JP2020024362A - toner - Google Patents

Abstract

To provide a toner that achieves low-temperature fixability, separability, and heat-resistant storage property.SOLUTION: A toner includes toner particles containing a binder resin and wax, and the binder resin contains an amorphous resin A. In dynamic viscoelasticity measurement of the toner, when a temperature at which the dynamic viscoelasticity is measured at a frequency of 1 Hz and the loss elastic modulus G'' is 1.00×10Pa is T(1Hz), a temperature at which the dynamic viscoelasticity is measured at a frequency of 20 Hz and the loss elastic modulus G'' is 1.00×10Pa is T(20Hz), and the maximum value in a range of 60°C or more and 90°C or less of the ratio (tanδ) of the loss elastic modulus G'' to the storage elastic modulus G' when the dynamic viscoelasticity is measured at a frequency of 20 Hz is tanδ(P), the following formulas (1) to (4) are satisfied. Formula (1) T(20 Hz)-T(1 Hz)≤7.0°C; formula (2) 0.80≤tanδ(P)≤1.90; formula (3) 60°C≤T(1 Hz)≤80°C; formula (4) 60°C≤T(20 Hz)≤80°C.SELECTED DRAWING: None

Description

  The present invention relates to a toner used to form a toner image by developing an electrostatic latent image formed by a method such as electrophotography, electrostatic recording, and toner jet recording.

In recent years, further power saving of printers and copiers has been demanded. In order to cope with this, a toner which melts quickly at a lower temperature, that is, is excellent in low-temperature fixability is preferable. In order to obtain a toner having excellent low-temperature fixability, studies have been made to use wax for the toner.
The wax is added for the purpose of plasticizing the binder resin. When the wax melted by heat becomes compatible with the binder resin, the viscosity of the toner at the time of melting is reduced, and excellent low-temperature fixability is obtained. From such a background, Patent Documents 1 to 5 propose a toner using an ester wax.

JP-A-2017-040772 JP 2017-044952 A Japanese Patent No. 6020458 JP 2012-63574 A JP 2006-267516 A

On the other hand, when the viscosity of the toner at the time of melting is reduced, the toner tends to adhere to the fixing member at the time of fixing (decrease in separability). As a result, the problem that the paper is wound around the fixing member is likely to occur. Further, when the toner separation property is reduced, a part of the image adheres to the fixing member, so that a spot is easily removed. Therefore, the low-temperature fixability may be reduced.
Further, the toner is required to have both excellent low-temperature fixability and heat-resistant storage stability. However, the wax added for the purpose of plasticizing the binder resin tends to have high compatibility with the binder resin and a low melting point. Therefore, when stored in a high-temperature environment, some of the wax contained in the toner may be melted or may seep out to the surface of the toner particles, resulting in reduced storage stability.
Therefore, in a toner using a wax, it is required to further achieve both low-temperature fixability, separability, and heat-resistant storage stability.
In the toners described in Patent Literatures 1 and 2, low-temperature fixability is improved by using an ester wax, but this is not sufficient from the viewpoint of sufficiently increasing the compatibility between the ester wax and the binder resin. In addition, due to the influence of the coating layer used for improving the developing property, the low-temperature fixing property of the ester wax may not be sufficiently exhibited in some cases, indicating that there is room for improvement.
In the toner described in Patent Document 3, an ester wax having high compatibility is used, but this is not sufficient from the viewpoint of appropriately controlling the melt viscosity of the toner to improve the separability. Specifically, a crosslinkable polymerizable monomer is added for compatibility with hot offset resistance, but the influence thereof may hinder low-temperature fixability. Further, regarding the design of the coating layer used for improving the storage stability, the compatibility between the coating layer and the ester wax was not considered, and it was found that there was room for improvement in the separability.
Further, in the toners described in Patent Documents 4 and 5, an ester wax having a high compatibility is used, but it is not sufficient from the viewpoint of keeping the melting point of the ester wax high and improving the heat-resistant storage stability.
The present invention provides a toner that solves the above-mentioned problems.
That is, the present invention provides a toner having both low-temperature fixability, separability, and heat-resistant storage stability.

The present invention is a toner having toner particles containing a binder resin and a wax,
The binder resin contains an amorphous resin A,
In the measurement of the dynamic viscoelasticity of the toner,
Measured at a frequency of 1 Hz, the temperature at which the loss elastic modulus G ″ becomes 1.00 × 10 ⁶ Pa is defined as T (1 Hz),
Measured at a frequency of 20 Hz, the temperature at which the loss elastic modulus G ″ becomes 1.00 × 10 ⁶ Pa is defined as T (20 Hz),
When the maximum value of the ratio (tan δ) of the loss elastic modulus G ″ to the storage elastic modulus G ′ when measured at a frequency of 20 Hz in the range of 60 ° C. or more and 90 ° C. or less is defined as tan δ (P), The present invention relates to a toner characterized by satisfying (1) to (4).
Formula (1) T (20 Hz) −T (1 Hz) ≦ 7.0 ° C.
Equation (2) 0.80 ≦ tan δ (P) ≦ 1.90
Formula (3): 60 ° C. ≦ T (1 Hz) ≦ 80 ° C.
Formula (4): 60 ° C. ≦ T (20 Hz) ≦ 80 ° C.

  According to the present invention, it is possible to provide a toner having both low-temperature fixability, separability, and heat-resistant storage stability.

Schematic diagram explaining the deformation speed and the magnitude of the force required for deformation FIG. 3 is a diagram showing the elastic modulus of a conventional toner measured at frequencies of 1 Hz and 20 Hz. FIG. 4 is a diagram illustrating the elastic modulus of the toner of the present invention measured at frequencies of 1 Hz and 20 Hz. The figure which measured the elastic modulus of the wax simple substance at the frequency of 1 Hz and 20 Hz.

In the present invention, description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit which are endpoints unless otherwise specified.
The ease with which the toner is deformed can be expressed by an elastic modulus. The elastic modulus is a numerical value of a force required to deform a material such as toner by a certain amount. For example, it can be said that the higher the elastic modulus at the storage temperature, the more difficult it is to deform, and the better the storage stability. Further, the lower the elastic modulus of the toner at the time of melting, the lower the melt viscosity of the toner at the time of fixing.
Further, one of the measurement parameters of the elastic modulus is a deformation speed. This is a speed at which the toner is deformed when measuring the elastic modulus, and is set as a frequency when using a dynamic viscoelasticity measuring device. For example, a large amount of force is required to quickly deform a certain amount of toner. However, even if the deformation amount is the same, the deformation can be performed with a small force as long as the deformation speed is slow (FIG. 1).
FIG. 2 shows an example in which the dynamic viscoelasticity of the toner is actually measured by changing the frequency. It can be seen that, when measured at a high frequency condition, a higher elastic modulus is obtained even at the same measurement temperature than when measured at a low frequency condition.

When the above-mentioned deformation speed is applied when actually using the toner, when the toner is stored for a long period of time or at a high temperature, a force is applied to the toner slowly and carefully. Therefore, it was considered that the heat storage stability of the toner had a high correlation with the elastic modulus measured under the condition of a low frequency. On the other hand, in the fixing step, pressure is instantaneously applied to the toner. Therefore, it was considered that the low-temperature fixability of the toner had a high correlation with the elastic modulus measured under the condition of high frequency.
As a result of repeated studies based on the above idea, the value of the elastic modulus measured under low frequency conditions is high, and the value of the elastic modulus measured under high frequency conditions is lowered, so that heat resistance storage stability and low temperature fixing It was found that gender compatibility was possible.

That is, in the dynamic viscoelasticity measurement of the toner, the temperature is measured at a frequency of 1 Hz, the temperature at which the loss elastic modulus G ″ becomes 1.00 × 10 ⁶ Pa is T (1 Hz), and the measurement is performed at a frequency of 20 Hz. When the temperature at which the elastic modulus G ″ becomes 1.00 × 10 ⁶ Pa is T (20 Hz), it is necessary to satisfy the following expression (1).
Formula (1) T (20 Hz) −T (1 Hz) ≦ 7.0 ° C.

Here, the measured value at a frequency of 1 Hz is an elastic modulus under a low frequency condition, and is considered to be a value corresponding to heat-resistant storage stability. The measured value at a frequency of 20 Hz is an elastic modulus under a high frequency condition, and is considered to be a value corresponding to the fixing property.
Specifically, the time during which the toner is pressurized in the fixing step is assumed to be about 50 ms, so that the frequency is 20 Hz in terms of frequency. Satisfying the expression (1) means that the difference between the elastic modulus at a frequency of 1 Hz and the elastic modulus at a frequency of 20 Hz is sufficiently small, and it is possible to achieve both high-temperature storage stability and low-temperature fixability at a high level. It means that
The value of 1.00 × 10 ⁶ Pa is a numerical value assuming an elastic modulus at which the toner can be fixed.
FIG. 3 shows an example of the measurement results of the elastic modulus of the toner of the present invention. Even when the value of T (20 Hz) -T (1 Hz) is small and the value of T (1 Hz) is increased to improve the heat-resistant storage stability, the value of T (20 Hz) is hardly increased, so that excellent low-temperature fixability is obtained. Can be obtained.

Normally, amorphous resins such as those used for toner have a large frequency dependence of the elastic modulus. This is because the entanglement of the molecules is softened by gradually loosening by heating, and when the frequency is increased, the interaction of the entanglement of the molecules becomes stronger, so that the elastic modulus increases (example shown in FIG. 2). .
On the other hand, crystalline materials such as wax have a small frequency dependence of the elastic modulus. In the case of a crystalline material, heating to a temperature higher than the melting point causes the crystal to collapse and melt. At this time, since the melting is performed irrespective of the entanglement of the molecules, even when the frequency is changed, the temperature at which the elastic modulus decreases does not change (FIG. 4). Therefore, by giving the toner a decrease in viscosity due to the melting of the wax, a characteristic that frequency dependency is small can be obtained.

Therefore, it is preferable to control the value of T (20 Hz) -T (1 Hz) using the plasticizing effect of wax. The higher the compatibility of the wax with the binder resin, the higher the plasticizing effect and the more the elastic modulus of the toner can be reduced, so that the value of T (20 Hz) -T (1 Hz) can be made smaller. Further, as the molecular weight of the wax is smaller, the effect of lowering the elastic modulus of the toner is higher, and the value of T (20 Hz) -T (1 Hz) can be made smaller.
T (20 Hz) -T (1 Hz) is preferably 4.5 ° C. or less. The lower limit is not particularly limited, but is preferably −1.0 ° C. or higher, and more preferably 0 ° C. or higher.

Simply satisfying the above-mentioned properties increases the adhesive force between the toner and the fixing member, so that the separability is reduced and the problem that the paper is wound around the fixing member is likely to occur. Therefore, the maximum value of the ratio (G ″ / G ′) (tan δ) of the loss elastic modulus G ″ to the storage elastic modulus G ′ when measured at a frequency of 20 Hz in the range of 60 ° C. or more and 90 ° C. or less is tan δ. When (P) is satisfied, the following equation (2) must be satisfied.
Equation (2) 0.80 ≦ tan δ (P) ≦ 1.90

The smaller the value of tan δ (P), the higher the value of the storage elastic modulus with respect to the loss elastic modulus, and thus the greater the force of the toner to return from the deformation. As a result, the force for separating the toner from the fixing member is increased, and the separability is improved. Therefore, the value of tan δ (P) is 1.90 or less. On the other hand, when tan δ (P) is smaller than 0.80, the deformation of the toner does not sufficiently occur, so that the low-temperature fixability decreases.
It is preferable that tan δ (P) satisfies the following expression (2 ′).
Formula (2 ′) 1.00 ≦ tan δ (P) ≦ 1.90
Further, tan δ (P) preferably satisfies the following equation (2 ″).
Formula (2 ″) 1.00 ≦ tan δ (P) ≦ 1.70

The meaning of using tan δ when measured at a frequency of 20 Hz is that winding and separation are phenomena during fixing. Further, since it is considered that the toner is heated to about 60 ° C. or more and about 90 ° C. or less at the time of fixing, the above-described tan δ (P) was used.
The value of tan δ (P) can be controlled by the molecular weight of the toner, the glass transition temperature Tg, the degree of crosslinking, the encapsulation (coating layer), and the like. From the viewpoint of compatibility with low-temperature fixability and heat-resistant storage stability, it is preferable to achieve this by controlling the coating layer.

Further, the toner of the present invention satisfies the following expressions (3) and (4).
Formula (3): 60 ° C. ≦ T (1 Hz) ≦ 80 ° C.
Formula (4): 60 ° C. ≦ T (20 Hz) ≦ 80 ° C.
When T (1 Hz) and T (20 Hz) are lower than 60 ° C., the heat-resistant storage stability decreases. When T (1 Hz) and T (20 Hz) are higher than 80 ° C., excellent low-temperature fixability cannot be obtained. It is preferable that the following formulas (3 ′) and (4 ′) are satisfied.
Formula (3 ′) 60 ° C. ≦ T (1 Hz) ≦ 70 ° C.
Formula (4 ′) 60 ° C. ≦ T (20 Hz) ≦ 75 ° C.

As a method of controlling the values of T (1 Hz) and T (20 Hz), the values can be controlled by the molecular weight of the toner, Tg, the amount of wax added, the melting point of the wax, and the like. It is convenient and preferable to control the melting point of the wax.
As described above, by satisfying the expressions (1) to (4), excellent low-temperature fixability and heat-resistant storage stability can be achieved, and at the same time, the separability which tends to occur in a toner having a reduced viscosity at the time of melting can be obtained. It is also possible to achieve a high level of reduction.
The method of measuring T (1 Hz), T (20 Hz) and tan δ (P) will be described later.

The toner particles preferably have a coating layer on the surface. By having the coating layer, excellent separability can be obtained even if the value of tan δ (P) is higher. As a result, it becomes easy to achieve both low-temperature fixability and separability.
When the separation property is to be improved by the coating layer, it is preferable that the wax constituting the coating layer has low compatibility with the wax. Due to the low compatibility, the coating layer is not plasticized by the wax at the time of fixing, and excellent separability can be obtained. On the other hand, with such a design, the coating layer exists in a hard state at the time of fixing and covers the binder resin, so that the low-temperature fixing property may be reduced.

However, in the present invention, low-temperature fixation is achieved by using a coating layer having low compatibility with wax on toner particles whose T (20 Hz) -T (1 Hz) is reduced by using wax having high compatibility with toner particles. And separability. The reason is speculated as follows.
The fact that T (20 Hz) -T (1 Hz) of the toner particles is small means that the elastic modulus of the toner is sufficiently reduced even when pressure is momentarily applied to the toner during fixing. As a result, the binder resin can quickly exude even from a slight crack (gap) of the coating layer on the surface of the toner particles caused by deformation of the toner at the time of fixing, so that the coating layer having low compatibility with the wax can be obtained. It is considered that the low-temperature fixability is improved even if the film is formed.

Furthermore, the lower the compatibility between the wax and the coating layer, the better the low-temperature fixability and the separability tend to be. From this, it is considered that the lower the compatibility between the wax and the coating layer, the less the interaction between the wax and the binder resin having high compatibility, and the more quickly the binder resin exudes.
As described above, by using a coating layer having low compatibility with wax for toner particles having a reduced T (20 Hz) -T (1 Hz), it is easier to achieve both low-temperature fixability and separability.

Further, the thickness of the coating layer is preferably from 10 nm to 200 nm. By being in this range, it becomes easy to control the value of tan δ (P) to a desired range. When the thickness of the coating layer is 10 nm or more, more excellent separability can be obtained, and when it is 200 nm or less, excellent low-temperature fixability can be obtained. More preferably, the thickness of the coating layer is 15 nm or more and 100 nm or less.
It is simple and preferable to control the thickness of the coating layer by the amount of the material used for the coating layer.
The method for measuring the presence or absence of the coating layer and the thickness will be described later.

The coating layer contains the amorphous resin B, and the glass transition temperature Tg of the amorphous resin B is preferably from 60 ° C to 90 ° C, more preferably from 60 ° C to 85 ° C.
When the temperature is 60 ° C. or higher, a high elastic modulus can be obtained even at the storage temperature and the fixing temperature of the toner, so that more excellent heat-resistant storage property and separation property can be obtained. When the temperature is 90 ° C. or lower, the coating layer is softened in the same temperature range as the melting temperature of the toner particles, so that the elastic modulus at the fixing temperature of the toner can be reduced, and more excellent low-temperature fixing property can be obtained.
The glass transition temperature of the amorphous resin B can be controlled by the composition of the monomer constituting the amorphous resin B.
The method for measuring the glass transition temperature of the amorphous resin B will be described later.

The resin that can be used for the amorphous resin B is not particularly limited, and resins that are conventionally used for toner can be used. For example, polyester resin; styrene acrylic resin; polyamide resin; furan resin; epoxy resin; xylene resin;
The amorphous resin B preferably contains a polyester resin, more preferably a polyester resin. Polyester resins have a high polarity and tend to have low compatibility with wax. Therefore, the coating layer is less likely to be plasticized by the wax, and it is possible to control tan δ (P) and to suppress the exudation of the wax during storage of the toner. As a result, better separability and heat-resistant storage stability are obtained.
The weight average molecular weight of the amorphous resin B is preferably 5,000 to 30,000.

As the polyester resin, a known polyester resin can be used.
Polyester resins include, for example, dibasic acids and derivatives thereof (carboxylic acid halides, esters and acid anhydrides) and dihydric alcohols, and if necessary, tribasic or higher polybasic acids and derivatives thereof (carboxylic acid halogens). Compounds, esters, acid anhydrides), monobasic acids, trihydric or higher alcohols, monohydric alcohols, and the like.
Examples of the dibasic acid include maleic acid, fumaric acid, itaconic acid, oxalic acid, malonic acid, succinic acid, dodecylsuccinic acid, dodecenylsuccinic acid, adipic acid, azelaic acid, sebacic acid, decane-1,10-dicarboxylic acid and the like. Aliphatic dibasic acids such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, hetonic acid, hymic acid, isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid Aromatic dibasic acid; 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, cis-4-cyclohexene-1 , 2-dicarboxylic acid, cis-1-cyclohexene-1,2-dicarboxylic acid , Norbornane carboxylic acid, norbornene dicarboxylic acid, and alicyclic dibasic acids such as 1,3-adamantane dicarboxylic acid.
The dibasic acids preferably include aromatic dibasic acids. Examples of the dibasic acid derivative include carboxylic acid halides, esterified products and acid anhydrides of the above-mentioned aliphatic dibasic acids, aromatic dibasic acids and alicyclic dibasic acids.

On the other hand, examples of the dihydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentaneddiol, 1,6-hexanediol, and diethylene glycol. Aliphatic diols such as phenol, dipropylene glycol, triethylene glycol and neopentyl glycol; bisphenols such as bisphenol A and bisphenol F; bisphenol A Bisphenol A alkylene oxide adducts such as ethylene oxide adducts and propylene oxide adducts of bisphenol A; aralkylene glycols such as xylylene diglycol; 1,4-cyclohexanedimethanol, isosorbide , Spiroglycol, hydrogenated bisphenol A, 1,4-cyclohexanediol, 1,2-cyclohexane Alicyclic such as sundiol, 1,3-cyclohexanediol, 4- (2-hydroxyethyl) cyclohexanol, 4- (hydroxymethyl) cyclohexanol, 4,4′-bicyclohexanol, 1,3-adamantanediol, etc. Diols and the like.
The dihydric alcohol preferably comprises a bisphenol A alkylene oxide adduct.

  Examples of the tribasic or higher polybasic acid and its anhydride include trimellitic acid, trimellitic anhydride, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4 , 5-cyclohexanetetracarboxylic acid, 1,2,3,4,5,6-cyclohexanehexacarboxylic acid, methylcyclohexentricarboxylic acid, methylcyclohexentricarboxylic anhydride, pyromellitic acid, pyromellitic anhydride and the like.

Among these materials, the polyester resin has a structure derived from at least one selected from the group consisting of ethylene glycol, oxalic acid, and an oxalic acid derivative (that is, represented by —O—CH ₂ —CH ₂ —O—. At least one of a structure and a structure represented by -C (= O) -C (= O)-). More preferably, the polyester resin has a structure derived from ethylene glycol (that is, a structure represented by —O—CH ₂ —CH ₂ —O—).
In the case of having such a structure, the number of ester groups in the polyester resin increases, so that the polyester resin has high polarity. Therefore, the compatibility with the wax is reduced, and the tan δ (P) can be designed in a preferable range. As a result, good separability and excellent low-temperature fixability are obtained.
The total content of the polyester resin having a structure derived from at least one selected from the group consisting of ethylene glycol, oxalic acid, and an oxalic acid derivative is defined as mol% based on all monomer units of the polyester resin. It is preferable that it is 0 mol% or more and 15.0 mol% or less.

It is also preferable that the polyester resin has a structure derived from isosorbide (that is, a structure represented by the following formula (A)). Since the structure derived from isosorbide has oxygen in the molecular structure, a polyester resin having high polarity and low compatibility with wax can be obtained. Furthermore, since isosorbide has a cyclic structure, when the wax is an aliphatic ester wax, a polyester resin having lower compatibility with the wax can be obtained. As a result, more excellent separability and excellent low-temperature fixability can be obtained.
The content in the polyester resin having a structure derived from isosorbide is preferably 2.5 mol% or more and 30.0 mol% or less, as mol% based on all monomer units of the polyester resin.

The binder resin contains the amorphous resin A. The amorphous resin A is a resin having a styrene-acrylic polymer site (more preferably a styrene-acrylic polymer, more preferably a styrene-acrylic copolymer), and a styrene-acrylic polymer site in the binder resin. Is preferably 50% by mass or more. It is more preferably at least 80% by mass. The upper limit is not particularly limited, but is preferably 100% by mass or less.
This means that the binder resin preferably contains a styrene acrylic resin as a main component. Styrene acrylic resins are not highly polar and therefore have high compatibility with wax, making it easy to effectively utilize the plasticizing effect of wax. Therefore, it is easy to control the value of T (20 Hz) -T (1 Hz), and it is possible to achieve both low-temperature fixing property and heat-resistant storage property.

As the binder resin, in addition to the amorphous resin A, a resin conventionally used for a toner may be used in combination.
For example, polyester resin; styrene acrylic resin; polyamide resin; furan resin; epoxy resin; xylene resin;
Examples of the polymerizable monomer capable of forming the styrene acrylic polymer site include the following.
Styrene monomers such as styrene, α-methylstyrene and divinylbenzene; such as methyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, t-butyl methacrylate, and 2-ethylhexyl methacrylate Unsaturated carboxylic esters such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acids such as maleic acid; unsaturated dicarboxylic anhydrides such as maleic anhydride; nitriles such as acrylonitrile Vinyl monomers; halogen-containing vinyl monomers such as vinyl chloride; nitro vinyl monomers such as nitrostyrene. These can be used alone or in combination of plural kinds.

The wax is not particularly limited, and known waxes used for the following toners can be used.
Esters of monohydric alcohols and aliphatic carboxylic acids, such as behenyl behenate, stearyl stearate, palmityl palmitate, or esters of monohydric carboxylic acids and aliphatic alcohols; dibehenyl sebacate, hexanediol dibehenate An ester of a dihydric alcohol and an aliphatic carboxylic acid, or an ester of a dihydric carboxylic acid and an aliphatic alcohol; an ester of a trihydric alcohol such as glycerin tribehenate and an aliphatic carboxylic acid, or Ester of a trivalent carboxylic acid and an aliphatic alcohol; an ester of a tetravalent alcohol and an aliphatic carboxylic acid such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate, or an ester of a tetravalent carboxylic acid and an aliphatic alcohol Ester; dipentaerythritol hex Ester of hexahydric alcohol and aliphatic carboxylic acid such as stearate, dipentaerythritol hexapalmitate, or ester of hexahydric carboxylic acid and aliphatic alcohol; polyhydric alcohol such as polyglycerin behenate Esters of aliphatic carboxylic acids or esters of polyhydric carboxylic acids and aliphatic alcohols; natural ester waxes such as carnauba wax and rice wax; petroleum waxes such as paraffin wax, microcrystalline wax and petrolatum and derivatives thereof; Fischer-Tropsch hydrocarbon wax and derivatives thereof; polyolefin waxes and derivatives thereof such as polyethylene wax and polypropylene wax; higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid; Amide wax.
These waxes may be used alone, or a plurality of types may be used.

Among these, the wax preferably contains an ester compound of a diol having 2 to 6 carbon atoms and an aliphatic monocarboxylic acid having 14 to 22 carbon atoms. The ester compound has a particularly high compatibility with the styrene acrylic resin and a small molecular weight, so that an excellent plasticizing effect can be obtained. Therefore, the value of T (20 Hz) -T (1 Hz) can be reduced, and more excellent low-temperature fixability and heat-resistant storage stability can be achieved.
In addition, since the chemical structure has a high linearity, the melting point and the crystallinity are high, so that better heat-resistant storage stability can be obtained. Further, it is more preferable to contain an ester compound of a diol having 2 carbon atoms and an aliphatic monocarboxylic acid having 14 to 22 carbon atoms.
The melting point of the wax is preferably from 60C to 90C.
The content of the wax in the toner is preferably from 5.0% by mass to 20.0% by mass. When the content is in the above range, low-temperature fixability and heat-resistant storage stability can be easily achieved at the same time. More preferably, it is not less than 8.0% by mass and not more than 15.0% by mass. A method for measuring the content of the wax in the toner will be described later.

The toner particles may contain a colorant. Examples of the coloring agent include a coloring agent for black, a coloring agent for yellow, a coloring agent for magenta, and a coloring agent for cyan.
Examples of the black colorant include carbon black.
As a colorant for yellow, yellow represented by monoazo compound; disazo compound; condensed azo compound; isoindolinone compound; isoindoline compound; benzimidazolone compound; anthraquinone compound; azo metal complex; methine compound; Pigments. Specifically, C.I. I. Pigment Yellow 74, 93, 95, 109, 111, 128, 155, 174, 180, 185 and the like.

Examples of the magenta colorant include monoazo compounds; condensed azo compounds; diketopyrrolopyrrole compounds; anthraquinone compounds; quinacridone compounds; basic dye lake compounds; naphthol compounds: benzimidazolone compounds; Pigments. Specifically, C.I. I. Pigment Red 2,3,5,6,7,23,48: 2,48: 3,48: 4,57: 1,81: 1,122,144,146,150,166,169,177,184. 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19 and the like.
Examples of the coloring agent for cyan include a cyan pigment represented by a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, a basic dye lake compound and the like. Specifically, C.I. I. Pigment Blue 1,7,15,15: 1,15: 2,15: 3,15: 4,60,62,66.
Further, various dyes conventionally known as colorants can be used together with the pigment.
The content of the colorant is preferably from 1.0 part by mass to 20.0 parts by mass with respect to 100 parts by mass of the binder resin.

  The toner particles may contain a known material such as a charge control agent, a charge control resin, and a pigment dispersant as needed. Further, the toner particles may have a known material such as an organosilicon compound or a thermosetting resin on the surface as necessary.

Further, the toner particles may be used as the toner as it is, or may be used as a toner by mixing an external additive and the like as necessary and attaching the mixture to the surface.
Examples of the external additive include inorganic fine particles selected from the group consisting of silica fine particles, alumina fine particles, and titania fine particles, and composite oxides thereof. Examples of the composite oxide include silica aluminum fine particles and strontium titanate fine particles.
The additive amount of the external additive is preferably from 0.01 to 8.0 parts by mass, and more preferably from 0.1 to 4.0 parts by mass, based on 100 parts by mass of the toner particles. Is more preferred.

  The toner weight average particle diameter (D4) is preferably from 4.0 μm to 9.0 μm. When the content is in the above range, the function of the thickness of the coating layer can be effectively exhibited, so that more excellent separation properties can be obtained. The weight average particle size (D4) is more preferably 4.0 μm or more and 8.0 μm or less. The weight average particle diameter (D4) of the toner can be controlled by additives of the toner and manufacturing conditions. The method for measuring the weight average particle diameter (D4) of the toner will be described later.

The weight average molecular weight Mw of the toner is preferably from 20,000 to 120,000. When the content is within the above range, excellent low-temperature fixability and excellent separation can be achieved at the same time. The weight average molecular weight Mw is more preferably from 30,000 to 80,000. The method for measuring the weight average molecular weight Mw of the toner will be described later.
The toner can be produced by a known method such as a pulverization method, a suspension polymerization method, an emulsion aggregation method, a dissolution suspension method, and the production method is not particularly limited.

Hereinafter, methods for measuring each physical property will be described.
<Method of Measuring T (1 Hz), T (20 Hz), and tan δ (P) of Toner>
As a measuring device, a rotating plate type rheometer “ARES” (manufactured by TA INSTRUMENTS) is used.
As a measurement sample, 0.1 g of the toner was weighed and added to a disk having a diameter of 8.0 mm and a thickness of 1.5 ± 0.3 mm using a tableting machine at room temperature (25 ° C.). Use a pressed sample.
The sample is mounted on a parallel plate having a diameter of 8.0 mm, heated from room temperature (25 ° C.) to 120 ° C. in 5 minutes, held for 3 minutes, and cooled to 50 ° C. in 10 minutes. Thereafter, the measurement is started after holding for 30 minutes. At this time, the sample is set so that the initial normal force becomes zero. Further, as described below, in the subsequent measurement, the effect of the normal force can be canceled by performing automatic tension adjustment (Auto Tension Adjustment ON). The measurement was performed under the following conditions.
(1) A parallel plate having a diameter of 8.0 mm was used.
(2) Frequency: 1 Hz or 20 Hz
(3) The initial value (Strain) of the applied strain was set to 0.2%.
(4) The measurement is performed at a temperature rising rate (Ramp Rate) of 2.0 [° C./min] in a temperature range of 50 ° C. or more and 120 ° C. or less. The measurement is performed under the following automatic adjustment mode setting conditions. The measurement is performed in the automatic distortion adjustment mode (Auto Strain).
(5) Set the maximum strain (Max Applied Strain) to 20.0%.
(6) Set the maximum torque (Max Allowed Torque) to 200.0 [g · cm] and set the minimum torque (Min Allowed Torque) to 0.2 [g · cm].
(7) Set the Strain Adjustment to 20.0% of Current Strain. In the measurement, an automatic tension adjustment mode (Auto Tension) is employed.
(8) The automatic tension direction (Auto Tension Direction) is set to the compression (Compression).
(9) The initial static force is set to 10 g, and the automatic tension sensitivity is set to 10.0 g.
(10) The operating condition of the automatic tension (Auto Tension) is set to 1.00 × 10 ⁶ Pa or more in Sample Modulus.
Under the above conditions, the temperature when the loss elastic modulus G ″ becomes 1.00 × 10 ⁶ (Pa) when measured at a frequency of 1 Hz is T (1 Hz), and the loss elasticity when measured at a frequency of 20 Hz. The temperature at which the rate G ″ becomes 1.00 × 10 ⁶ (Pa) is defined as T (20 Hz).
The maximum value of the ratio (G ″ / G ′) (tan δ) of the loss elastic modulus G ″ to the storage elastic modulus G ′ when measured at a frequency of 20 Hz in the range of 60 ° C. or more and 90 ° C. or less is tan δ. (P).

<Method of Measuring Glass Transition Temperature (Tg) of Toner and Amorphous Resin B>
The glass transition temperature (Tg) of the toner and the amorphous resin B is measured using a differential scanning calorimeter "Q1000" (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium.
Specifically, 1 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Using the modulation measurement mode, measurement is performed in the range of 0 ° C. to 100 ° C. at a temperature increase rate of 1 ° C./min and temperature modulation conditions of ± 0.6 ° C./60 seconds. Since a specific heat change is obtained during the temperature raising process, an intersection between the line of the midpoint of the baseline before and after the specific heat change appears and the differential heat curve is defined as a glass transition temperature (Tg).

<Method for measuring wax content in toner>
The content of the wax in the toner is measured using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium.
Specifically, first, the amount of heat absorbed by the wax alone is measured.
1 mg of the wax used for the toner (when a plurality of waxes are used, the wax mixed in the ratio used for the toner) is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. The temperature is raised from 0 ° C. to 150 ° C. at a rate of 10 ° C./min and maintained at 150 ° C. for 5 minutes. Thereafter, cooling is performed from 150 ° C. to 0 ° C. at a cooling rate of 10 ° C./min. Subsequently, after maintaining at 0 ° C. for 5 minutes, the temperature is raised from 0 ° C. to 150 ° C. at a rate of 10 ° C./min. The endothermic amount ΔH1 (J / g) at the endothermic peak in the DSC curve at this time is defined as the endothermic amount of the wax alone.
Subsequently, the amount of heat absorbed by the toner is measured. 1 mg of the toner is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. The temperature is increased from 0 ° C. to 150 ° C. at a rate of 10 ° C./min, and the endothermic amount ΔH2 (J / g) of the endothermic peak in the DSC curve at this time is defined as the endothermic amount of the toner.
From the endothermic amount of the wax alone and the endothermic amount of the toner measured by the above method, the content of the wax in the toner was measured according to the following equation.
Content (% by mass) of wax in toner = ΔH2 / ΔH1 × 100

<Presence or absence of coating layer, method of measuring thickness of coating layer>
The method of measuring the presence or absence of the coating layer and the thickness of the coating layer is measured from a cross-sectional image of the toner observed with a transmission electron microscope. The cross section of the toner observed with a transmission electron microscope is prepared as follows.
Hereinafter, a procedure for preparing a cross section of the ruthenium-stained toner will be described.
First, a toner is sprayed on a cover glass (Matsunami Glass Co., Ltd., square cover glass; square No. 1) so as to form a layer, and an Osmium plasma coater (filgen, OPC80T) is used to apply Os to the toner as a protective film. A film (5 nm) and a naphthalene film (20 nm) are applied.
Next, a tube made of PTFE (Φ1.5 mm × Φ3 mm × 3 mm) is filled with the photocurable resin D800 (JEOL Ltd.), and a cover glass is placed on the tube so that the toner contacts the photocurable resin D800. And put it quietly. After the resin is cured by irradiating light in this state, the cover glass and the tube are removed to form a columnar resin in which the toner is embedded on the outermost surface.
Using an ultrasonic ultramicrotome (Leica, UC7), at a cutting speed of 0.6 mm / s, the radius of the toner from the outermost surface of the cylindrical resin (for example, if the weight average particle diameter (D4) is 8.0 μm, 4 0.0 μm) to obtain a cross section of the toner center.
Next, the film is cut so as to have a film thickness of 100 nm, and a thin sample of a cross section of the toner is prepared. By cutting in such a manner, a cross section of the central portion of the toner can be obtained.
The obtained slice sample was stained for 15 minutes in an atmosphere of ruthenium tetroxide (RuO ₄ ) gas at 500 Pa using a vacuum electron staining device (VSC4R1H, manufactured by Filgen), and a transmission electron microscope (TEM) (JEM2800 manufactured by JEOL Ltd.) was used. A TEM image of the toner is prepared under the conditions of an acceleration voltage of 200 kV.
An image was obtained with a TEM probe size of 1 nm and an image size of 1024 × 1024 pixels.
The binder resin and the coating layer are observed as different contrasts in the TEM image of the toner. Although the difference in lightness and darkness differs depending on the material, in the present invention, a portion observed as a portion having a different contrast from the binder resin was used as the coating layer. When the covering layer is present in 80% or more of the length of the contour line of the toner particles, it is determined that the toner particles have the covering layer.
The thickness of the coating layer described below is measured using commercially available image analysis software, WinROOF (manufactured by Mitani Corporation).
In a TEM image of ten randomly selected toners, the thickness of the coating layer is measured at four points for each toner. Specifically, two straight lines that are perpendicular to the approximate center of the toner cross section are drawn, and the thickness of the coating layer at four points on the two straight lines that intersect the coating layer is measured. The thickness of the coating layer is the distance from the contour of the cross section of the toner to the interface between the binder resin and the coating layer. The average value of all the measured values was defined as the thickness of the toner coating layer.

<Method of measuring weight average molecular weight (Mw)>
The weight average molecular weight (Mw) of a resin, a toner or the like is measured by gel permeation chromatography (GPC) as follows.
First, a sample is dissolved in tetrahydrofuran (THF). Then, the obtained solution is filtered through a solvent-resistant membrane filter “Maisho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: High-speed GPC apparatus "HLC-8220GPC" [Tosoh Corporation]
Column: LF-604 duplex [Showa Denko KK]
Eluent: THF
Flow rate: 0.6 ml / min
Oven temperature: 40 ° C
Sample injection volume: 0.020 ml
In calculating the molecular weight of the sample, a standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-8)
0, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) Use the created molecular weight calibration curve.

<Method for Measuring Particle Size Distribution of Toner>
The particle size distribution of the toner is calculated as follows.
As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (trade name, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube by a pore electric resistance method is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, one prepared by dissolving a special grade sodium chloride in ion-exchanged water so as to have a concentration of 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter) can be used.
Before performing measurement and analysis, the dedicated software is set as follows.
On the “Change standard measurement method (SOM)” screen of the dedicated software, set the total count number in the control mode to 50,000 particles, set the number of measurements to 1, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “threshold / noise level measurement button”, the threshold and the noise level are automatically set. Also, the current is set to 1600 μA, the gain is set to 2, and the electrolytic solution is set to ISOTON II, and a check is made in “Flash aperture tube after measurement”.
In the “pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to a logarithmic particle size, the particle size bin is set to a 256 particle size bin, and the particle size range is set from 2 μm to 60 μm.

The specific measuring method is as follows.
(1) 200 mL of an aqueous electrolytic solution is put into a 250 mL round bottom beaker made of glass exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 revolutions / second. Then, the dirt and air bubbles in the aperture tube are removed by the “flash aperture tube” function of the dedicated software.
(2) Put 30 mL of the electrolytic aqueous solution into a 100 mL flat bottom glass beaker. A 10% by mass aqueous solution of a neutral detergent for washing a precision measuring instrument having a pH of 7 comprising a nonionic surfactant, an anionic surfactant, and an organic builder as a dispersant is used as a dispersant, Wako Pure Chemical Industries, Ltd. Was diluted 3 times with ion-exchanged water.
(3) An ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkaki Bios Co., Ltd.) having two oscillators having an oscillation frequency of 50 kHz and having a phase shifted by 180 degrees and having an electrical output of 120 W is prepared. 3.3 L of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and 2 mL of contaminone N is added to the water tank. (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker becomes maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of the above (4) is irradiated with ultrasonic waves, toner is added to the electrolytic aqueous solution little by little so that the toner becomes 10 mg, and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. The ultrasonic dispersion is appropriately adjusted so that the temperature of the water in the water tank is 10 ° C. or more and 40 ° C. or less.
(6) The electrolytic aqueous solution of the above (5) in which the toner is dispersed is dropped into the round bottom beaker of the above (1) installed in the sample stand using a pipette to prepare a measurement concentration of 5%. . Then, measurement is performed until the number of particles to be measured reaches 50,000.
(7) Analyze the measured data with dedicated software attached to the apparatus, and calculate the weight average particle diameter (D4) and the number average particle diameter (D1).

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In the examples, parts are based on mass unless otherwise specified.
Table 1 shows the names and physical properties of the waxes used in Examples and Comparative Examples.

<Production example of polyester resin 1>
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dehydration tube, and a decompression device, 1.00 mol of terephthalic acid as a monomer, 0.65 mol of an adduct of bisphenol A with 2 mol of propylene oxide, and 0.5 g of ethylene glycol were added. 35 mol was added and heated to a temperature of 130 ° C. with stirring. Thereafter, 0.52 parts of di (2-ethylhexanoate) tin as an esterification catalyst was added to 100.00 parts of the above monomer, and the temperature was raised to 200 ° C. to cause condensation polymerization until a desired molecular weight was reached. did.
Further, 3.00 parts of trimellitic anhydride was added to 100.00 parts of the above monomer to obtain a polyester resin 1.
The obtained polyester resin 1 had a weight average molecular weight (Mw) of 20,000, a glass transition temperature (Tg) of 75 ° C, and an acid value of 8.2 mgKOH / g.

<Production examples of polyester resins 2 to 8>
As shown in Table 2, polyester resins 2 to 8 were obtained in the same manner as in the production example of polyester resin 1, except that the types and the molar ratios of the acid component and the alcohol component were changed.
Further, in the production examples of the respective polyester resins, the reaction temperature and the time were adjusted so as to obtain a desired molecular weight.

In addition, the BPA-PO 2 mol adduct in the table indicates a propylene oxide 2 mol adduct of bisphenol A.
Table 3 summarizes the physical properties of the obtained polyester resins 1 to 8.

<Production example of polyester resin 6 fine particle dispersion>
Polyester resin 6: 144 parts Isopropyl acrylamide (produced by Kojin): 16 parts Ethyl acetate: 233 parts Aqueous sodium hydroxide solution (0.3 mol / L): 0.1 part The above components were placed in a 1000 ml separable flask, and The mixture was heated at ℃ and stirred to prepare a resin mixture. While further stirring this resin mixture, 373 parts of ion-exchanged water was gradually added, phase-inverted and emulsified, and the solvent was removed to obtain a dispersion liquid of polyester resin 6 fine particles (solid content: 30% by mass). The volume average particle size of the resin particles in the dispersion was 110 nm.

<Production Example of Polyester Resin 7 Fine Particle Dispersion>
A polyester resin 7 fine particle dispersion (solid content: 30%) was prepared in the same manner as in the polyester resin 6 fine particle dispersion, except that the polyester resin 6 was changed to the polyester resin 7 in the production example of the polyester resin 6 fine particle dispersion. % By mass). The volume average particle size of the resin particles in the dispersion was 190 nm.

<Production Example of Styrene Acrylic Resin Fine Particle Dispersion 1>
Styrene: 375 parts Dodecanethiol: 3.0 parts A solution prepared by dissolving 8.0 parts of anionic surfactant Dowfax (manufactured by Dow Chemical Company) in 800 parts of ion-exchanged water is added to a mixture of the above components and dissolved. Then, 50 parts of ion-exchanged water in which 6.0 parts of ammonium persulfate was dissolved was added while slowly mixing and stirring in a flask for 10 minutes. Next, after the atmosphere in the flask was replaced with nitrogen, the solution in the flask was heated to 70 ° C. in an oil bath while stirring, and the emulsion polymerization was continued for 5 hours. Obtained. The volume average particle diameter of the particles in the styrene acrylic resin fine particle dispersion liquid 1 was 90 nm, the solid content was 30% by mass, Tg was 100 ° C., and the weight average molecular weight Mw was 30,000.

<Production Example of Styrene Acrylic Resin Fine Particle Dispersion 2>
Styrene: 225 parts n-butyl acrylate: 75 parts 1,6-hexanediol diacrylate: 0.5 part dodecanethiol: 3.0 parts Anionic surfactant Dowfax (Dow. A solution prepared by dissolving 8.0 parts of 800 parts of ion-exchanged water in a flask was dispersed and emulsified in a flask, and slowly mixed with stirring for 10 minutes, and further, 4.0 parts of ammonium persulfate was dissolved. 50 parts of exchanged water were charged. Next, after purging with nitrogen in the flask, the solution in the flask was heated to 65 ° C. in an oil bath while stirring, and emulsion polymerization was continued for 5 hours, and the styrene acrylic resin fine particle dispersion 2 was removed. Obtained. The volume average particle diameter of the particles in the styrene acrylic resin fine particle dispersion liquid 2 was 80 nm, the solid content was 30% by mass, Tg was 54 ° C., and the weight average molecular weight Mw was 30,000.

<Production example of crystalline polyester>
To a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube, dehydration tube, and decompression device, add 1.0 mol of sebacic acid and 1.0 mol of 1,6-hexanediol to a temperature of 130 ° C. while stirring. Heated. After adding 0.7 parts of titanium (IV) isopropoxide to 100.0 parts of the above monomer as an esterification catalyst, the temperature is raised to 180 ° C., and the reaction is carried out until the desired molecular weight is reached while reducing the pressure. Then, a crystalline polyester was obtained. The weight average molecular weight (Mw) of the crystalline polyester was 15,000, and the melting point (Tm) was 68.1 ° C.
Hereinafter, a production example of the toner will be described. The toners 1 to 17 were manufactured as examples, and the toners 18 to 24 were manufactured as comparative examples.

<Production Example of Toner 1>
-60.0 parts of styrene-6.0 parts of coloring agent (CI Pigment Blue 15: 3, manufactured by Dainichi Seika)
The above material was charged into an attritor (manufactured by Mitsui Miike Kakoki Co., Ltd.), and further dispersed using zirconia particles having a diameter of 1.7 mm at 220 rpm for 5 hours to obtain a pigment dispersion.
・ Styrene 15.0 parts ・ n-butyl acrylate 25.0 parts ・ Polyester resin 1 8.0 parts ・ Wax 1 15.0 parts ・ Hydrocarbon wax HNP-9 (manufactured by Nippon Seiro, melting point 74 ° C.) 3.0 Parts, divinylbenzene 0.5 part The above materials were mixed and added to the pigment dispersion. The mixture obtained was kept warm at 60 ° C. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred at 500 rpm, uniformly dissolved and dispersed to prepare a polymerizable monomer composition.
On the other hand, 850.0 parts of a 0.10 mol / L-Na ₃ PO ₄ aqueous solution and 8.0 parts of 10% hydrochloric acid were added to a vessel equipped with a high-speed stirrer CLEARMIX (manufactured by M Technique Co., Ltd.), and the number of rotations was increased. It was adjusted to 15000 rpm and heated to 70 ° C. Here, 68.0 parts of a 1.0 mol / L-CaCl ₂ aqueous solution was added to prepare an aqueous medium containing a calcium phosphate compound.
After charging the polymerizable monomer composition into an aqueous medium, 7.0 parts of t-butyl peroxypivalate as a polymerization initiator is added, and the mixture is molded for 10 minutes while maintaining the number of revolutions at 15,000 rpm. Granulated. Thereafter, the stirrer was changed from a high-speed stirrer to a propeller stirring blade, and the mixture was reacted at 70 ° C. for 5 hours while refluxing.
After the completion of the polymerization reaction, the obtained slurry was cooled, hydrochloric acid was further added to the slurry to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. Thereafter, the slurry was washed with three times the amount of water, filtered, dried and classified to obtain toner particles.
Thereafter, silica fine particles (number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m) subjected to hydrophobic treatment with dimethyl silicone oil (20% by mass) as an external additive are added to 100.0 parts of the toner particles. ^{2 /} g), and the mixture was mixed at 3000 rpm for 15 minutes using a Mitsui Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain Toner 1.

<Production Examples of Toners 2 to 7, 10 to 15, 18 to 23, 25, and 26>
As shown in Table 4, toners 2 to 7 were prepared in the same manner as in the production example of toner 1 except that the type and amount of wax or crystalline polyester, the type and amount of polyester resin, and the amount of divinylbenzene were changed. 10 to 15, 18 to 23, 25 and 26 were obtained.
However, in the production of the toners 7 and 25, 1.0 part of an aluminum salicylate compound (Bontron E-88: manufactured by Orient Chemical Co.) was added without adding the polyester resin 1.

<Production Example of Toner 8>
A slurry of toner particles was produced in the same manner as in the production example of Toner 1.
To the slurry of the toner particles, a dispersion liquid of fine particles of the polyester resin 6 (5.0 parts of the solid content of the polyester resin 6 with respect to 100 parts of the solid content of the toner particles) was added under stirring, and stirring was continued for 30 minutes. The temperature was raised to 55 ° C.
Next, a 0.2 mol / L hydrochloric acid aqueous solution was added dropwise so that the pH of the slurry was lowered by 0.1 per minute, and the pH of the slurry was adjusted to 1.5. After the stirring was continued for 2 hours while maintaining the above temperature, the pH of the slurry was adjusted to 7.2 at a dropping rate of 1 mol / L aqueous sodium hydroxide at a rate of 10.0 parts by mass / minute with stirring. It was dripped until it became.
The slurry was heated to 70 ° C. and stirred for another 2 hours. After cooling the slurry to 20 ° C., hydrochloric acid was added to the slurry to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. Thereafter, the slurry was washed with three times the amount of water, filtered, dried and classified to obtain toner particles.
Thereafter, silica fine particles (number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m) subjected to hydrophobic treatment with dimethyl silicone oil (20% by mass) as an external additive are added to 100.0 parts of the toner particles. ^{2 /} g) and mixed using a Mitsui Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 3,000 rpm for 15 minutes to obtain toner 8.

<Production Example of Toner 9>
The polyester resin 6 fine particle dispersion was changed to the polyester resin 7 fine particle dispersion, and the addition amount of the polyester resin 7 fine particle dispersion was changed to 8.0 parts of the polyester resin 7 solids with respect to 100 parts of the toner particle solids. A toner 9 was obtained in the same manner as in the production example of the toner 8 except for the above.

<Production Example of Toner 17>
Toner slurry was obtained by adding, attaching and externally adding fine resin particles to the slurry of the toner particles obtained in the production example of the toner 23 in the same manner as in the production example of the toner 8. However, the dispersion liquid of the fine particles of the polyester resin 6 was changed to the dispersion liquid 1 of the styrene acrylic resin fine particles, and the amount of the dispersion liquid 1 of the styrene acrylic resin fine particles was changed based on 100 parts of the solid content of the toner particles. The solid content was 10.0 parts.

<Production Example of Toner 24>
A slurry of toner particles was manufactured in the same manner as in the example of manufacturing toner 23.
To the obtained toner slurry, 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) -propionamide) dissolved in 1.5 parts of methyl methacrylate and 20 parts of ion-exchanged water (Wako Pure Chemical Industries, Ltd.) (Trade name: VA-086) (0.15 parts). Then, it heated at 90 degreeC for 3 hours, and superposed | polymerized. After cooling the slurry to 20 ° C., hydrochloric acid was added to the slurry to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. Thereafter, the slurry was washed with three times the amount of water, filtered, dried and classified to obtain toner particles.
Thereafter, silica fine particles (number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m) subjected to hydrophobic treatment with dimethyl silicone oil (20% by mass) as an external additive are added to 100.0 parts of the toner particles. ^{2 /} g), and the mixture was mixed at 3000 rpm for 15 minutes using a Mitsui Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain toner 24.

<Preparation of wax dispersion>
Wax 1: 180 parts Anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 4.5 parts Ion-exchanged water: 410 parts Heat the above to 110 ° C. and homogenize (IKA: Ultrata) After dispersion using Lux T50), dispersion treatment was carried out with a Manton-Gaulin high-pressure homogenizer (Gaulin Co., Ltd.), wax particles having a volume average particle diameter of 0.20 μm were dispersed, and the concentration was adjusted with ion-exchanged water. A wax dispersion having a solid content of 30.0% was prepared.

<Preparation of colorant dispersion>
C. I. Pigment Blue 15: 3 (manufactured by Dainichi Seika): 250 parts Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC): 33 parts (active ingredient 60%, 8% based on colorant)
Ion-exchanged water: 280 parts The above was added to a stainless steel container, and the mixture was stirred using a stirrer until there was no unwet pigment, and sufficiently defoamed. After defoaming, 470 parts of the remaining ion-exchanged water was added, and the mixture was dispersed at 5,000 rpm for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA).
Subsequently, the dispersion liquid was dispersed at a pressure of 240 MPa using a high pressure impact type dispersing machine Ultimateizer (HJP30006, manufactured by Sugino Machine Co., Ltd.). The resulting dispersion was allowed to stand for 24 hours to remove precipitates, and ion-exchanged water was added to adjust the solid concentration to 20%. The volume average particle diameter of the particles in the colorant dispersion was 135 nm.

<Production Example of Toner 16>
Ion-exchanged water: 315 parts Styrene acrylic resin fine particle dispersion 2: 333 parts (solid content: 30% by mass)
Colorant dispersion: 29 parts (solid content 20%)
Wax dispersion: 50 parts (solid content 30%)
Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 20%): 3.8 parts The above components are placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer. While controlling the temperature with a heater, the temperature was maintained for 30 minutes at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm. Thereafter, a 0.3 mol / L nitric acid aqueous solution was added to adjust the pH in the aggregation step to 3.0.
Polyaluminum chloride prepared by dissolving 1.0 part of polyaluminum chloride (Oji Paper Co., Ltd .: 30% powder) in 10 parts of ion-exchanged water while dispersing with a homogenizer (IKA Japan: Ultra Turrax T50). An aqueous solution was added. Thereafter, the temperature was raised to 50 ° C. while stirring, and the particle size was measured with a Coulter Multisizer II (aperture diameter: 50 μm, manufactured by Coulter Co.) to make the volume average particle size 5.6 μm. Thereafter, 40 parts (solid content: 30%) of polyester resin 6 fine particle dispersion liquid was additionally added, followed by stirring for 30 minutes.
Subsequently, 30 parts of a 10% aqueous solution of NTA (nitrilotriacetic acid) metal salt (Kyrest 70: manufactured by Kyrest Co., Ltd.) was added, and the pH was adjusted to 9.0 with a 1 mol / L sodium hydroxide aqueous solution. Thereafter, the temperature was raised to 90 ° C., the temperature was maintained at 90 ° C. for 3 hours, and then cooled to 30 ° C. This was further redispersed in ion-exchanged water, and filtration was repeated. The filtrate was washed until the electric conductivity of the filtrate became 20 μS / cm or less, and then dried in a vacuum oven at 40 ° C. for 5 hours. Thus, toner particles were obtained.
Thereafter, silica fine particles (number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m) subjected to hydrophobic treatment with dimethyl silicone oil (20% by mass) as an external additive are added to 100.0 parts of the toner particles. ^{2 /} g) and mixed with a Mitsui Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 3,000 rpm for 15 minutes to obtain toner 16.
The physical properties of the obtained toners 1 to 26 were measured using the above-described methods. Table 5 summarizes the results.

In the table, PMMA indicates polymethyl methacrylate.
The performance of the obtained toners 1 to 26 was evaluated according to the following method. Table 6 shows the results.

[Low-temperature fixability]
The low-temperature fixing property is evaluated by evaluating a minimum fixing temperature at which a visible image defect does not occur in the fixed image.
The low-temperature fixing property is evaluated by evaluating a minimum fixing temperature at which a visible image defect does not occur in the fixed image.
The visible image defect that occurs at the time of low-temperature fixing mainly includes a cold offset that occurs due to the toner not being melted.
The evaluation was performed as follows.
A color laser printer (HP Color LaserJet 3525dn, manufactured by HP) from which the fixing unit was removed was prepared, and the toner was taken out of the cyan cartridge and filled with the toner to be evaluated instead.
Next, an unfixed toner image having a length of 2.0 cm and a width of 15.0 cm (toner application amount: 0.9 mg / cm ² ) was used on a receiving paper (Canon office planner; 64 g / m ² ) using the filled toner. ) Was formed at a position 1.0 cm from the upper end in the paper passing direction.
Next, the removed fixing unit was modified so that the fixing temperature and the process speed could be adjusted, and a fixing test of an unfixed image was performed using the modified unit.
First, in a normal temperature and normal humidity environment (23 ° C., 60% RH), the process speed is set to 300 mm / s, the initial temperature is set to 150 ° C., and the set temperature is sequentially increased by 5 ° C. to 230 ° C. To fix the unfixed image. The obtained fixed images were evaluated for low-temperature fixability according to the following criteria, with the fixing temperature at which no cold offset occurs as the minimum fixing temperature. D and above were judged to have obtained the effects of the present invention.
A: The minimum fixing temperature is 150 ° C.
B: The minimum fixing temperature is 155 ° C.
C: Minimum fixing temperature is 160 ° C.
D: Minimum fixing temperature is 165 ° C.
E: The minimum fixing temperature is 170 ° C.
F: Minimum fixing temperature is 175 ° C. or higher

[Separability from fixing member]
The separability from the fixing member is determined by evaluating a fixing temperature range in which paper can be passed without being wound around the fixing member during fixing.
In the fixing test described above, the separation property from the fixing member was evaluated according to the following criteria.
The evaluation criteria are as follows. D and above were judged to have obtained the effects of the present invention.
A: No winding around the fixing member occurs even at the minimum fixing temperature plus 45 ° C. B: Winding around the fixing member occurs at the minimum fixing temperature plus 45 ° C., but winding around the fixing member occurs at plus 40 ° C. or 35 ° C. No C: winding around the fixing member occurs at the minimum fixing temperature plus 35 ° C., but no winding around the fixing member at plus 30 ° C. or 25 ° C. D: winding around the fixing member at the minimum fixing temperature plus 25 ° C. E: winding around the fixing member does not occur at plus 20 ° C or 15 ° C. E: winding around the fixing member occurs at the minimum fixing temperature plus 15 ° C, but winding around the fixing member at plus 10 ° C or 5 ° C. Does not occur F: The temperature at which the winding around the fixing member does not occur is only the minimum fixing temperature, or there is no temperature at which the winding around the fixing member does not occur.

[Evaluation of heat-resistant storage stability]
A resin cup (100 mL) containing 5.0 g of the evaluation toner sample was allowed to stand in a high-temperature environment (temperature 50 ° C./relative humidity 50%) for 3 days. Then, it was moved to a normal temperature and normal humidity environment (temperature: 23 ° C./relative humidity: 50%) and left to stand for 1 hour. The measuring device is "Powder Tester PT-X" (manufactured by Hosokawa Micron Corp.), and the remaining amount of toner is measured under a normal temperature and normal humidity environment (temperature 23 ° C./relative humidity 50%) using a sieve having an opening of 75 μm. Was measured. The sieve amplitude was adjusted to 1.00 mm (peak-to-peak), the toner for evaluation was placed on the sieve, and vibration was applied for 40 seconds. Thereafter, the heat-resistant storage stability was evaluated based on the amount of aggregates of the toner remaining on the sieve, and the heat-resistant storage stability was evaluated according to the following evaluation criteria.
A: The remaining amount of toner on the mesh is 0.10 g or less.
B: The remaining amount of toner on the mesh exceeds 0.10 g and is 0.20 g or less.
C: The remaining amount of toner on the mesh exceeds 0.20 g and is 0.30 g or less.
D: The remaining amount of toner on the mesh exceeds 0.30 g and is 0.40 g or less.
E: The remaining amount of toner on the mesh exceeds 0.40 g and is 0.50 g or less.
F: The remaining amount of toner on the mesh exceeds 0.50 g.

Claims (10)

A toner having toner particles containing a binder resin and a wax,
The binder resin contains an amorphous resin A,
In the measurement of the dynamic viscoelasticity of the toner,
Measured at a frequency of 1 Hz, the temperature at which the loss elastic modulus G ″ becomes 1.00 × 10 ⁶ Pa is defined as T (1 Hz),
Measured at a frequency of 20 Hz, the temperature at which the loss elastic modulus G ″ becomes 1.00 × 10 ⁶ Pa is defined as T (20 Hz),
When the maximum value of the ratio (tan δ) of the loss elastic modulus G ″ to the storage elastic modulus G ′ when measured at a frequency of 20 Hz in the range of 60 ° C. or more and 90 ° C. or less is defined as tan δ (P), A toner satisfying (1) to (4).
Formula (1) T (20 Hz) −T (1 Hz) ≦ 7.0 ° C.
Equation (2) 0.80 ≦ tan δ (P) ≦ 1.90
Formula (3): 60 ° C. ≦ T (1 Hz) ≦ 80 ° C.
Formula (4): 60 ° C. ≦ T (20 Hz) ≦ 80 ° C.   The toner according to claim 1, wherein the toner particles have a coating layer on a surface.   3. The toner according to claim 2, wherein the thickness of the coating layer is from 10 nm to 200 nm. The coating layer contains an amorphous resin B,
The toner according to claim 2, wherein the amorphous resin B has a glass transition temperature of 60 ° C. or more and 90 ° C. or less.   The toner according to claim 4, wherein the amorphous resin B includes a polyester resin. The polyester resin has _the structure and -C (= O) -C (= O) represented by -O-CH 2 _-CH 2 -O- - to claim 5 having at least one of structures represented by The toner described in the above. The toner according to claim 5, wherein the polyester resin has a structure represented by the following formula (A).

The amorphous resin A is a resin having a styrene acrylic polymer site,
The toner according to any one of claims 1 to 7, wherein the content of the resin having the styrene acrylic polymer site in the binder resin is 50% by mass or more.   The toner according to any one of claims 1 to 8, wherein the wax contains an ester compound of a diol having 2 to 6 carbon atoms and an aliphatic monocarboxylic acid having 14 to 22 carbon atoms. The toner according to any one of claims 1 to 9, wherein the content of the wax in the toner is from 5.0% by mass to 20.0% by mass.

Images