JP2017203864A - Toner and toner manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner excellent in low-temperature fixability, capable of maintaining electrification characteristics even if continuous printing is carried out in a high-temperature/high-humidity environment, and also to provide a toner manufacturing method.SOLUTION: A toner includes: an aromatic polyester resin having a monomer unit derived from an aromatic polyvalent carboxylic acid and a monomer unit derived from aromatic polyhydric alcohol; an aliphatic polyester resin having a monomer unit derived from an aliphatic polyvalent carboxylic acid and a monomer unit derived from an aliphatic polyhydric alcohol; and a toner particle including a styrene acrylic polymer. The aliphatic polyester resin further includes a monomer unit derived from an aromatic monocarboxylic acid and/or a monomer unit derived from an aromatic monoalcohol. The styrene acrylic polymer is a polymer in which a styrene acrylic polymer is graft-polymerized to a polyolefin.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system, and a toner jet system, and a method for producing the toner.

In recent years, electrophotographic full-color copiers have become widespread and have started to be applied to the printing market. In the printing market, high speed, high image quality, and high productivity are demanded while supporting a wide range of media (paper types).
For example, even if the paper type is changed from thick paper to thin paper, there is a need for media speed that can continue printing without changing the process speed according to the paper type or changing the heat setting temperature of the fuser. Yes.
From the viewpoint of media isovelocity, the toner is required to properly complete fixing in a wide fixing temperature range from low temperature to high temperature.
Patent Document 1 proposes various toners in which a low-temperature fixing performance is improved by adding a crystalline resin having a sharp melt property to the toner as a softening agent in order to fix the toner in a wide range of fixable temperatures.

JP 2006-113473 A JP 2012-063559 A JP2013-257415A

However, in a toner containing a crystalline resin, there is a problem that the chargeability in a high-temperature and high-humidity environment and the maintenance of the charge are difficult because the crystallinity in the toner changes with time.
Since the crystalline resin has a lower volume resistance than the amorphous resin, the leakage of electric charges tends to occur easily. Therefore, in a toner containing a crystalline resin, particularly when continuous printing is performed for a long period of time in a high temperature and high humidity environment, a change in charging property is likely to occur due to a change in crystallinity, resulting in a decrease in image density. There is a problem that it occurs.
As measures against this, there is a process of detecting the density of the output image in the main body during continuous printing and putting in a control to correct the density. However, there is a problem that the printing time of the high-speed machine becomes long. is there.
Further, the dispersion state of the crystalline resin in the toner has a significant influence on the properties of the toner. In order to improve the chargeability of the toner, it is desired that the crystalline resin in the toner is fine and uniform.
In Patent Document 2, in order to control the dispersion state of the crystalline resin in the toner, a toner is proposed in which a dispersant for the crystalline polyester resin is used in addition to the main binder resin and the crystalline polyester resin as the softening agent. Has been.
On the other hand, Patent Document 3 discloses that the acid value of the crystalline polyester is controlled within a specific range in order to achieve excellent durability performance and fixing performance at the same time. Further, as a method for controlling the acid value of the crystalline polyester, it is disclosed that a carboxy group at a polymer terminal is sealed.
However, none of these satisfy both the low-temperature fixing property and the charging stability that have been required in recent years for higher speed and energy saving.
As described above, there is still room for study in order to control the dispersion state of the crystalline resin as the softening agent in the toner and satisfy the charging stability.
The present invention provides a toner that solves the above problems and a method for producing the toner. Specifically, the present invention provides a toner that is excellent in low-temperature fixability and that maintains chargeability even when continuous printing is performed in a high-temperature and high-humidity environment, and a method for producing the toner.

The present invention
An aromatic polyester resin having a monomer unit derived from an aromatic polycarboxylic acid and a monomer unit derived from an aromatic polyhydric alcohol;
An aliphatic polyester resin having a monomer unit derived from an aliphatic polycarboxylic acid and a monomer unit derived from an aliphatic polyhydric alcohol; and
A toner having toner particles containing a styrene acrylic polymer,
The aliphatic polyester resin further has a monomer unit derived from an aromatic monocarboxylic acid and / or a monomer unit derived from an aromatic monoalcohol,
The toner is characterized in that the styrene-acrylic polymer is a polymer in which a styrene-acrylic polymer is graft-polymerized to a polyolefin.
The present invention also provides:
An aromatic polyester resin having a monomer unit derived from an aromatic polycarboxylic acid and a monomer unit derived from an aromatic polyhydric alcohol;
An aliphatic polyester resin having a monomer unit derived from an aliphatic polycarboxylic acid and a monomer unit derived from an aliphatic polyhydric alcohol; and
A step of melt-kneading a composition containing a styrene acrylic polymer to obtain a kneaded product,
Cooling the kneaded product to obtain a cooled product,
Crushing the cooling material to obtain resin particles,
The aliphatic polyester resin further has a monomer unit derived from an aromatic monocarboxylic acid and / or a monomer unit derived from an aromatic monoalcohol,
A method for producing a toner, wherein the styrene acrylic polymer is a polymer in which a styrene acrylic polymer is graft-polymerized to a polyolefin.

  According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixability and that maintains chargeability even when continuous printing is performed in a high-temperature and high-humidity environment, and a method for producing the toner.

Schematic diagram of heat treatment equipment

The present invention
An aromatic polyester resin having a monomer unit derived from an aromatic polycarboxylic acid and a monomer unit derived from an aromatic polyhydric alcohol;
An aliphatic polyester resin having a monomer unit derived from an aliphatic polycarboxylic acid and a monomer unit derived from an aliphatic polyhydric alcohol; and
A toner having toner particles containing a styrene acrylic polymer,
The aliphatic polyester resin further has a monomer unit derived from an aromatic monocarboxylic acid and / or a monomer unit derived from an aromatic monoalcohol,
The present invention relates to a toner, wherein the styrene acrylic polymer is a polymer in which a styrene acrylic polymer is graft-polymerized to a polyolefin.
The present invention also provides:
An aromatic polyester resin having a monomer unit derived from an aromatic polycarboxylic acid and a monomer unit derived from an aromatic polyhydric alcohol;
An aliphatic polyester resin having a monomer unit derived from an aliphatic polycarboxylic acid and a monomer unit derived from an aliphatic polyhydric alcohol; and
A step of melt-kneading a composition containing a styrene acrylic polymer to obtain a kneaded product,
Cooling the kneaded product to obtain a cooled product,
Crushing the cooling material to obtain resin particles,
The aliphatic polyester resin further has a monomer unit derived from an aromatic monocarboxylic acid and / or a monomer unit derived from an aromatic monoalcohol,
The present invention relates to a method for producing a toner, wherein the styrene acrylic polymer is a polymer in which a styrene acrylic polymer is graft-polymerized to a polyolefin.
In addition, in this invention, the description of "XX or more and XX or less" or "XX to XX" indicating a numerical range means a numerical range including a lower limit and an upper limit as end points unless otherwise specified.
Moreover, the said monomer unit means the form which the monomer substance in a polymer or resin reacted. Furthermore, a crystalline resin is a resin in which an endothermic peak is observed in differential scanning calorimetry (DSC).

In the present invention, the toner particles contain an aromatic polyester resin having a monomer unit derived from an aromatic polyvalent carboxylic acid and a monomer unit derived from an aromatic polyhydric alcohol as a binder resin. The content of the aromatic polyester resin is preferably 50% by mass or more based on the total resin components constituting the toner particles, from the viewpoints of low-temperature fixability and charging stability in a high-temperature and high-humidity environment. The aromatic polyester resin is an amorphous resin.
The toner particles are derived from an aliphatic polycarboxylic acid-derived monomer unit and an aliphatic polyhydric alcohol-derived monomer unit, and an aromatic monocarboxylic acid-derived monomer unit and / or an aromatic monoalcohol as a softening agent. An aliphatic polyester resin having the following monomer units. The aliphatic polyester resin is a crystalline resin.
Further, the toner particles contain, as a dispersant for the aliphatic polyester resin, a polymer in which a styrene acrylic polymer is graft-polymerized to a polyolefin.

In general, when an aliphatic polyester resin having a monomer unit derived from an aliphatic polyvalent carboxylic acid and a monomer unit derived from an aliphatic polyhydric alcohol, which is a crystalline resin, is used as a softening agent in the toner, The molecular chain of the aliphatic polyester resin is folded in the toner to increase the crystallinity.
In addition, since the crystalline resin has a lower volume resistance than the amorphous resin, the leakage of electric charges tends to occur. As a result, a decrease in image density due to a decrease in chargeability may occur during continuous printing in a high temperature and high humidity environment.
The present inventor has made extensive studies and even if the toner contains an aliphatic polyester resin as a softening agent, the aliphatic polyester resin is a monomer unit derived from an aromatic monocarboxylic acid and / or a monomer derived from an aromatic monoalcohol. It has been found that the above-mentioned problems can be solved by containing a unit and a polymer in which a styrene acrylic polymer is graft-polymerized to polyolefin.

Although the reason for this is not clear, the following mechanism is presumed.
In a toner containing a styrene acrylic polymer in which a styrene acrylic polymer is graft-polymerized to a polyolefin, the graft-modified polyolefin portion has an affinity for the aliphatic polyester resin in the toner. For this reason, the domain of the aliphatic polyester resin and the styrene acrylic polymer is formed in the toner, and the aliphatic polyester resin can be finely and uniformly dispersed. As a result, low-temperature fixability can be satisfied, and charging stability can be further improved.
At this time, when a wax is present in the toner, the wax also has an affinity for the polyolefin portion, and therefore can be finely dispersed in the toner. As a result, hot offset resistance and blocking resistance can be satisfied.
However, in the aliphatic polyester resin, the molecular chain is folded with the passage of time immediately after the production of the toner, and the crystallinity becomes high. For this reason, the toner containing an aliphatic polyester resin as a softening agent tends to change its chargeability, and the image density is lowered during continuous printing in a high-temperature and high-humidity environment.
However, when the aliphatic polyester resin further has a monomer unit derived from an aromatic monocarboxylic acid and / or a monomer unit derived from an aromatic monoalcohol, the monomer unit is an end of a molecular chain constituting the aliphatic polyester resin. Will serve as an end cap.
Moreover, the aromatic ring site | part which exists in the molecular chain terminal of this aliphatic polyester resin interacts with the aromatic ring site | part of aromatic polyester resin which is binder resin, and expresses an anchor effect. Therefore, the molecular chain folding of the aliphatic polyester resin is reduced, and the crystallization degree of the aliphatic polyester resin hardly changes even after a lapse of time from the production of the toner. As a result, it is presumed that the charging stability is remarkably improved even when continuous printing is performed in a high-temperature and high-humidity environment while being excellent in low-temperature fixability.

Hereinafter, the structure of the toner will be described in detail, but it is not limited thereto.
<Aliphatic polyester resin>
The aliphatic polyester resin comprises a monomer unit derived from an aliphatic polycarboxylic acid and a monomer unit derived from an aliphatic polyhydric alcohol, and a monomer unit derived from an aromatic monocarboxylic acid and / or a monomer unit derived from an aromatic monoalcohol. Have.
The aliphatic polycarboxylic acid preferably has 2 to 22 carbon atoms, and more preferably has 6 to 12 carbon atoms.
The aliphatic polyhydric alcohol preferably has 2 to 22 carbon atoms, and more preferably 6 to 12 carbon atoms.
Among them, the aliphatic polyester resin includes a monomer unit derived from an aliphatic diol having 6 to 12 carbon atoms and a monomer unit derived from an aliphatic dicarboxylic acid having 6 to 12 carbon atoms from the viewpoint of low-temperature fixability and storage stability. It is more preferable to contain.

The reason why the low temperature fixability of the toner to which the aliphatic polyester resin is added is improved is that the aromatic polyester resin and the aliphatic polyester resin are compatible with each other, widen the molecular chain spacing of the aromatic polyester resin, and increase the intermolecular force. Because it weakens. As a result, the glass transition temperature (Tg) of the aromatic polyester resin can be greatly reduced, and the melt viscosity of the aromatic polyester resin can be lowered.
Therefore, the low temperature fixability tends to be improved by increasing the compatibility between the aromatic polyester resin and the aliphatic polyester resin.
In order to increase the compatibility between the aromatic polyester resin and the aliphatic polyester resin, the carbon number of the aliphatic polyvalent diol and / or aliphatic polyvalent carboxylic acid is shortened, the ester group concentration is increased, and the polarity is increased. Will be raised.
On the other hand, it is necessary to ensure storage stability in use and transportation in a high-temperature and high-humidity environment even for a toner whose Tg is significantly reduced. Here, if the ester group concentration of the aliphatic polyester resin is high and the compatibility between the aromatic polyester resin and the aliphatic polyester resin is too high, the storage stability of the toner is lowered.
From the above, when considering both low-temperature fixability and storage stability, the aliphatic polyester resin is a monomer unit derived from an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms. It is preferable to contain the derived monomer unit.

Although it does not specifically limit as a C2-C22 aliphatic polyhydric alcohol, It is preferable that it is a C2-C22 aliphatic diol. The aliphatic diol is preferably linear, and more preferably linear.
For example, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,4-butadiene glycol, 1,5-pentanediol, Neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12 -Dodecanediol.
Among these, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12 Preferred examples include linear aliphatic α, ω-diols such as dodecanediol.
In the present invention, the aliphatic polyester resin may contain a monomer unit derived from a polyhydric alcohol other than the above-mentioned monomer unit derived from an aliphatic diol having 2 to 22 carbon atoms to the extent that the effects of the present invention are not impaired.
Among the polyhydric alcohols, examples of the dihydric alcohol include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol and the like.
Among the polyhydric alcohols, trihydric or higher polyhydric alcohols include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4 -Aliphatic alcohols such as butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, etc. .

  In this invention, it is preferable that the content rate of the monomer unit derived from the said C2-C22 aliphatic diol in an aliphatic polyester resin is 50 to 100 mass% in all the monomer units derived from alcohol. More preferably, it is 70 mass% or more and 100 mass% or less.

On the other hand, the aliphatic polycarboxylic acid having 2 to 22 carbon atoms is not particularly limited, but is preferably an aliphatic dicarboxylic acid having 2 to 22 carbon atoms. The aliphatic dicarboxylic acid is preferably linear, more preferably linear.
For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid , Fumaric acid, mesaconic acid, citraconic acid, itaconic acid. In addition, hydrolyzed products of these acid anhydrides or lower alkyl esters are also included.
In the present invention, the aliphatic polyester resin may contain a monomer unit derived from a polyvalent carboxylic acid other than the monomer unit derived from the aliphatic dicarboxylic acid having 2 to 22 carbon atoms to such an extent that the effects of the present invention are not impaired. Good.
Among the polyvalent carboxylic acids, examples of the divalent carboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. These acid anhydrides or lower alkyl esters are also included.
Among the polyvalent carboxylic acids, trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2, Aromatic carboxylic acids such as 4-naphthalenetricarboxylic acid and pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylene Examples thereof include aliphatic carboxylic acids such as carboxypropane. Also included are derivatives such as these acid anhydrides or lower alkyl esters.

  In the present invention, the content ratio of the monomer unit derived from the aliphatic dicarboxylic acid having 2 to 22 carbon atoms in the aliphatic polyester resin is 50% by mass or more and 100% by mass or less in all the monomer units derived from the carboxylic acid. Is more preferable, and 70 mass% or more and 100 mass% or less are more preferable.

In the present invention, the aliphatic polyester resin further has a monomer unit derived from an aromatic monocarboxylic acid and / or a monomer unit derived from an aromatic monoalcohol.
When an aromatic monocarboxylic acid and / or aromatic monoalcohol is added in the process of synthesizing an aliphatic polyester resin having a small molecular weight, it reacts with the end of the molecular chain constituting the aliphatic polyester resin, and functions as an end cap. Therefore, the molecular chain is difficult to be too long.
Therefore, when synthesizing the aliphatic polyester resin, most of the unreacted free monomer reacts, so that the low molecular weight component derived from the unreacted monomer is reduced and the molecular weight distribution becomes sharp.
Examples of the aromatic monocarboxylic acid include naphthalenecarboxylic acid, benzoic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, benzeneethanoic acid, and benzenepropanoic acid.
Examples of the aromatic monoalcohol include phenol, methylphenol, and naphthol.
The aromatic monocarboxylic acid and aromatic monoalcohol may be used alone or in combination of two or more.
In the present invention, the monomer unit derived from the aromatic monocarboxylic acid and / or the monomer unit derived from the aromatic monoalcohol preferably includes a monomer unit derived from benzoic acid. When benzoic acid is used, the interaction between the aromatic ring site present at the end of the molecular chain of the aliphatic polyester resin and the aromatic ring site in the aromatic polyester resin is easy, and the anchor effect is easily exhibited.
As a result, even after a lapse of time from the production of the toner, the change in the crystallinity of the aliphatic polyester resin is further reduced. In addition, when benzoic acid is used, the styrene acrylic polymer is more likely to act, and the aliphatic polyester resin is more easily dispersed in the toner.

In the aliphatic polyester resin, the ratio of the total number of moles of the monomer unit derived from the aromatic monocarboxylic acid and / or the monomer unit derived from the aromatic monoalcohol relative to the total number of moles of the monomer unit constituting the aliphatic polyester resin, It is preferably 0.5 mol% or more and 15.0 mol% or less, and more preferably 3.0 mol% or more and 12.0 mol% or less.
When the ratio satisfies the above range, storage stability, charging stability, and low-temperature fixability are further improved.

  In the present invention, when the content of the aliphatic polyester resin is W1 parts by mass and the content of the styrene acrylic polymer is W2 parts by mass, the relationship of 0.5 ≦ W1 / W2 ≦ 2.0 is satisfied. Preferably, it is more preferable to satisfy the relationship of 0.5 ≦ W1 / W2 ≦ 1.25. When W1 / W2 satisfies the above relationship, the aliphatic polyester resin is easily finely dispersed in the toner.

  In the present invention, in order to further improve the low temperature fixability, the charging stability in a high temperature and high humidity environment, and the heat resistant storage stability, the content of the aliphatic polyester resin is 100 parts by mass of the aromatic polyester resin. It is preferably 0.5 parts by mass or more and 15.0 parts by mass or less, and more preferably 1.0 parts by mass or more and 10.0 parts by mass or less.

In the present invention, the aliphatic polyester resin has a weight average molecular weight of 5,000 or more and 14,000.
Or less, more preferably 6000 or more and 13000 or less.
When the weight average molecular weight is in the above range, it becomes easy to achieve both heat resistant storage stability and hot offset resistance and low temperature fixability.
In the present invention, the endothermic amount of the maximum endothermic peak derived from the aliphatic polyester resin measured using a differential scanning calorimetry (DSC) apparatus of the toner is ΔH [J / g], and the added number W of the aliphatic polyester resin is W. In this case, the value [ΔH / W] obtained by dividing ΔH by W is preferably 0.002 or more and 0.200 or less, and more preferably 0.005 or more and 0.100 or less.
When ΔH / W satisfies the above range, the degree of crystallinity of the aliphatic polyester resin relative to the number of added parts of the aliphatic polyester resin is low in the toner that has passed the time from manufacture. As a result, the low temperature fixability and the charging stability in a high temperature and high humidity environment are improved even after a lapse of time from the production of the toner.

The aliphatic polyester resin can be produced according to a normal polyester synthesis method. For example, an aliphatic polyester resin can be obtained by subjecting the carboxylic acid and alcohol to an esterification reaction or a transesterification reaction, and then performing a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. . Then, the desired aliphatic polyester resin is obtained by adding the said aromatic monocarboxylic acid and / or aromatic monoalcohol, and performing esterification reaction further.
In the esterification reaction or transesterification reaction, a normal esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, and magnesium acetate may be used as necessary.
The polycondensation reaction may be performed using a conventional polymerization catalyst, for example, a known catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide. it can. The polymerization temperature and the catalyst amount are not particularly limited, and may be determined appropriately.
In the esterification reaction, transesterification reaction or polycondensation reaction, all monomers may be charged at once in order to increase the strength of the resulting crystalline polyester, and a divalent monomer is first reacted to reduce low molecular weight components. After that, a trivalent or higher valent monomer may be added and reacted.

<Aromatic polyester resin>
The aromatic polyester resin has a monomer unit derived from an aromatic polyvalent carboxylic acid and a monomer unit derived from an aromatic polyhydric alcohol.
Examples of the aromatic polyvalent carboxylic acid include divalent or trivalent or higher carboxylic acids, acid anhydrides thereof, or lower alkyl esters thereof.
Examples of the aromatic polyhydric alcohol include divalent or trivalent or higher alcohols.
Here, when preparing a branched aromatic polyester resin, it is effective to partially cross-link in the molecule of the aromatic polyester resin. For that purpose, it is preferable to use a polyvalent compound having three or more valences. . That is, trivalent or higher carboxylic acids or acid anhydrides or lower alkyl esters thereof and / or trivalent or higher alcohols may be used.

Examples of the aromatic polyhydric alcohol include the following.
Examples of the divalent alcohol include hydrogenated bisphenol A, bisphenol derivatives represented by the following formula (A), and diols represented by the following formula (B).

［式中、Ｒはエチレン基又はプロピレン基であり、ｘ及びｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０以上１０以下である。］

[Wherein, R is an ethylene group or a propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 or more and 10 or less. ]

  Examples of the trivalent or higher alcohol include 1,3,5-trihydroxymethylbenzene. These divalent alcohols and trihydric or higher alcohols can be used alone or in combination.

Examples of the aromatic polyvalent carboxylic acid include the following.
Examples of the divalent carboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid. These acid anhydrides and their lower alkyl esters are also included.
Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and pyromellitic acid. These acid anhydrides or their lower alkyl esters are also included. These divalent carboxylic acids and trivalent or higher carboxylic acids can be used alone or in combination.

In the present invention, the aromatic polyester resin may contain a known polyvalent carboxylic acid-derived monomer unit other than the aromatic polyvalent carboxylic acid-derived monomer unit to the extent that the effects of the present invention are not impaired.
Moreover, aromatic polyester resin may contain the monomer unit derived from well-known polyhydric alcohols other than the monomer unit derived from said aromatic polyhydric alcohol to such an extent that the effect of this invention is not impaired.
In this invention, it is preferable that the content rate of the monomer unit derived from the said aromatic polyvalent carboxylic acid in aromatic polyester resin is 50 mass% or more in all the monomer units derived from carboxylic acid, More preferably, it is 70 mass. % Or more.
Moreover, it is preferable that the content rate of the said monomer unit derived from the aromatic polyhydric alcohol in an aromatic polyester resin is 50 mass% or more in all the monomer units derived from alcohol, More preferably, it is 70 mass% or more. .

The aromatic polyester resin contains other resin components as long as the main component is an aromatic polyester site composed of a monomer unit derived from an aromatic polyvalent carboxylic acid and a monomer unit derived from an aromatic polyhydric alcohol. It may be a hybrid resin. For example, a hybrid resin in which an aromatic polyester moiety and a vinyl polymer moiety are bonded is given. Here, the main component means that the content of the aromatic polyester portion in the hybrid resin is 50% by mass or more.
As a method for obtaining a reaction product of a vinyl resin or a vinyl copolymer and an aromatic polyester resin, such as a hybrid resin, it reacts with each of the vinyl resin or vinyl copolymer and the aromatic polyester resin. Where there is a polymer containing a monomer component that can be obtained, a method of conducting a polymerization reaction of one or both of the resins is preferred.
For example, examples of monomers that can react with the vinyl-based resin or vinyl-based copolymer among the monomers constituting the aromatic polyester resin include unsaturated dicarboxylic acids such as phthalic acid or anhydrides thereof. Among the monomers constituting the vinyl resin or vinyl copolymer, those that can react with the aromatic polyester resin include those having a carboxy group or a hydroxy group, and acrylic acid or methacrylic acid esters.
In the present invention, as the resin component constituting the toner particles, a known resin can be used in addition to the aromatic polyester resin, the aliphatic polyester resin, and the styrene acrylic polymer. Examples of such resins include phenol resin, natural resin-modified phenol resin, natural resin-modified male resin, acrylic resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin. , Polyvinyl butyral, terpene resin, coumaroindene resin, petroleum resin and the like.

In the present invention, from the viewpoints of low-temperature fixability and hot offset resistance, the aromatic polyester resin preferably has a peak molecular weight of 4,000 to 13,000.
Moreover, from the viewpoint of charging stability in a high temperature and high humidity environment, the acid value of the aromatic polyester resin is preferably 5 mgKOH / g or more and 30 mgKOH / g or less. Furthermore, from the viewpoints of low temperature fixability and storage stability, the hydroxyl value of the aromatic polyester resin is preferably 2 mgKOH / g or more and 20 mgKOH / g or less.
In the present invention, the aromatic polyester resin may be used by mixing a high molecular weight aromatic polyester resin C and a low molecular weight aromatic polyester resin D.
The content ratio (C / D) of the high molecular weight aromatic polyester resin C and the low molecular weight aromatic polyester resin D is 10/90 to 60/40 on a mass basis, which is low temperature fixability and hot offset resistance. It is preferable from the viewpoint.
The peak molecular weight of the high molecular weight aromatic polyester resin C is preferably 10,000 or more and 20,000 or less from the viewpoint of hot offset resistance. The acid value of the high molecular weight aromatic polyester resin C is preferably 15 mgKOH / g or more and 30 mgKOH / g or less from the viewpoint of charging stability in a high temperature and high humidity environment.
The peak molecular weight of the low molecular weight aromatic polyester resin D is preferably from 4,000 to 7,000 from the viewpoint of low-temperature fixability. The acid value of the low molecular weight aromatic polyester resin D is preferably 10 mgKOH / g or less from the viewpoint of charging stability in a high temperature and high humidity environment.

<Styrene acrylic polymer>
In the present invention, the styrene acrylic polymer is a polymer in which a styrene acrylic polymer is graft-polymerized to a polyolefin.
The polyolefin preferably has a peak temperature of a maximum endothermic peak measured using a differential scanning calorimeter (DSC) of 70 ° C. or higher and 90 ° C. or lower.
The polyolefin is preferably a hydrocarbon wax such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax.
In the styrene-acrylic polymer, the mass ratio of polyolefin to styrene-acrylic polymer is preferably 1:99 to 30:70, and more preferably 3:97 to 20:80.
Moreover, it is preferable to have a branched structure like a polypropylene from the viewpoint of the reactivity at the time of manufacture of this styrene acrylic polymer.
Further, since the polyolefin also has an affinity for the wax in the toner, the wax can be finely dispersed in the toner.
In the present invention, the method for graft polymerization of styrene acrylic polymer to polyolefin is not particularly limited, and conventionally known methods can be used.

The styrene acrylic polymer preferably has a monomer unit derived from cycloalkyl (meth) acrylate. Here, cycloalkyl (meth) acrylate means cycloalkyl acrylate or cycloalkyl methacrylate.
By having the monomer unit derived from the cycloalkyl (meth) acrylate, the aliphatic polyester resin in the toner can be finely dispersed. At the same time, the hydrophobic cycloalkyl group is considered to inhibit water adsorption more easily than conventional dispersants, so that the chargeability is maintained even when the toner is left under high temperature and high humidity.
The monomer unit derived from the cycloalkyl (meth) acrylate can be represented by the following formula (1).

［式（１）中、Ｒ_１は水素原子又はメチル基を表し、Ｒ_２はシクロアルキル基を表す。］

[In Formula (1), R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents a cycloalkyl group. ]

R ₂ is preferably a cycloalkyl group having 3 to 18 carbon atoms, and more preferably a cycloalkyl group having 4 to 12 carbon atoms.
Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a t-butylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
In addition, the cycloalkyl group may have an alkyl group, a halogen atom, a carboxy group, a carbonyl group, a hydroxy group, or the like as a substituent. As this alkyl group, a C1-C4 alkyl group is preferable.
In addition, the position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.
Specific examples of the cycloalkyl (meth) acrylate include cyclopropyl acrylate, cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, cyclopropyl methacrylate, cyclobutyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl. Examples include methacrylate, cyclooctyl methacrylate, dihydrocyclopentadiethyl acrylate, dicyclopentanyl acrylate, and dicyclopentanyl methacrylate.
Among these, cyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, and cyclooctyl methacrylate are preferable from the viewpoint of hydrophobicity.

In this invention, the content rate of the monomer unit represented by Formula (1) is 1.0 mass part or more and 4 mass parts or more with respect to 100 mass parts of all the monomer units which comprise a styrene acrylic polymer.
The amount is preferably 0.0 parts by mass or less, and more preferably 5.0 parts by mass or more and 15.0 parts by mass or less.

Examples of the constituent component of the styrene acrylic polymer include the following as monomers other than cycloalkyl (meth) acrylate.
Styrene monomers such as styrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene, benzylstyrene; methyl acrylate, ethyl acrylate, Alkyl esters of unsaturated carboxylic acids such as butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate (the alkyl has 1 to 18 carbon atoms); vinyl ester systems such as vinyl acetate Monomers; Vinyl ether monomers such as vinyl methyl ether; Halogen-containing vinyl monomers such as vinyl chloride; Dienes such as butadiene and isobutylene Monomer, and the like. These can be used alone or in combination of two or more.
In addition, it is preferable that the content rate of this styrene-type monomer unit is 60.0 mass parts or more and 90.0 mass parts or less with respect to 100 mass parts of all the monomer units which comprise a styrene acrylic polymer, 70.0 It is more preferable that the amount is not less than mass parts and not more than 85.0 parts by mass.

In the present invention, the styrene acrylic polymer preferably has a monomer unit represented by the following formula (2) from the viewpoint of low-temperature fixability of the toner.
When the styrene acrylic polymer has a monomer unit represented by the following formula (2), the glass transition temperature (Tg) of the styrene acrylic polymer can be lowered. As a result, when the styrene acrylic polymer is contained in the toner particles, the chargeability does not decrease even when the toner is left under high temperature and high humidity, and the low temperature fixability is further improved.
In addition, the content rate of the monomer unit represented by this following formula (2) is 5.0 to 30.0 parts by mass with respect to 100 parts by mass of all monomer units constituting the styrene acrylic polymer. It is preferably 10.0 parts by mass or more and 20.0 parts by mass or less.

［式（２）中、Ｒ_３は水素原子又はメチル基を表し、ｎは１以上１８以下の整数を表す。］
なお、ｎは、２以上７以下の整数であることがより好ましい。ｎが２以上７以下の整数である場合、ガラス転移温度（Ｔｇ）を効率よく低下させることができる。

[In Formula (2), R ₃ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 18. ]
In addition, it is more preferable that n is an integer of 2 or more and 7 or less. When n is an integer of 2 or more and 7 or less, the glass transition temperature (Tg) can be efficiently reduced.

In the present invention, the weight average molecular weight of the styrene acrylic polymer is preferably from 5,000 to 70,000, and more preferably from 10,000 to 50,000.
In the present invention, the melting point of the styrene acrylic polymer is preferably 100 ° C. or higher and 150 ° C. or lower, and more preferably 110 ° C. or higher and 135 ° C. or lower.
In the present invention, the glass transition temperature (Tg) of the styrene acrylic polymer is preferably 50 ° C. or higher and 90 ° C. or lower, and more preferably 60 ° C. or higher and 80 ° C. or lower.
In the present invention, the content of the styrene acrylic polymer is 1.0 part by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the aromatic polyester resin. It is preferable from the viewpoint of the dispersibility of the resin. More preferably, it is 4.0 parts by mass or more and 10.0 parts by mass or less.

<Wax>
In the present invention, the toner particles may contain a wax.
Examples of the wax include the following.
Low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of hydrocarbon wax such as oxidized polyethylene wax or block copolymer thereof Products: Waxes mainly composed of fatty acid esters such as carnauba wax; Deoxidized part or all of fatty acid esters such as deoxidized carnauba wax. Furthermore, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, and seryl alcohol , Saturated alcohols such as merisyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, and carnauvir alcohol , Esters with alcohols such as ceryl alcohol, melyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylenebisstearic acid amide, ethylene Saturated fatty acid bisamides such as scapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N ′ dioleyl adipic acid amide, N, N 'Unsaturated fatty acid amides such as dioleyl sebacic acid amide; m-xylene bis stearic acid amide, N, N' aromatic bisamides such as distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate , Aliphatic metal salts such as magnesium stearate (commonly referred to as metal soap); partial esterified products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; hydroxy groups obtained by hydrogenation of vegetable oils and fats Have Glycol ester compound.
Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, or fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of improving low-temperature fixability and hot offset resistance.
A hydrocarbon wax is more preferable in that the hot offset resistance is further improved.
The content of the wax is preferably 1.0 part by mass or more and 20.0 parts by mass or less, and 3.0 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the aromatic polyester resin. It is more preferable.
Further, from the viewpoint of achieving both toner storage stability and hot offset resistance, the peak temperature of the maximum endothermic peak of the wax is 45 ° C. or more and 140 ° C. or less in the endothermic curve at the time of temperature rise measured by a differential scanning calorimeter. It is preferable that it is 60 ° C. or higher and 100 ° C. or lower.

<Colorant>
In the present invention, the toner particles may contain a colorant. Examples of the colorant include the following.
Examples of the black colorant include carbon black; a yellow colorant, a magenta colorant, and a cyan colorant that are toned in black.
As the colorant, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.
Examples of the magenta toner pigment include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.
Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disper thread 9; I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.
Examples of the cyan toner pigment include the following. C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
Examples of cyan toner dyes include C.I. I. There is Solvent Blue 70.
Examples of the yellow toner pigment include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat yellow 1, 3, 20
Examples of the dye for yellow toner include C.I. I. There is Solvent Yellow 162.
It is preferable that content of a coloring agent is 0.1 to 30 mass parts with respect to 100 mass parts of aromatic polyester resins.

In the present invention, the toner may contain a charge control agent as required. As the charge control agent contained in the toner, known ones can be used. In particular, a metal compound of an aromatic carboxylic acid that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable.
As the negatively chargeable charge control agent, a salicylic acid metal compound, a naphthoic acid metal compound, a dicarboxylic acid metal compound, a sulfonic acid or a polymer compound having a carboxylic acid in the side chain, a sulfonate or a sulfonated product in the side chain. And a high molecular weight compound, a high molecular weight compound having a carboxylate or a carboxylic acid ester in the side chain, a boron compound, a urea compound, a silicon compound, and a calixarene.
Examples of the positively chargeable charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, and an imidazole compound.
The charge control agent may be added internally or externally to the toner particles.
The content of the charge control agent is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the aromatic polyester resin.

In the present invention, the toner may contain inorganic fine particles as necessary.
The inorganic fine particles may be added internally to the toner particles or may be mixed with the toner particles as an external additive. As the external additive, inorganic fine particles such as silica fine particles, titanium oxide fine particles, and aluminum oxide fine particles are preferable. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.
As an external additive for improving fluidity, inorganic fine particles having a specific surface area of 50 m ² / g or more and 400 m ² / g or less are preferable. For stabilization of durability, the specific surface area is 10 m ² / g or more and 50 m ^2. / G or less inorganic fine particles are preferable.
In order to achieve both improvement in fluidity and stabilization of durability, inorganic fine particles having a specific surface area in the above range may be used in combination.
The content of the external additive is preferably 0.1 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the toner particles. For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used.

Although the toner of the present invention can be used as a one-component developer, it is preferably mixed with a magnetic carrier and used as a two-component developer in order to further improve dot reproducibility. Also, it is preferably used as a two-component developer in that a stable image can be obtained over a long period of time.
Examples of magnetic carriers include oxidized iron powder or non-oxidized iron powder; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth, and alloys thereof Particles, or oxide particles thereof; a magnetic material such as ferrite; a magnetic material-dispersed resin carrier (so-called resin carrier) containing the magnetic material and a binder resin that holds the magnetic material in a dispersed state. Things can be used.
When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the toner content in the two-component developer is preferably 2% by mass or more and 15% by mass or less, and more preferably Is 4 mass% or more and 13 mass% or less.

The method for producing the toner of the present invention includes:
An aromatic polyester resin having a monomer unit derived from an aromatic polycarboxylic acid and a monomer unit derived from an aromatic polyhydric alcohol;
An aliphatic polyester resin having a monomer unit derived from an aliphatic polycarboxylic acid and a monomer unit derived from an aliphatic polyhydric alcohol; and
A step of melt-kneading a composition containing a styrene acrylic polymer to obtain a kneaded product,
Cooling the kneaded product to obtain a cooled product,
Crushing the cooling material to obtain resin particles,
The aliphatic polyester resin further has a monomer unit derived from an aromatic monocarboxylic acid and / or a monomer unit derived from an aromatic monoalcohol,
The styrene acrylic polymer is a polymer in which a styrene acrylic polymer is graft-polymerized to a polyolefin.

Hereinafter, a toner manufacturing procedure using the above pulverization method will be described.
First, as a toner material, an aliphatic polyester resin, an aromatic polyester resin, a styrene-acrylic polymer, and, if necessary, a predetermined amount of wax and the like are weighed and mixed and mixed. Examples of mixing devices include Henschel mixer (manufactured by Nihon Coke); Super mixer (manufactured by Kawata); Ribocorn (manufactured by Okawara Seisakusho); Nauter mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron); There are mixers (manufactured by Taiheiyo Kiko Co., Ltd.);
The mixed toner raw materials are melt-kneaded to melt the resins and finely and uniformly disperse the aliphatic polyester resin. As an example of a kneading apparatus, a TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); a TEX twin-screw kneader (manufactured by Nippon Steel Works); a PCM kneader (manufactured by Ikekai Iron Works Co., Ltd.); Etc. A continuous kneader such as a single-screw or twin-screw extruder is preferable to a batch kneader because of the advantage that it can be continuously produced.
Furthermore, the kneaded material obtained by melt-kneading the toner raw material is melt-kneaded, rolled with a two-roll roller, etc., and then cooled through a cooling process such as water cooling.
The cooled product obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization process, first, coarse pulverization is performed with a crusher, hammer mill, feather mill, etc., and further pulverized with a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.) to obtain resin particles. Good.
The obtained resin particles may be classified into resin particles having a desired particle size in the classification step. Examples of classifiers include turboplex, faculty, TSP, TTSP (manufactured by Hosokawa Micron); elbow jet (manufactured by Nippon Steel Mining).

The obtained resin particles are preferably subjected to a heat treatment step using the heat treatment apparatus shown in FIG. Below, the method of implementing heat processing to the resin particle is illustrated concretely.
The resin particles quantitatively supplied by the raw material fixed supply means 1 are guided to the introduction pipe 3 installed on the vertical line of the raw material supply means by the compressed gas adjusted by the compressed gas flow rate adjusting means 2. The processing chamber in which the mixture that has passed through the introduction pipe 3 is uniformly dispersed by a conical projection-like member 4 provided at the center of the raw material supply means, and is guided to the radially extending eight-direction supply pipe 5 to perform heat treatment. 6 leads.
At this time, the flow of the resin particles supplied to the processing chamber 6 is regulated by the regulating means 9 for regulating the flow of the resin particles provided in the processing chamber 6. Therefore, the resin particles supplied to the processing chamber 6 are cooled after being heat-treated while turning in the processing chamber 6.
Hot air for heat-treating the supplied resin particles is supplied from the hot air supply means 7, distributed by the distribution member 12, and swirled in the processing chamber 6 by the swirling member 13 for swirling the hot air. To be introduced. As the structure, the turning member 13 for turning hot air has a plurality of blades, and the turning of hot air can be controlled by the number and angle of the blades. The temperature of the hot air supplied into the processing chamber 6 is preferably 100 ° C. or higher and 300 ° C. or lower, more preferably 130 ° C. or higher and 170 ° C. or lower, at the outlet of the hot air supply means 7. If the temperature at the outlet portion of the hot air supply means 7 is within the above range, the particles can be uniformly treated while preventing the particles from being fused and coalesced due to excessive heating of the resin particles.
Hot air is supplied from the hot air supply means 7. Further, the heat-treated resin particles subjected to the heat treatment are cooled by the cold air supplied from the cold air supply means 8. The temperature of the cold air supplied from the cold air supply means 8 is preferably −20 ° C. or higher and 30 ° C. or lower. If the temperature of the cold air is within the above range, the heat treated resin particles can be efficiently cooled, and the heat treatment resin particles can be prevented from fusing or coalescing without inhibiting the uniform heat treatment of the resin particles. Can do. The absolute moisture content of the cold air is preferably 0.5 g / m ³ or more and 15.0 g / m ³ or less.
Next, the cooled heat treatment resin particles are recovered by the recovery means 10 at the lower end of the processing chamber 6. In addition, a blower (not shown) is provided at the tip of the collecting means 10 so that it is sucked and conveyed.
The powder particle supply port 14 is provided so that the swirling direction of the supplied resin particles is the same as the swirling direction of the hot air, and the collecting means 10 also maintains the swirling direction of the swirled resin particles. As shown, the outer circumferential portion of the processing chamber 6 is provided in the tangential direction. Further, the cold air supplied from the cold air supply means 8 is configured to be supplied from the outer peripheral portion of the apparatus to the peripheral surface of the processing chamber in a horizontal and tangential direction. The swirl direction of the pre-heat treatment resin particles supplied from the powder particle supply port 14, the swirl direction of the cool air supplied from the cold air supply means 8, and the swirl direction of the hot air supplied from the hot air supply means 7 are all the same direction. Therefore, turbulent flow does not occur in the processing chamber, the swirling flow in the apparatus is strengthened, a strong centrifugal force is applied to the resin particles before heat treatment, and the dispersibility of the resin particles before heat treatment is further improved, so there are few coalesced particles Thus, heat-treated resin particles having a uniform shape can be obtained.
The heat treatment step may be after the fine pulverization or after classification.
The average circularity of the toner of the present invention is preferably 0.960 or more, more preferably 0.965 or more. When the average circularity of the toner is in the above range, the toner transfer efficiency is improved.

Below, the measuring method of each physical property in connection with this invention is demonstrated.
<Measurement of peak temperature of maximum endothermic peak of wax, aliphatic polyester resin, polymer and toner>
The peak endothermic peak temperature (melting point) of the wax, aliphatic polyester resin, polymer and toner is measured using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments) under the following conditions.
Temperature increase rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 180 ° C
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, about 5 mg of a sample is precisely weighed, placed in an aluminum pan, and measured once. An aluminum empty pan is used as a reference.
In the present invention, the maximum endothermic peak means a peak having the maximum endothermic amount when there are a plurality of peaks. The peak temperature of the maximum endothermic peak is the melting point.
Further, when the toner is measured as a sample, a value obtained by dividing the endothermic amount ΔH [J / g] of the maximum endothermic peak derived from the aliphatic polyester resin by the added number W of the aliphatic polyester resin is ΔH / W. Here, the number W of added parts refers to the number of added parts of the aliphatic polyester resin when the aromatic polyester resin added in the toner production is 100 parts by mass.
The endothermic amount (ΔH) of the maximum endothermic peak is obtained from the peak area by calculation using analysis software attached to the apparatus.

<Measurement of glass transition temperature (Tg) of resin>
The glass transition temperature of the resin is measured in accordance with ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, 5 mg of resin is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference.
Measurement is performed at a temperature rising rate of 10 ° C./min within a measurement range of 30 to 180 ° C. Once the temperature is raised to 180 ° C. and held for 10 minutes, the temperature is then lowered to 30 ° C., and then the temperature is raised again. In the second temperature raising process, a specific heat change is obtained in the temperature range of 30 to 180 ° C. The temperature at the point where the straight line that is equidistant from the straight line extending the base line before and after the specific heat change at this time and the curve of the step change portion of the glass transition in the DSC curve intersects. And the glass transition temperature (Tg: ° C.) of the resin.

<Measurement of weight average molecular weight of aliphatic polyester resin>
The molecular weight distribution of the aliphatic polyester resin is measured as follows using gel permeation chromatography (GPC).
First, 50 mg of a sample is placed in 5 mL of chloroform and allowed to stand at 25 ° C. for several hours. Then, the sample is sufficiently shaken, mixed well with chloroform, and further left to stand for 24 hours or more until the samples are not united.
The obtained solution is filtered through a solvent-resistant membrane filter “Maysho Disc H-25-5” (manufactured by Tosoh Corporation) having a pore diameter of 0.5 μm to obtain a sample solution. Using this sample solution, measurement is performed under the following conditions.
Equipment: High-speed GPC equipment “Labsolutions GPC” (manufactured by Shimadzu Corporation)
Column: PLgel 5 μm MIXED-C 300 × 7.5 mm (Agilent
(Manufactured by Technologies): two, PLgel 5 μm Guard 50 × 7.5 mm (manufactured by Agilent Technologies): one eluent: chloroform flow rate: 1.0 ml / min
Oven temperature: 45 ° C
Sample injection volume: 60 μL
Detector: RI (refractive index) detector The molecular weight of the sample is standard polystyrene resin (trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F”). -20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 "manufactured by Tosoh Corporation) Are used to calculate the weight average molecular weight (Mw), number average molecular weight (Mn) and peak molecular weight (Mp).

<Measurement of weight average molecular weight of aromatic polyester resin or styrene acrylic polymer>
The molecular weight distribution of the aromatic polyester resin or styrene acrylic polymer is measured as follows using gel permeation chromatography (GPC).
First, a sample is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho 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 about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 "manufactured by Tosoh Corporation) Average molecular weight (Mw), number average molecular weight (Mn) and peak molecular weight (Mp) are calculated.

<Measurement of average circularity of toner>
The average circularity of the toner is measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.
A specific measurement method is as follows.
First, about 20 mL of ion-exchanged water from which impure solids and the like are previously removed is placed in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 mL of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
Further, about 0.02 g of a measurement sample is added, and a dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser (“VS-150” (manufactured by Vervo Creer)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Exchange water is added, and about 2 mL of the above-mentioned Contaminone N is added to this water tank.
The flow type particle image analyzer equipped with a standard objective lens (10 ×) was used for the measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode.
The binarization threshold at the time of particle analysis is set to 85%, and the analysis particle diameter is set to the equivalent circle diameter of 1.985 μm.
The average circularity of the toner is obtained by limiting to less than 39.69 μm.
In the measurement, automatic focus adjustment is performed using standard latex particles ("DISE Scientific AND RESPARTIC AND TEST PARTILES Latex Microsphere Suspensions 5200A" diluted with ion-exchanged water) before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
In addition, a flow type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

<Resin structure (NMR)>
Detailed structures of the aromatic polyester resin, aliphatic polyester resin, styrene acrylic polymer and the like are analyzed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR).
Measuring device: JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 1024 times Measurement solvent: DMSO-d6
Dissolve the sample in DMSO-d6 as much as possible and perform measurement under the above conditions. The detailed structure of the sample is determined from the chemical shift value of the spectrum obtained and the proton ratio.

  Hereinafter, the present invention will be described more specifically with reference to production examples and examples, but these do not limit the present invention in any way. All parts and percentages in the following formulations are based on mass unless otherwise specified.

<Example of production of aliphatic polyester resin A1>
-1,6-hexanediol: 34.5 parts (0.29 mol; 100.0 mol% with respect to the total number of polyhydric alcohols)
Dodecanedioic acid: 65.5 parts (0.28 mol; 100.0 mol% based on the total number of polycarboxylic acids)
-Tin 2-ethylhexanoate: 0.5 part The said material was weighed in the reaction tank provided with the cooling pipe, the stirrer, the nitrogen introducing pipe, and the thermocouple.
After replacing the inside of the reaction tank with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at 140 ° C.
Next, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was performed for 4 hours while maintaining the temperature at 200 ° C.
Further, after gradually releasing the pressure in the reaction tank and returning to normal pressure, 7.8 parts of benzoic acid (0.06 mol; relative to the total number of moles of monomer units constituting the aliphatic polyester resin, (9.5 mol%) and the mixture was reacted at 200 ° C for 2 hours under normal pressure.
Thereafter, the inside of the reaction vessel was again decompressed to 5 kPa or less and reacted at 200 ° C. for 3 hours to obtain an aliphatic polyester resin A1.
Table 1 shows the weight average molecular weight (Mw) and melting point of the resulting aliphatic polyester resin A1.

<Production example of aliphatic polyester resins A2 to A12>
In the production example of the aliphatic polyester resin A1, except that the conditions were appropriately changed so that the aromatic compound, the addition amount of the aromatic compound, or the weight average molecular weight (Mw) of the aliphatic polyester resin was as shown in Table 1, Operation similar to the manufacture example of aliphatic polyester resin A1 was performed, and aliphatic polyester resin A2-A12 was obtained.
Table 1 shows the weight average molecular weight (Mw) and melting point of the resulting aliphatic polyester resin.

<Production Example of Styrene Acrylic Polymer B1>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 300 parts of xylene and 10 parts of polypropylene (melting point: 75 ° C.) were sufficiently dissolved and purged with nitrogen. Thereafter, a mixed solution of 75.0 parts of styrene, 5.0 parts of cyclohexyl methacrylate, 10.0 parts of butyl acrylate and 250 parts of xylene was dropped at 180 ° C. for 3 hours for polymerization. Furthermore, it hold | maintained at this temperature for 30 minutes, solvent removal was performed, and the styrene acrylic polymer B1 was obtained. The obtained styrene-acrylic polymer B1 had a weight average molecular weight of 15000, a glass transition temperature (Tg) of 63 ° C., and a melting point of 120 ° C.

<Production Example of Styrene Acrylic Polymer B2>
In the production example of the styrene acrylic polymer B1, the same operation as in the production example of the styrene acrylic polymer B1 was performed except that styrene was changed to 80.0 parts and cyclohexyl methacrylate was not added. A polymer B2 was obtained. The obtained styrene acrylic polymer B2 had a weight average molecular weight of 12,000, a glass transition temperature (Tg) of 64 ° C., and a melting point of 118 ° C.

<Production example of aromatic polyester resin C1>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 72.0 parts (0.20 mol; 100.0 mol% based on the total number of polyhydric alcohols)
-Terephthalic acid: 28.0 parts (0.17 mol; 94.4 mol% with respect to the total number of polyvalent carboxylic acids)
-Tin 2-ethylhexanoate (esterification catalyst): 0.5 part The said material was weighed in the reaction tank provided with the cooling pipe, the stirrer, the nitrogen introducing pipe, and the thermocouple.
After replacing the inside of the reaction tank with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at 200 ° C.
Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, then cooled to 180 ° C. and returned to atmospheric pressure (first reaction step).
Trimellitic anhydride: 1.3 parts (0.01 mol; 5.6 mol% based on the total number of polycarboxylic acids)
Tert-Butylcatechol (polymerization inhibitor): 0.1 part Thereafter, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the temperature was maintained at 180 ° C. for 1 hour, ASTM D36 After confirming that the softening point measured according to −86 reached 120 ° C., the reaction was stopped by lowering the temperature (second reaction step).
The obtained aromatic polyester resin C1 had a glass transition temperature (Tg) of 57 ° C. and a peak molecular weight of 4800.

<Production example of resin C2>
-2000 parts of BPA-PO-250 parts of dodecenyl succinic acid-350 parts of terephthalic acid-40 parts of acrylic acid-15 parts of tin (II) dioctanoate In a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple, The material was weighed.
After replacing the inside of the reaction tank with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4.5 hours while stirring at 230 ° C.
Thereafter, once cooled to 160 ° C., 150 parts of trimellitic acid was added.
Next, a mixture of 2850 parts of styrene, 1250 parts of 2-ethylhexyl acrylate and 30 parts of dicumyl peroxide as a polymerization initiator was added dropwise at 160 ° C. over 2 hours. After completion of the dropping, the temperature was further raised to 200 ° C., and the reaction was carried out for 3 hours until the softening point reached 115 ° C. The obtained resin C2 had a glass transition temperature (Tg) of 60 ° C. and a peak molecular weight of 11,000.
The BPA-PO is a 2.1 mol adduct of bisphenol A propylene oxide.

<Production Example of Toner 1>
Aromatic polyester resin C1 100.0 parts Aliphatic polyester resin A1 7.5 parts Styrene acrylic polymer B1 5.0 parts Fischer-Tropsch wax 6.0 parts (hydrocarbon wax, peak temperature of maximum endothermic peak) 90 ° C)
・ C. I. Pigment Blue 15: 3 7.0 parts, aluminum 3,5-di-t-butylsalicylate compound 0.3 parts (Bontron E88 manufactured by Orient Chemical Industries)
The above materials were mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s ⁻¹ and a rotation time of 5 minutes, and then a twin-screw kneader (PCM-30) set at a temperature of 130 ° C. Kneading with a mold, manufactured by Ikegai Co., Ltd.). The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The obtained coarsely crushed material was finely pulverized with a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Furthermore, classification was performed using Faculty F-300 (manufactured by Hosokawa Micron Corporation) to obtain resin particles 1. The operating conditions were a classification rotor rotational speed of 130 s ⁻¹ and a distributed rotor rotational speed of 120 s ⁻¹ .
The obtained resin particles 1 were heat-treated using the heat treatment apparatus shown in FIG. The operating conditions were a feed amount of 5 kg / hr, a hot air temperature of 150 ° C., and a hot air flow rate of 6 m ³ / min. The cold air temperature is −5 ° C., and the cold air flow rate is 4 m ³ / min. , The blower air volume is 20 m ³ / min. , The injection air flow rate is 1 m ³ / min. It was.
100 parts of the toner particles 1, surface-treated hydrophobic silica with hexamethyldisilazane ^(BET: 200m 2 /g)1.0 parts, and titanium oxide fine particles surface-treated with isobutyl trimethoxysilane (BET: ^80m 2 / g ) 1.0 part was mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) at a rotation speed of 30 s ⁻¹ and a rotation time of 10 min to obtain toner 1. The average circularity of the obtained toner was 0.968.
Table 2 shows ΔH / W1 of the obtained toner, the added part W2 of the styrene acrylic polymer, and the value W1 / W2 obtained by dividing the added part W1 of the aliphatic polyester resin A by the added part W2 of the styrene acrylic polymer. .

<Production Example of Toners 2 to 22>
In the production example of the toner 1, the same operation was carried out except that the type of aliphatic polyester resin and the number of added parts, and the type and number of added parts of the styrene acrylic polymer were changed as shown in Table 2. 22 was obtained.

<Production example of toner 23>
A toner 23 was obtained in the same manner as in the production example of the toner 22 except that the aromatic polyester resin C1 was changed to the resin C2.

<Example of production of magnetic core particle 1>
-Process 1 (weighing / mixing process):
Fe ₂ O ₃ 62.7 parts MnCO ₃ 29.5 parts Mg (OH) ₂ 6.8 parts SrCO ₃ 1.0 parts The ferrite raw materials were weighed so that the above materials had the above composition ratio. Thereafter, the mixture was pulverized and mixed for 5 hours in a dry vibration mill using 1/8 inch diameter stainless steel beads.
-Process 2 (temporary baking process):
The obtained pulverized product was formed into pellets of about 1 mm square using a roller compactor. After removing the coarse powder from the pellets with a vibrating sieve having a mesh opening of 3 mm, and then removing the fine powders with a vibrating sieve having a mesh opening of 0.5 mm, using a burner-type firing furnace, under a nitrogen atmosphere (oxygen concentration of 0.1. And calcined at a temperature of 1000 ° C. for 4 hours to prepare calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393
-Step 3 (grinding step):
After crushing the obtained calcined ferrite to about 0.3 mm with a crusher, 30 parts of water was added to 100 parts of calcined ferrite using zirconia beads having a diameter of 1/8 inch, and crushed with a wet ball mill for 1 hour. . The obtained slurry was pulverized for 4 hours by a wet ball mill using alumina beads having a diameter of 1/16 inch to obtain a ferrite slurry (finely pulverized product of calcined ferrite).
-Process 4 (granulation process):
To the ferrite slurry, 1.0 part of ammonium polycarboxylate as a dispersing agent and 100 parts of polyvinyl alcohol as a binder are added to 100 parts of calcined ferrite, and spray particles (manufacturer: Okawara Kakoki) are used to form spherical particles. Granulated. After adjusting the particle size of the obtained particles, using a rotary kiln, it was heated at 650 ° C. for 2 hours to remove the organic components of the dispersant and the binder.
-Process 5 (firing process):
In order to control the firing atmosphere, the temperature was raised from room temperature to 1300 ° C. in a nitrogen atmosphere (oxygen concentration: 1.00 vol%) in an electric furnace in 2 hours, and then fired at a temperature of 1150 ° C. for 4 hours. Thereafter, the temperature was lowered to 60 ° C. over 4 hours, returned from the nitrogen atmosphere to the atmosphere, and taken out at a temperature of 40 ° C. or lower.
-Process 6 (screening process):
After crushing the agglomerated particles, the low-magnetic force product is cut by magnetic separation, and the coarse particles are removed by sieving with a sieve having an opening of 250 μm, and a 50% particle size (D50) of 37.0 μm based on volume distribution. Magnetic core particles 1 were obtained.

<Adjustment of coating resin 1>
Cyclohexyl methacrylate monomer 26.8% by mass
Methyl methacrylate monomer 0.2% by mass
Methyl methacrylate macromonomer 8.4% by mass
(Macromonomer having a weight average molecular weight of 5000 having a methacryloyl group at one end)
Toluene 31.3% by mass
Methyl ethyl ketone 31.3 mass%
Azobisisobutyronitrile 2.0% by mass
Among the above materials, cyclohexyl methacrylate monomer, methyl methacrylate monomer, methyl methacrylate macromonomer, toluene, methyl ethyl ketone are put into a four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube and a stirring device, and nitrogen is added. Gas was introduced and the system was replaced with nitrogen gas. Thereafter, the mixture was heated to 80 ° C., azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate a copolymer, and the precipitate was filtered off and dried under vacuum to obtain coating resin 1.
Next, 30 parts of the coating resin 1 was dissolved in 40 parts of toluene and 30 parts of methyl ethyl ketone to obtain a polymer solution 1 (resin solid content of 30% by mass).

<Preparation of coating resin solution 1>
Polymer solution 1 (resin solid content: 30% by mass) 33.3% by mass
Toluene 66.4% by mass
Carbon black (Regal 330; manufactured by Cabot) 0.3% by mass
(Primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² / g, DBP oil absorption 75 mL / 100 g) was dispersed with a paint shaker for 1 hour using zirconia beads having a diameter of 0.5 mm. The obtained dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

<Example of production of magnetic carrier 1>
(Resin coating process):
The coating resin solution 1 and the coating resin solution 1 were put into a vacuum degassing kneader maintained at room temperature (the amount of the coating resin solution 1 was 2 as a resin component with respect to 100 parts of the magnetic core particles 1. .5 parts). After the addition, the mixture was stirred for 15 minutes at a rotation speed of 30 rpm, and after the solvent was volatilized above a certain level (80% by mass), the temperature was raised to 80 ° C. while mixing under reduced pressure, and toluene was distilled off over 2 hours, followed by cooling. The obtained magnetic carrier is separated by low-magnetization by magnetic separation, passed through a sieve having an opening of 70 μm, and then classified by an air classifier, and a magnetic carrier having a 50% particle size (D50) of 38.2 μm based on volume distribution. 1 was obtained.

<Example of production of two-component developer 1>
To 92.0 parts of magnetic carrier 1, 8.0 parts of toner 1 was added and mixed with a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain a two-component developer 1.

<Production example of two-component developer 2-23>
In the production example of the two-component developer 1, the same operation was performed except that the toner was changed as shown in Table 3, and the two-component developers 2 to 23 were obtained.

<Example 1>
The obtained two-component developer 1 was used for evaluation.
As an image forming apparatus, a Canon digital commercial printing printer imageRUNNER ADVANCE C9280 PRO remodeling machine is used, and the two-component developer 1 is put in the developing device at the cyan position, and the amount of toner on the electrostatic latent image carrier or paper is set. A desired image was formed and evaluated as described below. As remodeling points, the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, the laser power, the fixing temperature, and the process speed were changed freely. In the image output evaluation, an FFh image (solid image) having a desired image ratio was output. FFh is a value in which 256 gradations are displayed in hexadecimal, 00h is the first gradation (white background part) of 256 gradations, and FFh is the 256th gradation (solid part) of 256 gradations. .
Evaluation is based on the following evaluation methods, and the results are shown in Table 4.

<Evaluation 1>
(Charge stability in high temperature and high humidity environment)
Paper: CS-680 (68.0 g / m ² )
(Sold from Canon Marketing Japan Inc.)
Amount of toner on paper: 0.35 mg / cm ² (FFh image)
Test environment: High temperature and high humidity environment, temperature 30 ° C./humidity 80% RH (hereinafter “H / H”)
As an endurance image output test, 10,000 sheets were output on A4 paper using an FFh output band chart with an image ratio of 0.1% in an H / H environment.
Thereafter, an image of 10 cm ² was placed at the center of the A4 paper, and the image density after output was measured. Subsequently, after leaving the developing unit in the evaluation machine in the H / H environment for 3 nights, an image of 10 cm ² is placed in the center of the A4 paper as before, and the image density after output is set. It was measured. The density difference between the two evaluation images was evaluated according to the following criteria.
(Evaluation criteria)
A: Density difference is less than 0.10 (very good)
B: Concentration difference is 0.10 or more and less than 0.15 (good)
C: Concentration difference is 0.15 or more and less than 0.25 (no problem level)
D: Density difference is 0.25 or more (unacceptable level)

<Evaluation 2>
(Low temperature fixability)
Paper: CS-680 (68.0 g / m ² )
(Sold from Canon Marketing Japan Inc.)
Amount of applied toner: 1.20 mg / cm ²
Evaluation image: An image of 10 cm ² is placed in the center of the A4 paper. Fixing test environment: Low temperature and low humidity environment, temperature 15 ° C./humidity 10% RH (hereinafter “L / L”)
Process speed: 450mm / sec
Fixing temperature: 130 ° C
Using the image forming apparatus, the low-temperature fixability of a fixed image output under the above conditions was evaluated.
Evaluation of low-temperature fixability was performed using the following image density reduction rate as an index.
For the image density reduction rate, an X-Rite color reflection densitometer (500 series: manufactured by X-Rite) is used to first measure the density of the fixed image at the center. Next, a load of 4.9 kPa (50 g / cm ² ) is applied to the portion where the density of the fixed image is measured, and the fixed image is rubbed (five reciprocations) with sylbon paper, and the density of the fixed image is measured again. To do. The reduction rate (%) of the density of the fixed image before and after rubbing was measured.
(Evaluation criteria)
A: Density reduction rate is less than 1.0% (very good)
B: Density reduction rate is 1.0% or more and less than 5.0% (good)
C: Density reduction rate is 5.0% or more and less than 10.0% (no problem level)
D: Density reduction rate is 10.0% or more (unacceptable level)

<Examples 2 to 20>
Evaluation was performed in the same manner as in Example 1 except that the two-component developers 2 to 20 as shown in Table 3 were used. The results are shown in Table 4.

<Comparative Examples 1-3>
Evaluation was performed in the same manner as in Example 1 except that the two-component developers 21 to 23 as shown in Table 3 were used. The results are shown in Table 4.

<Comparative Example 1>
The aliphatic crystalline polyester resin used for the toner 21 does not contain a monomer unit derived from an aromatic monocarboxylic acid and / or a monomer unit derived from an aromatic monoalcohol. Therefore, the aliphatic polyester resin is easily crystallized in the toner. As a result, it is inferred that charges leaked from the crystallized aliphatic polyester resin and the charging stability was lowered.
<Comparative example 2>
The toner 22 does not contain a styrene acrylic polymer. Since there is no styrene acrylic polymer that interacts with the aliphatic polyester resin, the aliphatic polyester resin is difficult to uniformly and finely disperse in the toner. As a result, since the aliphatic polyester resin exists as a domain in the toner and is easily crystallized, it is presumed that the charge is leaked and the charging stability is lowered.
<Comparative Example 3>
The toner 23 is a toner that does not contain a styrene acrylic polymer and uses a hybrid resin as a binder resin. As a result of the content of the aromatic polyester resin in the binder resin being reduced, the compatibility with the aliphatic polyester resin was reduced, and the effect as a softening agent was reduced. As a result, it is presumed that the low-temperature fixability has decreased. In addition, since the aliphatic polyester resin does not contain styrene acrylic polymer and the dispersion of the aliphatic polyester resin is insufficient, the aliphatic polyester resin in the toner is easily crystallized, and the charge is leaked and the charging stability is reduced. Inferred.

1. 1. Raw material quantitative supply means, 2. compressed gas flow rate adjusting means; 3. Introducing pipe, 4. Protruding member, 5. supply pipe, 6. processing chamber; Hot air supply means, 8. Cold air supply means, 9. Regulatory means, 10. Recovery means, 11. 11. Hot air supply means outlet, 12. distribution member; Swivel member, 14. Powder particle supply port

Claims (16)

An aromatic polyester resin having a monomer unit derived from an aromatic polycarboxylic acid and a monomer unit derived from an aromatic polyhydric alcohol;
An aliphatic polyester resin having a monomer unit derived from an aliphatic polycarboxylic acid and a monomer unit derived from an aliphatic polyhydric alcohol; and
A toner having toner particles containing a styrene acrylic polymer,
The aliphatic polyester resin further has a monomer unit derived from an aromatic monocarboxylic acid and / or a monomer unit derived from an aromatic monoalcohol,
A toner, wherein the styrene acrylic polymer is a polymer in which a styrene acrylic polymer is graft-polymerized to a polyolefin.   The ratio of the total number of moles of the monomer unit derived from the aromatic monocarboxylic acid and / or the monomer unit derived from the aromatic monoalcohol to the total number of moles of the monomer unit constituting the aliphatic polyester resin is 0.5 mole. The toner according to claim 1, wherein the toner is 1% or more and 15.0 mol% or less.   The toner according to claim 1, wherein the monomer unit derived from the aromatic monocarboxylic acid and / or the monomer unit derived from the aromatic monoalcohol includes a monomer unit derived from benzoic acid.   The relation of 0.5 ≦ W1 / W2 ≦ 2.0 is satisfied when the content of the aliphatic polyester resin is W1 parts by mass and the content of the styrene acrylic polymer is W2 parts by mass. The toner according to any one of 1 to 3.   The toner according to claim 1, wherein the styrene acrylic polymer has a monomer unit derived from cycloalkyl (meth) acrylate.   The content of the aliphatic polyester resin is 1.0 part by mass or more and 10.0 parts by mass or less based on 100 parts by mass of the aromatic polyester resin. toner.   The content of the styrene acrylic polymer is 1.0 part by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the aromatic polyester resin. Toner.   The toner according to claim 1, wherein the aliphatic polyester resin has a weight average molecular weight (Mw) of 5,000 or more and 14,000 or less. An aromatic polyester resin having a monomer unit derived from an aromatic polycarboxylic acid and a monomer unit derived from an aromatic polyhydric alcohol;
An aliphatic polyester resin having a monomer unit derived from an aliphatic polycarboxylic acid and a monomer unit derived from an aliphatic polyhydric alcohol; and
A step of melt-kneading a composition containing a styrene acrylic polymer to obtain a kneaded product,
Cooling the kneaded product to obtain a cooled product,
Crushing the cooling material to obtain resin particles,
The aliphatic polyester resin further has a monomer unit derived from an aromatic monocarboxylic acid and / or a monomer unit derived from an aromatic monoalcohol,
A method for producing a toner, wherein the styrene acrylic polymer is a polymer in which a styrene acrylic polymer is graft-polymerized to a polyolefin.   The ratio of the total number of moles of the monomer unit derived from the aromatic monocarboxylic acid and / or the monomer unit derived from the aromatic monoalcohol to the total number of moles of the monomer unit constituting the aliphatic polyester resin is 0.5 mole. The method for producing a toner according to claim 9, wherein the toner content is from 1% to 15.0 mol%.   The method for producing a toner according to claim 9, wherein the monomer unit derived from the aromatic monocarboxylic acid and / or the monomer unit derived from the aromatic monoalcohol includes a monomer unit derived from benzoic acid.   The relation of 0.5 ≦ W1 / W2 ≦ 2.0 is satisfied, where the content of the aliphatic polyester resin is W1 parts by mass and the content of the styrene acrylic polymer is W2 parts by mass. The method for producing a toner according to any one of 1 to 11.   The method for producing a toner according to claim 9, wherein the styrene acrylic polymer has a monomer unit derived from a cycloalkyl (meth) acrylate.   14. The content of the aliphatic polyester resin according to claim 9, wherein the content of the aliphatic polyester resin is 1.0 part by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the aromatic polyester resin. Toner manufacturing method.   The content of the styrene acrylic polymer is 1.0 to 10.0 parts by mass with respect to 100 parts by mass of the aromatic polyester resin. Toner production method. The method for producing a toner according to claim 9, wherein the aliphatic polyester resin has a weight average molecular weight (Mw) of 5,000 or more and 14,000 or less.

Images