JP2019117239A - Method for manufacturing toner for electrostatic charge image development - Google Patents

Abstract

To provide a method for manufacturing a toner for electrostatic charge image development exhibiting excellent cleanability.SOLUTION: A method for manufacturing a toner for electrostatic charge image development including a step of fusing, in an aqueous medium, aggregated particles that are aggregates of polyester resin particles, where in the fusing step, an acidic substance is added at a temperature equal to or higher than the glass transition temperature of the polyester resin in the aggregated particles, and the pH inside the aqueous medium is reduced by 0.1 or more and 3.0 or less compared with that before the addition of the acidic substance to fall within a pH range of 4.0 or more and 7.0 or less after the addition of the acidic substance; subsequently, a basic substance is added at a temperature equal to or higher than the glass transition temperature of the polyester resin in the aggregated particles, and the pH inside the aqueous medium is increased by 0.1 or more and less than 1.0 compared with that before the addition of the basic substance.SELECTED DRAWING: None

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 in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.

  In the field of electrophotography, with the development of electrophotographic systems, development of toners for electrophotography corresponding to higher image quality and higher speed is required. As a method to obtain toner with narrow particle size distribution and small particle size corresponding to high image quality, aggregation and fusion method is used to obtain toner by aggregating and fusing fine resin particles etc. in aqueous medium So-called chemical toner production is carried out by the aggregation method, aggregation and coalescence method).

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

  In Patent Document 2, a toner containing a polyester resin, a colorant and a release agent has an average circularity of 0.95 to 0.985, a turbidity of 35 to 60 measured under certain conditions, and a supernatant. An electrostatic charge image developing toner is described which is characterized in that the liquid contains a fatty acid metal salt having an average particle diameter of 2 to 4 μm and resin particles having an average particle diameter of 180 nm to 320 nm. It is described that the low temperature fixability, the cleanability and the image quality are excellent.

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

  In Patent Document 4, aggregated particles are formed from an emulsion containing a resin latex, a colorant, a wax, and an additive, and a shell is formed on the surface of the aggregates by adding a resin latex, The aggregation of the particles is stopped by raising the pH of the mixture of particles to a pH at which aggregation ceases, and then heated to a temperature to adjust to a predetermined fusion pH, and then the pH of the mixture is adjusted to a predetermined fusion pH A process is described for producing toner particles that fuse by lowering and heating to the fusing temperature.

JP, 2014-6453, A Unexamined-Japanese-Patent No. 2010-102057 JP, 2015-11346, A JP 2012-14169 A

A general chemical toner has a high degree of circularity and is inferior in cleaning ability as compared with a pulverized toner. Furthermore, in recent years, the speed of electrophotographic systems has been increased, and the cleaning performance of the photosensitive drum may be more prominent.
In addition, unlike crushed toners which are continuously manufactured, chemical toners are generally batch-produced, and therefore, efficient production of toners having excellent cleaning properties is required.
The present invention relates to a method of producing a toner for developing an electrostatic charge image exhibiting excellent cleaning properties.

In order to solve such problems, the present inventors focused on the step of fusing aggregated particles in a method of manufacturing a chemical toner. As a result, the fusion is promoted by adjusting the pH in the system during the fusion step, and in particular, after the fusion is advanced under the acidic conditions, the cleaning property is excellent by newly adding the basic compound. It was found that a good toner was obtained.
The present invention
A method for producing a toner for electrostatic charge image development, comprising the step of fusing aggregated particles, which are aggregates of polyester resin particles, in an aqueous medium,
In the step of fusing,
An acidic substance is added at a temperature above the glass transition temperature of the polyester resin of the aggregated particles, and the pH in the aqueous medium is lowered by 0.1 or more and 3.0 or less as compared to before the addition of the acidic substance, After the addition of the substance, the pH shall be in the range of 4.0 to 7.0,
Thereafter, a basic substance is added at a temperature above the glass transition temperature of the polyester resin of the aggregated particles, and the pH in the aqueous medium is increased by 0.1 or more and less than 1.0 before the addition of the basic substance. And a method of manufacturing a toner for developing an electrostatic charge image.

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

[Method of producing toner for developing electrostatic image]
The method for producing a toner for developing an electrostatic charge image of the present invention (hereinafter, also simply referred to as “toner”) is a step of fusing aggregated particles, which are aggregates of polyester resin particles, in an aqueous medium (hereinafter, “fusion Also referred to as “process”.
In the step of fusion bonding, an acidic substance is added at a temperature above the glass transition temperature of the polyester resin of aggregated particles, and the pH in the aqueous medium is 0.1 to 3.0 as compared to before the addition of the acidic substance. The pH is lowered to be in the range of pH 4.0 to 7.0 after addition of the acidic substance.
Thereafter, a basic substance is added at a temperature above the glass transition temperature of the polyester resin of the aggregated particles, and the pH in the aqueous medium is 0.1 or more and less than 1.0 before the addition of the basic substance. Raise it.
By the above method, a toner exhibiting excellent cleaning performance can be obtained.

Although the reason is not clear, it is considered as follows.
In the fusion step, fusion of aggregated particles is promoted by raising the temperature to a temperature higher than the glass transition temperature of the resin, but at this time the pH is adjusted to the acid side to disassociate acid groups such as carboxy groups. By suppressing and reducing the electrical repulsion, the fusion of agglomerated particles can proceed rapidly, and it becomes possible to obtain the desired fusion particles in a shorter time.
However, it has become clear that, even under such acidic conditions, fusion is likely to proceed even after fusion particles are obtained, and the degree of circularity is increased to cause a problem in the cleaning property.
Therefore, an acidic substance is added, and immediately after the fused particles are obtained, the basic substance is immediately added, and the progress of the fused particles is stopped by changing to a basic condition, thereby maintaining a low circularity. can do.
However, when a polyester-based resin is contained, hydrolysis of the polyester-based resin occurs under basic conditions, so that particles on the toner surface may be redispersed or molecular weight of the surface resin may be reduced. Therefore, it is considered that a toner having excellent cleaning performance 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 as the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (° C.) / Endothermic maximum peak temperature (° C.)) in the measurement method described in the examples described later. The crystalline resin is one having a crystallinity index of 0.6 or more and 1.4 or less. An amorphous resin is one having a crystallinity index of less than 0.6 or more than 1.4. The crystallinity index can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, the reaction time, and the cooling rate.
In the specification, the carboxylic acid component of the polyester resin includes not only the compound but also the anhydride which is decomposed during the reaction to form an acid, and the alkyl ester of each carboxylic acid (the carbon number of the alkyl group is 1 or more and 3 or less) Also included.
In the present specification, “binder resin” refers to a resin component contained in a toner including polyester resin A, polyester resin B and crystalline polyester resin C.
The “volume median particle diameter D ₅₀ ” is a particle diameter at which the cumulative volume frequency calculated by volume fraction is 50% as calculated from the smaller particle diameter.
The coefficient of variation of the particle size distribution (hereinafter, also simply referred to as “CV value”) is a value represented by the following formula. The volume average particle size in the following formula is the particle size obtained by dividing the particle size measured on a volume basis by the proportion of particles having that particle size value, and dividing the value obtained thereby by the number of particles. is there.
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 the step of fusing aggregated particles, which are aggregates of polyester resin particles, in an aqueous medium. In the step, the physically aggregated polyester resin particles are fused.
In the fusion step, the aggregated particles preferably include aggregated particles 1 which are aggregates of resin particles a containing polyester resin A and resin particles b containing polyester resin B attached to the surface thereof. Particle 2
The polyester resin A, the resin particle a, the aggregated particle 1, the polyester resin B, the resin particle b, and the aggregated particle 2 will be described in detail later.

The volume median particle size (D ₅₀ ) of the aggregated 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 below. The volume median particle size (D ₅₀ ) of the agglomerated particles can be determined by the method described in the examples below.

In the fusing step, the temperature at which the aggregated particles are fused (hereinafter, also referred to as “temperature T ₁ ”) is the viewpoint of obtaining a toner exhibiting excellent cleanability, and excellent fog suppression, chargeability and heat resistant storage stability. From the viewpoint of obtaining the toner shown, it is equal to or higher than the glass transition temperature of the polyester resin of aggregated particles.
Temperatures T ₁ means the temperature of the aqueous medium containing the aggregated particles, for example, it refers to a temperature measured by inserting a thermometer into a mixture of performing fusion.
When plural types of polyester resins are contained, the temperature T ₁ is preferably equal to or higher than the glass transition temperatures of all polyester resins having a glass transition temperature contained in the aggregated particles, and more specifically, In the aggregated particle 2 of the present invention, the temperature is 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 or more 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 toner fog suppression, chargeability and heat resistant storage stability. C. or higher, more preferably 5 C. or more higher than the glass transition temperature of the polyester resin of aggregated particles, still more preferably 8 C. or higher than the glass transition temperature of the polyester resin of aggregated particles, and preferably Is not more than 30 ° C. higher than the glass transition temperature of the polyester resin of aggregated particles, more preferably not more than 20 ° C. higher than the glass transition temperature of the polyester resin of aggregated particles, more preferably the glass transition of the polyester resin of aggregated particles The temperature is 15 ° C. higher than the temperature or lower.
The temperature T ₁ of the foregoing, if the polyester resin is contained more, a preferable range relative to the resin having the highest glass transition temperature.
The temperature T ₁ is preferably 65 ° C. or more, more preferably 68 ° C. or more, and still more preferably 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 temperature is 70 ° C. or higher, and preferably 95 ° C. or lower, more preferably 90 ° C. or lower, and still more preferably 85 ° C. or lower.
In this manufacturing method, it is preferable that the temperature during the addition of additives during and basic substances acidic substance is in the range of the T _1.

[Acid substance]
As an acidic substance, an inorganic acid and an organic acid are mentioned, for example.
Inorganic acids 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. Among these, carboxylic acid compounds are preferred.
Examples of carboxylic acid compounds 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, from the viewpoint of further improving the cleaning property of the toner, and from the viewpoint of further improving the fog suppression, the chargeability and the heat resistant storage stability, inorganic acids are preferable, and sulfuric acid is more preferable.

The acidic substance is preferably added to the system as an aqueous solution of the acidic substance, from the viewpoint of further improving the cleaning property, and from the viewpoint of further improving fog suppression, chargeability and heat resistant storage stability.
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 And preferably not more than 30% by mass, more preferably not more than 20% by mass, still more preferably not more than 15% by mass, still more preferably not more than 10% by mass, still more preferably not more than 5% by mass, still more preferably not more than 3% by mass It is.

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

As the aqueous medium, one 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 components other than water which can constitute an aqueous medium together with water, alkyl alcohol having 1 to 5 carbon atoms; dialkyl ketone having 3 to 5 carbon atoms such as acetone, methyl ethyl ketone and the like; dissolved in water such as cyclic ether such as tetrahydrofuran Organic solvents are used. Among these, from the viewpoint of preventing the mixing of the organic solvent into the toner, an alkyl alcohol having 1 to 5 carbon atoms which does not dissolve the polyester resin is preferable, and methanol, ethanol, isopropanol and butanol are more preferable.

The pH in the aqueous medium is from the viewpoint of obtaining a toner exhibiting excellent cleaning performance, and from the viewpoint of obtaining a toner exhibiting excellent fog suppression, chargeability and heat resistant storage stability, the addition of the acidic substance prior to the addition of the acidic substance More than 0.1 or less and less than 3.0.
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 to be fused using a pH meter.
The pH lowered by the addition of the acidic substance (hereinafter also referred to as “ΔpH”) is preferably from the viewpoint of further improving the cleaning property and from the viewpoint of further improving the fog suppression, the chargeability and the heat resistant storage stability. It is 15 or more, more preferably 0.2 or more, further preferably 0.3 or more, and preferably 2.5 or less, more preferably 2.0 or less, still more preferably 1.0 or less, more preferably 0 .8 or less.

  The pH in the aqueous medium before the addition of the acidic substance (hereinafter, also referred to as "the initial pH in the aqueous medium") further improves fog suppression, chargeability and heat resistant storage stability from the viewpoint of further improving the cleaning 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 addition of the acidic substance”) further improves fog suppression, chargeability and heat resistant storage stability, from the viewpoint of further improving the cleaning property. From the viewpoint, it is preferably 4.0 or more, more preferably 5.0 or more, further 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 addition of the acidic substance, it is preferable to maintain the temperature within the range of the temperature T _1.
The holding of the temperature within the range of the temperature T ₁ is preferably performed until the following degree of circularity is reached.

The circularity of the fused particles at the start of the 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 resistant storage stability. More preferably, it is 0.955 or more, more preferably 0.960 or more, and preferably 0.965 or less.
The roundness of the fused particles is according to the method described in the examples.
The fusion preferably monitors the circularity of the fused particles, and starts adding the basic substance when reaching an appropriate range.

[Basic substance]
Examples of the basic substance include hydroxides, carbonates, hydrogencarbonates and nitrogen-containing basic substances of alkali metals.
As a hydroxide of an alkali metal, sodium hydroxide, potassium hydroxide, lithium hydroxide is mentioned, for example.
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, from the viewpoint of further improving the cleaning property of the toner, and from the viewpoint of further improving the fog suppression, the chargeability and the heat resistant storage stability, hydroxides of alkali metals are preferable, and potassium hydroxide is more preferable.

The basic substance is preferably added to the system as an aqueous solution of the basic substance from the viewpoint of further improving the cleaning property and from the viewpoint of further improving the fog suppression, the chargeability and the heat resistant storage stability.
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.

From the viewpoint of obtaining a toner exhibiting excellent cleaning performance, and from the viewpoint of obtaining a toner exhibiting excellent fog suppression, chargeability and heat resistant storage stability, the pH in the aqueous medium is increased by adding a basic material. Raise 0.1 or more and less than 1.0 than before addition. At this time, by using a specific basic substance to raise the pH, excessive fusion processing is suppressed and the toner particles are prevented from becoming excessively circular.
The pH raised by the addition of the 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, the chargeability and the heat resistant storage stability. 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 addition of the basic substance”) is from the viewpoint of further improving the cleaning property, as well as suppressing fog, chargeability and heat resistant storage stability. From the viewpoint of improving, it is preferably 5.0 or more, more preferably 6.0 or more, further preferably 6.2 or more, further 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. Preferably it is 0.967 or less, More preferably, it is 0.965 or less.
The roundness of the fused particles is according to the method described in the examples.

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

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

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

«Polyester resin A»
Examples of the polyester resin A include polyester resins and composite resins containing a polyester resin segment and an addition polymerization resin segment. Among these, composite resins are preferable.
The polyester resin A is preferably an amorphous polyester resin A.

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 trivalent or higher polyhydric alcohols. Among these, aromatic diols are preferable.
The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably a compound of formula (I):

(Wherein, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are each independently an ethylene group or a propylene group, and x and y each represent the average addition mole number of alkylene oxide, and each is positive) And the value of the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, 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. One or more of these may be used.
Among these, 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%.

As a linear or branched aliphatic diol, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 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 alicyclic diols include hydrogenated bisphenol A [2, 2-bis (4-hydroxycyclohexyl) propane], and alkylene oxide adducts of hydrogenated bisphenol A having 2 or more and 4 or less carbon atoms (average added mole number 2) And 12 or less).
Examples of trivalent or higher polyhydric alcohols include glycerin, pentaerythritol, trimethylolpropane and sorbitol.
One or more of these alcohol components may be used.

Examples of the carboxylic acid component include dicarboxylic acids and trivalent or higher polyvalent carboxylic acids.
Examples of dicarboxylic acids 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 aromatic dicarboxylic acids 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 in the carboxylic acid component, and preferably It is 90 mol% or less, more preferably 80 mol% or less, still more preferably 75 mol% or less.

The carbon number of the linear or branched aliphatic dicarboxylic acid is preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less.
Examples of linear or branched aliphatic dicarboxylic acids include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid And succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. Examples of 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. Among these, fumaric acid and sebacic acid are preferable.
The amount of 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% in the carboxylic acid component. The following content 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 the 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. It is the above, and preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 15 mol% or less.
These carboxylic acid components may be used alone or in combination of two or more.

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

(Method of producing polyester resin)
The polyester resin is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component.
The polyester resin is, if necessary, an esterification catalyst such as di (2-ethylhexanoate) tin (II), dibutyltin oxide, titanium diisopropylate bistriethanolaminate, and the total amount of alcohol component and carboxylic acid component 100. 0.01 parts by mass or more and 5 parts by mass or less with respect to parts by mass; an esterification promoter such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) 100 parts in total of the alcohol component and the carboxylic acid component It may carry out polycondensation using 0.001 mass part or more and 0.5 mass part or less with respect to a part.
Moreover, when using the monomer which has unsaturated bonds, such as fumaric acid, for polycondensation, Preferably it is 0.001 mass part or more with respect to 100 mass parts of total amounts of an alcohol component and a carboxylic acid component as needed. You may use 0.5 mass part or less of radical polymerization inhibitors. As a radical polymerization inhibitor, 4-tert- butyl catechol is mentioned, for example.
The temperature of the polycondensation reaction is preferably 120 ° C. or more, more preferably 160 ° C. or more, still more preferably 180 ° C. or more, and preferably 250 ° C. or less, more preferably 240 ° C. or less. The polycondensation may be carried out in an inert gas atmosphere.

  The composite resin in the above example includes a polyester resin segment and an addition polymerization resin segment. The polyester resin which comprises a polyester resin segment is the same as that of the above-mentioned polyester resin.

The addition polymerization resin segment is, for example, an addition polymer of a raw material monomer containing a styrenic compound.
Examples of styrenic compounds include unsubstituted or substituted styrene. Examples of the substituent substituted by styrene include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfonic acid group or a salt thereof.
Examples of styrenic compounds include styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrene sulfonic acid or salts thereof. Among these, styrene is preferred.
The content of the styrenic 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, still more preferably 75% by mass or more, and 100% by mass or less Preferably it is 95 mass% or less, More preferably, it is 90 mass% or less, More preferably, it is 85 mass% or less.

Examples of starting monomers other than styrene compounds include (meth) acrylic esters such as alkyl (meth) acrylate, benzyl (meth) acrylate and dimethylaminoethyl (meth) acrylate; ethylene, propylene, butadiene, etc. Olefins; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinyl pyrrolidone . Among these, (meth) acrylic acid esters are preferable, and alkyl (meth) acrylates are more preferable.
The carbon number of the alkyl group in the alkyl (meth) acrylate is preferably 1 or more, more preferably 6 or more, further preferably 10 or more, and preferably 24 or less, more preferably 22 or less, still more preferably 20 It is below.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, butyl (meth) acrylate (iso or tertiary), (meth) ) Acrylic acid (iso) amyl, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylate (iso) octyl, (meth) acrylic acid (iso) decyl, (meth) acrylic acid (meth) acrylic acid Iso) dodecyl, (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, (meth) acrylic acid (iso) behenyl etc. may be mentioned, 2-ethylhexyl (meth) acrylate or (meth) Stearyl acrylate is preferred, and stearyl (meth) acrylate is more preferred.
Note that “(iso or tertiary)” and “(iso)” mean both the case where these prefixes are present and the case where they do not exist, and indicate the normal when these prefixes do not exist. Moreover, "(meth) acrylic acid" shows acrylic acid or methacrylic acid.

  The content of (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 It is at most mass%, more preferably at most 35 mass%, even more preferably at most 25 mass%.

  The total amount of the styrenic compound and (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, further preferably Is 100% by mass.

The composite resin preferably has a structural unit derived from a polyester resin segment and an addition polymerization resin segment and a bireactive monomer bonded via a covalent bond.
The “constituent unit derived from both reactive monomers” means a unit in which the functional group of the dual reactive monomer and the addition polymerizable group have reacted.
The addition polymerizable group includes, for example, a carbon-carbon unsaturated bond.
Examples of the dual reactive 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 addition polymerizable monomers 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 the 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 parts or more, still more preferably 8 mol part or more, with respect to 100 mol parts 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, and 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 It is at most mass%, more preferably at most 75 mass%.

  The content of the addition polymerization 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 mass% or less, More preferably, it is 45 mass% or less.

  The amount of the structural unit derived from both reactive monomers 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 constituent units derived from the polyester resin segment, the addition polymerization resin segment, and the dual reactive monomer in the composite resin is preferably 80% by mass or more, more preferably 90% by mass or more, and 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 a raw material monomer of an addition polymerization resin segment and a bireactive monomer.
The step B may be performed after the step A, the step A may be performed after the step B, and the steps A and B may be performed simultaneously.
In step A, a portion of the carboxylic acid component is subjected to a polycondensation reaction, and then step B is carried out, and then the remainder of the carboxylic acid component is added to the polymerization system, and the polycondensation reaction of step A and both reactions as required. Preferred is a method of further promoting the reaction with the monomer.

The conditions for the polycondensation are the same as those exemplified in the above-mentioned synthetic method of polyester resin.
Examples of radical polymerization initiators 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). It can be mentioned.
The use amount of the radical polymerization initiator 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 addition polymerization is preferably 110 ° C. or more, more preferably 130 ° C. or more, and preferably 230 ° C. or less, more preferably 220 ° C. or less, still more preferably 210 ° C. or less.

(Physical properties of polyester resin A)
The softening point of the polyester resin A is preferably 70 ° C. or more, more preferably 90 ° C. or more, still more preferably 100 ° C. or more, from the viewpoint of further improving the heat resistant storage property, and further improving the low temperature fixability. From the viewpoint, it is preferably 140 ° C. or less, more preferably 130 ° C. or less, still more preferably 125 ° C. or less.
The glass transition temperature of the polyester resin A is preferably 30 ° C. or more, more preferably 35 ° C. or more, still more preferably 40 ° C. or more, from the viewpoint of further improving the heat resistant storage property, and further improve the low temperature fixability. Preferably, the temperature is 80 ° C. or less, more preferably 70 ° C. or less, and still more preferably 60 ° C. or less.

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

  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, based on the total amount of the resin component of the aggregated particles 1 and 100 It is not more than mass%, preferably not more than 95 mass%, more preferably not more than 90 mass%, still more preferably not more than 80 mass%.

«Crystalline polyester resin C»
The crystalline polyester resin C is a polycondensation product of an alcohol component and a carboxylic acid component.
As the alcohol component, α, ω-aliphatic diols are preferred.
The carbon number of the α, ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, further preferably 6 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less. is there.
Examples of α, ω-aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol It 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 the 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, based on the alcohol component. It is not more than mol%, more preferably 100 mol%.

  The alcohol component may contain other alcohol components different from the α, ω-aliphatic diol. Other alcohol components include, for example, aliphatic diols other than α, ω-aliphatic diols such as 1,2-propanediol, neopentyl glycol and the like; aromatic diols such as alkylene oxide adduct of bisphenol A; glycerin, penta Examples thereof include trihydric or higher alcohols such as erythritol and trimethylolpropane. One or more of these alcohol components may be used.

As a carboxylic acid component, aliphatic dicarboxylic acid is preferable.
The carbon number of the aliphatic dicarboxylic acid is 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 aliphatic dicarboxylic acids 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. These carboxylic acid components may be used alone or in combination of two or more.

  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 in the carboxylic acid component, and 100 mol % Or less, more preferably 100 mol%.

  The carboxylic acid component may contain other carboxylic acid components different from the aliphatic dicarboxylic acid. Other carboxylic acid components include, for example, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and trivalent or higher polyvalent carboxylic acids. These carboxylic acid components may be used alone or in combination of two or more.

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

  The method for producing the crystalline polyester resin C may be, for example, the same method as the method for producing the polyester resin of the polyester resin A described above.

(Physical properties of crystalline polyester resin C)
The softening point of the crystalline polyester resin C is preferably 60 ° C. or more, more preferably 70 ° C. or more, still more preferably 80 ° C. or more, from the viewpoint of further improving the heat resistant storage property, and further improve the low temperature fixability. Preferably, the temperature is 150 ° C. or less, more preferably 120 ° C. or less, and still more preferably 100 ° C. or less.

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

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

  The softening point, melting point and acid value of the crystalline polyester resin C can be appropriately adjusted according to the type of raw material monomer and the amount thereof used, and the production conditions such as reaction temperature, reaction time, cooling rate, etc. It is determined by the method described in When two or more kinds of crystalline polyester resins C are used in combination, it is preferable that the values of the softening point, the melting point and the acid value obtained as the mixture thereof are respectively in 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, based on the total amount of the resin component of the aggregated particles 1 and Preferably it is 60 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 40 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 not more than 95/5, more preferably not more than 90/10, still more preferably not more than 80/20.

  The total amount of polyester resin A and 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 component of aggregated particles 1 The content is more preferably 95% by mass or more, and 100% by mass or less, and further preferably 100% by mass.

«Production method of resin particle 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 simultaneously dispersed to form resin particles a containing the crystalline polyester resin C, or separately from the resin particles a, it may be crystalline. Resin particles c containing a polyester resin C may be used. The dispersion of the resin particles c is also obtained by the same method as the method of producing the dispersion of the resin particles a.
As the aqueous medium, one containing water as a main component is preferable, and from the viewpoint of improving the dispersion stability of the dispersion of resin particles and from the environmental point of view, the content of water in the aqueous medium is preferably 80 mass. % Or more, more preferably 90% by mass or more, further preferably 95% by mass or more, further preferably 98% by mass or more, and 100% by mass or less, more preferably 100% by mass. As water, deionized water or distilled water is preferred. As components other than water which may be contained in the aqueous medium, for example, alkyl alcohol having 1 to 5 carbon atoms; dialkyl ketone having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; and dissolved in water such as cyclic ether such as tetrahydrofuran Organic solvents can be mentioned. Among these, methyl ethyl ketone is preferred.

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

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 use equivalent (mol%) of the neutralizing agent to the acid group of the resin contained in the resin particle a is preferably 10 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more Preferably it is 150 mol% or less, more preferably 100 mol% or less, still more preferably 70 mol% or less.
In addition, the use equivalent (mol%) of a neutralizing agent can be calculated | required by the following formula. The use equivalent of the neutralizing agent is the same as the neutralization degree in the case of 100 mol% or less.
Usage equivalent of neutralizing agent (mol%) = [{added mass of neutralizing agent (g) / equivalent of neutralizing agent} / [{weighted average acid value of resin constituting resin particle a (mg KOH / g) × Mass of resin that constitutes resin particle a (g)} / (56 × 1000)]] × 100

While stirring the organic solvent solution or the molten resin, the aqueous medium is gradually added to cause phase inversion.
The organic solvent solution temperature at the time of adding the aqueous medium is preferably not less than the glass transition temperature of the resin constituting the resin particles a, more preferably 50 ° C. or more, further preferably from the viewpoint of improving the dispersion stability of the resin particles a. Is 60 ° C. or more, and preferably 85 ° C. or less, more preferably 80 ° C. or less.

  After the phase inversion emulsification, the organic solvent may be removed from the obtained dispersion by distillation or the like, if necessary. In this case, the residual amount of the organic solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably substantially 0% in the aqueous dispersion.

  The content of the polyester 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 particle a contains the crystalline polyester resin C, the content of the polyester resin A is preferably 50% by mass or more, more preferably 60% by mass or more based on the total amount of the resin component of the resin particle a. More preferably, it is 65 mass% or more, and preferably 95 mass% or less, preferably 90 mass% or less, preferably 80 mass% or less.
When the resin particle a contains the crystalline polyester resin C, the content of the crystalline polyester resin C is preferably relative to the total amount of the resin component of the resin particle a from the viewpoint of improving the low temperature fixability of the toner. The content is 5% by mass or more, more preferably 10% by mass or more, further 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 diameter (D ₅₀ ) of the resin particles a in the dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more, from the viewpoint of obtaining a toner capable of obtaining a high quality image. Preferably it is 0.8 micrometer or less, More preferably, it is 0.4 micrometer or less, More preferably, it is 0.3 micrometer 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 from which a high quality image can be obtained. Is 35% or less, more preferably 30% or less.
The volume median particle size (D ₅₀ ) and the CV value of the resin particles can be determined by the method described in the examples below.

In addition, when using resin particle c containing crystalline polyester resin C, resin particle c can be obtained by the method similar to the above-mentioned.
The addition amount of the resin particles a and the resin particles c is preferably an amount to be the content of the polyester resin A and the crystalline polyester resin C described above.

〔Release agent〕
The agglomerated particles 1 may contain a release agent.
As the release agent, for example, polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax; hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, Sazol wax or oxides thereof; carnauba wax Montan wax or ester-based waxes such as deacidified waxes or fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts. One or more of these may be used.

The melting point of the release agent is preferably 60 ° C. or more, more preferably 70 ° C. or more, and preferably 160 ° C. or less, more preferably 150 ° C. or less, still more preferably 140 ° C. or less.
The content of the releasing agent is preferably 0.1 parts 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. It is the mass part or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.

(Dispersion liquid of release agent particles)
The release agent is preferably contained in the aggregated particles 1 by being mixed with the resin particles a as a dispersion liquid of the release agent particles and coagulated.
Although it is possible to obtain a dispersion of release agent particles using a surfactant, it is preferable to obtain it by mixing a release agent and a resin particle z described later. By preparing the releasing agent particles using the releasing agent and the resin particles z, the releasing agent particles are stabilized by the resin particles z, and the releasing agent can be contained in the aqueous medium without using any surfactant. It becomes possible to disperse. It is considered that the dispersion of the release agent particles has a structure in which a large number of resin particles z adhere to the surface of the release agent particles.

The resin constituting the resin particles z in which the releasing agent is dispersed is preferably a polyester resin, and from the viewpoint of improving the dispersibility of the releasing agent in an aqueous medium, it has a polyester resin segment and an addition polymerization resin segment. It is more preferable to use the composite resin D.
The softening point of the composite resin D is preferably 70 ° C. or more, more preferably 80 ° C. or more, and preferably 140 ° C. or less, more preferably 120 ° C. or less, still more preferably 100 ° C. or less.
The preferable range of the other resin characteristics of the composite resin D, the preferable examples of the raw material monomers constituting the resin, and the like are the same as the examples shown for 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, from the viewpoint of dispersion stability of the release agent particles, 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 releasing agent particle dispersion may be, for example, a releasing agent, a resin particle dispersion and, if necessary, an aqueous medium, at a temperature above the melting point of the releasing agent, such as a homogenizer, a high pressure dispersing machine or an ultrasonic dispersing machine. It is obtained by dispersing using a disperser.
The heating temperature at the time of dispersion is preferably 80 ° C. or more, more preferably 85 ° C. or more, still more preferably 90 ° C. or more, and preferably the softening of the resin contained in the resin particle z. The temperature is less than 10 ° C. higher than the point and 100 ° C. or less, more preferably 98 ° C. or less, still more preferably 95 ° C. or less.

  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, it is 70 mass parts or less, More preferably, it is 50 mass parts 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, and still more preferably 0.4 μm or more from the viewpoint of obtaining uniform aggregated particles by aggregation. And preferably 1 μm or less, more preferably 0.8 μm or less, and 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 measurement method of the volume median particle size (D ₅₀ ) of the release agent particles and the CV value is according to the method described in the examples.

[Colorant]
The aggregated particles 1 may contain a colorant.
As the colorant, any of dyes, pigments and the like used as colorants for toners can be used.
Examples of coloring agents 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, carmine 6B, and disazo yellow. Be 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. More preferably, it is 8 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less.

(Dispersion solution of colorant particles)
The colorant is preferably contained in the aggregated particles 1 by being mixed with the resin particles a as a dispersion of colorant particles and coagulated.
The dispersion of the colorant particles is preferably obtained by dispersing the colorant and the aqueous medium using a dispersing machine such as a homogenizer or an ultrasonic dispersing machine. The dispersion is preferably performed 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. 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 dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium lauryl ether sulfate and dipotassium alkenyl succinate. Among these, sodium dodecylbenzene sulfonate is preferable.

  The content of the surfactant in the dispersion of 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 amount is more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, 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, more preferably Preferably it is 0.2 micrometer or less.
The method for measuring the volume median particle size (D ₅₀ ) of the colorant particles is according to the method described in the examples.

  The agglomerated particles 1 further contain additives such as charge control agents, magnetic powders, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, anti-aging agents, and cleanability improvers. May be included.

[Surfactant]
In the step 1, it is preferable to coagulate 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 the resin particles a and optional components such as wax particles added as necessary. Examples of the surfactant include anionic surfactants such as alkyl benzene sulfonates and alkyl ether sulfates; and nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers.
When a surfactant is used, the amount thereof used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 10 parts by mass with respect to 100 parts by mass of resin particles a. It is preferably at most 5 parts by mass, more preferably at most 3 parts by mass.

  The above-described dispersion of the resin particles a and mixing of the optional components are carried out by a conventional method. From the viewpoint of efficiently performing aggregation, it is preferable to add a coagulant to the mixed dispersion obtained by the mixing.

[Flocculant]
The aggregated particles are obtained by aggregating polyester resin particles by adding an aggregating agent.
Flocculants include, for example, cationic surfactants of quaternary salts, organic flocculants such as polyethylene imine; inorganic metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride and calcium nitrate; ammonium sulfate, chloride Inorganic ammonium salts such as ammonium and ammonium nitrate; and inorganic coagulants such as metal complexes having two or more valences.
From the viewpoint of improving aggregation and obtaining uniform aggregated particles, an inorganic coagulant having a valence of 1 to 5 is preferable, an inorganic metal salt having a valence of 1 to 2 or less, an inorganic ammonium salt is more preferable, and an inorganic ammonium salt is More preferred is ammonium sulfate.

  For example, 5 parts by mass to 50 parts by mass of the aggregating agent is added to the mixed dispersion containing resin particles a at 0 ° C. or more and 40 ° C. or less with respect to 100 parts by mass of the total resin, A is aggregated in an aqueous medium to obtain aggregated particles 1. Furthermore, from the viewpoint of promoting aggregation, it is preferable to increase the temperature of the dispersion after adding the aggregating agent.

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 6 μm or less. The volume median particle size (D ₅₀ ) of the agglomerated particles 1 can be determined by the method described in the examples below.

<Step 2>
In the step 2, the resin particles b containing the polyester resin B are attached to the aggregated particles 1 to obtain the aggregated particles 2.
[Resin particle b]
The dispersion liquid of the resin particles b can be obtained by the same method as the method of manufacturing the dispersion liquid of the resin particles a described above.
In step 2, for example, the dispersion of resin particles b is added to the dispersion containing agglomerated particles 1 at 30 ° C. or more and 80 ° C. or less, thereby causing resin particles b to aggregate in the aqueous medium and aggregate the aggregated particles 1; The particles 2 are obtained.

«Polyester resin B»
Examples of the polyester resin B include polyester resins and composite resins containing a polyester resin segment and an addition polymerization resin segment.
The polyester resin B is preferably a non-crystalline polyester resin B.

The example of polyester-based resin B is the same as the illustration in the above-mentioned polyester-based resin A.
Hereinafter, the common illustration will be omitted, and a preferred embodiment as 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 still more preferably an alkylene oxide adduct of bisphenol A represented by 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%.

The carboxylic acid component is preferably at least one selected from aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids.
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, 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, and 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, based on the carboxylic acid component. More preferably, it is 20 mol% or less, still more preferably 15 mol% or less.

  The polyester-based resin B is obtained, for example, by the same method as the example of the polyester-based resin A described above.

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

  The glass transition temperature of the polyester resin B is preferably 30 ° C. or more, more preferably 40 ° C. or more, still more preferably 50 ° C. or more, from the viewpoint of further improving the heat resistant storage property, and further improve the low temperature fixability. Preferably, the temperature is 80 ° C. or less, more preferably 75 ° C. or less, and still more preferably 70 ° C. or less.

The acid value of the polyester resin B is preferably 5 mg KOH / g or more, more preferably 10 mg KOH / g or more, still more preferably 15 mg KOH / g or more, from the viewpoint of further improving the heat resistant storage stability and low temperature fixability. Preferably it is 40 mgKOH / g or less, More preferably, it is 35 mgKOH / g or less, More preferably, it is 30 mgKOH / g or less.
The softening point, glass transition temperature, and acid value of polyester resin B can be appropriately adjusted according to the type of raw material monomer and the amount used thereof, and the production conditions such as reaction temperature, reaction time, cooling rate, etc. The value of is determined by the method described in the examples.
In addition, when using polyester-type resin B in combination of 2 or more types, it is preferable that the value of the softening point obtained as those mixtures, a glass transition temperature, and an acid value is in the above-mentioned range, respectively.

In addition, the resin particle b containing polyester-type resin B is obtained by the method similar to the above-mentioned resin particle a, for example.
The degree of neutralization of the polyester resin B in the resin particles b is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably, from the viewpoint of further improving fog suppression by the addition of 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 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 polyester resin B to the total amount of polyester resin A and crystalline polyester resin C [the total amount of polyester resin B / polyester resin A and crystalline polyester resin C] is preferably 5/95. Or more, more preferably 10/90 or more, further 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 aggregated particles have grown to a suitable particle size as toner particles.
Examples of methods for stopping aggregation include a method of cooling the dispersion, a method of adding an aggregation stopper, a method of diluting the dispersion, and a method of changing pH. From the viewpoint of reliably preventing unnecessary aggregation, it is preferable to add an aggregation stopper to stop aggregation.

[Flocculant stop agent]
As an aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of anionic surfactants include alkyl benzene sulfonates, alkyl sulfates, alkyl ether sulfates, and polyoxyalkylene alkyl ether sulfates. The aggregation terminator may be used alone or in combination of two or more. The anticoagulation agent may be added in an aqueous solution.
The addition amount of the aggregation stopper is preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more, with respect to 100 parts by mass of the binder resin in the toner, from the viewpoint of surely preventing unnecessary aggregation. The amount is preferably 30 parts by mass or less, and more preferably 15 parts by mass or less, from the viewpoint of reducing the residue on the toner.

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 6 μm or less. The volume median particle size (D ₅₀ ) of the agglomerated particles can be determined by the method described in the examples below.

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

<Post-processing process>
A post-treatment step may be performed after step 3, and toner particles are obtained by isolating fused particles. Since the fused particles obtained in step 3 are present in an aqueous medium, it is preferable to first perform solid-liquid separation. Examples of solid-liquid separation include suction filtration, pressure filtration, and centrifugal filtration.
It is preferable to wash after solid-liquid separation. At this time, since it is preferable to also remove the added surfactant, it is preferable to wash with an aqueous medium at the cloud point or less of the surfactant. It is preferable to carry out washing several times.
It is preferable to dry next. As a drying method, for example, a vacuum low temperature drying method, a vibration type fluid drying method, a spray drying method, a freeze drying method, a flash drying method may be mentioned.

[Toner particles]
The toner particles may be used as the toner as they are, but it is preferable to use the one obtained by treating the surface of the toner particles as described later.
The volume median particle diameter (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, and 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. And preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less.

The degree of circularity of the toner particles is preferably 0.940 or more, more preferably 0.950 or more, and still more preferably 0.960 or more, from the viewpoint of further improving the heat resistant storage stability of the toner, and the toner cleaning property From the viewpoint of further improving the aspect ratio, 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 the circularity of the toner particles can be measured by the method described in the examples.
The content of 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 It is preferably 99% by mass or less.

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

  The toner for developing an electrostatic charge image obtained according to the present invention can be used as a one-component developer or as a two-component developer by mixing with a carrier.

The present invention will be described more specifically by the following Examples and the like.
In the following Examples etc., measurement and evaluation of each physical property were performed by the following method.

[Measuring method]
[Acid value of resin]
The acid value of the resin was measured according to JIS K 0070: 1992. However, the measurement solvent was a mixed solvent of acetone and toluene [acetone: toluene = 1: 1 (volume ratio)].

[Softening point, crystallinity index, melting point and glass transition temperature of resin]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a heating rate of 6 ° C./min, a load of 1.96 MPa is applied by a plunger to obtain a diameter It extruded from the nozzle of 1 mm and length 1 mm. The plunger drop of the flow tester was plotted against temperature, and the temperature at which half of the sample flowed out was taken as the softening point.
(2) Crystallinity Index 0.01 g of a sample is weighed on an aluminum pan using a differential scanning calorimeter “Q-100” (manufactured by TEA Instruments Japan Co., Ltd.), and the temperature decrease rate is 10 ° C./min. It cooled down. Next, 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 heat quantity. Among the observed endothermic peaks, the temperature of the peak having the largest peak area is taken as the maximum endothermic peak temperature (1) by (softening point (° C.)) / (Maximum endothermic peak temperature (1) (° C.)) The crystallinity index was determined.
(3) Melting point and glass transition temperature 0.01 g of a sample is weighed in an aluminum pan using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), and the temperature is raised to 200 ° C. It cooled to 0 degreeC at the temperature-fall rate of 10 degree-C / min from the temperature. Thereafter, the temperature was raised at a heating rate of 10 ° C./min, and the heat quantity was measured. Among the observed endothermic peaks, the peak temperature at which the peak area is the largest is taken as the maximum peak temperature (2) of the endotherm. In the case of a crystalline resin, the peak temperature was taken as the melting point. In the case of an amorphous resin, the glass transition temperature is the temperature at the intersection of the extension of the baseline below the maximum endothermic peak temperature and the tangent showing the maximum slope from the rising portion of the peak to the peak of the peak.

Melting point of mold release agent
0.01 g of a sample is weighed in an aluminum pan using a differential scanning calorimeter “Q-100” (manufactured by TEA Instruments Japan Co., Ltd.), and after raising the temperature to 200 ° C., the temperature decrease rate is 200 ° C. to 10 ° C. It cooled to 0 degreeC by / min. Next, the sample was heated at a temperature rising rate of 10 ° C./min, the heat quantity was measured, and the maximum peak temperature of the endotherm was taken as the melting point.

[Volume median particle diameter (D ₅₀ ) and CV value of resin particles, release agent particles, and colorant particles]
(1) Measuring device: Laser diffraction type particle size measuring device "LA-920" (manufactured by Horiba, Ltd.)
(2) Measurement conditions: A sample dispersion was taken in a cell for measurement, distilled water was added, and the volume median particle size (D ₅₀ ) and the volume average particle size were measured at a temperature at which the absorbance was in the appropriate range. Moreover, CV value was computed 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 Ketto Scientific Research Institute Co., Ltd.), 5 g of a measurement sample is dried at 150 ° C. under the conditions of measurement mode 96 (monitoring time 2.5 minutes, fluctuation range 0.05%) The water content (mass%) was measured by The solid concentration was calculated according to the following equation.
Solid content concentration (mass%) = 100-moisture (mass%)

[Volume median 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, Inc.)
・ Aperture diameter: 50μm
Analysis software: "Multisizer (registered trademark) III version 3.51" (manufactured by Beckman Coulter, Inc.)
-Electrolyte: "Isoton (registered trademark) II" (manufactured by Beckman Coulter, Inc.)
Measurement conditions: The particle diameter of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds by adding the sample dispersion to 100 mL of the electrolyte, and then 30,000 particles are measured again, and the particle diameter is measured. The volume median particle size (D ₅₀ ) was determined from the distribution.

[PH in aqueous medium]
Using the pH meter “SevenGo pH meter SG2” (manufactured by METTLER TOLEDO), connect “InLab Expert Go” (manufactured by METTLER TOLEDO) as an electrode, and dip the electrode of the pH meter in an aqueous medium to While stirring, pH was measured.

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

[Volume median particle diameter (D ₅₀ ) of toner particles]
The volume median particle size (D ₅₀ ) of the toner particles was measured as follows.
The measuring device, the aperture diameter, the analysis software, and the electrolytic solution were the same as those used in the measurement of the volume median particle diameter (D ₅₀ ) of the above-mentioned aggregated particles.
Dispersion: polyoxyethylene lauryl ether "Emulgen (registered trademark) 109P" (manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance) = 13.6) is dissolved in the above electrolyte, and a dispersion with a concentration of 5% by mass I got
Dispersion conditions: 10 mg of a measurement sample of dried toner particles is added to 5 mL of the dispersion, dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of an electrolyte is added, and further with an ultrasonic disperser The sample dispersion was prepared by dispersing for 1 minute.
Measurement conditions: The particle diameter of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds by adding the sample dispersion to 100 mL of the electrolyte, 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 size distribution.

[Evaluation method]
[Heat-resistant storage stability of toner]
In a state in which 20 g of toner was put in a wide-mouthed poly bottle having an inner volume of 100 mL and covered with a lid, it was allowed to stand in a dryer at a temperature of 50 ° C. for 48 hours. Thereafter, each sample was allowed to stand still for 12 hours or more while being sealed at a temperature of 25 ° C. and cooled. Next, a 250-μm sieve is set on a shaking table of “Powder Tester” (manufactured by Hosokawa Micron Corporation), 20 g of the toner is placed on it and vibrated for 30 seconds, and the amount of toner remaining on the sieve is measured. The degree of aggregation was calculated according to the following equation. The smaller the value, the better the toner is in heat-resistant storage stability.
Cohesion degree (%) = residual toner mass on the sieve [g] / 20 [g] × 100

[Cleanability of toner]
Using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Co., Ltd.), a solid development toner (a toner in which the amount of toner in solid printing is adhered to the photoconductor) is formed on the photoconductor, The solid development toner was not transferred to a transfer sheet but allowed to reach a cleaning device for cleaning, and the number of streaks on the surface of the photosensitive member after passing through a cleaning blade was visually confirmed. The smaller the number of streaks, the better the cleanability.

[Fogging suppression]
A 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, high quality paper "Excellent White" in an environmental test room with a temperature of 30 ° C and a relative humidity of 80%. Print using A4 size paper (Oki Data Co., Ltd.) and stop the machine when transferring to half of A4 size, and stop the machine, and clear mending tape "Scotch (registered trademark) mending on the surface of the photosensitive body before transfer. Affix the tape 810-3-18 (manufactured by 3M) and collect the toner on the surface of the photosensitive member.
A mending tape as a reference and a mending tape obtained by collecting the toner on the photosensitive member are attached on an unused excellent white paper surface, respectively, and a colorimeter “SpectroEye” (Gretag-Macbeth company, light emitting condition; CIE L ^* a ^* b ^* color on the mending tape as a reference and the mending tape from which the toner on the photosensitive member was collected using a standard light source D50, an observation field of view 2 °, a density reference DINNB, and an absolute white reference) 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 determined. The smaller ΔE is, the smaller the fog is.
ΔE = [(L ^* _1- L ^* ₂ ) ² + (a ^* _1- a ^* ₂ ) ² + (b ^* _1- b ^* ₂ ) ² ] ^1/2
[Wherein, L ^* ₁ , a ^* ₁ and b ^* ₁ indicate the measured values on the mending tape as a reference, and L ^* ₂ , a ^* ₂ and b ^* ₂ indicate the toners collected on the photosensitive member] Each measured value on a ding tape is shown. ]

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

[Production of resin]
Production Example A1 (Production of Amorphous Resin A-1)
The inside of a four-necked flask with an inner volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, 4200 g of propylene oxide (2.2) adduct of bisphenol A, 1355 g of terephthalic acid, Add 31 g of (2-ethylhexanoic acid) tin (II) and 3 g of gallic acid (3,4,5-trihydroxybenzoic acid), raise the temperature to 235 ° C with stirring under a nitrogen atmosphere, After holding for 5 hours, the pressure in the flask was reduced and held at 8 kPa for 1 hour. Thereafter, the pressure is returned to the atmospheric pressure, and the mixture is cooled to 160 ° C. and kept at 160 ° C. A mixture of 1819 g of styrene, 455 g of stearyl methacrylate, 138 g of acrylic acid and 227 g of dibutyl peroxide is dropped over 1 hour. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the pressure was kept at 8 kPa for 1 hour. Thereafter, the pressure is returned to atmospheric pressure and then cooled to 190 ° C., 223 g of fumaric acid, 230 g of trimellitic anhydride and 2.5 g of 4-tert-butylcatechol are added, and the temperature is raised to 210 ° C. at 10 ° C./hr. Then, the reaction was carried out at 4 kPa to the desired softening point to obtain amorphous resin A-1. Various physical properties of the resin were measured and are 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 purged with nitrogen, and 5363 g of ethylene oxide (2.2) adduct of bisphenol A, 1780 g of terephthalic acid, (2-ethylhexanoic acid) 40 g of tin (II) and 4 g of gallic acid are added, and the temperature is raised to 235 ° C. with stirring under nitrogen atmosphere and held at 235 ° C. for 8 hours, then the pressure in the flask is lowered. And 8 kPa for 1 hour. Thereafter, the pressure is returned to atmospheric pressure, and then cooled to 180 ° C., 287 g of fumaric acid, 221 g of dodecenyl succinic anhydride, 380 g of trimellitic anhydride and 2.5 g of 4-tert-butylcatechol are added, and 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 to a desired softening point at 10 kPa to obtain amorphous resin B-1. Various physical properties of the resin were measured and are 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 is purged with nitrogen, 4313 g of propylene oxide (2.2) adduct of bisphenol A, 818 g of terephthalic acid, and amber 727 g of acid, 30 g of tin (II) di (2-ethylhexanoate), and 3 g of gallic acid are added, and the temperature is raised to 235 ° C. with stirring under a nitrogen atmosphere and maintained at 235 ° C. for 5 hours; The pressure was lowered and maintained at 8 kPa for 1 hour. Thereafter, the pressure is returned to the atmospheric pressure, and the mixture is cooled to 160 ° C. and kept at 160 ° C. A mixture of 2755 g of styrene, 689 g of stearyl methacrylate, 142 g of acrylic acid, and 413 g of dibutyl peroxide is dropped over 1 hour. Then, after maintaining 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 performed at 8 kPa to a desired softening point to obtain amorphous resin D-1. Various physical properties of the resin were measured and are shown in Table 1.

Production Example C1 (Production of Crystalline Polyester Resin C-1)
The inside of a 10 L four-necked flask equipped with a nitrogen introducing tube, a dehydrating tube, a stirrer, and a thermocouple was purged with nitrogen, and 3416 g of 1,10-decanediol and 4084 g of sebacic acid were charged. While stirring, the temperature was raised to 135 ° C. and maintained at 135 ° C. for 3 hours, and then the temperature was raised from 135 ° C. to 200 ° C. over 10 hours. Thereafter, 23 g of di (2-ethylhexanoic acid) tin (II) is added, and the mixture is further maintained at 200 ° C. for 1 hour, and then the pressure in the flask is lowered and maintained at 8.3 kPa for 1 hour. C-1 was obtained. Various physical properties of the resin were measured and are shown in Table 2.

[Production of resin particle dispersion]
Production Example X1 (Production of Resin Particle Dispersion X-1)
210 g of amorphous resin A-1 and crystal in a container with an inner volume of 3 L equipped with a stirrer “SleeOne Motor BL300” (manufactured by Shinto Scientific Co., Ltd.), a reflux condenser, a dropping funnel, a thermometer and a nitrogen introducing pipe 90 g of the polyester resin C-1 and 300 g of methyl ethyl ketone were added, and the resin was dissolved at 73 ° C. for 2 hours. A 5% by mass aqueous solution of sodium hydroxide was added to the obtained solution so that the degree of neutralization was 60 mol% with respect to the acid value of the resin, and the solution was stirred for 60 minutes.
Next, while maintaining the temperature at 73 ° C., 600 g of deionized water was added over 60 minutes while stirring at 200 r / min (circumferential velocity 63 m / min) to perform phase inversion emulsification. The methyl ethyl ketone was distilled off under reduced pressure while maintaining the temperature at 73 ° C. continuously to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30 ° C. while stirring, and deionized water is added to adjust the solid content concentration to be 30% by mass, and then the solution is filtered through a 150 mesh wire mesh to obtain resin particle dispersion X -1 was obtained. The volume median particle size (D ₅₀ ) and CV value of the obtained resin particles are shown in Table 3.

Production Example Y1, Z1 (Production of Resin Particle Dispersion 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 to be used were combined in Table 3. The volume median particle diameter D ₅₀ and CV value of the obtained resin particles are shown in Table 3.

[Production of Release Agent Particle Dispersion]
Production Example W1 (Production of Releasing Agent Particle Dispersion W-1)
Add 120 g of deionized water, 53 g of resin particle dispersion Z-1 and 40 g of paraffin wax “HNP-9” (manufactured by Nippon Seiwa Co., Ltd., melting point 75 ° C.) to a beaker with an internal volume of 1 L, and adjust to 90-95 ° C. The temperature was maintained while melting and stirring to obtain a molten mixture. After performing dispersion processing for 20 minutes using ultrasonic homogenizer "US-600T" (made by Nippon Seiki Co., Ltd.), hold | maintaining temperature at 90-95 degreeC, it 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 releasing agent particle dispersion W-1. The volume median particle size (D ₅₀ ) was 0.45 μm, and the CV value was 26%.

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

[Manufacture of toner]
Example 1 (Production of Toner 1)
300 g of resin particle dispersion X-1, 49.7 g of releasing agent particle dispersion W-1, and colorant particle dispersion in a 3 L four-necked flask equipped with a dewatering tube, a stirrer and a thermocouple 33.8 g of P-1 and 9 g of nonionic surfactant "Emulgen (registered trademark) 150" (manufactured by Kao Corporation, 10 mass% aqueous solution of polyoxyethylene (average number of added moles: 50 lauryl ether)) 150.0 g of ionic water was mixed at a temperature of 25 ° C. Next, while stirring the mixture, a solution adjusted to pH 8.4 by adding 22.7 g of a 4.8 mass% aqueous potassium hydroxide solution to an aqueous solution in which 31.0 g of ammonium sulfate is dissolved in 468.4 g of deionized water was added dropwise over 10 minutes at 25 ° C., the temperature was raised over 2 hours to 62 ° C., to a volume median particle size of the aggregated particles _{(D 50)} is 5.1 .mu.m, and held at 62 ° C., aggregation A dispersion of particles 1 was obtained.
While lowering the temperature of the dispersion of agglomerated particles 1 to 55 ° C. and maintaining at 55 ° C., add a mixture of 60 g of resin particle dispersion Y-1 and 18.3 g of deionized water over 120 minutes, and aggregate A dispersion liquid of aggregated particles 2 in which resin particles are aggregated into particles was obtained.
18.9 g of an anionic surfactant "Emar (registered trademark) E-27C" (manufactured by Kao Corporation, polyoxyethylene lauryl ether sulfate, effective concentration of 27% by mass) in a dispersion liquid of aggregated particles 2; deionized water An aqueous solution mixed with 1871 g was added. Then, it heated up over 1 hour to 75 degreeC. At this time, the pH of the dispersion liquid of aggregated particles 2 was 7.0. After reaching 75 ° C., measure the circularity while adding 0.1 M aqueous sulfuric acid solution at a rate of 2 g / min and keep 75 ° C. until the circularity reaches the range of 0.950 to 0.965 A dispersion liquid of fused particles in which aggregated particles are fused is obtained. At this time, the pH of the dispersion was 6.4, and the added 0.1 M aqueous sulfuric acid solution was 118 g.
After adding 4.6 g of 4.8 mass% potassium hydroxide aqueous solution to the dispersion liquid of the obtained melt | fusion particle | grains, temperature was hold | maintained at 75 degreeC for 1.5 hours.
The resulting dispersion of fused particles is cooled to 30 ° C., suction filtered to separate solid content, washed with deionized water at 25 ° C., and vacuum dried at 35 ° C. for 48 hours to obtain toner particles. I got Physical properties 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 diameter: 0.04 μm), and hydrophobic silica “Cabosil (registered trademark) TS 720” (Kabot Japan Co., Ltd. 1.0 part by weight of a number average particle diameter: 0.012 μm) manufactured by a company was put into a Henschel mixer and stirred, and passed through a 150-mesh sieve to obtain a toner 1. Various evaluations were performed, and the results are shown in Table 4.

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

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

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

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

Comparative Example 1 (Production of Toner 51)
After the addition of a 0.1 M aqueous sulfuric acid solution, a toner 51 was obtained in the same manner as in Example 1, except that the 4.8 mass% aqueous potassium hydroxide 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 (Production of Toner 52)
A toner 52 was obtained in the same manner as in Example 1, except that the amount of the 4.8% by mass aqueous potassium hydroxide solution added to the dispersion of the fused particles was changed to 46 g. Various evaluations were performed, and the results are shown in Table 4.

Comparative Example 3 (Production of Toner 53)
A toner 53 was obtained in the same manner as in Example 1 except that the temperature was maintained for 1.5 hours without adding the 0.1 M aqueous sulfuric acid solution and the 4.8 mass% aqueous potassium hydroxide solution. 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 the toner having excellent cleaning properties can be obtained by the present invention.
In particular, in the examples, the temperature is maintained at 75 ° C. for 1.5 hours after the addition of the basic substance, but it can be seen that the increase in circularity is extremely low.
Further, from the results of Examples and Comparative Examples, it can be seen that the toner having excellent chargeability, fog suppression and heat resistant storage stability can be obtained by the present invention.

Claims (7)

A method for producing a toner for electrostatic charge image development, comprising the step of fusing aggregated particles, which are aggregates of polyester resin particles, in an aqueous medium,
In the step of fusing,
An acidic substance is added at a temperature above the glass transition temperature of the polyester resin of the aggregated particles, and the pH in the aqueous medium is lowered by 0.1 or more and 3.0 or less as compared to before the addition of the acidic substance, The pH after substance addition is in the range of 4.0 to 7.0,
Thereafter, a basic substance is added at a temperature above the glass transition temperature of the polyester resin of the aggregated particles, and the pH in the aqueous medium is increased by 0.1 or more and less than 1.0 before the addition of the basic substance. And a method of producing a toner for developing an electrostatic charge image.   2. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the pH in the aqueous medium is lowered by 0.1 or more and 1.0 or less as compared with before addition of the acidic substance by addition of the acidic substance.   The method for producing a toner for developing an electrostatic charge image according to claim 1 or 2, wherein the pH in the aqueous medium is increased by 0.1 or more and 0.6 or less as compared with that before the addition of the basic substance by the addition of the basic substance.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein the circularity of the fused particles at the start of the 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 A method of producing a toner for developing an electrostatic charge image according to any one of claims 1 to 4.   The agglomerated particles 2 are agglomerated particles 2 comprising agglomerated particles 1 which are agglomerates of resin particles a containing polyester resin A, and resin particles b containing polyester resin B attached to the surface thereof. The manufacturing method of the toner for electrostatic charge image development in any one of 1-5. The step of aggregating resin particles a containing polyester resin A to obtain aggregated particles 1, and the step of adhering resin particles b containing polyester resin B to aggregated particles 1 to obtain aggregated particles 2 Included before the process
The method for producing a toner for developing an electrostatic charge image according to claim 6, wherein the aggregated particles in the step of fusing are the aggregated particles 2.