JP2002072534A - Electrostatic charge image developing toner, method for manufacturing the same, electrostatic charge image developer, method for forming image and device for image formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner, which has superior low temperature fixing property and narrow distribution of grain size and with which images of high quality without irregular fixing state or fog in the base can be formed, and to provide an electrostatic charge image developer, a method for forming images and a device for image formation. SOLUTION: In the electrostatic charge image developing toner, containing at least crystalline resin having the melting point as the binder resin, the toner with an ester compound having a range of 6-32C alkyl group. The toner is used for the electrostatic charge image developer, the method for forming images and the device for image formation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic image developing toner suitable for forming a high-quality image by electrophotography and the like, a method of manufacturing the same, an electrostatic image developer, an image forming method, and an image forming apparatus. .

[0002]

2. Description of the Related Art A method of visualizing image information via an electrostatic charge image is currently widely used in various fields. Electrophotography is a method in which an electrostatic image is formed on a photoreceptor through a charging step, an exposure step, and the like, and the electrostatic image is visualized through a developing step, a transfer step, a fixing step, and the like.

[0003] In the electrophotographic method, an electrostatic image formed on a photoreceptor formed by a charging step, an exposure step, and the like is developed with a developer and transferred. The toner on the fixing base material that has undergone the transfer step is heated and melted by a fixing member provided with a heating unit in the fixing step to fix the toner image on the surface of the fixing base material. In the fixing step, the fixing member heats not only the toner but also the fixing base material to a required temperature, so that the toner is fixed to the fixing base material. If the heating of the fixing base material is insufficient, a so-called cold offset occurs in which only the toner melts and the toner adheres to the fixing member. On the other hand, if the temperature is excessively increased, the so-called hot offset occurs in which the viscosity of the toner decreases and a part or all of the fixed image adheres to the fixing member side. Therefore, for the heating from the fixing member, it is necessary to select a fixing region in which both the cold offset and the hot offset do not occur.

[0004] On the other hand, with the increasing demand for energy saving, in order to save power in the fixing process occupying a certain amount of power consumption in the copying machine and to expand the fixing area,
It is necessary to lower the fixing temperature of the toner. Lowering the toner fixing temperature means not only saving power and expanding the fixing area, but also shortening the so-called warm-up time, which is the waiting time until the fixing roll surface can be fixed when power is supplied to a copying machine. , Enabling a longer life of the fixing roll.

[0005] By the way, lowering the toner fixing temperature lowers the glass transition point of the toner at the same time, which causes a problem that the storage stability of the toner is deteriorated, and it has been difficult to achieve both. In order to achieve both low-temperature fixing and toner storability, it is necessary to have a so-called sharp melt property in which the toner viscosity rapidly decreases in a high temperature region while maintaining the glass transition point of the toner at a higher temperature. .

However, the resin used for the toner usually has a fluctuation range in the glass transition point, the molecular weight, and the like. Therefore, in order to obtain a sharp melt property, the resin composition and the molecular weight must be extremely uniform. In order to obtain such a resin, it is necessary to adjust the molecular weight of the resin by using a special manufacturing method or treating the resin with a chromatograph or the like, so that the production cost of the resin becomes extremely high, and At that time, unnecessary resin is produced as a by-product, which is not preferable from the viewpoint of environmental protection.

As a method of lowering the fixing temperature of the toner, it has been proposed to use a crystalline resin as a binder resin (Japanese Patent Application Laid-Open Nos. 62-129867 and 62-1).
No. 70971, JP-A-62-170972,
JP-A-62-205365, JP-A-62-276
565, JP-A-62-276566, JP-A-63-038949, JP-A-63-03895
0, JP-A-63-038951, JP-A-63-038951
3-038952, JP-A-63-038953, JP-A-63-038954, JP-A-63-19854
038955, JP-A-63-038956, JP-A-05-001217, JP-A-06-1
48936, JP-A-06-194874,
JP 05-005056 A, JP 05-112 A
No. 715).

In these methods, although the fixing temperature can be lowered, the gradient of the resin viscosity with respect to the temperature change is large, so that a sufficient viscosity cannot be obtained at the time of producing the toner, for example, at the time of kneading. Dispersibility of the release agent and the like is not stable, and it is easy to produce a toner having uneven coloring and fixing properties.In addition, it becomes difficult to pulverize the kneaded material, so that it is difficult to obtain a toner having a small particle diameter. Cause problems. In order to solve this problem, for example, there is a method of adding an auxiliary agent such as a thickener, a pulverizing auxiliary agent, but these auxiliary agents are dispersed in the resin to break the crystallinity of the binder resin. Therefore, it is not preferable.

In recent years, an agglomeration / fusion method has been proposed as a method for producing a toner in which the shape and surface composition of the particles are controlled according to the purpose (JP-A-63-282755, JP-A-6-282752).
-250439). The aggregation / melting method prepares a resin particle dispersion by an emulsion polymerization method or a dispersion emulsification method, and on the other hand, prepares a colorant dispersion liquid in which a colorant is dispersed in a solvent,
These are mixed to form aggregated particles corresponding to the particle size of the toner, and then heated and melted to obtain toner particles.
According to the agglomeration / melting method, it is possible to arbitrarily control the toner shape from an irregular shape to a spherical shape by selecting a heating temperature condition.

The agglomeration / melting method generally involves, for example, dispersing and emulsifying a polymerizable monomer using a surfactant in an emulsion polymerization step and polymerizing using a polymerization initiator. However, surfactants generally have the property of suppressing charging, and thus have a significant effect on the charging characteristics of the toner.
As a result, in the summer environment, the toner charge is too low, the toner separates from the developer, and the toner adheres to the photoreceptor, so-called ground fogging, and machine contamination easily occurs.
In a winter environment, there are problems such as the charging being too high and the image density being lowered.

To prevent this, attempts have been made to reduce the amount of remaining surfactant by lengthening the cleaning time of the toner. However, it is difficult to easily remove the surfactant. Requires a very long cleaning time, which leads to an increase in cost and is not a practical method.

Although a method of producing particles by so-called soap-free polymerization without using a surfactant is also conceivable, particles produced by soap-free polymerization generally have a broad particle size distribution, and agglomeration in the aggregation step. It becomes difficult to control the particle size distribution of the particles. In addition, particles prepared by soap-free polymerization are difficult to control the shape, specifically, spheroidization, and further, since the resin particles aggregate in the resin particle dispersion, the storage of the resin particle dispersion is There are many difficult problems such as a problem in sex.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in a toner for electrostatic charge development, particularly a full-color toner, and to achieve the following objects. 1) An object of the present invention is to provide a toner for developing an electrostatic image and an electrostatic image developer having a wide fixing temperature range and particularly excellent in low-temperature fixing property. 2) An object of the present invention is to provide a toner for developing an electrostatic image and an electrostatic image developer excellent in chargeability, particularly, environmental stability and stability over time. 3) It is an object of the present invention to provide a toner for developing an electrostatic image and an electrostatic image developer which have a simple manufacturing method, are excellent in reproducibility of a particle size, a particle size distribution and the like, and are excellent in manufacturing stability. . 4) An object of the present invention is to provide an electrostatic image developing toner and an electrostatic image developer which are excellent in production stability and storage stability of binder resin particles. 5) It is an object to provide a method for stably producing the toner for developing an electrostatic image. 6) It is an object of the present invention to provide a method capable of forming a stable image using the electrostatic image developing toner. 7) It is an object of the present invention to provide an apparatus capable of forming a stable image using the electrostatic image developing toner.

[0014]

The present invention has succeeded in solving the above-mentioned problems by adopting the following constitution. (1) An electrostatic image developing toner containing at least a crystalline resin having a melting point as a binder resin and having a carbon number of 6
A toner for developing an electrostatic image, comprising an ester compound having an alkyl group in the range of from 30 to 32, preferably from 10 to 24. (2) The toner for developing electrostatic images according to (1), wherein the ester compound has a molecular weight in the range of 200 to 1500, preferably in the range of 500 to 1000.

(3) The toner for developing an electrostatic image according to the above (1) or (2), wherein the monomer constituting the crystalline resin contains a polymerizable monomer containing a sulfonyl group. . (4) the crystalline resin has a melting point in the range of 45 to 110 ° C.,
Preferably in the range of 50 to 100 ° C, more preferably 55.
(1) to (3), wherein the temperature is in the range of ~ 90 ° C.
The toner for developing electrostatic images according to any one of the above.

(5) The value of the storage elastic modulus (G ′) and the loss elastic modulus (G ″) of the toner for developing an electrostatic image is from 40 to 11.
The toner for developing an electrostatic charge image according to any one of the above (1) to (4), wherein the toner has a region that changes by two digits or more per 10 ° C. in a temperature range of 0 ° C. (6) More preferable values of the storage elastic modulus (G ′) and the loss elastic modulus (G ″) of the toner for developing an electrostatic image are from 60 to 90.
(5) The toner for developing an electrostatic image according to the above (5), wherein the toner has a region which changes by two digits or more per 10 ° C of temperature difference in a temperature range of ° C.

(7) With respect to the melting point Tm of the toner for developing an electrostatic image, the storage elastic modulus at Tm + 20 ° C. is represented by G ′ (Tm + 20), Tm + 5
When the storage modulus at 0 ° C. is defined as G ′ (Tm + 50), the following expression is satisfied: 0 ≦ | logG ′ (Tm + 20) −logG ′ (Tm + 50) | ≦ 1.5 G ”(Tm + 20), Tm + 5
When the loss modulus at 0 ° C. is G ”(Tm + 50), the following expression is satisfied: 0 ≦ | logG ″ (Tm + 20) −logG ″ (Tm + 50) | ≦ 1.5 The electrostatic image developing toner according to any one of the above (1) to (6).

(8) The loss tangent tan δ at Tm + 20 ° C. with respect to the melting point Tm of the toner for developing an electrostatic charge image is 0.01 ≦ tan δ ≦ 2, preferably 0.1 ≦ at an angular frequency of 1 rad / sec. The toner for developing an electrostatic charge image according to any one of (1) to (7), wherein tan δ ≦ 1.8 is satisfied.

(9) The electrostatic image developing toner according to any one of (1) to (8), wherein the electrostatic image developing toner contains one or more release agents. toner. (10) The release agent is in the range of 45 to 110 ° C, preferably 6 to 110 ° C.
The toner for developing an electrostatic image according to the item (9), which has a softening point in a range of 0 to 90 ° C.

(11) The content of the release agent in the toner for developing an electrostatic image is in the range of 0.5 to 40% by weight, preferably 2 to 40% by weight.
(9) or being in the range of 15% by weight.
The toner for developing an electrostatic image according to (10). (12) The toner for developing an electrostatic image has an average particle diameter of 3 to 10 μm.
m, preferably in the range of 4 to 7 μm, the toner for developing an electrostatic image according to any one of the above (1) to (11).

(13) The binder resin particle dispersion, the colorant particle dispersion, and the ester compound particle dispersion are stirred and mixed to form an agglomerate containing at least the binder resin particles and the colorant particles. A particle dispersion is prepared, and the aggregated particles are integrated by heating to a temperature equal to or higher than the melting point of the crystalline resin of the binder resin. (1) to any one of (12) The method for producing a toner for developing an electrostatic image according to the above. (14) The static resin according to (13), wherein the crystalline resin material monomer containing the sulfonyl group-containing polymerizable monomer is polymerized to prepare and use the binder resin particle dispersion. A method for producing a toner for developing a charge image.

(15) An electrostatic image developer containing a carrier and a toner, wherein the toner is the electrostatic image developing toner according to any one of (1) to (12). Electrostatic image developer. (16) The electrostatic image developer according to the above (15), wherein the carrier has a resin coating layer.

(17) a step of forming an electrostatic latent image, a step of developing the electrostatic latent image with a developer, a step of transferring a toner image to a fixing substrate, and fixing the toner image to the fixing substrate An image forming method comprising the steps of using the electrostatic image developer according to the above (15) or (16). (18) The image forming method according to (17), wherein in the fixing step, the contact time between the fixing member and the unfixed image on the fixing substrate is adjusted to 0.01 to 0.05 seconds. (19) The image forming method according to (17) or (18), wherein a belt-type fixing machine is used in the fixing step.

(20) an electrostatic latent image carrier, an image writing unit, a developing unit for supplying a developer, a unit for transferring a toner image on the electrostatic latent image carrier onto a transfer body, In an image forming apparatus provided with a unit for fixing a toner image on a transfer body, a belt-type fixing machine including a pressure roll and a fixing belt is used, and the electrostatic image developer according to (15) or (16) is used. An image forming apparatus characterized by using:

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a dispersion liquid comprising a crystalline resin having a melting point as a binder resin and an ester compound having an alkyl group having 6 to 32 carbon atoms. It succeeded in securing the stability of the aggregated particles therein and maintaining the crystallinity of the binder resin. The stability of the agglomerated particles greatly improves the dispersibility of the colorant and release agent in the binder resin in the production of toner by the aggregating and melting method, and the crystallinity of the binder resin is maintained at low temperature fixability. As a result, it has become possible to provide an electrostatic image developing toner having excellent low-temperature fixability and color development.

In general, a crystalline resin has a melting point and therefore has a large decrease in viscosity at a specific temperature, and can reduce the temperature difference from the thermal activation of the resin molecules to the fixable region. Low-temperature fixability can be imparted. On the other hand, in the non-crystalline resin, after the resin molecules start to thermally activate at the glass transition point, the viscosity gradually decreases, so that the temperature difference up to the fixable region is large, and the low-temperature fixability can be ensured. Can not. Therefore, in the present invention,
A crystalline resin having a melting point can be used, and excellent low-temperature fixability can be secured.

The crystalline resin used in the present invention is 45 to 110 in order to ensure low-temperature fixability and storage stability of the toner.
Those having a melting point in the range of ° C are suitable. Melting point 45
When the temperature is lower than 110 ° C., it becomes difficult to store the toner.
The preferred range of the melting point of the crystalline resin is 50 to 100 ° C, and the more preferred range is 55 to 90 ° C. The melting point of the resin was determined by the method shown in JIS K-7121.

On the other hand, it is advantageous that the toner of the present invention has a small particle size and a narrow particle size distribution. Are suitable. In this method, first, aggregated particles are prepared by dispersing and emulsifying resin particles and colorant particles having a submicron diameter having a Brownian motion into approximately 1 to 2 μm due to the presence of an aggregating agent. Make,
It is considered that so-called thermal kinetic agglomeration occurs, and further, by heating this agglomerated particle dispersion, agglomeration of the agglomerated particles to adjust the particle size, that is, so-called fluidized agglomeration.

Since the thermal kinetic agglomeration and the fluid transport agglomeration do not proceed at the same time, in order to finally obtain particles having a narrow particle size distribution, it is necessary to stably produce the agglomerated particles of about 1-2 μm. There is. Before this thermal kinetic agglomeration proceeds sufficiently, when the agglomeration of the fluid transport agglomeration area is started,
Since the aggregation proceeds while the fine particles remain, the particle size distribution of the toner is undesirably widened.

The crystalline resin of the present invention is hardly affected by temperature in a temperature range lower than the melting point because part or all of the resin molecules are regularly arranged. Therefore, the stability of the aggregated particles of about 1 to 2 μm due to thermal kinetic aggregation tends to be low. Further, when an emulsifier such as a surfactant is used at the stage of emulsification, the stability of the aggregated particles is further reduced.

Accordingly, the present invention provides a toner containing a crystalline resin as a binder resin, by incorporating an ester compound having an alkyl group having 6 to 32 carbon atoms, thereby improving the low-temperature fixability of the crystalline resin. By maintaining the stability of the aggregated particles while maintaining the above, the dispersibility of the colorant and the release agent in the binder resin containing the crystalline resin was improved. That is, the ester compound having an alkyl group is slightly compatible with the crystalline portion of the crystalline resin, thereby improving compatibility with the colorant and the release agent, and improving the partial crystallinity of the crystalline resin. It is considered that the collapse enhances the stability of the aggregated particles due to the thermal kinetic aggregation and improves the dispersibility of the colorant and the release agent in the binder resin containing the crystalline resin. The dispersibility of the colorant and the release agent greatly improves the color development and fixability of the toner. In addition, since this compound has an ester group, the compatibility with the crystalline resin in a molten state is low,
Since the crystallinity of the binder resin is not hindered in the melting, cooling, and integration steps, the advantage of the low-temperature fixability of the crystalline resin can be utilized as it is.

The toner for developing an electrostatic image of the present invention has a storage elastic modulus (G ′) and a loss elastic modulus (G ″) of from 40 to 11.
By having a region that changes by two digits or more per 10 ° C. in a temperature range of 0 ° C., a necessary viscosity at a fixing temperature can be obtained, and low-temperature fixability can be secured. Without such a region, the viscosity required for fixing cannot be obtained, so that the fixing temperature must be increased, and the low-temperature fixing property cannot be obtained. More preferable values of the storage elastic modulus (G ′) and the loss elastic modulus (G ″) of the toner for developing electrostatic images are 2 per 10 ° C. in a temperature range of 60 to 90 ° C.
To have an area that changes by more than an order of magnitude.

The toner for developing an electrostatic image of the present invention has a melting point of Tm and a storage elastic modulus at Tm + 20 ° C. of G ′ (Tm + 2
0), when the storage elastic modulus at Tm + 50 ° C. is G ′ (Tm + 50), the following expression is satisfied: 0 ≦ | logG ′ (Tm + 20) −logG ′ (Tm + 50) | ≦ 1. 5 Further, the loss modulus at Tm + 20 ° C. is represented by G ″ (Tm + 20), Tm + 5
When the loss elastic modulus at 0 ° C. is defined as G ″ (Tm + 50), it is preferable to satisfy the following expression: 0 ≦ | logG ″ (Tm + 20) −logG ″ (Tm + 50) | ≦ 1.5 In any of the formulas, when both values exceed 1.5, the dependency on the fixing temperature becomes large, and hot offset tends to occur at the time of high-temperature fixing, which is not preferable.

The toner for developing an electrostatic image according to the present invention is characterized in that the loss tangent tan δ at Tm + 20 ° C. with respect to its melting point Tm satisfies 0.01 ≦ tan δ ≦ 2 at an angular frequency of 1 rad / sec. For example, it is possible to prevent excessive infiltration into the fixing base material, and to expand the temperature range in which fixing can be performed at the same time. Note that a preferable range of the loss tangent tan δ is 0.1 ≦ tan δ ≦ 1.8.

The crystalline resin used as the binder resin in the present invention is not particularly limited as long as it has a melting point in the range of 45 to 110 ° C. The preferred range of the melting point of the crystalline resin is 50 to 100 ° C, and the more preferred range is 55 ° C.
９０90 ° C. Further, the toner containing the binder resin of the present invention has a storage elastic modulus G ′ and a loss elastic modulus G ″ of 40 to 110 ° C. in a temperature range of 2 ° C. per 10 ° C.
It is preferable to use a crystalline resin capable of providing a region that changes by an order of magnitude or more. The preferred values of the storage elastic modulus G ′ and the loss elastic modulus G ″ of the toner containing the binder resin of the present invention provide an area in which the temperature varies from 60 to 90 ° C. by two digits or more per 10 ° C. in temperature difference. The use of a crystalline resin is possible.

The polymerizable monomer constituting the crystalline resin of the present invention is not limited, and specific examples include vinyl resins using the following monomers. Long chain alkyl dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecandioic acid, tridecandioic acid, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decane Polyester resins using diols of long-chain alkyl and alkenyl such as diols and batyl alcohol, amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, (meth) ) Nonyl acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, (meth) Oleyl acrylate, ( Data) long-chain alkyl, (meth) acrylic acid esters of alkenyl behenyl acrylate.

The crystalline resin of the present invention may contain a compound having a shorter chain alkyl group, alkenyl group, aromatic ring or the like in addition to the above polymerizable monomer for the purpose of adjusting the melting point, molecular weight and the like. Can be used. Specifically, the following can be mentioned. When the polymerizable monomer is a dicarboxylic acid, succinic acid,
Alkyl dicarboxylic acids such as malonic acid and oxalic acid; phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid,
Aromatic dicarboxylic acids such as 4,4-bibenzoic acid, 2,6-naphthalenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid; dipicolinic acid, dinicotinic acid, quinolinic acid,
When the nitrogen-containing aromatic dicarboxylic acid such as 2,3-pyrazinedicarboxylic acid or the polymerizable monomer is a diol, a short-chain alkyl diol such as succinic acid, malonic acid, acetonedicarboxylic acid or diglycolic acid; Examples of the vinyl-type polymerizable monomer having a chain alkyl include methyl (meth) acrylate, ethyl (meth) acrylate,
Short-chain alkyl and alkenyl (meth) acrylates such as propyl (meth) acrylate and butyl (meth) acrylate; vinyl nitriles such as acrylonitrile and methacrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether And the like; vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone; olefins such as ethylene, propylene, butadiene, isoprene and the like. These polymerizable monomers may be used alone or in combination of two or more.

Since crystalline resins are inherently poor in emulsifying and dispersing properties, an emulsifier such as a surfactant is added. However, the addition of an emulsifier decreases the charge amount of the particles or lengthens the washing step to prevent this. It is preferable to suppress the use of an emulsifier because it causes inconvenience. In the present invention, by dispersing the sulfonyl group-containing polymerizable monomer during the polymerization of the crystalline resin, the dispersion stability of the aggregated particles can be ensured even when the amount of the emulsifier used is reduced. The type of the sulfonyl group-containing polymerizable monomer is not particularly limited as long as it is copolymerizable.
As a specific example, when the resin is a polyester, a dicarboxylic acid compound in which a sulfonyl group is directly substituted on an aromatic ring such as sodium sulfonyl-terephthalate and sodium 3-sulfonylisophthalate, and a resin is vinyl In the case of a series resin, a styrene derivative having a sulfonyl group at any of ortho, meta and para positions, a sulfonyl group-substituted aromatic vinyl such as sulfonyl group-containing vinyl naphthalene and the like can be mentioned.

The crystalline resin particle dispersion of the present invention comprises:
Aggregation due to thermal kinetic aggregation is likely to occur. Aggregation can be suppressed by adding a dispersant, emulsifier, or the like, but as described above, there are disadvantages such as lowering the chargeability of the particles or using a longer washing step to prevent this. . The resin particle dispersion is preferably stored at a temperature of 40 ° C. or lower. It is more preferably at most 20 ° C. 40
Storing at a temperature higher than ° C is not preferable because the aggregated particles must be redispersed at the time of dispersion, and not only cannot uniform dispersion be obtained, but also unnecessary energy is required for stirring the aggregates.

The binder resin of the present invention may optionally contain a crosslinking agent for the purpose of preventing hot offset or the like during fixing in a high temperature region. The following can be used as specific examples of the crosslinking agent. Aromatic polyvinyl compounds such as divinylbenzene and divinylnaphthalene; aromatics such as divinyl phthalate, divinyl isophthalate, divinyl terephthalate, divinyl homophthalate, divinyl trimesate / trivinyl, divinyl naphthalene dicarboxylate, and divinyl biphenylcarboxylate Polyvinyl esters of polycarboxylic acids, divinyl esters of nitrogen-containing aromatic compounds such as divinyl pyridinedicarboxylate, unsaturated heterocyclic compounds such as pyrrole and thiophene, vinyl pyromutinate, vinyl furancarboxylate, and pyrrole-2 -Vinyl esters of unsaturated heterocyclic compounds such as vinyl carboxylate and vinyl thiophene carboxylate, vinyl esters of carboxylic acid, butanediol methacrylate, hexanediol acrylate, octanediol methacrylate, decane (Meth) acrylates of linear polyhydric alcohols such as acrylates and dodecanediol methacrylates; branched and substituted polyhydric alcohols such as neopentyl glycol dimethacrylate, 2-hydroxy, 1,3-diacryloxypropane; (Meth) acrylates, polyethylene glycol di (meth) acrylate, polypropylene polyethylene glycol di (meth) acrylates, divinyl succinate, divinyl fumarate, vinyl / divinyl maleate, divinyl diglycolate, vinyl / divinyl itaconate, Divinyl acetone dicarboxylate, divinyl glutarate, divinyl 3,3'-thiodipropionate, divinyl trans-aconiate / trivinyl, divinyl adipate, divinyl pimerate, divinyl suberate, azela Phosphate, divinyl sebacate, divinyl dodecanedioate divinyl a multi vinyl esters of polycarboxylic acids such as oxalic acid divinyl.

In particular, when the resin is a polyester, unsaturated polycarboxylic acids such as fumaric acid, maleic acid, itaconic acid, and trans-aconitic acid are copolymerized in the polyester. A method of cross-linking between portions or using another vinyl compound may be used. In the present invention, these crosslinking agents may be used alone or in combination of two or more.

These cross-linking methods may be a method in which a polymerizable monomer is polymerized together with a cross-linking agent and cross-linked, or an unsaturated portion is left in the resin to polymerize the resin or after the toner is prepared. A method of crosslinking an unsaturated portion by a crosslinking reaction may be used.

When the binder resin used in the toner of the present invention is a polyester, the polymerizable monomer can be polymerized by condensation polymerization. As the condensation polymerization catalyst, known catalysts can be used, and specific examples include titanium tetrabutoxide, dibutyltin oxide, germanium dioxide, antimony trioxide, tin acetate, zinc acetate, tin disulfide and the like. Can be.

When the binder resin used in the toner of the present invention is a vinyl resin, the polymerizable monomer can be polymerized by radical polymerization. The radical polymerization initiator is not particularly limited as long as it is capable of emulsion polymerization. Specifically, the following can be mentioned. Hydrogen peroxide, acetyl peroxide, cumyl peroxide, peroxide
tert-butyl, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide , 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid-tert
-Butyl hydroperoxide, tert-butylpermate, tert-butylperacetate, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylpermethoxyacetate, tert-butylperN- (3-toluyl) carbamate Peroxides such as butyl, 2,2'-azobispropane, 2,2'-dichloro-
2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2,2′-azobis (2-amidinopropane) hydrochloride, 2,2′-azobis (2-amidinopropane) nitrate , 2,2'-azobisisobutane, 2,2'-azobisisobutylamide, 2,2'-
Azobisisobutyronitrile, 2,2'-azobis-2
-Methyl methyl propionate, 2,2'-dichloro-
2,2'-azobisbutane, 2,2'-azobis-2-
Methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalonodi Nitrile, 4,4 '
-Azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-methylmalonodinitrile, 2
-(4-bromophenylazo) -2-allylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, dimethyl 4,4'-azobis-4-cyanovalerate,
2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,
2′-azobis-2-propylbutyronitrile, 1,
1′-azobis-1-chlorophenylethane, 1,1 ′
Azobis-1-cyclohexanecarbonitrile, 1,
1′-azobis-1-cycloheptanenitrile, 1,
1'-azobis-1-phenylethane, 1,1'-azobiscumene, ethyl 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1 ' Azo such as -azobis-1,2-diphenylethane, poly (bisphenol A-4,4'-azobis-4-cyanopentanoate) and poly (tetraethylene glycol-2,2'-azobisisobutyrate) Compounds, 1,4-bis (pentaethylene) -2-tetrazene,
1,4-dimethoxycarbonyl-1,4-diphenyl-
2-tetrazene and the like. The polymerization initiator can also be used as a crosslinking reaction initiator in the crosslinking step.

As the colorant used in the toner of the present invention, at least one selected from cyan, magenta and yellow pigments can be used. One type of pigment may be used alone, or two or more types of pigments of the same system may be used in combination. Further, two or more different types of pigments may be used in combination. Specific examples of the coloring agent include Chrome Yellow, Hansa Yellow, Benzidine Yellow, Slen Yellow, Quinoline Yellow, and Permanent Orange G.
TR, pyrazolone orange, balkan orange, watch young red, permanent red, brilliant carmine 3B, brilliant carmine 6B, Dupont oil red, pyrazolone red, lithol red, rhodamine B lake, lake red C, rose bengal, aniline blue, ultramarine blue , Calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate; various pigments; acridine, xanthene, azo, benzoquinone, azine, anthraquinone, dioxazine, thiazine, azomethine , Indigo, thioindigo, phthalocyanine, aniline black, polymethine, triphenylmethane,
Examples thereof include diphenylmethane-based, thiazole-based, and xanthene-based dyes. Black pigments such as carbon black to the extent that these colorants do not reduce the transparency,
Dyes may be mixed.

A release agent can be added to the toner of the present invention, if necessary. Specific examples of the release agent include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; silicones having a softening point upon heating; fatty acid amides such as oleic amide, erucamide, ricinoleamide and stearamide. Plant waxes such as carnauba wax, rice wax, candelilla wax, wood wax and jojoba oil; animal waxes such as beeswax; minerals such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax. -Petroleum wax and the like. These release agents may be used alone or in combination of two or more.

The addition amount of the release agent is preferably in the range of 0.5 to 50% by weight, more preferably 1 to 30% by weight, and further preferably 5 to 15% by weight. If the amount is less than 0.5% by weight, the effect of the release agent addition is ineffective, and if it exceeds 50% by weight, the chargeability is likely to be affected or the toner is easily broken inside the developing machine, and In addition to the adverse effects such as the occurrence of spent on the carrier and the decrease in electrification, the bleeding to the image surface during fixing tends to be insufficient when a color toner is used, for example. There is a possibility that the release agent remains in the toner and the transparency is deteriorated.

The ester compound used in the present invention has an alkyl group having a carbon number of 6 to 32, and preferably has a molecular weight of 200 to 1500. When the carbon number of the alkyl group is 5 or less, the hydrophilicity of the ester compound becomes too large, and the ester compound becomes water-soluble, and is not compatible with the crystalline resin. When the number of carbon atoms is 33 or more, it cannot move in the crystalline resin, and the dispersion stability of the aggregated particles cannot be secured. If the molecular weight of the ester compound is smaller than 200, the difference in viscosity from the crystalline resin is large, and the ester compound is difficult to conform to, so that the particle size distribution of the aggregated particles tends to be wide. On the other hand, if it exceeds 1500, impurities such as isomers are likely to be mixed into the ester compound, and controllability is undesirably reduced. On the other hand, a polymer having a very large number of carbon atoms, such as polyester, has poor orientation, and the effect of adding the ester compound of the present invention cannot be obtained. In addition, the preferable ester compound of this invention has carbon number in the range of 10-24, and molecular weight of 300-7.
00 range.

Specific examples of the ester compound used in the present invention include the following. In the present invention, one of these compounds may be used alone.
More than one species may be used in combination. Esters of higher fatty acids such as stearyl stearate and behenyl behenate with higher alcohols, higher fatty acids such as butyl stearate, propyl oleate, glyceride monostearate, glyceride distearate, pentaerythritol tetrabehenate and unit price or more Esters of higher fatty acids such as esters with dihydric lower alcohols, diethylene glycol monostearate, dipropylene glycol distearate, diglyceride distearate, triglyceride tetrastearate and esters of polyhydric alcohols, such as sorbitan monostearate Cholesterol higher fatty acid esters such as sorbitan higher fatty acid esters and cholesteryl stearate.

The toner of the present invention is used to obtain high image quality.
It is appropriate to adjust the volume average particle diameter in the range of 3 to 10 μm. If it exceeds 10 μm, the reproducibility of fine lines is inferior in the developing step, and the image quality is reduced. If the thickness is less than 3 μm, the life of the developer tends to be short, which is not preferable. In addition, the preferable volume average particle diameter of the present invention is in the range of 4 to 7 μm.

-Method for Producing Toner for Developing an Electrostatic Image-The toner for developing an electrostatic image of the present invention is prepared by preparing a resin particle dispersion by stirring and dispersing a resin in a dispersion, or by subjecting the resin to emulsion polymerization. A particle dispersion is prepared, mixed with a dispersion such as a pigment or a release agent and hetero-aggregated, and then the crystalline resin is melted to unite the particles to obtain toner particles.
It is manufactured by a melting method. This method is preferable for obtaining the above-mentioned effects. The electrostatic image developing toner of the present invention can also be produced by a solution suspension method or a suspension polymerization method.

In the aggregating method / melting of the present invention, at least a resin particle dispersion, a colorant dispersion and, if necessary, a release agent dispersion are mixed, and the resin particles and the colorant are aggregated to form aggregated particles. The method includes a step of preparing a particle dispersion (“aggregation step”) and a step of heating and melting the aggregated particles to form toner particles (“melting step”). In the aggregating step, an ionic surfactant having a polarity different from that of the agglomerated particles or a compound having a monovalent or higher charge such as a metal salt is added to stabilize the agglomerated particles and control the particle size / particle size distribution. The hetero-aggregation proceeds to form aggregated particles. In the melting step, toner particles are obtained by heating to a temperature equal to or higher than the melting point of the crystalline resin in the aggregated particles and melting.

The particles fused in the melting step are present as a colored particle dispersion in the aqueous medium, and are washed to remove the colored particles from the aqueous medium and at the same time to remove impurities and the like generated in each step. Thereafter, drying is performed to obtain toner particles. In the washing step, acidic or basic washing water is added to the colored particles in an amount several times that of the colored particles and stirred, and then filtered to obtain a solid content. Pure water is added several times with respect to the solid content, and after stirring, filtration is performed. This is repeated several times until the pH of the filtrate after filtration reaches about 7, to obtain colored particles. In the drying step, the colored particles obtained in the washing step are dried at a temperature lower than the melting point temperature. At this time, if necessary, a method such as circulating dry air or heating under vacuum conditions is employed.

In order to stabilize the dispersion of the resin particle dispersion, colorant dispersion and release agent dispersion used in the present invention, the resin particle dispersion of the present invention can be used as it is. However, when it is difficult to disperse the colorant dispersion and the release agent dispersion as they are, or in order to obtain the aging stability of the resin particle dispersion, a slight amount of a surfactant may be used.

Examples of the surfactant include anionic surfactants such as sulfate ester type, sulfonate type, phosphate ester type, and soap type; and cationic surfactants such as amine salt type and quaternary ammonium salt type. Nonionic surfactants such as polyethylene glycol-based, alkylphenol-ethylene oxide adduct-based and polyhydric alcohol-based surfactants. Of these, ionic surfactants are preferred, and anionic surfactants and cationic surfactants are more preferred.

In the production of the toner of the present invention, generally, an anionic surfactant has a strong dispersing power, and resin particles,
Since the dispersion of the colorant is excellent, a cationic surfactant is advantageous as the surfactant for dispersing the release agent. It is preferable that the nonionic surfactant is used in combination with the anionic surfactant or the cationic surfactant. The surfactant may be used alone,
Two or more kinds may be used in combination.

Specific examples of the anionic surfactant include fatty acid soaps such as potassium laurate, sodium oleate and castor oil sodium; and sulfate esters such as octyl sulfate, lauryl sulfate, lauryl ether sulfate and nonylphenyl ether sulfate. , Sodium alkylnaphthalenesulfonate such as laurylsulfonate, dodecylbenzenesulfonate, triisopropylnaphthalenesulfonate, dibutylnaphthalenesulfonate, naphthalenesulfonate formalin condensate, monooctylsulfosuccinate, dioctylsulfosuccinate, lauric amide sulfonate, oleic acid Sulfonates such as amide sulfonates; lauryl phosphate, isopropyl phosphate, nonylphate Phosphoric acid esters such as alkenyl ether phosphates; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate, such as sulfosuccinate salts such as sodium lauryl sulfosuccinate 2.

Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride,
Amine salts such as oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate; lauryltrimethylammonium chloride, dilauryldimethylammonium chloride, distearylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleyl Quaternary ammonium salts such as bispolyoxyethylene methylammonium chloride, lauroylaminopropyldimethylethylammonium ethosulfate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzenedimethylammonium chloride, and alkyltrimethylammonium chloride.

Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl Ethers, alkylphenyl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene laurate, polyoxyethylene stearate,
Alkyl esters such as polyoxyethylene oleate;
Alkyl amines such as polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene tallow amino ether; polyoxyethylene lauric amide, polyoxyethylene Alkyl amides such as stearic acid amide and polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide and the like Alkanolamides: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmiate, polyoxyethylene Nso sorbitan monostearate,
Sorbitan ester ethers such as polyoxyethylene sorbitan monooleate; and the like.

The content of the surfactant in the dispersion may be such that it does not impair the present invention, and is generally small. Specifically, in the case of the resin particle dispersion, 0.01 to 10%
The range of 1% by weight is suitable, preferably 0.02 to
It is 0.5% by weight, more preferably 0.1 to 0.2% by weight. When the content of the surfactant is less than 0.01% by weight, aggregation may occur particularly when the pH of the resin particle dispersion is not sufficiently basic. Further, the content of the surfactant in the colorant dispersion and the release agent dispersion is 0.01 to
A range of 10% by weight is suitable, preferably 0.1 to 5%.
%, More preferably 0.5 to 2% by weight. When the content of the coloring agent and the release agent is less than 0.01% by weight, there is a problem that the stability between the particles varies during aggregation and specific particles are released, and more than 10% by weight. This is not preferable because the particle size distribution of the particles becomes wide and the particle size control becomes difficult.

The toner of the present invention may contain other components such as an internal additive, a charge controlling agent, inorganic particles, organic particles, a lubricant and an abrasive, in addition to a binder resin, a colorant and a release agent, depending on the purpose. Can also be added. As internal additives,
A magnetic material such as ferrite, magnetite, reduced iron, cobalt, manganese, nickel and other metals, alloys, and compounds containing these metals can be used as long as the chargeability of the toner characteristics is not impaired.

The charge control agent is not particularly limited, but is preferably colorless or pale when used in a color toner. For example, a quaternary ammonium salt compound, a nigrosine compound, a dye composed of a complex of aluminum, iron, chromium, or the like, a triphenylmethane pigment, and the like can be given.

The inorganic particles include, for example, all particles usually used as an external additive on the surface of a toner, such as silica, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, and cerium oxide. As the organic particles, for example, vinyl resin, polyester resin,
Examples include all particles usually used as an external additive on the surface of a toner such as a silicone resin. In addition, these inorganic particles and organic particles can also be used as a flow aid, a cleaning aid, and the like.

Examples of the lubricant include fatty acid amides such as ethylenebisstearylamide and oleamide.
Fatty acid metal salts such as zinc stearate and calcium stearate are exemplified. Examples of the abrasive include the above-mentioned silica, alumina, cerium oxide and the like.

When the binder resin, the colorant and the release agent are mixed, the content of the colorant in the toner may be 50% by weight or less, and preferably in the range of 2 to 40% by weight. The content of other components may be such that the object of the present invention is not impaired, and is generally very small, specifically in the range of 0.01 to 5% by weight, preferably 0.1 to 5% by weight. It is in the range of 5 to 2% by weight.

In the present invention, a resin particle dispersion, a colorant dispersion,
As a dispersion medium in the release agent dispersion and the dispersion of other components, for example, an aqueous medium is used. Examples of the aqueous medium include water such as distilled water and ion-exchanged water, and alcohol. These may be used alone or in combination of two or more.

In the step of preparing the aggregated particle dispersion of the present invention,
It is preferred to add an aggregating agent to promote and stabilize the aggregation of the particles and to obtain aggregated particles having a narrower particle size distribution. The coagulant is preferably a compound having a charge of monovalent or more, specifically, ionic surfactants, water-soluble surfactants such as nonionic surfactants, hydrochloric acid, sulfuric acid,
Acids such as nitric acid, acetic acid, oxalic acid, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate,
Metal salts of inorganic acids such as sodium carbonate, sodium acetate,
Aliphatic acids such as potassium formate, sodium oxalate, sodium phthalate and potassium salicylate, metal salts of aromatic acids, metal salts of phenols such as sodium phenolate, metal salts of amino acids, triethanolamine hydrochloride,
And inorganic acid salts of aliphatic and aromatic amines such as aniline hydrochloride.

In consideration of the stability of the agglomerated particles, the thermal stability and the temporal stability of the aggregating agent, and the removal of the aggregating agent during washing, a metal salt of an inorganic acid is preferred in terms of performance and use. The amount of the coagulant added depends on the valency of the charge, but may be small in all cases, 3% by weight or less for monovalent and 1% for divalent.
% By weight, and in the case of trivalent, 0.5% by weight or less. Since a smaller amount of the coagulant is better, a compound having a higher valence is preferable.

The surface area of the toner for developing electrostatic images of the present invention is not particularly limited, and there is no problem as long as it is within the range used for ordinary toner. Specifically, 0.5 measured by the BET method
The range is suitably from 10 to 10 m ² / g, preferably from 1.0 to 7 m ² / g, and more preferably from 1.2 to ⁵ m ² / g.

The toner for developing an electrostatic charge image of the present invention has a surface on which inorganic particles such as silica, alumina, titania and calcium carbonate, and resin particles such as a vinyl resin, a polyester resin and a silicone resin are subjected to a shearing force in a dry state. You may mix and add while adding. These inorganic particles and resin particles are
It functions as an external additive such as a flow aid or a cleaning aid.

The charge amount of the toner for developing an electrostatic image is from 10 to
A range of 40 μC / g, preferably a range of 15 to 35 μC / g, is suitable. If the charge amount is less than 10 μC / g, background stains are likely to occur, and if it exceeds 40 μC / g, the image density tends to decrease. The ratio of the charge amount of the electrostatic image developing toner in summer to the charge amount in winter is in the range of 0.5 to 1.5, preferably 0.7 to 1.5.
The range of ~ 1.3 is appropriate. If the ratio is out of the above range, the toner has a high environmental dependency, and the charging stability is poor.

-Electrostatic Image Developer- The electrostatic image developer of the present invention is not particularly limited except that it contains the electrostatic image developing toner of the present invention, and an appropriate component composition is selected according to the purpose. be able to. The electrostatic image developer of the present invention may be prepared as a one-component developer using the toner for electrostatic image development alone, or may be prepared as a two-component developer when used in combination with a carrier. .

The carrier is not particularly limited, and a carrier known per se can be used. For example, Japanese Patent Application Laid-Open
Known carriers such as resin-coated carriers described in JP-A-39879 and JP-A-56-11461 can be used. Specific examples of the carrier include the following resin-coated carriers. Examples of the core particles of the carrier include ordinary iron powder, ferrite, and a molded product of magnetite, and the average particle size thereof is about 30 to 200 μm.

The coating resin for the core particles is, for example, styrenes such as styrene, parachlorostyrene, α-methylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, acrylic acid 2
-Ethylhexyl, methyl methacrylate, methacrylic acid, n-propyl methacrylate lauryl methacrylate 2
-Α-methylene fatty acid monocarboxylic acids such as ethylhexyl, nitrogen-containing acrylics such as dimethylaminoethyl methacrylate, vinyl nitriles such as acrylonitrile and methacrylonitrile, vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine, and vinyl Vinyl ethers such as methyl ether and vinyl isobutyl ether;
Vinyl methyl ketone, vinyl ethyl ketone, vinyl ketones such as vinyl isopropenyl ketone, olefins such as ethylene and propylene, vinylidene fluoride, tetrafluoroethylene, homopolymers such as vinyl fluorine-containing monomers such as hexafluoroethylene, Or copolymers of two or more monomers, methyl silicone, silicones such as methyl phenyl silicone, bisphenol,
Examples include polyesters containing glycol and the like, epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, polycarbonate resins, and the like. These resins may be used alone or
Alternatively, two or more kinds may be used in combination. The amount of the coating resin is about 0.1 to 10 parts by weight with respect to the core particles,
The range is preferably 0.5 to 3.0 parts by weight.

For the production of the carrier, a heating type kneader, a heating type Henschel mixer, a UM mixer and the like can be used. Can be. The mixing ratio of the toner and the carrier in the electrostatic image developer is not particularly limited, and can be appropriately selected depending on the purpose.

—Image Forming Method— The image forming method of the present invention includes an electrostatic latent image forming step, a toner image forming step, a transfer step, and a fixing step. Each step of image formation is a general step itself, which is described in, for example, JP-A-56-40868, JP-A-49-91231, and the like. It can be applied to a forming apparatus.

The formation of an electrostatic latent image is to form an electrostatic latent image on an electrostatic latent image carrier. In forming a toner image, the electrostatic latent image is developed by a developer layer on a developer carrier to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developer of the present invention. Transfer transfers the toner image onto a fixing substrate. In fixing, the toner image transferred onto the fixing base material is fixed on a fixing base material such as paper by heating from a fixing member.

The feature of the image forming method of the present invention is that the fixing temperature of a belt-type fixing device, a roll-type fixing device, or the like is set low by using the toner for developing an electrostatic image of the present invention having excellent low-temperature fixing property. Thus, high-speed fixing can be performed, and an energy saving effect and a warm-up time shortening effect can be obtained. In particular, in an image forming method employing a belt-type fixing device having a low heating capacity for fixing, there is an advantage that good image quality can be obtained without occurrence of background fogging or cold offset.

—Image Forming Apparatus— FIG. 1 shows an example of the image forming apparatus of the present invention. This device sequentially rotates around the photosensitive drum 1 along the rotation direction.
Charger 2, a laser beam or the like image writing means 3, a developing device 4, a primary transfer device 5, arranged a cleaning device 6, the black developing unit ₄₁ to ₄ of the developing device 4, yellow, magenta, cyan Each color toner is stored. The photosensitive drum 1 is brought into contact with the surface of the photosensitive drum 1 and
The intermediate transfer belt 7 running in the direction indicated by the arrow in FIG. A bias roll 10 and a belt cleaner 11 are disposed at opposing positions on the backup roll 9 and the tension roll 8a, respectively.

A portion where the primary transfer device 5 presses the photosensitive drum 1 via the intermediate transfer belt 7 is a primary transfer portion, and a portion where the bias roll 10 presses the backup roll 9 is a secondary transfer portion. Then, the transfer paper P supplied from the paper feed tray 13 to the secondary transfer unit is attached to the intermediate transfer belt 7.
The toner image is transferred to the fixing device 14 including a pressure roller 15 having a heater therein and a transfer belt 16 to fix the toner image. In addition, inside the transfer belt 16,
A pressure pad 17 for pressing the transfer belt 16 against the pressure roll 15 and a belt guide 18 are arranged.

[0081]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited to these examples. In the following, “parts” means parts by weight.
The average particle size of the toner was measured using a Coulter counter (TA2 type, manufactured by Beckman Coulter, Inc.). The particle size distribution of the toner is 5
This is the value obtained by dividing the particle size d ₅₀ that has become 0% by the particle size d ₁₆ that has become 16% (d ₅₀ / d ₁₆ ), and is represented by GSDv. The melting point of the resin constituting the toner particles was measured using a differential scanning calorimeter (DSC-50, manufactured by Shimadzu Corporation) under the condition of a temperature rising rate of 3 ° C./min.

The tangent loss (tan δ) was measured using a viscoelasticity measuring device (Rheometric Scientific FE,
ARES), a toner for developing an electrostatic image is formed into a tablet, the plate is set on a parallel plate having an interval of 8 mm, the normal force is set to 0, and then 1 rad / sec.
Vibration was applied at a vibration frequency of c. The measurement temperature started at 40 ° C. and continued up to 200 ° C. The measurement time interval was 120 seconds, and the heating rate after the start of the measurement was 1 ° C./min. Further, during the measurement, the amount of strain was appropriately maintained at each measurement temperature, and adjustment was appropriately performed so that an appropriate measurement value was obtained. The storage elastic modulus G ′ and the loss elastic modulus G ″ were monitored by monitoring the G ′ and G ″ with respect to the temperature every 2 minutes using the viscoelasticity measuring device (ARES manufactured by Rheometric Scientific FE). It measured by doing.

-Preparation of Resin Particle Dispersion (1)-789.0 parts of sebacic acid 310.5 parts of ethylene glycol 319.7 parts of sodium isophthalate-5-sulfonate 199.7 parts 40.7 parts of fumaric acid 2.0 parts of dibutyltin ( The above components are mixed in a flask, and mixed under reduced pressure atmosphere for 240 minutes.
The resin was heated for 6 hours and dehydrated and condensed for 6 hours to obtain a resin. After cooling, 150 parts of this resin was placed in 850 parts of distilled water, mixed and stirred with a homogenizer (Ultra Tarax, manufactured by IKA Japan) while heating to 85 ° C., and then cooled to room temperature to obtain a resin particle dispersion (1). I got The melting point of the obtained resin particles is 7
1 ° C.

—Preparation of Resin Particle Dispersion (2) —769.8 parts of succinic acid 450.5 parts of sodium isophthalate-5-sulfonic acid 199.7 parts 40.7 parts of fumaric acid 2.5 parts of dibutyltin (The above components were manufactured by Wako Pure Chemical Industries, Ltd.) The above components were dehydrated and condensed under the same conditions as those for the resin particle dispersion (1), and mixed by stirring to obtain a resin particle dispersion (2). The melting point of the obtained resin particles was 90 ° C.

—Preparation of Resin Particle Dispersion (3) — 734.0 parts of azelaic acid 450.5 parts of sodium isophthalic acid-5-sulfonate 199.7 parts 40.7 parts of fumaric acid 2.0 parts of dibutyltin (The above components were manufactured by Wako Pure Chemical Industries, Ltd.) The above components were dehydrated and condensed under the same conditions as for the resin particle dispersion (1), and were mixed by stirring to obtain a resin particle dispersion (3). The melting point of the obtained resin particles was 49 ° C.

—Preparation of Resin Particle Dispersion (4) — Terephthalic acid 647.8 parts Decanediol 871.5 parts Isophthalic acid-5-sodium sulfonate 199.7 parts Fumaric acid 40.7 parts Dibutyltin 2.0 parts ( The above components were manufactured by Wako Pure Chemical Industries, Ltd.) The above components were dehydrated and condensed under the same conditions as for the resin particle dispersion liquid (1) and mixed by stirring to obtain a resin particle dispersion liquid (4). The melting point of the obtained resin particles was 86 ° C.

-Preparation of Resin Particle Dispersion (5)-734.0 parts of sebacic acid 450.5 parts of ethylene glycol 199.7 parts of sodium isophthalate-5-sulfonate 40.7 parts of fumaric acid 2.0 parts of dibutyltin ( The above components were manufactured by Wako Pure Chemical Industries, Ltd.) The above components were subjected to dehydration condensation and stirring and mixing under the same conditions as for the resin particle dispersion (1) to obtain a resin particle dispersion (5). The melting point of the obtained resin particles was 70 ° C.

-Preparation of Resin Particle Dispersion (6)-200 parts of styrene 800 parts of stearyl acrylate 800 parts of sodium p-styrenesulfonate 50 parts 30 parts of dodecyl mercaptan (all manufactured by Wako Pure Chemical Industries, Ltd.) Decanediol diacrylic acid Ester 4 parts (manufactured by Shin-Nakamura Chemical Co., Ltd.) The above components were mixed and dissolved, and an anionic surfactant (manufactured by NOF CORPORATION: Newrex Paste H) was used.
20 parts was dissolved in 1300 parts of ion-exchanged water, dispersed in a flask, emulsified, and slowly mixed for 10 minutes while adding ammonium persulfate (Wako Pure Chemical Industries, Ltd.)
200 parts of ion-exchanged water in which 20 parts were dissolved,
After purging with nitrogen, the contents in the flask were heated in an oil bath until the temperature reached 70 ° C. while stirring, and the emulsion polymerization was continued for 6 hours. Thereafter, the reaction liquid was cooled to room temperature to prepare a resin particle dispersion liquid (6). The melting point of the obtained resin particles was 66 ° C.

—Preparation of Colorant Dispersion (1) — 250 parts of phthalocyanine pigment (PVFASTBLUE, manufactured by Dainichi Seika Co., Ltd.) 20 parts of anionic surfactant (neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 730 parts of exchanged water After mixing and dissolving the above components, a homogenizer (I
KA Corporation: Ultra Tarax) to prepare a colorant dispersion (1) in which a colorant (phthalocyanine pigment) is dispersed.

—Preparation of Colorant Dispersion (2) — 200 parts of yellow pigment (PY180 manufactured by Clariant Japan) 20 parts of anionic surfactant (Newrex R manufactured by NOF Corporation) 780 parts of ion-exchanged water After mixing and dissolving the above components, a homogenizer (I
Colorant dispersion liquid (2) obtained by dispersing using KA Co., Ltd .: Ultra Tarax) and dispersing a colorant (yellow pigment).
Was prepared.

—Preparation of Colorant Dispersion (3) — 300 parts of magenta pigment (PR122 manufactured by Dainichi Seika Co., Ltd.) 25 parts of anionic surfactant (Nurex R manufactured by NOF Corporation) Ion exchange Water 675 parts After mixing and dissolving the above components, a homogenizer (I
Colorant dispersion liquid (3) obtained by dispersing using a colorant (magenta pigment) using KA Corporation: Ultra Tarax).
Was prepared.

—Preparation of Colorant Dispersion (4) — 230 parts of carbon black (Regal 330 manufactured by Cabot) 25 parts of anionic surfactant (Newrex R manufactured by NOF Corporation) 745 parts of ion-exchanged water After mixing and dissolving the above components, a homogenizer (I
KA Co., Ltd .: Ultratarax) to prepare a colorant dispersion (4) in which a colorant (carbon black) is dispersed.

—Preparation of Release Agent Particle Dispersion— Polyethylene Wax (Molecular Weight = 730) 400 parts (Toyo Petrolite Co., Ltd .: Polywax 725) Anionic surfactant 20 parts (Nippon Oil & Fat Co., Ltd .: Newrex) R) 580 parts of ion-exchanged water After mixing and dissolving the above components, a homogenizer (I
KA Co., Ltd .: Dispersed using Ultra Turrax, followed by dispersion treatment with a pressure discharge type homogenizer to prepare a release agent particle dispersion in which release agent particles (polyethylene wax) were dispersed. This release agent particle dispersion was dried, and the softening point of the remaining release agent was measured.

—Preparation of Ester Compound Particle Dispersion Solution (1) —100 parts of stearyl stearate (manufactured by Riken Vitamin Co., Ltd .: Richemal SL-800) [Carbon number of alkyl group of ester compound = 17, molecular weight = 522] Anionic surface activity 2 parts (Nyulex R, manufactured by NOF Corporation) 300 parts of ion-exchanged water After mixing and dissolving the above components, a homogenizer (I
KA: Ultra Tarax), and then subjected to a dispersion treatment with a pressure discharge type homogenizer to disperse the ester compound particles, thereby dispersing the ester compound particles (1).
Was prepared.

—Preparation of Ester Compound Particle Dispersion Liquid (2) —100 parts of butyl stearate (manufactured by Nikko Chemicals: NIKKOLBS) [Carbon number of alkyl group of ester compound = 17, molecular weight = 354] Anionic surfactant 2 Part (manufactured by Nippon Yushi Co., Ltd .: Newrex R) 300 parts of ion-exchanged water After mixing and dissolving the above, a homogenizer (IKA)
(Ultra Tarax Co., Ltd.), and then subjected to a dispersion treatment using a pressure discharge type homogenizer to prepare an ester compound particle dispersion (2) in which ester compound particles are dispersed.

—Preparation of Ester Compound Particle Dispersion (3) —Butyl Laurate 100 parts (manufactured by NOF CORPORATION) [Carbon number of alkyl group of ester compound = 11, molecular weight = 256] Anionic surfactant 2 parts (Japan Oil and Fat Co., Ltd .: Newrex R) 300 parts of ion-exchanged water After mixing and dissolving the above components, a homogenizer (I
After dispersion using KA Co., Ltd .: Ultra Tarax), the mixture is subjected to a dispersion treatment with a pressure discharge homogenizer to disperse the ester compound particles, thereby dispersing the ester compound particles (3).
Was prepared.

—Preparation of Ester Compound Particle Dispersion Liquid (4) — Glycerin Mono Dibehenate 100 parts (manufactured by Riken Vitamin Co., Ltd .: Richemal B-200) [Carbon number of alkyl group of ester compound = 21, molecular weight = 617] Anion interface Activator 2 parts (Nippon Oil & Fats Co., Ltd .: Newrex R) 300 parts ion-exchanged water After mixing and dissolving the above components, homogenizer (I
KA: Dispersion using Ultra Turrax, dispersion treatment with a pressure discharge type homogenizer, and dispersion of ester compound particles (4).
Was prepared.

—Preparation of Ester Compound Particle Dispersion (5) — Sorbitan Monostearate 100 parts (manufactured by Nippon Emulsifier Co., Ltd .: Emarex SPE-100) [Carbon number of alkyl group of ester compound = 17, molecular weight = 431] Surfactant 2 parts (manufactured by NOF CORPORATION: Newrex R) 300 parts of ion-exchanged water After mixing and dissolving the above components, a homogenizer (I
KA Co., Ltd .: An ester compound particle dispersion liquid (5) obtained by dispersing using an ultra turrax and then performing a dispersion treatment with a pressure discharge type homogenizer to disperse the ester compound particles.
Was prepared.

—Preparation of Ester Compound Particle Dispersion (6) — Cholesteryl stearate 100 parts (manufactured by Nikko Chemicals) [Carbon number of alkyl group of ester compound = 17, molecular weight = 649] Anion surfactant 2 parts (Japan Oil and Fat Co., Ltd .: Newrex R) 300 parts of ion-exchanged water After mixing and dissolving the above components, a homogenizer (I
KA: Dispersion using Ultra Turrax, dispersion treatment with a pressure discharge type homogenizer, and dispersion of ester compound particles (6)
Was prepared.

—Preparation of Ester Compound Particle Dispersion Liquid (7) —100 parts of n-amyl n-valerate (manufactured by Wako Pure Chemical Industries, Ltd.) [The number of carbon atoms in the alkyl group of the ester compound = 5, the molecular weight = 172] Anionic surface activity 2 parts (Nyulex R, manufactured by NOF Corporation) 300 parts of ion-exchanged water After mixing and dissolving the above components, a homogenizer (I
KA Co., Ltd .: An ester compound particle dispersion liquid (7) obtained by dispersing using an ultra turrax, then dispersing with a pressure discharge type homogenizer, and dispersing the ester compound particles.
Was prepared.

(Example of Preparation of Electrostatic Charge Image Developer (1)) <Aggregating Step> -Preparation of Aggregated Particles- Resin Particle Dispersion (1) 2833 parts Colorant Dispersion (1) 100 parts Release Agent Particle Dispersion 125 Part Ester compound particle dispersion liquid (1) 200 parts Lauroyl peroxide 10 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries, Ltd.) ion-exchanged water 100 parts
After adjusting to 2.2 and dispersing using a homogenizer (Ultra Turrax T50 manufactured by IKA), the mixture was heated with stirring to 62 ° C. in a heating oil bath. After holding at 62 ° C. for 60 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 4.8 μm were formed. After maintaining the heating and stirring at 62 ° C. for further 30 minutes, when observed with an optical microscope, the average particle size was about 5.4.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.2. An aqueous solution of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.5% by weight was gently added thereto to adjust the pH to 5.5.
C. and held for 3 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle size of the obtained toner particles was 5.2 μm. Colloidal silica (R97, manufactured by Nippon Aerosil Co., Ltd.) was used for 100 parts of the toner particles.
2) One part was mixed with a Henschel mixer and externally added to obtain a toner for developing an electrostatic image.

-Preparation of electrostatic image developer- Ferrite particles (manufactured by Powder Tech, average particle size 50 μm)
m) 100 parts and 2.5 parts of a methacrylate resin (manufactured by Mitsubishi Rayon Co., Ltd., molecular weight 95,000) were mixed with toluene 500
The mixture was stirred and mixed at room temperature for 15 minutes, heated to 70 ° C. while mixing under reduced pressure, toluene was distilled off, cooled, and classified by using a 105 μm sieve to obtain ferrite. A carrier (resin-coated carrier) was produced. This ferrite carrier and the toner for developing an electrostatic image were mixed to prepare a two-component electrostatic image developer producing example (1) having a toner concentration of 7% by weight.

(Electrostatic image developer preparation example (2)) <Aggregation step> -Preparation of aggregated particles- Resin particle dispersion (2) 2833 parts Colorant dispersion (1) 100 parts Release agent particle dispersion 125 Part Ester compound particle dispersion liquid (1) 200 parts Lauroyl peroxide 10 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries, Ltd.) ion-exchanged water 100 parts
After adjusting to 2.0 and dispersing using a homogenizer (Ultra Turrax T50 manufactured by IKA), the mixture was heated to 82 ° C. with stirring in an oil bath for heating. After holding at 82 ° C. for 90 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 5.6 μm had been formed. After maintaining the heating and stirring at 82 ° C. for further 60 minutes, when observed with an optical microscope, the average particle size was about 5.9.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.1. An aqueous solution of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.5% by weight was gently added thereto to adjust the pH to 6.0.
C. and held for 5 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle size of the obtained toner was 5.
It was 7 μm. The obtained toner particles were used to prepare an electrostatic image developer in the same manner as in the electrostatic image developer preparation example (1), thereby preparing an electrostatic image developer preparation example (2).

(Example of preparing electrostatic image developer (3)) <Aggregating step> -Preparation of aggregated particles- Resin particle dispersion (3) 2833 parts Colorant dispersion (1) 100 parts Release agent particle dispersion 125 Part Ester compound particle dispersion liquid (1) 200 parts Lauroyl peroxide 12 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries) Ion-exchanged water 100 parts
It was adjusted to 2.0, dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA), and then heated with stirring to 46 ° C in a heating oil bath. After maintaining at 46 ° C. for 60 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 4.4 μm had been formed. After further heating and stirring at 46 ° C. for 60 minutes, when observed with an optical microscope, the average particle size was about 4.5.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.2. An aqueous solution obtained by diluting sodium bicarbonate (manufactured by Wako Pure Chemical Industries, Ltd.) to 0.5% by weight was gently added thereto to adjust the pH to 5.2.
Heated to 5 ° C and held for 4 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle size of the obtained toner was 3.
It was 7 μm. The obtained toner particles were used to prepare an electrostatic charge image developer in the same manner as in the electrostatic charge image developer manufacture example (1) to prepare an electrostatic charge image developer manufacture example (3).

(Example of preparing electrostatic image developer (4)) <Aggregating step> -Preparation of aggregated particles- Resin particle dispersion (4) 2833 parts Colorant dispersion (1) 100 parts Release agent particle dispersion 125 Part Ester compound particle dispersion liquid (1) 200 parts Lauroyl peroxide 10 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries, Ltd.) ion-exchanged water 100 parts
The dispersion was adjusted to 2.0, and dispersed using a homogenizer (trade name: Ultra Turrax T50, manufactured by IKA), and then heated to 86 ° C. with stirring in an oil bath for heating. After maintaining at 86 ° C. for 80 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 6.2 μm were formed. After maintaining the heating and stirring at 86 ° C. for further 90 minutes, when observed with an optical microscope, the average particle size was about 6.5.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.2. An aqueous solution of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.5% by weight was gently added thereto, and the pH was adjusted to 6.2.
Heated to 5 ° C. and held for 5 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle diameter of the obtained toner was 6.
It was 6 μm. The obtained toner particles were used to prepare an electrostatic image developer in the same manner as in the example (1) of preparing an electrostatic image developer, thereby preparing an example (4) of preparing an electrostatic image developer.

(Example of Preparation of Electrostatic Image Developer (5)) <Aggregating Step> —Preparation of Aggregated Particles— Resin Particle Dispersion (5) 2833 parts Colorant Dispersion (1) 100 parts Release Agent Particle Dispersion 125 Part Ester compound particle dispersion liquid (1) 200 parts Lauroyl peroxide 10 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries, Ltd.) ion-exchanged water 100 parts
The dispersion was adjusted to 2.0, dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA), and heated with stirring to 65 ° C. in a heating oil bath. After maintaining at 65 ° C. for 70 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 5.5 μm were formed. After maintaining the heating and stirring at 65 ° C. for further 60 minutes, when observed with an optical microscope, the average particle size was about 5.7.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.3. An aqueous solution prepared by diluting sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) to 0.5% by weight was gently added thereto, and the pH was adjusted to 5.5.
Heated to 0 ° C. and held for 5 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle diameter of the obtained toner was 5.
It was 9 μm. The obtained toner particles were used to prepare an electrostatic image developer in the same manner as in the electrostatic image developer preparation example (1), thereby preparing an electrostatic image developer preparation example (5).

(Example of preparing electrostatic charge image developer (6)) <Aggregating step> -Preparation of aggregated particles- Resin particle dispersion (6) 1063 parts Colorant dispersion (1) 100 parts Release agent particle dispersion 125 Part Ester compound particle dispersion liquid (1) 200 parts Lauroyl peroxide 8 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries, Ltd.) Ion-exchange water 1000 parts
The dispersion was adjusted to 2.0, and dispersed using a homogenizer (trade name: Ultra Turrax T50, manufactured by IKA), and then heated with stirring to 64 ° C. in a heating oil bath. After maintaining at 64 ° C. for 50 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 5.1 μm were formed. After further heating and stirring at 64 ° C. for 40 minutes, observation with an optical microscope revealed that the average particle size was about 5.2.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.2. An aqueous solution of sodium bicarbonate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.5% by weight was gently added thereto to adjust the pH to 7.2.
Heated to 0 ° C. and held for 6 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle size of the obtained toner was 5.
It was 4 μm. The obtained toner particles were used to prepare an electrostatic charge image developer in the same manner as in the electrostatic charge image developer manufacture example (1) to prepare an electrostatic charge image developer manufacture example (6).

(Electrostatic Charge Image Developer Production Example (7)) <Aggregating Step> —Preparation of Aggregated Particles— Resin Particle Dispersion (1) 2767 parts Colorant Dispersion (2) 117 parts Release Agent Particle Dispersion 125 Part Ester compound particle dispersion liquid (1) 200 parts Lauroyl peroxide 12 parts Aluminum sulfate 7 parts (manufactured by Wako Pure Chemical Industries, Ltd.) Ion-exchanged water 150 parts
The dispersion was adjusted to 2.0, and dispersed using a homogenizer (trade name: Ultra Turrax T50, manufactured by IKA), and then heated with stirring to 64 ° C. in a heating oil bath. After maintaining at 68 ° C. for 60 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 4.9 μm were formed. After further heating and stirring at 68 ° C. for 60 minutes, when observed with an optical microscope, the average particle size was about 5.3.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.5. An aqueous solution obtained by diluting sodium bicarbonate (manufactured by Wako Pure Chemical Industries, Ltd.) to 0.5% by weight was gently added thereto to adjust the pH to 5.2.
Heated to 0 ° C. and held for 6 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle diameter of the obtained toner was 5.
It was 5 μm. The obtained toner particles were used to prepare an electrostatic image developer in the same manner as in the electrostatic image developer preparation example (1), thereby preparing an electrostatic image developer preparation example (7).

(Example of Producing Electrostatic Image Developer (8)) <Aggregating Step> —Preparation of Aggregated Particles— Resin Particle Dispersion (1) 2667 parts Colorant Dispersion (3) 250 parts Release Agent Particle Dispersion 125 Part Ester compound particle dispersion liquid (1) 200 parts Lauroyl peroxide 7 parts Aluminum sulfate 7 parts (manufactured by Wako Pure Chemical Industries, Ltd.) Ion-exchanged water 120 parts
After adjusting to 2.0 and dispersing using a homogenizer (Ultra Turrax T50, manufactured by IKA), the mixture was heated with stirring to 68 ° C in a heating oil bath. After maintaining at 68 ° C. for 60 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 4.5 μm were formed. After further heating and stirring at 68 ° C. for 60 minutes, when observed with an optical microscope, the average particle size was about 5.0.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.4. An aqueous solution of sodium bicarbonate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.5% by weight was gently added thereto to adjust the pH to 7.2.
Heated to 0 ° C. and held for 4 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle diameter of the obtained toner was 5.
It was 2 μm. The obtained toner particles were used to prepare an electrostatic charge image developer in the same manner as in the electrostatic charge image developer manufacture example (1) to prepare an electrostatic charge image developer manufacture example (8).

(Example of Producing Electrostatic Image Developer (9)) <Aggregating Step> —Preparation of Aggregated Particles— Resin Particle Dispersion (1) 2833 parts Colorant Dispersion (4) 109 parts Release Agent Particle Dispersion 125 Part Ester compound particle dispersion liquid (1) 200 parts Lauroyl peroxide 10 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries, Ltd.) ion-exchanged water 100 parts
The dispersion was adjusted to 2.0 and dispersed using a homogenizer (trade name: Ultra Turrax T50, manufactured by IKA), and then heated with stirring to 67 ° C. in a heating oil bath. After maintaining at 67 ° C. for 60 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 4.8 μm were formed. After maintaining the heating and stirring at 67 ° C. for further 60 minutes, when observed with an optical microscope, the average particle size was about 5.0.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.3. An aqueous solution of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.5% by weight was gently added thereto to adjust the pH to 5.5.
Heated to 0 ° C. and held for 4 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle size of the obtained toner was 5.
It was 2 μm. The obtained toner particles were used to prepare an electrostatic image developer in the same manner as in the electrostatic image developer preparation example (1), thereby preparing an electrostatic image developer preparation example (9).

(Example of preparing electrostatic image developer (10)) <Aggregating step> -Preparation of aggregated particles- Resin particle dispersion liquid (1) 2833 parts Colorant dispersion liquid (1) 100 parts Release agent particle dispersion 125 Part Ester compound particle dispersion liquid (2) 200 parts Lauroyl peroxide 10 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries, Ltd.) ion-exchanged water 100 parts
The dispersion was adjusted to 2.0, dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA), and heated with stirring to 65 ° C. in a heating oil bath. After maintaining at 65 ° C. for 60 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 4.9 μm were formed. After maintaining the heating and stirring at 65 ° C. for further 60 minutes, when observed with an optical microscope, the average particle size was about 5.1.
It was confirmed that aggregated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.2. An aqueous solution of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.5% by weight was gently added thereto, and the pH was adjusted to 5.0.
Heated to 0 ° C. and held for 4 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle diameter of the obtained toner was 5.
It was 2 μm. The obtained toner particles were used to prepare an electrostatic image developer in the same manner as in the electrostatic image developer preparation example (1) to prepare an electrostatic image developer preparation example (10).

(Example of preparing electrostatic image developer (11)) <Aggregating step> -Preparation of aggregated particles- Resin particle dispersion liquid (1) 2833 parts Colorant dispersion liquid (1) 100 parts Release agent particle dispersion 125 Part Ester compound particle dispersion liquid (3) 200 parts Lauroyl peroxide 10 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries, Ltd.) Ion-exchanged water 100 parts
The dispersion was adjusted to 2.0, dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA), and heated with stirring to 65 ° C. in a heating oil bath. After maintaining at 65 ° C. for 60 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 4.5 μm were formed. After maintaining the heating and stirring at 65 ° C. for further 60 minutes, when observed with an optical microscope, the average particle size was about 4.8.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.2. An aqueous solution of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.5% by weight was gently added thereto, and the pH was adjusted to 5.0.
Heated to 0 ° C. and held for 4 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle diameter of the obtained toner was 5.
It was 0 μm. The obtained toner particles were used to prepare an electrostatic image developer in the same manner as in the electrostatic image developer preparation example (1), thereby preparing an electrostatic image developer preparation example (11).

(Example of Producing Electrostatic Charge Image Developer (12)) <Aggregating Step> —Preparation of Aggregated Particles— Resin Particle Dispersion (1) 2833 parts Colorant Dispersion (1) 100 parts Release Agent Particle Dispersion 125 Part Ester compound particle dispersion (4) 200 parts Lauroyl peroxide 10 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries, Ltd.) ion-exchanged water 100 parts
The dispersion was adjusted to 2.0, dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA), and heated with stirring to 65 ° C. in a heating oil bath. After maintaining at 65 ° C. for 60 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 4.9 μm were formed. After maintaining the heating and stirring at 65 ° C. for further 60 minutes, when observed with an optical microscope, the average particle size was about 4.9.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.2. An aqueous solution of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.5% by weight was gently added thereto to adjust the pH to 5.1.
C. and held for 4 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle diameter of the obtained toner was 5.
It was 1 μm. The obtained toner particles were used to prepare an electrostatic image developer in the same manner as in the electrostatic image developer preparation example (1), thereby preparing an electrostatic image developer preparation example (12).

(Example of preparing electrostatic image developer (13)) <Aggregating step> -Preparation of aggregated particles- Resin particle dispersion liquid (1) 2833 parts Colorant dispersion liquid (1) 100 parts Release agent particle dispersion 125 Part Ester compound particle dispersion liquid (5) 200 parts Lauroyl peroxide 10 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries, Ltd.) Ion-exchanged water 100 parts
The dispersion was adjusted to 2.0, dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA), and heated with stirring to 65 ° C. in a heating oil bath. After maintaining at 65 ° C. for 60 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 4.9 μm were formed. After maintaining the heating and stirring at 65 ° C. for further 60 minutes, when observed with an optical microscope, the average particle size was about 5.4.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.2. An aqueous solution of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.5% by weight was gently added thereto, and the pH was adjusted to 4.8.
Heated to 0 ° C. and held for 4 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle size of the obtained toner was 5.
It was 7 μm. The obtained toner particles were used to prepare an electrostatic image developer in the same manner as in the electrostatic image developer preparation example (1) to prepare an electrostatic image developer preparation example (13).

(Example of Producing Electrostatic Image Developer (14)) <Aggregating Step> —Preparation of Aggregated Particles— Resin Particle Dispersion (1) 2833 parts Colorant Dispersion (1) 100 parts Release Agent Particle Dispersion 125 Part Ester compound particle dispersion liquid (6) 200 parts Lauroyl peroxide 10 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries, Ltd.) ion-exchanged water 100 parts
The dispersion was adjusted to 2.0, dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA), and heated with stirring to 65 ° C. in a heating oil bath. After holding at 65 ° C. for 60 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 5.0 μm were formed. After maintaining the heating and stirring at 65 ° C. for further 60 minutes, when observed with an optical microscope, the average particle size was about 5.2.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.2. An aqueous solution prepared by diluting sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) to 0.5% by weight was gently added thereto, and the pH was adjusted to 5.2.
Heated to 0 ° C. and held for 4 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle diameter of the obtained toner was 5.
It was 3 μm. The obtained toner particles were used to prepare an electrostatic image developer in the same manner as in the electrostatic image developer preparation example (1), thereby preparing an electrostatic image developer preparation example (14).

(Example of Producing Electrostatic Image Developer (15)) <Aggregating Step> —Preparation of Aggregated Particles— Resin Particle Dispersion (1) 2833 parts Colorant Dispersion (1) 100 parts Release Agent Particle Dispersion 125 Part Ester compound particle dispersion liquid (1) 100 parts Ester compound particle dispersion liquid (6) 100 parts Lauroyl peroxide 10 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries) Ion-exchanged water 100 parts The above components are round stainless steel flasks Housed in pH
The dispersion was adjusted to 2.0, dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA), and heated with stirring to 65 ° C. in a heating oil bath. After holding at 65 ° C. for 60 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 4.8 μm were formed. After maintaining the heating and stirring at 65 ° C. for further 60 minutes, when observed with an optical microscope, the average particle size was about 5.1.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.2. An aqueous solution of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.5% by weight was gently added thereto, and the pH was adjusted to 5.0.
Heated to 0 ° C. and held for 4 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle size of the obtained toner was 5.
It was 5 μm. The obtained toner particles were used to prepare an electrostatic image developer in the same manner as in the electrostatic image developer preparation example (1), thereby preparing an electrostatic image developer preparation example (15).

(Example of preparing electrostatic image developer (16)) <Aggregating step> -Preparation of aggregated particles- Resin particle dispersion (1) 2833 parts Colorant dispersion (1) 100 parts Release agent particle dispersion 125 Part Lauroyl peroxide 10 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries) Ion-exchanged water 300 parts
The dispersion was adjusted to 2.0, dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA), and heated with stirring to 65 ° C. in a heating oil bath. After maintaining at 65 ° C. for 60 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 4.9 μm were formed. After maintaining the heating and stirring at 65 ° C. for further 60 minutes, when observed with an optical microscope, the average particle size was about 5.3.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.2. An aqueous solution of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.5% by weight was gently added thereto, and the pH was adjusted to 5.0.
Heated to 0 ° C. and held for 4 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle size of the obtained toner was 5.
Although it was 5 μm, the particle size distribution was rather wide. The obtained toner particles are used to form an electrostatic image developer in the same manner as in the electrostatic image developer manufacturing example (1), and the electrostatic image developer manufacturing example (1)
6) was prepared.

(Example of preparing electrostatic image developer (17)) <Aggregating step> -Preparation of aggregated particles- Resin particle dispersion liquid (1) 2833 parts Colorant dispersion liquid (1) 100 parts Release agent particle dispersion 125 Part Ester compound particle dispersion liquid (7) 100 parts Lauroyl peroxide 10 parts Aluminum sulfate 5 parts (manufactured by Wako Pure Chemical Industries, Ltd.) 300 parts ion-exchanged water
The dispersion was adjusted to 2.0, dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA), and heated with stirring to 65 ° C. in a heating oil bath. After holding at 65 ° C. for 60 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 4.8 μm were formed. After maintaining the heating and stirring at 65 ° C. for further 60 minutes, when observed with an optical microscope, the average particle size was about 5.1.
It was confirmed that agglomerated particles having a size of μm were formed.

<Melting Step> The pH of the aggregated particle dispersion was 2.2. An aqueous solution of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.5% by weight was gently added thereto, and the pH was adjusted to 5.0.
Heated to 0 ° C. and held for 4 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles.

<Evaluation> The average particle size of the obtained toner was 5.
Although it was 3 μm, the particle size distribution was rather wide. The obtained toner particles are used to form an electrostatic image developer in the same manner as in the electrostatic image developer manufacturing example (1), and the electrostatic image developer manufacturing example (1)
7) was prepared.

(Preparation of Image Forming Apparatus (1)) The fixing unit of the A-color 930 copying machine manufactured by Fuji Xerox Co., Ltd. was taken out, the release oil supply was removed, and ethylene-vinylidene fluoride was applied to the surfaces of the fixing roll and the pressure roll. An image forming apparatus (1) was prepared by mounting a fixing device coated with a film made of a tetrafluoroethylene copolymer.

(Preparation of Image Forming Apparatus (2)) An image forming apparatus (2) was prepared by mounting a fixing belt made of a polyimide film instead of the pressure roll of the fixing machine of the image forming apparatus (1).

[Example 1] Production example of electrostatic image developer (1)
Was placed in a developing machine of the image forming apparatus (1), and an unfixed image was adjusted so as to form a solid portion and a thin line portion. The rotation speed of the roll is adjusted so that the contact time between the fixing roll of the fixing device of the image forming apparatus (1) and the unfixed image is 0.04 seconds, and the surface of the fixing roll is heated from 60 ° C. to 20 ° C.
Fixing was performed every 5 ° C. until 0 ° C. A fold was formed inside the solid portion so as to be substantially at the center of the fixed image, and the destruction of the fixed image was evaluated. The fixing temperature at which no problem occurred was defined as the minimum fixing temperature. In addition, fine line reproducibility by visual inspection,
Land cover and hot offset were evaluated.

(Examples 2 to 15) Fixing was performed in the same manner as in Example 1 except that the developers of the electrostatic charge image developer preparation examples (2) to (15) were used. evaluated.

Example 16 The developer of Example (1) of preparing an electrostatic image developer was put into a developing machine of an image forming apparatus (2), and an unfixed image was adjusted so as to form a solid portion and a thin line portion. did. This was adjusted by adjusting the belt speed such that the contact time between the fixing belt of the fixing device of the image forming apparatus (2) and the unfixed image became 0.08 seconds, and fixing the other conditions in the same manner as in Example 1. Was performed and the image was evaluated.

[Comparative Example 1] Example of producing electrostatic image developer (1
Fixing was performed in the same manner as in Example 1 except that the developer of 6) was used, and evaluation was performed in the same manner as in Example 1.

[Comparative Example 2] ACol manufactured by Fuji Xerox Co., Ltd.
Fixing was performed in the same manner as in Example 1 except that the developer for or936 was used, and evaluation was performed in the same manner as in Example 1.

[Comparative Example 3] Example of producing electrostatic image developer (1
Fixing was performed in the same manner as in Example 1 except that the developer of 7) was used, and evaluation was performed in the same manner as in Example 1.

(Evaluation) For the above Examples 1 to 15 and Comparative Examples 1 to 3, the characteristics of the toner used are shown in Table 1, and the average particle diameter, the particle size distribution GSDv and the fixing characteristics are shown in Table 2. Here, Tm is the melting point of the toner, G '(30) is the storage modulus at 30 ° C., G ′ (Tm) and G ′ (Tm + 10) are the melting point and the melting point + 10 ° C.
Storage modulus, G ″ (Tm), G ″ (Tm + 10) are melting point and loss modulus at melting point + 10 ° C., Δlog G ′ is | log
G ′ (Tm + 20) −log G ′ (Tm + 50) | and Δlog G ″
Indicates | log G "(Tm + 20) -log G" (Tm + 50) |.

[0162]

[Table 1]

[0163]

[Table 2]

As is clear from Tables 1 and 2, the electrostatic charge developers containing the toner for electrostatic charge development of Examples 1 to 15 are as follows:
Compared to the electrostatic charge developer containing the electrostatic charge development toner of Comparative Examples 1 to 3, the particle size distribution is narrow, that is, since the particle size of each toner can be uniform, excellent fine line reproducibility,
In addition, an electrostatic charge developing toner free from background fog was obtained. Further, the electrostatic charge developer containing the same toner for electrostatic charge development as in Example 1 was loaded into the image forming apparatus (2) equipped with a fixing belt, and the image quality was evaluated. It was possible to stably form an excellent image with no ground fog.

[0165]

According to the present invention, by adopting the above constitution, it is possible to provide an electrostatic image developing toner having excellent low-temperature fixability and having a colorant and a release agent uniformly dispersed therein. Even in a belt-type fixing machine having a low heating capacity at the time of fixing and a high-speed fixing machine, it is possible to stably form an excellent image.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of an example of an image forming apparatus for performing an image forming method of the present invention.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Norito Fukushima 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (72) Inventor Takashi Imai 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Fuji Xerox Co., Ltd. F-term (Reference) 2H005 AA01 AA06 AA21 AB03 BA06 CA01 CA08 CA14 DA05 DA06 EA03 EA06 EA10 2H033 AA02 AA09 AA30 BA11 BA12 BA58 BB01 BB28 CA36

Claims (10)

[Claims] 1. An electrostatic image developing toner containing at least a crystalline resin having a melting point as a binder resin,
An electrostatic image developing toner comprising an ester compound having an alkyl group having 6 to 32 carbon atoms. 2. The toner according to claim 1, wherein the toner for developing an electrostatic image has a storage elastic modulus (G ′) and a loss elastic modulus (G ″) of 40 to 110.
2. The toner for developing an electrostatic image according to claim 1, wherein the toner has a region that changes by two digits or more per 10 [deg.] C. in a temperature range of [deg.] C. 3. The electrostatic image developing toner according to claim 1, wherein the electrostatic image developing toner contains one or more release agents. 4. The dispersion of the binder resin particles, the dispersion of the colorant particles, and the dispersion of the ester compound particles are stirred and mixed, and the dispersion of aggregated particles containing at least the binder resin particles and the colorant particles is performed. The electrostatic charge image according to any one of claims 1 to 3, wherein a liquid is prepared and heated to a temperature equal to or higher than the melting point of the crystalline resin of the binder resin to integrate the aggregated particles. A method for producing a developing toner. 5. An electrostatic charge image developer containing a carrier and a toner, wherein the toner is the toner for developing an electrostatic charge image according to claim 1. Image developer. 6. The electrostatic image developer according to claim 5, wherein the carrier has a resin coating layer. 7. A step of forming an electrostatic latent image, a step of developing the electrostatic latent image with a developer, a step of transferring a toner image to a fixing base material, and a step of fixing the toner image to the fixing base material An image forming method comprising: using the electrostatic image developer according to claim 5. 8. The image forming method according to claim 7, wherein in the fixing step, the contact time between the fixing member and the unfixed image on the fixing base material is adjusted to 0.01 to 0.05 seconds. 9. The image forming method according to claim 7, wherein a belt-type fixing machine is used in the fixing step. 10. An electrostatic latent image carrier, an image writing unit, a developing unit for supplying a developer, a unit for transferring a toner image on the electrostatic latent image carrier onto a transfer body, and the transfer 7. An image forming apparatus provided with a means for fixing a toner image on a body, wherein a belt-type fixing machine including a pressure roll and a fixing belt is used, and the electrostatic image developer according to claim 5 or 6 is used. An image forming apparatus comprising: