JP2013049821A - Novel polyester, electrostatic charge image developing toner, electrostatic charge image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polyester in which stench of rosin is controlled.SOLUTION: The polyester is a condensation polymer of a carboxylic acid component including modified rosin by a compound shown by General Formula (1), and an alcohol component. In the General Formula (1), Rdenotes a hydrogen atom or a methyl group; and L denotes a divalent linking group chosen from the group that consists of an ester group, a chain alkylene group, a cyclic alkylene group, a phenylene group, and a combination of them.

Description

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

  Patent Document 1 proposes a printing ink resin obtained by subjecting a rosin, an α, β-unsaturated carboxylic acid or anhydride thereof, an aliphatic polybasic acid, and a polyhydric alcohol to a heat reaction.

  Patent Document 2 proposes a polyester for toner obtained by polycondensation of an alcohol component and a carboxylic acid component containing (meth) acrylic acid-modified rosin.

  Patent Document 3 includes an alcohol component containing at least a binder resin and a colorant, wherein the binder resin contains an aliphatic polyhydric alcohol, and a carboxylic acid component containing a (meth) acrylic acid-modified rosin. An image forming apparatus using a toner containing a polyester resin obtained by condensation polymerization has been proposed.

JP 2001-011164 A JP 2007-292815 A JP 2007-292869 A

  An object of this invention is to provide the novel polyester which suppressed the odor of rosin.

The invention according to claim 1
It is a polyester which is a condensation polymer of a carboxylic acid component containing a modified rosin by a compound represented by the following general formula (1) and an alcohol component.

In general formula (1), R ¹ represents a hydrogen atom or a methyl group. L represents a divalent linking group selected from the group consisting of ester groups, chain alkylene groups, cyclic alkylene groups, phenylene groups, and combinations thereof.

The invention according to claim 2
2. The polyester according to claim 1, wherein the content of a low molecular weight component having a weight average molecular weight (Mw) of 500 or less is 11% by mass or less in the polyester.

The invention according to claim 3
An electrostatic charge image developing toner comprising the polyester 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
Storing the electrostatic image developing toner according to claim 3;
The toner cartridge is detachable from the image forming apparatus.

The invention according to claim 6
Containing the electrostatic charge image developer according to claim 4;
Developing means for developing an electrostatic image formed on the surface of the image carrier with the electrostatic image developer to form a toner image;
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 image carrier;
Development means for containing the electrostatic charge image developer according to claim 4 and developing the electrostatic charge image with the electrostatic charge image developer to form a toner image;
Transfer means for transferring the toner image to a recording medium;
Fixing means for fixing the toner image on 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 image carrier;
A developing step of developing the electrostatic charge image with the electrostatic charge image developer according to claim 4 to form a toner image;
A transfer step of transferring the toner image to a recording medium;
A fixing step of fixing the toner image on the recording medium;
Is an image forming method.

According to the invention of claim 1, the rosin odor is suppressed compared to the polyester polycondensed using a carboxylic acid component containing a rosin modified with a compound other than the compound represented by the general formula (1). Is obtained.
According to the invention of claim 2, the odor is suppressed as compared with the polyester of claim 1, wherein the content of the low molecular weight component having a weight average molecular weight (Mw) of 500 or less is more than 11% by mass in the polyester. The finished polyester is obtained.
According to the invention of claim 3, compared with the case where a polyester polycondensed using a carboxylic acid component containing a rosin modified with a compound other than the compound represented by the general formula (1) is applied, An electrostatic charge image developing toner with suppressed odor can be obtained.
According to the invention of claim 4, an electrostatic charge image developing toner using a polyester polycondensed using a carboxylic acid component containing a rosin modified with a compound other than the compound represented by the general formula (1) is applied. As a result, an electrostatic charge image developer in which the odor of rosin is suppressed is obtained.

  According to the fifth, sixth, seventh, and eighth aspects of the invention, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming that can realize image formation in which the odor of rosin caused by the electrostatic image developing toner is suppressed. Provide a method.

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>
The polyester according to the present embodiment includes a carboxylic acid component containing a modified rosin (hereinafter sometimes referred to as “specific carboxylic acid-modified rosin”) by a compound represented by the following general formula (1), and an alcohol component. Polyester which is a condensation polymer.

In general formula (1), R ¹ represents a hydrogen atom or a methyl group. L represents a divalent linking group selected from the group consisting of ester groups, chain alkylene groups, cyclic alkylene groups, phenylene groups, and combinations thereof.

  Here, as a feature of rosin, it is difficult to contain water because of its bulky structure and high hydrophobicity. As a method for introducing a rosin having such properties into a polyester, for example, it is known to use a carboxylic acid-modified rosin modified with a carboxylic acid as a polyvalent carboxylic acid component.

  However, since rosin has a peculiar odor, the odor of rosin tends to remain in the polyester using the carboxylic acid-modified rosin.

On the other hand, in the polyester according to this embodiment, the odor of rosin is suppressed by polycondensation of the specific carboxylic acid-modified rosin and the alcohol component.
Although this reason is not certain, it is thought to be due to the following reasons.

The specific carboxylic acid-modified rosin is modified by a compound represented by the general formula (1) having a divalent linking group L linking a carboxyl group and (C═C (R ¹ ) —CO ₂ —). Therefore, in the specific carboxylic acid-modified rosin, the carboxyl group imparted by the compound represented by the general formula (1) is bonded to the condensed ring of the rosin via the divalent linking group L, It does not bond directly to the fused ring (see, for example, Structural Formula (I) below).
That is, the specific carboxylic acid-modified rosin is considered to have the structure shown below. For example, the position of the carboxyl group is rosin as compared with the acrylic acid-modified rosin modified with acrylic acid or the like shown in the following structural formula (II). It is located away from the condensed ring.
Therefore, it is considered that the carboxyl group of the specific carboxylic acid-modified rosin is less affected by steric hindrance from the condensed ring and rich in reactivity.
Furthermore, since the specific carboxylic acid-modified rosin is a primary carboxylic acid, it is considered to be rich in reactivity.

  Therefore, since the specific carboxylic acid-modified rosin is rich in reactivity, the polycondensation reaction between the specific carboxylic acid-modified rosin and the alcohol component at the time of manufacturing the polyester according to this embodiment easily proceeds. It is considered that the residual polyester component and oligomer component resulting from the unreacted specific carboxylic acid-modified rosin are reduced in the obtained polyester.

  From the above, it is considered that the odor of rosin is suppressed in the polyester according to this embodiment.

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

  The polyester according to this embodiment is a condensation polymerization of a carboxylic acid component containing a specific carboxylic acid-modified rosin and an alcohol component.

First, the carboxylic acid component will be described.
The carboxylic acid component includes a specific carboxylic acid-modified rosin, but may include other carboxylic acids other than the carboxylic acid component.
However, the specific carboxylic acid-modified rosin is preferably contained in an amount of 50% by mass or more and 100% by mass or less, and more preferably 70% by mass or more and 100% by mass or less, based on the total carboxylic acid component.

-Specific carboxylic acid modified rosin-
First, the specific carboxylic acid-modified rosin contained in the carboxylic acid component will be described.
The specific carboxylic acid-modified rosin includes, for example, those obtained by subjecting the rosin before modification to an addition reaction of the compound represented by the general formula (1) (unsaturated carboxylic acid). More specifically, For example, it is obtained through Diels-Alder reaction under heating with an acid having a conjugated double bond in the main components of rosin before modification and an unsaturated carboxylic acid.
As the specific carboxylic acid-modified rosin, an acrylic acid-modified rosin modified with acrylic acid having little steric hindrance is desirable from the viewpoint of reaction activity in Diels-Alder reaction.

  The degree of modification of rosin (hereinafter referred to as the degree of modification with unsaturated carboxylic acid) is, for example, from 5 to 105, preferably from 20 to 105, from the viewpoint of increasing the molecular weight of the polyester and reducing the low molecular weight oligomer component. It is preferably 40 or more and 105 or less, and more preferably 60 or more and 105 or less.

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

Here, the SP value is a softening temperature measured by a ring and ball automatic softening point tester. Specifically, the SP value is a value obtained by pouring a target sample in a molten state into a ring, cooling to room temperature (for example, 25 ° C.), and measuring under the following conditions based on JIS B7410.
Measuring instrument: Ring and ball automatic softening point tester ASP-MGK2 (manufactured by Meitec)
・ Raising rate: 5 ° C / min
-Temperature rise start temperature: 40 ° C
-Measurement solvent: Glycerin Further, the saturated SP value is the SP value when the reaction of unsaturated carboxylic acid and rosin is caused to react until the SP value of the obtained specific carboxylic acid-modified rosin reaches the saturation value.

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

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

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

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

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

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

-Unsaturated carboxylic acid-
In the compound represented by the following general formula (1), R ¹ represents a hydrogen atom or a methyl group. L represents a divalent linking group selected from the group consisting of ester groups, chain alkylene groups, cyclic alkylene groups, phenylene groups, and combinations thereof.

In the general formula (1), R ^1, from the viewpoint of the reaction activity in the Diels-Alder reaction, it is desirable that R ¹ is a hydrogen atom.
Specific examples of L in the general formula (1) include at least one selected from structures represented by the following general formulas (2) to (4).

In the general formula (2), X ¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms. X ¹ is preferably an ethylene group or a pentylene group.
In the general formula (3), X ² represents a linear or branched alkylene group having 1 to 10 carbon atoms, and Y ¹ represents a linear, branched or cyclic group having 1 to 10 carbon atoms. An alkylene group or a phenylene group. X ² is preferably an ethylene group, and Y ¹ is preferably an ethylene group, a cyclohexylene group or a phenylene group.
In the general formula (4), X ³ represents a linear or branched alkylene group having 1 to 10 carbon atoms, and Y ² represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. Represents a group or a phenylene group, and n represents an integer of 1 to 5. X ³ is preferably an ethylene group or a pentylene group, and Y ² is preferably a cyclohexylene group.

  Although an exemplary compound is shown as a specific example of a compound shown by General formula (1) below, this-application embodiment is not limited to these.

-Method for producing specific carboxylic acid-modified rosin-
Although it does not specifically limit as a manufacturing method of specific carboxylic acid modified rosin, For example, by mixing rosin and unsaturated carboxylic acid and heating to 180 degreeC or more and 260 degrees C or less (desirably 180 degreeC or more and 210 degrees C or less), An unsaturated carboxylic acid is added to an acid having a conjugated double bond contained in rosin by Diels-Alder reaction to obtain a specific carboxylic acid-modified rosin.
The specific carboxylic acid-modified rosin may be used as it is after the reaction, or may be used after purification through an operation such as distillation.

  The ratio between the rosin and the compound represented by the general formula (1) is preferably 30 to 120 mol, more preferably 50 to 110 mol, relative to 100 mol of rosin.

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

  In the Diels-Alder reaction, it is desirable to use a polymerization inhibitor in order to prevent polymerization of the compounds represented by the general formula (1).

Preferred examples of the polymerization inhibitor include phenols, and preferred examples of the phenols include divalent phenols and phenolic compounds having a substituent at least in the ortho position with respect to the hydroxyl group (hereinafter, hindered phenols). Is a hindered phenol.
The divalent phenol is a compound in which two OH groups are bonded to a benzene ring and has no other substituent, and specific examples thereof include hydroquinone.

  Examples of the hindered phenol include mono-t-butyl-p-cresol, mono-t-butyl-m-cresol, t-butylcatechol, 2,5-di-t-butylhydroquinone, 2,5-di- t-amylhydroquinone, propylgardo, 4,4'-methylenebis (2,6-t-butylphenol), 4,4'-isopropylidenebis (2,6-di-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), butylhydroxyanisole, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butylphenol, 2,6-di-t-butyl- 4-ethylphenol, 2,4,6-tri-t-butylphenol, octadecyl-3- (4-hydroxy-3 ', 5'-di-t-butylphenol Nyl) propionate, distearyl (4-hydroxy-3-methyl-5-t-butyl) benzyl malonate, 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bisoctylthio -1,3,5-triazine, 2,6-diphenyl-4-octadecanoxyphenol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4- Ethyl-6-tert-butylphenol), 2,2′-isobutylidenebis (4,6-dimethylphenol), 2,2′-dihydroxy-3,3′-di- (α-methylcyclohexyl) -5 , 5′-dimethyldiphenylmethane, 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), tris [β- (3,5-di-t-butyl-4- Idroxyphenyl) propionyloxyethyl isocyanurate], 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, tris (3,5-di-tert-butyl) -4-hydroxyphenol) isocyanurate, 1,1,3′-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,6-bis (2′-hydroxy-3′-t) -Butyl-5'-methylbenzyl) -4-methylphenol, N, N'-hexamethylene bis (3,5-di-t-butyl-4-hydroxyhydrocinnamate), hexamethylene glycol bis [β- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [β- (3-t-butyl) -5-methyl-4-hydroxyphenyl) propionate], tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenylpropionate) methane, and the like. From the viewpoint of suppressing polymerization of unsaturated carboxylic acids represented by (1), for example, t-butylcatechol and 2,5-di-t-butylhydroquinone are desirable.

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

-Carboxylic acids other than modified rosin-
As the carboxylic acid other than the modified rosin contained in the carboxylic acid component, at least one selected from the group consisting of aromatic dicarboxylic acids and aliphatic dicarboxylic acids is used. 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.

-Alcohol component-
As the alcohol component, for example, at least one selected from aliphatic diols is used. Specific examples of the aliphatic diol include 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, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, dimer diol, 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethylpropanoate, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene Although glycol etc. are mentioned, it is not limited to these. These aliphatic diols may be used alone or in combination of two or more.
Among these, considering availability, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are desirable.
Moreover, in this embodiment, you may further use etherified diphenol with an aliphatic diol, for example. 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. It is desirable that it is 2 to 16 moles.

-Manufacturing method of polyester-
The polyester according to this embodiment is prepared by a known and commonly used production method using a carboxylic acid component and an alcohol component as raw materials. As the reaction method, for example, either a transesterification reaction or a direct esterification reaction may be applied. Further, polycondensation may be promoted by a method of increasing the reaction temperature by pressurization, a method of reducing the pressure, or a method of flowing an inert gas under normal pressure. Depending on the above reaction, for example, 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 weight or more and 1.5 parts by weight or less, and 0.05 parts by weight or more with respect to 100 parts by weight of the total amount of the polyvalent carboxylic acid component and the polyhydric alcohol component. 1.0 mass part or less is more desirable. The reaction temperature is, for example, a temperature of 180 ° C. or higher and 300 ° C. or lower.

  In addition, when the polyester which concerns on this embodiment is hydrolyzed, it will decompose | disassemble into each monomer (a carboxylic acid component and an alcohol component). Polyester is, for example, a 1: 1 condensate of carboxylic acid and alcohol (for example, diol), so the resin composition is estimated from the decomposition product.

-Characteristics of polyester-
In the polyester according to this embodiment, the content of a low molecular weight component having a weight average molecular weight (Mw) of 500 or less is desirably 11% by mass or less in the total polyester.
The smaller the content of the low molecular weight component having a weight average molecular weight (Mw) of 500 or less, the less the unreacted unsaturated carboxylic acid-modified rosin in the polyester, and the low molecular weight component having a weight average molecular weight (Mw) of 500 or less. The odor is suppressed as compared with the polyester according to this embodiment in which the content is more than 11% by mass in the polyester.
The content of the low molecular weight component of 500 or less is more preferably 3.6% by mass or less, and still more preferably 1.5% by mass or less.
The content of the low molecular weight component is measured by high performance liquid chromatography (HPLC) (manufactured by Shimadzu Corporation) using the synthesized polyester as a sample. Measurement is performed at a detection wavelength of 210 nm using an acetonitrile / sodium phosphate buffer solution as an eluent.

The weight average molecular weight of the polyester according to the exemplary embodiment is desirably 4000 or more and 1000000 or less, and more desirably 7000 or more and 300000 or less, from the viewpoint of toner durability and offset resistance.
For the measurement of the weight average molecular weight Mw and the number average molecular weight Mn, two “HLC-8120GPC, SC-8020 (6.0 mm ID × 15 cm) manufactured by Tosoh Corporation” were used, and THF (tetrahydrofuran) was used as an eluent. Use. As experimental conditions, an experiment is performed 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 a RI (refractive index) detector (differential refractive index detector). The calibration curve is “Polystyrene standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A” -2500 "," F-4 "," F-40 "," F-128 ", and" F-700 ".

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

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

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

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

When the polyester of this embodiment is used as a binder resin for an electrostatic charge image developing toner, an electrostatic charge image developing toner in which the odor of rosin is suppressed can be obtained.
To the toner of the present embodiment, a known binder resin, for example, a vinyl resin such as styrene-acrylic resin, an epoxy resin, a polycarbonate, a polyurethane, or the like is used in combination as long as the effects of the present embodiment are not impaired. However, the content of the polyester of the present invention is preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably 100% by weight in the binder resin.
However, the use of the polyester according to the present embodiment is not limited to the electrostatic charge image developing toner.

<Toner for electrostatic image development>
The electrostatic charge image developing toner according to the present embodiment (hereinafter sometimes referred to as “toner”) includes the polyester according to the present embodiment.

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

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

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

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

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

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

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

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

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

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

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

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

-Toner particle characteristics-
The toner particles may be toner particles having a single layer structure, or toner particles having a so-called core / shell structure composed of a core (core particle) and a coating layer (shell layer) covering the core. May be.
The toner particles having a core / shell structure include, for example, a binder resin (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 size of the toner particles is, for example, preferably from 2.0 μm to 10 μm, and more preferably from 3.5 μm to 7.0 μm.
As a method for measuring the volume average particle diameter of the toner particles, 0.5 mg to 50 mg of a measurement sample is added to 2 ml of a 5% by weight aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate as a dispersant. The electrolyte was added to 100 ml to 150 ml. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment for 1 minute with an ultrasonic disperser, and the particle size of the particle size is measured with the Coulter Multisizer II type (manufactured by Beckman-Coulter) using an aperture having an aperture diameter of 100 μm. Is a particle size distribution of particles in the range of 2.0 μm or more and 60 μm or less. 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 scattered on the surface of the slide glass is taken into a Luzex image analyzer through a video camera, and the maximum length and projected area of 100 particles are obtained, calculated by the above equation (1), and the average value is calculated. It is obtained by seeking.

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

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

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

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

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

(Resin particle dispersion preparation process)
First, together with a resin particle dispersion in which polyester resin particles are dispersed, for example, a colorant particle dispersion in which colorant particles are dispersed and a release agent dispersion in which release agent particles are dispersed are prepared.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Synthesis of unsaturated carboxylic acid-modified rosin]
(Unsaturated carboxylic acid-modified rosin (1))
Gum rosin 400 g, β-carboxyethyl acrylate (Daicel Co., Ltd.), which was purified by distillation (distillation conditions: 6.6 kPa, 220 ° C.) in a stainless steel reaction vessel equipped with a stirrer, a heating device, a condenser, and a thermometer. ), Exemplified Compound (1) 210 g and t-butylcatechol 0.3 g were added and reacted at 220 ° C. for 12 hours to obtain an unsaturated carboxylic acid-modified rosin (1).
Thereafter, distillation was performed at 220 ° C. under a reduced pressure of 6.6 kPa to distill off unreacted β-carboxyethyl acrylate. The distillate was 21 g.
The obtained unsaturated carboxylic acid rosin had a modification degree of 95.

(Unsaturated carboxylic acid-modified rosin (2))
400 g of gum rosin, purified by distillation (distillation conditions: 6.6 kPa, 220 ° C.) in a stainless steel reaction vessel equipped with a stirrer, a heating device, a cooling tube and a thermometer, EO-modified succinic acrylate (trade name HOA) -MS, 315 g of Exemplified Compound (3) manufactured by Kyoeisha Chemical Co., Ltd. and 0.4 g of t-butylcatechol were added and reacted at 220 ° C. for 12 hours to obtain an unsaturated carboxylic acid-modified rosin (2).
Thereafter, distillation was performed at 220 ° C. under a reduced pressure of 6.6 kPa, and unreacted EO-modified succinic acrylate was distilled off. The distillate was 26.5g.
The obtained unsaturated carboxylic acid rosin had a modification degree of 90.

(Unsaturated carboxylic acid-modified rosin (3))
400 g of gum rosin, ω-carboxy-polycaprolactone monoacrylate (purified by distillation (distillation conditions: 6.6 kPa, 220 ° C.)) in a stainless steel reaction vessel equipped with a stirrer, a heating device, a cooling tube and a thermometer Product name Aronix M-5300, manufactured by Toa Gosei Co., Ltd., 435 g of Exemplified Compound (5)) and 0.6 g of t-butylcatechol were added and reacted at 220 ° C. for 12 hours to give unsaturated carboxylic acid-modified rosin (3). Obtained.
Then, distillation was performed at 220 ° C. under a reduced pressure of 6.6 kPa to distill off unreacted ω-carboxy-polycaprolactone monoacrylate. The distillate was 38 g.
The obtained unsaturated carboxylic acid rosin had a modification degree of 94.

(Unsaturated carboxylic acid-modified rosin (4))
400 g of gum rosin subjected to purification by distillation (distillation conditions: 6.6 kPa, 220 ° C.) in a stainless steel reaction vessel equipped with a stirrer, a heating device, a condenser, and a thermometer, EO-modified succinic acid methacrylate (trade name HO- MS, Kyoeisha Chemical Co., Ltd. make, exemplary compound (2) 333g, t-butylcatechol 0.4g was added, and it was made to react at 220 degreeC for 12 hours, and unsaturated carboxylic acid modified rosin (4) was obtained.
Thereafter, distillation was performed at 220 ° C. under a reduced pressure of 6.6 kPa, and unreacted EO-modified succinic acid methacrylate was distilled off. The distillate was 28 g.
The obtained unsaturated carboxylic acid rosin had a modification degree of 95.

(Unsaturated carboxylic acid-modified rosin (1) for comparative example)
400 g of gum rosin, purified by distillation (distillation conditions: 6.6 kPa, 220 ° C.) in a stainless steel reaction vessel equipped with a stirrer, heating device, cooling tube, and thermometer, acrylic acid (Wako Pure Chemical Industries, Ltd.) ) 105 g and 0.2 g of t-butylcatechol were added and reacted at 220 ° C. for 12 hours to obtain comparative modified rosin (1). Then, distillation was performed at 220 ° C. under a reduced pressure of 6.6 kPa to distill off unreacted acrylic acid. The distillate was 15 g.
The obtained unsaturated carboxylic acid rosin had a modification degree of 94.

[Synthesis of polyester]
(Polyester (1))
223 g of unsaturated carboxylic acid-modified rosin (1) as the carboxylic acid component, 38 g of 1,2-propanediol (manufactured by Wako Pure Chemical Industries, Ltd.) as the alcohol component, and tetra-n-butyl titanate (Tokyo Chemical Industry) as the reaction catalyst (Made by Co., Ltd.) 0.5 g was charged into a stainless steel reaction vessel equipped with a stirrer, a heating device, a thermometer, a fractionation device, and a nitrogen gas introduction tube, and stirred for 10 hours at 230 ° C. with stirring in a nitrogen atmosphere. After condensation, the molecular weight and acid value were confirmed, and polyester (1) was synthesized.
It was 3.5 mass% when the residual amount of the low molecular weight component of the weight average molecular weight (Mw) 500 or less was measured by HPLC.

-Identification of polyester (1)-
2 g of the synthesized specific polyester resin (1) was taken and hydrolyzed by heating at 150 ° C. for 3 hours in 10 ml of heavy dimethyl sulfoxide and 2 ml of a heavy methanol solution of sodium hydroxide (7N). Thereafter, heavy water was added, ¹ H-NMR measurement was performed, and it was confirmed that the resin was composed of the unsaturated carboxylic acid-modified rosin (1) and 1,2-propanediol according to the charged values.

(Polyester (2) to (10), Comparative polyester (1))
Polyesters (2) to (10) and comparative polyester (1) were synthesized using the monomers shown in Table 1 below in the same manner as the synthesis of polyester (1). The molecular weight, acid value, glass transition temperature (Tg), softening temperature, measurement result of unsaturated carboxylic acid-modified rosin and the type of rosin are shown.

-Identification of polyesters (2) to (10)-
When the obtained polyesters (2) to (10) were examined in the same manner as the polyester (1), it was confirmed that the resin was constituted according to the charged values, and the obtained compounds were respectively polyesters (2) to ( 10).

[Example 1]
(Manufacture of toner particles 1)
Polyester (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 developer 1)
-Production of Toner Composition 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 composition 1.

  Using a carrier made of ferrite having a particle size of about 50 μm coated with the toner composition 1 and a methyl methacrylate-styrene copolymer, 7 parts by mass of the toner composition 1 is added to 100 parts by mass of the carrier, and a tumbler shaker mixer is added. To obtain developer 1.

[Evaluation]
(Odor evaluation)
The obtained toner particles 1 were subjected to odor sensory evaluation.
Odor sensory evaluation was performed on 10 randomly selected testers using toner particles heated to 150 ° C. on a hot plate.
The evaluation criteria are as follows.
◎: 10 out of 10 people do not feel odor ○: 2 out of 10 people feel odor △: 5 out of 10 people feel odor ×: 8 out of 10 people feel odor

[Examples 2 to 5, Comparative Example 1]
Toner particles 2 to 5, Comparative toner particles 1 and toner in the same manner as in Example 1 except that the polyester (1) and magenta pigment (CI Pigment Red 57) are changed to the polyester and pigment shown in Table 2. Compositions 2 to 5, Comparative toner composition 1, Developers 2 to 5, and Comparative developer 1 were obtained.
The evaluation results are shown in Table 2 below.

[Example 6]
(Preparation of polyester (6) particle dispersion)
200 parts by mass of polyester (6) 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 polyester (6) particle dispersion having a volume average particle size 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 by 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 Ion-exchanged water 80 parts by mass

(Preparation of crystalline 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 obtained by solid-liquid separation was dried under vacuum at 40 ° C. to obtain a crystalline polyester.

  The following composition was heated to 120 ° C. using the obtained crystalline polyester, dispersed with IKA Ultra Turrax T50, then dispersed with a pressure discharge homogenizer, and the volume average particle diameter reached 180 nm. It was collected. Thus, a crystalline resin particle dispersion having a solid content of 20% by mass was obtained.

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

(Manufacture of toner particles 6)
-Polyester (6) 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-exchanged water 100 parts by mass 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 a heating oil bath. After maintaining at 48 ° C. for 60 minutes, 70 parts by mass of the polyester (6) 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. When the pH of the filtrate reached 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 (6).
The volume average particle size of the toner particles 6 was measured with a coal 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 size of 20 nm, which is the reaction product, are added so that the coverage of each colored particle surface is 40%, mixed with a Henschel mixer, and toner particles 6 are mixed. Produced.

(Preparation of developer 6)
Using the prepared toner particles 6, 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. -The developer 6 was prepared by mixing.

(Evaluation)
The obtained toner particles 6 and developer 6 were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 2 below.

[Examples 7 to 10, Comparative Example 2]
Toner particles 7 to 10, comparative toner particles 2, developer 7 to 10, and comparative developer 2 were obtained in the same manner as in Example 6 except that the polyester (6) was changed to the polyester shown in Table 2.
The obtained toner particles and 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, the odor was suppressed compared to the comparative example.

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

Claims (8)

A polyester which is a condensation polymer of a carboxylic acid component containing a modified rosin by a compound represented by the following general formula (1) and an alcohol component.
(In General Formula (1), R ¹ represents a hydrogen atom or a methyl group. L is selected from the group consisting of an ester group, a chain alkylene group, a cyclic alkylene group, a phenylene group, and combinations thereof. Represents a valent linking group)   The polyester according to claim 1, wherein the content of a low molecular weight component having a weight average molecular weight (Mw) of 500 or less is 11% by mass or less in the polyester.   An electrostatic image developing toner comprising the polyester according to claim 1.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 3. Storing the electrostatic image developing toner according to claim 3;
A toner cartridge to be attached to and detached from the image forming apparatus. Containing the electrostatic charge image developer according to claim 4;
Developing means for developing an electrostatic image formed on the surface of the image carrier with the electrostatic image developer to form a toner image;
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 image carrier;
Development means for containing the electrostatic charge image developer according to claim 4 and developing the electrostatic charge image with the electrostatic charge image developer to form a toner image;
Transfer means for transferring the toner image to a recording medium;
Fixing means for fixing the toner image on 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 image carrier;
A developing step of developing the electrostatic charge image with the electrostatic charge image developer according to claim 4 to form a toner image;
A transfer step of transferring the toner image to a recording medium;
A fixing step of fixing the toner image on the recording medium;
An image forming method comprising: