JP2013068911A - Polyester resin for electrostatic charge image development toner, electrostatic charge image development toner, electrostatic charge image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin for an electrostatic charge image development toner that suppresses a deterioration in liquidity of an electrostatic charge image development toner after storage in a high-humidity environment.SOLUTION: A polyester resin for an electrostatic charge image development toner is a polycondensate that comprises a cyclic sugar alcohol including at least one hetero element and a monomer including rosin at least as polycondensation components.

Description

  The present invention relates to a polyester resin for electrostatic image developing toner, an electrostatic image developing toner, an electrostatic image developer, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method.

  A method of visualizing image information through an electrostatic latent image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic latent image formed on a photoreceptor by a charging process and an exposure process is developed with a developer containing toner, and visualized through a transfer process and a fixing process.

For example, Patent Document 1 proposes “a toner comprising at least a binder resin and a colorant and having a radioactive carbon isotope 14C concentration of 10.8 pMC or more”.
Patent Document 2 proposes “a polyester for toner obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing purified rosin, and a toner containing the polyester for toner”. .
Patent Document 3 discloses that “a polyester for toner obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing (meth) acrylic acid-modified rosin, and a toner containing the polyester for toner”. Has been proposed.
Patent Document 4 discloses that “a polyester for toner obtained by condensation polymerization of an alcohol component containing an aliphatic polyhydric alcohol and a carboxylic acid component containing a (meth) acrylic acid-modified rosin, and the toner Toners containing polyester have been proposed.

JP 2009-288739 A JP 2007-137910 A JP 2007-292815 A JP 2007-292816 A

  An object of the present invention is to provide a polyester resin for an electrostatic charge image developing toner that suppresses deterioration of fluidity after storage in a high humidity environment in the electrostatic charge image developing toner.

The above problem is solved by the following means. That is,
The invention according to claim 1
A polyester resin for an electrostatic charge image developing toner, which is a polycondensate comprising at least one cyclic sugar alcohol containing a hetero element and a monomer containing rosin as a polycondensation component.

The invention according to claim 2
The polyester resin for electrostatic image developing toner according to claim 1, wherein the monomer containing rosin is at least one of a polyvalent carboxylic acid and a polyhydric alcohol.

The invention according to claim 3
The polyester resin for an electrostatic charge image developing toner according to claim 1, wherein a skeleton derived from the rosin is 70% by mass or less based on the entire polyester resin.

The invention according to claim 4
The polyester resin for electrostatic image developing toner according to any one of claims 1 to 3, wherein the cyclic sugar alcohol is a cyclic sugar alcohol having a cyclic structure containing at least one hetero element and two hydroxyl groups. .

The invention according to claim 5
The polyester resin for electrostatic charge image developing toner according to claim 1, wherein the cyclic sugar alcohol is at least one selected from isosorbite and isoidide.

The invention according to claim 6
An electrostatic image developing toner comprising the polyester resin for electrostatic image developing toner according to any one of claims 1 to 5.

The invention according to claim 7 provides:
An electrostatic charge image developer comprising at least the electrostatic charge image developing toner according to claim 6.

The invention according to claim 8 provides:
Containing the electrostatic image developing toner according to claim 6;
A toner cartridge to be attached to and detached from the image forming apparatus.

The invention according to claim 9 is:
A developing unit that contains the electrostatic charge image developer according to claim 7 and that develops the electrostatic charge image formed on the image carrier as a toner image with the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus.

The invention according to claim 10 is:
An image carrier,
Charging means for charging the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Development means for containing the electrostatic charge image developer according to claim 7 and developing the electrostatic charge image formed on the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the image carrier onto a transfer target;
Fixing means for fixing the toner image transferred onto the transfer medium;
An image forming apparatus comprising:

The invention according to claim 11 is:
A charging step for charging the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic image formed on the image carrier as a toner image by the electrostatic image developer according to claim 7;
A transfer step of transferring a toner image formed on the image carrier onto a transfer target;
A fixing step of fixing the toner image transferred onto the transfer medium;
An image forming method comprising:

According to the invention according to claims 1, 4 and 5, in the polyester resin having a cyclic sugar alcohol containing at least one hetero element as a polycondensation component, compared with a case where a monomer containing rosin as a polycondensation component is not used in combination. In addition, it is possible to provide a polyester resin for an electrostatic charge image developing toner that suppresses deterioration of fluidity after storage in a high humidity environment in the electrostatic charge image developing toner.
According to the invention of claim 2, the electrostatic image development is excellent in the low-temperature fixability of the electrostatic image developing toner as compared with the case where the monomer containing rosin is not at least one of a polyvalent carboxylic acid and a polyhydric alcohol. A polyester resin for toner can be provided.
According to the invention of claim 3, it is possible to provide a polyester resin for an electrostatic charge image developing toner that is superior in low-temperature fixability of the electrostatic charge image developing toner as compared with a case where the skeleton derived from rosin is outside the above range.

  According to the inventions according to claims 6 and 7, in the polyester resin having a cyclic sugar alcohol containing at least one hetero element as a polycondensation component, the toner includes a polyester resin not using a monomer containing rosin as the polycondensation component. Compared to the above, it is possible to provide an electrostatic charge image developing toner and an electrostatic charge image developer in which deterioration of fluidity after storage in a high humidity environment is suppressed.

  According to the inventions according to claims 8, 9, 10, and 11, in a polyester resin having a cyclic sugar alcohol containing at least one hetero element as a polycondensation component, a polyester not using a monomer containing rosin as a polycondensation component A toner cartridge, a process cartridge, an image forming apparatus, and an image forming method in which image defects caused by deterioration of fluidity after storage in a high humidity environment are suppressed compared to the case where toner containing resin is provided Can be provided.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows an example of the process cartridge which concerns on this embodiment.

  Hereinafter, an embodiment which is an example of the present invention will be described in detail.

[Polyester resin for electrostatic image developing toner]
The polyester resin for electrostatic charge image developing toner according to the present embodiment (hereinafter sometimes simply referred to as “polyester resin”) includes a cyclic sugar alcohol containing at least one hetero element, a monomer containing rosin, Is a polycondensate containing at least a polycondensation component.

  Here, in recent years, as a substitute for bisphenol A in the production of a polyester resin for toner, “cyclic sugar alcohol containing at least one hetero element (hereinafter simply referred to as“ cyclic sugar alcohol ”) represented by isosorbite. ”) Is being considered.

  However, since the cyclic sugar alcohol has deliquescence, the water absorption is high, and due to this property, the polyester resin using the cyclic sugar alcohol has increased hydrophilicity, and the toner containing the polyester resin has a high humidity environment. There is a strong tendency for fluidity to deteriorate after storage underneath.

On the other hand, in the polyester resin according to the present embodiment, a monomer containing rosin is used as a polycondensation component together with a cyclic sugar alcohol containing at least one hetero element, so that the toner is in a high humidity environment (for example, , Deterioration of fluidity after storage in an environment of 85% humidity) is suppressed.
Although this reason is not certain, it is thought to be due to the following reasons.

As described above, cyclic sugar alcohols typified by isosorbite have deliquescence and increase the hydrophilicity of the polyester resin using this as a polycondensation component, whereas rosin is highly lipophilic. It is considered that a polyester resin using a monomer containing rosin in one molecule as a polycondensation component suppresses an increase in hydrophilicity of the entire resin.
This is because the rosin having a lipophilic property has a bulky structure composed of a large number of atoms, so that the volume fraction of the rosin in the entire polyester resin is larger than that of the cyclic sugar alcohol. This is because the property of oiliness is considered to be dominant in the properties of the entire polyester resin.

  From the above, with the polyester resin according to the present embodiment, it is considered that deterioration of fluidity after storage in a high-humidity environment (for example, an environment with a humidity of 85%) in the toner is suppressed.

  Hereinafter, the polyester resin according to the present embodiment will be described in detail.

The polyester resin according to the present embodiment is a polycondensate having at least a polysaccharide component containing a cyclic sugar alcohol containing at least one hetero element and a monomer containing rosin.
Specific examples of the polyester resin according to this embodiment include the polycondensates shown below. Among these, from the viewpoint of improving the low-temperature fixability of the electrostatic charge image developing toner, the rosin-containing monomer is applied as at least one of polyvalent carboxylic acid and polyhydric alcohol 1), 2), and 3) A polycondensate is preferred.
1) a polyvalent carboxylic acid component containing a polyvalent carboxylic acid having a rosin and optionally another polyvalent carboxylic acid; a polyhydric alcohol component containing a cyclic sugar alcohol and optionally another polyvalent alcohol; Polycondensate of
2) A polycondensation product of a polyvalent carboxylic acid component containing another polyvalent carboxylic acid and a polyhydric alcohol component containing a polyhydric alcohol having a rosin, a cyclic sugar alcohol and, if necessary, another polyhydric alcohol.
3) Polyhydric carboxylic acid component containing polyvalent carboxylic acid having rosin and other polycarboxylic acid if necessary, polyhydric alcohol having rosin, cyclic sugar alcohol and optionally other polyhydric alcohol A polycondensate with a polyhydric alcohol component.
4) A polycondensate of rosin, a polyvalent carboxylic acid component containing another polyvalent carboxylic acid, and a polyhydric alcohol component containing a cyclic sugar alcohol and, if necessary, another polyhydric alcohol.
5) The weight of rosin, a polyvalent carboxylic acid component containing other polyvalent carboxylic acid, and a polyhydric alcohol component containing rosin, a polyhydric alcohol having rosin, a cyclic sugar alcohol and, if necessary, other polyhydric alcohol Condensate.

That is, the monomer containing rosin includes rosin (rosin before modification), polyvalent carboxylic acid having rosin, and polyhydric alcohol containing rosin. By using these monomers as a polycondensation component, rosin (rosin skeleton) is contained in the polyester resin (in its molecule).
However, the content of the skeleton derived from the rosin contained in the polyester resin (hereinafter referred to as the content of the rosin skeleton) is, for example, 70% by mass or less, desirably 5% by mass or more and 70% by mass or less, and more desirably. It is 10 mass% or more and 45 mass% or less.
By setting the upper limit of the content of the rosin skeleton to 70% by mass or less, the low-temperature fixability of the toner is hardly inhibited.
By setting the lower limit of the content of the rosin skeleton to 5% by mass or more, deterioration in fluidity after storage in a high humidity environment in the electrostatic charge image developing toner is easily suppressed. The reason for this is considered that excessive moisture absorption of the electrostatic charge image developing toner when stored in a high humidity environment can be suppressed due to the hydrophobicity of rosin.
The content of the rosin skeleton is adjusted according to the type of monomer containing rosin and the amount of the rosin used in the synthesis of the polyester resin.
Here, the content of the rosin skeleton means the abundance of the rosin skeleton (that is, the rosin bonded to the polyester resin) present in the polyester resin obtained by polycondensation of a rosin-containing monomer as a polycondensation component. .
The content of the rosin skeleton is measured by separating the constituent components of the polyester resin using NMR, LC-MS, GC-MS, etc., and then quantifying the components.

  In addition, other polyhydric carboxylic acids are carboxylic acids other than polyhydric carboxylic acids having rosin, and other polyhydric alcohols are polyhydric alcohols other than polyhydric alcohols having rosin and cyclic sugar alcohols.

(Rosin)
Rosin is a general term for resin acids obtained from trees, and the main component is a substance derived from natural products including abietic acid, which is one of tricyclic diterpenes, and isomers thereof. Specific examples of the rosin include, in addition to abietic acid, parastrinic acid, neoabietic acid, pimaric acid, dehydroabietic acid, isopimaric acid, sandaracopimalic acid, and the rosin used in the present embodiment. It is a mixture.

The rosin is roughly classified into three types according to the collection method: tall rosin using pulp as a raw material, gum rosin using raw pine oil as a raw material, and wood rosin using a raw material as a pine stump.
Since rosin is easily available, at least one of gum rosin and tall rosin is desirable.

The rosin may be a purified rosin. The purified rosin is a high molecular weight substance that is considered to have been generated from a resin acid peroxide from an unpurified rosin, or a non-purified rosin. It was obtained by removing the saponified product.
The purification method is not particularly limited, and various known purification methods are selected. Specifically, methods such as distillation, recrystallization, extraction and the like can be mentioned. Industrially, purification by distillation is desirable. The distillation is usually selected in consideration of the distillation time at a pressure of 200 ° C. or more and 300 ° C. or less and 6.67 kPa or less. The recrystallization is performed, for example, by dissolving unpurified rosin in a good solvent and then distilling off the solvent to obtain a concentrated solution, and adding a poor solvent to the solution. Good solvents include aromatic hydrocarbons such as benzene, toluene and xylene, chlorinated hydrocarbons such as chloroform, alcohols such as lower alcohols, ketones such as acetone, and acetates such as ethyl acetate. Examples of the poor solvent include hydrocarbon solvents such as n-hexane, n-heptane, cyclohexane, and isooctane. Extraction can be performed by, for example, converting an unpurified rosin into an alkaline aqueous solution using alkaline water, extracting an insoluble unsaponified product contained therein with an organic solvent, and then neutralizing the aqueous layer to purify the purified rosin. Is the way to get.

The rosin may be a disproportionated rosin. Disproportionated rosin is a rosin containing abietic acid as a main component heated at high temperature in the presence of a disproportionation catalyst to eliminate unstable conjugated double bonds in the molecule. A mixture of dehydroabietic acid and dihydroabietic acid.
Examples of the disproportionation catalyst include various known catalysts such as supported catalysts such as palladium carbon, rhodium carbon, and platinum carbon, metal powders such as nickel and platinum, and iodides such as iodine and iron iodide.

  The rosin may be a hydrogenated rosin for the purpose of eliminating unstable conjugated double bonds in the molecule. For the hydrogenation reaction, known hydrogenation reaction conditions are selected. That is, it is carried out by heating rosin under hydrogen pressure in the presence of a hydrogenation catalyst. Examples of the hydrogenation catalyst include various known catalysts such as supported catalysts such as palladium carbon, rhodium carbon and platinum carbon, metal powders such as nickel and platinum, and iodides such as iodine and iron iodide.

  Note that the disproportionation rosin and the hydrogenation rosin may be provided with the purification step before and after the disproportionation treatment or the hydrogenation treatment.

(Carboxylic acid component)
-Polycarboxylic acid with rosin-
Polycarboxylic acid having rosin (hereinafter sometimes referred to as carboxylic acid-modified rosin) reacts rosin with α, β-unsaturated carboxylic acid (eg, α, β-unsaturated carboxylic acid or acid anhydride thereof). Specifically, for example, rosin modified with carboxylic acid (for example, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, (anhydrous) citraconic acid) It is done.
Representative examples of the carboxylic acid-modified rosin include (meth) acrylic acid-modified rosin, fumaric acid-modified rosin, and maleic acid-modified rosin.
The rosin before modification is the same as the rosin used as the above-described polycondensation component of the polyester resin.

The (meth) acrylic acid-modified rosin is a rosin modified with (meth) acrylic acid.
Specific examples of (meth) acrylic acid-modified rosin include, for example, those obtained by addition reaction of (meth) acrylic acid to rosin before modification. More specifically, for example, rosin before modification It was obtained through a Diels-Alder reaction under heating with an acid having a conjugated double bond and (meth) acrylic acid among the main components.
As the (meth) acrylic acid-modified rosin, an acrylic acid-modified rosin modified with acrylic acid having little steric hindrance is preferable from the viewpoint of reaction activity in the Diels-Alder reaction.

  “(Meth) acryl” means acrylic or methacrylic. That is, “(meth) acrylic acid” is acrylic acid or methacrylic acid. The “(meth) acrylic acid modified rosin” is a rosin modified with acrylic acid or rosin modified with methacrylic acid.

  In (meth) acrylic acid-modified rosin, the degree of modification of rosin with (meth) acrylic acid (hereinafter referred to as (meth) acrylic acid modification degree) is, for example, from the viewpoint of increasing the molecular weight of the polyester and reducing the low molecular weight oligomer component. It is preferably 5 or more and 105 or less, desirably 20 or more and 105 or less, more desirably 40 or more and 105 or less, and further desirably 60 or more and 105 or less.

The (meth) acrylic acid modification degree Xa is calculated by the formula (Aa). In addition, it shows that the degree of modification | denaturation is so high that the value of Formula (Aa) is large.
Formula (Aa): Xa = [(Xa1-Y) / (Xa2-Y)] × 100
In the formula (Aa), Xa1 represents the SP value of the (meth) acrylic acid-modified rosin for calculating the degree of modification. Xa2 represents a saturated SP value of (meth) acrylic acid-modified rosin obtained by reacting 1 mol of (meth) acrylic acid and 1 mol of rosin. Y represents the SP value of rosin.

Here, the SP value is a softening point measured by a ring and ball automatic softening point tester. Specifically, the SP value is a value obtained by pouring a target sample in a molten state into a ring, cooling to room temperature, and measuring under the following conditions based on JIS B7410.
Measuring instrument: Ring and ball automatic softening point tester ASP-MGK2 (manufactured by Meitec)
・ Raising rate: 5 ° C / min
-Temperature rise start temperature: 40 ° C
-Solvent for measurement: Glycerin Further, the saturated SP value is the SP value when the reaction of (meth) acrylic acid and rosin is reacted until the SP value of the obtained (meth) acrylic acid-modified rosin reaches the saturation value. It is.

Although it does not specifically limit as a manufacturing method of (meth) acrylic acid modification rosin, For example, rosin before modification | denaturation and (meth) acrylic acid are mixed, for example, 180 degreeC or more and 260 degrees C or less (desirably 180 degreeC or more and 210 degrees (Meth) acrylic acid-modified rosin is obtained by adding (meth) acrylic acid to an acid having a conjugated double bond contained in rosin by Diels-Alder reaction.
The (meth) acrylic acid-modified rosin may be used as it is after the above reaction, or may be used after purification through an operation such as distillation.

The fumaric acid-modified rosin is a rosin modified with fumaric acid.
Specific examples of the fumaric acid-modified rosin include those obtained by addition reaction of fumaric acid to the rosin before modification, and more specifically, a conjugated double bond among the main components of the rosin before modification. And those obtained through a Diels-Alder reaction under heating with an acid having an acid and fumaric acid.

  In the fumaric acid-modified rosin, the degree of modification of the rosin with fumaric acid (hereinafter referred to as fumaric acid modification degree) is preferably 5 or more and 105 or less, more preferably 20 or more and 105 or less, from the viewpoint of increasing the molecular weight of the polyester and increasing the glass transition point. More preferably, it is 40 or more and 105 or less, More preferably, it is 60 or more and 105 or less.

The fumaric acid modification degree Xf is calculated by the following formula (Af). In addition, it shows that the degree of modification | denaturation is so high that the value of Formula (Af) is large.
Formula (Af): Xf = [(Xf1-Y) / (Xf2-Y)] × 100
In the formula (Af), Xf1 represents the SP value of the fumaric acid-modified rosin for calculating the degree of modification. Xf2 represents the SP value of a fumaric acid-modified rosin obtained by reacting 1 mol of fumaric acid with 0.7 mol of rosin. Y represents the SP value of rosin.

  Here, the SP value is a softening point measured by a ring and ball automatic softening point tester, and specifically, a value measured by the method described above.

The method for producing the fumaric acid-modified rosin is not particularly limited. For example, rosin and fumaric acid are mixed and heated to 180 ° C. or higher and 260 ° C. or lower (preferably 180 ° C. or higher and 210 ° C. or lower) to obtain Diels-Alder. By the reaction, fumaric acid is added to an acid having a conjugated double bond contained in rosin to obtain a fumaric acid-modified rosin.
The fumaric acid-modified rosin may be used as it is after the reaction, or may be used after purification through an operation such as distillation.

  In the method for producing a fumaric acid-modified rosin, the rosin and fumaric acid are preferably reacted in the presence of phenols. The reaction efficiency between rosin and fumaric acid is easily improved.

Preferable examples of phenols include divalent phenols and phenolic compounds having a substituent at least in the ortho position with respect to a hydroxyl group (hereinafter, hindered phenols), preferably hindered phenols.
The divalent phenol is a compound in which two OH groups are bonded to a benzene ring and has no other substituent. Specifically, for example, hydroquinone is preferably exemplified.
Specific examples of the hindered phenol include t-butylcatechol.

  The amount of phenol used is preferably 0.001 part by mass or more and 0.5 part by mass, preferably 0.003 part by mass or more and 0.1 part by mass or less, with respect to 100 parts by mass of the raw material monomer of fumaric acid-modified rosin. More desirably, it is 0.005 parts by mass or more and 0.1 parts by mass or less.

Maleic acid-modified rosin is rosin modified with maleic acid or maleic anhydride.
Specific examples of the maleic acid-modified rosin include those obtained by addition reaction of maleic acid or maleic anhydride to the rosin before modification, and more specifically, for example, the main rosin before modification. It is obtained through a Diels-Alder reaction under heating with an acid having a conjugated double bond and maleic acid or maleic anhydride.

  In the maleic acid-modified rosin, the degree of modification of rosin with maleic acid or maleic anhydride (hereinafter, maleic acid modification degree) is preferably 30 or more and 105 or less from the viewpoint of increasing the molecular weight of the polyester and reducing the low molecular weight oligomer component. It is preferably 40 or more and 105 or less, more preferably 50 or more and 105 or less, further preferably 60 or more and 105 or less, and particularly preferably 70 or more and 105 or less.

The maleic acid modification degree Xm is calculated by the following formula (Am). In addition, it shows that the degree of modification | denaturation is so high that the value of Formula (Am) is large.
Formula (Am): Xm = [(Xm1-Y) / (Xm2-Y)] × 100
In the formula (Am), Xm1 represents the SP value of maleic acid-modified rosin for calculating the degree of modification. Xm2 represents a saturated SP value of maleic acid-modified rosin obtained by reacting 1 mol of maleic acid with 1 mol of rosin at 230 ° C. Y represents the SP value of rosin.

Here, the SP value is a softening point measured by a ring and ball automatic softening point tester, and specifically, a value measured by the method described above.
The saturated SP value is the SP value when the reaction of maleic acid and rosin is reacted until the SP value of the resulting maleic acid-modified rosin reaches the saturation value.

Although it does not specifically limit as a manufacturing method of maleic acid modification rosin, For example, rosin before modification and maleic acid or maleic anhydride are mixed, and it is 80 ° C or more and 260 ° C or less (desirably 180 ° C or more and 210 ° C or less) By heating, maleic acid or maleic anhydride is added to an acid having a conjugated double bond contained in rosin by Diels-Alder reaction to obtain maleic acid-modified rosin.
The maleic acid-modified rosin may be used as it is after the above reaction, or may be used after purification through an operation such as distillation.

The production method and modification degree of itaconic acid-modified rosin and citraconic acid-modified rosin can be similarly synthesized and calculated.

  These carboxylic acid-modified rosins are preferably contained in an amount of 5 to 70% by mass (desirably 10 to 60% by mass) with respect to the total polyvalent carboxylic acid component.

-Other polycarboxylic acids-
As another polyvalent carboxylic acid, a dicarboxylic acid is preferably exemplified. Examples of the dicarboxylic acid include at least one selected from the group consisting of aromatic dicarboxylic acids and aliphatic dicarboxylic acids. For example, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid; oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid , Glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dimer acid, alkyl succinic acid having 1 to 20 carbon atoms having a branched chain, alkenyl having an alkenyl group having 1 to 20 carbon atoms having a branched chain Aliphatic dicarboxylic acids such as succinic acid; anhydrides of these acids and alkyl (1 to 3 carbon atoms) esters of these acids. Among these, aromatic dicarboxylic acids are desirable from the viewpoints of toner durability, fixability, and colorant dispersibility.

  Other polyvalent carboxylic acids include trivalent or higher polyvalent carboxylic acids. Examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid, pyromellitic acid, and citric acid.

(Alcohol component)
-Cyclic sugar alcohol-
The cyclic sugar alcohol is a polyhydric alcohol containing at least one hetero element (for example, oxygen, nitrogen, sulfur, etc.).
Specifically, examples of the cyclic sugar alcohol include polyhydric alcohols having a cyclic structure containing a hetero element and two or more hydroxyl groups.
Among these, from the viewpoint of suppressing deterioration of fluidity after storage in a high-humidity environment in an electrostatic charge image developing toner, as the cyclic sugar alcohol, for example, a cyclic structure containing a hetero element, two hydroxyl groups, A polyhydric alcohol having

  Specific examples of the cyclic sugar alcohol include, for example, isosorbide (1,4-3,6-dianhydrosorbitol), isoidide (1,4-3,6-dianhydroiditol), isomannide (1,4-3, 6 dianhydromannitol), isoitide, isogalactide, and the like. In particular, isosorbide and isoidide are preferable from the viewpoint of suppressing deterioration of fluidity after storage in a high humidity environment in an electrostatic charge image developing toner.

  The cyclic sugar alcohol may be contained in an amount of 5 to 50% by mass (desirably 10 to 40% by mass) with respect to the total alcohol components.

-Polyhydric alcohol containing rosin-
A preferred example of the polyhydric alcohol containing rosin is a diol containing rosin (hereinafter, rosin diol).
Here, the rosin diol is preferably a dialcohol compound containing rosin as two rosin ester groups in one molecule. The rosin ester group means a residue obtained by removing a hydrogen atom from a carboxyl group contained in rosin.

Rosin diol is synthesized by a known method, for example, by reaction between rosin and a bifunctional epoxy compound.
The rosin used for the synthesis is the same as the rosin used as a polycondensation component of the polyester resin.

  The reaction between rosin and the bifunctional epoxy compound proceeds mainly by a ring-opening reaction between the carboxyl group of rosin and the epoxy group of the bifunctional epoxy compound. At that time, the reaction temperature is preferably higher than the melting temperature of both components or a temperature at which uniform mixing is realized, and specifically, a range of 60 ° C. or higher and 200 ° C. or lower is common. In the reaction, a catalyst for promoting the ring-opening reaction of the epoxy group may be added.

  Catalysts used for the reaction of rosin with bifunctional epoxy compounds include amines such as ethylenediamine, trimethylamine and 2-methylimidazole, quaternary ammonium salts such as triethylammonium bromide, triethylammonium chloride and butyltrimethylammonium chloride, and triphenyl. And phosphine.

  The reaction between the rosin and the bifunctional epoxy compound can be carried out by various methods. In general, in the case of a batch system, heating with a cooling pipe, a stirring device, an inert gas inlet, a thermometer, etc. can be performed. The flask is charged with rosin and a bifunctional epoxy compound at a desired ratio, heated and melted, and the reaction product is sampled by following the reaction. The degree of progress of the reaction can be confirmed mainly by a decrease in the acid value, and the reaction is completed when it reaches the stoichiometric end point or near the end point.

  The reaction ratio of rosin and bifunctional epoxy compound is not particularly limited, but the molar ratio of rosin and bifunctional epoxy compound is 1.5 mol or more and 2.5 mol or less of rosin with respect to 1 mol of bifunctional epoxy compound. It is desirable to make it react in this range.

  The bifunctional epoxy compound is a bifunctional epoxy compound containing two epoxy groups in one molecule, and examples of the bifunctional aromatic epoxy compound include diglycidyl ether of aromatic diol and diglycidyl ether of aromatic dicarboxylic acid. Examples of the bifunctional aliphatic epoxy compound include diglycidyl ether of chain aliphatic diol, diglycidyl ether of alicyclic diol, and alicyclic epoxide.

  Representative examples of diglycidyl ethers of aromatic diols include bisphenol A, bisphenol A derivatives such as bisphenol A polyalkylene oxide adducts, and bisphenol F derivatives such as bisphenol F and bisphenol F polyalkylene oxide adducts. Bisphenol S, derivatives of bisphenol S such as polyalkylene oxide adducts of bisphenol S, resorcinol, t-butylcatechol, biphenol and the like.

  Representative examples of diglycidyl ethers of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid and the like.

  Typical examples of diglycidyl ethers of chain aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Hexanediol, neopentyl glycol, 1,9-nonanediol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.

  Representative examples of diglycidyl ethers of alicyclic diols include hydrogenated bisphenol A, hydrogenated bisphenol A derivatives such as hydrogenated bisphenol A polyalkylene oxide adducts, and cyclohexanedimethanol.

  A representative example of the alicyclic epoxide is limonene dioxide.

  The bifunctional epoxy compound can be obtained, for example, by a reaction between a diol and epihalohydrin, and may be polycondensed to have a high molecular weight depending on the amount ratio.

  Although the exemplary compound of rosin diol is shown below, this embodiment is not limited to these.

  In the exemplified compound of rosin diol, n represents an integer of 1 or more.

  Rosin diol (polyhydric alcohol containing rosin) is preferably contained in an amount of 15 to 98% by mass (desirably 20 to 95% by mass) with respect to the total alcohol components.

-Other polyhydric alcohols-
Examples of the other polyhydric alcohol include at least one selected from the group consisting of aliphatic diols and etherified diphenols.
Examples of the aliphatic diol include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3 -Butanediol, 1,4-butenediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 2-ethyl-2-methylpropane-1,3-diol, 2- Butyl-2-ethylpropane-1,3-diol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,4-dimethyl-1, 5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1, -Nonanediol, 1,10-decanediol, 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethylpropanoate, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol Etc. These aliphatic diols may be used alone or in combination of two or more.
Etherified diphenol is a diol obtained by addition reaction of bisphenol A and alkylene oxide. Examples of the alkylene oxide include ethylene oxide and propylene oxide. The average added mole number of the alkylene oxide is 1 of bisphenol A. What is 2 mol or more and 16 mol or less with respect to mol is desirable.

(Production method of polyester resin)
The polyester resin according to this embodiment is prepared by a known and commonly used production method using polyvalent carboxylic acid and polyhydric alcohol as raw materials. As the reaction method, either transesterification reaction or direct esterification reaction may be applied. Further, polycondensation may be promoted by a method of increasing the reaction temperature by pressurization, a method of reducing the pressure, or a method of flowing an inert gas under normal pressure. Depending on the above reaction, a known and commonly used reaction catalyst such as at least one metal compound selected from antimony, titanium, tin, zinc, aluminum and manganese may be used to accelerate the reaction. The addition amount of these reaction catalysts is preferably 0.01 parts by mass or more and 1.5 parts by mass or less, and 0.05 parts by mass or more and 1.0 parts by mass with respect to 100 parts by mass of the total amount of polyvalent carboxylic acid and polyhydric alcohol The following is more desirable. The reaction temperature is, for example, 180 ° C. or higher and 300 ° C. or lower.

  In addition, when the polyester resin which concerns on this embodiment is hydrolyzed, it will decompose | disassemble into each monomer (a polyhydric carboxylic acid component and a polyhydric alcohol component). Since the polyester resin is, for example, a 1: 1 condensate of a polyvalent carboxylic acid (for example, dicarboxylic acid) and a polyhydric alcohol (for example, diol), the configuration of the resin is estimated from the decomposed product.

(Characteristics of polyester resin)
The weight average molecular weight of the polyester resin according to the exemplary embodiment is preferably 4000 or more and 1000000 or less, and more preferably 7000 or more and 300000 or less, from the viewpoint of toner durability and offset resistance.

The weight average molecular weight of the polyester resin is measured by the following method.
Two “HLC-8120GPC, SC-8020 (6.0 mm ID × 15 cm) manufactured by Tosoh Corporation” were used, and THF (tetrahydrofuran) was used as an eluent. As experimental conditions, the sample concentration is 0.5%, the flow rate is 0.6 ml / min, the sample injection amount is 10 μl, the measurement temperature is 40 ° C., and the measurement is performed using an RI detector. The calibration curve is “Polystyrene standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A” -2500 "," F-4 "," F-40 "," F-128 ", and" F-700 ".

The softening temperature of the polyester resin according to the exemplary embodiment is preferably 80 ° C. or higher and 160 ° C. or lower, and more preferably 90 ° C. or higher and 150 ° C. or lower, from the viewpoints of toner fixability, storage stability, and durability.
As for the softening temperature, Koka-type flow tester CFT-500 (manufactured by Shimadzu Corporation) was used, the diameter of the pores of the die was 0.5 mm, the pressure load was 0.98 MPa (10 Kg / cm 2), and the heating rate. Is obtained as a temperature corresponding to ½ of the height from the start point to the end point when a 1 cm 3 sample is melted and flowed out under the condition of 1 ° C./min.

The glass transition temperature of the polyester resin according to this embodiment is preferably 35 ° C. or higher and 80 ° C. or lower, and more preferably 40 ° C. or higher and 70 ° C. or lower from the viewpoints of fixability, storage stability, and durability. The softening temperature and glass transition temperature are easily adjusted by adjusting the raw material monomer composition, polymerization initiator, molecular weight, catalyst amount, etc., or by selecting reaction conditions.
The glass transition temperature is measured by using “DSC-20” (manufactured by Seiko Denshi Kogyo Co., Ltd.) and heating 10 mg of a sample at a constant heating rate (10 ° C./min).

The acid value of the polyester resin according to the exemplary embodiment is preferably 1 mgKOH / g or more and 50 mgKOH / g or less, and more preferably 3 mgKOH / g or more and 30 mgKOH / g or less from the viewpoint of chargeability of the toner.
The acid value is determined according to JIS K0070 and measured by a neutralization titration method. That is, an appropriate amount of a sample is taken, 100 ml of a solvent (diethyl ether / ethanol mixed solution) and a few drops of an indicator (phenolphthalein solution) are added, and shaken sufficiently until the sample is completely dissolved in a water bath. This was titrated with a 0.1 mol / l potassium hydroxide ethanol solution, and the end point was when the indicator was light red for 30 seconds. When the acid value is A, the sample amount is S (g), the 0.1 mol / l potassium hydroxide ethanol solution used for the titration is B (ml), and f is the factor of the 0.1 mol / l potassium hydroxide ethanol solution. , A = (B × f × 5.611) / S.

  The polyester resin according to the present embodiment may be a modified polyester. Examples of the modified polyester include grafting and blocking with phenol, urethane, epoxy and the like by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. Polyester.

[Electrostatic image developing toner]
The electrostatic charge image developing toner according to the present embodiment (hereinafter sometimes referred to as “toner”) includes the polyester resin according to the present embodiment.

  Hereinafter, details of the toner according to the exemplary embodiment will be described.

  The toner according to the exemplary embodiment includes, for example, toner particles and, if necessary, external additives.

(Toner particles)
The toner particles will be described.
The toner particles include a binder resin and, if necessary, a colorant, a release agent, and other additives.
The binder resin includes an amorphous resin, and the polyester resin according to the present embodiment is applied as the amorphous resin.
As the binder resin, a crystalline resin may be used in combination with the amorphous resin.
As the binder resin, other amorphous resins other than the polyester resin according to the present embodiment may be used together with the polyester resin according to the present embodiment.
However, the content of the polyester according to the present embodiment is desirably 70 parts by mass or more and more desirably 90 parts by mass or more with respect to 100 parts by mass of the total binder resin.

Here, the amorphous resin is not a clear endothermic peak but a stepwise endothermic change in thermal analysis using differential scanning calorimetry (DSC). A solid that is thermoplasticized at a temperature above the glass transition temperature.
On the other hand, the crystalline resin means a resin having a clear endothermic peak instead of a stepwise endothermic amount change in differential scanning calorimetry (DSC).
Specifically, for example, the crystalline resin means that the half-value width of the endothermic peak when measured at a heating rate of 10 ° C./min is within 10 ° C., and the amorphous resin means the half-value width. Means a resin having a temperature exceeding 10 ° C. or a resin having no clear endothermic peak.

Examples of the crystalline resin include crystalline polyester resins, polyalkylene resins, and long-chain alkyl (meth) acrylate resins. However, a sharp change in viscosity due to heating appears more, and mechanical strength and low-temperature fixability From the viewpoint of achieving both, a crystalline polyester resin is desirable.
The crystalline polyester resin is preferably a condensation polymer of an aliphatic dicarboxylic acid (including its acid anhydride and acid chloride) and an aliphatic diol, for example, from the viewpoint of realizing low-temperature fixability.
The content of the crystalline resin is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the total binder resin.
In the present embodiment, the low temperature fixing means that the toner is heated and fixed at about 120 ° C. or less.

  Other non-crystalline resins include known binder resins such as vinyl resins such as styrene-acrylic resins, other resins such as epoxy resins, polycarbonates, and polyurethanes.

-Colorant-
The colorant may be, for example, a dye or a pigment, but a pigment is desirable from the viewpoint of light resistance and water resistance.
Examples of the colorant include carbon black, aniline black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lamp black, and rose bengal. Quinacridone, benzicine yellow, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 185, C.I. I. Pigment red 238, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 74, C.I. I. Pigment blue 15: 1, C.I. I. A known pigment such as CI Pigment Blue 15: 3 may be used.

As the colorant, a surface-treated colorant may be used as necessary, or a pigment dispersant may be used.
By selecting the type of colorant, yellow toner, magenta toner, cyan toner, black toner and the like can be obtained.

  As content of a coloring agent, the range of 1 to 30 mass parts is desirable with respect to 100 mass parts of binder resin.

-Release agent-
Examples of the release agent include paraffin wax such as low molecular weight polypropylene and low molecular weight polyethylene; silicone resin; rosins; rice wax; carnauba wax; The melting temperature of these release agents is preferably 50 ° C. or higher and 100 ° C. or lower, and more preferably 60 ° C. or higher and 95 ° C. or lower.

The content of the release agent is desirably 0.5 parts by mass or more and 15 parts by mass or less, and more desirably 1.0 part by mass or more and 12 parts by mass or less with respect to 100 parts by mass of the binder resin.
When the content of the release agent is 0.5% by mass or more, the occurrence of defective peeling is prevented particularly in oilless fixing. When the content of the release agent is 15% by mass or less, the fluidity of the toner is not deteriorated, and the image quality and the reliability of image formation are improved.

-Other additives-
Known charge control agents may be used, but azo metal complex compounds, metal complex compounds of salicylic acid, and resin type charge control agents containing polar groups may be used.

-Toner particle characteristics-
The toner particles may be toner particles having a single layer structure, or toner particles having a so-called core / shell structure composed of a core (core particle) and a coating layer (shell layer) covering the core. May be.
The toner particles having a core / shell structure include, for example, a binder resin (the polyester resin and the crystalline polyester resin according to the present embodiment) and, if necessary, other additives such as a colorant and a release agent. It is good to be comprised by the core part and the coating layer comprised including binder resin (polyester resin which concerns on this embodiment).

The volume average particle size of the toner particles is, for example, preferably from 2.0 μm to 10 μm, and more preferably from 3.5 μm to 7.0 μm.
As a method for measuring the volume average particle diameter of the toner particles, 0.5 mg to 50 mg of a measurement sample is added to 2 ml of a 5% by weight aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate as a dispersant. The electrolyte was added to 100 ml to 150 ml. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the above-mentioned Coulter Multisizer II type (manufactured by Beckman-Coulter) is used to produce particles using an aperture having an aperture diameter of 100 μm. The particle size distribution of particles having a diameter in the range of 2.0 μm to 60 μm is measured. The number of particles to be measured is 50,000.
For the particle size range (channel) obtained by dividing the obtained particle size distribution, the volume cumulative distribution is subtracted from the small particle size side, and the particle size that becomes 50% cumulative is defined as the volume average particle size D50v.

The shape factor SF1 of the toner particles is, for example, preferably from 110 to 150, and preferably from 120 to 140.
Here, the shape factor SF1 is obtained by the following equation (1).
SF1 = (ML ² / A) × (π / 4) × 100 (1)
In the above formula (1), ML represents the absolute maximum length of the toner, and A represents the projected area of the toner.

  SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and is calculated as follows, for example. That is, an optical microscope image of particles scattered on the surface of the slide glass is taken into a Luzex image analyzer through a video camera, and the maximum length and projected area of 100 particles are obtained, calculated by the above equation (1), and the average value is calculated. It is obtained by seeking.

(External additive)
Examples of the external additive include inorganic particles. Examples of the inorganic particles include SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, and CaO. , K ₂ O, Na ₂ O, ZrO ₂ , CaO.SiO ₂ , K ₂ O. (TiO ₂ ) _n , Al ₂ O ₃ .2SiO ₂ , CaCO ₃ , MgCO ₃ , BaSO ₄ , MgSO _{4 and the} like. .

The surface of the inorganic particles as an external additive may be previously hydrophobized. The hydrophobic treatment is performed, for example, by immersing inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents and the like. These may be used individually by 1 type and may use 2 or more types together.
The amount of the hydrophobizing agent is usually about 1 part by mass or more and about 10 parts by mass with respect to 100 parts by mass of the inorganic particles, for example.

  Examples of external additives include resin particles (resin particles such as polystyrene, PMMA, and melamine resin), cleaning activators (for example, metal salts of higher fatty acids typified by zinc stearate, and particles of fluorine-based high molecular weight particles). Also mentioned.

  The external addition amount of the external additive is, for example, preferably 0.01 parts by mass or more and 5 parts by mass or less, more preferably 0.01 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the toner particles. It is.

(Toner production method)
Hereinafter, a toner manufacturing method according to the exemplary embodiment will be described.
First, toner particles may be produced by a dry process (for example, a kneading and pulverization method), a wet process (for example, an aggregation coalescence method, a suspension polymerization method, a solution suspension granulation method, a solution suspension method, a solution emulsion aggregation method, or the like. ). There is no restriction | limiting in particular in these manufacturing methods, A well-known manufacturing method is employ | adopted.
Among these, it is preferable to obtain toner particles by an aggregation and coalescence method.

Specifically, it is as follows.
In the following description, a method of obtaining toner particles containing a colorant and a release agent will be described. However, the colorant and the release agent are used as necessary. Of course, you may use other additives other than a coloring agent and a mold release agent.

-Preparation step of resin particle dispersion-
First, together with a resin particle dispersion in which polyester resin particles are dispersed, for example, a colorant particle dispersion in which colorant particles are dispersed and a release agent dispersion in which release agent particles are dispersed are prepared.

  Here, the resin particle dispersion is prepared, for example, by dispersing polyester resin particles in a dispersion medium with a surfactant.

Examples of the dispersion medium used for the resin particle dispersion include an aqueous medium.
Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together.

The surfactant is not particularly limited. For example, anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; amine salt type, quaternary ammonium salt type Nonionic surfactants such as polyethylene glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based, and the like. Among these, an anionic surfactant and a cationic surfactant are particularly mentioned. The nonionic surfactant may be used in combination with an anionic surfactant or a cationic surfactant.
Surfactant may be used individually by 1 type and may use 2 or more types together.

Examples of a method for dispersing polyester resin particles in a dispersion medium in a resin particle dispersion include general dispersion methods such as a rotary shearing homogenizer, a ball mill having a medium, a sand mill, and a dyno mill. Further, depending on the type of resin particles used, the resin particles may be dispersed in the resin particle dispersion using, for example, a phase inversion emulsification method.
The phase inversion emulsification method is a method in which a resin to be dispersed is dissolved in a hydrophobic organic solvent in which the resin is soluble, and a base is added to the organic continuous phase (O phase) to neutralize the aqueous medium. (W phase) is added to convert the resin from W / O to O / W (so-called phase inversion) to form a discontinuous phase and disperse the resin in an aqueous medium in the form of particles. It is.

Examples of the volume average particle diameter of the polyester resin particles dispersed in the resin particle dispersion include a range of 0.01 μm or more and 1 μm or less, and may be 0.08 μm or more and 0.8 μm or less, or 0.1 μm or more. It may be 0.6 μm.
The volume average particle diameter of the resin particles is measured with a laser diffraction particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.). Hereinafter, unless otherwise specified, the volume average particle diameter of the particles is measured in the same manner.

  Examples of the content of the polyester resin particles contained in the resin particle dispersion include 5% by mass to 50% by mass, and may be 10% by mass to 40% by mass.

  In addition, similarly to resin particle dispersion, for example, a colorant dispersion and a release agent dispersion are also prepared. In other words, regarding the volume average particle size of the particles in the resin particle dispersion, the dispersion medium, the dispersion method, and the content of the particles, the colorant particles dispersed in the colorant dispersion and the release agent dispersed in the release agent dispersion are used. The same applies to the mold agent particles.

-Aggregated particle formation process-
Next, the colorant particle dispersion and the release agent dispersion are mixed together with the resin particle dispersion.
The polyester resin particles, the colorant particles, and the release agent particles are hetero-aggregated in the mixed dispersion to have a diameter close to the diameter of the target toner particles, and the polyester resin particles, the colorant particles, and the release agent particles. And agglomerated particles are formed.

Specifically, for example, a flocculant is added to the mixed dispersion, and the pH of the mixed dispersion is adjusted to acidic (for example, pH is 2 or more and 5 or less), and a dispersion stabilizer is added as necessary. Thereafter, the polyester resin particles are heated to a glass transition temperature (specifically, for example, a glass transition temperature of the polyester resin particles of −30 ° C. or higher and a glass transition temperature of −10 ° C. or lower), and the particles dispersed in the mixed dispersion liquid. Are aggregated to form aggregated particles.
In the agglomerated particle forming step, for example, the aggregating agent is added at room temperature (for example, 25 ° C.) while stirring the mixed dispersion with a rotary shearing homogenizer, and the pH of the mixed dispersion is acidic (for example, the pH is 2 or more and 5 or less). ), And after adding a dispersion stabilizer as necessary, the heating may be performed.

Examples of the flocculant include surfactants having a polarity opposite to that of the surfactant used as the dispersant added to the mixed dispersion, for example, inorganic metal salts and divalent or higher-valent metal complexes. In particular, when a metal complex is used as the flocculant, the amount of the surfactant used is reduced, and the charging characteristics are improved.
If necessary, an additive that forms a complex or a similar bond with the metal ion of the flocculant may be used. As this additive, a chelating agent is preferably used.

Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include metal salt polymers.
A water-soluble chelating agent may be used as the chelating agent. Examples of the chelating agent include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, iminodiacid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), and the like.
Examples of the addition amount of the chelating agent include a range of 0.01 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the polyester resin particles, and 0.1 parts by mass or more and less than 3.0 parts by mass. It may be.

-Fusion / unification process-
Next, the aggregated particle dispersion in which the aggregated particles are dispersed is heated to, for example, a glass transition temperature or higher of the polyester resin particles (for example, a temperature of 10 to 30 ° C. higher than the glass transition temperature of the polyester resin particles), The aggregated particles are fused and united to form toner particles.

Through the above steps, toner particles are obtained.
In addition, after obtaining the aggregated particle dispersion in which the aggregated particles are dispersed, the aggregated particle dispersion and the resin particle dispersion in which the polyester resin particles (the polyester resin particles according to the present embodiment) are further dispersed Mixing and aggregating the polyester resin particles on the surface of the agglomerated particles to form second agglomerated particles, and heating the second agglomerated particle dispersion in which the second agglomerated particles are dispersed. Then, the toner particles may be produced through a process of fusing and coalescing the second aggregated particles to form toner particles having a core / shell structure.

Here, after completion of the fusion / unification process, toner particles formed in the solution are dried through a known washing process, solid-liquid separation process, and drying process to obtain toner particles.
In the washing step, it is desirable to sufficiently perform substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, etc. are preferably used from the viewpoint of productivity. Furthermore, the drying process is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used.

  The toner according to the exemplary embodiment is manufactured, for example, by adding an external additive to the obtained dry toner particles and mixing them. Mixing is preferably performed by, for example, a V blender, a Henshur mixer, a ladyge mixer or the like. Further, if necessary, coarse toner particles may be removed using a vibration classifier, a wind classifier, or the like.

[Static charge image developer]
The electrostatic charge image developer according to the exemplary embodiment includes at least the toner according to the exemplary embodiment.
The electrostatic image developer according to this embodiment may be a one-component developer including only the toner according to this embodiment, or may be a two-component developer mixed with the toner and a carrier.

  There is no restriction | limiting in particular as a carrier, A well-known carrier is mentioned. Examples of the carrier include a resin-coated carrier, a magnetic dispersion carrier, a resin dispersion carrier, and the like.

  In the two-component developer, the mixing ratio (mass ratio) of the toner according to the exemplary embodiment and the carrier is preferably in the range of toner: carrier = 1: 100 to 30: 100, and about 3: 100 to 20: 100. The range of is more desirable.

[Image Forming Apparatus / Image Forming Method]
Next, the image forming apparatus / image forming method according to the present embodiment will be described.
An image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the image carrier, an electrostatic image forming unit that forms an electrostatic image on the surface of the charged image carrier, and an electrostatic image development. A developing means for accommodating the developer and developing the electrostatic image formed on the image carrier as a toner image by the electrostatic image developer, and transferring the toner image formed on the image carrier onto the transfer target And a fixing unit that fixes the toner image transferred onto the transfer target. The electrostatic image developer according to the present embodiment is applied as the electrostatic image developer.

  In the image forming apparatus according to the present embodiment, for example, the part including the developing unit may have a cartridge structure (process cartridge) that is detachable from the image forming apparatus. As the process cartridge, for example, A process cartridge that accommodates the electrostatic charge image developer according to the exemplary embodiment and includes a developing unit is preferably used.

  The image forming method according to the present embodiment contains a charging step for charging the image carrier, an electrostatic charge image forming step for forming an electrostatic charge image on the surface of the charged image carrier, and an electrostatic charge image developer. A developing step of developing the electrostatic image formed on the image carrier as a toner image with an electrostatic charge image developer, and a transfer step of transferring the toner image formed on the image carrier onto the transfer target; And a fixing step of fixing the toner image transferred onto the transfer medium. The electrostatic image developer according to the present embodiment is applied as the electrostatic image developer.

  Hereinafter, an example of the image forming apparatus according to the present embodiment will be described, but the present invention is not limited thereto. The main parts shown in the figure will be described, and the description of the other parts will be omitted.

  FIG. 1 is a schematic configuration diagram showing a four-tandem color image forming apparatus. The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter sometimes simply referred to as “units”) 10Y, 10M, 10C, and 10K are arranged in parallel at a predetermined distance from each other in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the main body of the image forming apparatus.

Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a driving roller 22 and a support roller 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other from the left to the right in the drawing. The vehicle travels in the direction toward the unit 10K. A force is applied to the support roller 24 in a direction away from the drive roller 22 by a spring or the like (not shown), and tension is applied to the intermediate transfer belt 20 wound around the both. Further, an intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the driving roller 22.
Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of the units 10Y, 10M, 10C, and 10K has yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The toner including the four color toners is supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K described above have the same configuration, here, the first image that forms the yellow image disposed on the upstream side in the intermediate transfer belt traveling direction is formed. The unit 10Y will be described as a representative. Note that the second to fourth components are denoted by reference numerals with magenta (M), cyan (C), and black (K) instead of yellow (Y) in the same parts as the first unit 10Y. Description of the units 10M, 10C, and 10K will be omitted.

The first unit 10Y includes a photoreceptor 1Y that functions as an image holding member. Around the photosensitive member 1Y, a charging roller 2Y for charging the surface of the photosensitive member 1Y to a predetermined potential, and the charged surface is exposed by a laser beam 3Y based on the color-separated image signal to form an electrostatic charge image. An exposure device (electrostatic image forming means) 3 for forming, a developing device (developing means) 4Y for supplying the charged toner to the electrostatic image and developing the electrostatic image, and transferring the developed toner image onto the intermediate transfer belt 20 A primary transfer roller 5Y (primary transfer unit) that performs the transfer and a photoconductor cleaning device (cleaning unit) 6Y that removes toner remaining on the surface of the photoconductor 1Y after the primary transfer are sequentially arranged.
The primary transfer roller 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rollers 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roller under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described. First, prior to the operation, the surface of the photoreceptor 1Y is charged to a potential of about −600V to −800V by the charging roller 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate (volume resistivity at 20 ° C .: 1 × 10 −6 Ωcm or less). This photosensitive layer usually has a high resistance (a resistance equivalent to that of a general resin), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, a laser beam 3Y is output to the surface of the charged photoreceptor 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic charge image of a yellow print pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic charge image is an image formed on the surface of the photoreceptor 1Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam 3Y, and the charged charge on the surface of the photoreceptor 1Y flows. On the other hand, this is a so-called negative latent image formed by the charge remaining in the portion not irradiated with the laser beam 3Y.
The electrostatic charge image formed on the photoreceptor 1Y in this way is rotated to a predetermined development position as the photoreceptor 1Y travels. At this development position, the electrostatic charge image on the photoreceptor 1Y is visualized (developed image) by the developing device 4Y.

  In the developing device 4Y, for example, an electrostatic charge image developer according to the present embodiment including at least yellow toner and a carrier is accommodated. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged charge on the photoreceptor 1Y, and a developer roll (developer holder). Is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image is developed with the yellow toner. . The photoreceptor 1Y on which the yellow toner image is formed continues to run at a predetermined speed, and the toner image developed on the photoreceptor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoreceptor 1Y is conveyed to the primary transfer, a primary transfer bias is applied to the primary transfer roller 5Y, and an electrostatic force from the photoreceptor 1Y toward the primary transfer roller 5Y acts on the toner image. Then, the toner image on the photoreceptor 1Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time is a (+) polarity opposite to the polarity (−) of the toner, and is controlled to about +10 μA by the control unit (not shown) in the first unit 10Y, for example.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rollers 5M, 5C, and 5K after the second unit 10M is also controlled according to the first unit.
Thus, the intermediate transfer belt 20 onto which the yellow toner image has been transferred by the first unit 10Y is sequentially conveyed through the second to fourth units 10M, 10C, and 10K, and the toner images of the respective colors are superimposed and transferred in a multiple manner. The

  The intermediate transfer belt 20 onto which the four color toner images have been transferred in multiple layers through the first to fourth units is arranged on the image transfer surface side of the intermediate transfer belt 20, the support roller 24 in contact with the inner surface of the intermediate transfer belt 20. The secondary transfer roller (secondary transfer means) 26 is connected to a secondary transfer portion. On the other hand, the recording paper (transfer object) P is fed at a predetermined timing to the gap where the secondary transfer roller 26 and the intermediate transfer belt 20 are pressed against each other via the supply mechanism, and the secondary transfer bias is supported. Applied to the roller 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording paper P is applied to the toner image, so The toner image is transferred onto the recording paper P. Note that the secondary transfer bias at this time is determined according to the resistance detected by a resistance detecting means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

  Thereafter, the recording paper P is sent to the pressure contact portions (nip portions) of the pair of fixing rolls in the fixing device (roll-type fixing unit) 28, and the toner image is fixed on the recording paper P, thereby forming a fixed image.

Examples of the transfer target to which the toner image is transferred include plain paper, OHP sheet, and the like used for electrophotographic copying machines and printers.
In order to further improve the smoothness of the image surface after fixing, it is desirable that the surface of the transfer target is also smooth. For example, coated paper in which the surface of plain paper is coated with resin, art paper for printing, etc. Preferably used.

The recording paper P on which the color image has been fixed is carried out toward the discharge unit, and a series of color image forming operations is completed.
The image forming apparatus exemplified above is configured to transfer the toner image onto the recording paper P via the intermediate transfer belt 20, but is not limited to this configuration, and the toner image is directly transferred from the photoreceptor. It may be a structure that is transferred to a recording sheet.

(Process cartridge, toner cartridge)
FIG. 2 is a schematic configuration diagram showing an embodiment of a preferred example of a process cartridge containing an electrostatic charge image developer according to this embodiment. In the process cartridge 200, a charging roller 108, a developing device 111, a photoconductor cleaning device 113, an opening 118 for exposure, and an opening 117 for static elimination exposure are combined using a mounting rail 116 together with the photoconductor 107. , And integrated. In FIG. 2, reference numeral 300 denotes a transfer target.
The process cartridge 200 is detachable from an image forming apparatus including a transfer device 112, a fixing device 115, and other components not shown.

  The process cartridge 200 shown in FIG. 2 includes a charging device 108, a developing device 111, a cleaning device 113, an opening 118 for exposure, and an opening 117 for static elimination exposure. May be combined. In the process cartridge according to the present embodiment, in addition to the photosensitive member 107, the charging device 108, the developing device 111, the cleaning device (cleaning means) 113, the opening 118 for exposure, and the opening 117 for static elimination exposure. At least one selected from the group consisting of:

  Next, the toner cartridge according to this embodiment will be described. The toner cartridge according to the present exemplary embodiment is a toner cartridge that is detachably attached to the image forming apparatus and stores at least a replenishment electrostatic charge image developing toner to be supplied to a developing unit provided in the image forming apparatus.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which toner cartridges 8Y, 8M, 8C, and 8K are attached and detached, and the developing devices 4Y, 4M, 4C, and 4K are each developing device (color And a toner supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge becomes low, the toner cartridge is replaced.

  Hereinafter, although an example is given and this embodiment is explained concretely, this embodiment is not limited only to an example shown below. In the examples, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.

[Synthesis of carboxylic acid-modified rosin]
(Synthesis of fumaric acid-modified rosin)
A 2 L flask was charged with 500 g of tall rosin and 100 g of fumaric acid, fitted with a fractionation tube and a condenser tube, and reacted at 200 ° C. for 4 hours to obtain a fumaric acid-modified rosin (fumaric acid-modified abitienic acid).
The characteristic of the obtained fumaric acid-modified rosin was a degree of modification of 85.

[Synthesis of carboxylic acid-modified rosin]
(Synthesis of maleic acid-modified rosin)
To a 2 L flask, 500 g of purified rosin and 100 g of maleic anhydride were added and reacted at 220 ° C. for 7 hours. The degree of maleic acid modification was 100.

[Synthesis of rosin diol]
(Synthesis of Rosindiol A (Exemplary Compound (18)))
113 g of bisphenol A diglycidyl ether (trade name jER828, manufactured by Mitsubishi Chemical Corporation) as a bifunctional epoxy compound, 200 g of disproportionated rosin (trade name Pine Crystal KR614, manufactured by Arakawa Chemical Industries, Ltd.) as a rosin, and reaction catalyst Tetraethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged into a stainless steel reaction vessel equipped with a stirrer, heating device, cooling tube and thermometer, the temperature was raised to 130 ° C., and the rosin acid group and epoxy compound epoxy A ring-opening reaction with the group was carried out. The reaction was continued for 4 hours at the same temperature, and when the acid value reached 0.5 mgKOH / g, the reaction was stopped to obtain rosindiol A.

(Rosindiol B (Synthesis of Exemplified Compound (33))
110 g of hydrogenated bisphenol A diglycidyl ether (trade name Denacol EX252 manufactured by Nagase Chemtech) as the bifunctional epoxy compound, 200 g of disproportionated rosin (trade name Pine Crystal KR614, manufactured by Arakawa Chemical Industries, Ltd.) as the rosin, and reaction catalyst Tetraethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged into a stainless steel reaction vessel equipped with a stirrer, heating device, cooling tube and thermometer, the temperature was raised to 130 ° C., and the rosin acid group and epoxy compound epoxy A ring-opening reaction with the group was carried out. The reaction was continued at the same temperature for 4 hours, and when the acid value reached 0.5 mg KOH / g, the reaction was stopped to obtain rosin diol B.

(Rosindiol C (Synthesis of Exemplified Compound (9))
75 g of ethylene glycol diglycidyl ether (trade name Denacol EX810, manufactured by Nagase Chemitech) as a bifunctional epoxy compound, 200 g of purified rosin (trade name KR-85, manufactured by Arakawa Chemical Industries, Ltd.) as rosin, and tetraethylammonium bromide as a reaction catalyst (Manufactured by Tokyo Chemical Industry Co., Ltd.) is charged into a stainless steel reaction vessel equipped with a stirrer, heating device, cooling tube and thermometer, the temperature is raised to 130 ° C., and the rosin acid group and epoxy compound epoxy group are opened. A ring reaction was performed. The reaction was continued for 5 hours at the same temperature, and when the acid value reached 0.5 mgKOH / g, the reaction was stopped to obtain rosindiol C.

[Synthesis of polyester resin]
(Synthesis of polyester resin 1)
55 g of purified disproportionated rosin (“KR-614” manufactured by Arakawa Chemical Co., Ltd.) as rosin, 35 g of terephthalic acid (TPA), 30 g of dodecenyl succinic acid (DSA), 10 g of trimellitic acid (TMA) As a monohydric alcohol component, isosorbide (cyclic sugar alcohol: (manufactured by Sanko Chemical Co., Ltd.) 20 g, bisphenol A ethylene oxide adduct (BPA-EO) 45 g, 1,2-propylene glycol (PG) 13 g, and tetra-n- as a reaction catalyst 0.3 g of butyl titanate was charged into a stainless steel reaction vessel equipped with a stirrer, a heating device, a thermometer, a fractionator, and a nitrogen gas introduction tube, and subjected to a polycondensation reaction at 230 ° C. for 7 hours with stirring in a nitrogen atmosphere. After confirming that the predetermined molecular weight and acid value were reached, polyester resin 1 was synthesized.

(Synthesis of polyester resin 2)
As the polyvalent carboxylic acid component, 150 g of fumaric acid-modified rosin, 15 g of isophthalic acid (IPA), 3 g of trimellitic acid (TMA), and as the polyhydric alcohol component, isosorbide (cyclic sugar alcohol: (manufactured by Sanko Chemical Co., Ltd.) 25 g, 1 , 2-Propylene glycol (PG) 12 g, 1,6-hexanediol 18 g and tetra-n-butyl titanate 0.3 g as a reaction catalyst are equipped with a stirrer, heating device, thermometer, fractionation device, nitrogen gas introduction pipe The reaction mixture was charged into a stainless steel reaction vessel and subjected to a polycondensation reaction at 230 ° C. for 7 hours with stirring in a nitrogen atmosphere to confirm that the predetermined molecular weight and acid value had been reached, and polyester resin 2 was synthesized.

(Synthesis of polyester resin 3)
As a rosin, 55 g of tall rosin (“X-R” manufactured by Harima Chemicals), as a polyvalent carboxylic acid component, 35 g of terephthalic acid (TPA), 30 g of dodecenyl succinic acid (DSA), 10 g of trimellitic acid (TMA), as a polyhydric alcohol component , Isosorbide (cyclic sugar alcohol: (manufactured by Sanko Chemical Co., Ltd.) 20 g, bisphenol A ethylene oxide adduct (BPA-EO) 45 g, 1,2-propylene glycol (PG) 13 g and tetra-n-butyl titanate 0 as a reaction catalyst .3 g was charged into a stainless steel reaction vessel equipped with a stirrer, heating device, thermometer, fractionator, and nitrogen gas inlet tube, and subjected to a polycondensation reaction at 230 ° C. for 7 hours with stirring in a nitrogen atmosphere to obtain a predetermined molecular weight. After confirming that the acid value was reached, polyester resin 3 was synthesized.

(Synthesis of polyester resin 4)
As a polyvalent carboxylic acid component, 70 g of terephthalic acid (TPA), 20 g of dodecenyl succinic acid (DSA), as a polyhydric alcohol component, 20 g of isosorbide (cyclic sugar alcohol: manufactured by Sanko Chemical Co., Ltd.), bisphenol A propylene oxide adduct (BPA- PO) 100 g, rosindiol A 48 g, and tetra-n-butyl titanate 0.3 g as a reaction catalyst were charged into a stainless steel reaction vessel equipped with a stirrer, heating device, thermometer, fractionation device, nitrogen gas inlet tube, A polycondensation reaction was carried out at 230 ° C. for 9 hours under stirring in a nitrogen atmosphere, and it was confirmed that the predetermined molecular weight and acid value had been reached, and polyester resin 4 was synthesized.

(Synthesis of polyester resin 5)
As a polyvalent carboxylic acid component, 70 g of terephthalic acid (TPA), 20 g of dodecenyl succinic acid (DSA), as a polyhydric alcohol component, 7 g of isosorbide (cyclic sugar alcohol: manufactured by Sanko Chemical Co., Ltd.), 430 g of rosindiol A, and reaction catalyst As a sample, 0.3 g of tetra-n-butyl titanate was charged into a stainless steel reaction vessel equipped with a stirrer, a heating device, a thermometer, a fractionator, and a nitrogen gas introduction tube, and stirred at 230 ° C. for 9 hours in a nitrogen atmosphere. A polycondensation reaction was performed, and it was confirmed that the predetermined molecular weight and acid value had been reached, and a polyester resin 5 was synthesized.

(Synthesis of polyester resin 6)
As polyvalent carboxylic acid component, 63 g of terephthalic acid (TPA), 30 g of dodecenyl succinic acid (DSA), 4 g of trimellitic acid, as polyhydric alcohol component, 15 g of isosorbide (cyclic sugar alcohol: manufactured by Sanko Chemical Co., Ltd.), bisphenol A ethylene oxide addition 30 g of product (BPA-EO), 35 g of bisphenol A propylene oxide adduct (BPA-PO), 195 g of rosindiol B, and 0.3 g of tetra-n-butyl titanate as a reaction catalyst, stirring device, heating device, thermometer, minute Polyester resin is charged in a stainless steel reaction vessel equipped with a distillation apparatus and a nitrogen gas introduction tube, and subjected to a polycondensation reaction at 230 ° C. for 9 hours with stirring in a nitrogen atmosphere to confirm that the molecular weight and acid value have been reached. 6 was synthesized.

(Synthesis of polyester resin 7)
85 g of terephthalic acid (TPA) as the polyvalent carboxylic acid component, 14 g of isosorbide (cyclic sugar alcohol: manufactured by Sanko Chemical Co., Ltd.) as the polyhydric alcohol component, 280 g of rosindiol C, and tetra-n-butyl titanate 0 as the reaction catalyst .3 g was charged into a stainless steel reaction vessel equipped with a stirrer, heating device, thermometer, fractionator, and nitrogen gas inlet tube, and subjected to a polycondensation reaction at 230 ° C. for 7 hours with stirring in a nitrogen atmosphere to obtain a predetermined molecular weight. After confirming that the acid value was reached, polyester resin 7 was synthesized.

(Synthesis of polyester resin 8)
45 g of fumaric acid-modified rosin as the polyvalent carboxylic acid component, 50 g of terephthalic acid (TPA) as the polyvalent carboxylic acid component, 20 g of dodecenyl succinic acid (DSA), isosorbide (cyclic sugar alcohol: Sanko Chemical Co., Ltd.) as the polyhydric alcohol component 14 g, 95 g of bisphenol A ethylene oxide adduct (BPA-EO), 95 g of rosin diol A, and 0.3 g of tetra-n-butyl titanate as a reaction catalyst, stirring device, heating device, thermometer, fractionating device, nitrogen gas Polyester resin 8 was synthesized by charging into a stainless steel reaction vessel equipped with an introduction tube and subjecting it to a polycondensation reaction at 230 ° C. for 9 hours with stirring in a nitrogen atmosphere to confirm that the molecular weight and acid value were reached.

(Synthesis of polyester resin 9)
35 g of purified disproportionated rosin (“KR-614” manufactured by Arakawa Chemical Co., Ltd.) as rosin, 60 g of terephthalic acid (TPA) as polyvalent carboxylic acid component, 26 g of dodecenyl succinic acid (DSA), isosorbide (cyclic) as polyhydric alcohol component 14 g of sugar alcohol: Sanko Chemical Co., Ltd.), 68 g of bisphenol A propylene oxide adduct (BPA-PO), 190 g of rosindiol A, and 0.3 g of tetra-n-butyl titanate as a reaction catalyst, stirring device, heating device, thermometer , Charged into a stainless steel reaction vessel equipped with a fractionator and a nitrogen gas inlet tube, and subjected to a polycondensation reaction at 230 ° C. for 8 hours with stirring in a nitrogen atmosphere, confirming that the predetermined molecular weight and acid value were reached, A polyester resin 9 was synthesized.

(Synthesis of polyester resin 10)
As polyvalent carboxylic acid component, maleic acid-modified rosin 50 g, isophthalic acid (IPA) 55 g, dodecenyl succinic acid (DSA) 15 g, (as polyhydric alcohol component, isosorbide (cyclic sugar alcohol: manufactured by Sanko Chemical Co., Ltd.) 14 g, bisphenol A 130 g of propylene oxide adduct (BPA-PO) and 0.3 g of tetra-n-butyl titanate as a reaction catalyst were added to a stainless steel reaction vessel equipped with a stirrer, heating device, thermometer, fractionator, and nitrogen gas inlet tube. Polyester resin 10 was synthesized by charging and performing polycondensation reaction at 230 ° C. for 7 hours with stirring in a nitrogen atmosphere, and confirming that the prescribed molecular weight and acid value had been reached.

(Synthesis of polyester resin 11)
As the polyvalent carboxylic acid component, 45 g of fumaric acid-modified rosin, 75 g of terephthalic acid (TPA), (as the polyhydric alcohol component, 50 g of isosorbide (cyclic sugar alcohol: manufactured by Sanko Chemical Co., Ltd.), 45 g of 1,2-propylene recall, and As a reaction catalyst, 0.3 g of tetra-n-butyl titanate was charged into a stainless steel reaction vessel equipped with a stirrer, a heating device, a thermometer, a fractionation device, and a nitrogen gas introduction tube, and stirred at 230 ° C. in a nitrogen atmosphere. A polycondensation reaction was carried out for 7 hours to confirm that the predetermined molecular weight and acid value had been reached, and a polyester resin 11 was synthesized.

(Synthesis of polyester resin 12)
As the polyvalent carboxylic acid component, 23 g of fumaric acid-modified rosin, 63 g of terephthalic acid (TPA), 26 g of dodecenyl succinic acid, (as the polyhydric alcohol component, 22 g of isosorbide (cyclic sugar alcohol: Sanko Chemical Co., Ltd.), 1,2-propylene 10 g of recall, 70 g of bisphenol A propylene oxide adduct (BPA-PO), and 0.3 g of tetra-n-butyl titanate as a reaction catalyst were equipped with a stirrer, heating device, thermometer, fractionator, and nitrogen gas inlet tube. Polyester resin 12 was synthesized by charging it into a stainless steel reaction vessel and subjecting it to a polycondensation reaction at 230 ° C. for 7 hours with stirring in a nitrogen atmosphere to confirm that it had reached a predetermined molecular weight and acid value.

(Comparative polyester resin 1)
As the polyvalent carboxylic acid component, 60 g of terephthalic acid (TPA), 26 g of dodecenyl succinic acid (DSA), 8 g of trimellitic acid (TMA), as the polyhydric alcohol component, 22 g of isosorbide (cyclic sugar alcohol: manufactured by Sanko Chemical Co., Ltd.), bisphenol A ethylene oxide adduct (BPA-EO) 45 g, polyethylene glycol (PG) 8 g, and tetra-n-butyl titanate 0.3 g as a reaction catalyst, stirrer, heater, thermometer, fractionator, nitrogen gas inlet tube And a polycondensation reaction was carried out at 230 ° C. for 7 hours with stirring in a nitrogen atmosphere to confirm that the predetermined molecular weight and acid value were reached, and a comparative polyester resin 1 was synthesized.

  The characteristics of each synthesized polyester resin are listed below in Table 1.

[Preparation of resin particle dispersion]
(Preparation of resin particle dispersion 1)
Polyester resin 1: 100 parts by mass was charged into a reactor equipped with a stirrer, dissolved and mixed at 120 ° C. for 30 minutes, and then 800 parts by mass of ion-exchanged water heated to 95 ° C., 1.0 mass of sodium dodecylbenzenesulfonate. The aqueous solution for neutralization, in which 1.0 part by mass of 1N NaOH aqueous solution was dissolved, was put into a flask, emulsified with a homogenizer (Ultra Tallax, manufactured by IKA) for 5 minutes, and further shaken in an ultrasonic bath for 10 minutes. After completion, the flask was cooled with room temperature water. As a result, a resin particle dispersion 1 having a median diameter of resin particles of 250 nm and a solid content of 20% by mass was obtained.

(Preparation of resin particle dispersions 2 to 12)
Resin particle dispersions 2 to 12 were produced in the same manner as the resin particle dispersion 1, except that polyester resins 2 to 12 were used instead of the polyester resin 1, respectively.

(Preparation of comparative resin particle dispersion 1)
A comparative resin particle dispersion 1 was prepared in the same manner as the resin particle dispersion 1 except that the comparative polyester resin 1 was used instead of the polyester resin 1.

[Production of toner]
(Production of Toner 1)
-Preparation of Colorant Particle Dispersion 1-
Cyan pigment: 50 parts by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., copper phthalocyanine, CI Pigment Blue 15: 3)
-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R): 5 parts by mass-Ion-exchanged water: 200 parts by mass The above components are mixed and dissolved, and a homogenizer (manufactured by IKA, Ultra Turrax) 5 minutes And an ultrasonic bath for 10 minutes to obtain a Sian colorant particle dispersion 1 having a center diameter of 190 nm and a solid content of 21.5%.

-Preparation of release agent particle dispersion 1-
-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R): 2 parts by mass-Ion exchange water: 800 parts by mass-Paraffin wax (manufactured by HNP-9 Nippon Seiki Co., Ltd.): 200 parts by mass The mixture was heated to 120 ° C. and dispersed with a pressure discharge type gorin homogenizer to obtain a 20% by mass release agent dispersion having a volume average particle size of 170 nm.

-Preparation of toner-
-Resin particle dispersion 1: 315 parts by mass (63 parts by mass of resin)
Colorant particle dispersion 1: 40 parts by mass (8.6 parts by mass of pigment)
-Release agent particle dispersion 1: 40 parts by weight (release part 8.0 parts by weight)
-Polyaluminum chloride: 0.15 parts by mass-Ion-exchanged water: 300 parts by mass After the components were sufficiently mixed and dispersed in a round stainless steel flask using a homogenizer (IKA, Ultra Turrax T50) The flask was heated to 42 ° C. while stirring the flask in a heating oil bath, and held at 42 ° C. for 60 minutes, and then 105 parts by mass (21 parts by mass of resin) of the resin particle dispersion 1 was added and gently stirred. Thereafter, the pH in the system was adjusted to 6.0 with a 0.5 mol / liter aqueous sodium hydroxide solution, and then heated to 95 ° C. while stirring was continued. While the temperature was raised to 95 ° C., the pH in the normal system dropped to 5.0 or less, but here, an aqueous sodium hydroxide solution was further added dropwise to keep the pH from becoming 5.5 or less.
After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then solid-liquid separated by Nutsche suction filtration. Then, it was redispersed in 3,000 parts of ion-exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was repeated 5 times, followed by solid-liquid separation by Nutsche suction filtration, and then vacuum drying for 12 hours to obtain toner particles. The obtained toner particle 1 was designated as toner 1.
When the particle size of Toner 1 (Toner Particle 1) was measured by Coulter Multisizer II type, the cumulative volume average particle size D50 was 5.9 μm, and the volume average particle size distribution index GSDv was 1.24. Further, the shape factor SF1 of the toner particles obtained from the shape observation by Luzex was 126 potato shapes.

(Preparation of toner particles 2 to 12)
Toners 2 to 12 were produced in the same manner as the toner 1 except that the resin dispersions 2 to 12 were used instead of the resin dispersion 1, respectively.

(Preparation of toner particles 13)
The following mixture was kneaded with an extruder and pulverized with a surface pulverizer. after that,
Wind classifier (turbo classifier (TC-15N), manufactured by Nissin Engineering Co., Ltd.)
The process of classifying fine particles and coarse particles and obtaining intermediate size particles was repeated three times to obtain Syan toner particles 13 having a volume average particle size of 8.5 μm.
Polyester resin 4: 100 parts Cyan pigment: manufactured by Dainichi Seika Kogyo Co., Ltd., copper phthalocyanine, C.I. I. Pigment Blue 15: 3): 3 copies

(Preparation of Comparative Toner Particle 1)
Comparative toner 1 was prepared in the same manner as toner 1 except that comparative resin dispersion 1 was used instead of resin dispersion 1.

(Development of developers 1 to 13 and comparative developer 1)
To 50 parts of the obtained toner particles, 1.5 parts of hydrophobic silica (Cabot, TS720) was added and mixed with a sample mill to obtain externally added toners.
Then, a ferrite carrier having an average particle diameter of 50 μm coated with 1% of polymethyl methacrylate (manufactured by Soken Chemical Co., Ltd., Mw 75,000) is weighed, and each of the obtained externally added toners is weighed so that the toner concentration becomes 5%. Both were stirred and mixed with a ball mill for 5 minutes to prepare a developer. The obtained developers were designated as Developers 1 to 13 and Comparative Developer 1.

  The properties of each toner and developer produced are listed below in Table 2.

[Evaluation]
(Liquidity)
The fluidity of each produced toner was examined as follows.
Using a powder tester (manufactured by Hosokawa Micron Corporation), sieves having openings of 53 μm, 45 μm, and 38 μm are arranged in series from the upper stage, and 2 g of toner (1) accurately weighed on the 53 μm sieve is charged with an amplitude of 1 mm. Then, vibration was applied for 90 seconds, and the toner mass on each sieve after vibration was measured, added with weights of 0.5, 0.3, and 0.1, respectively, and calculated as a percentage. In general, this calculated value can be used without any practical problem if the toner mass after vibration is 40 or less, and more preferably 30 or less.
The evaluation of this fluidity was carried out for each of the toner after preparation, after being left for 24 hours in a high temperature and high humidity environment (50 ° C., 50% RH), and after being left for 7 days.
The evaluation criteria are as follows.
○: Calculated value is 30 or less Δ +: Calculated value exceeds 30 and 35 or less Δ: Calculated value exceeds 35, 45 or less Δ−: Calculated value exceeds 45, 50 or less × +: Calculated value is 50 Exceeding, 60 or more ×: The calculated value exceeds 60

(Low temperature fixability)
The low-temperature fixability of each produced toner was examined as follows.
The image was a solid image of 40 mm × 50 mm, the toner amount was 1.5 mg / cm ² , and the recording paper was mirror-coated platinum paper (basis weight: 127 gsm), and was manually evaluated. Subsequently, the fixing device of DocuPrint C2220 was remodeled so that the fixing temperature was variable, and the fixing property was evaluated while the fixing temperature was gradually increased from 100 ° C.
For low-temperature fixability, a good fixed image without image loss due to defective release is bent using a predetermined load weight, and the degree of image loss at that portion is graded, and fixing that exceeds a certain grade The temperature was taken as the minimum fixing temperature and used as an index for low-temperature fixability.
The evaluation criteria are as follows.
○: 140 ° C. or less Δ: Over 140 ° C., 160 ° C. or less X: 160 ° C. or more

From the above results, it can be seen that the present example is superior in fluidity as compared with the comparative example.
It can also be seen that the toner examples including a polyester resin using a monomer having a rosin as a carboxylic acid component or an alcohol component are excellent in low-temperature fixability as compared with, for example, the toner 1 and 3 examples.
Further, it can be seen that the example including the rosin (rosin skeleton) in an appropriate range is superior in the low-temperature fixability to the example of the toner 7.

1Y, 1M, 1C, 1K, 107 photoconductor (an example of an image carrier)
2Y, 2M, 2C, 2K, 108 Charging roller (an example of charging means)
3Y, 3M, 3C, 3K Laser beam 3, 110 Exposure device (an example of electrostatic charge image forming means)
4Y, 4M, 4C, 4K, 111 developing device (an example of developing means)
5Y, 5M, 5C, 5K Primary transfer rollers 6Y, 6M, 6C, 6K, 113 Photoconductor cleaning devices 8Y, 8M, 8C, 8K Developer cartridges 10Y, 10M, 10C, 10K Image forming unit 20 Intermediate transfer belt 22 Drive Roller 24 Support roller 26 Secondary transfer roller (an example of transfer means)
28, 115 Fixing device (an example of fixing means)
30 Intermediate transfer member cleaning device 112 Transfer device 116 Mounting rail 117 Opening 118 for static elimination exposure Opening 200 for exposure Process cartridge,
P, 300 Recording paper (transfer object)

Claims (11)

  A polyester resin for an electrostatic charge image developing toner, which is a polycondensate comprising at least one cyclic sugar alcohol containing a hetero element and a monomer containing rosin as a polycondensation component.   The polyester resin for electrostatic image developing toner according to claim 1, wherein the monomer containing rosin is at least one of a polyvalent carboxylic acid and a polyhydric alcohol.   The polyester resin for an electrostatic charge image developing toner according to claim 1, wherein the content of the skeleton derived from the rosin is 70% by mass or less based on the whole polyester resin.   The polyester resin for electrostatic image developing toner according to any one of claims 1 to 3, wherein the cyclic sugar alcohol is a cyclic sugar alcohol having a cyclic structure containing at least one hetero element and two hydroxyl groups. .   The polyester resin for electrostatic charge image developing toner according to claim 1, wherein the cyclic sugar alcohol is at least one selected from isosorbite and isoidide.   An electrostatic image developing toner comprising the polyester resin for electrostatic image developing toner according to any one of claims 1 to 5.   An electrostatic charge image developer comprising at least the electrostatic charge image developing toner according to claim 6. Containing the electrostatic image developing toner according to claim 6;
A toner cartridge to be attached to and detached from the image forming apparatus. A developing unit that contains the electrostatic charge image developer according to claim 7 and that develops the electrostatic charge image formed on the image carrier as a toner image with the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus. An image carrier,
Charging means for charging the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Development means for containing the electrostatic charge image developer according to claim 7 and developing the electrostatic charge image formed on the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the image carrier onto a transfer target;
Fixing means for fixing the toner image transferred onto the transfer medium;
An image forming apparatus comprising: A charging step for charging the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic image formed on the image carrier as a toner image by the electrostatic image developer according to claim 7;
A transfer step of transferring a toner image formed on the image carrier onto a transfer target;
A fixing step of fixing the toner image transferred onto the transfer medium;
An image forming method comprising: