JP2003255586A - Electrostatic charge image developing toner, method for manufacturing the same, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner having excellent thin line reproducibility and not causing defacing of characters, a method for manufacturing the electrostatic charge image developing toner, and an image forming method. <P>SOLUTION: In the electrostatic charge image developing toner manufactured through a step for fusion-bonding resin particles and colorant particles in an aqueous medium, 1-1,000 ppm compound represented by the formula R<SB>1</SB>O(R<SB>2</SB>O)<SB>n</SB>H is contained. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing toner and a method for producing an electrostatic charge image developing toner.

[0002]

2. Description of the Related Art Today, an electrostatic latent image developing method represented by an electrophotographic method is widely used as an image forming method for printers, copying machines, facsimiles and the like.

The reason for this is that it is a method with a high degree of perfection in which a high-quality image can be stably obtained at a high speed, but some problems still remain.

For example, in the conventional toner prepared by the pulverization method, the material dispersed in the toner is nonuniformly present on the fracture surface, the surface properties of the toner are difficult to be constant, and variations occur in the transfer process. However, there is a problem that the color reproducibility as a color image is deteriorated.

On the other hand, the electrostatic latent image developing toner is desired to have a small particle size from the viewpoint of high image quality. As a method for producing a toner having a small particle diameter, development of a polymerization toner has been active in recent years. In this polymerization method, resin particles and colorant particles are optionally associated with or salted out, aggregated, and fused to prepare an amorphous toner, or a radically polymerizable monomer and a colorant are dispersed. Then, there is a method in which droplets are dispersed in an aqueous medium or the like so as to have a desired toner particle diameter, and suspension polymerization is performed.

However, since the toner particles produced by applying the suspension polymerization method can form a spherical toner having a uniform surface property, the toner particles have high uniformity but have a spherical shape. Therefore, the adhesiveness to the latent image carrier is increased, and there is a problem that the transferability is reduced.

Therefore, in JP-A-11-194540, resin particles polymerized in an aqueous medium containing a surfactant are coagulated with a coagulant having a concentration higher than the critical coagulation concentration of the resin particles, and an organic solvent infinitely soluble in water. Non-spherical particles are disclosed which are characterized in that they have been treated with.

In the technique described above, the use of a divalent or trivalent metal salt as the aggregating agent provides an image with excellent shape uniformity and charge amount uniformity and high sharpness.
The presence of a monovalent or trivalent metal salt raises the Kraft point of the surfactant and forms a precipitate that is sparingly soluble in water. These deposits are present in a state of adhering to the toner even after the colored particles, that is, the toner is separated from the aqueous medium, and there are problems that the fine line reproducibility is likely to be deteriorated and that characters are likely to be crushed.

[0009] In particular, conventionally known nonionic surfactants have been used as emulsifiers for emulsion polymerization. The difference in biodegradability due to their structure and the controllability of toner particle size (stability during toner aggregation) The characteristics are various such as the difference in emulsifying power depending on the number of moles of alkylene oxide added, and the present situation is that the search for emulsifiers suitable for emulsion polymerization systems continues.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrostatic charge image developing toner excellent in fine line reproducibility and free from character collapse, a method for producing the electrostatic charge image developing toner and an image forming method. That is.

[0011]

The above objects of the present invention have been achieved by the following constitutions 1 to 7.

1. In the toner for developing an electrostatic charge image produced through the step of fusing resin particles and colorant particles in an aqueous medium, 1 p of the compound represented by the general formula (1) is added.
A toner for developing an electrostatic charge image, which comprises pm to 1000 ppm.

2. In the whole compound represented by the general formula (1), the ratio of the compound in which n is in the range of 3 to 6 in the whole compound is 20% to 80%, and Toner for charge image development.

3. The HLB value of the compound represented by the general formula (1) is 15 to 20,
Or the toner for developing an electrostatic charge image as described in 2 above.

4. The cloud point of the compound represented by the general formula (1) is 60 ° C. or higher, and
5. The toner for developing an electrostatic charge image according to any one of 1.

5. The method for producing the toner for developing an electrostatic charge image according to any one of 1 to 4 above, characterized by comprising a step of polymerizing a polymerizable monomer in an aqueous medium to produce resin particles. Method for producing toner for developing electrostatic image.

6. In producing the toner for developing an electrostatic charge image according to any one of 1 to 4, the toner particles are produced through a step of aggregating and fusing resin particles in an aqueous medium. A method for producing a toner for developing a charge image.

7. A step of forming an electrostatic charge image on an electrostatic charge image carrier, a step of developing the electrostatic charge image with a developer containing a toner for developing an electrostatic charge image to form a toner image, and a step of transferring the toner image on a transfer body. 5. An image forming method comprising the step of transferring to the electrostatic charge image developing toner according to any one of 1 to 4 as the electrostatic charge image developing toner.

The present invention will be described in detail below. The present inventors have made various studies on the problems described above, and as a result, claim 1
In the toner for developing an electrostatic charge image produced through the step of fusing resin particles and colorant particles in an aqueous medium as described in 1., the toner is represented by the general formula (1) in the aqueous medium. As a toner for developing an electrostatic charge image which is characterized by containing a compound in an amount of 1 ppm to 1000 ppm, a toner for developing an electrostatic charge image which is excellent in fine line reproducibility and has no crushed characters has been found. Further, from the viewpoint of more preferably obtaining the effect described in the present invention, the content of the compound represented by the general formula (1) in the aqueous medium is preferably adjusted to the range of 5 ppm to 500 ppm.

As means for adjusting the content of the compound represented by the general formula (1) in the toner for developing an electrostatic image of the present invention to the content described above, the preparation of (a) latex. , The amount of the colorant used at the time of dispersion, (b) the preparation of the washing conditions during the production of the colored particles, (c) after the production of the colored particles,
It can be adjusted by selecting an appropriate one from among things such as post-addition after the preparation of the toner or the preparation of the developer.

The compound represented by the general formula (1), which is present in the step of preparing a dispersion of resin particles relating to the toner for developing an electrostatic charge image of the present invention, and fusing the resin particles and the colorant particles together. Will be described.

In the general formula (1), R ₁ has 10 carbon atoms.
It represents an aliphatic hydrocarbon group having 22 to 22 carbon atoms or a distyrenecapphenyl group, preferably an aliphatic hydrocarbon group having 10 to 20 carbon atoms, and more preferably an aliphatic hydrocarbon group having 10 to 18 carbon atoms. is there.

Examples of the aliphatic hydrocarbon group having 10 to 22 carbon atoms represented by R ₁ include n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group and n-
Alkyl groups such as pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-docosadecyl group, decenyl group, dodecenyl group, tridecenyl group, pentadecenyl group, 5- (3-pentenyl) -3,
6,8-decatriene-1-ynyl group, 6- (1,3-
Pentadienyl) -2,4,7-docodecatriene-9
-Inyl group, 6- (1-pentene-3-ynyl) -2,
Unsaturated aliphatic hydrocarbon group such as 4,7,9-undecatetraenyl group (alkenyl group, alkadienyl group, alkatrienyl group and alkapolyenyl group); Cyclic aliphatic such as octylcyclohexyl group and nonylcyclohexyl group A carbon group etc. are mentioned. These aliphatic carbon groups may be linear or branched.

The distyrenated phenyl group represented by R ₁ may be unsubstituted or may have a substituent. The substituent is preferably an aliphatic hydrocarbon group, for example, an alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.), an alkenyl group (vinyl group, allyl group, isopropenyl group, pentenyl group, octenyl group). Groups and the like). Further, these alkyl group and alkenyl group are
Each may further have a substituent.

In the general formula (1), R ₂ has 2 to 2 carbon atoms.
It represents an alkylene group having 6 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms.

Examples of the alkylene group having 2 to 6 carbon atoms represented by R ₂ include ethylene group, trimethylene group, tetramethylene group, propylene group and ethylethylene group.

In the general formula (1), n is an integer of 1 to 11, preferably 2 to 10 and more preferably 2.
5 and particularly preferably 2-3.

<< Measurement of Average Molecular Weight of Compound Represented by General Formula (1) >> The average molecular weight of the compound represented by General Formula (1) can be measured by GPC (gel permeation chromatography).

<< GPC measurement conditions >> Model: HLC-8120 (manufactured by Tosoh Corporation) Measurement column TSK gel SuperH4000 (manufactured by Tosoh Corporation) TSK gel SuperH3000 (manufactured by Tosoh Corporation) TSK gel SuperH2000 (manufactured by Tosoh Corporation) Column temperature : 40 ° C. Detector: RI Measuring solvent: Tetrahydrofuran Flow rate: 0.6 ml / min Sample concentration: 0.25%, Injection volume: 10 μl Standard sample: At least eight types of polyoxyethylene glycols each having a different molecular weight (manufactured by Tosoh Corporation) ; TSK
STANDARD POLYETHYLENE OX
A calibration curve was created using IDE).

Data processing apparatus: SC-8020 (manufactured by Tosoh Corporation) << Ratio of compounds in which n is in the range of 3 to 6 in the whole compound >> In the present invention, the compound represented by the above general formula (1) In the whole, the proportion of the compound in which n is in the range of 3 to 6 in the whole compound is preferably 20% to 80%, more preferably 23% to 50%.

Here, the ratio of the compound in which n is in the range of 3 to 6 to the total amount of the compounds is a value in the total area of the chromatographic curve obtained from the above GPC measurement.

<< HLB of Compound Represented by General Formula (1)
Value >> The compound represented by the general formula (1) according to the present invention is
From the viewpoint of improving the emulsifying power, HLB is preferably 15 to 20, more preferably 17 to 19, and particularly preferably 17 to 18. Here, HLB is
HLB (Hydrophile-Lip) calculated by summing the numerical values indicating organicity and inorganicity (Oda, Teramura, "Synthesis of surfactants and their applications", page 501, Maki Shoten)
It is the Yahoo!

<< Cloud Point of Compound Represented by General Formula (1) >>
From the viewpoint of improving emulsifying power and dispersibility, the compound represented by the general formula (1) according to the present invention preferably has a cloud point (cloud point) of 60 ° C. or higher, more preferably 80 ° C. or higher. Yes, particularly preferably 85 ° C to 100 ° C
Is the range.

Here, the cloud point can be measured by a method known to those skilled in the art. For example, an aqueous solution containing the general formula (1) may be prepared and the cloud point may be determined by visually observing the temperature at which solid-liquid separation occurs while gradually raising the temperature. It may be obtained from the change in the transmittance of When more accurate measurement is required, the conventionally known method of measuring the cloud point of a surfactant by an optical method can be applied as it is.

Specific examples of the surfactant represented by the general formula (1) are shown below, but the present invention is not limited thereto.

Compound (1): C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₄ H Compound (2): C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₄ H Compound (3): C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₃ H compound (4): C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₅ H In the general formula (1), R ₁ has a distyrenated phenyl group. , Neugen EA-167,
EA-177 (made by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like can be mentioned.

The compound represented by the general formula (1) according to the present invention is an alkylene oxide addition type nonionic surfactant, and is disclosed in JP-A-10-130690 and JP-A-2002-2002.
It can be produced by the method described in JP-A-53895, JP-A-2002-53897, or the conventionally known alkylene oxide addition reaction.

Specifically, under a reaction catalyst, 70 ° C. to 200 ° C.
It can be produced by adding ethylene oxide, propylene oxide, butylene oxide or the like to alcohol at a temperature of ° C by a specific addition method. For example, an alkali (eg, KOH) or acid (eg, BF3) catalyst is added to a higher alcohol having 10 to 22 carbon atoms, a mixture of ethylene oxide and propylene oxide is randomly added under a nitrogen atmosphere, and then ethylene oxide is block-added. And then block-adding propylene oxide.

Further, as described in claim 2, n is 3 to
A compound having a range of 6 has a ratio of 2 in the whole compound.
In order to narrow the so-called molecular weight distribution, such as 0% to 80%, a calcined magnesium oxide-containing compound (JP-A-1-164437) and a calcined hydrotalcite (JP-A-1-164437) are used as catalysts during the reaction. 2-71841),
A catalyst selected from perchlorate (US Pat. No. 4,112,231), perhalogenic acid (salt), sulfuric acid (salt), nitric acid (salt) and divalent or trivalent metal alcoholate is preferably used. .

In the present invention, from the viewpoints of keeping the charge retention function of the toner in a good state, suppressing fog generation at high temperature and high quality, and improving transferability, and suppressing increase in charge amount at low temperature and low humidity. From the viewpoint of stabilizing the development amount,
The content of the surfactant represented by the above general formula (1) in the toner for developing an electrostatic image of the present invention is 1 ppm.
~ 1000 ppm is preferred, more preferably 5 ppm
To 500 ppm, particularly preferably 7 ppm to 1
It is 00 ppm.

By incorporating a surfactant in the toner in the above-mentioned range, the electrostatic property of the toner for developing an electrostatic charge image of the present invention is not affected by the influence of the environment and is always uniformly and stably applied. , Can be maintained.

The content of the surfactant represented by the general formula (1) described above in the toner for developing an electrostatic image of the present invention is measured by an absorptiometry (also referred to as a colorimetric method) shown below. Using.

(Analysis of Content by Absorptiometry) Toner 1
g in ion-exchanged water 50 ml and filtered to extract the compound represented by the general formula (1) in the aqueous phase, and then extract 1
A 0 ml portion is taken and 10 ml of cobalt ammonium thiocyanate reagent solution (ammonium thiocyanate 112.4 g
And 59.4 g of cobalt nitrate dissolved in water, 250 ml
8 g of sodium chloride) and shake for 1 minute. Next, 10 ml of benzene is added and shaken for 5 minutes to separate benzene. This absorbance is measured at wavelength 320
The content in the toner was measured from a calibration curve prepared in advance in the concentration range of 90 ppm or less.

In the present invention, a metal salt is preferably used as the aggregating agent in the step of salting out, aggregating and fusing the resin particles from the dispersion liquid of the resin particles prepared in an aqueous medium, more preferably 2 The use of a monovalent or trivalent metal salt as an aggregating agent. The reason is that the divalent or trivalent metal salt has a smaller critical aggregation concentration (coagulation value or coagulation point) than the monovalent metal salt.

The metal salt used as the aggregating agent or the aggregation terminator according to the present invention will be described.

Examples of the metal salt include monovalent metal salts such as alkali metal salts such as sodium, potassium and lithium, and 2
Valent metals, for example, salts of alkaline earth metals such as calcium and magnesium, divalent metal salts such as manganese and copper, iron,
Examples thereof include trivalent metal salts such as aluminum. Specific examples of these metal salts are shown below.

Specific examples of the metal salt of a monovalent metal include sodium chloride, potassium chloride, lithium chloride and the like. Examples of the metal salt of a divalent metal include magnesium chloride, calcium chloride, calcium nitrate, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate and the like.
Examples of the trivalent metal salt include aluminum chloride and iron chloride. These are appropriately selected according to the purpose.

The above-mentioned critical coagulation concentration is an index relating to the stability of the dispersion in the aqueous dispersion, to which a coagulant is added,
The concentration at the point where aggregation occurs is shown. This critical coagulation concentration greatly changes depending on the latex itself and the dispersant.
For example, Seizo Okamura et al., Polymer Chemistry 17,601 (19)
60) etc., and its value can be known by following these descriptions.

As another method, a desired salt is added to the target particle dispersion liquid at various concentrations, and ζ of the dispersion liquid is added.
It is also possible to measure the potential and set the salt concentration at the point where the ζ potential starts to change as the critical aggregation concentration.

The polymer fine particle dispersion is treated with the above-mentioned metal salt according to the present invention so as to have a concentration higher than the critical aggregation concentration. At this time, as a matter of course, whether the metal salt is directly added or added as an aqueous solution is arbitrarily selected according to the purpose. When it is added as an aqueous solution, the added metal salt needs to have a critical coagulation concentration of the polymer particles or more with respect to the volume of the polymer particle dispersion and the total volume of the metal salt aqueous solution.

The concentration of the metal salt used as the coagulant is
It may be added at a critical coagulation concentration or higher, but preferably 1.2 times or more, more preferably 1.5 times or more the critical coagulation concentration.

It should be noted that composite resin particles (when the particles have a multi-layered structure or when the particles contain other constituent components such as additives, etc. are called composite resin particles) and colorant particles are dispersed. The temperature of the dispersion when adding the aggregating agent to the dispersion is preferably not higher than the glass transition temperature (Tg) of the composite resin particles, and specifically in the range of 5 to 55 ° C. The temperature is preferably set to 10 ° C to 45 ° C.

The temperature of the dispersion when adding the coagulant is
When the glass transition temperature (Tg) of the composite resin particles is equal to or higher than the glass transition temperature (Tg), it is difficult to control the particle size, and giant particles are easily generated.

In the salting-out, aggregating, and fusing step, the temperature of the dispersion liquid in which the composite resin particles and the colorant particles are dispersed is the glass transition temperature (T
g) At the following times, the flocculant is added while stirring the dispersion, and then the heating of the dispersion is immediately started,
The temperature is preferably equal to or higher than the glass transition temperature (Tg) of the composite resin particles.

Further, in the present invention, the resin particles and the colorant are salted out, aggregated and fused in an aqueous medium to obtain colored particles (in the present invention, referred to as toner particles), and then the toner particles are water-based. When separated from the medium, it is preferably carried out at a temperature not lower than the Kraft point of the surfactant present in the aqueous medium, and more preferably at a temperature range of Kraft point to (Craft point + 20 ° C.). is there.

The Kraft point is the temperature at which the aqueous solution containing the surfactant begins to turn cloudy, and the Kraft point is measured as follows.

<Measurement of Kraft Point> An aqueous medium used in the steps of salting out, aggregating, and fusing is prepared by adding a coagulant in an amount actually used to the solution, and the solution is prepared at 1 ° C. Stored for 5 days. The solution was then heated slowly with stirring until it became transparent. The temperature at which the solution became clear is defined as the Kraft point.

From the viewpoint of suppressing excessive charging of the toner particles and imparting uniform charging property, the toner for developing an electrostatic image of the present invention comprises the toner of the present invention for stabilizing and maintaining the charging property especially to the environment. Metal element described above (as a form, metal,
250 to 20 in the toner)
The content is preferably 000 ppm, more preferably 800 to 5000 ppm.

In the present invention, the total value of the divalent (trivalent) metal element used as the aggregating agent and the monovalent metal element added as the aggregating terminator described later is 350 to 35,000 pp.
It is preferably m.

The residual amount of metal ions in the toner is measured by using a fluorescent X-ray analyzer "System 3270" (manufactured by Rigaku Denki Kogyo Co., Ltd.), and the metal species of the metal salt used as a coagulant (for example, It can be determined by measuring the intensity of fluorescent X-rays emitted from calcium (derived from calcium chloride, etc.). As a specific measuring method, a plurality of toners having a known content ratio of the aggregating agent metal salt are prepared, 5 g of each toner is pelletized, and the content ratio of the aggregating agent metal salt (mass p
pm) and the fluorescent X-ray intensity (peak intensity) from the metal species of the metal salt are measured (calibration curve). Next, the toner (sample) whose content ratio of the coagulant metal salt is to be measured is similarly pelletized, and fluorescence X from the metal species of the coagulant metal salt is collected.
By measuring the line strength, the content ratio, that is, the “residual amount of metal ions in the toner” can be obtained.

A method of manufacturing the toner for developing an electrostatic image of the present invention will be described. The toner of the present invention forms composite resin particles in the absence of a colorant, adds a dispersion of colorant particles to a dispersion of the composite resin particles, salts out the composite resin particles and the colorant particles, It is prepared by aggregating and fusing.

Thus, by carrying out the preparation of the composite resin particles in a system in which no colorant is present, the polymerization reaction for obtaining the composite resin particles is not hindered. Therefore, according to the toner of the present invention, the excellent offset resistance is not impaired, and the contamination of the fixing device and the image stain due to the accumulation of the toner do not occur.

Further, as a result of the polymerization reaction being surely carried out to obtain the composite resin particles, no monomer or oligomer remains in the obtained toner particles, and the image forming method using the toner can be used. No offensive odor is generated in the heat fixing step.

Further, the surface characteristics of the obtained toner particles are uniform and the distribution of charge amount is sharp, so that an image having excellent sharpness can be formed for a long period of time.

The "composite resin particles" constituting the toner of the present invention are made of a resin having a molecular weight and / or a composition different from that of the resin forming the core particles so as to cover the surface of the core particles made of the resin. Alternatively, it means a resin particle having a multilayer structure in which two or more coating layers are formed.

The "central part (nucleus)" of the composite resin particles means "nucleus particles" constituting the composite resin particles.

The "outer layer (shell)" of the composite resin particles means the outermost layer of the "one or more coating layers" constituting the composite resin particles.

The "intermediate layer" of the composite resin particles means a coating layer formed between the central portion (nucleus) and the outer layer (shell).

The molecular weight distribution of the composite resin particles is not monodisperse, and the composite resin particles usually have a molecular weight gradient from the central part (nucleus) to the outer layer (shell).

In the present invention, it is preferable to use the "multistage polymerization method" to obtain the composite resin particles from the viewpoint of controlling the molecular weight distribution, that is, from the viewpoint of securing the fixing strength and the offset resistance. In the present invention, the “multi-stage polymerization method” for obtaining the composite resin particles means that a single amount is present in the presence of the resin particles (n) obtained by polymerizing the monomer (n) (nth stage). The polymer (n + 1) is subjected to a polymerization treatment (n + 1th stage), and a polymer of the monomer (n + 1) (dispersed with the constituent resin of the resin particles (n) and / or composition is formed on the surface of the resin particles (n). A method of forming a coating layer (n + 1) made of different resins will be shown.

Here, when the resin particles (n) are core particles (n = 1), a "two-step polymerization method" is used, and when the resin particles (n) are composite resin particles (n≥2). In other words, it is a multi-step polymerization method of three or more steps.

In the composite resin particles obtained by the multistage polymerization method, a plurality of resins having different compositions and / or molecular weights are present. Therefore, the toner obtained by salting out, aggregating, and fusing the composite resin particles and the colorant particles has extremely small variations in composition, molecular weight, and surface characteristics among the toner particles.

Such a toner having a uniform composition, molecular weight, and surface characteristics among the toner particles has good adhesiveness (high fixing strength) to an image support in an image forming method including a fixing step by a contact heating method. It is possible to improve the anti-offset property and the anti-wrapping property while maintaining the above value), and it is possible to obtain an image having an appropriate gloss.

An example of the method for producing the toner for developing an electrostatic charge image of the present invention will be specifically described. (1) The release agent and / or the crystalline polyester is a region other than the outermost layer (central portion or intermediate layer). Multi-stage polymerization step (I) for obtaining composite resin particles prepared so as to be contained in 1., (2) salting-out, aggregating and fusing composite resin particles and colorant particles to obtain toner particles Step (II) of aggregating and fusing, (3) Toner particles filtered from the dispersion system of toner particles to remove a surfactant and the like from the toner particles, a washing step, (4) washing-treated toner The method comprises a drying step of drying the particles and (5) a step of adding an external additive to the dried toner particles.

Each step will be described below. << Multistage Polymerization Step (I) >> The multistage polymerization step (I) is performed by a multistage polymerization method in which a coating layer (n + 1) made of a polymer of a monomer (n + 1) is formed on the surface of the resin particles (n). This is a step of producing resin particles. Where the manufacturing stability,
From the viewpoint of the crush strength of the obtained toner, it is preferable to employ a multi-stage polymerization method of three or more stages.

The two-step polymerization method and the three-step polymerization method, which are typical examples of the multi-step polymerization method, will be described below.

<< Explanation of Two-Stage Polymerization Method >> The two-stage polymerization method is a core part (nucleus) formed from a high molecular weight resin containing a release agent.
And a method for producing composite resin particles composed of an outer layer (shell) formed of a low molecular weight resin. That is, the composite resin particles obtained by the two-step polymerization method are composed of the core and one coating layer.

This method will be described in detail. First, a monomer solution obtained by dissolving a release agent in a monomer (H) is dispersed in an aqueous medium (an aqueous solution of a surfactant) as oil droplets. Then, by subjecting this system to a polymerization treatment (first stage polymerization),
A dispersion liquid of high molecular weight resin particles (H) containing a release agent is prepared.

Then, to the dispersion liquid of the resin particles (H),
Polymerization initiator and monomer (L) for obtaining low molecular weight resin
Is added, and the monomer (L) is subjected to a polymerization treatment (second-stage polymerization) in the presence of the resin particles (H), so that a resin having a low molecular weight (mono) is added to the surface of the resin particles (H). A coating layer (L) made of a polymer of the polymer (L) is formed.

<< Explanation of Three-Step Polymerization Method >> The three-step polymerization method comprises a central part (nucleus) formed of a high molecular weight resin, an intermediate layer containing a release agent, and an outer layer formed of a low molecular weight resin ( shell)
And a method for producing composite resin particles composed of That is, the composite resin particles obtained by the three-step polymerization method are composed of a core and two coating layers.

This method will be described in detail. First, a dispersion of resin particles (H) obtained by a polymerization treatment (first-stage polymerization) according to a conventional method is treated with an aqueous medium (aqueous solution of a surfactant). And a dispersion of the monomer solution obtained by dissolving the release agent in the monomer (M) in the aqueous medium to disperse the oil droplets, and then the system is subjected to a polymerization treatment (second-stage polymerization). Thus, a coating layer (M) (intermediate layer) made of a resin (polymer of monomer (M)) containing a release agent is formed on the surface of the resin particles (H) (core particles). A dispersion liquid of the following composite resin particles [high molecular weight resin (H) -intermediate molecular weight resin (M)] is prepared.

Then, a polymerization initiator and a monomer (L) for obtaining a low molecular weight resin are added to the obtained dispersion liquid of the composite resin particles, and the monomer is added in the presence of the composite resin particles. By polymerizing (L) (third stage polymerization), a low molecular weight resin (monomer (L) is formed on the surface of the composite resin particles.
To form a coating layer (L).

In this three-stage polymerization method, resin particles (H)
When the coating layer (M) is formed on the surface of the resin, the dispersion liquid of the resin particles (H) is added to the aqueous medium (aqueous solution of the surfactant), and a release agent is added to the aqueous medium in a single amount. A method of polymerizing the system (second-stage polymerization) after dispersing a monomer solution dissolved in the body (M) into oil droplets to disperse the release agent finely and uniformly be able to.

As for the addition treatment of the dispersion liquid of the resin particles (H) and the oil droplet dispersion treatment of the monomer solution, any of them may be carried out in advance as described below, or they may be carried out simultaneously. May be.

(A) When the intermediate layer constituting the composite resin particles is formed, the resin particles to be the central portion (nucleus) of the composite resin particles are added to the aqueous solution of the surfactant, and then the aqueous solution of the surfactant is added. A mode in which a monomer composition containing a release agent / crystalline polyester is dispersed and this system is subjected to a polymerization treatment, and (b) a release agent / crystallinity when forming an intermediate layer constituting composite resin particles. A monomer composition containing polyester is dispersed in an aqueous solution of a surfactant, and then resin particles to be the central part (nucleus) of the composite resin particles are added to the aqueous solution to polymerize this system. Aspect, (c) When forming the intermediate layer constituting the composite resin particles, at the same time as adding the resin particles to be the central portion (nucleus) of the composite resin particles to the aqueous solution of the surfactant,
A mode in which a monomer composition containing a release agent / crystalline polyester is dispersed in the aqueous solution and the system is subjected to a polymerization treatment is included.

As a method for forming the resin particles (nucleus particles) or the coating layer (intermediate layer) containing the release agent, the release agent is dissolved in the monomer, and the resulting monomer solution is added to the aqueous medium. A method of obtaining latex particles by dispersing oil droplets in the above and polymerizing this system can be adopted.

Here, the "aqueous medium" means water 50 to 10
A medium composed of 0 mass% and a water-soluble organic solvent of 0 to 50 mass%. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran, and alcohol-based organic solvents that do not dissolve the obtained resin are preferable.

A polymerization method suitable for forming resin particles or a coating layer containing a release agent is as follows. An aqueous medium prepared by dissolving a surfactant at a concentration not higher than the critical micelle concentration is used.
A monomer solution prepared by dissolving a release agent in a monomer is dispersed into oil droplets by using mechanical energy to prepare a dispersion liquid, and a water-soluble polymerization initiator is added to the obtained dispersion liquid. Then, a method of radical polymerization in oil droplets (hereinafter referred to as "mini-emulsion method") can be mentioned. Instead of adding the water-soluble polymerization initiator, or while adding the water-soluble polymerization initiator, an oil-soluble polymerization initiator may be added to the monomer solution.

According to the mini-emulsion method of mechanically forming oil droplets, unlike the usual emulsion polymerization method, the release agent dissolved in the oil phase is not released and the formed resin particles or A sufficient amount of release agent can be introduced into the coating layer.

The dispersing machine for dispersing oil droplets by mechanical energy is not particularly limited, and the stirring device "CLEARMIX" (MEAR TECHNIQUE) equipped with a rotor rotating at high speed is used. (Manufactured by K.K.), an ultrasonic disperser, a mechanical homogenizer, Manton-Gaulin, and a pressure homogenizer. The dispersed particle size is 10 to 1
000 nm, preferably 50 to 1000 nm, more preferably 30 to 300 nm.

A known method such as an emulsion polymerization method, a suspension polymerization method or a seed polymerization method can be adopted as a polymerization method for forming the resin particles or the coating layer containing the release agent. Further, these polymerization methods can also be adopted to obtain resin particles (core particles) or a coating layer constituting the composite resin particles, which does not contain a release agent and crystalline polyester.

The particle size of the composite resin particles obtained in this polymerization step (I) is determined by the electrophoresis light scattering photometer "ELS-80".
0 "(manufactured by Otsuka Electronics Co., Ltd.) is preferably in the range of 10 to 1000 nm as the weight average particle diameter.

Further, the glass transition temperature (T
g) is preferably in the range of 48 to 74 ° C, more preferably 52 to 64 ° C. The softening point of the composite resin particles is preferably in the range of 95 to 140 ° C.

<< Step (II) of salting out, aggregating, and fusing >> The step (II) of salting out, aggregating, and fusing includes the composite resin particles obtained by the multistage polymerization step (I) and colorant particles. Is a step of obtaining amorphous (non-spherical) toner particles by salting out, aggregating, and fusing (simultaneously causing salting out and fusing).

In the step (II) of salting out, aggregating, and fusing, internal additive particles such as a charge control agent (having a number average primary particle size of 10 to 1 are used together with the composite resin particles and the colorant particles.
Fine particles of about 000 nm) may be salted out, aggregated, and fused.

The colorant particles may be surface-modified. Here, as the surface modifier, a conventionally known one can be used.

The colorant particles are subjected to salting out, aggregation and fusion treatment in a state of being dispersed in an aqueous medium. Examples of the aqueous medium in which the colorant particles are dispersed include an aqueous solution in which the surfactant is dissolved at a concentration equal to or higher than the critical micelle concentration (CMC).

As the surfactant, the same surfactant as used in the multistage polymerization step (I) can be used.

The disperser used for the dispersion treatment of the colorant particles is not particularly limited, but it is preferable that the stirring device “CLEARMIX” equipped with a rotor rotating at high speed is used.
X) "(manufactured by M Technique Co., Ltd.), ultrasonic disperser,
Examples thereof include a pressure homogenizer such as a mechanical homogenizer, Manton-Gaulin, a pressure homogenizer, and a medium type homogenizer such as a Getzman mill and a diamond fine mill.

In order to salt out, aggregate and fuse the composite resin particles and the colorant particles, a flocculant having a critical coagulation concentration or more is added to the dispersion liquid in which the composite resin particles and the colorant particles are dispersed. At the same time, it is preferable to heat the dispersion liquid to the glass transition temperature (Tg) or higher of the composite resin particles.

More preferably, the aggregation stopper is used at the stage when the composite resin particles have reached a desired particle diameter with the aggregating agent. As the aggregation stopper, monovalent metal salts, especially sodium chloride, are preferably used.

The temperature range suitable for salting out, aggregating, and fusing is (Tg + 10) to (Tg + 50 ° C.), and particularly preferably (Tg + 15) to (Tg + 40 ° C.).
It is said that In addition, an organic solvent infinitely soluble in water may be added in order to effectively carry out the fusion.

Examples of the "aggregating agent" used for salting out, aggregating, and fusing include the above-mentioned alkali metal salts and alkaline earth metal salts.

Salting out and agglomeration according to the present invention will be described. In the present invention, "salting out, aggregating, and fusing" means
Salting out (aggregation of particles) and fusion (disappearance of interface between particles) occur at the same time, or the action of causing salting out and fusion at the same time.

In order to carry out salting out and fusion at the same time,
Glass transition temperature (Tg) of resin constituting composite resin particles
It is preferable to aggregate the particles (composite resin particles, colorant particles) under the above temperature conditions.

The toner for developing an electrostatic image of the present invention forms composite resin particles in the absence of a colorant, and the dispersion liquid of the colorant particles is added to the dispersion liquid of the composite resin particles to obtain the composite resin particles. It is preferably prepared by salting out, aggregating, and fusing with the colorant particles.

Thus, by carrying out the preparation of the composite resin particles in a system in which no colorant is present, the polymerization reaction for obtaining the composite resin particles is not hindered. Therefore, according to the toner of the present invention, the excellent offset resistance is not impaired, and the contamination of the fixing device and the image stain due to the accumulation of the toner do not occur.

Further, as a result of the reliable polymerization reaction for obtaining the composite resin particles, no monomer or oligomer remains in the obtained toner particles, and the image forming method using the toner can be used. No offensive odor is generated in the heat fixing step.

Further, the surface characteristics of the obtained toner particles are uniform and the distribution of the charge amount is sharp, so that an image having excellent sharpness can be formed for a long period of time. Such a toner having a uniform composition, molecular weight, and surface characteristics among toner particles maintains good adhesiveness (high fixing strength) to an image support in an image forming method including a fixing step by a contact heating method. However, it is possible to improve the anti-offset property and the wrapping prevention property, and it is possible to obtain an image having an appropriate gloss.

The release agent used in the toner of the present invention will be described. The content of the release agent constituting the toner for developing an electrostatic image of the present invention is usually 1 to 30% by mass, preferably 2 to 20% by mass, more preferably 3 to 1%.
It is set to 5% by mass.

A low-molecular weight polypropylene (number average molecular weight = 1500 to 9000), low-molecular-weight polyethylene or the like may be added to the releasing agent, and a preferable releasing agent is preferably an ester compound represented by the following general formula.

In the general formula R _1- (OCO-R ₂ ) _n , n represents an integer of 1 to 4, preferably 2 to 4, more preferably 3 to 4, and particularly preferably 4.

R ₁ and R ₂ represent a hydrocarbon group which may have a substituent. R _1: a carbon number = 1-40, preferably 1-20, more preferably 2 to 5 R _2: the number of carbon atoms = 1-40, preferably 16-30, more preferably to 18 to 26 below, the general formula Specific examples of the ester compound represented by are shown below, but the present invention is not limited thereto.

[0114]

[Chemical 1]

[0115]

[Chemical 2]

The amount of the releasing agent and the fixing improving agent represented by the general formula to be added is 1 to 30% by mass, preferably 2 to 20% by mass, and more preferably the total amount of the toner for developing an electrostatic image. It is 3 to 15 mass%.

The preferred molecular weight, molecular weight range, peak molecular weight, etc. of the resin component constituting the electrostatic image developing toner of the present invention will be described.

The toner of the present invention has a peak or shoulder of 100,000 to 1,000,000, and 1,
000 to 50,000, more preferably 100,000 to 1.00 peaks or shoulders.
20,000, 25,000-150,000, 1,
More preferably, it exists in the range of 000 to 50,000.

The molecular weight of the resin of the toner is 100,000.
A high molecular weight component having a peak or shoulder in the region of 1,000,000 to 1,000 to 50,
A resin containing at least both low molecular weight components having a peak or shoulder in a region of less than 000 is preferable. More preferably, the peak molecular weight is 15,
It is to use an intermediate molecular weight resin having a peak or a shoulder in the range of 000 to 100,000.

The molecular weight is measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a column solvent.

Specifically, 1 mg of the measurement sample was used for T
1 ml of HF is added, and the mixture is stirred at room temperature using a magnetic stirrer to sufficiently dissolve it. Then, after being treated with a membrane filter having a pore size of 0.45 to 0.50 μm, it is injected into GPC. The measurement conditions of GPC are as follows: stabilize the column at 40 ° C, and add THF at 1 m / min.
at a flow rate of 1 l and a sample with a concentration of 1 mg / ml is about 100
Inject μl and measure. As the column, it is preferable to use a commercially available polystyrene gel column in combination. For example, Shodex GPC manufactured by Showa Denko KK
KF-801, 802, 803, 804, 805, 80
Combination of 6,807 and TSKgelG1 manufactured by Tosoh Corporation
000H, G2000H, G3000H, G4000
H, G5000H, G6000H, G7000H, TS
A combination of K guard columns and the like can be mentioned.

A refractive index detector (IR detector) or a UV detector is preferably used as the detector. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve prepared using monodisperse polystyrene standard particles. It is preferable to use about 10 points as polystyrene for preparing the calibration curve.

The filtration / washing process relating to the production of the electrostatic image developing toner of the present invention will be described.

In this filtering / washing step, a filtering treatment for filtering the toner particles from the dispersion system of the toner particles obtained in the above step, and the filtered toner particles (cake-like aggregate)
A cleaning process is performed to remove adhering substances such as a surfactant and an aggregating agent.

Here, the filtration method is not particularly limited, such as a centrifugal separation method, a reduced pressure filtration method using a Nutsche or the like, or a filtration method using a filter press or the like.

<< Drying Step >> This step is a step of drying the washed toner particles.

Examples of the dryer used in this step include a spray dryer, a vacuum freeze dryer, a vacuum dryer and the like. A stationary shelf dryer, a mobile shelf dryer, a fluidized bed dryer, a rotary dryer It is preferable to use a dryer or a stirring dryer.

The water content of the dried toner particles is preferably 5% by mass or less, more preferably 2% by mass or less.

When the dried toner particles are aggregated by a weak attraction force between particles, the aggregate may be crushed. Here, as the crushing treatment device, a mechanical crushing device such as a jet mill, a Henschel mixer, a coffee mill, a food processor or the like can be used.

The polymerizable monomer according to the present invention will be described. (1) Hydrophobic Monomer The hydrophobic monomer constituting the monomer component is not particularly limited, and conventionally known monomers can be used. Further, one kind or a combination of two or more kinds can be used so as to satisfy the required characteristics.

Specifically, a monovinyl aromatic monomer,
(Meth) acrylic acid ester-based monomer, vinyl ester-based monomer, vinyl ether-based monomer, monoolefin-based monomer, diolefin-based monomer, halogenated olefin-based monomer, etc. may be used. it can.

Examples of vinyl aromatic monomers include:
Styrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n- Examples thereof include styrene-based monomers such as octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, 2,4-dimethylstyrene, and 3,4-dichlorostyrene, and derivatives thereof. .

As the acrylic monomer, acrylic acid,
Methacrylic acid, methyl acrylate, ethyl acrylate,
Butyl acrylate, 2-ethylhexyl acrylate,
Cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, γ-aminoacrylate propyl, stearyl methacrylate, methacrylic Examples thereof include dimethylaminoethyl acid salt and diethylaminoethyl methacrylate.

Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl benzoate and the like.

Examples of vinyl ether type monomers include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like.

Examples of the mono-olefin type monomer include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene and the like.

Examples of the diolefin-based monomer include butadiene, isoprene, chloroprene and the like.

(2) Crosslinkable Monomer A crosslinkable monomer may be added to improve the properties of the resin particles. As the crosslinkable monomer, divinylbenzene,
Divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate,
Examples thereof include those having two or more unsaturated bonds such as diallyl phthalate.

(3) Monomer having acidic polar group As the monomer having an acidic polar group, (a) an α, β-ethylenically unsaturated compound having a carboxyl group (—COOH) and (b) a sulfone An α, β-ethylenically unsaturated compound having a group (—SO ₃ H) can be mentioned.

Examples of the α, β-ethylenically unsaturated compound having a —COO group (a) include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, and monobutyl maleate. Examples thereof include esters, maleic acid monooctyl esters, and metal salts thereof such as Na and Zn.

(B) Examples of the α, β-ethylenically unsaturated compound having a sulfo group (--SO ₃ H group) are sulfonated styrene, its Na salt, allylsulfosuccinic acid, octyl allylsulfosuccinate, and its Na salt. Etc. can be mentioned.

The initiator (also referred to as a polymerization initiator) used for the polymerization of the polymerizable monomer according to the present invention will be described.

The polymerization initiator used in the present invention can be appropriately used if it is water-soluble. For example, persulfates (potassium persulfate, ammonium persulfate, etc.), azo compounds (4,4′-azobis-4-cyanovaleric acid and salts thereof,
2,2'-azobis (2-amidinopropane) salt, etc.),
Examples thereof include peroxide compounds such as hydrogen peroxide and benzoyl peroxide.

Further, the above-mentioned polymerization initiator can be used as a redox type initiator in combination with a reducing agent, if necessary. By using the redox type initiator, the polymerization activity can be increased, the polymerization temperature can be lowered, and further shortening of the polymerization time can be expected.

Any temperature may be selected as the polymerization temperature as long as it is at least the minimum radical generation temperature of the polymerization initiator, but for example, a range of 50 ° C. to 80 ° C. is used. It is also possible to polymerize at room temperature or a temperature close to it by using a combination of a polymerization initiator which starts at room temperature, for example, hydrogen peroxide-reducing agent (ascorbic acid etc.).

The chain transfer agent used in the present invention will be described. In the present invention, for the purpose of adjusting the molecular weight of the resin particles produced by polymerization of the polymerizable monomer,
Conventionally known and commonly used chain transfer agents can be used.

The chain transfer agent is not particularly limited, but a compound having a mercapto group is preferably used because a toner having a sharp molecular weight distribution can be obtained and the storage stability, fixing strength and offset resistance are excellent. For example, octyl mercaptan, dodecyl mercaptan, t
A compound having a mercapto group such as ert-dodecyl mercaptan is used.

Preferable ones are, for example, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate,
2-ethylhexyl thioglycolate, octyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, thioglycolic acid ester of ethylene glycol, thioglycolic acid ester of neopentyl glycol, thioglycolic acid ester of pentaerythritol, etc. Can be done.

Among them, n-octyl-3-mercaptopropionic acid ester is preferably used from the viewpoint of suppressing the odor at the time of heating and fixing the toner.

The colorant according to the present invention will be described. The colorant relating to the toner for developing an electrostatic image of the present invention is, from the viewpoint of improving the uniformity of charging of the toner, salting out with the resin particles during the production of the toner, salting out, aggregation and fusion of the above-mentioned composite resin particles. It is preferable that the toner particles are aggregated, fused, and contained in the toner particles.

Examples of the colorant (colorant particles used for salting out, aggregation, and fusion with the composite resin particles) constituting the toner of the present invention include various inorganic pigments, organic pigments, and dyes. . As the inorganic pigment, conventionally known ones can be used. Specific inorganic pigments are exemplified below.

Examples of black pigments include furnace black, channel black, acetylene black,
Carbon black such as thermal black and lamp black, and magnetic powder such as magnetite and ferrite are also used.

These inorganic pigments can be used alone or in combination of two or more as desired. Further, the amount of the pigment added is 2 to 20% by mass, preferably 3 to 15% by mass, based on the polymer.

When used as a magnetic toner, the above magnetite can be added. In this case, from the viewpoint of imparting predetermined magnetic characteristics, 20 to 1 is included in the toner.
It is preferable to add 20% by mass.

Known organic pigments and dyes can be used. Specific organic pigments and dyes are exemplified below.

As the magenta or red pigment,
C. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16,
C. I. Pigment Red 48: 1, C.I. I. Pigment Red 53: 1, C.I. I. Pigment Red 57:
1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 139,
C. I. Pigment Red 144, C.I. I. Pigment Red 149, C.I. I. Pigment Red 166, C.I.
I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 222 and the like.

Pigments for orange or yellow include C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 43, C.I. I. Pigment Yellow 12,
C. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I.
I. Pigment Yellow 17, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I.
Pigment Yellow 138, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185, C.I.
I. Pigment Yellow 155, C.I. I. Pigment Yellow 156 and the like.

As a pigment for green or cyan,
C. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3,
C. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7 and the like.

As the dye, C.I. I. Solvent Red 1, 49, 52, 58, 63, 111,
122, C.I. I. Solvent Yellow 19, 44,
77, 79, 81, 82, 93, 98, 103, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93,
Id. 95 and the like can be used, and a mixture thereof can also be used.

These organic pigments and dyes may be used alone or in combination of two or more as desired. Further, the amount of the pigment added is 2 to 20% by mass, preferably 3 to 15% by mass, based on the polymer.

The colorant (colorant particles) constituting the electrostatic image developing toner of the present invention may be surface-modified.
Here, as the surface modifier, conventionally known ones can be used, and specifically, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent and the like can be preferably used.

Examples of silane coupling agents include alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane and diphenyldimethoxysilane, siloxanes such as hexamethyldisiloxane, γ-chloropropyltrimethoxysilane and vinyl. Trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
γ-ureidopropyltriethoxysilane and the like can be mentioned.

Examples of titanium coupling agents include:
TTS, 9S, 38S, 41B, 46B, 5 sold under the trade name "Planeact" manufactured by Ajinomoto Co., Inc.
5, 138S, 238S, etc., a commercial product A- manufactured by Nippon Soda Co., Ltd.
1, B-1, TOT, TST, TAA, TAT, TL
A, TOG, TBSTA, A-10, TBT, B-2,
B-4, B-7, B-10, TBSTA-400, TT
S, TOA-30, TSDMA, TTAB, TTOP and the like can be mentioned.

Examples of the aluminum coupling agent include "Planeact AL-M" manufactured by Ajinomoto Co., Inc., and the like.

The amount of these surface modifiers added is preferably 0.01 to 20% by mass, more preferably 0.1 to 5% by mass, based on the colorant.

Examples of the surface modification method of the colorant particles include a method of adding a surface modifier to the dispersion liquid of the colorant particles and heating this system to react.

The surface-modified colorant particles are collected by filtration, washed with the same solvent and filtered, and then dried.

The toner particles constituting the toner of the present invention may contain an internal additive other than the release agent, such as a charge control agent.

As the charge control agent contained in the toner particles, a nigrosine dye, a metal salt of naphthenic acid or a higher fatty acid, an alkoxylated amine, a quaternary ammonium salt compound, an azo metal complex, a salicylic acid metal salt or a salt thereof. Examples thereof include metal complexes.

The external additive used in the toner of the present invention will be described. As the inorganic fine particles that can be used as an external additive, conventionally known ones can be mentioned. Specifically, silica fine particles, titanium fine particles, alumina fine particles and the like can be preferably used. These inorganic fine particles are preferably hydrophobic.

Specific examples of the silica fine particles include commercially available products R-805, R-976, and R- manufactured by Nippon Aerosil Co., Ltd.
974, R-972, R-812, R-809, HVK-2150, H-200 manufactured by Hoechst Co., Ltd., and commercial products TS-720, TS-530, TS manufactured by Cabot Co., Ltd.
-610, H-5, MS-5, etc. are mentioned.

Specific examples of titanium fine particles include, for example,
Commercial products T-805 and T-60 manufactured by Nippon Aerosil Co., Ltd.
4. Commercial products MT-100S, MT-1 manufactured by Teika Co., Ltd.
00B, MT-500BS, MT-600, MT-60
0SS, JA-1, commercial product TA- manufactured by Fuji Titanium Co., Ltd.
300SI, TA-500, TAF-130, TAF-
510, TAF-510T, commercial products IT-S, IT-OA, IT-OB, IT-OC manufactured by Idemitsu Kosan Co., Ltd. and the like can be mentioned.

Specific examples of the alumina fine particles include, for example, commercial products RFY-C and C- manufactured by Nippon Aerosil Co., Ltd.
604, a commercial product TTO-55 manufactured by Ishihara Sangyo Co., Ltd., and the like.

Examples of organic fine particles that can be used as an external additive include spherical fine particles having a number average primary particle diameter of about 10 to 2000 nm. Examples of the constituent material of such organic fine particles include polystyrene, polymethylmethacrylate, and styrene-methylmethacrylate copolymer.

Examples of the lubricant that can be used as an external additive include metal salts of higher fatty acids. Specific examples of such metal salts of higher fatty acids include zinc stearate, aluminum stearate, copper stearate, magnesium stearate, calcium stearate, and other stearic acid metal salts; zinc oleate, manganese oleate, iron oleate, and olein. Oleic acid metal salts such as copper acid and magnesium oleate; Metal palmitate salts such as zinc palmitate, copper palmitate, magnesium palmitate and calcium palmitate; Metal linoleate salts such as zinc linoleate and calcium linoleate; Ricinol Examples thereof include metal salts of ricinoleic acid such as zinc acid salt and calcium ricinoleate.

The addition amount of the external additive is preferably about 0.1 to 5 mass% with respect to the toner.

The process of adding the external additive will be described. This step is a step of adding an external additive to the dried toner particles.

The equipment used for adding the external additive includes a Turbuler mixer, a Hensiel mixer,
Various known mixing devices such as a Nauta mixer and a V-type mixer can be mentioned.

The particle size of the electrostatic charge image developing toner of the present invention will be described. The number average particle diameter of the toner of the present invention is preferably 3 to 10 μm, and more preferably 3 to 8 μm. This particle size can be controlled by the concentration of the aggregating agent, the amount of the organic solvent added, the fusing time, and the composition of the polymer in the toner production method described in detail later.

When the number average particle diameter is 3 to 10 μm, the number of toner fine particles having a large adhesive force that fly and adhere to the heating member to generate an offset in the fixing step decreases, and the transfer efficiency increases. The image quality of halftone is improved, and the image quality of thin lines and dots is improved.

The number average particle diameter of the toner is, Coulter Counter TA-II, Coulter Multisizer, SLAD
1100 (a laser diffraction particle size measuring device manufactured by Shimadzu Corporation) can be used for the measurement.

In the present invention, a Coulter Multisizer was used, and an interface (manufactured by Nikkaki Co., Ltd.) for outputting the particle size distribution and a personal computer were connected and used. The 100 μm aperture was used in the Coulter Multisizer, and the volume distribution of the toner of 2 μm or more (for example, 2 to 40 μm) was measured to calculate the particle size distribution and the average particle size.

The shape factor of the toner particles of the present invention will be described. The shape factor of the toner of the present invention is represented by the following formula, and indicates the degree of roundness of toner particles.

Shape factor = ((maximum diameter / 2) ² × π) / projected area Here, the maximum diameter means the parallel line when a projected image of toner particles on a plane is sandwiched by two parallel lines. Refers to the width of the particles at which the interval is maximum. The projected area means the area of the projected image of the toner particles on the plane.

In the present invention, this shape factor is determined by taking a photograph of toner particles magnified 2000 times with a scanning electron microscope, and then using the photograph, "SCANNING" is taken.
It was measured by analyzing a photographic image using "IMAGE ANALYZER" (manufactured by JEOL Ltd.). At this time, the shape factor of the present invention was measured by the above calculation formula using 100 toner particles.

In the above constitutions (1) and (9), it is preferable that the number of toner particles having the shape factor in the range of 1.0 to 1.6 is 65% by number or more, and more preferably 70% by number. % Or more. More preferably, the number of toner particles having the shape factor in the range of 1.2 to 1.6 is 65% by number or more, and more preferably 7
It is 0% by number or more.

When the number of toner particles having the shape factor in the range of 1.0 to 1.6 is 65% by number or more, the triboelectrification property in the developer carrying member becomes more uniform, and the excessively charged toner is obtained. Is not accumulated and the toner is more easily exchanged than on the surface of the developer transport member, so that problems such as development ghost are less likely to occur. Further, the toner particles are less likely to be crushed, the contamination of the charging member is reduced, and the charging property of the toner is stabilized.

Further, in the above-mentioned constitution (16), it is necessary that the number of toner particles having the shape factor in the range of 1.2 to 1.6 is 65% by number or more, preferably,
70% by number or more.

The method of controlling the shape factor is not particularly limited. For example, a method of spraying toner particles in a hot air stream, a method of repeatedly applying mechanical energy by impact force in a gas phase in a gas phase, or a method of adding a toner to a solvent that does not dissolve toner to give a swirling flow, etc. To prepare a toner having a shape factor of 1.0 to 1.6, or 1.2 to 1.6, and add the toner to an ordinary toner so that the toner falls within the range of the present invention. There is. Also, the overall shape is controlled at the stage of adjusting the so-called polymerization toner, and the shape factor is 1.0 to 1.6,
Alternatively, there is a method in which a toner adjusted to 1.2 to 1.6 is similarly added to a normal toner for adjustment.

In the toner of the present invention, when the particle diameter of the toner particles is D (μm), the natural logarithm lnD is plotted on the horizontal axis, and the horizontal axis is on the basis of the number divided into a plurality of classes at intervals of 0.23. In the histogram showing the particle size distribution, the sum (M) of the relative frequency (m1) of toner particles contained in the most frequent class and the relative frequency (m2) of toner particles contained in the next most frequent class. ) Is preferably 70% or more.

When the sum (M) of the relative frequency (m1) and the relative frequency (m2) is 70% or more, the dispersion of the particle size distribution of the toner particles becomes narrow, so that the toner is used in the image forming process. As a result, the occurrence of selective development can be reliably suppressed.

In the present invention, the histogram showing the number-based particle size distribution has a natural logarithm lnD (D: particle size of individual toner particles) in a plurality of classes (0 to 0) at intervals of 0.23.
0.23: 0.23 to 0.46: 0.46 to 0.69:
0.69 to 0.92: 0.92 to 1.15: 1.15
1.38: 1.38 to 1.61: 1.61 to 1.84:
1.84-2.07: 2.07-2.30: 2.30-
2.53: 2.53 to 2.76 ...), which is a histogram showing a number-based particle size distribution, and the histogram shows particle size data of a sample measured by a Coulter Multisizer according to the following conditions. Is transferred to a computer via an I / O unit and is created by the particle size distribution analysis program in the computer.

<< Measurement Conditions >> (1) Aperture: 100 μm (2) Sample Preparation Method: Electrolyte [ISOTON R-1
1 (manufactured by Coulter Scientific Japan)
An appropriate amount of a surfactant (neutral detergent) is added to 50 to 100 ml and stirred, and 10 to 20 mg of a measurement sample is added thereto. This system is prepared by subjecting it to an ultrasonic disperser for 1 minute.

The “cornerless toner particles” according to the present invention will be described with reference to FIG. In the toner according to the present invention, the proportion of toner particles having no corners in the toner particles constituting the toner is preferably 50% by number or more, more preferably 70% by number or more.

When the proportion of the toner particles having no corners is 50% by number or more, the voids of the transferred toner layer (powder layer) are reduced, the fixing property is improved, and the offset hardly occurs. Further, the toner particles that are easily worn or broken and the toner particles having a portion where the electric charge is concentrated are reduced, the charge amount distribution becomes sharp, the chargeability becomes stable, and good image quality can be formed for a long time.

Here, the "toner particles having no corners" refer to toner particles which do not substantially have projections where electric charges are concentrated or projections which are easily worn by stress.
Specifically, the following toner particles are referred to as cornerless toner particles. That is, as shown in FIG. 1A, the toner particles T
When the major axis of L is L, a circle C of radius (L / 10)
When the inside of the toner particle T is rolled while making contact with the inside of the toner particle T at one point, the case where the circle C does not substantially extend outside the toner T is referred to as “toner particle without corners”. The term “when substantially not protruding” means a case where there is one or less protrusions with protruding circles. Also,
The “major axis of toner particles” refers to the width of the particles that maximizes the distance between the parallel lines when the projected image of the toner particles on a plane is sandwiched by two parallel lines. Note that FIGS. 1B and 1C show projected images of toner particles having corners, respectively.

The proportion of toner particles having no corners was measured as follows. First, a photograph of a magnified toner particle is taken with a scanning electron microscope and further magnified to 15,0.
A photographic image of 00 times is obtained. Then, the presence or absence of the above-mentioned corner is measured for this photographic image. This measurement was performed on 100 toner particles.

The method for obtaining a toner having no corners is not particularly limited. For example, as described above as a method of controlling the shape factor, a method of spraying toner particles in a hot air flow, a method of repeatedly applying mechanical energy due to impact force in a gas phase, or a method of dissolving toner It can be obtained by adding it to a solvent that does not contain it and imparting a swirling flow.

The toner obtained by fusing has a circularity of 0.930 to 0.930 as expressed by the following formula.
Those having 0.980, preferably 0.940 to 0.975 are preferably used.

Circularity = (circular circumference obtained from equivalent circle diameter)
/ (Perimeter of projected image of particle) Further, it is preferable that the shape factor distribution is sharp,
The standard deviation of circularity is preferably 0.10 or less, and the CV value calculated by the following formula is preferably in the range of 15 to 25.

CV value = {(standard deviation of circularity) / (average circularity)} × 100 By setting the average circularity to 0.930 to 0.980, the shape of the toner is made irregular to some extent. Therefore, heat transfer can be made efficient, and the fixing property can be further improved. That is, the average circularity is 0.9
When it is 80 or less, the fixability can be improved.
Further, by setting the average circularity to 0.930 or more, the degree of irregular shape of the particles can be suppressed, and the crushability of the particles due to stress during long-term use can be suppressed.

The developer used in the present invention will be described. The toner of the present invention may be used as a one-component developer or a two-component developer.

When used as a one-component developer, 0.1 to 0.5 μm is contained in a non-magnetic one-component developer or toner.
A magnetic one-component developer containing a certain amount of magnetic particles can be used, and any one can be used.

Further, it can be used as a two-component developer by mixing with a carrier. In this case, as the carrier magnetic particles, metals such as iron, ferrite and magnetite,
Conventionally known materials such as alloys of these metals with metals such as aluminum and lead can be used. Ferrite particles are particularly preferable. The volume average particle diameter of the magnetic particles is 15 to 100 μm, and more preferably 25 to 8 μm.
0 μm is preferable.

The volume average particle diameter of the carrier is typically measured by a laser diffraction type particle size distribution measuring apparatus “HELOS” (sympatic (SYMP)
(Made by ATEC)).

The carrier is preferably one in which magnetic particles are further coated with a resin, or a so-called resin dispersion type carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited, but, for example, an olefin resin, a styrene resin, a styrene-acrylic resin, a silicone resin, an ester resin, a fluorine-containing polymer resin, or the like is used. The resin for forming the resin-dispersed carrier is not particularly limited, and known ones can be used. For example, styrene-acrylic resin, polyester resin, fluorine resin, phenol resin, etc. are used. be able to.

The image forming method of the present invention will be described.
The toner of the present invention comprises an image forming method including a step of passing an image forming support on which a toner image is formed between a heating roller and a pressure roller constituting a fixing device to fix the image forming support (image forming of the present invention. Method).

FIG. 2 is a cross-sectional view showing an example of a fixing device used in the image forming method of the present invention. The fixing device shown in FIG. 2 includes a heating roller 10 and a pressure roller 20 contacting the heating roller 10. I have it. In FIG. 2, T
Is a toner image formed on a transfer paper (image forming support).

The heating roller 10 has a coating layer 12 made of a fluororesin or an elastic material formed on the surface of a core metal 11, and contains a heating member 13 made of a linear heater.

The core metal 11 is made of metal and has an inner diameter of 10 to 70 mm. The metal forming the cored bar 11 is not particularly limited, but examples thereof include metals such as iron, aluminum, and copper, and alloys thereof.

The core metal 11 has a wall thickness of 0.1 to 15 mm, and is determined in consideration of the balance between the demand for energy saving (thinning) and the strength (depending on the constituent materials). For example,
In order for the core metal made of aluminum to maintain the same strength as the core metal made of iron of 0.57 mm, it is necessary to make the wall thickness 0.8 mm.

The fluororesin constituting the coating layer 12 includes PTFE (polytetrafluoroethylene) and P.
FA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) etc. can be illustrated.

The thickness of the coating layer 12 made of fluororesin is 1
The thickness is 0 to 500 μm, and preferably 20 to 400 μm.

The coating layer 12 made of fluororesin has a thickness of 1
When the thickness is less than 0 μm, the function as the coating layer cannot be sufficiently exhibited, and the durability as the fixing device cannot be ensured. On the other hand, there is a problem in that the surface of the coating layer having a thickness of more than 500 μm is easily scratched by paper dust, and toner or the like adheres to the scratched portion, resulting in image stain.

As the elastic body forming the coating layer 12, it is preferable to use silicone rubber or silicone sponge rubber having good heat resistance such as LTV, RTV and HTV.

Asker C which is an elastic body constituting the coating layer 12
The hardness is less than 80 °, preferably less than 60 °.

The thickness of the cover layer 12 made of an elastic material is 0.1 to 30 mm, preferably 0.1 to 20 mm.
It is said that

Asker C, which is an elastic material constituting the coating layer 12
If the hardness exceeds 80 ° and the thickness of the coating layer 12 is less than 0.1 mm, the fixing nip cannot be increased, and the effect of soft fixing (for example, the smoothed interface Effect of improving color reproducibility by toner layer)
Can't exert.

As the heating member 13, a halogen heater can be preferably used. The pressure roller 20 is
A coating layer 22 made of an elastic body is formed on the surface of the cored bar 21. The elastic body forming the coating layer 22 is not particularly limited, and various soft rubbers such as urethane rubber and silicone rubber and sponge rubber can be exemplified. The silicone rubbers exemplified as those forming the coating layer 12 and It is preferable to use silicone sponge rubber.

Asker C, which is an elastic material constituting the coating layer 22
The hardness is less than 80 °, preferably less than 70 °, and more preferably less than 60 °.

The coating layer 22 has a thickness of 0.1 to 30 m.
m, preferably 0.1 to 20 mm.

Asker C, which is an elastic material constituting the coating layer 22
If the hardness exceeds 80 ° and the thickness of the coating layer 22 is less than 0.1 mm, the fixing nip cannot be increased and the soft fixing effect cannot be exhibited.

The material for the cored bar 21 is not particularly limited, but examples thereof include metals such as aluminum, iron and copper, and alloys thereof.

The contact load (total load) between the heating roller 10 and the pressure roller 20 is usually 40 to 350 N, preferably 50 to 300 N, and more preferably 50.
~ 250N. This contact load is applied to the heating roller 1
The strength is defined as 0 (thickness of the core metal 11), and for a heating roller having a core metal of, for example, 0.3 mm of iron, it is preferably 250 N or less.

From the viewpoint of offset resistance and fixing property, the nip width is preferably 4 to 10 mm, and the surface pressure of the nip is 0.6 × 10 ⁵ Pa to 1.5.
It is preferably × 10 ⁵ Pa.

If one example of the fixing conditions by the fixing device shown in FIG. 2 is shown, the fixing temperature (surface temperature of the heating roller 10)
Is set to 150-210 ° C, and the fixing linear velocity is 80-640m.
m / sec.

The fixing device used in the present invention may be provided with a cleaning mechanism if necessary. In this case, as a method of supplying silicone oil to the upper roller (heating roller) of the fixing unit, a method of supplying and cleaning with a pad, roller, web, etc. impregnated with silicone oil can be used.

As the silicone oil, one having a high heat resistance is used, and polydimethyl silicone, polyphenylmethyl silicone, polydiphenyl silicone or the like is used. Since those having a low viscosity have a large outflow amount at the time of use, those having a viscosity at 20 ° C. of 1 to 100 Pa · s are preferably used.

However, the effect of the present invention is particularly remarkable when the step of forming an image is performed by a fixing device that does not supply silicone oil or the supply amount of silicone oil is extremely low. Therefore, even if silicone oil is supplied, the amount supplied is 2 mg.
/ A4 or less is preferable.

The supply amount of silicone oil was 2 mg / A4.
Transfer paper after fixing (image support) by
The amount of silicone oil adhered to the transfer paper is reduced, there is no difficulty in writing with an oil-based pen such as a ballpoint pen due to the silicone oil adhered to the transfer paper, and the writing property is not impaired.

Further, it is possible to avoid problems such as deterioration of offset resistance due to deterioration of silicone oil over time, and contamination of optical system and band electrode by silicone oil.

[0232] Here, the amount of silicone oil supplied was set to the fixing device (between rollers) heated to a predetermined temperature to transfer paper (A
100 sheets of 4 sizes of white paper) are continuously passed, and the mass change (Δw) of the fixing device before and after passing the paper is measured and calculated (Δw / 100).

[0233]

The present invention is described in detail below with reference to examples, but the present invention is not limited to these.

Example 1 Latex 1HML and Latex 2 were prepared as follows.
L (for shelling) and a colorant dispersion were prepared, and colored particles 1 were prepared using them.

<< Preparation of Latex >> (Preparation of Latex 1HML) (1) Preparation of Latex (1H) (First Stage Polymerization: Adjustment of Core Particles) 5000 ml equipped with a stirrer, temperature sensor, cooling tube, nitrogen introducing device In a separable flask of 1.6 g, compound (1), anionic surfactant (Neogen SC:
(Daiichi Kogyo Kagaku Co., Ltd.) 2.4 g, ion-exchanged water 3000
A surfactant solution (aqueous medium) dissolved in g is charged,
The internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream.

An initiator solution prepared by dissolving 10 g of a polymerization initiator (potassium persulfate: KPS) in 400 g of ion-exchanged water was added to this surfactant solution, and the temperature was adjusted to 75 ° C., then 560 g of styrene and n- Butyl acrylate 200
g, 40 g of methacrylic acid are added dropwise over 1 hour, and the system is heated at 75 ° C. for 2 hours with stirring to carry out polymerization (first-stage polymerization) to obtain a latex (high molecular weight). A dispersion liquid of resin particles consisting of resin was prepared. This is designated as "latex (1H)".

(2) Preparation of latex (1HM) (second-stage polymerization: formation of intermediate layer) In a flask equipped with a stirrer, styrene 9 was added.
5 g, n-butyl acrylate 36 g, methacrylic acid 9
g, n-octyl-3-mercaptopropionic acid ester 0.59 g, in a monomer mixture liquid, as a crystalline substance, the compound represented by the formula (19) (hereinafter, referred to as “exemplary compound (19)”). .) 77 g was added, and the mixture was heated to 90 ° C. and dissolved to prepare a monomer solution.

On the other hand, 0.2 g of the compound (1), an anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Kagaku Co., Ltd.)
A surfactant solution obtained by dissolving 3 g in 1560 ml of ion-exchanged water was heated to 98 ° C., and after adding 28 g of the latex (1H), which is a dispersion liquid of core particles, in terms of solid content to the surfactant solution, A monomer solution of the exemplified compound (19) was mixed and dispersed for 8 hours by a mechanical disperser having a circulation path "CLEARMIX" (manufactured by M Technique Co., Ltd.) to obtain a dispersed particle diameter (284n).
Dispersion (emulsion) containing emulsion particles (oil droplets) having m)
Was prepared.

Then, to this dispersion (emulsion) was added an initiator solution prepared by dissolving 5 g of a polymerization initiator (KPS) in 200 ml of ion-exchanged water, and the system was heated and stirred at 98 ° C. for 12 hours. Polymerization (second-stage polymerization)
Then, a latex (dispersion liquid of composite resin particles having a structure in which the surface of resin particles made of a high molecular weight resin is coated with an intermediate molecular weight resin) was obtained. This is "latex (1H
M) ”.

When the latex (1HM) was dried and observed with a scanning electron microscope, particles (4) containing the exemplary compound (19) not surrounded by the latex as a main component were obtained.
(0 to 1000 nm) was observed.

(3) Preparation of Latex 1HML (Third Stage Polymerization: Formation of Outer Layer) In the latex (1HM) obtained as described above, 6.8 g of a polymerization initiator (KPS) was dissolved in 265 ml of deionized water. The added initiator solution was added, and styrene 249 g, n-butyl acrylate 88.
A monomer mixture liquid consisting of 2 g, 24.3 g of methacrylic acid and 7.45 g of n-octyl-3-mercaptopropionic acid ester was added dropwise over 1 hour. After completion of the dropping, polymerization (third stage polymerization) was carried out by heating and stirring for 2 hours, followed by cooling to 28 ° C. and latex (a central part made of a high molecular weight resin, an intermediate layer made of an intermediate molecular weight resin,
A composite resin particle dispersion having an outer layer made of a low molecular weight resin and containing the exemplary compound (19) in the intermediate layer was obtained. This latex is "Latex 1HML"
And

The composite resin particles constituting this latex 1HML are 138,000, 80,000 and 13,
The composite resin particles had a peak molecular weight of 000 and the weight average particle diameter of the composite resin particles was 122 nm.

(Preparation of latex 2L: for shelling)
In a 5000 ml separable flask equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introducing device, 1.6 g of compound (1), an anionic surfactant (Neogen SC:
(Daiichi Kogyo Kagaku Co., Ltd.) 2.4 g, ion-exchanged water 3000
A surfactant solution (aqueous medium) dissolved in g is charged,
The internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream.

To this surfactant solution, an initiator solution prepared by dissolving 10 g of a polymerization initiator (potassium persulfate: KPS) in 400 g of ion-exchanged water was added, and the temperature was adjusted to 75 ° C., then 560 g of styrene and n- Butyl acrylate 200
g, 40 g of methacrylic acid, and 25 g of n-octyl-3-mercaptopropionic acid ester were added dropwise over 1 hour, and the system was heated at 75 ° C. for 2 hours with stirring to perform polymerization. Then, a dispersion containing resin particles for shelling was prepared. This is designated as "latex 2L".

<< Dispersion of Coloring Agent >> 59.0 g of an anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Kagaku Co., Ltd.) was dissolved in 1600 ml of ion-exchanged water with stirring. While stirring this solution, gradually add 420.0 g of carbon black (Regal 330R: manufactured by Cabot), and then stirrer "Clearmix" (M Technique Co., Ltd.).
A dispersion liquid of colorant particles (hereinafter referred to as “colorant dispersion liquid 1”) was prepared by performing a dispersion treatment using The particle size of the colorant particles in this colorant dispersion 1 was measured by using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.) and found to be 110 nm.

<< Preparation of Colored Particle 1 >> (Aggregation, fusion, and association of composite resin particles of latex 1HML and colorant particles) 420.7 g (solid content) of latex (1HML), 900 g of ion-exchanged water and 200 g
The “colorant dispersion liquid 1” of 1 was placed in a reaction container (four-necked flask) equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device and stirred. After adjusting the temperature in the container to 30 ° C., a 5 mol / liter sodium hydroxide aqueous solution was added to this solution to adjust the pH to 8 to 11.0.

Then, 12.1 g of magnesium chloride.
An aqueous solution obtained by dissolving hexahydrate in 1000 ml of ion-exchanged water was added with stirring at 30 ° C. over 10 minutes. Three
The temperature was started after standing for a minute, and the system was heated to 90 ° C. over 60 minutes. In that state, the particle size of the associated particles was measured with "Coulter Counter TA-II", and when the number average particle size reached 4 µm to 7 µm, 40.2 g of sodium chloride was dissolved in 1000 ml of ion-exchanged water. The aqueous solution was added to stop the particle growth, and as a maturing treatment, the mixture was heated and stirred at a liquid temperature of 98 ° C. for 6 hours to continue aggregation, fusion and association.

(Shelling operation) 96 g of latex 2L (dispersion of shelling resin particles) was added after the aggregation, fusion and association treatments described above, and heating and stirring was continued for 3 hours to prepare latex 1HML. Resin particles for coloring and particles of colorant were aggregated, fused, and the resin particles for shelling (latex 2L) were fused on the surfaces of the associated particles. Here, add 40.2 g of sodium chloride, and add 30% under the condition of 8 ° C / min.
Cool to ℃, add hydrochloric acid to adjust the pH to 2.0,
The stirring was stopped. The salted-out, aggregated, and fused particles produced are filtered, washed with 45 ° C. ion-exchanged water, which is 120 times the solid content of the colored particles, and then dried with hot air at 40 ° C. to give colored particles. Got 1.

<< Preparation of Colored Particle 2 >> In the production example of colored particle 1, latex (1H) and latex (1H
M) and colored particles 2 in the same manner except that compound (2) was used instead of compound (1) used in the preparation of latex 2L.
Was produced.

<< Preparation of Colored Particle 3 >> In the production example of colored particle 1, latex (1H) and latex (1H
M) and colored particles 3 in the same manner except that the compound (1) used in the preparation of latex 2L was changed to the compound (3).
Was produced.

<< Preparation of Colored Particle 4 >> In the production example of colored particle 1, latex (1H) and latex (1H
M) and colored particles 4 in the same manner except that compound (4) was used instead of compound (1) used in the preparation of latex 2L.
Was produced.

<< Preparation of Colored Particle 5 >> In the production example of colored particle 1, latex (1H) and latex (1H
M) and colored particles 5 were prepared in the same manner except that the compound (1) used in the preparation of the latex 2L was changed to the comparative compound (5).

<< Preparation of Colored Particle 6 >> In the production example of colored particle 1, latex (1H) and latex (1H
M), the colored particles 6 were prepared in the same manner except that the compound (1) used in the preparation of the latex 2L was changed to the comparative compound (6): nonionic surfactant (Nonipol 400: manufactured by Sanyo Kasei Co., Ltd.). did.

<< Preparation of Electrostatic Image Developing Toners 1 to 4 and Comparative Toners 1 and 2 >> Colored Particles 1 to 4 prepared above.
1% by mass of hydrophobic silica (number average primary particle size = 12 nm, hydrophobicity = 68) and hydrophobic titanium oxide (number average primary particle size = 20 nm, hydrophobicity = 63) were used for the comparative colored particles 5 and 6, respectively. ) Is added and mixed by a Henschel mixer, and toners 1 to 4 for electrostatic image development and toners 1 and 2 for comparison are added.
Were obtained respectively.

Regarding the physical properties such as shape and particle size, there is no difference between the colored particles and the toner produced using the colored particles.

Table 1 below shows the physical properties of the compound represented by the general formula (1) contained in the toner and the obtained toner.

[0257]

[Table 1]

<< Preparation of Developer >> Electrostatic Image Developing Toner 1
~ 4, a ferrite carrier coated with a silicone resin and having a volume average particle diameter of 60 µm was mixed with each of Comparative toners 1 and 2, and a developer was prepared so that the toner concentration was 6%. These are the developers 1 to 4 and the comparative developers 1 and 2.
And

The characteristics of each of the obtained developers were evaluated as follows. << Conditions for live-action photography >> Commercially available digital copying machine Konica Sitios
Using 7075 as an evaluation machine, line width evaluation and character crushing evaluation were performed as follows.

<< Line Width Evaluation: Fine Line Reproducibility Evaluation >> The line width of the line image corresponding to the image signal of 2 dot lines is printed by the printing evaluation system "RT2000" (YAMAN Co., Ltd.).
Manufactured). Both the line width of the first formed image and the line width of the 200,000 formed image are 200
If the line width is less than 10 μm and the change in line width is less than 10 μm, it can be said that fine line reproducibility is not a problem.

[Character crushing (evaluation of readability)] 3 points,
A 5-point character image was formed and ranked as follows.

◎: 3 points, 5 points are clear and easily readable ○: Some unreadable characters occur at 3 points, 5 points are clear and easily readable ×: 3 points Table 2 shows the results obtained when most of the characters were unreadable and even 5 points were partially or completely unreadable.

[0263]

[Table 2]

It is clear from Table 2 that the sample of the present invention has better thin line reproducibility and character collapse (readability) than the comparison.

[0265]

According to the present invention, it is possible to provide an electrostatic charge image developing toner which is excellent in reproducibility of fine lines and has no crushed characters, a method for producing the electrostatic charge image developing toner and an image forming method.

[Brief description of drawings]

FIG. 1A is an explanatory diagram showing a projected image of toner particles without corners, and FIGS. 1B and 1C are explanatory diagrams showing projected images of toner particles with corners.

FIG. 2 is a sectional view showing an example of a fixing device used in the present invention.

[Explanation of symbols]

8 recording materials 10 heating roller 11 core 12 coating layer 13 Heating member 20 pressure rolls 21 core 22 coating layer T Toner image formed on recording material

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tomoko Tanma             2970 Ishikawa-cho, Hachioji-shi, Tokyo Konica stock             In the company F-term (reference) 2H005 AA06 AB03 AB06 CA23 EA03                       EA07 EA10 FB02

Claims (7)

[Claims] 1. A toner for developing an electrostatic charge image produced through a step of fusing resin particles and colorant particles together in an aqueous medium, wherein 1 pp of a compound represented by the following general formula (1) is added.
A toner for developing an electrostatic charge image, characterized by containing m to 1000 ppm. Formula (1) _{R 1 O (R 2 O)} n H [wherein, R ₁ represents an aliphatic hydrocarbon group or, distyrenated phenyl group having 10 to 22 carbon atoms, R ₂ is 2 carbon atoms 6 represents an alkylene group. n represents a number of 1 to 15. ] 2. In the whole compound represented by the general formula (1), the ratio of the compound in which n is in the range of 3 to 6 in the whole compound is 20% to 80%. Item 1. The toner for developing an electrostatic image according to Item 1. 3. H of the compound represented by the general formula (1)
The LB value is 15 to 20.
Or the toner for developing an electrostatic charge image as described in 2 above. 4. The cloud point of the compound represented by the general formula (1) is 60.degree. C. or higher.
5. The toner for developing an electrostatic charge image according to any one of 1. 5. A step of producing a resin particle by polymerizing a polymerizable monomer in an aqueous medium in producing the toner for developing an electrostatic charge image according to claim 1. A method for producing a toner for developing an electrostatic charge image, which comprises: 6. A toner particle is manufactured through a step of aggregating and fusing resin particles in an aqueous medium in manufacturing the toner for developing an electrostatic image according to claim 1. A method for producing a toner for developing an electrostatic charge image, comprising: 7. A step of forming an electrostatic charge image on an electrostatic charge image carrier, a step of developing the electrostatic charge image with a developer containing a toner for developing an electrostatic charge image to form a toner image, and the toner. An image forming method including a step of transferring an image onto a transfer body, wherein the electrostatic charge image developing toner according to any one of claims 1 to 4 is used as the electrostatic charge image developing toner. Image forming method.