher, more preferably 85 ° C. or higher, further preferably 90 ° C. or higher, and preferably softening of the resin contained in the resin particles z. The temperature is less than 10 ° C. higher than the point and 100 ° C. or lower, more preferably 98 ° C. or lower, still more preferably 95 ° C. or lower.

The amount of the resin particles z is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, and preferably 100 parts by mass or less with respect to 100 parts by mass of the release agent. , More preferably 70 parts by mass or less, still more preferably 50 parts by mass or less.

The volume median particle diameter (D ₅₀ ) of the release agent particles is preferably 0.05 μm or more, more preferably 0.2 μm or more, still more preferably 0.4 μm or more, from the viewpoint of obtaining uniform aggregated particles by aggregation. Yes, and it is preferably 1 μm or less, more preferably 0.8 μm or less, still more preferably 0.6 μm or less.
The CV value of the release agent particles is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, more preferably 35% or less, still more preferably 30% or less.
The method for measuring the volume median particle diameter (D ₅₀ ) and the CV value of the release agent particles is as described in the examples.

[Colorant]
The agglomerated particles 1 may contain a colorant.
As the colorant, all dyes, pigments and the like used as colorants for toner can be used.
Examples of the colorant include carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmin 6B, and disazoero. Be done. The toner may be either black toner or color toner.

The content of the colorant 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 binder resin from the viewpoint of improving the image density of the toner. It is more preferably 8 parts by mass or more, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less.

(Dispersion of colorant particles)
The colorant is preferably contained in the agglomerated particles 1 by mixing with the resin particles a and aggregating the colorant as a dispersion liquid of the colorant particles.
The dispersant of the colorant particles is preferably obtained by dispersing the colorant and the aqueous medium using a disperser such as a homogenizer or an ultrasonic disperser. The dispersion is preferably carried out in the presence of a surfactant from the viewpoint of improving the dispersion stability of the colorant. Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants, and from the viewpoint of improving the dispersion stability of the colorant particles, anionic surfactants are preferable. It is an agent. Examples of the anionic surfactant include sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium lauryl ether sulfate, and dipotassium alkenyl succinate. Of these, sodium dodecylbenzene sulfonate is preferable.

The content of the surfactant in the dispersion liquid of the colorant particles is preferably 1 part by mass or more, more preferably 5 parts by mass with respect to 100 parts by mass of the colorant, from the viewpoint of improving the dispersion stability of the colorant. The above is more preferably 10 parts by mass or more, preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.

The volume median particle size (D ₅₀ ) of the colorant particles is preferably 0.05 μm or more, more preferably 0.08 μm or more, still more preferably 0.1 μm or more, and preferably 0.3 μm or less. It is preferably 0.2 μm or less.
The method for measuring the volume median particle size (D ₅₀ ) of the colorant particles is the method described in the examples.

The agglomerated particles 1 also contain additives such as a charge control agent, a magnetic powder, a fluidity improver, a conductivity modifier, a reinforcing filler such as a fibrous substance, an antioxidant, an antiaging agent, and a cleaning property improving agent. It may be included.

[Surfactant]
In step 1, it is preferable to agglomerate the resin particles a after preparing the mixed dispersion.
When preparing the mixed dispersion, it may be carried out in the presence of a surfactant from the viewpoint of improving the dispersion stability of arbitrary components such as the resin particles a and the wax particles added as needed. Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates and alkyl ether sulfates; and nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers.
When a surfactant is used, the amount used is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and preferably 10 parts by mass with respect to 100 parts by mass of the resin particles a. Parts or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.

The above-mentioned dispersion liquid of the resin particles a and the mixing of arbitrary components are carried out by a conventional method. From the viewpoint of efficient aggregation, it is preferable to add an aggregating agent to the mixed dispersion obtained by the mixing.

[Coagulant]
The agglomerated particles are obtained by aggregating the polyester resin particles by adding an aggregating agent.
Examples of the flocculant include a cationic surfactant of a quaternary salt, an organic flocculant such as polyethyleneimine; an inorganic metal salt such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride and calcium nitrate; ammonium sulfate and chloride. Inorganic ammonium salts such as ammonium and ammonium nitrate; inorganic flocculants such as divalent or higher metal complexes can be mentioned.
From the viewpoint of improving the cohesiveness and obtaining uniform agglomerated particles, an inorganic flocculant having a valence of 1 or more and a valence of 5 or less is preferable, an inorganic metal salt having a valence of 1 or more and a divalent or less, an inorganic ammonium salt is more preferable, and an inorganic ammonium salt is preferable. Further preferred, ammonium sulfate is even more preferred.

Using a flocculant, for example, a flocculant of 5 parts by mass or more and 50 parts by mass or less is added to a mixed dispersion containing resin particles a of 0 ° C. or higher and 40 ° C. or lower with respect to 100 parts by mass of the total amount of the resin, and the resin particles. a is agglomerated in an aqueous medium to obtain agglomerated particles 1. Further, from the viewpoint of promoting aggregation, it is preferable to raise the temperature of the dispersion after adding the flocculant.

The volume median particle size (D ₅₀ ) of the agglomerated particles 1 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, still more preferably. It is 6 μm or less. The volume median particle size (D ₅₀ ) of the agglomerated particles 1 is determined by the method described in Examples described later.

<Step 2>
In step 2, the resin particles b containing the polyester-based resin B are attached to the agglomerated particles 1 to obtain the agglomerated particles 2.
[Resin particles b]
The dispersion liquid of the resin particles b can be obtained by the same method as the above-mentioned method for producing the dispersion liquid of the resin particles a.
In step 2, for example, the resin particles b are aggregated in the agglomerated particles 1 by adding the dispersion of the resin particles b to the dispersion containing the agglomerated particles 1 having a temperature of 30 ° C. or higher and 80 ° C. or lower, and the resin particles b are aggregated in an aqueous medium. Obtain particle 2.

≪Polyester resin B≫
Examples of the polyester resin B include a polyester resin and a composite resin containing a polyester resin segment and an addition polymerization resin segment.
The polyester-based resin B is preferably an amorphous polyester-based resin B.

The example of the polyester-based resin B is the same as the example in the polyester-based resin A described above.
Hereinafter, common embodiments will be omitted, and preferred embodiments of the polyester resin B will be described.
The alcohol component is preferably an aromatic diol, more preferably an alkylene oxide adduct of bisphenol A, and even more preferably an alkylene oxide adduct of bisphenol A represented by the formula (I). As the alkylene oxide adduct of bisphenol A, an ethylene oxide adduct of bisphenol A is preferable.
The content of the alkylene oxide adduct of bisphenol A is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less in the alcohol component. More preferably, it is 100 mol%.

As the carboxylic acid component, at least one selected from aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids is preferable.
As the aromatic dicarboxylic acid, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
The amount of the aromatic dicarboxylic acid is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, and preferably 95 mol% or less, more preferably 95 mol% or more, in the carboxylic acid component. It is 90 mol% or less, more preferably 85 mol% or less.

As the linear or branched aliphatic dicarboxylic acid, fumaric acid, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms is preferable.
The amount of the linear or branched aliphatic dicarboxylic acid is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, still more preferably 15 mol% or more in the carboxylic acid component. And, preferably 40 mol% or less, more preferably 30 mol% or less, still more preferably 25 mol% or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, and examples thereof include trimellitic acid.
The amount of the trivalent or higher polyvalent carboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% or more, and preferably 30 mol% or less in the carboxylic acid component. , More preferably 20 mol% or less, still more preferably 15 mol% or less.

The polyester-based resin B can be obtained, for example, by the same method as in the above-mentioned example of the polyester-based resin A.

(Physical characteristics of polyester resin B)
The softening point of the polyester resin B is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher, and further improves low-temperature fixability, from the viewpoint of further improving heat-resistant storage stability. From the viewpoint, it is preferably 140 ° C. or lower, more preferably 130 ° C. or lower, still more preferably 125 ° C. or lower.

The glass transition temperature of the polyester resin B is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, still more preferably 50 ° C. or higher, and further improves low-temperature fixability, from the viewpoint of further improving heat-resistant storage stability. From the viewpoint of keeping the temperature, it is preferably 80 ° C. or lower, more preferably 75 ° C. or lower, and further preferably 70 ° C. or lower.

The acid value of the polyester resin B is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and more preferably 15 mgKOH / g or more, from the viewpoint of further improving heat-resistant storage and low-temperature fixability. It is preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, still more preferably 30 mgKOH / g or less.
The softening point, glass transition temperature, and acid value of the polyester resin B can be appropriately adjusted depending on the type and amount of the raw material monomer used, and the production conditions such as reaction temperature, reaction time, and cooling rate, and they can be appropriately adjusted. The value of is obtained by the method described in Examples.
When two or more kinds of polyester resins B are used in combination, it is preferable that the softening point, the glass transition temperature and the acid value obtained as a mixture thereof are within the above-mentioned ranges.

The resin particles b containing the polyester-based resin B can be obtained, for example, by the same method as the above-mentioned resin particles a.
The degree of neutralization of the polyester-based resin B in the resin particles b is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 20 mol% or more, from the viewpoint of further improving the fog suppression by adding the metal compound in step 3. It is 30 mol% or more, more preferably 40 mol% or more, and preferably 100 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less.

The content of the polyester-based resin B is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass, based on the total amount of the resin components of the resin particles b. % Or more, and 100% by mass or less, more preferably 100% by mass.
The mass ratio of the polyester resin B to the total amount of the polyester resin A and the crystalline polyester resin C [total amount of the polyester resin B / polyester resin A and the crystalline polyester resin C] is preferably 5/95. The above is more preferably 10/90 or more, still more preferably 15/85 or more, and preferably 30/70 or less, more preferably 25/85 or less, still more preferably 20/80 or less.

Aggregation may be stopped when the agglomerated particles have grown to an appropriate particle size as toner particles.
Examples of the method for stopping the aggregation include a method of cooling the dispersion, a method of adding an aggregation inhibitor, a method of diluting the dispersion, and a method of changing the pH. From the viewpoint of surely preventing unnecessary aggregation, a method of adding an aggregation terminator to stop aggregation is preferable.

[Coagulation terminator]
As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, and polyoxyalkylene alkyl ether sulfates. As the aggregation terminator, one kind or two or more kinds may be used. The aggregation terminator may be added in an aqueous solution.
The amount of the aggregation terminator added is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the binder resin in the toner from the viewpoint of surely preventing unnecessary aggregation. Yes, and from the viewpoint of reducing the residue on the toner, it is preferably 30 parts by mass or less, more preferably 15 parts by mass or less.

The volume median particle size (D ₅₀ ) of the agglomerated particles 2 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, still more preferably. It is 6 μm or less. The volume median particle size (D ₅₀ ) of the agglomerated particles is determined by the method described in Examples described later.

<Process 3>
In step 3, the agglomerated particles 2 are fused in an aqueous medium. In this step, the agglomerated particles 2 are fused under the conditions shown in the above-mentioned fusion step.
The volume median particle size (D ₅₀ ) of the fused particles obtained by fusion after the addition of the basic substance is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 4 μm or more. It is 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less.
The volume median particle size (D ₅₀ ) of the fused particles after the addition of the basic substance is according to the method described in Examples.

<Post-treatment process>
A post-treatment step may be performed after step 3, and toner particles are obtained by isolating the fused particles. Since the fused particles obtained in step 3 are present in the aqueous medium, it is preferable to first perform solid-liquid separation. Examples of the solid-liquid separation include a suction filtration method, a pressure filtration method, and a centrifugal filtration method.
It is preferable to perform cleaning after solid-liquid separation. At this time, since it is preferable to remove the added surfactant as well, it is preferable to wash with an aqueous medium below the cloud point of the surfactant. It is preferable to perform washing multiple times.
Next, it is preferable to perform drying. Examples of the drying method include a vacuum low temperature drying method, a vibration type fluid drying method, a spray drying method, a freeze drying method, and an air flow drying method.

[Toner particles]
The toner particles can be used as they are as toner, but it is preferable to use the toner particles whose surface is treated as described later.
The volume median particle size (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, from the viewpoint of obtaining a high-quality image and further improving the cleaning property of the toner. Yes, and it is preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less.

The circularity of the toner particles is preferably 0.940 or more, more preferably 0.950 or more, still more preferably 0.960 or more, and the cleaning property of the toner, from the viewpoint of further improving the heat storage stability of the toner. From the viewpoint of further improving the above, it is preferably 0.990 or less, more preferably 0.980 or less, still more preferably 0.970 or less, still more preferably 0.968 or less, still more preferably 0.965 or less.
The volume median particle size (D ₅₀ ) and circularity of the toner particles can be measured by the method described in Examples.
The content of the toner particles in the toner is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less. Yes, preferably 99% by mass or less.

[External agent]
Although the toner particles can be used as they are as the toner, it is preferable to use the toner particles obtained by adding a fluidizing agent or the like as an external agent to the surface of the toner particles.
Examples of the external additive include inorganic material fine particles such as hydrophobic silica, titanium oxide, alumina, cerium oxide and carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate and silicone resin. Of these, hydrophobic silica is preferred.
When the surface treatment of the toner particles is performed using an external additive, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 2 parts by mass, based on 100 parts by mass of the toner particles. It is 3 parts by mass or more, preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and further preferably 4 parts by mass or less.

The toner for static charge image development obtained by the present invention can be used as a one-component developer or mixed with a carrier as a two-component developer.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like.
In the following examples and the like, the measurement and evaluation of each physical property was performed by the following method.

[Measuring method]
[Acid value of resin]
The acid value of the resin was measured according to JIS K0070: 1992. However, the measurement solvent was a mixed solvent of acetone and toluene [acetone: toluene = 1: 1 (volume ratio)].

[Resin softening point, crystallinity index, melting point and glass transition temperature]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), a 1 g sample is heated at a heating rate of 6 ° C./min while a load of 1.96 MPa is applied by a plunger to give a diameter of 1.96 MPa. Extruded from a 1 mm, 1 mm long 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 used as the softening point.
(2) Crystallinity index Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 g of a sample into an aluminum pan and measure it at a temperature lowering rate of 10 ° C / min to 0 ° C. Cooled down to. Then, the sample was allowed to stand still for 1 minute, and then the temperature was raised to 180 ° C. at a heating rate of 10 ° C./min to measure the calorific value. Of the observed endothermic peaks, the temperature of the peak with the largest endothermic area is defined as the maximum endothermic temperature (1), and is determined by (softening point (° C)) / (maximum endothermic temperature (1) (° C)). The crystallinity index was calculated.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 g of the sample into an aluminum pan and raise the temperature to 200 ° C. From that temperature, the temperature was cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. Then, the temperature was raised at a temperature rising rate of 10 ° C./min, and the amount of heat was measured. Among the observed endothermic peaks, the peak temperature having the largest peak area was defined as the maximum endothermic temperature (2). In the case of crystalline resin, the peak temperature was taken as the melting point. In the case of an amorphous resin, the temperature at the intersection of the extension of the baseline below the maximum peak temperature of heat absorption and the tangent line showing the maximum slope from the rising portion of the peak to the peak of the peak was defined as the glass transition temperature.

[Melting point of mold release agent]
Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), 0.01 g of the sample is weighed in an aluminum pan, the temperature is raised to 200 ° C, and then the temperature is lowered from 200 ° C to 10 ° C. It was cooled to 0 ° C. at / min. Next, the sample was heated at a heating rate of 10 ° C./min, the amount of heat was measured, and the maximum peak temperature of endotherm was taken as the melting point.

[Volume-medium particle size (D ₅₀ ) and CV value of resin particles, mold release agent particles, and colorant particles]
(1) Measuring device: Laser diffraction type particle size measuring machine "LA-920" (manufactured by HORIBA, Ltd.)
(2) Measurement conditions: A sample dispersion was taken in a measurement cell, distilled water was added, and the volume median particle size (D ₅₀ ) and volume average particle size were measured at a temperature at which the absorbance was within an appropriate range. The CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) x 100

[Solid content concentration of resin particle dispersion, release agent particle dispersion, colorant particle dispersion]
Using an infrared moisture meter "FD-230" (manufactured by Ketsuto Kagaku Kenkyusho Co., Ltd.), 5 g of the measurement sample was dried at a drying temperature of 150 ° C., and the measurement mode was 96 (monitoring time 2.5 minutes, fluctuation range 0.05%). Moisture (% by mass) was measured at. The solid content concentration was calculated according to the following formula.
Solid content concentration (% by mass) = 100-moisture (% by mass)

[Volume medium particle size of aggregated particles (D ₅₀ )]
The volume median particle size (D ₅₀ ) of the agglomerated particles was measured as follows.
-Measuring machine: "Coulter Multisizer (registered trademark) III" (manufactured by Beckman Coulter Co., Ltd.)
・ Aperture diameter: 50 μm
-Analysis software: "Multisizer (registered trademark) III version 3.51" (manufactured by Beckman Coulter Co., Ltd.)
-Electrolytic solution: "Isoton (registered trademark) II" (manufactured by Beckman Coulter Co., Ltd.)
-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 again, and the particle size is measured. The volume median particle size (D ₅₀ ) was determined from the distribution.

[PH in water-based medium]
Using the pH meter "SevenGo pH meter SG2" (manufactured by Metler Toledo), connect "InLab Expert Go" (manufactured by Metler Toledo) as an electrode, and immerse the electrode of the pH meter in an aqueous medium to lower the temperature at each temperature. The pH was measured in a stirred state.

[Circularity of toner particles (fused particles)]
The circularity of the toner particles was measured under the following conditions.
-Measuring device: Flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation)
-Preparation of dispersion: The dispersion of toner particles was prepared by diluting it with deionized water so that the solid content concentration was 0.001 to 0.05% by mass.
-Measurement mode: HPF measurement mode

[Volume medium particle size of toner particles (D ₅₀ )]
The volume median particle size (D ₅₀ ) of the toner particles was measured as follows.
The measuring device, aperture diameter, analysis software, and electrolytic solution used were the same as those used in the above-mentioned measurement of the volume median particle size ( _D50 ) of the aggregated particles.
Dispersion: Polyoxyethylene lauryl ether "Emargen (registered trademark) 109P" (HLB (Hydrophile-Lipophile Balance) = 13.6, manufactured by Kao Corporation) is dissolved in the electrolytic solution, and the concentration is 5% by mass. Got
Dispersion conditions: 10 mg of the measured sample of the dried toner particles is added to 5 mL of the dispersion liquid, dispersed for 1 minute with an ultrasonic disperser, then 25 mL of an electrolytic solution is added, and further with an ultrasonic disperser. A sample dispersion was prepared by dispersing for 1 minute.
-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 again, and the particles are measured. The volume median particle size (D ₅₀ ) and the volume average particle size were determined from the diameter distribution.

[Evaluation methods]
[Heat-resistant storage of toner]
20 g of toner was put in a wide-mouthed polybin having an internal volume of 100 mL, and the mixture was allowed to stand in a dryer at a temperature of 50 ° C. for 48 hours with a lid. Then, each sample was allowed to stand for 12 hours or more while being sealed at a temperature of 25 ° C. to cool. Next, set a flue with a mesh opening of 250 μm on the shaking table of a "powder tester" (manufactured by Hosokawa Micron Co., Ltd.), place 20 g of the toner on it, and vibrate for 30 seconds to measure the mass of toner remaining on the flue. , The degree of cohesion was calculated from the following formula. The smaller the value, the better the heat-resistant storage stability of the toner.
Cohesion (%) = Mass of residual toner on the fluid [g] / 20 [g] x 100

[Toner cleaning property]
Using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Corporation), a solid developing toner (a toner amount for solid printing is adhered to the photoconductor) is formed on the photoconductor. This solid developing toner was not transferred to the transfer paper but reached the cleaning device for cleaning, and the number of streaks on the surface of the photoconductor after passing through the cleaning blade was visually confirmed. The smaller the number of streaks, the better the cleaning property.

[Fog suppression]
Toner is mounted on a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Co., Ltd.), and a white image without an image is produced on high-quality paper "Excellent White" in an environmental test room with a temperature of 30 ° C and a relative humidity of 80%. Printing is performed using "Paper A4 size" (manufactured by Oki Data Co., Ltd.), the machine is stopped when half of A4 is transferred, and the transparent mending tape "Scotch (registered trademark) mending" is applied to the surface of the photoconductor before transfer. "Tape 810-3-18" (manufactured by 3M) is attached, and the toner on the surface of the photoconductor is collected.
A mending tape as a reference and a mending tape from which toner on the photoconductor was collected were attached on an unused excellent white paper, respectively, and the colorimeter "SpectroEye" (manufactured by Gretag-Macbeth), light irradiation conditions; CIE L ^* a ^* b ^* color on the mending tape as a reference and on the mending tape from which the toner on the photoconductor was collected using the standard light source D50, observation field 2 °, density standard DINNB, absolute white standard). The hue (L ^* a ^* b ^* value) in the coordinate system was measured, and the color difference (ΔE) between the two represented by the following equation was obtained. The smaller ΔE, the less fog.
ΔE = [(L ^* ₁ -L ^* ₂ ) ² + (a ^* ₁ -a ^* ₂ ) ² + (b ^* ₁ -b ^* ₂ ) ² ] ^1/2
[In the formula, L ^* ₁ , a ^* ₁ and b ^* ₁ are the measured values on the mending tape as a reference, and L ^* ₂ , a ^* ₂ and b ^* ₂ are the men from which the toner on the photoconductor was collected. Each measured value on the ding tape is shown. ]

[Evaluation of toner chargeability]
When a solid image was printed on excellent white paper (80 g / m ² paper manufactured by Oki Data Corporation) using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Corporation) and transferred to half of A4. The machine was stopped at, 1 cm × 2 cm jigs were attached to 3 cm portions from both ends on the developing roller, and the charge amount was measured using a Q / m meter “210HS” (manufactured by Trek). The chargeability is negative, and the higher the absolute value of the charge amount, the higher the chargeability.

[Manufacturing of resin]
Production Example A1 (Production of amorphous resin A-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 4200 g of a propylene oxide (2.2) adduct of bisphenol A, 1355 g of terephthalic acid, and di. 31 g of (2-ethylhexanoic acid) tin (II) and 3 g of gallic acid (3,4,5-trihydroxybenzoic acid) were added, and the temperature was raised to 235 ° C. at 235 ° C. with stirring under a nitrogen atmosphere. After holding for 5 hours, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 160 ° C. and kept at 160 ° C., and a mixture of 1819 g of styrene, 455 g of stearyl methacrylate, 138 g of acrylic acid, and 227 g of dibutyl peroxide was added dropwise over 1 hour. Then, after holding at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 190 ° C., 223 g of fumaric acid, 230 g of trimellitic acid anhydride, and 2.5 g of 4-tert-butylcatechol were added, and the temperature was raised to 210 ° C. at 10 ° C./hr. Then, the reaction was carried out at 4 kPa to a desired softening point to obtain an amorphous resin A-1. Various physical properties of the resin were measured and shown in Table 1.

Production Example B1 (Production of amorphous resin B-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 5363 g of an ethylene oxide (2.2) adduct of bisphenol A, 1780 g of terephthalic acid, and di. Add 40 g of (2-ethylhexanoic acid) tin (II) and 4 g of gallic acid, raise the temperature to 235 ° C while stirring under a nitrogen atmosphere, hold at 235 ° C for 8 hours, and then lower the pressure in the flask. , 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 180 ° C., 287 g of fumaric acid, 221 g of dodecenyl succinic anhydride, 380 g of trimellitic acid anhydride, and 2.5 g of 4-tert-butylcatechol were added, and the temperature was 10 ° C. to 220 ° C. The temperature was raised at / hr, then the pressure in the flask was lowered, and the reaction was carried out at 10 kPa to the desired softening point to obtain the amorphous resin B-1. Various physical properties of the resin were measured and shown in Table 1.

Production Example D1 (Production of amorphous resin D-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and bisphenol A propylene oxide (2.2) adduct 4313 g, terephthalic acid 818 g, and succinic acid were added. Add 727 g of acid, 30 g of di (2-ethylhexanoic acid) tin (II), and 3 g of gallic acid, heat the temperature to 235 ° C with stirring under a nitrogen atmosphere, hold at 235 ° C for 5 hours, and then in the flask. The pressure was lowered and the mixture was held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 160 ° C. and kept at 160 ° C., and a mixture of 2755 g of styrene, 689 g of stearyl methacrylate, 142 g of acrylic acid, and 413 g of dibutyl peroxide was added dropwise over 1 hour. Then, after holding the temperature at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the reaction was carried out at 8 kPa to a desired softening point to obtain an amorphous resin D-1. Various physical properties of the resin were measured and shown in Table 1.

Production Example C1 (Production of crystalline polyester resin C-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3,416 g of 1,10-decanediol and 4084 g of sebacic acid were added. The temperature was raised to 135 ° C. with stirring, kept at 135 ° C. for 3 hours, and then raised from 135 ° C. to 200 ° C. over 10 hours. Then, 23 g of di (2-ethylhexanoic acid) tin (II) was added and held at 200 ° C. for 1 hour, then the pressure in the flask was lowered and held at 8.3 kPa for 1 hour to obtain a crystalline polyester resin. Obtained C-1. Various physical properties of the resin were measured and shown in Table 2.

[Manufacturing of resin particle dispersion]
Production Example X1 (Production of Resin Particle Dispersion Liquid X-1)
210 g of amorphous resin A-1 and crystals in a container with an internal volume of 3 L equipped with a stirrer "Three One Motor BL300" (manufactured by Shinto Kagaku Co., Ltd.), a reflux condenser, a dropping funnel, a thermometer and a nitrogen introduction tube. 90 g of the sex polyester resin C-1 and 300 g of the methyl ethyl ketone were added, and the resin was dissolved at 73 ° C. for 2 hours. A 5 mass% sodium hydroxide aqueous solution was added to the obtained solution so as to have a neutralization degree of 60 mol% with respect to the acid value of the resin, and the mixture was stirred for 60 minutes.
Then, while maintaining the temperature at 73 ° C. and stirring at 200 r / min (peripheral speed 63 m / min), 600 g of deionized water was added over 60 minutes for phase inversion emulsification. Methyl ethyl ketone was distilled off under reduced pressure while the temperature was continuously maintained at 73 ° C. to obtain an aqueous dispersion. Then, after cooling the aqueous dispersion to 30 ° C. while stirring, deionized water was added to adjust the solid content concentration to 30% by mass, and the mixture was filtered through a 150 mesh wire mesh to obtain a resin particle dispersion liquid X. I got -1. Table 3 shows the volume median particle diameter (D ₅₀ ) and CV value of the obtained resin particles.

Production Examples Y1, Z1 (Production of resin particle dispersions Y-1, Z-1)
Resin particle dispersions Y-1 and Z-1 were obtained in the same manner as in Production Example X1 except that the amorphous resin and the crystalline polyester resin used were combined in Table 3. Table 3 shows the volume median particle diameter _D50 and the CV value of the obtained resin particles.

[Manufacturing of mold release agent particle dispersion]
Production Example W1 (Production of release agent particle dispersion liquid W-1)
To a beaker with an internal volume of 1 L, add 120 g of deionized water, 53 g of resin particle dispersion, and 40 g of paraffin wax "HNP-9" (Melting point 75 ° C., manufactured by Nippon Seiwa Co., Ltd.) to 90 to 95 ° C. The temperature was maintained, the mixture was melted, and the mixture was stirred to obtain a molten mixture. While maintaining the temperature at 90 to 95 ° C., the dispersion treatment was performed for 20 minutes using an ultrasonic homogenizer "US-600T" (manufactured by Nissei Tokyo Office Co., Ltd.), and then cooled to room temperature. Deionized water was added to the obtained dispersion to adjust the solid content concentration to 20% by mass to obtain a release agent particle dispersion liquid W-1. The volume median particle size (D ₅₀ ) was 0.45 μm, and the CV value was 26%.

[Manufacturing of colorant particle dispersion]
Production Example P1 (Production of Colorant Particle Dispersion Liquid P-1)
In a beaker with an internal volume of 1 L, 116.2 g of copper phthalocyanine pigment "ECB-301" (manufactured by Dainichi Seika Kogyo Co., Ltd.) and anionic surfactant "Neoperex (registered trademark) G-15" (manufactured by Kao Co., Ltd.) 154.9 g of (15 mass% sodium dodecylbenzene sulfonate aqueous solution) and 340 g of deionized water were mixed and dispersed at room temperature for 3 hours using a homogenizer, and then deionized water was adjusted to a solid content concentration of 24% by mass. Was added to obtain a colorant particle dispersion liquid P-1. The volume median particle size (D ₅₀ ) of the colorant particles in the dispersion was 0.12 μm.

[Manufacturing of toner]
Example 1 (Manufacturing of Toner 1)
300 g of resin particle dispersion liquid X-1, 49.7 g of release agent particle dispersion liquid W-1, and 49.7 g of colorant particle dispersion liquid in a four-mouthed flask having an internal volume of 3 L equipped with a dehydration tube, a stirrer, and a thermocouple. 33.8 g of P-1, and 9 g of the nonionic surfactant "Emulgen (registered trademark) 150" (manufactured by Kao Co., Ltd., 10% by mass aqueous solution of polyoxyethylene (average number of added moles 50) lauryl ether), removed. 150.0 g of ionized water was mixed at a temperature of 25 ° C. Next, while stirring the mixture, 22.7 g of a 4.8 mass% potassium hydroxide aqueous solution was added to an aqueous solution prepared by dissolving 31.0 g of ammonium sulfate in 468.4 g of deionized water to prepare a solution adjusted to pH 8.4. After dropping at 25 ° C. for 10 minutes, the temperature was raised to 62 ° C. over 2 hours, and the mixture was held at 62 ° C. until the volume median particle size ( _D50 ) of the aggregated particles became 5.1 μm, and aggregated. A dispersion of particles 1 was obtained.
The temperature of the dispersion liquid of the agglomerated particles 1 was lowered to 55 ° C., and while maintaining the temperature at 55 ° C., a mixed liquid of 60 g of the resin particle dispersion liquid Y-1 and 18.3 g of deionized water was added over 120 minutes to aggregate. A dispersion liquid of agglomerated particles 2 in which resin particles were agglomerated on the particles was obtained.
Anionic surfactant "Emar (registered trademark) E-27C" (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration 27% by mass) 18.9 g, deionized water in the dispersion of agglomerated particles 2. An aqueous solution containing 1871 g was added. Then, the temperature was raised to 75 ° C. over 1 hour. At this time, the pH of the dispersion liquid of the aggregated particles 2 was 7.0. After reaching 75 ° C., the circularity is measured while adding a 0.1 M sulfuric acid aqueous solution at a rate of 2 g / min, and the temperature is maintained at 75 ° C. until the circularity reaches the range of 0.950 to 0.965. , A dispersion liquid of fused particles in which aggregated particles were fused was obtained. At this time, the pH of the dispersion was 6.4, and the added 0.1 M sulfuric acid aqueous solution was 118 g.
After adding 4.6 g of a 4.8 mass% potassium hydroxide aqueous solution to the obtained dispersion of fused particles, the temperature was maintained at 75 ° C. for 1.5 hours.
The obtained dispersion of fused particles was cooled to 30 ° C., suction-filtered to separate solids, washed with deionized water at 25 ° C., vacuum dried at 35 ° C. for 48 hours, and the toner particles were subjected to vacuum drying. Got The physical characteristics of the obtained toner particles are shown in Table 4.
100 parts by mass of toner particles, 2.5 parts by mass of hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd., number average particle size; 0.04 μm), and hydrophobic silica "Cabosil (registered trademark) TS720" (Cabot Japan Co., Ltd.) Company-manufactured, number average particle size; 0.012 μm) 1.0 part by mass was placed in a Henshell mixer and stirred, and passed through a 150 mesh sieve to obtain toner 1. Various evaluations were performed and the results are shown in Table 4.

Example 2 (Manufacturing of Toner 2)
Toner 2 was obtained in the same manner as in Example 1 except that the amount of the 4.8 mass% potassium hydroxide aqueous solution added to the dispersion liquid of the fused particles was 3.5 g. Various evaluations were performed and the results are shown in Table 4.

Example 3 (Manufacturing of Toner 3)
Toner 3 was obtained in the same manner as in Example 1 except that the amount of the 4.8 mass% potassium hydroxide aqueous solution added to the dispersion liquid of the fused particles was 7.0 g. Various evaluations were performed and the results are shown in Table 4.

Example 4 (Manufacturing of Toner 4)
Toner 4 was obtained in the same manner as in Example 1 except that the amount of the 0.1 M sulfuric acid aqueous solution added at the time of fusion was 95 g. Various evaluations were performed and the results are shown in Table 4.

Example 5 (Manufacturing of Toner 5)
Toner 5 was obtained in the same manner as in Example 1 except that the 4.8% by mass potassium hydroxide aqueous solution added to the dispersion of the fused particles was 2.7 g of the 2.5% by mass ammonia aqueous solution. Various evaluations were performed and the results are shown in Table 4.

Comparative Example 1 (Manufacturing of Toner 51)
After adding the 0.1 M sulfuric acid aqueous solution, the toner 51 was obtained in the same manner as in Example 1 except that the 4.8 mass% potassium hydroxide aqueous solution was not added and the temperature was maintained for 1.5 hours. Various evaluations were performed and the results are shown in Table 4.

Comparative Example 2 (Manufacturing of Toner 52)
Toner 52 was obtained in the same manner as in Example 1 except that the amount of the 4.8 mass% potassium hydroxide aqueous solution added to the dispersion liquid of the fused particles was 46 g. Various evaluations were performed and the results are shown in Table 4.

Comparative Example 3 (Manufacturing of Toner 53)
Toner 53 was obtained in the same manner as in Example 1 except that the 0.1 M sulfuric acid aqueous solution and the 4.8 mass% potassium hydroxide aqueous solution were not added and the temperature was maintained for 1.5 hours. Various evaluations were performed and the results are shown in Table 4.

From the results of Examples and Comparative Examples, it can be seen that a toner having excellent cleaning properties can be obtained by the present invention.
In particular, in the examples, after the addition of the basic substance, the temperature is maintained at 75 ° C. for 1.5 hours, but it can be seen that the increase in circularity is suppressed to an extremely low level.
Further, from the results of Examples and Comparative Examples, it can be seen that the present invention provides a toner having excellent chargeability, fog suppression and heat storage stability.

Claims (7)

A method for producing a toner for static charge image development, which comprises a step of fusing agglomerated particles, which are agglomerates of polyester-based resin particles, in an aqueous medium.
In the process of fusing,
The temperature is equal to or higher than the glass transition temperature of the polyester resin having the highest glass transition temperature contained in the agglomerated particles, 20 ° C. or higher than the glass transition temperature , and an acidic substance is added to the inside of the aqueous medium. The temperature of the above-mentioned acid substance was lowered by 0.1 or more and 3.0 or less from that before the addition of the acidic substance, and the pH after the addition of the acidic substance was set in the range of 4.0 or more and 7.0 or less.
After that, a basic substance was added at a temperature equal to or higher than the glass transition temperature of the polyester resin having the highest glass transition temperature contained in the aggregated particles and 20 ° C. higher than the glass transition temperature . Production of static charge image development toner that raises the pH in the aqueous medium by 0.1 or more and less than 1.0 from before the addition of the basic substance to obtain toner particles having a circularity of 0.950 or more and 0.968 or less. Method. The method for producing a toner for static charge image development according to claim 1, wherein the addition of the acidic substance lowers the pH in the aqueous medium by 0.1 or more and 1.0 or less as compared with that before the addition of the acidic substance. The method for producing a toner for static charge image development according to claim 1 or 2, wherein the pH in the aqueous medium is raised by 0.1 or more and 0.6 or less by the addition of the basic substance as compared with that before the addition of the basic substance. The method for producing a toner for static charge image development according to any one of claims 1 to 3, wherein the circularity of the fused particles at the start of addition of the basic substance is 0.950 or more and 0.965 or less. The pH in the aqueous medium after the addition of the acidic substance is 4.0 or more and 6.8 or less, and the pH in the aqueous medium after the addition of the basic substance is 5.0 or more and 6.9 or less. The method for producing a toner for static charge image development according to any one of claims 1 to 4. The agglomerated particles are the agglomerated particles 2 having the agglomerated particles 1 which are aggregates of the resin particles a containing the polyester-based resin A and the resin particles b containing the polyester-based resin B adhering to the surface thereof. The method for producing a toner for static charge image development according to any one of 1 to 5. The step of aggregating the resin particles a containing the polyester-based resin A to obtain the agglomerated particles 1 and the step of adhering the resin particles b containing the polyester-based resin B to the agglomerated particles 1 to obtain the agglomerated particles 2 are fused. Including before the process of making
The method for producing a toner for static charge image development according to claim 6, wherein the agglomerated particles in the fusing step are the agglomerated particles 2.