JP2014077085A - Polyester resin for electrostatic charge image development toner, electrostatic charge image development toner, electrostatic charge image developer, toner cartridge, process cartridge, image formation device and image formation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin for electrostatic charge image development toner which suppresses decrease in electrification performance of electrostatic charge image development toner.SOLUTION: A polyester resin for electrostatic charge image development toner is a polycondensate of: an alcohol component; and a carboxylic acid component including dicarboxylic acid that is a reaction product of rosin monool that is a reaction product of any one of an epoxy compound, a carbonic acid ester compound and an oxetane compound and rosin, and trifunctional carboxylic acid or the anhydride.

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.

Patent Document 1 discloses a polyester for toner obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a purified rosin, and a toner containing the polyester for toner.
Patent Document 2 discloses 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 toner polyester. Has been.
Patent Document 3 discloses, as a binder resin for a toner, a polyester resin in which an acid component is composed of an aromatic dicarboxylic acid and a disproportionated rosin, and an alcohol component is composed of a trihydric or higher polyhydric alcohol. ing.

JP 2007-137910 A JP 2007-292815 A JP 2010-20170 A

  An object of the present invention is to provide a polyester resin for an electrostatic image developing toner that suppresses a decrease in chargeability of the electrostatic image developing toner.

The invention according to claim 1
An alcohol component,
Carboxylic acid component containing dicarboxylic acid which is reaction product of rosin monool which is reaction product of any one of epoxy compound, carbonate compound and oxetane compound and rosin and trifunctional carboxylic acid or anhydride thereof When,
Is a polyester resin for electrostatic image developing toner.

The invention according to claim 2
The polyester resin for electrostatic image developing toner according to claim 1, wherein the rosin is a disproportionated rosin.

The invention according to claim 3
An electrostatic image developing toner comprising the polyester resin for electrostatic image developing toner according to claim 1.

The invention according to claim 4
An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 3.

The invention according to claim 5
Containing the electrostatic charge image developing toner according to claim 3;
The toner cartridge is detachable from the image forming apparatus.

The invention according to claim 6
A developing means for accommodating the electrostatic charge image developer according to claim 4 and developing the electrostatic charge image formed on the image carrier as a toner image by the electrostatic charge image developer,
It is a process cartridge that can be attached to and detached from the image forming apparatus.

The invention according to claim 7 provides:
An image carrier,
Charging means for charging the surface of 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 image developer according to claim 4 and developing the electrostatic image formed on the image carrier as a toner image by the electrostatic image developer;
Transfer means for transferring the toner image formed on the image carrier to a recording medium;
Fixing means for fixing the toner image transferred to the recording medium;
An image forming apparatus.

The invention according to claim 8 provides:
A charging step for charging the surface of 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 the electrostatic image formed on the image carrier as a toner image with the electrostatic image developer according to claim 4;
A transfer step of transferring the toner image formed on the image carrier to a recording medium;
A fixing step of fixing the toner image transferred to the recording medium;
Is an image forming method.

According to the first aspect of the present invention, there is provided a polyester resin for an electrostatic charge image developing toner that suppresses a decrease in chargeability as compared with a case where a carboxylic acid component containing (meth) acrylic acid-modified rosin is used as a polycondensation component. can get.
According to the second aspect of the present invention, there can be obtained a polyester resin for an electrostatic charge image developing toner having excellent storage stability as compared with the case where gum rosin or hydrogenated rosin is used as the rosin.
According to the invention of claim 3, the charging property is higher than that of the electrostatic charge image developing toner containing the polyester resin for electrostatic charge image developing toner using the carboxylic acid component containing (meth) acrylic acid-modified rosin as the polycondensation component. An electrostatic image developing toner in which the decrease is suppressed is obtained.
According to the invention of claim 4, compared to the case where an electrostatic charge image developing toner including a polyester resin for electrostatic charge image developing toner using a carboxylic acid component containing (meth) acrylic acid-modified rosin as a polycondensation component is applied. Thus, an electrostatic charge image developer in which a decrease in chargeability is suppressed can be obtained.
According to the inventions according to claims 5, 6, 7 and 8, there is provided an electrostatic charge image developing toner comprising a polyester resin for electrostatic charge image developing toner having a carboxylic acid component containing (meth) acrylic acid-modified rosin as a polycondensation component. A toner cartridge, a process cartridge, an image forming apparatus, and an image forming method capable of obtaining an image in which an image defect due to a decrease in chargeability is suppressed as compared with the case of applying is obtained.

It is a figure explaining the state of a screw about an example of a screw extruder used for manufacture of toner concerning this embodiment. 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 this embodiment (hereinafter referred to as “polyester resin”) is a polycondensate of a carboxylic acid component and an alcohol component.
The carboxylic acid component includes a monoolized rosin monool which is a reaction product of any one of an epoxy compound, a carbonate ester compound and an oxetane compound (hereinafter referred to as “specific reactive compound”) and rosin. A dicarboxylic acid that is a reaction product of a trifunctional carboxylic acid or an anhydride thereof (hereinafter referred to as “specific rosin dicarboxylic acid”) is included.

  The polyester resin according to the present embodiment suppresses a decrease in chargeability of the electrostatic charge image developing toner. The reason is not clear, but it is thought to be due to the following reasons.

As a polyester resin into which a rosin skeleton is introduced, for example, a polycondensate using purified rosin as a carboxylic acid component, a polycondensate using (meth) acrylic acid-modified rosin as a carboxylic acid component, and the like are known.
Here, the polycondensate using purified rosin as a carboxylic acid component is a tertiary carboxylic acid and has low reactivity with the alcohol component, and therefore contains a large amount of unreacted monomers. As a result of the high acid value of the polycondensate, it is considered that the chargeability of the electrostatic charge developing toner tends to decrease when it is contained in the electrostatic charge developing toner.
On the other hand, a polycondensate using (meth) acrylic acid-modified rosin as a carboxylic acid component is obtained as follows. First, a (meth) acrylic acid-modified rosin is obtained by a reaction between (meth) acrylic acid and rosin. Here, since the reactivity of the reaction for obtaining the modified rosin is low, unreacted monomers are likely to be included. Subsequently, the obtained (meth) acrylic acid-modified rosin is subjected to a polycondensation reaction with an alcohol component as a carboxylic acid component to obtain a polycondensate. Here, in this polycondensation reaction, since the carboxyl group derived from (meth) acrylic acid was introduced into the rosin, the reactivity of the polycondensation reaction increased compared to the polycondensation reaction with the alcohol component of the unmodified rosin. Although the content of unreacted monomer is reduced, it is still not sufficient, and unreacted monomer may be contained. As described above, when the unreacted monomer is contained and the acid value of the polycondensate is increased, the chargeability of the electrostatic charge developing toner tends to be lowered when it is contained in the electrostatic charge development toner. Conceivable.
In addition, an unreacted monomer shows an unreacted monomer among the monomers (for example, monomer which has a hydroxyl group or a carboxyl group) which influences a raise of an acid value.

  Therefore, the polyester resin according to the present embodiment is a polycondensate of a carboxylic acid component containing a specific rosin dicarboxylic acid and an alcohol acid component (hereinafter sometimes referred to as “specific polyester resin”).

The specific rosin dicarboxylic acid is obtained as follows. First, rosin and a specific reactive compound are reacted to obtain rosin monool. Subsequently, the rosin monool obtained is reacted with a trifunctional carboxylic acid or anhydride thereof to obtain rosin dicarboxylic acid. Here, since the reactivity of the two reactions for obtaining a specific rosin dicarboxylic acid from rosin is higher than the reaction for obtaining a (meth) acrylic acid-modified rosin, it is considered that the residual unreacted monomer is suppressed. .
The reason why the above two reactions occur efficiently is considered to be that the reactivity of the specific reactive compound is particularly high and it reacts quickly with the tertiary carboxylic acid of rosin.
In addition, the reaction of polycondensation with a specific rosin carboxylic acid as a carboxylic acid component and an alcohol component, a polycondensation reaction using purified rosin as a carboxylic acid component, and (meth) acrylic acid modified rosin as a carboxylic acid component Since the reactivity is higher than that of the polycondensation reaction, it is considered that residual unreacted monomers are suppressed.
As a result, the specific polyester resin containing specific rosin dicarboxylic acid as a carboxylic acid component and obtained by polycondensation reaction with an alcoholic acid component is a polyester resin in which residual unreacted monomers are suppressed. For this reason, it is thought that it becomes the polyester resin by which the raise of the acid value was suppressed.

  As described above, the polyester resin according to the present embodiment suppresses a decrease in chargeability of the electrostatic charge image developing toner.

  In addition, the polycondensate using the specific rosin dicarboxylic acid as the carboxylic acid component tends to be less susceptible to steric hindrance due to the rosin skeleton than the polycondensate using the purified rosin as the carboxylic acid component. Therefore, the reactivity of the polycondensation reaction is high, and it is considered that the residual unreacted monomer is suppressed. Therefore, the polyester resin according to the present embodiment also has the chargeability of the electrostatic charge image developing toner. It is thought to suppress the decrease.

  In addition, the polycondensate using the specific rosin dicarboxylic acid as the carboxylic acid component suppresses the residual unreacted monomer as described above, and the softening effect of the polycondensate due to the residual monomer is reduced. The polyester resin for electrostatic charge developing toner according to this embodiment is considered to suppress the deterioration of the heat storage property of the electrostatic charge image developing toner.

  Hereinafter, the components of the polyester resin according to this embodiment will be described in detail.

<Carboxylic acid component>
The carboxylic acid component contains a specific rosin dicarboxylic acid, and may contain other carboxylic acids as necessary.

(Specific rosin dicarboxylic acid)
The specific rosin dicarboxylic acid can be obtained by reacting rosin monool, which is a reaction product of rosin and a specific reactive compound, with a trifunctional carboxylic acid or its anhydride by various methods.
A scheme for synthesizing a specific rosin dicarboxylic acid is shown below as an example.
Reaction scheme 1 is a specific rosin dicarboxylic acid produced by the reaction of rosin monool (3) produced by the reaction of rosin (1) and carbonate compound (2) and trifunctional carboxylic acid anhydride (4). It is a scheme which shows reaction which synthesize | combines (5). In Reaction Scheme 1, dehydroabietic acid is used as an example of rosin (1), carbonate compound (ethylene carbonate) is used as an example of specific reactive compound (2), and trifunctional carboxylic acid anhydride (4) is used as an example. Each merit acid anhydride is used.

  Reaction scheme 2 shows the specific rosin dicarboxylic acid (7) produced by the reaction of rosin monool (7) produced by the reaction of rosin (1) and epoxy compound (6) and trifunctional carboxylic acid anhydride (4). It is a scheme which shows the reaction which synthesize | combines 8). In Reaction Scheme 2, dehydroabietic acid is used as an example of rosin, epoxy compound (6) is used as an example of specific reactive compound, and trimellitic anhydride is used as an example of trifunctional carboxylic acid anhydride (4). ing.

-Rosin monool-
The rosin monool used for the synthesis of the specific rosin dicarboxylic acid is a compound obtained by reacting rosin with a specific reactive compound.
Specific examples of the rosin monool include the compound (3) in Scheme 1 and the compound (7) in Scheme 2, but this embodiment is not limited to these compounds.

-Rosin-
The rosin in the present embodiment is a generic name 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 components include, for example, parastrinic acid, neoabietic acid, pimaric acid, dehydroabietic acid, isopimaric acid, sandaracopimalic acid in addition to abietic acid, and the rosin used in this embodiment is a mixture thereof. is there. Rosin is roughly classified into three types according to the collection method: tall rosin with pulp as raw material, gum rosin with raw pine oil as raw material, and wood rosin with raw material as pine stump. Gum rosin and / or tall rosin is preferred because rosin used in this embodiment is easily available.

  These rosins are preferably purified to remove high molecular weight substances thought to have arisen from resin acid peroxides from unpurified rosins and unsaponified products contained in unpurified rosins. As a result, purified rosin can be obtained. The purification method is not particularly limited, and various known purification methods can be selected. Specifically, methods such as distillation, recrystallization, extraction and the like can be mentioned. Industrially, purification by distillation is preferably performed. 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 of this embodiment 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, iodides such as iodine and iron iodide, and phosphorus compounds. . The amount of the catalyst used is usually preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.01% by mass or more and 1% by mass or less, and the reaction temperature is 100 ° C. or more and 300 ° C. or less with respect to rosin. It is preferably 150 ° C. or higher and 290 ° C. or lower. As a method for controlling the amount of dehydroabietic acid, for example, dehydroabietic acid isolated by a method of crystallizing from disproportionated rosin as an ethanolamine salt (J. Org. Chem., 31, 4246 (1996)) is aimed. It may be added to a disproportionated rosin prepared by heating at high temperature in the presence of a disproportionation catalyst so that the amount of dehydroabietic acid becomes.

The rosin of this embodiment may be a hydrogenated rosin. Hydrogenated rosin contains tetrahydroabietic acid and dihydroabietic acid as main components, and can be obtained by eliminating unstable conjugated double bonds in the molecule by a known hydrogenation reaction. The hydrogenation reaction is carried out by heating an unpurified rosin in the presence of a hydrogenation catalyst, usually under a hydrogen pressure of 10 Kg / cm ² or more and 200 Kg / cm ² or less, preferably 50 Kg / cm ² or more and 150 Kg / cm ² or less. . 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. The amount of the catalyst used is usually 0.01% by mass or more and 5% by mass or less, preferably 0.01% by mass or more and 1.0% by mass or less with respect to rosin, and the reaction temperature is 100 ° C. or more and 300 ° C. or less. Preferably they are 150 degreeC or more and 290 degrees C or less.
These disproportionated rosin and hydrogenated rosin may be provided with the purification step before and after the disproportionation treatment or the hydrogenation treatment.
Of these, disproportionated rosin is preferable from the viewpoint of storage stability of the electrostatic charge image developing toner.

-Specific reactive compounds-
The specific reactive compound used for the synthesis of rosin monool is a compound that is reacted with rosin to obtain rosin monool, and examples thereof include an epoxy compound, a carbonate compound, and an oxetane compound. Among these, from the viewpoint of high reactivity with rosin, an epoxy compound or a carbonate compound is preferable, and a carbonate compound is desirable.

  Examples of the epoxy compound include compounds represented by the following general formula (1).

In general formula (1), R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group.

The alkyl group may be linear or branched.
Further, the number of carbon atoms of the alkyl group is preferably 1 or more and 15 or less, and more preferably 2 or more and 10 or less.

Examples of the substituent in the alkyl group or alkenyl group include an ether group. That is, for example, R ¹ may represent an alkyloxy group or an alkenyloxy group.

  Specific examples of the epoxy compound include 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxyoctene, 1,2-epoxydecene, t-butyl glycidyl ether, and 2-ethylhexyl glycidyl ether are preferable. , 2-epoxypentane, 1,2-epoxyoctene, 2-ethylhexene Glycidyl ether is more desirable.

  Examples of the carbonate compound include compounds represented by the following general formula (2).

In general formula (2), R ² and R ³ each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group.
Further, in the compound represented by the general formula (2), R ² and R ³ are connected to form a ring composed of the carbon atom of the carbonyl group and each oxygen atom bonded to the carbon atom. May be.

The alkyl group may be linear or branched.
Further, the number of carbon atoms of the alkyl group is preferably 1 or more and 15 or less, and more preferably 1 or more and 10 or less.

Examples of the substituent in the alkyl group or alkenyl group include an ether group. That is, for example, R ² and R ³ may represent an alkyloxy group or an alkenyloxy group.

  Specific examples of the carbonate compound include ethylene carbonate, propylene carbonate, 4- (1-propenyloxymethyl) -1,3-dioxolane-2-one, and the like, and ethylene carbonate and propylene carbonate are more preferable. .

  As an oxetane compound, the compound shown by the following general formula (3-1) or general formula (3-2) is mentioned.

In general formula (3-1) and general formula (3-2), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group.

The alkyl group may be linear or branched.
Further, the number of carbon atoms of the alkyl group is preferably 1 or more and 15 or less, and more preferably 2 or more and 10 or less.

  Specific examples of the oxetane compound include trimethylene oxide and 3,3-dimethyloxetane, and 3,3-dimethyloxetane is more preferable.

-Method of synthesizing rosin monool-
The reaction between the rosin and the specific reactive compound is carried out by various known methods. For example, in the case of a batch system, a cooling pipe, a stirring device, an inert gas inlet, a thermometer and the like and a heating function are provided. The flask is charged with the rosin and the specific reactive compound in a target ratio, heated and melted, and the reaction product is sampled, and the reaction progress is monitored. The degree of progress of the reaction is confirmed mainly by a decrease in the acid value, and the reaction is completed when it reaches the stoichiometric end point or near it.
The reaction temperature is preferably 60 ° C. or higher and 220 ° C. or lower, preferably 100 ° C. or higher and 210 ° C. or lower, and more preferably 130 ° C. or higher and 200 ° C. or lower.
Moreover, you may add a catalyst in the case of reaction.

  Examples of the catalyst used include amines such as ethylenediamine, trimethylamine, and 2-methylimidazole, quaternary ammonium salts such as triethylammonium bromide, triethylammonium chloride, and butyltrimethylammonium chloride, and triphenylphosphine.

The reaction ratio between rosin and the specific reactive compound is preferably such that rosin is reacted in the range of 0.8 mol to 1.2 mol, and 0.9 mol to 1.2 mol with respect to 1 mol of the specific reactive compound. Desirably, 0.9 mol or more and 1.1 mol or less are more desirable.
It is considered that when the rosin is 0.8 mol or more, the specific reactive compound is suppressed from remaining in the specific polyester resin production process, and the decrease in chargeability due to an increase in acid value is suppressed.
In addition, it is considered that the phenomenon of causing gelation due to an increase in molecular weight due to the action as a crosslinking agent is suppressed by suppressing these residuals.
Moreover, it is thought that when the amount of rosin is 1.2 mol or less, the remaining unreacted rosin is suppressed, and a decrease in chargeability due to an increase in acid value is suppressed.

-3 functional carboxylic acid or its anhydride-
The trifunctional carboxylic acid used for the synthesis of the specific rosin dicarboxylic acid is a carboxylic acid in which three carboxyl groups are bonded in one molecule. For example, trimellitic acid (1,2,4-benzenetricarboxylic acid), 1,2,4-naphthalenetricarboxylic acid, citric acid, 1,3,5-cyclohexanetricarboxylic acid and the like. The trifunctional carboxylic acid anhydride used for the synthesis of the specific rosin dicarboxylic acid is a carboxylic acid anhydride in which two of the three carboxyl groups in one molecule are dehydrated and condensed. For example, trimellitic acid anhydride Etc.
Of these compounds, trimellitic acid, citric acid, and trimellitic anhydride are preferable, and trimellitic anhydride is more preferable from the viewpoint of chargeability of the toner.
Of these trifunctional carboxylic acids or anhydrides thereof, trifunctional carboxylic acid anhydrides are preferable from the viewpoint of easily obtaining the target specific rosin dicarboxylic acid. This is because the reaction site of the trifunctional carboxylic acid anhydride and the site where the carboxyl group is dehydrated and condensed differ in the reactivity of the rosin monool with respect to the hydroxyl group. This is because oar is considered to react regioselectively.

-Method for synthesizing specific rosin dicarboxylic acid-
The reaction of rosin monool with trifunctional carboxylic acid or its anhydride is carried out by various known methods. For example, in the case of batch type, a cooling tube, a stirring device, an inert gas inlet, a thermometer, etc. A rosin monool and a trifunctional carboxylic acid or anhydride thereof are charged into a flask equipped with a heating function at a desired ratio, followed by monitoring the progress of the reaction by heating and melting and sampling the reaction product. Is called. The degree of progress of the reaction is confirmed mainly by a decrease in the acid value, and the reaction is completed when it reaches the stoichiometric end point or near it. Further, a trifunctional carboxylic acid or an anhydride thereof may be charged into a flask in which rosin monool has been synthesized, and specific rosin dicarboxylic acid may be synthesized following the synthesis of rosin monool.
The reaction temperature is preferably 100 ° C. or higher and 230 ° C. or lower, preferably 120 ° C. or higher and 220 ° C. or lower, and more preferably 150 ° C. or higher and 210 ° C. or lower.
Moreover, you may add a catalyst in the case of reaction.

  Examples of the catalyst used include known and commonly used reaction catalysts such as at least one metal compound selected from antimony, titanium, tin, zinc, aluminum and manganese.

The reaction ratio of rosin monool to trifunctional carboxylic acid or anhydride thereof is to react rosin monool within a range of 0.8 mol or more and 1.2 mol or less with respect to 1 mol of trifunctional carboxylic acid or anhydride thereof. 0.9 mol or more and 1.2 mol or less is desirable, and 0.9 mol or more and 1.1 mol or less is more desirable.
By the rosin monool being 0.8 mol or more, the trifunctional carboxylic acid or its anhydride is suppressed from remaining in the specific polyester resin production process, and thus acts as a crosslinking agent in the polyester resin synthesis. It is considered that the phenomenon of causing gelation and causing molecular weight increase is suppressed.
Further, when the rosin monool is 1.2 mol or less, the remaining unreacted rosin monool is suppressed, and in the polyester resin synthesis, the termination of the polymerization reaction due to resin end capping is suppressed due to the rosin monool. it is conceivable that.

(Other carboxylic acids)
Examples of other carboxylic acids include polyvalent carboxylic acids other than trivalents, and examples of the dicarboxylic acid component 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 carboxylic acid compounds are desirable from the viewpoints of toner durability, fixability, and colorant dispersibility.

  Examples of the tetravalent or higher carboxylic acid include specific aromatic carboxylic acids such as pyromellitic acid, anhydrides thereof, and lower alkyl esters thereof. These may be used individually by 1 type and may use 2 or more types together.

  Moreover, as an acid component, the dicarboxylic acid component which has a sulfonic acid group other than aliphatic dicarboxylic acid and aromatic dicarboxylic acid may be contained.

-Content of specific rosin dicarboxylic acid-
The content of the specific rosin dicarboxylic acid in all carboxylic acid components is preferably 10% by mass or more and 95% by mass or less, preferably 30% by mass or more and 90% by mass or less, and more preferably 40% by mass or more and 85% by mass or less.

<Alcohol component>
Examples of the alcohol component include polyhydric alcohols, and examples of the diol component 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.
In the present embodiment, etherified diphenol may be used. Etherified diphenol is a diol obtained by addition reaction of bisphenol A and alkylene oxide. The alkylene oxide is ethylene oxide or propylene oxide, and the average added mole number of alkylene oxide is 1 mol of bisphenol A. The amount is preferably 2 mol or more and 16 mol or less.
Among these, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1 from the viewpoint of toner durability, fixability, and dispersibility of the colorant. 1,4-butanediol, 2,3-butanediol, and etherified diphenol are preferred.

<Method for producing specific polyester resin>
The specific polyester resin is prepared by a known and commonly used production method using a carboxylic acid component containing a specific rosin dicarboxylic acid and an alcohol component as raw materials. As the reaction method, either a transesterification reaction or a direct esterification reaction is 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 or less with respect to 100 parts by mass of the total amount of the carboxylic acid component and the alcohol component. desirable. The reaction temperature is 180 ° C to 300 ° C.

<Characteristics of specific polyester resin>
The softening temperature of the specific polyester resin is preferably from 80 ° C. to 160 ° C., and preferably from 90 ° C. to 150 ° C.
The softening temperature was measured according to the ring and ball method described in JIS K2871.

The glass transition temperature of the specific polyester resin is preferably 35 ° C. or higher and 80 ° C. or lower, and preferably 40 ° C. or higher and 70 ° C. or lower, from the viewpoints of fixability, storage stability, and durability.
The glass transition temperature was measured by using “DSC-20” (manufactured by Seiko Denshi Kogyo Co., Ltd.) and heating 10 mg of a sample at a heating rate (10 ° C./min).

  The softening temperature and the glass transition temperature are easily adjusted by adjusting the raw material monomer composition, the polymerization initiator, the molecular weight, the catalyst amount, etc., or selecting the reaction conditions.

The acid value of the specific polyester resin 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 was measured according to JIS K5400.

The weight average molecular weight Mw of the specific polyester resin is preferably from 4,000 to 1,000,000, and more preferably from 7,000 to 300,000.
The weight average molecular weight is preferably 40000 or more from the viewpoint of heat storage property.
The weight average molecular weight is preferably 150,000 or less from the viewpoint of low-temperature fixability.
The number average molecular weight (Mn) is preferably from 2,000 to 7,000, preferably from 3,000 to 6,500, and more preferably from 3,500 to 6,000, from the same viewpoint as the weight average molecular weight.
The weight average molecular weight Mw and the number average molecular weight Mn are measured using two “HLC-8120GPC, SC-8020 (6.0 mm ID × 15 cm, manufactured by Tosoh Corporation)” and THF (tetrahydrofuran) as an eluent. It was. As experimental conditions, the experiment was conducted using a sample concentration of 0.5%, a flow rate of 0.6 ml / min, a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and 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 specific polyester resin may be a modified polyester. Examples of the modified polyester resin include grafting or blocking with phenol, urethane, epoxy or the like by the method described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. Modified polyester resins are included.
The specific polyester resin has a weight average molecular weight (Mw) of 40000 to 150,000 and a molecular weight distribution (Mw / Mn) of 12 to 25.

[Electrostatic image developing toner]
The electrostatic image developing toner according to the present embodiment includes the polyester resin (specific polyester resin) for electrostatic image developing toner according to the present embodiment.
Details of the electrostatic charge image developing toner (hereinafter referred to as “toner”) according to this embodiment will be described below.

  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.

(Binder resin)
Examples of the binder resin include amorphous resins, and the specific polyester resin is used as the amorphous resin.
As the binder resin, a crystalline resin may be used in combination with the amorphous resin.
As the binder resin, an amorphous resin other than the specific polyester resin may be used in combination with the specific polyester resin.
However, the content of the specific polyester resin is preferably 70 parts by mass or more, more preferably 90 parts by mass or more, and further preferably 100 parts by mass 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), and is a solid at room temperature (25 ° C.). In this case, the material is thermoplasticized at a temperature equal to or higher than 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, 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 that the half-value width is 10 ° C. It means a resin having a temperature exceeding 0 ° 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, and 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.

(Coloring agent)
The colorant may be a dye or a pigment, for example, but a pigment is preferable 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 mass part or more and 30 mass parts or less is good 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 from 50 ° C. to 100 ° C., and preferably from 60 ° C. to 95 ° C.

The content of the release agent is preferably 0.5 parts by mass or more and 15 parts by mass or less, and preferably 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.

(Characteristics of toner particles)
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 (polyester and 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 which concerns on this embodiment).

The volume average particle diameter of the toner particles is preferably 2.0 μm or more and 10 μm or less, for example, and preferably 3.5 μm or more and 7.0 μm or less.
In addition, the following method is mentioned as a measuring method of the volume average particle diameter of toner particles. First, 0.5 mg to 50 mg of a measurement sample is added to 2 ml of a 5 wt% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate as a dispersant, and this is added to 100 ml to 150 ml of the electrolytic solution. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for 1 minute, and a particle size of 100 μm with an aperture diameter of 100 μm is used with a Coulter Multisizer II type (manufactured by Beckman-Coulter). The particle size distribution of particles 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 particles, and A represents the projected area of the toner particles.

  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 dispersed on the surface of a slide glass is taken into a Luzex image analyzer through a video camera, the maximum length and projected area of 100 particles are obtained, calculated by the above equation (1), and an average value thereof Is obtained.

<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, and BaO. , 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. Can be mentioned.

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 the external additive include resin particles (resin particles such as polystyrene, polymethyl methacrylate resin (PMMA), and melamine resin), cleaning activators (for example, metal salts of higher fatty acids represented by zinc stearate, fluorine-based high additives, etc. Molecular weight particle powder) and the like.

  The amount of the external additive added is, for example, preferably 0.01 parts by mass or more and 5 parts by mass or less, and 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 desirable.

<Toner production method>
Hereinafter, a toner manufacturing method according to the exemplary embodiment will be described.
The toner particles may be produced by a dry production method (for example, a kneading pulverization method) or a wet production method (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). You may manufacture by either. There is no restriction | limiting in particular in these manufacturing methods, A well-known manufacturing method is employ | adopted.
Hereinafter, a method for obtaining toner particles by the aggregation and coalescence method and the kneading and pulverization method will be described.

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.

(Aggregation method)
-Preparation step of resin particle dispersion-
First, together with a resin particle dispersion in which polyester resin particles (particular polyester resin particles) are dispersed, for example, a colorant particle dispersion in which colorant particles are dispersed, a release agent dispersion in which release agent particles are dispersed Prepare.

  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 And nonionic surfactants such as polyethylene glycol-based, alkylphenol ethylene oxide adduct-based and polyhydric alcohol-based surfactants. 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 the method for dispersing the polyester resin particles in the dispersion medium in the resin particle dispersion include general dispersion methods such as a rotary shear type 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, the flocculant is added to the mixed dispersion, and the pH of the mixed dispersion is adjusted to acidic (for example, the pH is 2 or more and 5 or less), and a dispersion stabilizer is added as necessary. The polyester resin particles are heated to a glass transition temperature (specifically, for example, the glass transition temperature of the polyester resin particles is −30 ° C. or higher and the glass transition temperature is −10 ° C. or lower), and the particles dispersed in the mixed dispersion 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 inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic substances 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 preferable to sufficiently carry out 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.

-External addition process, sieving process-
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. Furthermore, if necessary, coarse toner particles may be removed using a vibration classifier, a wind classifier, or the like.

(Kneading and grinding method)
The kneading and pulverizing method is a method for producing toner particles by kneading a kneaded product after kneading a toner forming material containing a binder resin to obtain a kneaded product.
More specifically, the kneading and pulverizing method is divided into a kneading step for kneading the toner forming material containing the binder resin and a pulverizing step for pulverizing the kneaded product. You may have other processes, such as a cooling process which cools the kneaded material formed by the kneading process as needed.
Each step will be described in detail.

-Kneading process-
In the kneading step, the toner forming material including the binder resin is kneaded.
In the kneading process, 0.5 to 5 parts by mass of an aqueous medium (for example, water such as distilled water or ion-exchanged water, alcohols, or the like) may be added to 100 parts by mass of the toner forming material. desirable.

  Examples of the kneader used in the kneading process include a single screw extruder, a twin screw extruder, and the like. Hereinafter, as an example of a kneading machine, a kneading machine having a feed screw part and two kneading parts will be described with reference to the drawings, but the invention is not limited thereto.

FIG. 1 is a diagram illustrating a screw state of an example of a screw extruder used in a kneading process in the toner manufacturing method according to the present embodiment.
The screw extruder 11 includes a barrel 12 having a screw (not shown), an inlet 14 for injecting a toner forming material as a raw material of the toner into the barrel 12, and an aqueous medium added to the toner forming material in the barrel 12. A liquid addition port 16 for discharging the toner, and a discharge port 18 for discharging the kneaded material formed by kneading the toner forming material in the barrel 12.

  The barrel 12 has a feed screw portion SA for transporting the toner forming material injected from the injection port 14 to the kneading portion NA in order from the side closer to the injection port 14, and the toner forming material is melt-kneaded by the first kneading process. A kneading part NA, a feed screw part SB for transporting the toner forming material melted and kneaded in the kneading part NA to the kneading part NB, and the toner forming material is melted and kneaded in a second kneading process. It is divided into a kneading part NB that forms the smelted product and a feed screw part SC that transports the formed kneaded product to the discharge port 18.

  The barrel 12 is provided with temperature control means (not shown) that is different for each block. That is, the temperature may be controlled at different temperatures from the block 12A to the block 12J. FIG. 1 shows a state in which the temperatures of the block 12A and the block 12B are controlled to t0 ° C., the temperatures of the blocks 12C to 12E are controlled to t1 ° C., and the temperatures of the blocks 12F to 12J are controlled to t2 ° C. Yes. Therefore, the toner forming material of the kneading part NA is heated to t1 ° C., and the toner forming material of the kneading part NB is heated to t2 ° C.

  When the toner forming material containing the binder resin is supplied from the inlet 14 to the barrel 12, the toner forming material is sent to the kneading portion NA by the feed screw portion SA. At this time, since the temperature of the block 12C is set to t1 ° C., the toner forming material is fed into the kneading portion NA in a state of being heated and changed into a molten state. Since the temperatures of the block 12D and the block 12E are also set to t1 ° C., the toner forming material is melted and kneaded at the temperature of t1 ° C. in the kneading portion NA. The binder resin is in a molten state at the kneading portion NA and is subjected to shearing by the screw.

Next, the toner forming material that has been kneaded in the kneading part NA is sent to the kneading part NB by the feed screw part SB.
Next, the aqueous medium is added to the toner forming material by injecting the aqueous medium into the barrel 12 from the liquid addition port 16 in the feed screw portion SB. Moreover, although the form which inject | pours an aqueous medium in the feed screw part SB is shown in FIG. 1, it is not restricted to this, An aqueous medium may be inject | poured in the kneading part NB, The feed screw part SB and the kneading part NB In both cases, an aqueous medium may be injected. That is, the position and the injection location for injecting the aqueous medium are selected as necessary.

As described above, when the aqueous medium is injected into the barrel 12 from the liquid addition port 16, the toner forming material and the aqueous medium in the barrel 12 are mixed, and the toner forming material is cooled by the latent heat of vaporization of the aqueous medium. The temperature of the toner forming material is maintained appropriately.
Finally, the kneaded material formed by being melted and kneaded by the kneading part NB is transported to the discharge port 18 by the feed screw part SC and discharged from the discharge port 18.
As described above, the kneading process using the screw extruder 11 shown in FIG. 1 is performed.

-Cooling process-
The cooling step is a step of cooling the kneaded product formed in the kneading step. In the cooling step, the cooling temperature is 40 ° C. at an average temperature decrease rate of 4 ° C./sec or more from the temperature of the kneaded product at the end of the kneading step. It is preferable to cool to below. Rapid cooling at the above average cooling rate is preferable because the dispersion state immediately after the kneading process is maintained. In addition, the said average temperature-fall rate means the average value of the speed | rate to temperature-fall from the temperature of the kneaded material at the time of the completion | finish of a kneading process (for example, t2 degreeC when using the screw extruder 11 of FIG. 1) to 40 degreeC. .
Specific examples of the cooling method in the cooling step include a method using a rolling roll in which cold water or brine is circulated, a sandwiching cooling belt, and the like. When cooling is performed by the above method, the cooling rate is determined by the speed of the rolling roll, the flow rate of brine, the supply amount of the kneaded material, the slab thickness at the time of rolling the kneaded material, and the like. The slab thickness is preferably 1 to 3 mm.

-Crushing process-
The kneaded material cooled by the cooling process is pulverized by the pulverization process, and particles are formed. In the pulverization step, for example, a mechanical pulverizer or a jet pulverizer is used.

-Classification process-
The particles obtained by the pulverization step may be classified by a classification step in order to obtain toner particles having a volume average particle diameter in a target range, if necessary. In the classification process, conventionally used centrifugal classifiers, inertia classifiers, etc. are used, and fine powder (particles smaller than the target particle size) and coarse powder (target particle size). Larger particles) are removed.

-External addition process, sieving process-
The obtained toner particles may be provided with an external addition step and a sieving step in the same manner as in the aggregation and coalescence method.

[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. A range of is desirable.

[Image forming apparatus / image forming method]
Next, the image forming apparatus / image forming method according to the present embodiment will be described.
The image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the surface of the image carrier, an electrostatic image forming unit that forms an electrostatic image on the surface of the image carrier, and an electrostatic image development. Developing means for containing an agent and developing the electrostatic image formed on the image carrier with the electrostatic image developer as a toner image, and transfer means for transferring the toner image formed on the image carrier to a recording medium And fixing means for fixing the toner image transferred to the recording medium.
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 contains the electrostatic charge image developer according to the present embodiment and includes developing means for developing the electrostatic charge image formed on the image holding member as a toner image with the electrostatic image developer is preferably used.

The image forming method according to the present embodiment includes a charging step for charging the surface of 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 for developing the electrostatic image formed on the image carrier as a toner image, a transferring step for transferring the toner image transferred on the recording medium, and a fixing step for fixing the toner image transferred to the recording medium. Have.
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. 2 is a schematic configuration diagram showing a four-tandem color image forming apparatus. The image forming apparatus shown in FIG. 2 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, a recording medium (transfer object) P is fed at a predetermined timing into a gap where the secondary transfer roller 26 and the intermediate transfer belt 20 are pressed through a 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 medium P is applied to the toner image, so The toner image is transferred onto the recording medium 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 medium 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 medium P, thereby forming a fixed image.

Examples of the recording medium 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 recording medium is also smooth. For example, coated paper in which the surface of plain paper is coated with resin, art paper for printing, etc. are suitable. Used for.

The recording medium P on which the color image has been fixed is unloaded to 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 to the recording medium 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 transferred to a recording medium.

[Process cartridge, toner cartridge]
FIG. 3 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. 3, reference numeral 300 denotes a recording medium.
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. 3 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. 2 is an image forming apparatus having a configuration in which the toner cartridges 8Y, 8M, 8C, and 8K are attached and detached. The developing devices 4Y, 4M, 4C, and 4K each have a 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 specific rosin monomer)
-Synthesis of specific rosin monomer (1)-
200 parts of gum rosin (Mw 302.45) subjected to purification treatment (distillation conditions: 6.6 kpa, 220 ° C.) as a rosin component, 58 parts of ethylene carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.), and tetraethylammonium as a reaction catalyst 0.5 parts of bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged into a stainless steel reaction vessel equipped with a stirrer, heating device, cooling tube, nitrogen gas introduction tube and thermometer, and the temperature was raised to 170 ° C. A reaction between a carboxylic acid group and ethylene carbonate was performed. Continued at the same temperature for 4 hours. When the acid value reached 0.5 mgKOH / g, the temperature was lowered to 150 ° C., and then trimellitic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) 127 parts And the reaction was carried out at the same temperature for 1 hour to obtain a specific rosin monomer (1).

-Synthesis of specific rosin monomer (2)-
Identified in the same manner as specified rosin monomer (1) except that disproportionated rosin (trade name Ronchisu R, manufactured by Arakawa Chemical Industries, Ltd.) was used instead of gum rosin that had been purified by distillation as the rosin component. The rosin monomer (2) was synthesized.

-Synthesis of specific rosin monomer (3)-
Same as the specific rosin monomer (1) except that the rosin component was subjected to a purification treatment by distillation (distillation conditions: 6.6 kpa, 220 ° C.), and hydrogenated rosin modified with hydrogenated rosin. The specific rosin monomer (3) was synthesized by the method described above.

-Synthesis of specific rosin monomer (4)-
200 parts of disproportionated rosin (trade name Ronchisu R, manufactured by Arakawa Chemical Co., Ltd.) as a rosin component, 58 parts of 1,2-epoxypentane (manufactured by Tokyo Chemical Industry Co., Ltd.), and triphenylphosphine ( 0.7 parts (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged into a stainless steel reaction vessel equipped with a stirrer, heating device, cooling tube, nitrogen gas introduction tube and thermometer, and the temperature was raised to 170 ° C. The group was reacted with the epoxy group of the epoxy compound. Continued at the same temperature for 4 hours. When the acid value reached 0.5 mgKOH / g, the temperature was lowered to 150 ° C., and then trimellitic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) 127 parts And the reaction was carried out at the same temperature for 1 hour to obtain a specific rosin monomer (4).

-Synthesis of specific rosin monomer (5)-
200 parts of disproportionated rosin (trade name Ronchis R, manufactured by Arakawa Chemical Co., Ltd.) as a rosin component, 58 parts of 3,3-dimethyloxetane (manufactured by Aldrich), and 2-methylimidazole (Tokyo Chemical Industry ( Co., Ltd.) 0.5 parts was charged into a stainless steel reaction vessel equipped with a stirrer, heating device, cooling tube, nitrogen gas introduction tube and thermometer, the temperature was raised to 170 ° C., rosin carboxylic acid group and oxetane compound Reaction with the oxetane group. Continued at the same temperature for 4 hours. When the acid value reached 0.5 mgKOH / g, the temperature was lowered to 150 ° C., and then trimellitic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) 127 parts And the reaction was conducted at the same temperature for 1 hour to obtain a specific rosin monomer (5).

[Synthesis of comparative rosin monomer]
-Synthesis of acrylic modified rosin-
A three-necked flask containing 400 parts by mass of gum rosin subjected to purification by distillation (distillation conditions: 6.6 kpa, 220 ° C.), 105 parts by mass of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.2 parts by mass of t-butylcatechol And allowed to react at 220 ° C. for 12 hours. Subsequently, distillation under reduced pressure was performed to obtain an acrylic-modified rosin having a softening point of 90 ° C. and an acid value of 280 mgKOH / g.

[Synthesis of specific polyester resin]
-Specific polyester resin (1)-
267 parts of specific rosin monomer (1) as the carboxylic acid component, 81 parts of nonanediol (Wako Pure Chemical Industries, Ltd.) as the alcohol component, and tetra-n-butyl titanate (Tokyo Chemical Industry Co., Ltd.) as the reaction catalyst 5 parts are charged into a stainless steel reaction vessel equipped with a stirrer, heating device, thermometer, fractionator, and nitrogen gas inlet tube, and subjected to polycondensation at 200 ° C. for 15 hours with stirring in a nitrogen atmosphere to obtain the desired molecular weight. After confirming that the acid value was reached, a specific polyester resin (1) was synthesized.
The molecular weight, acid value, glass transition temperature and softening temperature were measured by the methods described above.

-Specific polyester resins (2) to (10), comparative polyester resins (1), (2)
The synthesis of the specific polyester resins (2) to (10) and the comparative polyester resins (1) and (2) was performed in the same manner as the specific polyester resin except that the carboxylic acid component and the alcohol component were changed as shown in Table 1. went.
The molecular weight, acid value, glass transition temperature and softening temperature were measured by the methods described above.

[Example 1]
(Manufacture of toner particles 1)
Specific polyester resin (1) 100 parts by mass Magenta pigment (CI Pigment Red 57) 3 parts by mass The above composition was kneaded with an extruder and pulverized with a surface pulverizer. Thereafter, the process of classifying fine particles and coarse particles with a wind classifier (turbo classifier (TC-15N), manufactured by Nisshin Engineering Co., Ltd.) to obtain particles of intermediate size is repeated three times, and the volume average particle size = 8 μm of magenta toner particles 1 were obtained.

(Manufacture of electrostatic charge image developer 1)
-Production of Toner 1-
To 100 parts by mass of magenta toner particles 1, 0.5 part by mass of silica (trade name: R812 (manufactured by Nippon Aerosil Co., Ltd.)) was added and mixed with a high speed mixer to obtain toner 1.

Using a carrier made of ferrite having a particle diameter of about 50 μm coated with toner 1 and a methyl methacrylate-styrene copolymer, 7 parts by mass of toner 1 is added to 100 parts by mass of the carrier, and mixed with a tumbler shaker mixer. An electrostatic charge image developer 1 was obtained.
The environmental conditions for mixing the toner and the carrier are the summer environment (30 ° C., relative humidity 85%) and the winter environment (5 ° C., relative humidity 10%). Charge image developer 1 was obtained.

(Evaluation)
The electrostatic charge image developer 1 was evaluated for the following items.
The evaluation results are shown in Table 2 below.

-Measurement of charge amount-
The toner charge amount (μC / g) of the electrostatic image developer 1 was measured using a Toshiba blow-off charge amount measuring machine. As a result, the electrostatic charge image developer produced in the summer environment showed a charge amount of −35.1 μC / g, and the electrostatic charge image developer produced in the winter environment showed a charge amount of −55.4 μC / g. 63. It is to be noted that the closer the ratio between the two is to 1, the smaller the charge amount between the summer environment and the winter environment, which is a desirable result.

-Evaluation of blocking-
A developer of an electrophotographic copying machine (trade name: A-color, manufactured by Fuji Xerox Co., Ltd.) is filled with an electrostatic charge image developer 1, and a print test chart having an image density of 1% is obtained using this electrophotographic copying machine. 10,000 images were output and a copy test was performed.
The appearance of white streaks in the image solid portion after printing 10,000 sheets was observed, and the state of toner in the developing unit was visually observed. Based on these observations, blocking resistance was evaluated according to the following criteria.
The evaluation result is ○, and there is no problem in use.

A: No white streak is generated, and almost no toner is blocked in the developing unit.
○: No white streak is generated, but a slight amount of blocked toner is observed in the developing device.
Δ: Little white streak is generated, and some blocked toner is observed in the developing device.
X: Generation of white streaks is clearly seen, and toner blocked in the developing device is seen.

-Evaluation of toner storage stability-
After 10,000 images were formed in the above blocking evaluation, the surface of the toner remaining in the developing unit was observed with an electron microscope. 100 toners were observed, the number of crushed toners was counted, and the toner storage stability was evaluated according to the following criteria.
The evaluation result is ○, and there is no problem in use.

A: There is no crushed toner.
○: One or more crushed toners are seen.
Δ: Three to five crushed toners are seen.
X: Ten or more crushed toners are seen.

[Examples 2 to 4, Comparative Example 1]
Except that the specific polyester resin (1) is changed to the resin shown in Table 2, the toner particles 2 to 4, the comparative toner particles 1, the toner 2 to 4, the comparative toner 1 and the electrostatic charge image are produced in the same manner as in Example 1. Developers 2 to 4 and Comparative electrostatic image developer 4 were obtained.
These electrostatic charge image developers were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 2 below.

[Example 5]
(Preparation of specific polyester resin (5) particle dispersion)
200 parts by mass of the specific polyester resin (5) was placed in a high-temperature / high-pressure emulsifier (Cabitron CD1010, manufactured by Eurotech Co., Ltd.), and heated and melted at a temperature of 120 ° C. A 0.37% by mass diluted ammonia water obtained by diluting reagent ammonia water with ion-exchanged water is placed in a separately prepared aqueous medium tank, and heated in a heat exchanger at 120 ° C. at a rate of 0.1 liter / min. Transferred. The Cavitron was operated under conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm 2 to obtain a specific polyester resin (5) particle dispersion having a volume average particle diameter of 160 nm and a solid content of 30% by mass.

(Preparation of colorant dispersion)
The following components were mixed and dispersed for 1 hour with a high-pressure impact disperser Ultimizer (HJP30006, manufactured by Sugino Machine Co., Ltd.) to obtain a colorant particle dispersion having a volume average particle size of 180 nm and a solid content of 20% by mass.
Cyan pigment (Pigment Blue 15: 3, manufactured by Dainichi Seika Kogyo Co., Ltd.) 10 parts by mass Anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts by mass

(Preparation of crystalline polyester resin particle dispersion)
115 parts by mass of dodecanedioic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 101 parts by mass of dodecanediol (manufactured by Ube Industries, Ltd.) are charged into a flask, the temperature is raised to 160 ° C. over 1 hour, and the reaction system is stirred. Then, 0.02 part by mass of dibutyltin oxide was added. Further, while distilling off generated water, the temperature was raised from the same temperature to 200 ° C. over 6 hours, and the dehydration condensation reaction was continued at 200 ° C. for further 4 hours to complete the reaction. After cooling the reaction solution, the solid material obtained by solid-liquid separation was dried under vacuum at 40 ° C. to obtain a crystalline polyester resin.

  The following composition was heated to 120 ° C. using the obtained crystalline polyester resin and dispersed with IKA Ultra Turrax T50, and then dispersed with a pressure discharge type homogenizer, resulting in a volume average particle size of 180 nm. By the way, it was recovered. Thus, a crystalline polyester resin particle dispersion having a solid content of 20% by mass was obtained.

-Composition-
-Crystalline polyester resin 50 parts by mass-Anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts by mass-Ion-exchanged water 200 parts by mass

(Manufacture of toner particles 5)
-Specific polyester resin (5) particle dispersion 150 parts by mass-Colorant particle dispersion 25 parts by mass-Crystalline resin particle dispersion 50 parts by mass-Polyaluminum chloride 0.4 part by mass-Ion exchange water 100 parts by mass

In accordance with the above formulation, the components were mixed and dispersed in a round stainless steel flask using Ultra Turrax T50 (manufactured by IKA), and then heated to 48 ° C. while stirring the flask in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, 70 parts by mass of the specific polyester resin (5) particle dispersion was added thereto.
Then, after adjusting the pH in the system to 8.0 using a 0.5 mol / L sodium hydroxide aqueous solution, the stainless steel flask was sealed, and the stirring shaft seal was magnetically sealed while continuing stirring. Heat to 90 ° C. and hold for 3 hours.
After completion of the reaction, the temperature was lowered at a rate of 2 ° C./min, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed with 3 L of ion exchange water at 30 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was further repeated 6 times, and when the pH of the filtrate became 7.54 and the electric conductivity was 6.5 μS / cm, No. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued for 12 hours to obtain toner particles (5).

The volume average particle diameter of the toner particles 5 was measured with a call counter and found to be 5.2 μm. Further, this toner was mixed with silica (SiO ₂ ) particles having an average primary particle diameter of 40 nm and surface-hydrophobized with hexamethyldisilazane (hereinafter sometimes abbreviated as “HMDS”), metatitanic acid and isobutyltrimethoxysilane. The metatitanic acid compound particles having a primary particle size average particle diameter of 20 nm, which is the reaction product of the above, are added so that the coverage of the surface of each colored particle is 40%, mixed with a Henschel mixer, and toner particles 5 are mixed. Produced.

(Manufacture of electrostatic charge image developer 5)
-Production of Toner 5-
0.5 parts by mass of silica (trade name: R812 (manufactured by Nippon Aerosil Co., Ltd.)) was added to 100 parts by mass of the toner particles 5 and mixed with a high speed mixer to obtain toner 5.

Using the produced toner 5, a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by mass of polymethacrylate (manufactured by Soken Chemical Co., Ltd.) is weighed so that the toner concentration becomes 5% by mass and stirred for 5 minutes with a ball mill By mixing, an electrostatic charge image developer 5 was prepared.
The environmental conditions for mixing the toner and the carrier are the summer environment (30 ° C., relative humidity 85%) and the winter environment (5 ° C., relative humidity 10%). An electrostatic charge image developer 5 was obtained.

(Evaluation)
The obtained electrostatic charge image developer 5 was evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 2 below.

[Examples 6 to 10, Comparative Example 2]
Toner particles 6 to 10 and comparative toner in the same manner as in Example 5 except that the specific polyester resin (5) was changed to specific polyester resins (6) to (10) and comparative polyester resin (2) shown in Table 2. Particles 2, electrostatic charge image developer 6 to 10, and comparative electrostatic charge image developer 2 were prepared.
The obtained toner particles and electrostatic image developer were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 2 below.

  From the above results, it can be seen that in this example, better results were obtained with respect to charge amount, blocking property, and toner storage stability than in the comparative example.

1Y, 1M, 1C, 1K, 107 photoconductor (image carrier)
2Y, 2M, 2C, 2K, 108 Charging roller 3Y, 3M, 3C, 3K Laser beam 3 Exposure device 4Y, 4M, 4C, 4K, 111 Developing device (developing means)
5Y, 5M, 5C, 5K Primary transfer rollers 6Y, 6M, 6C, 6K, 113 Photoconductor cleaning device (cleaning means)
8Y, 8M, 8C, 8K Toner cartridges 10Y, 10M, 10C, 10K Unit 20 Intermediate transfer belt 22 Drive roller 24 Support roller 26 Secondary transfer roller (transfer means)
28,115 Fixing device (fixing means)
30 Intermediate transfer member cleaning device 32 Transport roll (discharge roll)
112 Transfer device 116 Mounting rail 117 Opening 118 for static elimination exposure Opening 200 for exposure Process cartridge,
P, 300 recording medium (transfer object)

Claims (8)

An alcohol component,
Carboxylic acid component containing dicarboxylic acid which is reaction product of rosin monool which is reaction product of any one of epoxy compound, carbonate compound and oxetane compound and rosin and trifunctional carboxylic acid or anhydride thereof When,
Polyester resin for electrostatic image developing toner, which is a polycondensate of   The polyester resin for electrostatic image developing toner according to claim 1, wherein the rosin is a disproportionated rosin.   An electrostatic image developing toner comprising the polyester resin for electrostatic image developing toner according to claim 1.   An electrostatic image developer comprising the electrostatic image developing toner according to claim 3. Containing the electrostatic charge image developing toner according to claim 3;
A toner cartridge to be attached to and detached from the image forming apparatus. A developing means for accommodating the electrostatic charge image developer according to claim 4 and developing the electrostatic charge image formed on the image carrier as a toner image by 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 surface of 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 image developer according to claim 4 and developing the electrostatic image formed on the image carrier as a toner image by the electrostatic image developer;
Transfer means for transferring the toner image formed on the image carrier to a recording medium;
Fixing means for fixing the toner image transferred to the recording medium;
An image forming apparatus comprising: A charging step for charging the surface of 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 the electrostatic image formed on the image carrier as a toner image with the electrostatic image developer according to claim 4;
A transfer step of transferring the toner image formed on the image carrier to a recording medium;
A fixing step of fixing the toner image transferred to the recording medium;
An image forming method comprising:

Images